PosterPresentationAbstracts-Session1Name Institution Poster#/Area Title Advisor Coauthors

Abstract

ClairePage

UCLA

1Biochem

UnexploredHybridPolyketideSynthaseMotifRevealsUnprecedentedDimethyltransferaseandcis-ActingThioesteraseActivity

YiTang

LeibnezHang

Fungalpolyketidesrepresentalargeportionofmodernpharmaceuticals,howeverlittleisknown about the chemistry of fungal polyketide biosynthetic enzymes. Due to recentwork in fungal genome sequencing, a multitude of uninvestigated fungal polyketidesynthasegeneshavebeenfoundandgroupedintofamiliesaccordingtohomology.Onefamilyofhighly-reducingpolyketidesynthases(HRPKS)isparticularlyinterestingbecauseithasanadjoineddomainwithstrongsimilaritytocarnitineo-acyltransferase(cAT).WereportthefirstcharacterizationofonesuchHRPKS-cATenzymefromTrichodermavirens.This enzyme shows unprecedented activity of dimethyl transferase and cis-actingthioesterases to produce a polyketide-polyol conjugate with a rare gem-dimethylcomponent.Invitrocharacterizationoftheenzymeshowsitcatalyzestheproductionofthe gem-dimethyl moiety through two convergent routes. In the first route, the ACP-bound polyketide chain is directly dimethylated. In the second route, the secondmethylation occurs after the monomethylated product is released from the ACP. Thedependenceof the second routeon thepresenceof thecATdomainandACPsuggeststhe second round of methylation is assisted by the retro-transacylation of the α-monomethylpolyketidebackontotheACP.

CarisseGeronimo CSUBakersfield 2Biochem FluorescenceStudiesofLysylOxidase KarloLopez

Lysyl oxidase, an extracellular enzyme, is responsible for catalyzing the formation ofcrosslinksbetweenelastinandcollagen.Itsmechanismisakeycontributorinthestabilityand proper development of organisms, especially for skin and connective tissues inhumans. Much research has been done in recent years to discover more about itsphysical characteristics. One way of analyzing the structure of proteins is throughfluorescence spectrophotometry; the emission of light by each protein sample isindicativeofitsrelativedegreeofexposuretowater.Anexcitation-emissionmatrix(EEM)has been produced for each of the following variations of lysyl oxidase (LOX): pLOX02(wild-type), pLOX09 (with solubility tagNus-A), aswell as pLOX20 (H303Dmutant) andpLOX21 (H303E mutant). The preliminary results show excitation-emission maxima of(336 nm, 276 nm) for pLOX02, (341 nm, 282 nm) for pLOX09, (339 nm, 280 nm) forpLOX20, and (340 nm, 284 nm) for pLOX21. When compared to the wild-type, it issuggestedthatlargeremissionwavelengths(relativelylessenergeticemissions)indicateaprotein that ismore exposed to water/less tightly packed. These data can be used topiecetogetherthestructuralinfluencesofdifferentmutations/variationsoflysyloxidase.

LisaSitu UCLA 3Biochem AdenovirusProteinE4ORF6/7Alters

OxidativeMetabolismofHumanEpithelialCellsThroughInteractionwithCellularE2F-1

HeatherChristofk

ShivaniK.Thaker,andHeatherR.Christofk

Cancers and viruses reprogram cellular metabolism to promote biosynthesis ofmacromoleculesthatsupportproliferationandreplication.Strongselectionpressureforefficiency enables viruses to accomplish similar metabolic changes as those seen incancersbyactivationofonlythemostcriticalnodespivotaltoanabolicmetabolism.Ourresearchusesadenoviral infectionasamodel tohighlightkey transcription factorsandmetabolic genes thatmay also be relevant formetabolic reprogramming in the cancercontext.Notably,manyhumantumorsdecreaseoxygenconsumptionrate(OCR)eveninaerobic conditions.Our lab has shown that adenovirus infection also decreasesOCR inhumanbreastepithelial(MCF10A)cells.Althoughthemechanismsbywhichcancersandviruses inhibit OCR are currently unknown, if a decrease in OCR confers a growthadvantage, then identification of key regulators can point to therapeutic targets.Adenovirus protein E4ORF6/7 binds cellular transcription factor E2F-1 to activateadenoviralgenes.BecauseE2F-1 inhibitsoxidativemetabolism,wehypothesizethattheinteractionbetweenE4ORF6/7andE2F-1decreasesOCRduringinfection.WeperformedshRNA-mediated E2F-1 knockdown, which increased OCR and protein levels of theelectron transport chain (ETC).WestablyoverexpressedwildtypeormutantE4ORF6/7,withthemutantbeingunabletobindE2F-1.OverexpressionofwildtypeE4ORF6/7,butnotmutantE4ORF6/7,decreasedOCR.Furthermore,wildtypeE4ORF6/7overexpressionincreasedE2F-1 levelswhiledecreasing levelsofspecificETCsubunits.Ourexperimentssuggest thatE4ORF6/7’sability todecreaseOCRreliesondirect interactionwithE2F-1.Our work thus highlights a potential mechanism through which adenovirus infectionaltershostoxidativemetabolism.

KatiaLopez UCLA 4Biochem CharacterizationofaNovelAged-ProteinRepairPathwayinSaccharomycescerevisiaeYeast

StevenClarke RebeccahWarmackandStevenClarke

The spontaneous chemical reactions that damage biomolecules are a hallmark of theaging process. The non-enzymatic isomerization and racemization of asparaginyl andaspartylresiduestoL-isoaspartylresidues isacommontypeofproteindamageinagingorganisms.Mostoftheseorganismsareabletorepairsomeofthisdamagethroughtheprotein-l-isoaspartyl (d-aspartyl)O-methyltransferase (PCMT), which methylates D-aspartylandL-isoaspartylresiduesspecifically,leadingtothereformationofL-aspartate.Althoughtheenzymeispresentinalmostallorganisms,ithasbeenofgreatinterestthatthebuddingyeastSaccharomycescerevisiaedoesnotexpressthisproteinbut isabletomaintainverylowlevelsofL-isoaspartylresiduesincomparisontoorganismswithPCMT.Thisindicatesthepresenceofapotentiallynovelproteinrepairmechanism.IncubationofS.cerevisiaeproteinextractsrevealedanincreasedaccumulationofL-isoaspartyldamagein the presence of the metal chelator ethylenediaminetetraacetic acid (EDTA). Theseresults suggest that at least one of the proteins responsible for L-isoaspartyl damagerepair in yeast may be a metal dependent protease or peptidase. Examination of L-isoaspartate levels from individual single metal dependent protease knockout strains,however,didnotrevealanystrainswithincreasedaccumulationofL-isoaspartylresidues.Further metal rescue experiments directed towards finding themetal co-factor of ourprotein of interest revealed that this repair protein is most likely dependent onmagnesiumorcalcium,possiblysuggestinganon-proteolyticpathwaysinceyeastcellsdonotcontainproteasesactivatedbytheseions.

AndrewSmithandGastonMoorhead

USD 5Biochem Progresstowardsthedevelopmentofnovelnucleicacid-basedtherapeutics.

AnthonyJ.Bell GastonMoorhead Theobjectiveofthisstudywastoevaluatetheviabilityofusingintramolecularfour-wayjunctions(4WJs)foruseastherapeuticinhibitorsagainsttheDNA-bindingcytokine,HighMobility Group B1 (HMGB1). Reports suggest HMGB1 should be considered a lupusbiomarkerbecausetheproteinislinkedwithseveralkeystagesofpathogenesis[1,2].Thestrategy touse4WJs to targetHMGB1 is grounded in classic in vitro studies that showHMGB1 binds to cruciform/bent DNAwith a very high affinity [3-5]. Our initial studiesfocus on investigating the nuclease stability of 4WJs. Three 4WJs are currently beingevaluated;two4WJsreferredtoasiJ1andJ4arecomposedofnaturalDNAwiththymine-thymineendcaps.Thefinal4WJreferredtoastDNAiscomposedDNAwiththiollinkagesvs. phosphatebonds. Thepresenceof end caps in i-J1 and J4 are intended toenhancenuclease stabilitybypreventing favorable contactswithnucleases.The thiol linkages intDNA are known to enhance stability because these bonds are not recognized bynucleases.Nucleasedigestionassaysareconductedat20oand37oCusingnucleasesthatdigestdouble(DNaseI,⎣Exo,andExoIII)andsinglestrandedDNA(ExoVandT5Exo).Ourpreliminary reports show that as expected thepresenceof thymineend-caps and thiollinkagesenhancetherelativenucleaseresistanceofintramolecular4WJsvs.unmodifiedDNA4WJs.

EdwardNjooandLarryPalato

LMU

6Biochem

DeterminingAmyloidogenicityinIsletAmyloidPolypeptide(IAPP)AcrossMammalianSpecies

DavidA.Moffett

LarryPalato,ShannonPilcher,DillonRinauro,AngelaTun,KateMenefee,andDavidA.Moffet

It isestimated that25.8millionchildrenandadults in theUnitedStateshavediabetes,approximately8.3%ofourpopulationwithnearly2millionnewcaseseachyear.Whilethecauseoftype2diabetesremainsunknown,itisknownthatasthediseaseprogresses,patients lose pancreatic β cells (the cells that produce insulin) with up to 45% loss ofpancreasmassinseverecasesofthedisease.Itisbelievedthattheprotein,IAPP,isoneof the agents responsible for thismassivedeathof β cells. For unknown reasons, IAPPaccumulates in the pancreaswhere it aggregates into a variety of toxic forms that areknowntokillβcells.IthasbeenknownthattheIAPPofmiceandratsdoesnotaggregateand that these two species do not develop type-II diabetes; however, the IAPP ofmonkeys, humans, and cats does aggregate and these species do develop type-IIdiabetes.TodetermineifacorrelationexistsbetweenamyloidogenecityofIAPPandthepropensityforanindividualtodeveloptype-IIdiabetes,alistofmammalsthatdoanddonot develop diabetes has been compiled. By determining the amyloidogenicity of theIAPPsequencesoftheseanimals,weexpecttofindacorrelationbetweentheabilitytocontractdiabeteswiththepropensityofIAPPtoaggregate.

AmericaHidalgo

CalBaptistU.

7Biochem

AntioxidantActivityStudyinAgaveUsing1,1-diphenyl-2picrylhydrazyl(DPPH)radicalAssay

Y.Hu

M.A.Hamrick,I.Davis-Ward,andY.Hu

AgaveisapopularplantinthehotterclimatesofthesouthwesternUnitedStatesandMexico.Itiswellknownforitsnutritional,industrialandmedicinalapplications.Inthisstudy,weinvestigatedtheantioxidantactivityinfreshAgavebyusinga1,1-Diphenyl-2-picrylhydrazyl(DPPH)radicalassay.FreshAgavewascollectedatSanManuelReservationinearlyApril,2016.Samplesweresortedforquality,maturity,fieldheatremoved,cooled,weighedintowhirlpackbags,treatedwithliquidnitrogen,storedinultra-lowat-80°andstudiedinSeptember,2016.TheresultsshowanIC50valueof2.20mg/mLforthefreshAgave.TheIC50ofthereference,ascorbicacid,is0.146mg/mL.TheantioxidantactivityofAgaveisrelativelyhighcomparedtootherplantderivedspeciesstudiedinthearea,suchasyuccablossom(21.85mg/mL)andstingingnettle(414.42mg/mL).Furtherresearchisproposedtoinvestigatehowacookingmethodwillinfluencetheantioxidantactivityoftheagave.

MartinAmezcua CSUFullerton 8Biochem SynthesisandEvaluationofSmall

MoleculeInhibitorsasTherapeuticsagainstBoNT/A

NicholasSalzameda

SandraBeltran,RicardoCruz,andNicholasSalzameda

The Botulinum neurotoxin serotype A (BoNT/A) is a metabolic byproduct of theClostridium botulinum bacteria and is responsible for causing Botulism, a paralyticdisease.Theneurotoxin is themost lethal toxinknowntoman. Itspotencyandeaseofextractionfromthebacteriacauseamajorconcernthatitcanbeusedasabioterrorismweaponandinwarfare.TheBoNT/Aiscomposedofaheavychain(HC),andalightchain(LC).Uponexposure,theHCbindingdomainbindstoneuralcells,whiletheHCaidstheLC into the cytosol. The LC is a zinc metalloprotease, and its metal ion active site isresponsibleforcleavingSNAREproteins.CleavingoftheSNAREproteinisanirreversibleprocess that terminates neurotransmissions and results in flaccid paralysis, which canleadtodeath.Currentavailabletherapeuticssuchasintensivecareandphysicaltherapyare not readily available for large scale infections. Therefore, it is vital to developalternative therapeutics against BoNT/A. Previously, the laboratory discovered aninhibitorthatcontainedfourmajorcomponentstothescaffold:(1)Hydroxamicacid,(2)Isoleucine,(3)Sulfonamidebond,and(4)4-Chlorobiphenyl,thathadgoodinhibition.Wehypothesized that increasing theaminoacidson the scaffoldwould increase itsaffinityfor the enzyme. The amino acids were coupled to the resin in varied sequences foranalysis, the 4-chlorobiphenyl 4-sulfonyl chloridewas added to give the sulfonyl-amidebond, and the small molecule was cleaved from the resin with trifluoroacetic acid. Inhindsight, chlorobiphenyl ring system and sulfonamide bond were altered to study itsimpact on inhibition. Fluorescence Resonance Energy Transfer assay was utilized toevaluatethemoleculesasinhibitors.Thesequencescontainingisoleucine-phenylalanine,isoleucine-valine, and isoleucine-isoleucine displayed 84% or greater inhibition of theBoNTLCataconcentrationof15µM.Changingthechlorobiphenylringsystemandthesulfonamidebondonthemoleculeshadadecreaseininhibitionofover50%,asignificantdecrease.Thedecreaseininhibitionconfirmedtheimportanceofthesulfonamidebondandthechlorobiphenylcomponentofthemolecule.

HarrisonShawa

UCLA

9Biochem

Howareproteinsintheeyelensprotectedagainstisomerization-associateddamageduringtheagingprocess?

StevenClarke

BinsenLi,RebeccahWarmack,andStevenClarke

As amammal ages, amino acids in their long-lived eye lens proteins can racemize andisomerize.Thesemodificationscandamagetheproteinsandleadtothedeclineinvisualintegrity that accompanies aging. Eye lens fiber cells lack protein turnovermachinery,thustheproteinsmustremainfortheentirelifespanofanindividual,andthedamagingmodifications can accumulate. The isomerization of L-aspartyl residues to form L-isoaspartate is an especially prevalent form of spontaneous damage. In a majority oftissues, the protein carboxyl methyltransferase (PCMT) and its cofactorS-adenosylmethioninerepairthisdamage.Wehavediscoveredthatthisenzymeispresentandactiveinthelens,butdamaginglevelsofL-isoaspartatestillincreasegreatlywithage.Despite the accumulation of L-isoaspartate with age, lens PCMT activity remainsconstant.OurdatasuggeststhattheconcentrationofPCMTactuallyincreases,butstillisunabletorepairmanyL-isoaspartatesites. BothL-isoaspartateaccumulationandPCMTactivityappeartobeconsistentacrossthedifferentregionsofthelens,butonlyspecificproteinsappeartobereceivingthemajorityoftheenzyme’srepairactivity.

ChristianTotoiu

UCI

10Biochem

EngineeringtheHumanInsulinReceptorforIntegrationintoaReal-timeInsulinBiosensor

GregoryA.Weiss

Sen,S.R.;Majumdar,S.;Crawley,E;Piercy,M.;Gabriel,K.N.,Weiss,G.A.

Type I diabetes (T1D) affects 1.25 million Americans and is predicted to affectapproximately 5 million, by 2050.[1] Disease management involves frequent glucosemonitoringandinsulinadministration.Theartificialpancreas(AP)usescontrolalgorithmsto automate and link continuous glucosemonitoringwith insulin administration.Whileglucose is directly measured in these devices, the control algorithm indirectly andbelatedly estimates insulin levels, thus increasing a patient’s risk of hypoglycemia(excessive blood insulin) or hyperglycemia (insufficient blood insulin). Direct insulinmonitoring would allow for faster regulation and more accurate glucose control.Therefore,weaimtodevelopacontinuous,real-timeinsulinbiosensorforAPdevices.Tomimicnature’sreal-timeinsulindetectionsystem,ourbiosensor isengineeredfromthewildtype human insulin receptor (wtInR). Novel InR variants were designed using acombination of wtInR insulin binding sites and supporting domains. The variants werebuiltusing ligation independentcloningandwereexpressed inE.coliandthroughM13bacteriophage-display. Insulin binding was examined using enzyme-linkedimmunosorbent assays (ELISA). Since insulin binding causes conformational changes inthe wtInR, we incorporated Förster Resonance Electron Transfer (FRET) in our InRvariantstorelayitsinsulin-dependentconformationalchangesasalightsignal.ThissignalcanthenbecapturedbyaphotodetectionsystemintheAPdeviceandexactinsulinlevelscan be quantitatively analyzed. Thus far, our results demonstrate that our InR variantsbindmonomeric insulin. Our lab’s research is directed towards creating and analyzingcorresponding FRET-based variants in functional and kinetic assays, in preparation forfuture in vivodevice studies.Our insulin receptorbiosensor canmakedevices, suchastheAP,saferandmoreeffectiveforthemillionsofT1Dpatientsthatwilldependon it.Furthermore, the promise of such biomimetic sensors opens doors to continuous real-timeinvivosensingofregulatorycomponentsinnumerousotherdiseases.

RochelleRadzyminski

UCI

11Biochem

ElucidatingStructureDependencyandGeneticDeterminantsinPhageandAmoebaeInteractionswithPseudomonasaeruginosa

AlbertSiryaporn

Pseudomonas aeruginosa is a multidrug resistant pathogen that exploits immune-weakenedhostsincludinghospitalpatients,suchasthoseonbreathingmachinesorwithwounds and burns. We are most interested in the central role of the opportunisticpathogenP.aeruginosainpatientswithcysticfibrosis(CF).P.aeruginosacellsarefoundin high density communities known as biofilms, which secrete polymers that obstructantibiotic diffusion into the biofilm. Thus,we look to use bacteriophage therapy as analternativetreatmentforCF.Wehypothesizethatbiofilmorganizationcontributestoitssusceptibility to being lysed by phage, and that the structure is influenced byphysiologicalandmetabolicconditions.Throughfluorescencemicroscopytime-lapsesofphage-bacteria interactions, we have found that phage not only lyses non-resistantbacteria,butalsoinhibitsregularcellfunctionsofresistantbacteria.Phagepreventsthedivisionofcells.Attheendofa24-hourperiod,bacteriacellsgrowintolong,worm-likestructures. A spike in fluorescence intensity occurs prior to rapid phage lysis, which

appears tocorrespondwithan increase inprotein translation—anothereffectofphageon cell functions. These altered functions are significant because theymay potentiallyinhibitthebacteria’svirulence,whichwewill test forwithsubsequentvirulenceassays.We are also infecting a 100,000-mutant transposon insertion library for P. aeruginosawith phage and DNA sequencing the resistant cells to determine the geneticdeterminantsinvolvedinbiofilmclearing.Aswecontinuevaryingtheoxygenlevels,pH,nutrient availability, and substrate stiffness tomimic theCF lung,wewill gain abetterunderstanding of the biofilm structure’s role in its resistance to antibiotics. This, inconjunction with our DNA sequencing of resistant cells, will allow us to look towardsalternativeCFtreatmentsusingphage.

MicheleRamosCorrea

CSUNorthridge

12Biochem

ComparingExpressionofGenesInvolvedinCarbohydrateMetabolisminWild-TypeandLPL-Knock-DownMuscleCells

JheemMedh

Lipoprotein Lipase (LPL) catalyzes the hydrolysis of triglycerides into glycerol and freefattyacids(FFA).Thus,LPLregulatestheentryofFFAsintoskeletalmuscletissue,whichisaninsulin-responsivetissue.WhenLPLactivityishighitreleasesFFAthatareoxidizedforenergy,butwhenLPLactivity is low,musclecellsoxidizeglucoseforenergy.Hence,thedownregulationofLPLforcesthemusclecellstouseglucoseforenergyandinturn,canmakethecellmoreinsulin-sensitive.WewanttostudytheeffectsofLPLlevelsinL6ratskeletalmusclecellsoninsulinaction.WeusedwildtypeL6cellsandLPL-deficient(LPL-KD) cells to compare theexpressionofdifferent genes thatplay important roles in themetabolic actions of insulin.We used reverse transcriptase polymerase chain reactionandagarosegelelectrophoresistoquantifygeneexpressioninthesecells.Preliminarygelresults confirmed a role for LPL in theregulationof genes involved in carbohydratemetabolism.

HannahFejzic,KaylaGarcia,SimbarashePeresuh,KaythrynRager,

CSUSanBernardino

13Biochem UsingDrosophilaReporterstoEvaluateMetalUptake,ROSProduction,andChelationinDrosophilaS2CellsandHumanHeLaandNeuroblastomaCells

YuJungKim

The goal of our project is to determine the rates of metal uptake and reactive oxygen species (ROS)productioninDrosophilaS2cellsandhumanHeLaandneuroblastomacellsusingaDrosophilametal-andROS-sensitiveluciferasereporter.Anadditionalgoalwastousethesereporterstoexaminetheeffectsofmetal chelation in ROS production in these cells since metal chelators are suggested as potentialtherapeutics for neurodegenerative diseases. First,we performed time course experiments to estimatetheratesofmetaluptakeandROSproductioninS2cellsbymeasuringtheluciferasesignalsfromtheMtnandSODpromotersaftertreatingthecellswithCu,Fe,andZnfordifferenttimeperiods.Fromthisstudy,we foundthat the luciferasesignal fromtheMtnpromoterconstruct increased linearlyover timewhenthe cells were treated with Cu and Zn, but not with Fe. This trend was also observed with the SODpromoterconstruct.Forourchelationtests,weusedEDTA,citrate,andhistidinebecausetheyhavebeensuggested as potential therapeutics for neurodegenerative diseases. We performed the chelationexperiments inDrosophilaS2cellsandhumanHeLaandSHSYcellsbymeasuringtheluciferaseactivitiesfromtheMtnandSODpromotersincellstreatedeitherwithCu,Fe,orZninthepresenceorabsenceofEDTA, histidine, or citrate. Of the nine metal-chelator combinations tested in S2 cells, the onlycombination that led to a significant decrease in Mtn-luciferase activity was Zn and citrate, whichcorrelatedwithacorrespondingdecreaseinSOD-luciferaseactivity.ThesameeffectwasobservedinHeLaandSHSY-5YcellswiththeMtnpromoterconstruct.Additionally,wefoundthatinHeLacellstreatedwithCu and histidine, there was a 2-fold decrease in Mtn-luciferase activity relative to cells treated withhistidinealone.

LuisPena

CSUDominguezHills

14Biochem

UsingproteomictechnologytostudytheDNAmethylation

TieliWang

MariaNava,ShevaSaif,AnthonyDiaz,ArumugamThangavel,andTieliWang

DNA methylation has been shown to affect chromatin structure and influence histone methylation.Hypermethylationof thepromoterofmethylguaninemethyltransferase (MGMT) in gliomabrain cancerpatientsisusedasafavorableprognosticbiomarkerandincreasesdrugsensitivitysincealoweramountoftheenzymeisavailabletorepairTMZ-inducedlesions.Inthispresentation,westudiedthemethylationofDNAusingproteomictechnology.DNAmethylationreactionbytemozolomidewascomparedwiththeoneusing formaldehyde in the presence of sodium cyanoborohydride. Both reactions showed the similarmethylation pattern. We found that anticancer drug temozolomide and formaldehyde can producedimethylatedDNAattheaminegroup.

SamMahdi

CSUNorthridge

15Biochem

StructuralanddynamicdifferencesinfluencetheaffinityofRGS4andRGS7forGαi1

KarinCrowhurst

Misregulationofsignal-transmittingGproteinsislinkedtomanyneurologicaldiseases,suchasParkinson’sand Huntington’s. Regulators of G protein signaling (RGS proteins) are responsible for accelerating thedeactivationofGproteins.RGS4selectivelytargetsGαi;however,studieshaveshownthatRGS7targetsprimarily Gαo,with lower affinity (and selectivity) for Gαi1. Considering that residues in the RGS4 andRGS7bindingsitesdifferatonlytwopositions(F33andY82forRGS7,andY34andR84forRGS4),itisnotfully understoodwhy the difference in Gα selectivities exist.We hypothesize that proteinmotions areimportantcontributorstothecontactsbetweenGαi1andthe“box”domainsofRGS4andRGS7,andthatthese motions influence the selectivity and affinity of each RGS for this specific Gα. Our goal for thisprojectwasthereforetouseNMRandSPRspectroscopiestoprobethesemotionsandtotesttheeffectofRGS7mutations on its interactionswithGαi1. PreviousHD exchange and backbone dynamic data haveindicatedapoRGS7primarilyexhibitsps-nstimescalemotionandismoreflexibleoverall,whereasRGS4hasµs-mstimescalemotion.Todeterminewhetherthesedynamicdifferencesorthe2differingresidueswithin the binding site play roles in affinity and/or selectivity,we recorded backbonedynamics on apoRGS7-F33YandRGS7-Y82RandranSPRonGαi1binding toRGS7,RGS4,andbothRGS7mutants.RGS7-F33Yshoweddecreasedps-nstimescalemotionandnostructuralchangewhencomparedtoWT.RGS7-Y82R showednochange indynamics, exceptat the siteof themutation,but showed structural changearound the mutation site due to charge-charge repulsion caused by the positively charged amine ofarginine. SPR unexpectedly showed the highest KD value for RGS4 and the lowest KD value for RGS7.Overlays of apo and holo structures of RGS4 show that it undergoes significant conformational changeupon binding to Gαi1, whereas the conformation of RGS7 is already close to optimal for binding.Furthermore,RGS7-F33Yshoweda faster rateofbinding thanRGS7due to the increased rigidityof themutant.RGS7-Y82Rshowedadecreasedrateofbindingduetostructuralchanges,butalsoadecreasedrateofdissociationduetotheincreasedstabilityofthehydrogenbondfromarginine.SPRandrelaxationdataofapoRGS4,RGS7andbothmutantsindicatedynamicandstructuraldifferencesaffecttheaffinitiesofRGS4andRGS7forGαi1.

