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Summer 2006 Vol. LXXXIV, No. 10

2006 ElectionResults

Student Affiliates atAtlanta ACS Meeting

2006 Norris Award toBrian P. Coppola

Summer Scholar Report

2 The Nucleus Summer 2006

EVENING GRADUATE PROGRAMIN CHEMISTRY

The Original Part-Time Evening Graduate Programin New England

Take courses to:• keep up-to-date• improve professional qualifications• apply toward part-time Master’s program

All courses meet for a two-and-a-half hour period one evening per week andcarry three semester-hours of graduate credit toward the 30 semester-hour

requirement for a coursework M.S. degree

Courses are taught by Full-time Faculty in their area of expertise

GRADUATE CLASSES OFFERED FALL SEMESTER(Classes begin September 6, 2006)

Principles of Mass SpectrometryAnalytical SeparationsOrganic Synthesis 1Mechanistic and Physical Organic ChemistryThermodynamicsMolecular ModelingBioorganic Chemistry (Prerequisites: Organic Synthesis 1 & 2)

Eight more courses will be offered in the Spring Semester

Students new to the program must have completed an application for admission.Please note that the application deadline for the Fall semester is August 1, 2006.

For more information on graduate programs, see www.chem.neu.edu

For additional information contact: Jean HarrisDepartment of Chemistry & Chemical BiologyNortheastern UniversityBoston, MA 02115Tel: (617) [email protected]

The Nucleus is distributed to the members of the Northeastern Section of the American Chemical Society, to the secretaries of the Local Sections, and to editors of all local A.C.S. Section publications.Forms close for advertising on the 1st of the month of the preceding issue. Text must be received by theeditor six weeks before the date of issue.Editor: Michael P. Filosa, editor, Ph.D., ZINK Imaging Incorporated, 1265 Main Street,

Waltham, MA 02451 Email: Michael.Filosa(at)zink.com; Tel: 781-386-8479.Associate Editors: Myron S. Simon, 20 Somerset Rd., W. Newton, MA 02465, Tel: 617-332-5273

Nancy Simons, Analytical Chemist, Corporate R&D, Boston Scientific Corp., 1 Boston Scientific Place A4, Natick, MA 01760-1537. Email: Nancy.Simons(at)bsci.com; Tel. 508-650-8603; Fax 508-647-2329Sheila E Rodman, Malden, MA. Email:serodman(at)hotmail.com Tel: 781-771-4116.

Board of Publications: Mary Mahaney (Chair), Martin Idelson, Vivian K. Walworth Business Manager: Karen Piper, 19 Mill Rd., Harvard, MA 01451, Tel: 978-456-8622Advertising Manager: Vincent J. Gale, P.O. Box 1150, Marshfield, MA 02050,

Tel: 781-837-0424; FAX: 781-837-1453Contributing Editors: Morton Hoffman, Feature Editor; Dennis Sardella, Book Reviews; Calendar Coordinator: Sheila Rodman, email: serodman(at)hotmail.comPhotographers: Morton Z. Hoffman, Ying Wei and James PhillipsProofreaders: Donald O. Rickter, Myron S. Simon, Vivian K. WalworthWebpage: Webmaster: Sathish Rangarajan, sathish.rangan2(at)gmail.comCopyright 2006, Northeastern Section of the American Chemical Society, Inc.

The Nucleus Summer 2006 3

The Northeastern Section of the AmericanChemical Society, Inc.Office: Marilou Cashman, 23 Cottage St., Natick, MA 01760. 1-800-872-2054 (Voice or FAX) or 508-653-6329. e-mail: mcash0953(at)aol.comAny Section business may be conducted via the business office above.NESACS Homepage:http://www.NESACS.orgSathish Rangarajan, WebmasterACS Hotline, Washington, D.C.: 1-800-227-5558Officers 2006Chair:Patricia MabroukChemistry Department, Northeastern UniversityBoston, MA 02115617 373 2845; p.mabrouk(at)neu.eduChair-Elect:Mukund Chorghade14 Carlson Circle, Natick, MA 01760-4205508-651-7809 and 508-308-3891Chorghade(at)comcast.netImmediate Past Chair:Amy TapperPeptimmune64 Sidney Street, Suite 380, Cambridge, MA 02139617-715-8005; amy.tapper(at)peptimmune.comSecretary:Michael SingerSigma RBI3 Strathmore Rd. Natick, MA 01760-2447508-651-8151x291 msinger(at)sial.comTreasurer:James Piper19 Mill Rd., Harvard, MA 01451978-456-3155 piper28(at)attglobal.netAuditor:Anthony RosnerArchivist:Myron S. Simon20 Somerset Rd. Newton, MA 02465; 617-332-5273romysimon(at)mindspring.comTrustees:Joseph A. Lima, Esther A.H. Hopkins, Michael E. Strem Councilors Alternate CouncilorsTerm Ends 12/31/2006Michaeline F. Chen Wallace J. GleekmanCatherine E. Costello Howard R. MaynePatricia A. Mabrouk Alfred ViolaJulia H. Miwa Barbara G. WoodDorothy J. Phillips David WarrTerm Ends 12/31/2007Thomas R. Gilbert Arlene W. LightMichael J. Hearn Timothy B. FrigoMichael Singer Mary MahaneyPamela Nagafuji Mark FroimowitzTerm Ends 12/31/2008Doris I. Lewis Patrick M. GordonMorton Z. Hoffman Michael P. FilosaChristine Jaworek-Lopes Lawrence ScottMary Burgess Liming ShaoDonald O. Rickter S. B. Rajur