OmairQureshi

USC

16Biochem

InvestigatingmechanismoftargetDNArecognitionbyaCRISPR-Cas9nuclease

PeterZ.Qin

The type II RNA-guided CRISPR-Cas9 nuclease, which has revolutionized genome engineering, targetsdouble-strandedDNA at sites determinedby the complementarity between a single-stranded region ofRNAanda segmentof the targetDNA (designatedas theprotospacer), aswell as a short protospacer-adjacent-motif(PAM).IthasbeenestablishedthattheCas9/RNAcomplexfirstrecognizestheDNAatthePAM,then initiatesunwindingof thePAM-adjacentsegmentof theprotospacer.Withacognate target,formationofWatson-CrickbasepairingbetweentheunwoundDNAandthesingle-strandguidesegmentof the RNA allows further unwinding of the DNA duplex, eventually enabling formation of an R-loopstructurethatstabilizestheternaryCas9/RNA/DNAcomplexforcleavage.UnwindingofthetargetDNAtoallowR-loop formation andhybridizationbetween theDNAprotospacer and sgRNAguide is a hallmarkstep of the CRISPR-Cas9 mechanism. The mechanism of DNA unwinding by Cas9, which is critical indiscriminatingacorrectvs.anincorrectDNAtarget,isinvestigatedandreportedthroughacombinationofbiochemicalandbiophysicalassays.Specifically,DNAconstructscontainingnicksorgapswithineitherthetargetstrandornon-targetstrandprotospacerregionareevaluatedfortheir impactonternarycomplexformation. Preliminary findings suggest that discontinuity at various sites along the non-target strandprotospacer region of the target DNA do not impede complex formation. Further experiments arecurrently underway to determine how discontinuitywithin the target strand protospacer region of theDNAduplexaffects ternarycomplex formationandDNAtargeting.Thisstudywill lay the foundation forexaminingDNAelements that contribute to Cas9 recognition and target specificity,whichwill facilitatefurther investigation on the overall mechanism of CRISPR-Cas9 as well as its applications in genomeediting.

CyrusJin

UCLA

17Biochem

KineticCharacterizationofPRMT1and5

StevenClarke

KanishkJain,StevenClarke

Histone H4 is an important target for gene regulation through posttranslational modifications such asargininemethylation.Proteinargininemethyltransferase(PRMT)5isknowntosymmetricallydimethylatehistoneH4R3,whichcanresult insilencingofcertaingenes.Additionally,variousstudiesreportthelinkbetweenlevelsofPRMT7andsymmetricdimethylarginine(SDMA)athistoneH4R3catalyzedbyPRMT5.WetestedthehypothesisthathistoneH4R17and/orhistoneH4R19affectPRMT5’sabilitytomethylateH4R3,amarkofgenerepression,bybeingmonomethylatedbyPRMT7.Phosphocellulosepaperbindingassayswereusedtooptimize linearreactionconditionsandcalculatekineticparametersforthehistoneH4wild-typeN-terminalpeptide(1-21)andpeptideswiththeR17andR19residuesmutatedorchemicallymodified.Results indicatepositive cooperativebehavior forPRMT5aswell as the importanceofR17 inaffecting catalytic activityand reducing its allostericnatureoncemonomethylated. Similar studieswereconductedwithPRMT1asacontrolandbecauseitasymmetricallydimethylatesH4R3.Likewise,PRMT1exhibitspositivecooperativebehaviorandR17affectsPRMT1-mediatedmethylationonH4R3.However,the positive cooperativity of PRMT1 remains when using the R17 monomethylarginine substrate,highlightingtheuniquelinkbetweenPRMT5andPRMT7.

NingLiu UCLA 18Inorg/Mat Photo-responsivehydrogel

materialsbasedonAuNP-incorporatedthermal-responsivehydrogelPNIPAM

XiminHe Throughbillionsofyearofevolution,livingformshavedevelopedmanyself-adaptivecapabilitiesinordertorespondtoambientenvironmentinanenergyefficientway,suchasself-regulatedtemperatureandpHvalue in animals, heliotropism in plants. However, self-adaptive functionalities are rarely exhibited insynthetic material systems. This project focuses on developing an intelligent material system that iscapableofdetectingandtrackinganincidentlightsourceself-adaptivelywithhigh-energyefficiency.Herewedevelopedaphoto-thermal-responsivehydrogelbyincorporatingphotonicabsorbersinthematerialssystembyphysicaltrapping. Inspecific,PNIPAMwasselectedtoprovidethermalresponsesowingto itswell-knownphase transition around its Lower Critical Solution Temperature (LCST).On the other hand,gold nanoparticles (Au NPs) were developed as photo-absorption particles that can convert incidentphotonic energy into thermal energy that elevates the temperature. PNIPAMhydrogelwill expelwatercontent at temperatures above human body temperature (around 32℃), and experience dramaticshrinkage at even higher temperature. Therefore, upon radiation, PNIPAM/AuNP nanocomposite willshrinkat thepositionwhere light incidents,andgraduallypropagate to theadjacent regions, creatingaspecialgradientofbothtemperatureanddeformation.AuNPwerefabricatedviacitratesynthesismethodunderdifferentconditionstoprovidecontrollablephotonicabsorbance.UV-visiblespectroscopywasthenemployed to characterize the absorbance andwavelength of AuNP. By far, a set of reliable recipes forseveralconcentrationsofAuNPhasbeendevelopedforoneparticularabsorptionwavelengthtofacilitatetheproductionofPNIPAM/AuNPmicropillarswitha rangeofAuNPconcentrations.Wealsomodify thesurface of AuNPswith different linkers to covalently bondwith the hydrogel, to study their effects onPNIPAM/AuNPinterfaceonthethermalconductivity.Furtheroptimizationofthematerialssystemwillbeconductedinnearfuture.TheoptimizationshouldincludemoredetailedAuNPdesign,suchasgeometry,surfacetreatment,etc.tomanipulatephysicalpropertiesofthematerialsysteminabsorptionwavelength,mechanical(flexuralmodulus)andthermalproperties(thermalconductivity).Theprojectwouldpavetheway toward a class of smart, self-adaptive,multi-stimuli-responsivematerial system that could benefitwidescopeofapplications,suchasall-opticalphotonics,optoelectronics, lownoisecommunicationsandstimuliguidedbiomedicalapplications.

KarenTom

CSUFullerton

19Inorg/Mat

SynthesisofPotentialIonic-ConductingMaterialsXAgTa4O11(X:Na,K,Cs,Rb)

AllysonFry-Petit

Silver tantalates with the structure, AgTa4O11, appear to have promising applications for materialsdevelopment of ion transporters, particularly for use in batteries. XAgTa4O11 (X: Na, K, Cs, Rb) haveadoptedasimilarstructuretothatoftheknownP21/nmonocliniccompound,NaAgNb4O11.Distinctivepores in the known structure of NaAgNb4O11 exist that house the sodium and silver ions, furtherstimulating interest in the potential ion conducting properties of the proposed system of NaAgTa4O11analogs.XAgTa4O11(X:Na,K,Cs,Rb)havebeensynthesizedusinga fluxgrowthtechniquefollowedbystandard solid state techniques. X-ray powder diffraction and Rietveld refinement were used tosuccessfully refine the structures of the proposed systemof conductingmaterials.Due to the lack of dorbitalelectrons, intheproposedNaAgTa4O11analogs,molybdenumwasdoped intotheKanalogwiththehopesthatKAgTa4-xMoxO11hasagreaterchanceofconsistingofconductiveproperties,whicharenecessarytorealizeionconductionaswell.

PedroPenaRodriguez

UCR

20Inorg/Mat

OptoelectricalCharacterizationofMoS2

LudwigBartels

MiguelIsarrarazandDanielLu

Since the discovery of graphene, 2D materials have been extensively researched. Unlike graphene,transitionmetaldichalcogenides(TMDs),suchasmolybdenumdisulfide(MoS2),exhibitadirectbandgapat the monolayer limit. This makes them ideal for optoelectronic devices. We utilize chemical vapordeposition (CVD) for the growth ofmonolayerMoS2, whichwe characterize by scanning photocurrentmicroscopy(SPCM).ByopticallyexcitingtheMoS2devices,westudythephotoconductivenatureofthematerial. Preliminary results show that photocurrent is localized near the contacts, showing that thesecontact-materialinterfacesplayalargeroleinthese2Dmaterials.

AlexanderMalinick

UniversityofLaVerne

21Inorg/Mat

SynthesisofFe/MnBimetallicMagneticNanoparticles

RicardoMorales

Cancertreatmentcanbejustasdeadlyasthecanceritself.Anoninvasivecancertreatmentwouldnotonlysave lives but also save patients from the suffering that chemotherapy can cause. Magnetizednanoparticlescansolvethesufferingcausedbychemotherapyviadrugdeliverytothetargetedarea.Withtheaidofnanoparticles,chemotherapywillbecomepreciseandaffectonlythetargetedareaviamagnets,thusmakingtheprocessmuchlessharmful.Inthisexperiment,nanoparticlesweresynthesizedatvariousratiosofiron(II),iron(III),andamixbetweenmanganese(III)andmanganese(II).Thesetwometalswereselected due to the low toxicity and proximity in the periodic table. In this study different ratioswereselected with the goal of yielding the smallest, most uniform particles and to study the difference inmagneticproperties.Thesampleswereanalyzedbymeansoftransmissionelectronmicroscopy(TEM)todetermine the size and shape of nanoparticles. Qualitatively, all tested samples showed magneticproperties; however, the 2:1 Fe2+:Mn3+ samples showed themost. At this point, the type ofmetal tometalratioseemstoaffectthemagneticpropertiesofthesample.

LuisGaray CSU

Fullerton22Inorg/Mat Non-cooperativeOctahedralTilting

TransitionofDouble-PerovskitesCa2SrWO6andSr2.9Ca0.1WO6

AllysonFry-Petit

Double-perovskiteoxidesA2B’B”O6arederivativesofthebasicperovskitestructuresoftheformABO3.Inthisexperiment,thestructuresoftwoknownperovskiteswereinvestigatedtodetermineiftheyadoptanon-cooperative octahedral tilting (NCOT) structure. The double perovskite Ca2SrWO6was reported toshare the cooperative structure of the basic perovskite Ca3WO6 with the space group P21/n. TheconvergedRietveldrefinementofCa2SrWO6suggestedthatthecorrectformulaisSrCaCaWO6,indicatingthatSr,duetoitsrelativelylargesize,occupiestheA/A'site.AttemptstolowerthespacegroupsymmetryofCa2SrWO6fromP21/ntoP1producedbondvalencesumaveragesthatcloselymatchedtheoxidationstateofeachatom,suggestingthatthepreviouslyreportedstructurewasnotabletochemicallydescribethe structure. Further data analysis of Ca2SrWO6 indicated that theCc space group,which is the high-temperatureNCOTstructureoftheSr3WO6compound,wasabetterfitthanthecooperativestructureofCa3WO6.FurtherinvestigationintotheabilitytocontrolthestructureofNCOTcompoundswasexploredthroughcalciumdopingofNCOTSr3WO6.Dopingofcalciumof0.033%showedthatthehigh-temperatureNCOT structure observed in Ca2SrWO6 could be induced in Sr3WO6 without the application oftemperature, but instead the applicationof chemical pressure. The full solid solutionbetween Sr3WO6andCa2SrWO6was investigated toprobe theeffectof chemicalpressureonNCOTcompounds further.Neutrondiffractiondata is currently being collected to allow for amore accurate determinationof thestructuresofCa2SrWO6andSr2.9Ca0.1WO6.

DonghyeokKim

UCLA

23Inorg/Mat

HomogenousAmplifiedDigitalImmunoassay

DinoDiCarlo

DonghyukKim,OmaiGarner,AydoganOzcan,andDinoDiCarlo

Today,healthcareconcernscontinuetostresstheimportanceofanaccurate,earlydiagnosisofdiseases.Thechallengeliesinprovidingasimple,quick,andreliabledetectionofbiomolecularmarkers(e.g.,nucleicacidsorproteins)inphysiologicalsamples.Herein,wepresenthomogenousentropy-drivenbiomolecularassay (HEBA)1,anamplifiedassaywhichcandetectvariousbiomolecules ina robustand rapidone-potreaction. We use an easily-programmable DNA machinery that catalytically2 drives a series of DNAhybridization/displacementreactions(Fig.1A)whichgenerateanamplifiedsignalinpresenceofananalyte(i.e., proteinor nucleic acid).Wedemonstrate theutility ofHEBAbyusing viral protein, viral RNA, andmicroRNA as analytes. Consequently, HEBA was able to successfully detect these molecules within 10minuteswithoutanywashingstepsoradditionalinstrumentation(e.g.,thermalcontrol)ineitherabufferor physiological fluids (i.e., undiluted blood and plasma). Furthermore,HEBA provided fM level limit ofdetection for all examined analytes (Fig.1B and 1C and 1E), which is orders of magnitudes highercomparedtoconventional,alikemethods(Fig.1E)Lastly,weexploitedHEBAinadigitalassayformatusinga microfluidic well array, by which we achieved successful detection of a few tens of viral proteinmolecules (Fig. 1D). Further development of HEBA we believe will lead to a development of newadvanced,point-of-carediagnostics

AnnieWongandDanishPirzada

UCR

24Inorg/Mat

EffectofElectrodepositionVariablesontheTopographyandPhotoelectronKineticsofZincOxideNanorodsgrownonGraphene

AshokK.Mulchandan

ClaudiaVillarreal,AshokK.Mulchandan

Thegrowthofverticallyalignedzincoxidenanorods(ZVNRs)hasrecentlygainedinterestduetothepossibilityofgrowinghighqualitysinglecrystalline2Dsemiconductorswithlargesurfacearea.ZnOislargelyappliedaselectronacceptormaterialinavarietyofsolarenergyharvestingdevices,includingdyesensitizedsolarcells.ThisworkfocusesonthegrowthofthesecaxisorientedZVNRsoncarbonbasedflexiblegraphene.TheapplicationoflargeareagraphenegrownbychemicalvapordepositionisbeinginvestigatedasthetransparentconductorintheZnOphotoanodes.Therobustoptoelectronicpropertiesofgrapheneandtheabundanceofrawmaterialsforitsproductionmakesitanattractivereplacementtothecommonlyused fluorine-dopedorindiumtinoxide(FTOandITOrespectively),whicharenotonlycostlyandbrittlebutalsoderivedfromconflictminerals.ThemainobjectiveofthisresearchistostudyhowthegeometryoftheZVNRsongrapheneaffectstheperformanceofthishybridasphotoanodeplatform.TheZVNRsaregrownbyelectrodepositionongraphenecoatedglass.Variationsinthedepositionconditionssuchasprecursorconcentration,temperature,time,appliedpotential,speedofmixingandtheuseofadditivesseemtohaveanobservableeffectonthegeometryoftheZVNRs.Bytuningtheelectrodepositionconditionsweareabletoobtaindistinctgeometriesandachieveourultimategoalofahybridoptoelectronicmaterialwithefficientchargeseparation,fastchargetransfer,andlowelectroninterfacialrecombination.ZVNR/Gwascharacterizedusingvariousanalyticalmethods:Xraydiffraction,Ramanspectroscopy,scanningelectronmicroscopyandUVvisibletransmittancespectroscopymeasurements.WethenusedtheZVNR/Gplatformtofabricatedyesensitizedsolarcellsandmeasuretheirperformance.Theinternalresistanceelementsandchargetransferkineticsweredeterminedwiththetechniquesofopencircuitvoltagedecayandelectrochemicalimpedancespectroscopy.Thisway,theelectrodepositionvariableswerecorrelatedtothekineticsofphotoelectronsgeneratedinthehybrid.

DerekDeming ConcordiaUniversity

25Org SpectroscopicMeasurementsofBrownCarboninAtmosphericPollutantsinSouthernCalifornia

JohnW.Kenney,III

Recentstudieshaveshownthatorganicaerosolsareoneofthemajorconstituentsofairpollutioninbothurbanandruralenvironments.Theseorganicaerosolsarereferredtoasbrowncarbon(BrC).[1]BrC isabyproduct of incomplete combustion of fuels, biomass burning/decay, mobile vehicle emissions,stationary factory emissions, and emissions from common household appliances such as stoves andfurnaces.Benzene(C6H6),toluene(C6H5CH3),andxylene(C8H10)arelaboratorychemicalsthatarealsoconstituentsofatmosphericBrC.EachoftheseknownBrCcompoundswasdilutedintowatertoduplicatethe characteristics of atmospheric BrC. These solutions were measured and analyzed spectroscopicallyusinganultraviolet-visible (UV) spectrophotometer. The control solutionsprovided reference spectra inthenear-UV.Environmentalair sampleswerecollectedviaawatercapture techniqueon theConcordiaUniversity campusandweremeasuredandanalyzed spectroscopically.Dependingon the localweatherconditionsatthepointofsamplecollection,someoftheenvironmentalsamplesdisplayedsimilarspectracomparedtothelaboratorycontrolBrCsolutions.Basedonthispreliminarystudy,itwasverifiedthatUV-visible spectroscopy can be used to detect BrC in the atmosphere. This initial study suggested thatweather conditions may affect BrC levels at a given site. Future experimental studies will considercorrelations betweenBrC levels andweather factors such as prevailingwinds from LosAngeles towardConcordiaUniversity,Irvineandheavydewconditions.

GiovannaCano

CSUFullerton

26Org

SynthesisofPeptidomimeticsforInhibitionofNS2B-NS3Protease

NicholasSalzameda

West Nile virus infection (WNV) has been shown in some cases to lead to the development ofneuroinvasiveconditions.TheCDCestimatesthatabout1%oftheestimatedUSincidencesofWNVleadtoa neuroinvasive condition such asmeningitis or encephalitis. As of 2016, 2,038 cases ofWNV infectionwerereportedtotheCDCwith1,140ofthesecasespresentingneuroinvasiveconditions.Currently,thereare no vaccines or therapeutic methods to treatWNV. The virus is composed of (+)ssRNA and a viralenvelopewhich infectsthehostcell.TheencapsulatedRNAistranslatedintothreestructuralandsevennonstructuralpeptidesthatareessentialforviralreplicationinhostcells.OneofthesecomponentsistheNS2B-NS3 protease, which contains serine protease, nucleoside triphosphate, and helicase activitynecessary for cleaving the structural and nonstructural portions of the polyprotein of the new viralcomponents..Stoppingtheprotease’senzymaticactivitytherebyendsWNVreplication.Throughorganicsynthesisour research focusesonthedevelopmentofarginineand lysinepeptidomimetics.Ourcurrentresearch has yielded inhibition of the NS2B-NS3 protein protease. As improvements are made thesecompounds are then tested through competitive enzyme assays to find better inhibition at lowerconcentrations.TheresultsoftheseenzymeassayscouldleadtotreatmentsforWNV.

NataliaNerisandAngelicaCarmona

MountSaintMary'sUniversity

27Org

TransesterificationofHypophosphorousEsters:AMethodologyStudy

SylvineDeprele

Large oil spills in the ocean are catastrophic events, posing a great threat to marine life and theenvironment.Ourprojectwas influencedby theDeepWaterHorizonoil spill inApril 2010.Releasing acarbon-basedsolvent/surfactantmixtureintotheoceanallowsforbioremediationandthedecompositionof toxic compounds found in oil. Our objective is to synthesize a phosphorous-based surfactant due totheir environmentally friendly properties.Our three-step synthetic route involves hypophosphite estersand a palladium-catalyzed hydrophosphinylation with bromoalkenes, followed by a trimethylaminereaction.Wehaveestablishedstep1ofourthree-stepprocessbysynthesizinglong-chainhypophosphiteesters, employing two different methodologies: one-pot one-step and one-pot two-step. Thetransesterificationmethod involves varying classes of alcohols (primary, secondary, and tertiary), broadsolvent scope (acetonitrile, hexane, toluene, and cyclohexane) and varyingequivalenceof alcohol (2, 4,and6)alongwithasiliconderivative. Inaone-potone-stepsynthesisweaddthealcohol,concentratedH3PO2,andTEOSallatonce intheselectedsolventand let it refluxfor2hours. Inaone-pottwo-stepsynthesisweaddtheconcentratedH3PO2andTEOSandletitrefluxfor2hours,andthenaddthealcoholforatotalrefluxtimeof4hours.Theresultsforone-potone-stepandone-pottwo-stepshowedthatthebest conditionswere4equivalenceof alcohol in acetonitrile and tolueneyielding31P crudeNMRyieldrange of 32% to 88% product. Future directions include product yield optimization andhydrophosphinylationoftheesterssynthesizedunderPd/Nicatalyzedconditions.

RonnieGarcia UCLA 28Org EfficientSynthesisofPentiptycene:

SymmetricOrganicBuildingBlocksforNewMaterial

MiguelGarcia-Garibay

Iptycenesareagroupofmoleculesthathavemanyapplicationsduetotheirrigidsymmetricalstructures.Triptycenes,amemberoftheiptycenefamily,havebeenusedasbuildingblocksformolecularmachines,1polymers,2andothermaterials.3Extendedanalogsof triptycenes calledpentiptyceneshave the similarpromise, but they have not been explored as extensively, in part due to their difficult and inefficientsyntheses.Currentstrategies involve the laborious introductionof functionalgroupsat thebeginningofthesynthesis,withalow-yieldingstepneartheend,whichcausesmuchoftheearlyworktobewasted.Thisworkaddresses those issuesby formulatingahighyielding,divergentsyntheticpathwaywherethelow-yieldingconstructionofthepentiptycenescaffoldisaccomplishedviaaquinoneintermediatebeforeadding the functional groups to create the desired derivatives. Previously reported synthesis of thepentiptycenequinoneworksin100mg,4whilethenewmethoddevelopedshowsa70%yieldregardlessofthescaleofthereaction.Thepentiptycenequinoneisthenreducedtothehydroquinoneandalkylatedtoformthepentiptycenescaffoldforlaterfunctionalization.Thealkylation,whichisnecessaryforsolubilitypurposes, ismosteffective intheabsenceofoxygenbecausethehydroquinonecanbeoxidizedbacktothequinone,whichseparatespoorlyfromthedesiredproduct.Thus,areactionclosedtotheenvironmentraisestheyieldofthesynthesis.Optimizingthesynthesiswillprovideaccesstoavarietyoffunctionalizedpentiptycenes,whichhavepotentialusesinsolid-statemachineryandmaterialsapplications.

KatrinaNgoandSusanAndersen

SDSU

29Org

tCc–ANewFamilyofFluorescentNucleosides

ByronPurse

DillonD.BurnsandByronPurse

Fluorescentnucleotidescanactasusefulmolecularprobesaswellasfluorescentmarkersforthestudyofnucleic acids, but brighter probes are needed for new applications including fluorescence microscopy.Previousworkdoneinourgrouponnucleosideanalogueshasledtothedevelopmentofanewgenerationofmodifiedfluorescentanaloguesknownastricycliccytosines(tC),whichareabletoparticipateinnormalG:CbasepairsinDNAwhilefunctioningasmolecularprobes.ThepropertiesofthesetCcompoundsledustoproposeanewstructure for fluorescentnucleotidedesign, tCc.Wehypothesize that tCc compoundswill be themost fluorescent of the cytidine analogues because of the stronger conjugated system thatexistswithin themolecule.Weusedanefficientseriesofsynthetic reactions toconstruct themolecule,andwecharacterizedtheintermediatesandproductsusing1HNMRspectroscopyandmassspectrometry.Themain ring system of themoleculewas built using a series of reactions that included the VilsmeierreactionandtheKnoevenagelcondensationforcriticalC–Cbondformingsteps.Theuniquecarbon-carbonbondlinkingthesugartothenucleobasewasachievedbyutilizingtheHeckreactionandournucleosideanaloguewasconfirmedviaNMRspectroscopyandmassspectrometry.InitialobservationsshowthattheparenttCCcompoundisfluorescent,butfurthertuningwillbeneededtomaximizeitsbrightness.Inthefuture, we intend to synthesize derivatives consisting of various electron withdrawing and electrondonatinggroupstofurthertunetheconjugation.Futuresteps includetransformingournucleosides intonucleosidephosphoramiditesandincorporatingthemintoDNAusingsolid-phasesynthesis.

ChristianMoreno

CalPolyPomona

30Org

TowardtheSynthesisofCyclicCarbonatesBasedonFAMEDerivatives

MichaelF.Z.Page

VictorWyattandMichaelF.Z.Page

Vastamountsofpetroleumisusedeverydaytogenerateelectricity,fuelourvehicles,andformplastics.Biodieselisarenewable,clean-burningdieselalternativethatcouldassistinreducingU.S.dependenceonforeign petroleum and help meet our current energy needs. Fatty acid methyl esters (FAMEs) aresynthesized through a transesterification between a triacylglyceride andmethanol in the presence of acatalyst. Previously, the Page group synthesized green polyurethanes from seed oils with varyingequivalentsofpolyolsfromFAMEsthatwerecrosslinkedwithpetroleum-baseddiisocyanate.Isocyanatescan cause skin irritation, asthma, and bronchitis. In 2015, Hybrid Coating Technologies won thePresidentialGreenChallengefordesigningahybridnon-isocyanatepolyurethane.Thisnon-isocyanateβ-hydroxyurethaneformedfromareactionbetweencycliccarbonatesandaliphaticpolyamines.Currently,the Page group plans to synthesize a non-isocyanate polyurethane using waste oil FAMEs as the onlystartingmaterials.Theproposedsynthesisinvolvesaconversionofthealkenewithinthefattychaintoacyclic carbonate. In the preliminary steps methyl oleate (1) is converted to epoxide 2 with a key 1Hchemical resonance at 2.889 ppm. In the subsequent step, 2 will eventually be converted to cycliccarbonate 3. Following characterization, 3 will be primed to be polymerized with a polyamine fromanotherrelatedFAMEderivative;ultimatelyleadingtoadiisocyanate-freepolyurethanematerial.

MasisParunyan,EleniePhilippas,JenniferJensen

CSUNorthridge

31Org

Understandingthemetabolictransformationsofresveratrolbyhumanenzymes

GagikMelikyan

Experimentalresearchsuggeststhatthemetabolicoxidationofresveratrol,apolyhydroxylatedstilbenoidfoundinredwine,bycytochromeP450enzymes(CYPs)ofthehumandigestivesystemmayhaveseveredeleterioushealtheffects.Enzymatictransformationsofresveratrolandits3’-hydroxylatedderivativepiceatannolwereinvestigatedbyexposingthemtohumanesophagealandhepaticCYPs(CYP4F3,3A4,1A1,4F12,2C8,2C9,2E1,2A6,2C18).Metabolicprofileswerestudiedbyusinghigh-pressureliquidchromatography(HPLC)method.Gradientelutionwasappliedtoenhanceseparationbetweenresveratrolanditshydroxylatedderivatives,establishingareliablequalitativemethodfortheidentificationofstructurallyrelatedmetabolites.Resveratrol-derivedpiceatannolwasoxidizedinvitrotoyieldthecarcinogenicorthoquinone,4-[(E)-2-(3,5-dihydroxyphenyl)ethenyl]benzene-1,2-dione,characterizedby1H/13CNMRspectroscopyandmassspectrometry.Stabilitystudiesindicatethatinanenvironmentmimickingphysiologicalconditionsthisquinonemayhavealifetimeofseveraldaysorevenweeks.Thenegativeramificationsforpublichealthwillbediscussedalongwiththeprudenceofsellingresveratroltothegeneralpublicasafoodsupplement.

SarahBaker CSU

Fullerton32Org TheIntramolecularreactionsof

OximeandOximeEtherRadicalsandRadicalCationsusingAlkenesasaPotentialNucleophileorRadicalTrap

H.J.PeterdeLijser

NicholasR.Armada,EmmieHo,AndrewS.Petit,andH.J.PeterdeLijser

The formationof radicalsandradicalcationsresult fromoxidativeprocesses.Whenoxidationofoximesand oxime ethers occur, iminoxyl radicals and oxime radicals are produced. The reactivity of theseintermediatesislargelyunexploredandtolearnaboutthefundamentalreactivityofiminoxylradicalsandoximeether radical cations,wehavebegunan investigationon intramolecular reactionsof oximes andoximeethersusingbuilt-inalkenesasapotentialnucleophileor radical trap.Previously,built-inalkyneswerefoundtoactasradicaltrapswhereasaromaticringswerefoundtoactasnucleophiles.Thisprojectexploresthereactivityofalkenefunctionalgroupsundersimilaroxidativeconditions.Wehypothesizethatthealkenefunctionalgroupmayactasanucleophileandasaradical traptoformthecyclizedproduct.Photolysisofthesubstrateat420nmwith9,10-dicyanoanthracene(DCA)asthephotosensitizerleadstothe formationof the iminoxyl radical (oxime)or radicalcation (oximeether) intermediate thatcanthencyclize. Studies on the PET reactions of the vinyl oxime (1a) and oxime ether (1b) did not show anyevidence of cyclization. Preliminary results suggest that cyclization occurs at the nitrogen for the 2-isopropenylderivativeforboththeoxime(2a)andtheoximeether(2b).NMRanalysisofbothreactionsuponirradiationat420nminthepresenceofDCAforupto4hoursshowstheformationofnewproductsover time; theproductmixturesof theoximeandoximeethershowverydistinctsimilaritiessuggestingthattheproductsformedareverysimilar.TheNMRresultsareconsistentwithstructuresformedusingacyclization pathway. The exact identity of the cyclic product formed in these reactions is unclear andfurtheranalysisofthereactionmixturesisbeingcompletedusingNMRandGC/MS.Computationalstudiesarebeingperformedtoobtainmechanistic insights intowhythepresenceorabsenceofamethylgrouponthealkenegrouphassuchapronouncedimpactonthereaction.Theresultsofthesestudies,aswellasthoseoftheE-andZ-propenylderivatives(3a,3b,4a,and4b)willbediscussed.

CatherineTaylor CSUFullerton

33Org SynthesisofComplexRingSystemsviaPhotoinducedOxidativeCyclizationReactionsofBenzaldehydeOximesandOximeEthers

H.J.PeterdeLijser

AbdullahAlshreimi,MimiLe,andH.J.PeterdeLijser

Theuseofoxidativecyclizationwithradicalorradicalionintermediatesisapotentiallyusefulandefficientstrategytoachievethesynthesisofnovelheteroaromaticstructures.Oximeetherswithbuiltinaromaticgroupshavebeenshowntoundergoacyclizationreaction inwhichthearomaticringactsanucleophileattackingtheoximeetherradicalcation.Usingthissamemethodology,aromaticnucleophileswithbuiltinheteroatoms could lead to potential new synthetic pathways of interesting and complicatedheteroaromatic ring systems. To determinewhether heteroaromatic rings can be used as nucleophilesunder oxidative cyclization conditions,we prepared a series of benzaldehyde oximes and oxime etherssubstitutedwithheteroaromatics ringscontainingnitrogen,oxygen,andsulfur.ThepurifiedoximesandoximeethersweresubjectedtophotooxidationprocessesincontrolledconditionsandweremonitoredbyGC/MS andNMR for product formation. The result from these studies suggest that the oximes formedtheir parent aldehydes but did not show signs of cyclization. Several oxime etherswere found to yieldwhat is believed to be a cyclized product via nucleophilic attack by the heteroaromatic ring on thenitrogenoftheoximeether.Themostpromisingresultswereobtainedwiththethiophenylderivativesoftheoximeethers.To furtherdetermine if the thiophenyloximeetherderivativesdid in fact cyclize, thereactionisbeingoptimizedsotheproductcanbeisolatedandcharacterized.Intheprocessofsynthesizingthefuranylandthiophenyloximederivativesanunknown,possiblycyclized,sideproductisformed.Thesesideproductsarebeinganalyzedandcharacterized.Themechanisticpathwayofthisproductformationisalsobeinginvestigated.

HuyTBui

CalPolyPomona

34Org

AStudyofMolybdenumCatalystsfortheDeoxydehydrationReaction

AlexJohn

NathanW.Green,AlexJohn

We report a study on molybdenum catalysts of the type LMoO2 supported over ancillary ligands forconverting vicinal diols into olefins. Fossil resourceswhich includenatural gas, coal, andpetroleumarecurrently theprimaryenergyandmaterial feedstock.Unfortunately, theseresourcesare finiteandhaveadverseenvironmentaleffects.Researchersareworkingtowards identifyingandutilizingrenewableandsustainable resources such as wind, sun, water, and biomass to accommodate our current and futureenergyandmaterialneeds.A fundamentaldifferencebetweenbiomassandpetroleum is thatbiomass,suchascellulose, ishighly functionalizedwhereaspetroleumisofhydrocarbonnature.Therefore,beingable to convertmolecules that have characteristics of biomass to those that are hydrocarbon-like is acriticalstepineffortstoincorporatebiomass-derivedintochemicalprocesses.Apromisingreactioninthisdirection is deoxydehydration (DODH), that transforms a vicinal diol into an olefin. In the recent past,rhenium(Re)hasbeenthemetalofchoiceforitsefficiencyasacatalystintheDODHreaction.However,itisnoteconomicallyfeasibleanditslowabundanceintheearth’scrustaddstotheconcern.Alternatively,molybdenum(Mo)isareasonablesubstituteforReintheDODHreactionbecauseofitssimilarchemicalpropertiesandlowcost.Thefocusofthisprojectistosynthesizeandexplorethereactivityandselectivityof various molybdenum catalysts (LMoO2) supported over salan type ligands for the DODH reaction.Deoxydehydrationstudiesusingthesemolybdenumcatalystswillbediscussed.

StephannieJimenezandStephaniaLuna

MountSaintMary'sUniversity

35PhysAnal/Theory ACorrelationStudyBetweenParticulateMatterandPAHConcentrations:TheBio-monitoringofPineTreeLeaves

SylvineDeprèle

Polycyclicaromatichydrocarbonsareorganiccompoundscomposedoftwoormorefusedbenzenerings.They arenaturally found in theenvironmentbut, can alsobeman-made. PAHs are created throughanincompletecombustionreactionwithanunknownamountofoxygen, resulting inunwantedbyproductssuch as carbonmonoxide andPAHs.They aredetrimental to our healthbecause they are carcinogenic,teratogenic,andmutagenic.PAHsareinherentinparticulatematter,whichisamixtureofsolidparticlesand liquiddroplets in theair.Due to their toxicproperties, it is important toqualifyaswellasquantifyPAHs.Here,weproposethebio-monitoringofPAHsthroughpinetreeleavesfromtheItalianBlueCyprustree intwodesignatedareasneartheI-405FreewayandontheMountSaintMary’sUniversitycampus.PAHs were extracted via a continuous Soxhlet extraction, further processed and analyzed by the GasChromatographyMassSpectrometer (GCMS).ASelected IonMonitoring (SIM) tablewasused tosearchforthe16mostcommonPAHsfoundinthesample(EnvironmentalProtectionAgency(EPA)standardwasused for reference). Through a series of calculations, the concentration of the PAHswere graphed andcomparedwith the values of PMs reported by the EPA. Since PAHs fallwithin the family of particulatematter, adirect correlationbetween the concentrationofPAHsandPMvalues reportedwasexpected.Samplescollectedfromthefreewayandcampusareashowedadirectcorrelationwithfewdiscrepanciesthatcanbelinkedtoweatherpatterns.Analysisofthedataconfirmedthatourcampuslocation,ontopofahill,displayshigherlevelsofPAHsthantheI-405freewayarea.Forfuturedirections,wewillcontinuetomonitor PMs and PAHs during different seasons and analyze previous data acquired to finalize thequantificationandqualificationofPAHandPMconcentrationsfoundwithinthedesignatedareas.

RahiaSolomon MountSaint

Mary'sUniversity

36Phys/Anal/Theory Enantiomericinteractionsofaminoacidsadsorbedinzeolites:AninvestigationusingSolid-StateNMRandMolecularModelling

DenizCizmeciyan

In the past years we studied zeolites as amedium for enriching the enantiomeric excess of solutions.Zeolitebeingachiral,donotpreferoneenantiomerovertheother.However,iftheD-andL-enantiomersadsorb together as a heterodimer, the enantiomeric excess of the solution they leave behind isaugmented.WeusedNMRtoexploretheadsorptionbehaviorsofD-,L-,andDL-N-acetylLeucine,AlanineandMethionineintoZeoliteNaY.ThesolidstateNMRspectraofthepureD-andL-acetylLeucineshowedthe same results as the racemic mixture of N-acetyl-DL-Leucine, indicating a preference to formmicrocrystalsofpureDandLforms. Incontrastdifferences inthesolidstateNMRspectraareobservedforN-Acetyl-DL-MethionineandN-acetyl-DL-Alaninefromtheirpureenantiomers.Thisimpliedthatbothformamixedcrystal.Howeverwhenadsorbedontothezeolite,N-AcetylMethionineandN-acetyl-Alanineexhibit thesamebehavioras itsLeucinecounterpart indicatingthat theyareadsorbedashomodimers.Recently, inorderto investigatethisbehaviorfurtherwedecidedtostudythesamesetofsystemswithmolecularmodelling. As a starting point, considering only Van derWaals interactions,we investigatedhowtheseaminoacidswerefittingintothezeolitecage.WefoundthatAlaninegetsadsorbedbetterthanLeucineandMethionine.Wewillpresenttheresultsofcomputersimulationsregardingthedynamicsandenergeticsoftheenantiomer-zeoliteinteractions.

TaehoonHa CSUSanMarcos

37Phys/Anal/Theory ExtractionoftheActiveComponentofKratomLeaves

KarnoNg Kratom,alsoknownasMitragynaspeciosa,isatropicalevergreentreeinthecoffeefamily.ItisnativetoSoutheastAsia.Kratomleaveshavebeenusedforhundredsofyearsintraditionalmedicinetorelievethepain.Theleavescanbechewedinrawandcanalsobeprocessedintotabletsandcapsules.Intherecentyears, there is an increase of uses of Kratom leaves as a recreational drug. The primary active alkaloidsubstance, Mitragynine, found in the Kratom leaves affects the same receptor as the opioids such asheroine, morphine, and codeine. Consumption of Kratom leaves can lead to psychotic symptoms andmentaladdition.ThepotentialeffectsofKratomleavesonhumansdrawinternationalconcerns.InsomecountriessuchasFinlandandHungary, theuseand/or importationofKratom leavesarerestricted.TheDrugEnforcementAgency(DEA)hadinitiatedanattempttomoveKratomtocontrolledsubstance list (Schedule1)in2016.ThepurposeofthisstudyistodevelopanefficientextractionmethodformitragyninefromKratomleaves.OnegramofcrushedKratomleavesweresoakedinmethanolandsonicated.Attheendofthesoakingperiod,solventwasevaporatedundervacuumtoyieldthemethanolextractthatisrichin alkaloid. The methanol extract was mixed with 90% acetic acid and the content was partitionedbetweentheaqueousandpetroleumether.Theaqueous layer iscollectedandbasifiedwithNa2CO3topH9.Thealkoloidwasthenextracted intochloroform.TheextractwaswashedwithdistilledwateranddriedoverNa2SO4anhydrous.Theextractwasthenloadedtothepackedsilicacolumnandelutedwithchloroform. Theelute is evaporatedand the resultingextractwasdissolved in 1.5mLofmethanol andthenfilteredthrougha0.45mmsyringefilterpriortoinjectiontoHPLCwithaC-18column.Thesampleiselutedisocraticallywithamobilephaseof0.05%formicacidandacetonitrileatpH5.0(50:50,v/v),flowrate=1.0ml/min.Mitragynineisdetectedat223nm.

LauraMarsalla

CSUFullerton

38Phys/Anat/Theory

UnderstandingtheReactivityofIminoxylRadicalswithBuilt-InAlkynylRadicalTraps

AndrewPetit

PeterdeLijser,AndrewPetit

Recently,thedeLijserlabusedphotoinducedelectrontransfer(PET)topreparereactiveradicalcationsandiminoxylradicalintermediatesfromoximederivativescontainingabuilt-inalkynylgroup.Theyusednuclearmagneticresonance(NMR)tomonitorthereactionmixtureandlookforevidenceofintramolecularcyclization.Theirresultssuggestthatoncetheiminoxylradicalforms,thealkynylgroupcanactasaradicaltrapcausingintramolecularcyclization.Isolationofthecyclizedproductshasbeendifficult,preventingtheirexperimentalcharacterization.Inordertoaidintheidentificationofthecyclizedproducts,wecalculatedNMRchemicalshiftsforaseriesofpossibleproductsusingcomputationalchemistry.Ourresultssuggestthatfive-memberedheterocyclicexoproductswereformedviaintramolecularcyclizationoftheiminoxylradical.

ZacharyTo

UCRiverside

39Phys/Anal/Theory

GrowthofMonolayerMolybdenumDisulfideThroughChemicalVaporDepositiononSiliconDioxideSubstrates

LudwigBartels

Transition metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS2), have been gainingpopularityduetotheirsemiconductingpropertiesatthemonolayerlimit.Theresearchgoalistofindandoptimize a facile method to grow consistent MoS2using a chemical vapor deposition tube furnace.Characterization methods such as ramanand photoluminescence spectroscopy are used to assess thequality of the growth. Raman spectroscopy is used to observe the molecular vibrations, andphotoluminescence measures the band-gap by exciting the electrons in the valence band with light.MonolayerMoS2exhibitsadirectband-gapat1.85eV,andshowspromisingspintronicandoptoelectronicproperties.TheapplicationofTMDscancreateelectronicsflexible,energyefficient,andfasterelectronics.

AdanGarcia CSUSan

Marcos40Phys/Anal/Theory ExtractionandDetectionofCancer

TreatmentDrugwithPhenytoininBiologicalSamples

KarnoNg KarnoNg Among patients with cancer, in particular brain tumors, seizures can become a daily routine in theireverydaylives.Tocounter-acttheseizures,anantiepilepticdrugsuchasphenytoinisadministeredtoactasananticonvulsantthatisinessenceamusclerelaxant.Dexamethasoneisclassifiedasacorticosteroidandhasmanyuses incancertreatment.Oneoftheusesofdexamethasoneamongcancerpatients istodecrease the amount of swelling around the tumor. Dexamethasone is also used for the treatment ofnauseacausedbychemotherapy.Inaddition,dexamethasoneisusedasacancertreatmentforavarietyof cancers, such as leukemia, lymphoma, and multiple myeloma. Phenytoin and dexamethasone arefrequently administrated concurrently to brain cancer patients. A previous study has shown thatphenytoin serum concentration decreaseswhen it is administrated concurrentlywith dexamethasone.1Thus, it is important tomonitor the concentrationof these twodrugs inbiological samples, inorder toensurethattheproperdosagesareadministratedtothepatients.Thepurposeofthisstudyistodevelopan effective extraction and detectionmethod for dexamethasone and phenytoin. A reverse phase highperformance liquid chromatography (HPLC) method with UV/VIS detection has been developed toseparate phenytoin and dexamethasone at 219 nm and 241 nm respectively from urine samples. Themobile phase consists of a mixture of 0.01 M KH2PO4, acetonitrile and methanol adjusted to pH 5.6(48:32:20)and ispumpedata flowrateof1.0mL/min.Calibrationcurveswereprepared forphenytoinand dexamethasone. The calibration curves show good linearity (r2 >0.99). The detection limit forphenytoin and dexamethasone is 0.625 g/mL and 0.053 g/mL respectively. An efficient solid phaseextractionmethodwiththeuseofC-18cartridgesonurinesampleswasdeveloped.Thepercentrecoveryforphenytoinanddexamethasoneis90.46%and89.53%respectively.

KateyMcCoy

CSUFullerton

41Phys/Anal/Theory

MeasurementoftheHygroscopicGrowthofBrownCarbonMixturesusingaTandemDifferentialMobilityAnalyzer

PaulaK.Hudson

AliSaad,DamarisChavezandPaulaK.Hudson

Atmosphericaerosolsaresmallparticlesthatcanaffectclimatebydirectlyabsorbingandscatteringsolarradiation.Further,aerosolparticleshavetheabilitytoactascloudcondensationnuclei(CCN)throughtheuptakeofwater. Dependingon theamountofwateranaerosolabsorbsasaCCN, it could formhighlyreflectivewhitecloudswhichwouldthenhaveacoolingeffectonclimateasincomingsunlightisreflectedbackintospace.However,thedegreeofcoolingisdependentontheaerosolparticlecomposition.Browncarbon,onetypeofaerosol,canbeformedinanumberofwaysbutiscommonlyformedbyreactinganaldehyde,glyoxal,withanitrogencontainingcompoundsuchasglycineorammoniumsulfate.Giventhatthesethreeparticularcompoundsusedtoformbrowncarbonhavedifferentwateruptakeproperties,andthat reactants and products can change with atmospheric processing, it is important to study thehygroscopic properties of brown carbon aerosol. In this study, a tandem differential mobility analyzer(TDMA) is used to measure the hygroscopic growth, the uptake of water, of brown carbon aerosolparticlesbymeasuring theparticle sizebeforeandafterexposure to relativehumidity.Thehygroscopicgrowth of brown carbon samples generated from mixtures of glyoxal and glycine, or glyoxal andammonium sulfate, in mole ratios of 1:1, 1:0.5, 0.5:1, before and after photolysis, were measured todeterminetheeffectsofvariouscompositionsofbrowncarbonandtheirabilitytoactasCCN.Ingeneral,the hygroscopic growth of brown carbon generated from ammonium sulfatemixtures are higher thanglycinemixtures which would result in the formation ofmore reflective clouds and a stronger coolingeffect.Thisstudyprovidesinformationtobeusedbyclimatemodelerstoimprovethepredictivecapabilityofclimatechangeduetodifferentbrowncarbonsources.

PosterPresentationAbstracts-Session2

Name Institution Poster#/Area Title Advisor Coauthors Abstract

SylviaAlejo

UCI

1Biochem

FilterbindingassaygeneratesabindingaffinityconstantofaptamerandNogo-66,whichcorrespondstotherapeuticapplicationtoneuralgrowthinmouseprimaryneurons

MelanieCocco

VernaVu,AliAlhoshani,MelanieCocco

Injury and deterioration of adult mammalian neurons in the central nervous system has long beenthoughtofasimpervioustoanytreatmentincomparisontoperipheralnerves.Reticulon-4containsa66residueregioncalledNogo-66thatbindstotheNogoreceptor1(NgR1);this interactionisresponsiblefornervegrowthinhibition(GrandPreetal.,2000,Fournieretal.2001).Throughasystematicevolutionofligandsbyexponentialenrichment(SELEX)procedure,tightbindingaptamerswereselectedforNogo-66(Jayasenaetal.,1999).Thiswasdonebysubsequentstepsofselectionandamplificationofsingle-strandedDNAfromarandomlygeneratedlibraryofssDNAoligonucleotide.Thus,itishypothesizedthatthe aptamer sequenced is able to disrupt the Nogo-66/NgR1 interaction. Functional assays wereconductedusingmouseprimaryneuronswhichshowedasignificantincreaseinaxonalgrowth.FurtheranalysiswasdonebydeterminingthebindingaffinityoftheaptamertoNogo-66usingafilterbindingassay. The aptamerwas taggedwith γ-32P thatwas then incubatedwith increasing concentration ofNogo-66.TheseresultsshowthataptamerandNogo-66bindingoccursinthenanomolarrangemakingourselectedaptamerapotentialtherapeuticmolecule.Theuseofaptamers,withitsthree-dimensionalstructure that rivals antibody binding, is justified by its cost-effective approach in terms of labor andreproducibility.Theseoligonucleotidesaremuchmoreeasytoidentify,manufactureandstoreasfuturetherapeutic drugs than antibodies. Pilot studies are underway to test the efficacy of the aptamer onanimalmodels.

NikolayMaslov

CSUSanBernardino

2Biochem

Developingchemicalinhibitorstoinvestigatethefunctionoffalcilysin,anessentialmalarialprotease

JeremyMallari

TheprotozoanparasitePlasmodiumfalciparumcausesapproximatelyoverhalfofmillionfatalcasesofmalaria per year, mostly occurring in Africa. Falcilysin (FLN) is a metalloprotease expressed by theparasite—it isnecessaryfor itsdevelopmentinthehostredbloodcell.However, itsfunctionispoorlyunderstood.WearedevelopingcompetitiveinhibitorsofFLNwithapiperazinehydroxamicacid-basedscaffold.PreviousstudiesinourlabhaveshownthatthisclassofcompoundshasgoodinhibitoryactivityagainstrecombinantFLNandculturedP.falciparum.Ourteamissynthesizinginhibitorsthrougha4-steproute and purifying them with a combination of extraction and flash chromatography. Eight of thecompoundsweretestedfor inhibition inaFRET-basedsubstratecleavageassay.Duringthisstudy,wehave identified several features important for inhibitor against FLN. Specifically, introduction of anamide group at the N4 position leads to a significant improvement in activity compared to similaramines.ThisstrategyproducedourmostpotentinhibitoragainstFLNsofar(IC50<10µM).

RandallOrtega CSU

Fullerton3Biochem PurificationandPreliminary

CrystallizationofaBacterialDihydromethanopterinReductase(DmrA)InvolvedinTetrahydromethanopterinBiosynthesisinMethylobacteriumextorquens

MadelineE.Rasche

MadelineE.Rasche

The one-carbonmetabolismofmethane-producing archaea andmethylotrophic bacteria requires thecofactor tetrahydromethanopterin (H4MPT), an uncommon tetrahydrofolate analog. In archaea, thefinal step of H4MPT biosynthesis is the reduction of dihydromethanopterin to H4MPT bydihydromethanopterin reductase X (DmrX). Curiously, noDmrX homolog exists in the genome of thebacterium Methylobacterium extorquens AM1. Instead, the final reaction is catalyzed by DmrA, ahomologofbacterialdihydrofolatereductase(DHFR).ThisfindinghasledtothehypothesisthatDmrAevolved from duplication and mutation of an ancestral dhfr gene. To gain insight into evolutionarychanges thatmayhave altered the substrate specificity fromdihydrofolate to dihydromethanopterin,computationalmodelingandcrystallographystudieswereinitiated.UsingDHFRasatemplate,ICM-ProwasabletopredicttheoverallproteinfoldofDmrAandtheNADPHbindingsite,butwasunsuccessfulinmodeling a dihydromethanopterin binding site. Therefore, in preparation for crystallography, wedeveloped a strategy to increase the solubility of recombinant DmrA and decrease its potential foraggregation.ShorteningtheN-terminalhistidinetagfromsixtofourhistidinesandstoringthecellsatpH 8 instead of pH 6.8 allowed purification of a single quaternary structure. Following nickel affinitychromatographyanddesalting,aproteinconcentrationof4.11µg/µLwasobtained.SDS-PAGEshowedgreater than95%puritywithamainbandat17kDa,whileasinglebandat396kDawasobtainedbynative PAGE. A preliminary crystallization trial resulted in successful light precipitation using buffercontaining0.1MTrishydrochloride,2.0MAmmoniumsulfate,pH8.5witha2:1ratioofsample:buffer.However, a crystallization screenwith 288 conditions resulted in noprecipitate or crystals, indicatingthatahigherproteinconcentrationmightbebeneficialforcrystallography.Futureresearchwillfocusonidentifying protein concentration, salt, and buffer conditions suitable for DmrA crystallization andstructuredetermination.