All Chairs of standingCommittees, the editor of THE NUCLEUS, and the Trustees of SectionFunds are members of theBoard of Directors. AnyCouncilor of the American Chemical Societyresiding within the section area is an ex officiomember of the Board of Directors.

Contents2006 Election Results, ALMA Meeting Report________________4NESACS Vendor Fair ____________________________________5Norris and Richards Scholarship Awardees __________________5News from the ACS Meeting______________________________6NESACS Student Affiliates Score Big in Chemvention Competion

A Chemistry Yankee Goes South by Amy Kallmerten _____________7ACS Designates Historical Chemical Landmark in RI __________8Announcements________________________________________8Lyman C. Newell Grants, 5th Annual New England Environmental ResearchSymposium

NERM Announcement ___________________________________9Chemistry of Understanding by Bal Ram Singh ________________10NEACT Summer Conference Announcement ________________11National Chemistry Week Announcement __________________122006 Norris Award to Brian P. Coppola____________________13Argentine Chemists Receive Journal Donations______________13Summer Scholar Report ________________________________14Historical Notes ______________________________________20Cover: ACS and GDCh-JungChemikerForum Organizing Committees planning the2007 exchange: (l-r) seated: Kurt Begitt (GDCh), Ivan Korendovych (Tufts University),Stefan Picker (University of Münster), Claudia Halter (University Hospital Freiburg);standing: Mike Strem (Strem Chemicals), Morton Hoffman (Boston University), Ruth Tanner (University of Massachusetts Lowell) (Photo: Courtesy of Morton Z. Hoffman)

Deadlines: October 2006 Issue: August 18, 2006November 2006 Issue: September 15, 2006

1st Meeting-April 4, 2006by Lynne GaroneOn Tuesday, April 4th, the inauguralmeeting of the Analytical LaboratoryManager’s Association (ALMA) local“beanpot” chapter was held and hostedby Cabot Corporation in Billerica,MA. This was the first opportunity formany lab managers to meet their localcolleagues and discuss common issues.The main part of the program was atalk by Dr. Lawrence Murphy, CabotCorporation, Analytical Director, onthe topic of “Outsourcing” reflectingLarry’s approach and strategy. Alongwith an overview of the internationalALMA organization, the attendees dis-cussed topics for future meetings andmeeting logistics. The meeting con-cluded with lunch and a tour of theCabot Analytical Laboratories. Thiswas not your typical conference whereeveryone sits and listens to the speaker.The concept here is that there is activesharing among the participants and

that’s exactly what happened. Theenergy in the room was exhilarating.Everyone present was interested inrepeating their experience and the nextmeeting has already been set up forTuesday, June 15th at 9:30 at ThermoElectron, Waltham, MA. WayneCollins, an active member of ALMAand frequent author and current editorfor “Managing the Modern Labora-

tory”, a quarterly journal published byALMA will be speaking on, “”UsingBenchmarking Metrics to ImproveLaboratory Productivity.”

For additional information, pleasecontact: Lynne Garone at lgarone(at)eink.com. ◆◆

ALMA Meeting Report


Chair-ElectMarietta Schwartz 419

TreasurerJames U. Piper 422

AuditorAnthony L. Rosner 416

TrusteeJoseph A. Lima 413

Councilor/AlternateCatherine E. Costello 331(##)Patricia A. Mabrouk 295(##)Amy E. Tapper 295(##)Michaeline F. Chen 265(##)Dorothy J. Phillips 265(##)Julia H. Miwa 253(#)Alfred Viola 252(#)Eva Binnun 218(#)Robert B. Grubbs 210(#)Wallace J. Gleekman 205(#)Jerry P. Jasinski 203Marietta Schwartz 202

Councilor/Alternate coninuedEdward J. Brush 197Michael Hurrey 182Denyce K. Wicht 158Mukund S. Chorghade 153Angeles Dios 144

Director-at-LargeGary R. Weisman 249Cassandra Celatka 239W. Harry Mandeville 207Ivan V. Korendovych 140