CarolineAziz

ChapmanUniversity

4Biochem

PartialAminoAcidSequenceandAnti-CancerousActivityofaLipidTransferProteinfromFennel(Foeniculumvulgare)Seeds

AftabAhmed

RukhsanaLalani,MekdesMegeressa,UmeshT.Sankpal,RiyazBasha,andAftabAhmed

Fennel(Foeniculumvulgare)isabiennialEgyptianmedicinalplantwithanaromaticodorthatbelongstothefamilyApiaceae (Umbelliferae).Fennel seedsarecommonlyused in traditionalmedicineas theyareknowntohaveanti-inflammatory,anti-fungalandanti-canceractivities.Themajorconstituentsofthefennelseedsaresugars,minerals,essential fatty acids, proteins and fibers. Although, there are numerous studies on the medicinal properties ofessentialoilsofthefennelseeds,theyarenotmuchfocusedontheproteinsandpeptides.Theobjectiveofcurrentprojectistofullycharacterizetheprimarystructureofproteinsandtotesttheirbiologicalactivities.Wepresentherethepreliminarydataontheaminoacidsequenceof lipidtransferprotein(LTP)fromfennelseedsanditsbiological(anti-cancer)activityusinghumancancercells.TheproteinswereextractedinTris/HClpH8.0bufferandsuccessfullypurifiedbytwodimensionalliquidchromatography(2D-LC),usinggelfiltrationchromatographyfollowedbyreversephaseHPLC (RP-HPLC). Thepurity of isolated LTPproteinwas judgedby the SDS gel electrophoresis. Thepurifiedprotein was loaded on to the PVDF disc and sequenced by automated amino acid sequencer, model PPSQ-31A(Shimadzu).ThepartialaminoacidsequenceofintactLTPproteinwassuccessfullyestablishedupto23aminoacidresidues. The amino acid sequence searchwas performedby Protein BLASTwhich confirmed it as a lipid transferprotein. The Cell viability assaywas performedon the isolated LTP protein using the CellTiter-Glo (Promega). Theresults of the assay demonstrated anti-proliferative activity against prostate (PC3) and breast (MCF7) cancer celllines,showingadecreaseincellviabilityapproximately30%and60%inPC3andMCF7celllinesrespectively.

LucyChen Chapman

University5Biochem ExtractionandPurificationofProteins

fromTurmeric(Curcumalonga)RootAftabAhmed Rukhsana

LalaniandAftabAhmed

Herbalmedicineshavebeeninusesinceancienttimesforthetreatmentofvariousailments.Accordingto WHO about 80% of the world population relies on plant-based herbal medicine. Despite theadvancements in modern medicine, traditional medicines involving the use of plants have graduallybeen accepted as a complementarymedicine throughout theworld. Turmeric is one such plant thatplaysan important roleasacommonspiceandalsowell-knownfor itsmedicinalproperties. InSouthAsian countries such as India and Pakistan, turmeric is often used to treat diseases such asgastrointestinaldisorders,arthritis,depression,asthma,anddiabeticwounds.Thisplanthasalsobeenextensively studied for its anti-tumor, antimicrobial, and antioxidant activity. In this poster, we arepresenting the preliminary data on the extraction and purification of proteins from of turmeric(Curcuma longa), which belongs to the plant family of Zingiberaceae. Proteins were extracted frompowderedturmericin20mMTris/HClpH8,50mMsodiumacetatepH5.2,10mMsodiumphosphatepH 7 and 0.1% acetic acid in water. Purification of proteins was carried out using gel filtrationchromatography using Sephacryl-S200 10/60 column. Fractions were pooled and analyzed byTris/Tricine gel electrophoresis. Further purificationwas successfully achieved by reverse-phase HPLCusingAeriesProtein(4.6x25mm)column.FurtherworkisinprogresstoestablishthecompleteprimarystructureofthepurifiedproteinsusingtheautomatedEdmansequencingtechnique.

BrandonYeshoua UniversityofSouthernCalifornia

6Biochem CombiningAntibacterialAntibodiestoEnhanceOpsonophagocytosisofAcinetobacterbaumannii

B.Spellberg B.Pascual,T.B.Nielsen,B.Spellberg

Wearedevelopingmonoclonalantibodies(MAbs)asanoveltherapeuticapproachtohighlyantibiotic-resistantAcinetobacterbaumannii infections. A.baumannii ishighlydiverse,withanestimated>100serotypes.AsaresultacombinationMAbregimenwillbenecessarytocoversufficientclinicalisolatesto establish a viable therapeutic. One concern about combining multiple MAbs targeting a singlepathogen is thepotential forantagonismtooccur,asoneMAbmay interferewithbindingofanotherMAb to its epitope target. We investigated the effect (synergistic, antagonistic, or neither) onopsonophagocytosisuponcombiningtwoanti-Acinetobacterbaumanniimonoclonalantibodies(MAbs)in vitro: MAb C8 and MAb 39. We first used flow cytometry to select strains of the bacterium A.baumannii that were bound by both, either, or neither antibody (Table 1). After selecting suitablestrains,wethenperformedaphagocytosisassayusingRAW264.7mousemacrophagestoquantifythevariableuptakeofbacteriaduetoantibodyopsonization.WewereabletoconfirmthatcombiningthetwoantibodiesforopsonophagocytosisenabledmacrophagestophagocytizepathogenstowhichonlyoneoftheMAbsbound,andthatantagonismbetweentheMAbswasnotobserved. Thus,combiningMAbsisaviableapproachtotargetingA.baumannii,whichwillenablecoverageofmultipleserotypeswithoutantagonism.Weseektoconfirmtheseresultsinvivo.

ErvinIrimpan UCI 7Biochem StructureofCDItoxinrevealsanovel

bacterialmemberoftheRNaseAsuperfamily

CeliaW.Goulding

GaëlleBatot,KarolinaMichalska,GregEkberg,GrazynaJoachimiak,RobertJedrzejczak,GyorgyBabnigg,ChristopherS.Hayes,AndrzejJoachimiak,CeliaW.Goulding

Contact Dependent growth Inhibition (CDI) is one mechanism that Gram negative bacteria utilize tocommunicatewitheachother.TheCdiAproteinisalargecellsurfaceproteinthatdeliversitsC-terminaltoxindomain(CdiA-CT)toneighboringbacteriacellsuponcelltocellcontact.CDI+bacteriacanexpressacognate immunityprotein (CdiI)whichbinds tightly to itscognate toxin thereby rendering the toxininactive. Our collaborators solved the X-ray crystal structure of the CdiA-CT/CdiI toxin-immunity pairfrom Yersinia kristensenii. The toxin (CdiA-CT) has structural homology to the mammalian RNase Asuperfamily, however, the toxin did not retain the characteristic disulfide bonds and has little to nosequencesimilaritytoRNaseAparalogs.Inmylaboratory,wepurifiedwild-typetoxinalonealongwithaseriesofmutationstoprobetheirroleinitspredictedRNasefunction.WeshowedthatthetoxindidpossessRNaseactivityandmutationalanalysisofHis175,Arg186,Thr276andTyr278showthattheseresiduescontributetoitsactivity.WealsodemonstratedthatCdiIinhibitsthetoxin’sRNaseactivity.TheCdiA-CT toxin from Y.kristensenii is the first non-vertebrate protein found to possess the RNase Asuperfamily fold, and homologs of this toxin have been discovered throughout bacterial secretionsystemswhich are associatedwith inter bacterial communication inmany Gram-negative and Gram-positivebacteria.

SarahCastillo MountSaintMary'sUniversity

8Biochem CharacterizationofGlutathioneInhibitionofOxidativeDNA-ProteinCrosslinking

EricStemp MaryBekarian,SarahCastillo,MarySafaeipour,MaritzaSanchez,JulietteJaureguiandEricStemp

Glutathioneisasmallcysteine-containingpeptideresponsibleforredoxbufferinginthecell.Here,weinvestigatedwhether itmight bepossible for glutathione, a strong reductant, to inhibitDNAdamage(e.g. DNA-protein crosslinks) by engaging in redox repair of the 1-electron oxidized guanine base asformedby the flash-quenchmethod. Samples containingRu(phen)2dppz 2+ [phen=phenanthroline,dppz=dipyridophenazine],Co(NH3)5Cl2+,histoneprotein,calf thymusDNAwere irradiated for0-240secondsintheabsenceorpresenceofglutathionewith442nmlighttoeffectguaninedamage.Inthechloroform extraction assay, we found that the 260 nm absorption of free DNA decreased withincreasingirradiationtime,consistentwithcrosslinking,andthatthecrosslinkingplateauedatahighervaluewhenthehistoneconcentrationwasincreased.Inaseparateexperiment,theDNAsampleswerealsosubjectedtoultrafiltrationtoremovetheglutathione,whichwasthenanalyzedbyreversedphaseHPLC.Separationof the reducedandoxidizedglutathionewasobservedbymonitoringabsorbanceatthe 220 nmwavelength. As irradiation time increased, the intensity of the oxidized glutathione peakincreased,consistentwiththeredoxrepairmechanismdescribedabove.Furthermore,wecomparedtheeffectofreducedandoxidizedglutathioneinoursamplesviathegelshiftassayanditwasobservedthattheoxidizedformhadlittletonoeffectonreducingthecrosslinking,whilethereducedformdecreasedcrosslinking.Lastly,we investigatedwhetherornotglutathione interferedwiththequenchingprocessbydoingemission spectroscopyexperiments. We found thatglutathioneonly slightly interferedwiththe quenching of Ru(phen)2dppz 2+ , indicating that it most likely reacts with the guanine radicaldirectly.

DanielA.Coello CSU

DominguezHills

9Biochem Histonemethylationstatusbytemozolomideintumorcells

TieliWang HugoMora,MariaNava,LiliNyugen,AnthonyDiaz,AmandaParker,JamesGallo,andTieliWang

Histone methylation is a well-known mechanism of epigenetic regulation. The epigenetic event is apotential driver of acquired chemo-resistance. Temozolomide (TMZ) is a methylating agent used forclinicaltreatmentofseveraltypesofcancersandremainsasthemainchemotherapyagentbasedonitsabilitytoincreasethemediansurvivalofthepatient.Inourpreviousstudy,wehavefoundthatTMZwasable tomethylate recombinant histone using the proteomic technology. In this presentation,we areinterestedinidentifyingthehistonemethylationsstatusfollowingtheTMZtreatmentinbrainandtriplenegative breast cancer cells to findoutwhether TMZwill alternate thehistonemethylation status intumorcellsusingwesternblotanalysis.OurresultsshowedthathistonemethylationwasdecreasedasweincreasetheconcentrationofTMZinbraintumorcellswhilethehistonemethylationstatuswasnotsignificantly affected by TMZ in triple negative brain cancer cells. The results indicate that histoneassociatedproteinsmaybeatargetofTMZinbraintumorcellsbutnotintriplenegativebreastcancercells.

RimaSanyal ChapmanUniversity

10Biochem StructureActivityRelationshipStudiesofaDiarylpentanoidthatInducesReactiveOxygenSpeciesinProstateCancerCells

MarcoBisoffi JustinO’NeillandMarcoBisoffi

Prostatecancer,orprostaticadenocarcinomahasbeenshowntothriveonthehighconcentrationsofandrogensecretedbythetesticularandadrenalglands.Curcuminanaloganddiarylpentanoidca27(5-bis(2-hydroxylphenyl)-1,4-pentadien-3-one) has been shown to induce reactive oxygen species (ROS)which have been shown to down regulate the androgen receptor in prostate cancer cells and thusimpede tumor progression. Curcumin, ca27, various other analogs with a hydroxyl (OH) group atdifferentpositions (ortho-meta-para)onthearyl rings,andanalogsofca27withoutanyOHgroupsorMichael acceptor groupswereused to treat LNCaPprostate cancer cells todetermine theamountofROS induced. LNCaP cells were incubated in black 96-well plates with the compounds at multipleconcentrationsalongsideDMSOasacontrolandhydrogenperoxideasastandardROS.ROS inductionwas determined via dichlorofluorescein (DCF) mediated fluorescence and glutathione (GSSG/GSG)detection assay. DCF data was normalized using Hoechst dye. Our preliminary data shows that allanalogsanalyzed inducemoreROSthancurcuminandthatanalogc58(OHgroupatmetapositiononarylgroups)showedthelowestoxidantpotential,indicatingthatthepresenceofMichaelacceptorsandthepositionofOHgroupsdeterminethepotentialofdiarylpentanoidstoinduceROSanddown-regulatetheandrogenreceptor. It isexpectedthatourstructureactivityrelationship(SAR)studieswill identifypharmacophoresthatcanbeused in furtherdrugdevelopmenteffortstowardsatherapeuticstrategyagainstprostatecancer.

Quang-MinhDang

UCI 11Biochem UnderstandingtheRolesandFunctionsofCryptochromeinMagnetoreception

AlbertSiryaporn

Manyeukaryoticorganismsdetectmagneticfields,butthemolecularmechanismsofmagnetoreceptionareunknown.RecentworkhypothesizedthatCryptochrome1(Cry1) isamagnetosensor.Wetestthishypothesis by creating a custom and working model for Eukaryotic Cryptochrome in bacteria. Weconstructed a chimera of Cry1with CpxA, a two-component system histidine kinase, in E. coli. Two-componentsystemsaresignaltransductionpathwaysinwhichhistidinekinasesphosphorylateresponseregulators,whicharetypicallytranscriptionfactors,andcanbeobservedwithactivationoffluorescentproteins. Thus, a Cry1 two-component system hybrid system in E. coli represents a way to probemagnetoreception using a finely tuned signal transduction pathway. To characterize the photon andmagneto-responsive characteristics of Cry1, we will use blue light activation and a two-componentsystemreporter.Aphotoresponseisconsideredanymeasurablechemicalorbiologicalresponsetolightandmagnetoresponseisaresponsethatallowsanorganismtoperceiveamagneticfieldforpurposesofdirectionandorientation.Thisresearchaimstotesttheexpressionofthereportersystemunderseveralblue light activation and magnetic fields in vivo in order to learn more about the functions ofcryptochrome. Lightactivation involvesmeasurements in lux for illuminanceandmagneticactivationsmeasurementsinteslaformagneticfluxdensity.WewillalsouseadirectionalevolutionaryapproachtoinsertCpxAatrandomlocationsinCry1andscreenforamagneto-responseandopticalresponse.Muchofthepreliminaryworkhasbeencompletedandtheresultsareencouragingforanimplementationofourtestingtechniques.

DennyBijuandDianaRios

CSUBakersfield

12Biochem

TheImpactofRoastingLevelonthePhenolicAcidProfileofCoffee

SarahForester

AccordingtotheAmericanCancerSociety,cancerisbecomingoneoftheleadingcausesofdeathintheUnitedStates,affectingmorethanamillionpeopleeachyear.OralcancerisoneofthemostcommontypesofcancerintheUnitedStatesforbothmenandwomen.Morethan59,000menandwomenarediagnosedwithoralcancer,andpartofthetreatmentincludesconsumingahealthydietrichinphenoliccompounds.Phenolicacidsareaclassofphenoliccompoundsthatareproducedbyplantsinresponsetoultravioletlight,pestsanddisease.Chlorogenic,caffeic,andgallicacidsareparticularlyabundantincoffee, a widely consumed beverage. Consumption of these coffee-derived components could havemanybeneficialhealtheffectsincludingpreventionoforalcancer.Theconcentrationofthesephenoliccompounds aredependenton roast levels of coffee. In this study, the anticancer activitiesof variousfreezedried coffee beverageswere compared, differing only in their roast treatments. Thedifferentroasting stages selected for this study were “Green”, “Cinnamon”/Blonde, “City”/Medium, “FullCity”/Medium-Dark,and“FullCityPlus”/Dark. The freeze-driedcoffee sampleswere re-suspended inwaterandmethanol.Thetotalphenoliccontentandtotalantioxidantactivityofeachextractwasalsodetermined by the Folin-Ciocalteu, HPLC (high pressured liquid chromatography), and ORAC (oxygenradical absorbance capacity) assays, respectively. Data collected from the Folin-Ciocalteu methodshowedthatthe“Cinnamon”/Blonderoastedcoffeecontainsthemostamountofphenoliccompounds,which likelyhelps in the inhibitionof thecancercellgrowth50%more thantheothercoffeeextractsexperimented upon. Observed data, through HPLC, displayed high peak areas at 280 nanometers(mAUs) for caffeic acid and gallic acid in the “Cinnamon”/Blonde roasted coffee and high peaks ofchlorogenicacidwereobservedinthe“Green”roastedcoffee.The“Cinnamon”/Blondealsoshowedthemostamountoftotalantioxidantactivitycomparedtotheotherextractsaccordingtothedatacollectedfrom theORACassay. In conclusion, the consumptionof lighter roasted coffee (“Cinnamon”/Blonde),alongwithahealthyandbalanceddiet,maycontributetothepreventionoforalcancer.

MinhVyTranNguyen

MountSaintMary'sUniversity

13Biochem DeterminationofTheEffectofMeringueUnderDifferentConditions

EricStemp

Meringue is commonly used in various dessert recipes. The formation ofmeringue is created via theblendingof liquidprotein fromraweggwhites,whippingcreamsandchickpea liquidandair fromtheatmosphere.Thestabilityofthemeringuemaybeaffectedduetotheingredientsthatareavailableandtheadditional acidic contentsadded to theproteinmixture.Onecommonacidic addition is creamoftartarandvinegar.Thecreamoftartarisalsoknownaspotassiumbitartratewhichisapotassiumacidsaltof tartaricacidthathastheability tobreaktheproteincomponentandstabilizethemeringue. Inthis study,weexaminehow thedifferentprotein, fat andacidity components control themeringue’sstability.Theprocedureincludestheexactlysimilarvolumeofroom-temperaturemixturesofeggwhite,whippingcreamandchickpeasolutionaremixedwithdifferentamountofcreamoftartarandvinegar.Astheresult,thestiffmeringueformsfasterwitheggwhiteandchickpealiquid.However,thewhippingcream takes longer to form the stiff meringue. Themeringue’s stability is promoted depend on theprotein,fatandacidityratio.Infutureexperiments,wehopetouseNMRspectroscopytoexaminethephysical and chemical properties of molecules present in egg white, whipping cream and chickpeasolution.

MaiAbdusamad UCLA 14Biochem CharacterizationofZyg11AasaNovelMitoticProtein

JorgeTorres JorgeTorresandAnkurGholkar

Duringmitosis, cellsarehighly regulated toensureproper formationof themitotic spindleandequalchromosomesegregation.Asadisturbedmitoticspindleisafeatureofmanycancercells,oneapproachincancer treatmenthasbeento target thespindleassembly to triggerapoptosis.To identifyproteinsinvolvedinthemitoticspindleassembly,aproteomicanalysisofco-purifiedmicrotubuleasterproteinswaspreviouslyperformed.Ofthe592proteins identifiedbymassspectrometry,Zyg11Aemergedasapotentialkeyplayerincelldivisionaspreviousliteraturehasshownthatdown-regulationofZyg11Ahasbeen linked todefects in chromosome condensation and cytoplasmicorganization.While Zyg11Ahasbeen identifiedasamemberof theCullin-2E3 ligasecomplex that regulatesseveralkeyprocessesofcelldivision,thespecificroleofZyg11Aisunknown.PreliminaryimmunofluorescencedataindicatesthatZyg11Alocalizestothenuclearenvelope,themicrotubulesandthecytokineticbridge.Thissuggeststhatitmay have a crucial role in cell division, particularly during spindle assembly. To better understandZyg11A’sroleincelldivision,weperformedpulldownsoftaggedZyg11Atoidentifyproteininteractingpartners by mass spectrometry. Further functional analysis of these proteins may prove vital tounderstandingofZyg11A’sroleincelldivisionandsubsequentlydiscoveringnewtherapeutictargetsforcancertreatment.

NguyenPham UCLA 15Biochem Aconservedputativekinaseisrequired

forcoenzymeQbiosynthesis:Functionalinsightsfromyeastgenetics

CatherineF.Clarke

CatherineF.Clarke

Coenzyme Q (ubiquinone or Q) is an essential lipid functioning as electron carrier in the electrontransportchainduringcellularrespiration.At least11Coqpolypeptides involved intheQbiosyntheticpathway have been characterized inSaccharomyces cerevisiae.Several of the Coq polypeptidesessential for efficient Q biosynthesis organize into a high weightmolecular complex localized to theinner mitochondrial membrane, designated the ‘CoQ-synthome’. Coq8 was identified as an atypicalkinaseresponsibleforsustainingthestabilityoftheCoQsynthome.OverexpressionofCOQ8hasbeenshowntorestoresteadystatelevelsofCoqproteinsinseveraloftheyeastcoqnullmutants.However,thespecificfunctionofCoq8remainsunknown.Previously,amutantyeaststrainharboringthecoq8-3allele was shown to encode the A197W substitution within the conserved kinase motif 1, and wassuspected to disrupt the putative kinase activity of Coq8p. The yeast coq8-3mutant lacks Q, isrespiratorydeficient,anddoesnotgrowonnon-fermentablemedia.Theyeastcoq8-3mutantexhibitsadramatic decrease in the steady-state levels of the Coq4 and Coq9 polypeptides. To gain insight intoCoq8 function, thecoq8-3mutant was selected for further investigation. Six spontaneous revertantswere isolated from the coq8-3mutant. Each of the six revertants was able to grow on a non-fermentable carbon source and retained the parentalcoq8-3point mutation. Analysis of the sixrevertants by LC/MS-MS revealed Q6content was restored. Three out of six revertants appeared tocontainrecessivesecondarymutations,whileonerevertantdisplayedadominantsupressormutationasdemonstrated by complementation tests. Here we report our investigation of the spontaneousrevertants with recessive suppressor mutations. Elucidation of how they function to restore Qbiosynthesisinthecoq8-3mutantmayhelpclarifythefunctionofCoq8inQbiosynthesis.ThisresearchwassupportedbyNSFMCB-1330803.

EmmieHo CSUFullerton

16Biochem ComputationalStudiesofTheIntramolecularCyclizationoftheRadicalCationsofE/Z2-Propenylbenzaldoxime

AndrewPetit

The functional groups –C=NOH and –C=NO-R are commonly found in pharmaceutical and pesticides.Compounds containing these functional groups are known as oximes and oxime ethers respectively.Oxime ether radical cations and iminoxyl radicals are the reactive intermediates produced by theoxidation of oximes and oxime ethers.When oximes and oxime ethers aremetabolized, radicals areformedinthecells,whichcouldcauseharmfulreactionsthatdamagetissuesandDNA.Thereactivityofoximeetherradicalcationsandiminoxylradicalsisstillrelativelyunexplored.Dr.deLijser’slabhasbeenusing photochemistry to oxidize oximes and oxime ethers and produce reactive radical cationintermediatesthatcanundergofurtherintramolecularreactions.Basedontheresults,theyfoundthataryl groupsandalkynylsgroupactasnucleophilesand radical traps respectively; and formedcyclizedproducts.Alkenegroupshavetheabilitytoactaseithernucleophilesorradicaltraps.Thealkenewithno methyl group (2- vinylbenzaldoxime ether) and alkene with one methyl group cis (2-isopropenylbenzaldoxime methyl ether, 2-isopropenylbenzald-oxime) both yield similar cyclizationproductsThedeLijserlabalsoconsideredtheisomers2-(E)-propenylbenzaldoximemethylether,2-(E)-propenylbenzaldoxime,2-(Z)-propenylbenzaldoximemethylether,and2-(Z)-isopropenylbenzaldoxime.These(E/Z)-propenylalkenesseemtoallproducethesameproduct,howevertheNMRdataappearstobeinconsistentwiththecyclizedproductsobservedwiththeotheralkenes.BecausethedeLijserlabhasnotyetbeenableto isolatetheproductoftheoximesandoximeetherscontainingapropenylgroup,weuse computational chemistry tohelp to solve theproblemby calculating theNMRchemical shiftsandJcouplingconstantsofmanypossibleproducts.Wealsomappedouttheradicalcationminimaaswell as the transition states connecting them. Although we have not yet definitively identified the

product,outresultshaveruledoutmanydifferentpossibilitiesaswellasimprovedourunderstandingofthe mechanism by which the alkene oxime and oxime ther radical cations undergo intramolecularcycilzation.

KevinYe UniversityofSouthernCalifornia

17Inorg/Mat PerovskiteChalcogenidesforSolarEnergyConversion.

JayakanthRavichandra

As the energy needs of the planet are likely to doublewithin the next 50 years, alternative formsofenergy are being explored to supplement the Earth’s depleting oil reserves. Solar energy remains astrong candidate, with the Sun feeding 10,000 times more energy than the global population’sconsumptioninayear.Hence,photovoltaicscanbeasuitablerenewablesourceofenergy.However,amajor limitation of the leading photovoltaic material, crystalline silicon, is its poor absorptioncharacteristics.Thisleadstotheneedfor180–300μmthickwaferstoabsorbsunlightinsteadofafewhundreds of nanometers for materials with higher absorption characteristics. Thus, it is crucial todevelop high performance and cost effective functional materials to enable sustainable, large scalephotovoltaics. Transitionmetal perovskite chalcogenides are a new class of versatile semiconductorswithhighabsorptioncoefficientsandhighluminescenceefficiency.Firstprinciplecalculationsshowthatthese materials are promising candidates for optoelectronic applications in the visible and IRwavelengths.Theseperovskitematerialsweremadeusingaone-shotsynthesiswithiodineasacatalyst.Polycrystallinesamplesweresynthesizedwithexperimentalbandgapvaluesinthevisiblelightrange,asdetermined by photoluminescence measurements. Three distinct phases of perovskites werecharacterized,withoneofthephasesapproachingtheexternalluminescenceefficiencyofsinglecrystalssuchas InPandCdSe.Bystudying themechanismof their synthesisand resultingphysicalproperties,theuseoftheperovskitechalcogenidesforharvestingsolarenergyshallbeexplored

MarisolHerrera-Ruiz

UCR

18Inorg/Mat

GrowthandCharacterizationofNbSe2MonolayerFilm

LudwigBartels

DarrickWang,MichaelValentin,SaharNaghibi,ArianaNguyen,VelvethKlee,I-HisLu,EdwinPreciado,LudwigBartels

Niobium diselenide has become an attractive material for making nano superconducting quantuminterference devices. Charge density wave (CDW) distortions have been observed in transitionmetaldichalcogenides(TMDs)andonlythemonolayerlimitdisplaysthesuperconductingcharacteristic.Here,NbSe2 is synthesized through chemical vapor deposition (CVD) on SiO2/Si substrates to achieveatomicallythincrystallinestructures.Comparedtomechanicalexfoliation,CVDensuresmoreconsistentandscalablegrowththatcanbeeasilyadoptedbythesemiconductorindustry.NbSe2displaystheE2gandA1gRamansignalsat238and228cm-1,respectively.Adirectbandgapat1.34eVemergesatthemonolayer limit.Thesuccessfulgrowthof thisnewTMDmaterialpromises theadvancementofnanoquantumdevices.

JonathanStoffel

CalPolyPomona

19Inorg/Mat

Investigationofthereductionofcobaltnitrosylcomplexes

S.ChantalE.Stieber

Carbondioxide(CO2)isoftentimesafocusforpollutionremediation,however,lesserknownpollutantssuchasnitrogenoxides(NOx)poseasimilarthreat.WhilebiologicalcyclesconvertNOxintolessharmfulinertgasses,theconversioniscarriedoutatanunfavorableratetodiminishtheatmosphericlevelstoafavorablelevel.Thisprojectaimstosynthesizecobaltmetalcomplexesthathavethecapabilitytoreactwith NOx species. These transition metal centers may be able to provide insights towardscharacterizationof intermediates in thebiologicalcycle.The long-termgoalof thisproject is toutilizethemetalcomplextotransformNOxspeciesinchemicalconversions.

NanehVartan,DanyalCave,JakiLiu,andJasonHernandez

PasadenaCityCollege

20Inorg/Mat NanotechnologyinChemicalEducation:DNAOrigamiandnanoART

JillianL.Blatti DanyalCave,JohnGarcia,JiaqiLiu,FelixMonge,FriedaSchwebel,EllenChan,JasonHernandez,JillianL.Blatti

Through theEarlyCareerUndergraduateResearchProgram (eCURe)atPasadenaCityCollege,weareinvolvedininterdisciplinaryresearchprojectsatthecuttingedgeofscience,attheart-scienceinterface,and those that canbe translated into lessons to inspireK-12 students.Our goal is tomakeadvancedscientific research accessible to all students through simplification, using affordable materials, andimplementingeffectiveteachingpedagogies,suchasactivelearning,groupwork,andemployinghands-onmanipulatives to illustrate concepts.WeusednanoARTandDNAorigami to introduce students tonanotechnologyinacreativeandengagingway.DNAorigami,thenanoscalefoldingofDNAinto2Dand3Dshapes,emphasizestheinterdisciplinarynatureofscience,bringingtogetherchemistry,biology,andcomputer science, which is important to show in modern science curricula, beginning early in one’seducation.We chose to design a 2DDNA origami shamrock as a platform for our lesson plan, as itssymmetrical shapeallows foreasydesign.TheDNAorigami shamrockwasdesignedusing free,open-source software (caDNAno.org; cando-dna-origami.org), facilitating scalability of the lesson. The DNAorigamishamrockwasimagedusingAtomicForceMicroscopy(AFM),whichcanbeaccessedremotely1.After implementing the lesson in an underrepresented high school in Los Angeles and analyzingassessment data, itwas clear thatDNAorigami andnanoART generated student interest and lead togreaterunderstandingofnanotechnology.Byteachingstudentsscienceincontext,showingthemhowitcan be applied towards solving current global challenges, and introducing them to careers in thesefields,theybecomemotivatedtousetheirscienceeducationtochangetheworld.

Chien-FuFrankHuang

UCLA 21Inorg/Mat ControllingtheMorphologyofPolymerSolarCellsusingSequentialProcessing

BenjaminJ.Schwartz

TaylorJ.Aubry,MatthewT.Fontana,BenjaminJ.Schwartz

Organic solar cells are a potential solution for resolving energy needs because of their low cost,flexibility, lightweight,andeaseofmanufacturing.Thedonormaterial,usuallyaconductingpolymer,absorbssunlighttocreateaboundelectronholepairknownasanexciton.Toseparatetheexciton,thedonormaterialmustbepairedwithanacceptormaterial,usuallyafullerenederivative.Thedonorandacceptormaterialmustcreateasufficientlymixed,bicontinuousandinterpenetratingnetwork,knownasabulk-heterojunction(BHJ),toefficientlysplittheexcitons.HerewecarefullycontrolthemorphologyofPTB7andPCBMbasedBHJsusinganewprocessingtechnique,SequentialProcessing(SqP),andstudytheeffectsonchargetransferwithphotoluminescencequenchingmeasurements.WithSqP,theactivelayer is formed through separate and sequential depositions of the donor and acceptor layers. Theformation of a mixed active layer is therefore dependent on the swelling of the underlying donorpolymerbytheacceptorsolutionandinter-diffusionoftheacceptor.Additionally,co-solventblendsforacceptor deposition extend the work to any polymer system by tuning the ratio of swelling to non-swelling solvents in the blend. Building on prior group work, we study the use of solvent blends ofswelling solvent 2-chlorophenol (2-CP) pairedwith non-swelling co- solvent isopropyl alcohol (IPA) sothatthesolventblendmayoptimallyswellthepolymeracceptor,PTB7withoutdissolution.[1]Bytuningthe fraction of 2-CP to IPA in the fullerene casting solution, we observe the evolution from a quasi-bilayerstructuretoawell-mixedactivelayer,asevidencedbyincreasedPLquenching,todissolutionofthe polymer under layer. The optimal ratio of solvents is between 60-70% 2-CP (40-30% IPA,respectively).Thisworkwillnowbeextended toBHJ solar cells thatemployperylenediimides (PDIs),commonly used as car paints, as alternative acceptors because of their even lower cost and strongabsorptioninthevisiblespectrum.

AshishStreatfield

PomonaCollege

22Inorg/Mat

MechanisticInvestigationofSO2InsertionintoOrganopalladium(II)ComplexesusingSolidSO2AdductsandLewisAcids

NicholasD.Ball

Metal-catalystincorporationofsulfurdioxide(SO2)intoorganicmoleculesusingbench-stableSO2isofintense interestasanatom-economicalway toaccess sulfonylatedcompounds,often inone reactionvessel. Compared to the intensive literature regard of SO2 insertion in metal-carbon bonds usinggaseous SO2, comparable studies of SO2 migratory insertion using bench-stable SO2 reagents likeDABSOandDMAP·SO2arerare.InvestigationsofSO2insertionofmodelorganopalladium(II)complexesusingDABSOandvariousLewisacidswillbediscussed.IntermediatesisolatedandcharacterizedbyNMRspectroscopyprovideevidenceofSO2migratoryinsertioncomparedtotheNMRofliteraturereactionsinvolvinggaseousSO2insertion.FuturestudieswillfocusonselectiveSO2arylC–PdbondandalkylC–PdbondinsertionanddemonstratingtheelementarystepsofPd-catalyzedsulfoneandsulfonylfluorideformation.

SooihkRo

UCLA

23Inorg/Mat

Yttriumandindiumalkoxidecomplexesasredoxswitchablecatalysts

PaulaL.Diaconescu

AlexanderLaughlin,PaulaL.Diaconescu

The activities of redox-switchable yttrium and indium alkoxide complexes supported by a ferrocene-based ligand during ring-opening polymerizations of L-lactide and trimethylene carbonate areinvestigated. Switching the metal complexes in situ between their oxidized and reduced states withredoxreagentschangestherateofpolymerizationofL-lactideandtrimethylenecarbonate.Theyttriumand indium alkoxide complexes showed opposite behavior in the polymerization of monomers. Theactivitiesofvariousmetalcomplexeswereinvestigatedasafunctionoftheligandsubstituents.

TateReuter

UCLA

24Inorg/Mat

FerroceneChelatingHeteroscorpionateCompounds

PaulaDiaconescu

MarkAbubekerovandPaulaDiaconescu

Ferrocene-chelating heteroscorpionate compounds based on [fc(PPh2)(BH[(3-R-5-R’-1-H)2pz]2)] (fc =1,1’-ferrocenediyl,pz=pyrazole), are studiedandcharacterized for their role in thecatalysisofblockcopolymerization. The ferrocene scaffold supports the heteroscorpionate adduct that binds latetransitionmetals.Azinccomplex,[fc(PPh2)(BH[(3,5-Me-1-H)2pz]2)]ZnCl,wassynthesizedpreviouslyandshowntoexistinadimericstate.Herein,thesubstituentsonthepyrazolefragmentsofthescorpionateare replacedwith bulkier groups to force a steric interaction. The aim is to produce a catalyst in themonomeric state that can be characterized and utilized in biodegradable polymer synthesis withpotentialforredoxswitchability.

PaulChong

UCLA

25Inorg/Mat

B12(OR)12reagentsastunableone-electronoxidants

AlexanderM.Spokoyny

WereportthediscoverythatperfunctionalizedicosahedraldodecaborateclustersofthetypeB12(OCH2Ar)12(Ar=PhorC6F5 )canactaspowerfulmetal-freephotooxidants.Theseclustercompounds,whenirradiatedwithblueLEDlight,exhibitexcitedstatereductionpotentialsashighas~3voltsvs.SCE,makingthemthestrongestmolecularphotooxidantsknowntodate.Photo-excitationoccursasaresultof charge transfer between low-lying orbitals of the benzyl substituents and an unoccupied orbitaldelocalized throughout theboron cluster core.We show that these species are able toparticipate inelectron transfer processes with a broad range of electron-rich and electron-deficient styrenesubstrates,initiatingtheirpolymerizationatclusterloadingsaslowas0.005mol%.Furthermore,photo-excitationofB12(OCH2C6F5)12inthepresenceofisobutylene,alessactivatedolefin,resultsintheproductionofhighlybranchedpoly(isobutylene).Thisworkintroducesanewclassofrobust,metal-freephoto-redoxreagentscapableofmediatingchemicaltransformations.

MichaelPardo

CSULongBeach

26Org

DevelopmentofanAboriginalChemicalProcesstoMakeBiodiesel

SergioMendez

JamesBorgeseandSergioMendez

This research project can potentially benefit impoverished, rural communities that have a need forsubstitutesorsupplementstopetroleumfuels.Wehavedevelopedan“aboriginal”chemicalprocesstomakebiodieselwith the following constraints:minimal cost, reactantsare readilyavailable from localarea, relatively simple chemistry, and that it be environmentally friendly. The two reactants for thisprocesswouldbeanoilandethanolderivedfrom localplants. Highpurityethanolwasdistilled frompalmwineusingtapiocaasahygroscopicagent.Sincethebiodieseltransesterificationreactionrequiresacatalyst,weutilizedwasteeggshellsthatwerecalcinedintocalciumoxide,aheterogeneouscatalyst.FTIRspectroscopywasusedtoconfirmthesynthesisofbiodiesel.

NicoleLukaskoandMeganChisesi

CalPolySanLuisObispo

27Org InvestigationofArtemisiacalifornicaandUmbellulariacalifornicaAntibacterialCompounds.

JenniferCarroll

M.Chisesi,J.Carroll,A.Yep,J.Yost

CaliforniaNativeAmericansusedavarietyofnativeplantspeciestotreatfevers,wounds,andbacterialinfections.TheleavesofnativeCalifornianplantscontainavarietyofterpenoids,alkaloids,flavonoids,cyanogens,andtannins,allofwhichhavebeenshowntobeactiveagainstbacteria,fungi,viruses,andprotozoa.We obtained plant extracts of Umbellularia californica (California bay laurel) and Artemisiacalifornica (California sagebrush) through steam distillation and tested them against Escherichia coli,Bacillus subtillis, and Staphylococcus epidermidis. Extracts of A. californica were active against bothGram positive species, B. subtillis and S. epidermidis. A previous study identified two flavonoidcompounds active against E. coli (Gram negative), but the compounds active against Gram positivebacterial species have yet to be elucidated. We found that the U. californica extract was effectiveagainst bothGrampositive andGramnegative species. While the active compounds have yet to beclearly identified, we validate the use of these species to fight microbial infections of both GramnegativeandGrampositivebacterialspecies.

JocelynOchoa CSULongBeach

28Org SynthesisofEnantioenrichedButylCholinylPhenylPhosphateIodideanditsInhibitionAgainstButyrylcholinesterase

K.Nakayama T.Tran,M.,J.Gonzalez,J.Schwans,andK.Nakayama

IthasbeenshownthatpatientswithAlzheimer’sdisease(AD)haveabnormalactivitylevelsofthetwocholinesterases,acetylcholinesterase(AChE)andbutyrylcholinesterase(BChE).AChEtendstodecreaseits activitybyup to45%,whileBChEactivity increasesby40-90%.CurrentAD treatment attempts toinhibit AChE activity with the aim of restoring cholinergic levels and consequently, cognition of ADpatients.Our laboratoryhasbeen interested in thesynthesisandstudyofcompounds that target theother cholinesterase, BChE. Previouswork from our laboratory indicated that dialkyl aryl phosphateswere potent inhibitors of BChE, among which analogs containing a cholinyl moiety showed greaterinhibitionwith inhibition constant (KI) values down to 0.6 µM. Since these cholinyl-group containingphosphatespossessachiralcenter,wedecidedtosynthesizeenantiomericallyenrichedformsofthesephosphates. Employing chiral auxiliary 2-(methoxymethyl)-(2S)-pyrrolidine, (S)-butyl cholinyl phenylphosphate (54% ee) was prepared in 4 steps: reaction between the chiral auxiliary and diphenylchlorophosphate; treatment with 2-dimethylaminoethanol; reaction with 1-butanol under acidicconditions;andfinallymethylationwithmethyliodide.TheKIvalueofthiscompoundwasdeterminedtobe7.2μMwhileitsracemicformhadaKIvalueof10.6µM.Thisposterpresentsthesynthesisoftheenantioenriched (R)-butyl cholinyl phenyl phosphate. By comparing the KI values of the twoenantiomers,wewillbeabletodeterminethekeyinteractionsinvolvedbetweeneachenantiomerandBChE.ThisshouldassistinthefuturedesignofBChEinhibitors.

GregoryDawson

SDSU

29Org

TheCinchona-AlkaloidCatalyzedNucleophilicDynamicKineticResolutionofAtropisomericAryl-Naphthoquinones

JeffreyGustafson

SeanMaddox,NickRoschester,GregoryDawson,JeffreyGustafson

Atropisomerismisaformofchiralitythatarisesfromthehinderedrotationaboutabond,resulting inrotational enantiomers. BINOL and BINAP are two examples of privileged ligands in enantioselectivecatalysisthatcontainastablechiralaxis.Themild,enantioselectivesynthesisoftheseligandshasonlyrecently been reported; and few general strategies exist to enantioselectively synthesize diverseatropisomeric scaffolds. A general enantioselective synthesis towards diverse enantioenrichedatropisomeric ligands would provide access to catalysts with unique geometries and structuralproperties.Herein,wediscloseadynamickineticresolutionofbiarylnaphthoquinoneatropisomersviathe nucleophilic addition of thiophenol proximal to the chiral axis. Various biaryl naphthoquinoneatropisomerswereamenabletothisstrategy,oftenyieldingenantiomericratiosofgreaterthan90:10.Theresultingenantioenriched1,4-dimethoxynaphthoquinoneatropisomerscanbefurthermodifiedtocontaindesirablefunctionalgroupsincatalysis(i.e.aminesphosphines)withhighenantioretention.

ValeriaGarcia

SDSU

30Org

StructuralOptimizationofAtropisomericPyrrolopyrimidineStructures

JeffreyGustafson

SeanToenjes,JefferyGustafson

Kinaseproteinsareabundantinthehumangenomeandtheiraberrantactivitycanleadtovariouslifethreatening diseases. Consequently, a dense amount of medicinal research has been focused in thedevelopment of effective kinase inhibitors. Even though kinase proteins are widely accessible, thetargetedactivesitesofeacharehighlyconserve.Asaresult,thekinaseinhibitorsbindnotonlytothetargetactivesites,butalsotooff-targetsites,leadingtounwantedsideeffects.Awidevarietyofkinaseinhibitorsexistintheformofatropisomers,anextendedformofchiralitythatcompromisesofatleastone rotational axis between two aromatic centers. Many of these kinase inhibitors exist as rapidlyinterconverting atropisomeric racemic mixtures. From these mixtures only a single atropisomericconformationbindstothetargetedactivesite,whiletheotherconformationbindstooff-targetsites.nresearchdonebytheGustafsonlab,atropisomerismisexploitedtoincreasekinaseinhibitionselectivityofPyrrolopyrimidinebasedcompounds. Inthereport,theyrigidifiedabiarylaxisbyaddingstericbulkadjacenttotheaxisandfoundthe(R)-conformertobe5xmoreselectivetowardsRETkinasethanthe(S)-conformeraftersubjecting theconformers toapartialkinomescreen. Onedrawbackto thisworkwasalossinpotencyfromtheparentcompound(nostericbulk).Tofullyexploitthestrategyofspatialpre-organizinganinhibitorasaselectivityfilter,theanalogsneedtobeoptimizedforbothpotencyandselectivity. To accomplish this, we first identified potential analogs by screening various substituentcombinations(Figure1)ofthe(R)-configurationagainstRETusingMOE,amolecularmodelingsoftware.Thedockingresultssortedbydihedralangles(determinantofRandS)andthenrankedbybothbindingscore (potency) and ΔR/S (atropisomer preference) in order to establish priority molecules tosynthesize. The optimizedmolecules were synthesized and their R and S conformers (separated viaHPLC)werescreenedinvitroagainstRETusingADP-Glokinaseinhibitionassay.Preliminaryinvitrodata(consistent with in silico studies fromMOE) demonstrated that any loss of potency from the parentcompoundmayberegainedwhilemaintainingRET’satropisomerpreference.

MicaelleMorales,CoreyMyers,andLuisSalazar

CSUBakersfield

31Org AOne-PotEnvironmentallyBenignSyntheticRouteforIsoxazolineDerivatives

DanielleSolano

The avail of isoxazoline rings in pharmaceuticals entails a greenermethod for the synthesis of theseheterocycles.Isoxazolinesarewidelysynthesizedfortheirbiologicaleffectsasanticancer,antibacterial,anti-HIVandanti-inflammatoryagents.Thestandardsyntheticrouteoftheseheterocyclesinvolvestheuse of toxic solvents such as dichloromethane (DCM). The Solano Research Group has developed anenvironmentallybenignandmoreefficientmethodforisoxazolinesynthesis,whichreplacestheuseofdichloromethaneforwaterasthemainsolvent.Thesyntheticprotocolemployedinthegreenmethoduses sodium dodecyl sulfate (also known as SDS, a common ingredient in soap) as a surfactant andwaterasthereactionmediumfortheformationoftheisoxazolinering.Thisone-potmethodoccursviathe reaction of an aldehyde to form a nitrile oxide intermediate which then undergoes 1,3-dipolarcycloaddition with a dipolarophile. The micelles created by the SDS form a hydrophobic cavity thatmakes it possible for organic compounds to dissolve and cause the reaction to occur. The researchfocusesontestingavarietyofdipolarophilesandelucidatetheirscopeofthereaction.

AlejandroTorres

CSUFullerton

32Org

SynthesisofSmallMoleculeInhibitorsforTheNS2B/NS3Protease

NicholasSalzameda

WestNileVirus(WNV)infectsmillionsofpeopleeveryyeargloballyviamosquitobites.Approximately1% of WNV cases lead to a fatal neurological condition. Currently, there are no vaccines or othertherapeuticmethodstotreatWNVinfections.TheWNVcontainspositive,single-strandedRNAinaviralenvelope invade host cells through endocytosis. Cleavage of the viral polypeptide by the NS2B-NS3proteaseleadstoactivestructuralandnonstructuralproteinsinhostcellsthatresultinWNVreplication.TheNS2B-NS3proteaseisatherapeutictargetforWNVinfectionsbyinhibitingtheNS2B-NS3protease,asmallmoleculeinhibitorcouldpreventtheenzymaticactivity,therebyendingWNVreplicationinhostcells.Ourresearchfocusesonthedevelopmentofsmallmoleculeinhibitorsfeaturingargininemimetics.The synthesis of these mimetics is accomplished through a multi-step synthesis from 1,4-cyclohexanedione to 5 varying arginine mimetics. The arginine mimetics will be coupled to variouscarboxylic acids to produce a library of compounds that will be screened for NS2B-NS3 proteaseinhibition.

JillianDawleyandRyanEllson

ChapmanUniversity

33Org SynthesisandevaluationofdyederivativesasG-quadruplex-stabilizingmolecules

JeremyMcCallum

NicolasVentigan,JeremyMcCallum

DNAG-quadruplexes representanew,promising targetofanticancer therapies.G-Quadruplexeshavebeen shown to stop unrestricted cell growth in cancerous cells by inhibiting the enzyme telomerasefromextendingDNAlength.ThegoalofourresearchistosynthesizenovelmoleculesthatstabilizetheG-quadruplexstructure.Throughthederivatizationofazobenzeneandindigobaseddyes,asmalllibraryof novel organic compounds was synthesized in 2-3 steps. These compounds were purified,characterized, and then tested for G-quadruplex stabilizing abilities bymeasuring changes inmeltingpoint curves of telomericDNA asmeasured by circular dichroism. Several of the drugs increased themelting temperature of the DNA, demonstrating that these core structures possess the ability tostabilize the telomeric G-quadruplex structure.Through the derivatization of azobenzene and indigo-baseddyes,asmalllibraryofG-quadruplexligandswassynthesizedandcharacterized.Compoundswithvarioustertiaryaminesidechainsweresynthesizedin2-3stepsingoodyields.ModerateG-quadruplexstabilization, asmeasured by changes inDNAmelting curves,was achievedwith several compounds.ThesedyederivativesrepresentnewcorestructuresthathaveG-quadruplexstabilizingpropertiesandthepotentialfornovelanticancertherapies.

JustinHathaway CSU

DominguezHills

34Phy/Anal/Theor Maker'sElectrochemistry:BuildingaLow-CostPotentiostatforCyclicVoltammetry

BarbaraBelmont

This poster is a progress report on a research project to build a low cost potentiostat for use inundergraduateelectrochemistrycyclicvoltammetryexperiments.Cyclicvoltammetryisapotentiometricmethodthatisusefulforstudyingelectrochemicalreactionsthatcreatecurrents.Thetechniqueisusedto quantify chemical compounds, discover reaction kinetics, and elucidate reactionmechanisms. Theinstrumentusedforcyclicvoltammetryexperimentsisapotentiostat,whichlinearlyvariesanelectrodepotential over a specific range at a specific rate, while monitoring the current that develops.Commercially, potentiostats and some variation of voltammetry or chronoamperometry are thefoundation of myriad chemical sensors such as glucose sensors, on-chip protein biosensors, and gassensors.Eventhoughextremelyusefulinbiomedicalandindustrialhygieneapplications,littleissaidofcyclicvoltammetryorpotentiostats in theundergraduatechemistry laboratorycurriculum.Oneof thereasons for this is that cyclic voltammetry measurements can be tedious and unforgiving. Anotherreasonisthatthemeasurementequipmentcanbeveryexpensive,withmostlaboratorypotentiostatsretailingfor$5000to>$10000.Ourresearchgrouphaspreviouslydemonstratedthattheopensource“Cheapstat” device coupled with screen-printed electrodes is suitable for an undergraduate cyclicvoltammetry experiment, for a startup cost of $160. To incorporate a student-built measurementsystemintotheexperiment,wearenowdevelopingalowcostpotentiostatusingopensourcesoftware,theArduinofamilyofmicro-controllers,andtheTexas InstrumentsLMLP91000programmableanalogfront-endchip.A successfulprojectwillprovideanopportunity for students tobecomemore familiarwithbothelectrochemistryandelectronics/computerinterfacing,forare-usablestudentkitstartupcostoflessthan$30.

ReginaCordova MountSt.Mary'sUniversity

35Phy/Anal/Theor InvestigatingMotionviaDeuteriumLineshapesimulations

DenizCizmeciyan

Deuterium is a nucleus which is NuclearMagnetic Resonance (NMR) active and has a spin quantumnumberof1whichgives rise toanon-spherically symmetricnuclearchargedensity.Thedistortionofthechargedensity is thecauseofdeuterium’squadrupolemomentwhich interactswiththeelectricalfield gradients around the nucleus. This quadrupolar interaction dominates the solid state deuteriumNMR Spectra. Deuterium line shapes which are called Pake Patterns are very sensitive to molecularmotionandprovidevaluableinformation.WeareinvestigatingthemolecularmotionofD2OinGypsumwherepresenceofwaterinGypsummightcauseittohavefireretardantsproperties.UsingalgorithmsinDr.AlanBenesi’sbook“APrimerinNMRTheorywithCalculationsinMathematica”wearesimulatingtherotationratesofdeuteriumnucleiforwateringypsum.OurresultsindicatethattheD2OinGypsumat220Cperformsa2sitehopaboutthebisectorangleof54.80attherateof>5x107Hz.TheQuadrupoleCouplingConstantandtheasymmetryparameterη,usedare216KHzand0.15respectively.At00Cthelineshapeissimilarwiththesameparameters.At-250C,thelineshapeshowssomebroadeningwithaQCCof223kHzandηof0.13.Ourgoal is tosimulatedeuteriumspectraformanytemperaturestobeableextracttheactivationenergyforthismotionfromanArrheniusplot.

EileenLek UCR 36Phy/Anal/Theor ConstructionofaCavityEnhanced

AbsorptionSpectrometerforHONODetection

JingsongZhang

MixtliCamposandJingsongZhang

Nitrousacid(HONO)isamajorsourceofreactivehydroxylradicalsthatreactwithothertracespeciestoformozoneandperoxyacetalnitrateinthetroposphere.GiventhatHONOplaysanimportantroleinthesubsequent formation of ozone, it is critical to study its presence in the atmosphere. Thus, thedevelopmentofsensitiveinstrumentationsuchastheCavityEnhancedAbsorptionSpectrometer(CEAS)allowsforthedetectionofambientHONO.TheconstructionprocessoftheCEASconsistedofaligningthelightemittingdiodewithtwobi-convexlensesandtwohighreflectivitymirrors.Aheliumneongaslaserwasutilized for thealignment inorder tooptimizemirror reflectivitycapacity.Anadjustable iriswas included in the setup to reduce thebackgroundnoise and therefore increase the signal tonoiseratio.Additionally,a flowsystemofN2,NO2,andHONOwasconstructedand installed into theCEASsetupforcalibration.HONOwascontinuouslygeneratedfromareactionsetupofNaNO2,HCl,andAr(g)and flowed into the CEAS cavity. Experiments were conducted by alternating a background N2measurementwithstepwisedilutionconcentrationsofHONO.Bystatisticallyanalyzingthepreliminarymeasurements inthewavelengthrangeof340nm–390nm,theCEASyieldedamirrorreflectivityof97.31%withthelowestdetectionlimitof800ppbvforHONO.Fromthecalculations,thesensitivityoftheCEASmustbeimprovedeitherbyreconfiguringthelightemittingdiodesetupormakingadditionaladjustmentstothehighreflectivitymirrors.AlowerdetectionlimitofHONOmustbeachievedbeforethe instrument is sensitive enough to measure ambient levels of HONO. Future work is focused onimprovingtheCEASsetupdesignby identifyingtheunderlying factors thatcontributetoastatisticallysignificantdifferenceintheCEASmeasurements.

CourtneyMayhew

CSUChannelIslands

37Phy/Anal/Theor AnalysisofRiceDeterminingifitisaSignificantSourceofMercurytoHumans

SimoneAloisio

Mercury is a persistent, global and toxic contaminant. The more common organic species,methylmercury has been a public health concern for decades because of its high toxicity and readilybiomagnifies in foodchains.High levelsofmercuryandmethylmercurycanaccumulate in ricegrains;recent literature has identified rice as a bioaccummulator plant species ofmethylmercury. Thisworkpresents the results ofmercurymeasurements of different types of commercially available rice. Theresults of this study suggest that the consumptionof rice canbe a significant source for exposure tomercury and methylmercury in the human body. The concentrations of mercury were measured bythermal decomposition, amalgamation followed by atomic absorption spectroscopy. The samplescollectedforanalysisweredifferenttypesofriceincludingbrown,whiteandorganicrangingfromshortgrainandlonggrains.Averagemercuryconcentrationsinwhiteshortgrain:6.9±3.5ppb,brownshortgrain:9.4±2.6ppb,brownshortgrainorganic:9.2±3.3ppb,whitejasminerice:5.4±3.4ppb,brownjasminerice:2.8±1.4ppb,brownlonggrainrice:12.5±1.3ppb,andbrownlongriceorganic:8.2±4.1ppb. While the concentrations of mercury in these rice samples seems to be low. Mercuryconcentrationsperservingofriceareonesixthofchunkwhitetuna.Sincericeisadominantstaplecropfor more than half the world’s population, however, rice may be a significant source of mercury inhumans.

SamanthaTsumaki

CSUDominguezHills

38Phy/Anal/Theor

Cis-3-hexenol in Kabocha (Cucurbita maxima)

BarbaraBelmont

Parlimentet.al.hasreportedcis-3-hexenoltobepresentasamajorcomponentinthevolatilefractionof Connecticut-grown pumpkins (Cucurbita pepo). This alcohol, which is found in many plants, isresponsible for the scent of freshly cut grass, and plays a major role in the flavor and fragrance ofcooked pumpkin.We hypothesize that the Japanese pumpkin, kabocha (Cucurbitamaxima), will alsocontain cis-3-hexenol, andhaveundertakenan investigation toassess thishypothesisusingGC-MSofextractsofcookedanduncookedkabocha.

JaclynPittman SDSU 39Phy/Anal/Theor MeasuringMetalComplexationCapacityofUnknownFulvicAcidSubstancesviaCapillaryElectrophoresis

ChristopherHarrison

MPXA, a lignite-derived agricultural product, is used to complex and deliver key micronutrients toplants. The fulvic and humic substances inMPXAmore easily allow for the chelation of metals thatwould otherwise be difficult to deliver to the plants. TheMPXA provides an effective alternative totraditionalfertilizersandhasbeenshowntopromotemoreplantgrowthwithlessproduct.Inordertomaximizetheefficacyandeconomyofthisproduct,itiscrucialtheMPXA-metalratiobeoptimized.Forthis reason, the extent to which MPXA complexes important plant micronutrients, such as calcium,magnesium,andzinc,mustbedetermined.ThisspecificanalysisofMPXAcanbeperformedbywayofcapillary electrophoresis (CE), an analytical tool used to separate aqueous phase ions. MPXA willdeprotonateandbecomeanionic inaqueoussolutions,possessinganelectrophoreticmobilityspecifictothecompound.DuetoCE’slackofdifferentiationofpolymersofdifferentsizes,MPXAmigratesinasinglepeak,regardlessofthesizeofthepolymer,duringtheseparation,intheabsenceofmetal.WhenthemetalisaddedandbindstotheMPXA,thecationicchargeofthemetalreducestheoverallanionicchargeof theMPXA, thereby reducing theelectrophoreticmobilityof the complex. This leads to tworesults: the migration time of the complex is increased, and the separation produces two peaks ofMPXA, onewith and onewithout themetal. Increasing the amount ofmetalmixedwithMPXA andquantifying the differences between the two peaks allow us to evaluate the extent of complexation.TwocomplementaryapproacheshavebeenemployedfortheanalysisofMPXAcomplexation;micellarelectrokinetic chromatography separation, with the cationic surfactant cetyltrimethylammoniumbromide,andcapillaryzoneelectrophoresis,withthecationicsurfactantdidodecyldimethylammoniumbromide as a capillary coating. These two approaches facilitate this unique study of the agriculturalproduct MXPA. Results from both methods are compared and presented for evaluation of thecomplexationofseveralimportantplantmicronutrientmetalswithMPXA.

StephanieSalas CalPoly

Pomona40Phy/Anal/Theor AnalysisofChloride,Nitrate,andSulfate

inWaterSamplesYanLiu

Waterisacrucialandessentialpartofaneverydaylifeforahuman.Inorganicspeciessuchassulfate,chloride, and nitrate in water are closed related to the anthropogenic and biogenic activities. Forexample,sulfateandnitratearethemajorcomponentsintheacidrain,whilechloridemaycomefromindustrial sources. Therefore, my project is to determine the concentration of chloride, nitrate, andsulfate in water samples.In order to determine the concentration of the desired ions in water, acalibrationcurvemust firstbemadewithstandardsolutionswithconcentrationsof2,4,6,8,and10ppm.ThesolutionsweretransferredintotheIonChromatographyinstrumentvialsandloadedintotheauto-sampleroftheICinstrument.Atriplicaterunforeachsolutionwascarriedout,andthepeakheightandareasofeachanionwasrecorded.Itwasdeterminedthatthemigrationofchloridewas4.1min,themigrationtimeofnitratewas6.7min,andthemigrationofsulfatewas10.8min,respectively.Duetothestrongrainstormsduringthewintermonths,theconcentrationsoftheinorganicionspeciesweretobehighlyaffected inwater.FourteendifferentwatersampleswereretrievedfromtheWaterAnalysisgraduatecourse.Thesamplescamefromvariouslocationssuchasariver,rainbarrel,orwaterservedata restaurant. The same procedure was done to the sample solutions as it was performed for thestandard solutions with the triplicate run for each; it was found that each sample had distinctiveconcentrationsofeachanionbeinganalyzed.

PhanPhu CalPolyPomona

41Phy/Anal/Theor QuantifyingNOActivationandCoordinationModesinNickelandCobaltComplexesbyX-rayEmissionSpectroscopy

S.ChantalE.Stieber

Nitrous oxide (N2O) is the third most potent greenhouse gas and has global warming potential 310timeshigherthancarbondioxide.ReducingtheconcentrationofN2Oischemicallychallenging,howeverbiological systems can reduce N2O through chemical reactions at copper centers within enzymes.Understanding themechanismof nitrousoxide formationwouldbe a significant benefit for pollutantcontrolandalsoofpossibleenvironmental significance.Thisprojectaims toexploreactivationmodesrelevant to the conversion of N2O to NO.We investigated howmetal compounds interact with NOspecies through synthesis, X-ray emission spectroscopy (XES) and calculations. XES probes transitionsfromfilledvalenceorbitalsandcanbeusedtoinformligandidentity,metalligandbonding,andmetalspin state. While XES is a sensitive probe for the identification of metal-bound ligands and thequantificationofsmall-moleculebondactivation,themethodisstillbeingdeveloped.WehaveusedXESin combination with computational chemistry to understand chemical interactions between NO andnickel,andtoquantifyNOactivationandcoordinationmodes.CobalthasalsoshownsensitivitytowardN2reductionandreactivitytowardNO,sosynthesisofCo-N2andCo-NOcomplexesisunderwayinourlaboratorytobeusedforfutureXESstudies.TheXESdevelopmentinthisworkoffersnewtechniquesforcharacterizingcomplexsystemsandunderstandingmechanismsofN2Oreduction.

MorningOralPresentationAbstracts

Name Institution Session/Area Title Advisor Coauthors

Abstract

HillaryBeloGonzalez

CSUDominguezHills

Analytical

ExploringMethylParabenContentofFreshBlueberries

BarbaraBelmont

Onlinesourceshavecitedthatmethylparaben,anesterofp-hydroxybenzoicacid,canbenaturallyfoundin plants, including blueberries and thale cress. However, primary literature sources containing datasupportingthenaturaloccurrenceofmethylparabeninblueberrieshasnotbeenfound.Methylparabeniswidelyusedas apreservative in foodsand cosmetics. Thus, the conclusion that itmaybe found inblueberriesmaybeduetoitsuseincommercialextracts.Furthermore,previousstudentresearchintothepresenceofmethylparabeninblueberriesusingHPLC-MSconcludedthatmethylparabencannotbefound inblueberries at a concentrationdetection limit of 1 ppm. This studyexpandson thepreviousstudent research by lowering the concentration detection limit. GC-MS analysis of concentratedblueberry extracts showed that methylparaben was not found fresh blueberries at a concentrationdetection limit of 0.1 ppm. Future studies include lowering the concentration detection limit evenfurtherby freeze-drying freshblueberries,exploring themethylparabencontentofdifferentblueberryspecies,otherberries,andorganicblueberries.

MonnaTabarani

CSUFullerton

Analytical

ComparisonofGCandHPLCAnalyticalTechniquesfortheDeterminationofAtmosphericallyRelevantReactionProducts

PaulaHudson

ChristineWang,PaulaHudson

Atmosphericaerosolaresmallsolidorliquidphaseparticlessuspendedintheairthatplayakeyroleinthechemistryoftheatmosphere.Aerosolparticlescanbegeneratedfromanthropogenicandbiogenicsources.Organiccompounds,specificallydicarboxylicacids,compriseasmuchas2%ofthetotalaerosolmass originating from both sources. Further, aerosol particle composition can change while in theatmosphere throughreactionwithsolar radiationorotheratmosphericcompounds. It is important tonot only identify atmospheric reactants but also identify the reaction products that form to fullycomprehendtheeffectaerosolparticleshaveonclimate.Theaqueousphasephotolysisofaprevalentdicarboxylic acid, succinic acid (C4), with hydroxyl radical, a prevalent atmospheric oxidizer, wasperformed in order to determine the photo-oxidation products as a function of hydroxyl radicalconcentration. It is common, in the atmospheric community, to analyze aerosol samples using gaschromatography coupled to a flame ionization detector (GC-FID). However, this method requiressamplestobedriedandchemicallyderivatizedpriortoanalysis,aprocesswheremorevolatilereactionproductscouldbelostorcouldresultininaccurateconcentrationsduetoincompletederivatization.Inthisstudy,themethodsofhighperformanceliquidchromatography(HPLC),whichrequiresnoadditionalsample preparation, and GC-FID were used to independently identify and quantify photo-oxidationproducts.Resultsshowthatforsamplesthatunderwentthedryingstep,alowerconcentrationofmorevolatileproductslikeoxalicacidweredetected.

RubyMoranandStephanieCortez

MountSaintMary'sUniversity

Analytical ACorrelationStudyBetweenParticulateMatterandPAHConcentrationsthroughtheBio-MonitoringofPineTreeLeaves

SyvineDeprèle

PAHsarepolycyclicaromatichydrocarbonscomposedof twoormore fusedhydrocarbon rings.Thesecompoundsarearesultofanincompletecombustioninwhichahydrocarbonreactswithanunknownamountofoxygentoproducecarbondioxide,water,andunwantedby-products:carbonmonoxideandPAHs.ExposuretoPAHsareprevalentinforestfires,tar,carexhaust,andsmoke.Theyaredetrimentalto our health because they are carcinogenic, teratogenic, and mutagenic. PAHs are inherent inparticulatematter;particulatematterisamixtureofsolidparticlesandliquiddropletsintheair.Duetotheirdeleteriousproperties,itisimportanttoqualifyaswellasquantifyPAHs.Herein,weproposethebio-monitoring of PAHs through pine tree leaves from the Italian Blue Cyprus tree in two designatedareasnear the I-405Freewayandon theMount SaintMary’sUniversity (MSMU) campus.PAHswereextracted via a continuous Soxhlet extraction, further processed and analyzed by the GasChromatographyMassSpectrometer(GCMS).ASelectedIonMonitoring(SIM)tablewasusedtosearchforthe16mostcommonPAHsfoundinthesample.Throughaseriesofcalculations,theconcentrationofthePAHsweregraphedandcomparedwiththevaluesofPMsreportedbytheEPA.SincePAHsfallwithinthefamilyofparticulatematter,adirectcorrelationbetweentheconcentrationofPAHsandPMvalues reportedwasexpected.Samples collected fromthe freewayandcampusarea showedadirectcorrelation with few discrepancies that can be linked to weather patterns. Analysis of the dataconfirmedthattheMSMUcampuslocationdisplayshigherlevelsofPAHsthantheI-405freewayarea.Forfuturedirections,wewillcontinuetomonitorPMsandPAHsduringthespringseasonandanalyzeprevious data acquired to finalize the quantification and qualification of PAH and PM concentrationsfoundwithinthedesignatedareas.

AzinSaebi UCLA Biochem1 DevelopmentofCarborane-BasedHistoneDeacetylaseInhibitors

AlexanderM.Spokoyny

JonathanC.Axtell,RafalM.Dziedzic,JoshuaL.Martin,TimurKatsnelsonandAlexanderM.Spokoyny

Carbon-rich molecules have been historically utilized as building blocks for assembly of complexmoleculararchitecturesdue to thevastdevelopmentofmethods for fine-tuning theirproperties.Yet,the classical toolbox of 2D aromatic building blocks presents inherent topological limitations, whichsometimes is referred to as “molecular flatland”. Carboranes (C2B10H12), the three-dimensionalaromaticanaloguesofbenzene, introduceapotentiallypowerfulsolutionforaddressingthis limitationby offering an inherently rigid, three-dimensionally defined scaffold available for densefunctionalization.Here, thedense functionalizationof carboranes isexploited inbiological systems, inorder to develop a library of isoform-specific small molecule inhibitors targeted toward histonedeacetylase (HDAC) enzymes. HDAC enzymes are critical regulators of gene expression and theiraberrant regulation in the brain has been linked to many neurological disorders. Currently, ourunderstanding of such HDAC- mediated disorders is limited due to lack of adequate means formeasurement ofHDAC expression and function in the brain. Furthermore, over 19 isoforms ofHDACproteinsareexpressedinthebodythataredifferentiallyinvolvedindiseases,yetthereisnomethodforselective tracking and in vivo quantification of each in the brain. Incorporation of carboranes in thedesign of the inhibitors is aimed to 1) facilitate higher binding selectivity of themolecule toward itstarget HDAC isoform via tuning the carborane-protein interactions and 2) confer the desiredhydrophobicity for blood-brain barrier penetration. The recent advancements in the field of boroncluster chemistry by our group and others have granted access to newmethods for selective vertexfunctionalization,providingapotentialmeanforsynthesisoftheseHDACinhibitors.Inthispresentation,wedemonstratethelatestadvancementsinsynthesisofthecarborane-basedHDACinhibitors.

ImagineDavis-WardandMadisonHamrick

CalBaptistUniversity

Biochem1 AntioxidantActivityStudyinAgaveUsing1,1-diphenyl-2picrylhydrazyl(DPPH)radicalAssay

Y.Hu AmericaHidalgo,Y.Hu

AgaveisapopularplantinthehotterclimatesofthesouthwesternUnitedStatesandMexico.Itiswellknown for its nutritional, industrial and medicinal applications. In this study, we investigated theantioxidantactivity infreshAgavebyusinga1,1-Diphenyl-2-picrylhydrazyl(DPPH)radicalassay.FreshAgavewas collected at SanManuelReservation in earlyApril, 2016. Sampleswere sorted for quality,maturity,fieldheatremoved,cooled,weighedintowhirlpackbags,treatedwithliquidnitrogen,storedinultra-lowat-80°andstudiedinSeptember,2016.TheresultsshowanIC50valueof2.20mg/mLforthefreshAgave.TheIC50ofthereference,ascorbicacid,is0.146mg/mL.TheantioxidantactivityofAgaveisrelatively high compared to other plant derived species studied in the area, such as yucca blossom(21.85mg/mL)andstingingnettle(414.42mg/mL). Furtherresearch isproposedto investigatehowacookingmethodwillinfluencetheantioxidantactivityoftheagave.

KellyAraujo

MountSaintMary'sUniversity

Biochem1

TheEffectofPeruvianTeasonMammalianCells

LuizaNogaj

DesareyMorales,SylvineDeprèle,andLuizaNoga

Twocompoundfamilieswereanalyzedwithinthisresearch:polycyclicaromatichydrocarbonsandpolyphenols.Polycyclicaromatichydrocarbons(PAHs)areorganiccompoundsconsistingoftwoormorebenzenerings.Thesecompoundsareknowntobeteratogenic,mutagenic,andcarcinogenic.Weareexposedtothesecompoundsthroughdermalabsorption,consumption,andinhalation.Polyphenolsareorganicchemicals,characterizedbythepresenceofmultiplephenolstructuralgroups.Theyareantioxidantsthathelppreventdegenerativediseasesandfreeradicaldamage.Polyphenoliccompoundsarefoundinabundantquantitieswithinourfoodsources,includingteas.ThisstudyinvolvedextractingpolyphenolsfrommedicinalPeruvianteasusingvarioussolventsystemsthroughaSoxhletapparatus.Theteaextractsweresubjectedtoachloroformextractiontoremoveexcesscaffeineandpigments,followedbyanextractionwithethylacetate.Allsampleswereconcentrated,filteredandre-suspendedinthepropersolvent/buffer.ExtractswerefurtheranalyzedbyGasChromatography/MassSpectrometer(GCMS)priortotheiradditiontoHeLacellsandsubsequentincubationfor24hours.AMTTassaywasperformedtotesttheeffectsoftheteaextractsoncellviability.Ourfindingsdeterminedthatthreeactiveteasthatconsistofherbalremediesaimedtowardspotentialaideinillness,gaveconsistentandpositiveresultswithcellviability.Allteasdisplayingactivitywereextractedinethanol/acetoneandspecificallyblendedfornaturalreliefinnerves,prostate,andstomachacid/diuresismedicalproblems.Furtherexperimentationwillsubjecttheextractstofractioningviacolumnchromatography,where,basedonpolarity,onewholeteaextractwillbeseparatedinpartsandfurtheranalyzed.

KristenFregoso Mount

SaintMary'sUniversity

Biochem1 TheeffectsofEbenaceaediospyros&AnnonamuricataonMammalianTissueCulture

LuizaNogajandSylvineDeprele

Natural products have been used in medicine as a treatment for numerous diseases such as cancer.Annona muricata, the soursop, is an angiosperm that is cultivated in humid environments. For thisreason,thesoursopisaplantthatisusedinmanythirdworldcountriesasaprimarysourceoftreatmentagainst cancer.Ebenaceaediospyros, thepersimmon, is anangiosperm thathasdisplayedbenefits fordiabetesandrenaldysfunctionwhenaccompaniedwithothercompoundslikegreentealeaves.Bothofthesespeciescontainphytoconstituentcompoundssuchaspolyphenolsandalkaloids.Phytoconstituentsarecompoundsinplantsknownfortheircolorandodorthatmaycontributetothebeneficialeffectsoftheseplants.Theobjectiveofthisstudyistoexaminetheeffectsofsoursopandpersimmonextractsontheviabilityofmammaliantissueculture.OurresultsshowthatsoursopextractswithandwithoutskindecreasedHeLa cell viability using anMTT assay, a cytotoxicity assay, and an apoptosis kit. However,persimmon extract has shown no effect on cell viability. GC/MS analysis identifiedmany compoundspresentinthesoursopextractsthatcouldserveaspotentialcandidatesforfurtheranti-canceranalysis.Additionalbiologicalandchemicalanalysisisnecessarytoexaminespecificactivecompoundspresentinthesoursopthatcontributetothiseffect.

MonicaKirollos UCLA Inorg1 DevelopingAtomicallyPreciseBoronCluster-BasedNanoparticlesviaPerfluoroaryl-thiolNucleophilicAromaticSubstitutionChemistry

AlexanderM.Spokoyny

Undesirableprotein-protein interactions (PPIs)within thebodyhavebeenknownto lead tonumerousdiseases,1 and over the past few decades, research on multivalent nanoparticles such as goldnanoparticles has yielded promising results.2 However, many of these systems have importantfundamentallimitationsthatinhibittheirfullpotential,suchasthelackofprecisecontrolovertheirsizesandcompositions.3Therefore,ourlabhasfocusedoncreatingatomicallypreciseorganomimeticclusternanomolecules (OCNs). Furthermore, since all the bonds are fully covalent, the synthesizedOCNs arestable under biological conditions.4 This method shows how dodecaborate clusters perfunctionalizedwith pentafluoroaryls can be efficiently conjugated with various thiols through nucleophilic aromaticsubstitution (SNAr) under mild conditions. The pentafluoroaryl-terminated linkers can be furtherextendedthroughSuzukicross-couplingreactions,andthedifferent lengthsofthearyl linkersusedforthe cluster synthesis allow facile tuning of theOCNs. The results show thatOCNs exhibited increasedstabilityincomparisontothiol-cappedgoldnanoparticles.Lastly,thisassemblystrategyalsoallowedustocreateglycosylatedOCNs,whichwascapableofmultivalentinteractionswithamodelprotein.

YiShen

UCLA

Inorg1

ZirconiumComplexesSupportedbyFerrocene-BasedLigandasRedoxSwitchesforHydroaminationReactions

PaulaL.Diaconescu

ScottM.Shepard,PaulaL.Diaconescu

Theactivityofzirconiumcomplexessupportedbyferrocene-basedligandforringopeningpolymerizationreactions is well studied in previous work by Diaconescu group. Here we report the synthesis of(thiolfan*)Zr(NEt2)2 (thiolfan*= 1, 1'-bis(2,4-di-tert-butyl-6-thiophenoxy) ferrocene), and its activity inhydroaminationreactions.Switchingthemetalcomplex insitubetweenitsoxidizedandreducedstateswith redox reagents resulted in selectivity for the two catalytically active species.We found that thereduced form of (thiolfan*)Zr(NEt2)2can catalyze hydroamination reactions of primary aminoalkenes,whereas the oxidized form, [(thiolfan*)Zr(NEt2)2][BAr

F] can catalyzed hydroamination reactions ofsecondary aminoalkene. We also found that both the reduced and oxidized forms of the zirconiumcomplexcancatalyzeintramolecularhydroaminationofprimaryalkylaminoalkyneswithdifferentrates.

AlexanderLaughlin

UCLA

Inorg1

SubstituentEffectsonRedox-SwitchableCatalysisforOrthogonalPolymerizationsofBiodegradableBlockCopolymers

PaulaL.Diaconescu

SoohikRho,JonathanBrosmer,PaulaDiaconescu

Controlovertherateofring-openingpolymerizationhasbeenrealizedviaredox-switchablecatalysis.Inthis vein, biodegradableblock copolymershavebeen synthesized. By altering the ligand scaffold, newmodalities of controlmay be accessible. Therefore, a series of ferrocene-based proligands, phosfen =1,10-di(2-tert-butyl-6-diphenylphosphiniminophenoxy)ferrocene) with altered substituents para to thephenoxide group are being synthesized to investigate the reactivity of their yttrium and indiumcomplexes.Theelectron-donatingorelectron-withdrawingnatureofthesemodificationsmayallowforagreaterscopeofviablemonomericprecursors.

JoshuaMartin UCLA Inorg1 Cage-Walking:VertexDifferentiationbyPalladium-CatalyzedIsomerizationofB(9)-Bromo-meta-Carborane

AlexanderM.Spokoyny

WereportthefirstobservedPd-catalyzed“cage-walking”processfeaturingametalB-boundcarboranylmoiety. As such, isomerization of 9-Br-meta-carborane during Pd-catalyzed cross-coupling enablesformationofB–OandB–Nbondsatallboronvertices(B(2),B(4),B(5),andB(9))ofmeta-carboraneviaaproposed “cage-walking” mechanism. Experimental and theoretical studies suggest this isomerizationmechanismisstrongly influencedbythestericcrowdingatthePdcatalystbyeitherabiarylphosphineligand and/or substrate. Ultimately, this isomerization process can provide a unique pathway topreferentially introduce functional groups at the B(2) vertex using B(9)-bromo-meta-carborane as thesolestartingmaterialthroughsubstratecontrol.

CassidyFeltenberger

USC Materials/Theory SynthesisandApplicationsofSingletFissionDimerLigandsonPbSNanocrystalsforUseinOrganicPhotovoltaics

MarkE.Thompson

One of themost apparent issues inmodern technologies that have gained the attention of scientistsglobally is the necessity for effective and affordable renewable energy sources. The application oforganicphotovoltaic units is a promising, viable and sustainablemethodof utilizing solar energy.Onecurrentchallengefacingtheprogressionandwidespreadapplicationoforganicphotovoltaicsisthelowefficiency of these units. Singlet fission, a process by which the absorption of a single photon by anorganicsemiconductorresultsintheformationoftwotripletexcitons,hasbeenstudiedasamechanismto increase energy harvesting efficiencies in organic photovoltaics. During efforts to understand theprocess of singlet fission more thoroughly, tetracene dimers including ortho-bis-ethynyltetracenyl-benzene(o-BETB)weresynthesizedandtheirphotophysicalpropertiesmeasured.After identifyingandconfirmingthato-BETBexhibitssingletfissionatasignificantrate,thechallengebecomesharvestingtheenergy from the two triplet excitons into useful energy, rather than wasted thermal or light energy.

Previous studies have reported triplet energy transfer from organic acene molecules to inorganicnanocrystals by way of Dexter energy transfer. By synthesizing an organic ligand that exhibits singletfission,canbedirectlyattachedtothenanocrystalmaterial,andcanbealtered in the lengthbetweenthe coupled chromophores and the nanocrystal, the energy transfer from the organic ligand to theinorganicsemiconductormaterialwillideallybecomemoreefficient.Thesyntheticprocessofcreatingano-BETB analog that maintains the molecule’s physical properties but also creates a mechanism forattachmenttoPbSnanocrystalsconsistsofseveralsteps.Currently,theproposedsyntheticschemeforthe o-BETB analog has been completed up to the step prior to the addition of the coupled tetracenechromophores, which will allow for the molecule to exhibit singlet fission. Finally, the singlet fissiondimerwill be attached to the nanocrystalmaterial by reacting the terminal thiol groupswith the PbSnanocrystals.ProvidedthattheenergyofthetwotripletexcitonsresonateswiththebandgapenergyofthePbSnanocrystalmaterial,energytransferwillideallyoccur.

PaulRobinson UCLA Materials/Theory Borides:Bonding,Hardness,andAnisotropy"isinthedisciplineofTheoretical&ComputationalChemistry

AnastassiaAlexandrova

Since pre-historic times, there has been a need for ultra-hard materials to be used for tools. Untilrecently, mostly carbides were used as such materials, though they are not ultra-hard. The hardestmaterialsknownarediamondandcubicboronnitride,buttheyareveryexpensive.Also,diamondturnsinto carbides upon contact with ferrous metals at high T, making manufacturing of cutting toolsproblematic.Recently,itwasdiscoveredthatboridesofheavytransitionmetalsareultra-hard;theycanscratch diamond in certain crystallographic orientations. It is exceptionally exciting as it offers a newroute to ultra-hardness that could be fundamentally free of the limitations of diamond-likematerials.Theunderstanding of ultra-hardnesswas in its rudimentary stage, however, and, as a result,manyoftheirproperties remainedunexplainedandunpredictable.Wewilldiscussseveralborides,WB4,ReB2,OsB2,SmB6.Ourchemicalbondinginsightintothesematerialsislocalandcluster-based.Wewillshowhow hitherto unsuspected M-B bonding contributes to boride superhardness, and explains thecounterintuitive anisotropy of the stiffness against sheer stress ofWB4.Wewill explainwhy the (B)nsheetschangefromflattoextremelybentintheseries:TiB2,ReB2,OsB2.Wenotethatingeneral,itisnot understoodwhy the geometries of the B-networkwithin borides can be anything from chains tosheets to cages, depending on the metal. Finally, we will explain the outstanding question of mixedvalencyinSmB6.Inthissolid,Smexistsintheoxidationstatesof+2and+3ina50/50mix.Weshowhowthatphenomenonemerges,withouteverengaginginthechangeofthenatureoftheoccupiedelectronicstates.Allpresentedresultsarenewandunpublished.

AlexisRochelleBasa

CSULosAngeles

Materials/Theory ChemotacticBehavioronPaperMicrofluidicPlatforms

FrankGomez GrenalynnIlacas,AyusmanSen,andFrankA.Gomez

Microfluidics serves as a prominent platform for the design and development of amyriad of devicesowingtotheirreducedreagentconsumptionrateandshortsampling-to-result time.Chemotaxis is themovement of materials, particularly biological species, in response to the influence of chemicalstimulation. Recently, chemotactic behavior in poly(dimethylsiloxane) (PDMS)-based microfluidicplatformsintheseparationofenzymespecieshasbeendescribed.Wehypothesizethatpaperisabetterplatform for proving chemotaxis. Herein, we describe for the first-time chemotactic behavior on amicrofluidic paper analytical device using as amodel enzyme-substrate system glucose oxidase (GOx)and glucose. Glucose oxidase and glucose migrate through chromatography paper and chemotaxis isprovenbyexaminingvaryingintensitiesofcolor,whichsignifychemotacticmovementofGOxtoglucoseor lack thereof.Color,on-chip, isachievedby theadditionofhorseradishperoxidase (HRP) tocatalyzethereactionbetweentheproductofglucoseandGOx,hydrogenperoxide,andpotassiumiodide. Ourresults show that, with the appropriate microfluidic arrangement, molecular chemotaxis can affordproductsnotobtainableunderotherexperimentalconditionsandthatcanbepredictedbymodelingandsimulation. Microfluidic paper analytical devices are easily fabricated by patterning hydrophobicmaterials inhydrophilicpaper.Theyare lowcost,compatiblewithbiologicalsamples,andhaveshownpromiseasplatformsforvariousapplicationsandinresource-limitedsettings.Currentworkisfocusedonoptimizing the design of the microfluidic paper analytical device and its application to enzymeseparations.

ParastooAliPour UCI Materials/Theory Tuningparticlewettabilityfortheformationofbicontinuousinterfaciallyemulsiongels

AliMohraz MaxKaganyukandAliMohraz

Experimentally discovered in 2007, bicontinuous interfacially jammed emulsion gels (bijels) are a new class of multiphase soft materials that exhibit a peculiar microstructure comprised of two independently continuous fluid domains separated by a monolayer of jammed particles, as seen in Figure 1. This unique morphology makes bijels ideal soft matter templates for the synthesis of a variety of advanced materials for energy and health care applications. Bijels are prepared by the spinodal decomposition of two partially miscible liquids, which is halted by the jamming of near neutral-wetting colloidal particles at the fluid interfaces. Successful formation of bijels requires the wetting properties of the colloidal particles to be carefully tuned to make them neutrally wetting with respect to the two fluids. The specific binary fluid system that I work with is water and 2,6-lutidine, and the particles are monodispersed silica particles tagged with fluorescent dye and synthesized through a modified Stober method in our laboratory. The silica synthesis occurs in two steps. The initial step is the coupling of a fluorescent dye, Rhodamine B Isothiocyanate (RITC) with 3-Aminopropyltriethoxysilane (APS). Fluorescent silica particles are produced in the second step through the reaction of this aps-dye conjugate with Tetraethyl Orthosilicate (TEOS), resulting in particles with surface chemistry as schematically depicted in Figure 2. However, the surface coverage and number of different ligands bonding to the particle surfaces can vary depending on the amount of each reagent present in the reaction, which, in turn, affects the particle’s wettability by each fluid. Thus, a more systematic study is necessary to study the effects of each reagent in the silica synthesis process and to determine the optimal amounts and ratios of the reagents in the reactions to achieve near neutral-wetting particles. Our preliminary results suggest that hydrophilicity increases with increasing the APS amount in the initial reaction, which presumably displaces surface hydroxyl groups with amine groups (see Figure 2). In this talk I will discuss the systematic experiments performed to determine the effects of RITC, TEOS, and APS on particle wettability and bijel formation

IfehAkano,MatthewDeSilva,JeremyArmas

CalPolySanLuisObispo

Materials/Theory Characterizationofthemechanicalstabilityofchemicallyfunctionalizedcarbonnanotubesbyscanningprobemicroscopy

GregoryScott Chemically functionalized carbon nanotubes have received a great deal of interest in recent yearsbecauseoftheirpotentialuseinavarietyofelectronic,materials,sensing,andbiomedicalapplications.Many methods for functionalizing carbon nanotubes have been developed, yet the local effects offunctionalization chemistry are not well understood. The addition of functional groups can affect thematerial properties including the mechanical stability of the carbon nanotubes. We have found thatwhennanotubesareacid-treatedtocreatecarboxylicacidfunctionalgroupsasastartingpoint fortheadditionofmanydifferent functionalmoieties, thematerials canbedegraded controllablyundermildconditions (i.e. normal scanning conditions) by a scanning tunneling microscope (STM). In order tooptimize cutting conditions, we are currently constructing a high-vacuum STM system to reduce thenoise produced in ambient conditions. Through this research, we propose that the degree offunctionalization of carbon nanotubes can be optimized as function of reaction time with acid. Thiscovalentfunctionalizationallowsforlow-voltagetemplatecuttingofcarbonnanotubesbySTM.Becauseidentificationof functionalgroupsby scanningprobemicroscopycanbedifficult,wecovalentlyattachgoldnanoparticles to thesidewallsof thecarbonnanotubesviaa thiolbridge. Inaddition toSTMandAFM measurements, chemical modification is verified by Raman, UV-Vis, and FT- IR spectroscopictechniques

RicardoS.Cruz CSUFullerton

OrganicI SmallMoleculeInhibitorsfortheBotulinumNeurotoxin

NicholasT.Salzameda

The Botulinum neurotoxin (BoNT) is secreted and/or can be easily extracted from the Clostridiumbotulinumbacteria.TheneurotoxinisoneofthemostlethaltoxinsknowntomanwithaLD50ofabout1ng/kgofbodyweight.ThepotencyofthetoxinanditseaseofextractionfromthebacteriamakesBoNTathreatforuseasabiologicalweapon.BoNTsarecomposedofaheavychain(HC)andalightchain(LC),whichareheldtogetherbydisulfidelinkage.TheLCsareazincmetalloprotease,whichareresponsiblefor thecleavingofSolubleN-ethylmaleimide-Sensitive-factorAttachmentReceptor (SNARE)proteins intheaxonterminal.Cleavingoftheseproteincomplexresultsinfailureofneurotransmissionsthatleadtobotulism, a deadly muscle-paralysis causing disease. Cleavage of the SNARE protein is irreversible;therefore, treatments are needed to prevent botulism. Current treatments for BoNT intoxication aredesignedforpre-exposurethroughtheuseofantibodyvaccines.Currentlyavailabletreatmentsarenotdesignedtodealwithalargeinfectedpopulation,areinefficientwithlongdelaysbetweenexposureandtreatment,andifaccessiblethecostisimmense.Consequently,ifthetoxinisdispersedworldwidesuchasinaterroristattackorutilizedinwarfare,thoseinfectedwouldnotbetreatedintime.Ourlabfocusesonsmallmoleculetherapeuticstoinhibitthisproteaseandtreatthedisease.Previously,ourlaboratorydiscovered a biphenyl sulfonamide isoleucine hydroxamic acid inhibitor for the BoNT LC. We haveexpandedonthisinhibitorbyincreasingthenumberofaminoacidsinthescaffoldwhilemaintainingthebiphenylsulfonylN-terminalandthehydroxamicacidattheC-terminal.Wehypothesizedthatincreasingthenumberofaminoacidswouldimprovebindingtotheprotease.ThenewinhibitorswerecreatedviaasolidphasesyntheticstrategywithHydroxylamineWangResin.Aminoacidswerecoupledtotheresininspecificsequencesandthesulfonylchloridewasaddedtogivethesulfonyl-amidebond.The libraryofinhibitorswasevaluatedusingaFluorescenceResonanceEnergyTransferassayandinsilicodockingwasperformed tovisualizeanddevelopoptimization routesbasedonpossiblebinding interactionsof leadmoleculeswithactivesiteresidues.

SandraRodriguez CSU

FullertonOrganicI Structureactivityrelationshipstudyof

isoleucinesulfonamidehydroxamicacidinhibitorsfortheBotulinumNeurotoxin

NicholasT.Salzameda

Botulism, a severe paralytic disease caused by the botulinum neurotoxin (BoNT), is produced by thebacteriumClostridiumbotulinum.TheBoNTiscomposedofheavy(HC)andlight(LC)chains.TheLC,azincmetalloprotease,cleavesSNAREproteinswhichcancausefatalmuscleparalysis.BoNTisthemostpoisonous toxin known toman and due to its ease of production, there are concerns the neurotoxincouldbeusedforbioterrorism.OurlaboratoryisworkingoninhibitingtheBoNTLCasanoveltreatmentoptionduetolackofviabletreatmentoptionsforlargepopulations.Inourpreviousstudies,wedesignedmoleculesthatsuccessfullyinhibitedtheBoNTLC.Thesemoleculeswerecomposedonafunctionalizedaminoacidwithabiphenyl ring,sulfonamidebondandahydroxamicacid. The3stepsynthetic routebegunwiththecouplingofisoleucine,aSuzukicouplingtobuildthebiphenylstructureandhydrolysistoform the hydroxamic acid. We sought to study how substituents on the biphenyl affect inhibitionalongside with the importance of the sulfonamide. Based on an enzymatic assay, the position andnumber of chlorine on the biphenyl ring drastically affected inhibitor activity. Additionally, due tostereochemistry, D-isoleucine resulted in greater inhibition than L-isoleucine. When D-Isoleucine wasreplaced L-Isoleucine, the sulfonamide small molecule with 2-chloro phenyl ring increased inhibitionfrom50%to90%andthebenzofuranmoleculeincreasedinhibitoractivityfrom61%to94%.

KevinKossick CSUNorthridge

OrganicI N,N-diarylbenzimidazoliumCompounds TaeboemOh Axially chiral N,N-diarylbenzimidazolium saltsmay be useful enantioselective hydrogen bonding Diels-Aldercycloadditioncatalysts,aswellasNHCligandsforenantioselectivemetalcatalysis.AnewroutetoN,N-diarylbenzimidazolium salt synthesis was studied by combining copper catalyzed cross couplingarylation of the 1-position nitrogen, followed by the employment of diaryliodonium reagents for thearylation of the 3-position nitrogen. We also investigated the barrier of rotation around thebenzimidazole-arylbondsviavariabletemperatureprotonNMRspectroscopy. Ithasbeendeterminedthat naphthyl and 2-isopropyl N-substituted moieties can induce axial chirality, both havingapproximatelya70kJ/molenergybarrier. Other substitutedarylgroupswillbe investigated in futurestudiestofindanoptimalbarrierofrotationfortheirpotentialuseascatalysts.

GarryLeonard CaliforniaStateUniversityNorthridge

OrganicI Synthesisof2,6-diarylpyridineand2,6-diaryllutidineforatropeisomerisminvestigations

TaeOh CarolinaYulek,TaeOh

Toexploretheatropeisomerismof2,6-diarypyridinesystems,wehavesynthesized2,6-diarypyridineviapalladiumcoupling.2,6-(2-Methylphenyl)pyridinewasshowntohaveatropismerismwithabarrierof9.4Kcal/moleasexaminedbyDNMR.Wealsoexamined2,6-(3-methylphenyl)pyridineand2,6-(dinaphth-1-yl)pyridine was examined. We next proceeded to synthesize the 2,6-(diaryl)-3,5-dimethylpyridine toexamineitsbarriertorotation.

EmilSamson UCI OrganicI Two-TieredForceSensingviaTandem

MechanophoreActivationZhibinGuan Recently,significantefforthasgoneintothedesignofmechanophores,whicharemoleculesthatrupture

at one specific covalent bond upon an applied force. A small library of these molecules has beensynthesizedtobecomevisuallyactive,releasesmallmolecules,orundergomolecularremodelingwhenstressed.Thus,mechanophoreshavethepotentialtoidentifystressconcentration,dissipateenergy,andsense the presence of acid. To further the utility ofmechanophores, we are en route to creating anelastomeric material capable of multi-level force sensing via tandem mechanophore activation. Theproposedmaterialwillexhibitcolorchangeswhenexposedtospecificamountsofforcetoeasilyidentifystressbuildup.Toobtainforcesensingproperties,atwo-tierednetworkcontainingbothspiropyran(SP)and a HCl-generating mechanoacid will be fabricated. Without any applied force, the material iscolorless.Underlowforce(X),thematerialturnspurpleduetotheringopeningofSPtoitszwitterionicmerocyanine (MC) isomer. Under high force, the material turns yellow as the HCl mechanophore isactivated to protonate the MC isomers. Through tandem activation of these mechanophores, weanticipateamaterialwithfacilevisualizationofdamageviadistinctcolorchanges.

VivianLeeandAnnGonzalez

MountSaintMary'sUniversity

Organic1 SurfactantSynthesisofHypophosphiteEstersInvolvingPhosphorusChemistry

SylvineDeprele

TherecentDeepwaterHorizonoilspillimpactedthewildlife,causingriseinalgaebloomsandaffectedthewildlife. Two carbon based oil dispersants, Corexit 9527A® and 9500A® that were used as clean upmethodscontainedtoxiccomponents,thusharmingthemarinelife.Thisledustofocusonsynthesizinganenvironmental friendly, phosphorous-based surfactant. Our research involves a three step synthesis. InStep 1, a long, nonpolar chain is attached to a hypophosphorus acid to form hypophosphorus estersthroughdirectesterification.ThisprocessisdonewiththeDean-Starkapparatus,whichallowswatertoberemoved as it accumulates during esterification. Step 2 involves elongating the nonpolar chain with abromoalkeneandapalladiumcatalysttoproducealkyl(5-bromo-pentyl)phosphinate.Thisproductisthenreactedwithatrimethylamineinstep3.Resultsshowthatnonanol,cyclohexanol,heptanoland2-octanolrespectivelyyieldof50%,61%,54%and54%forStep2.Wearecurrentlyworkingontheisolationoftheproductsinordertospecificallyidentifybetweenthelinearandbranchedproducts.Itisexpectedthatbothlinearandbranchedproductswillformfromthehydrophosphinylationstep.Concurrently,weareworkingon achieving higher product yields and expanding the scope of alcohols used for this study. Futuredirections include using different alcohols and equivalences to maximize step 1 and step 2 productformation.

AfternoonOralPresentationAbstracts

Name Institution Session/Area Title Advisor Coauthors

Abstract

EllishaDavis

MountSaintMary'sUniversity

Biochem2

TheExtractionofPolyphenolsfromPeruvianteasandtheeffectoftheteafractionsonHeLacells

LuizaNogaj

SylvineDeprèleandLuizaNogaj

Polyphenolsareagroupofnaturallyoccurringorganiccompounds,consistingoneormorephenolrings.Anti-carcinogenichealthbenefitsofpolyphenolshavebeenobservedduetotheirantioxidantspropertiesandabilitytomodulateenzymeactivityandcellsignals.Theintakeofpolyphenolsactivateenzymesfordetoxification,therefore,stimulatingdefenseswithintoxicenvironment.PolyphenolswereextractedfromvariousPeruvianTeamixtureswhich advocate to treatmedical problems. The extractionswere performed by using aSoxhletsetupwithsolventmixturesofethanolandacetoneata1:1ratioandwater.Thesampleswere thenwashedwithchloroform to removecaffeineandpigments, followedby ethyl acetate to separate the polyphenols.The samples were further concentrated,filtered and subjected to Gas Chromatography Mass Spectrometer (GC-MS) analysisafterre-suspensioninasolvent.ThesampleswereaddedtoHeLacellsandanMTTassaywasperformedonthecellstoanalyzetheanti-carcinogeniceffectsoftheteaextractionsfrom each tea mixture. It was found that the tea mixture made to alleviate nervoussystemcancer(Tea1EA)andtheteatoalleviateprostatecancer(Tea5W)demonstratedaccuratecorrelationstoinhibitcellgrowth,andwerethereforefurtheranalyzed.Theteaextractions were fractioned by flash column chromatography using a solvent gradientfromnon-polar topolar.GC-MSanalysis anda24-hour incubationofMTTassayon theHeLacellswererepeatedonfractions1-8obtainedfromTea1EAand2-8obtainedfromTea5W. Our results show,one fraction fromTea1EA, fraction6,displayeda trend forloweringcellviabilityinHeLacellsastheconcentrationofthefractionincreased,andtwofractions,fraction3and4,fromTea5Wfollowedthistrend.Acompoundtableprovidedby theGC-MSshowed thepresenceofpolyphenolderivativesandPAHs in theeffectivefractions from Tea 1EA and Tea 5W. In future experiments, standards of polyphenolsfoundintheeffectivefractionswillbeinsertedintotheHeLacellstoanalyzetheireffects.Inaddition,cytotoxicityassaywillbeperformedusingthesamples.

PatriciaPerezandMelissaMartinez

MountSaintMary'sUniversity

Biochem2 DNA-ProteinCrosslinkingviaGreenTea EricStemp Oxidativedamage is involved in the formationof free radicals,which can cause variousdiseases.InDNA,thisdamageisobservedprimarilyatguanine(G)becauseitisthemosteasilyoxidizedbaseandoneformofoxidativedamageisDNA-proteincrosslinking.Here,weexaminedwhichbrands,conditionsandconcentrationsofgreenteaaremosteffectivein preventing oxidative DNA damage. Oxidation was effected by the flash-quenchtechnique,amethodthatisusedforguanineoxidationandthatcaninduceDNA-proteincrosslinking. In the flash quench technique, the intercalator, Ru(phen)2dppz2+[phen =phenanthroline,dppz=dipyridophenazine],isexcitedwithalaserandgivesanelectrontothequencher,Co(NH3)5Cl2+ . The intercalator takesanelectron fromguanine, creatingthe guanine radical, which then reacts with protein. In our experiment, samplescontainingRu(phen)2dppz2+,Co(NH3)5Cl2+,histoneprotein,calf thymusDNAandeitherwaterorgreenteawereirradiatedfor0-4minuteswithbluelaserlightfromaHeCdlasertoeffectguaninedamage.Theextentofcrosslinkingwasdeterminedbythechloroformextraction assay, whereby protein and DNA-protein crosslink is extracted away fromunreactedDNA.Our results showedas the irradiation time increased, theabsorptionoffreeDNAdecreased less in thepresenceofgreentea,consistentwith inhibitionofDNAoxidation. In addition, agarose gel electrophoresis experiments of samples containingpUC19 DNA with tea that was stored at cold temperatures showed that the free DNAbandpersistedatdilutionsofgreenteaupto1:10000.Additionally,apro-oxidativeeffectwasobservedathighteaconcentrations.Infuturework,experimentswillbecarriedoutto determine a more accurate concentration range for the antioxidative effects of thegreenteaandto identifythemolecularcomponentsresponsible,aswellasexaminethedamage seen at high concentrations of tea; analogous experimentswith small peptidessuggestthatphenolscouldproducetheinhibitoryeffectbyreducingguanineradicals.

ChristineHua UCI Biochem2 NovelLuciferase-LuciferinPairsforMulti-component

ImagingJenniferPrescher

KrystenJones,WilliamPorterfield,ColinRathbun

Bioluminescence imaging (BLI) is a powerful technique for visualizing cells and otherbiologicalprocesses invivo.Thistechnologyreliesonenzymes(luciferases)thatcatalyzelightemission throughoxidationof their smallmolecule substrates (luciferins). Sincenoexcitationlightsourceisrequired,bioluminescenceprovidesanextremelyhighsignal-to-noiseratio,makingitwell-suitedforsensitiveimagingapplications.Despiteitsversatility,BLI has been confined to tracking only one cell type at a time, since themost optimalluciferases bind the same small substrate. To address this limitation, we report anapproachtoengineerselective(i.e,orthogonal)bioluminescentprobes.Weimposedsite-directed mutagenesis to craft mutant luciferases that can selectively process syntheticluciferinanalogs.Librariesofmutantenzymeswerescreenedusingatwo-tieredprocessagainst chemically modified luciferins to identify unique enzyme-substrate pairs. Weadditionally applied our screening strategy to evaluate a mutant luciferase librarydesigned by statistical coupling analysis (SCA) methods. From our preliminary data onboththesite-directed(SD)andSCAlibraries,we identifiedfunctionalmutantsthatwererobust light-emitters when combined with distinct luciferin analogs. Furthermore, theresults provided insight into SD and SCA library designs, suggesting that diversemutagenesis approaches may enable practical evolution of orthogonal pairs. Based ontheirsubstrateselectivity,theseorthogonalluciferase-luciferinpartnersholdpotentialforbroaderapplicationsinmulticellularimagingandrapidexpansionofthebioluminescencetoolkit.

JohannaBautista CSULosAngeles

Biochem2 AnalysisoflipidtransferproteinsinArabidopsisthalianabymeansofepitopetagstodeciphertheroleofLTP4'slipidinplantsenescence

RobertLuisVellanoweth

RNAiknockdownof two lipid transferproteins thatareup-regulatedduring theboltingstageinArabidopsisthalianaproduceamutantplantthatcontinuestoflowerafterhavingalreadycompletedsenescenceandapparentdeath.WehypothesizethattheseLTPscarrya lipid signal that mediates meristem death. The objective of this work is to insert anepitope tagged lipid transfer protein 4 (LTP4) gene into theArabidopsis thaliana plantwhichwillallowustouseareagenttospecificallypullout this lipidcarryingprotein foranalysis.Weexpectthatthisapproachwilluncoverthe identityoftheLTP4-boundlipid.Also, using the epitope tag on the LTP4 protein,wewill track the process inwhich theLTP4 protein carries the unknown lipid through the plant in senescence. Currently, thebinaryvectorshavebeenconstructedandthefloraldipmethodhasbeenusedto insertthemodifiedgene.Selectionforthemodifiedplantsisunderway.ThiswillgiveusourfinaltransgenicplantsthatwillhaveanepitopetaggedLTP4geneandallowustouncovertheunknownlipidsignal.

JennyLee UCSan

DiegoBiochem3 TheRoleofCyclicdi-AMPinSynechococcuselongatus SusanS.

Golden

Cyclic di-AMP (c-di-AMP) has recently been elucidated as the newest member of thenucleotide signaling family, and has been found to have broad distribution andimportance. Our work in the Golden lab has shown the presence of c-di-AMP and theresponsibleenzyme in the cyanobacteria, SynechococcuselongatusPCC7942,which is amodelorganismforphotosynthesisandthecircadianclock.Wehaveidentifiedputativec-di-AMP interacdting proteins using a pull-down assay, and following up on the findingsfrom unbiased screens, I created targeted mutations of the genes encoding for theseproteinsandassayedthemutantsforphenotypessharedbythecyclaseresponsibleforc-di-AMP production. This work will vastly improve our understanding of the signalingmolecule'sroleinaphotsyntheticorganismsuchasS.elongatus.

JeffWang UCLA Biochem3 InteractionBetweenSpireandRabGTPasesanditsEffectontheDevelopingDrosophilaOocyte

MargotQuinllan

Mammalian Spire, an actin nucleator, and mammalian Rab GTPases, effectors formembrane trafficking have been shown to interact directly. Drosophila Spire has aputativerab-bindingsequence,theSpir-box,locatedintheC-terminalhalfoftheprotein.InitialfertilityassaystestingflieslackingtheSpir-box,showedafertilitydecreaseofabout50%,supportingtheideathatinteractionbetweenDrosophilaSpireandDrosophilaRabsis functionally significant. SpecificallywhichRab(s) remainsunclear.Herewe investigatewhichDrosophilaRabsinteractwithDrosophilaSpireandwhetherit isthroughdirectorindirect means. Based on data showing Rab 6 and Rab 11 interactions in mammaliansystems and Rab expression patterns in the developing oocyte, we chose to probe forbinding interactions starting with Rabs 5, 6, and 11. Binding interactions were testedthroughan invitroGSTpulldownassaywithGSTtaggedRab5,6and11andC-terminalconstructs of Spire. So far the pulldown assay does not indicate a direct interaction.Further optimization of experimental conditions will allow for a more conclusiveassessmentof thepresenceor absenceof a direct interaction.However, this raises thepossibility of indirect interactions or the requirement of additional components tostabilizethecomplex.Co-IPexperimentsfromovarylysatewillbeperformedtoprobeforindirect binding between Spire and Rab 5, 6 or 11. Once specific Rabs have beenidentified,thecomplexwillbefurthercharacterizedbiochemicallywiththelong-termgoalofmodifying the binding sites in vitro and determining the functional consequences ofthesechangesinvivo.

KatayounYazdi-Nejad

UCI

Biochem3

DNAEXTRACTIONFROMAPTAMER-TREATEDMICEANDREAL-TIMEPCRANALYSISOFTHEEXTRACTS

MelanieCocco

Theinabilityoftheaxonsinthecentralnervoussystem(CNS)toregenerateandregrowisthemainreasonwhyCNSinjuriesremainpermanentandincurable.ThecomplexofNogo-A, a protein localized on the membrane of the oligodendrocytes, and NgR1, Nogo-A’sreceptorontheaxons,isknowntocauseinhibitionoftheaxonalregeneration.Inordertoinhibit the formation of this complex, DNA apatamer sequences are designed to blockNogo-A and stop it from binding to NgR-1. After successful in- vitro trials, this study isaiming at determiningwhether or not aptamers can be detected in the brain tissue ofMultiple Sclerosis (MS)modelmice thatwere retro-orbitally injectedwith the aptamerperiodicallyafterMS-diseaseonset.ByusingReal-TimePCRtechniques,wewereabletoshowthatretro-orbitalinjectionoftheaptamersdoesnotresultinthepresenceofthemin thebrain tissue. Thismight bedue to thepresenceof thebloodbrainbarrier (BBB),which aptamers should pass before getting to the brain. For future research, it can bestudied whether or not coupling the apatemrs with BBB- penetrating proteins cansuccessfullytaketheaptamersintothebraintissueandenhancetheaxonalregeneration.

AndrewSmith USD Biochem3 Progresstowardsthedevelopmentofnovelnucleicacid-basedtherapeutics.

AnthonyJ.Bell

AnthonyJ.Bell Theobjectiveofthisstudywastoevaluatetheviabilityofusingintramolecularfour-wayjunctions(4WJs)foruseastherapeutic inhibitorsagainsttheDNA-bindingcytokine,HighMobility Group B1 (HMGB1). Reports suggest HMGB1 should be considered a lupusbiomarkerbecausetheproteinislinkedwithseveralkeystagesofpathogenesis[1,2].Thestrategy to use 4WJs to targetHMGB1 is grounded in classic in vitro studies that showHMGB1 binds to cruciform/bent DNAwith a very high affinity [3-5]. Our initial studiesfocus on investigating the nuclease stability of 4WJs. Three 4WJs are currently beingevaluated; two 4WJs referred to as i- J1 and J4 are composed of natural DNA withthymine-thymineendcaps.Thefinal4WJreferredtoastDNAiscomposedDNAwiththiollinkages vs. phosphate bonds. The presence of end caps in i-J1 and J4 are intended toenhance nuclease stability by preventing favorable contacts with nucleases. The thiollinkagesintDNAareknowntoenhancestabilitybecausethesebondsarenotrecognizedbynucleases.Nucleasedigestionassaysareconductedat20oand37oCusingnucleasesthatdigestdouble(DNaseI,⎣Exo,andExoIII)andsinglestrandedDNA(ExoVandT5Exo).Our preliminary reports show that as expected the presence of thymine end-caps andthiol linkages enhance the relative nuclease resistance of intramolecular 4WJs vs.unmodifiedDNA4WJs.

LoiNguyen

CSUFullerton

Inorg2

TheEffectofIonicRadiiontheFormationofNCOTPerovskites

AllysonM.Fry-Petit

Perovskites with their robust structures have many intriguing properties, such aspiezoelectricity, pyroelectricity, nonlinear optic response, and ferroelectricitywhich canmake them useful in such technologies as memory devices, photovoltaics, and light-emitting diodes (LEDs). The Fry-Petit group has suggested that double perovskites,AAʹBBʹX6adoptnon-cooperativeoctahedral tilting (NCOT) structurewhendifferences inionicradii(∆IR),∆IRB-Bʹ≥0.50Å,∆IRA-Aʹ<20%and∆IRcounterions<0.50Åaresatisfied.ThissuggeststhatCa3WO6,Ba3WO6andBa2CaMoO6shouldallpossessNCOTstructuresdespite being reported as cooperative structures. Powder X-ray diffraction andRietveldrefinementareusedtoprobethestructureofCa3WO6.TheCcspacegroupgivesabettergoodness of fit and more accurate bond valence sum than the P21/n refinement.Ba2CaMoO6 isa tiltedperovskiteat roomtemperature,however low temperaturedatashows splitting of diffraction peaks indicative of a NCOT structure. Analysis of neutronpowderdiffractiondataonbothcompounds isunderwaytocorroboratethesefindings.This research explores the structure-property relationships toward the design of newmaterials. Fully understanding the structures helps control the properties of novelmaterialsfordesiredpurposes.

KelciSkinner CSUCI Inorg2 GiantBrownKelpasBiosentinelofEnvironmentalMercuryDiffersGeographically

SimoneAloisio

JeylaS.Fendi,SimoneAloisio

Mercury in its organic and inorganic forms is a global health concern, and persists as apollutant in themarineenvironment. It isprojected to increaseover timedue toglobalclimatechange,makingitamatterofinterest.Asmercuryenterstheaquaticsystemitisconverted into its organic form,methylmercury. This form is one that biomagnifies andbecomes toxic as it travels up the food chain. Our study investigated establishingMacrocystispyrifera(giantbrownkelp)asabiosentinelofenvironmentalmercuryduetobeingafast-growingproducerthatisbothwidespreadandabundant.Thisspecieshasthepotential to serve as an indicator of current levels of mercury in the ocean surface,through the contributions of non-point and point source pollution. The study areaincludedkelpforestsoffofthecoastofSouthernCaliforniafromSantaBarbara,Ventura,Los Angeles, Long Beach and Santa Rosa Island. Mercury was quantified in samplesthrough thermal decomposition, followed by amalgamation and atomic absorptionspectroscopy. Results showed high levels ofmercury near the Port of Long Beach (avg:125.5 ppb, std: 25.1) and low levels in Ventura County (avg: 0.36 ppb, std: 0.2).Anthropogenic factors aswell as point sourcepollution couldbe the reason for varyingconcentrationsamongbeaches.SantaRosa Islandhadmoderate levelsofmercury (avg:46.1ppb, std:9.8),whichmaybea resultofupwellinganduniqueoceancurrents fromsurrounding waters. The implications of this study showed that there are locationaldifferences affecting the concentrations of mercury in Giant Brown Kelp. This must betakenintoconsiderationwhenusingthisspeciesasabioindicatorformercuryanalysis.

MadelineRiffel UCLA Inorg2 PolymerizationthroughRedoxSwitchableCatalysis PaulaL.

DiaconescuJunnianWei,PaulaL.Diaconescu

Polymersareusedineverydaylifeandthechemistryofpolymerizationhasbeenaroundsincebeforetheearly1900s.However,syntheticchemistshavenotbeenabletoachievethesamecontroloverthepolymerstructureasnaturehas.Redoxswitchablecatalysisisanewareathatcouldleadtosequence-controlledpolymers.Weareresearchingtheuseofcatalysts, such as (thiolfan)AlOᵗBu, that can switch between their oxidized and reducedstatesduringreactions.Certainchain-formingmonomershavebeenfoundtopolymerizein one redox state, but not the other. By using this selectivity, the composition ofpolymerscanbemanipulated.

KevinSwartz UCLA Inorg2 PhysicalCharacterizationofMulti-BlockCopolymersandtheEffectofIncreasingBlockNumbers

PaulaL.Diaconescu

MarkAbubekerov,PaulaDiaconescu

The synthesis of multiblock copolymers using a zinc scorpionate complex with a redoxswitchable ferrocene backbone is described. Practical methods for casting films of thecorresponding block copolymers using a volatile solvent are described. The Young’smodulus, ultimate tensile strength, and the elongation at break of the polymers weremeasured to illustrate changes in themechanical properties as the block numbers of acertain monomer increased. Differential scanning calorimetry (DSC) was used todeterminetheglasstransition,andmeltingtemperaturesofthepolymers.

ShannenGuarina CSU

NorthridgeOrganic2 TheCH/π-coordinationasaconformationaltoolfor

acceleratingspontaneousradicalcouplingreactionsGagikMelikyan

Wefoundthat introducingamethylgroupbeta toacobalt-complexedpropargyl radicaldramatically accelerates the spontaneous radical coupling. The parent reaction wasdiscovered in 2003 (Org. Lett. 5, 3395) and consists of the temperature-dependentconversionofdiamagneticpropargylcationstoparamagneticpropargylradicalsπ-bondedto a dicobalthexacarbonyl core. Replacing an alpha phenyl nuclei with vinyl groupsallowedforprojectionof theradicalcenterwithinanallylic triad (alpha-to-gamma),andalsoforintroducingsubstituentsalongthecarbonframework(α-,β-,γ-).Whileα-andγ-methylgroupsyieldedrequisitepropargylcations,β-methylgroup“failed”toproduceanexpectedcation,undergoing insteadthespontaneousradicaldimerizationreactionevenat -20°C! Kinetic studies revealed that in comparison with an alpha-phenyl propargylcation,spontaneousreactionisacceleratedbyatleast132times(<5minvs660min).Thetentative mechanism of the acceleration effect will be discussed alleging a CH/π-coordinationbetweenamethylgroupandanaromatichexagonlocatedattheacetylenicterminus. The scope of the reaction yielding E,E-γ,γ-dimers in a highly stereoselectivemannerandingoodyields,wasexpandedbyalteringthenatureofthesubstituentsatthetriple bond, as well as the location of the alkyl groups along the allylic triad. Dimericcobalt-complexes were oxidized with ceric ammonium nitrate to yield polysubstituted3E,7E-diene-1,9- decadiynes in four-step synthetic sequences. Computation datawill bepresented to corroborate experimental findings, and to also make predictions withrespect to the nature and bulkiness of the beta substituents that could have anacceleratingimpactupontherateofthespontaneousreaction.

ElenArtashyan CSU

NorthridgeOrganic2 Cobalt-mediatedradicalcyclizations:Novelgatewayto

linearlyfusedcarbocyclesGagikMelikyan

Thecoordinationoftriplebondswithadicobalthexacarbonylcorehaslongproventobeanefficientwayofstabilizingthealphacations,precludinganunwantedacetylene-allenerearrangement, and stereodirecting propargyl radicals in inter- and intramolecularreactions.Thelattercanbecarriedoutwithtopologicallydiverseacetylenicdiolsinwhichthetriplebondsarepositionedeitherwithin,oroutsideacarbocycle.Thesecondtypeofsubstratesconstitutesthefocalpointofourstudy.Therequisitebis-cobaltcomplexesof1,9-decadiyne-3,8-diolsweresynthesizedinfourstepsfromcommercialdicarboxylicaciddichloridessuchasadipoylchloride,orinfivestepsfromcommercialcarboxylicacidssuchas phenylene dicarboxylic acid. With a flexible carbon tether between triple bonds,diastereomericdiolswerechromatographicallyinseparable,whilearigidityintroducedbyaphenylgroupallowedforisolationofindividuald,l-andmeso-diastereomers,andtheircharacterization by means of X-ray crystallography. The generation of bis-cations wascarriedoutbyareverseadditionprotocol,inalow-polaritymedium,inordertooptimizetheformationofthesix-memberedring.Asreducingagents,zincandcobaltocenewereused, each in its specific temperature domain (Zn +20°C; Cp2Co -78°C).Diastereoselectivity of cyclization reactions was dependent upon the topology ofsubstrates, rigidity of the carbon tether, configuration of diynediols, nature of reducingagents, and reaction temperature. Propargyl bis-cationswere studied bymeans of low-temperaturemultinuclearNMRspectroscopyinanattempttocorrelatetheconfigurationof intermediate ionic species with that of the requisite diols and radical cyclizationproducts.Theprojectprovidesaccesstolinearlyfusedpolycarbocyclesandpaveswayfortargetedsynthesisofnovelestrogenmimicsandestrogenreceptormodulators.

CiaraOrdner CalTech Organic2 SynthesisofChiralTetrahydropyransbyaTandemSakurai

Allylation/Intramolecular6-Exo-TetCyclizationJulieL.Hofstra

SarahE.ReismanandJulieL.Hofstra

Heterocyclesareubiquitousinavarietyofbioactivenaturalproducts,manyofwhichhavefound use as potential drug targets. The potency of these molecules with regards totreatingdiseaseisoftendependentupontheirchirality.Whileseveralmethodshavebeendevelopedtosynthesizeavarietyofchiralheterocycles,weproposeanewmethodthatutilizes chiral allyl silane substrates and proceeds through a stereospecific cascadereaction.Thesynthesisofavarietyofchiralallylsilanescontainingpendantelectrophileswas achieved via a nickel-catalyzed cross-coupling method recently developed in ourlaboratory. We have since shown that these allyl silanes can provide the desiredtetrahydropyran heterocyclic product under Lewis acid-catalyzed conditions. Thismechanism proceeds through an intermolecular Sakurai allylation followed by anintramolecular6-exo-tetcyclization.Wereporton thedevelopmentandoptimizationofthis cascade reaction and envision using thismethod to access a variety of other chiralheterocycles,includingtetrahydrofurans,piperidines,pyrrolidines,andbutyrolactones.

HectorAlarcon

CalPolyPomona

Organic2

DeoxydehydrationofBiomass-DerivedCarbohydratestoOlefinsusingMolecularVanadiumCatalysts

S.ChantalE.Stieber

Futureriskoffossilfueldepletionanddocumentedclimatechangeserveasincentivesforstudyingalternativeand sustainable sourcesofenergyandchemical feedstock.Biomassfrom dry plant matter is the most abundant raw material on earth and is currentlyindustriallyunderutilized.Byremovingoxygenfrombiomass,chemicalfeedstockcouldbegeneratedthatwouldotherwisebeobtainedfromfossilfuelsthroughcracking.Thisworkaims to improve theconversionofvicinaldiols toalkeneswithnewvanadiumcatalysts.NewvanadiumcomplexesweresynthesizedusingtwodifferentbidentateN-heterocycliccarbene ligands. Results were compared to previous reports by establishingreproducibilityforreportedreactionswithcommerciallyavailablevanadiumsaltspriortotesting new vanadium catalysts. Successfully improving the conversion of 1,2cyclohexanediolcouldbeusefulinatransitiontolargerscaleDODHconversionofglycolstousefulhydrocarbons.

AnnabelleCantu CSULong

BeachOrganic3 Palladium(II)-CatalyzedDirectedanti-Hydrochlorinationof

UnactivatedAlkyneswithInSituGeneratedHClKearyEngle

A regioselective anti-hydrochlorination of unactivated alkynes is reported. The reactionutilizes in situ generated HCl as both the Cl- and H+ source and is catalyzed bypalladium(II) acetate. Removable picolinamide and aminoquinoline bidentate directinggroupsareusedtocontroltheregioselectivityofthechloropalladationstepandstabilizethe resulting vinylpalladium(II) intermediate for subsequent protodepalladation. Thismethodprovidesaccesstoabroadarrayofsubstitutedvinylchloridesinexcellentyieldsand with high regioselectivity. The reaction proceeds under mild conditions and iscompatiblewithcatalystloadingsaslowas25ppm.

KristineClaudineTeppang

SDSU Organic3 MonitoringDNADuplexFormationwithaChemicallyModifiedTricyclicCytidineAnalogue

ByronPurse DillonBurns,RaymondLee,MelissaLokensgard,ByronPurse

Fluorescent nucleoside analogues are valuable molecular probes in biochemistry andbiophysics.WithstructuralsimilaritiestotheirnativecounterpartsinDNA,theymaintainconventionalWatson-Crickhydrogenbondingcharacteristics.ThesefluorescentanaloguescanactasfluorescentlabelsorbeutilizedinphotophysicalstudiestoreportavarietyofpropertiessuchasenvironmentalchangesanddetectionofDNAabasicsites.Duetotheneed for a variety of molecular probes, the Purse lab is investigating the relationshipbetween structural and photophysical properties to provide an expanded tool kit ofpractical fluorescent probes with various applications. Contrary to many fluorescentnucleoside analogues available, tricyclic cytidine (tC and tCO) derivativesmaintain theirbrightness when incorporated into duplex DNA. Our group has made chemicalmodificationstothetCandtCOscaffoldandstudiedtheeffectsofelectrondonatingandelectronwithdrawingsubstituentsonphotophysicalpropertiesbymeansoffluorescencespectroscopy. By investigating their photophysical properties when incorporated intooligonucleotides,wecanexplorepatternsforasystematicdesignoffuturefluorophores.The Purse lab has recently discovered a new analogue that has a distinct fluorescenceresponsetotheformationofduplexDNA.Uniqueotherfluorescentnucleosideanalogues,8-diethylamino-tC (8-DEA-tC) becomes notably brighter once incorporated into double-stranded DNA. Quantum yield measurements of 8-DEA-tC show up to a twenty foldincrease in quantum yield from nucleoside to duplex formation where base pairingprotects the analogue from quenching by excited state proton transfer. Abasic andmismatch studies reveal that correctWatson-Crickbasepairing is requiredand that thefluorescence-turnoneffectislargelydependentonneighboringbases.DuetoitsabilitytoreportonDNAduplex formation,weare investigatingtheanalogue’suseasaprobeforenzymaticDNAsynthesis.

TylerLiebel CalPoly

PomonaOrganic3 CollaborativeApproachestowardstheSynthesisof

PolyurethanesfromWasteOilsF.Z.Page TylerLiebel,

FranciscoLeyva,ChristianMoreno,VictorWyatt,MichaelFZ.Page

Petroleumisafiniteresourceusedubiquitouslyasafuelandinthemanufactureofplasticmaterials.Duetothegrowingconcernsregardingtheenvironmentalimpactandfutureofpetroleum as a chemical feedstock, extensive efforts have focused on providingalternative innovations that still meet consumer needs in a sustainable manner.Previously, in thePagegroup, seedoilshavebeenchemicallymodifiedandcross-linkedusing diisocyanate to form carbamates. Diisocyanate, however, is acutely toxic andexposureoftencausessevererespiratoryproblemsinadditiontobeingadetrimenttotheenvironment. The goal of this project is to synthesize a diisocyanate-free, 100% greenpolyurethane using waste oils from the USDA. One of the key intermediates is thesynthesisofa fattyacidmethylester (FAME)derivativewithtwoaminemoieties. Inthefirst step, the alkenes of compound 1 are converted to diols through hydroboration-oxidation,whichdisplayakey13CNMRresonanceat71.9ppm.Inthesubsequentstep,compound 2 is oxidized turning the alcohol groups into ketones using Dess-Martinperiodinane, which display a key 1H resonance at and 2.29 ppm (2H, t) and 13C NMRresonanceat211.6ppm.Currently,theproject is finalizingthesynthesisofcompound4througha reductiveaminationusingRaney-Nickel in thepresenceofH2gas.Diamine4will be polymerized with another FAME derivative that contains cyclic carbonates(compound5)resultingina100%greenpolyurethane.

JustinMin

UCR

Organic3

DirectandIndirectImpactsofBlackLightsonSecondaryOrganicAerosolsformedfromOxidationof1-methylnapthalene

RoyaBahreini

Directly emitted air pollutants react with atmospheric oxidants such as hydroxyl (OH.)radicals to form secondary organic aerosols (SOA). This uncontrolled,multigenerationaloxidationintheatmosphereyieldssecondaryproductsthatformSOAspecies.Theopticalproperties of SOA are not well characterized although SOA species contribute to asignificant amount of direct radiative forcing. In addition, it is uncertain how stable theabsorbingcomponentsofaerosolsareinthepresenceofsunlight.Inthisinvestigation,weconsideredtheoxidationof1-methylnapthaleneandthechangesinopticalpropertiesofSOA aged in the presence and absence of black lights. SOA reactionswith varying lightintensitiesweremeasured and comparedwith experimentswhere lightswere constantaftertheinjectionof1-methylnapthalene.Weuseda2m3Teflonchamberflankedwithblack lightsat thepeak radiationof λ=350nm;OH.Radicalsweregenerated from thephotolysisofH2O2.Intheseexperiments,wemeasuredaerosolabsorptionandscatteringcoefficientsat375nm,aerosolsizedistributionandcomposition,andconcentrationofgasphase tracers. To characterize the differences in gas phase oxidation conditions amongdifferentexperimentsandthesubsequentchangesinaerosolcomposition,wecomparedthedecayrateof1-methylnapthaleneandinvestigatedchanges intheoxidationstateofcarbon inSOA.Theoxidation stateof carbonwas then related to theopticalpropertiesandmassabsorptionefficiency.