Nominating CommitteeThomas R. Gilbert 277Patrick M. Gordon 220Arthur Greenberg 181Mark Froimowitz 135

Norris Award CommitteeMary Jane Shultz 312Morton Z. Hoffman 220Dean Wilcox 189Todd Wimpfheimer 118

Corporate Patrons and GolfIridiumAstra Zeneca R&D BostonGenzyme Drug Discovery & DevHovioneIBMIRIX PharmaceuticalsJohnson-Matthey Pharma SolutionsLyophilization Service of New Eng-

landPhasex CorporationStrem Chemicals, Inc.Zone Enterprises

Corporate Sponsors and GolfRhodiumAerodyne Research, Inc.Cambridge Isotope LaboratoriesCambridge Major LaboratoriesNew England BioLabs, Inc.PfizerSigma-RBIShasun Pharma Solutions

Donors and Golf TungstenConsulting Resources Corp.Dishman PharmaceuticalsAnd Chemicals LimitedHoughton Chemical CompanyOrganix, Inc.Vertex

2006 Election Results

top row: John DeMeo (Thermo);Susan Smits (Mabbett);Alice Digioia (Waters); Kathryn Landes(Genzyme);Peter Anes (Genzyme);Julie MacIntosh (VHG Labs)bottom row: Qing Liao(Harvard);Marta Portoles (Millipore);Jeanette Vass;Jennifer Baily(Sonoscan); Lynne Garone (E Ink); Larry Murphy (Cabot)

## Elected Councilor # Elected Alternate CouncilorUnderlined Candidates were elected to their respective positions. ◆◆

Hoffman ReceivesACS Service AwardMorton Z. Hoffman, emeritus professor of chemistry atBoston University, was selected to receive the 2007 ACSAward for Volunteer Service to ACS. Hoffman was selectedfor his outstanding contributions to education on a regional,national and international level. Along with Professor Hoff-man, S. Allen Heininger, was selected to receive the 2007Charles Lathrop Parsons Award.

Chemical Abstracts Service will become a NationalHistoric Chemical Landmark in 2007. ◆◆


NortheasternSection-AmericanChemical SocietyVendor FairJoint with Medicinal ChemistrySymposiumThursday, September 21, 2006 3-7 PM Holiday Inn Select, 15 Middlesex Canal Park Road-Woburn, MA

Network with >100 Qualified Prospects Exhibiting will give you an opportunity to:• Meet face-to-face with existing customers • Generate new business opportunities• Introduce new products and services

You need to be here . . .Since you have technical products and services forPharmaceutical, Medicinal and Analytical Chemists,Biochemists and other technical disciplines. Contact: Marilou Cashman, NESACS Office 1-800-872-2054. [email protected]: $400 per 6-foot table (address checks toNESACS)

The James FlackNorrisAnd TheodoreWilliam RichardsUndergraduateSummer ResearchScholarshipsThe Northeastern Section of the American Chemical Society(NESACS) established the James Flack Norris andTheodore William Richards Undergraduate Summer Schol-arships to honor the memories of Professors Norris andRichards by promoting research interactions between under-graduate students and faculty. Research awards of $3250have been given for the summer of 2006. The studentstipend is $2750 for a minimum commitment of ten weeksof full-time research work. The remaining $500 of theaward goes to the research advisor to use on supplies, travel,and other items relevant to the student project. The 2006scholarships have been awarded to:Kerry Heinzelmann, Boston College; The Synthesis ofNew Inhibitors of Dihydrooratase; Prof. Evan Kantrowitz,AdvisorJessica Lynch, MIT; Engineering a Monovalent Avidin withFemtomolar Affinity; Prof. Alice Ting, AdvisorChayasith Uttamapinat, Harvard University; The Synthesis of 4’-Fluorinated Oligonucleotides; Prof.Gregory Verdine, AdvisorTodd Andrade, University of Massachusetts Dartmouth;DNA Adduct Formation in Plants by Interaction with Phe -noxy and Carbamate Pesticides; Donald Boerth, Advisor

Award winners are required to submit a report of their sum -mer projects by November 2006 for publication in THENUCLEUS. They are also required to participate in theNortheast Student Chemistry Research Conference(NSCRC) in April 2007. ◆◆

Looking for seminars in theBoston area?

Check out the NESACS Calendar

www.nesacs.org/seminars


News from the ACSMeetingNESACS Student Affiliates Chapters Score Bigin Chemvention CompetitionThe Student Affiliates (SA) Chapters from BridgewaterState College and Northeastern University were among thefive finalists in the ACS 2005 Chemvention competition tocreate a toy that teaches concepts of chemistry. The topaward, presented on Sunday, March 26, 2006, at the NationalSA Awards Ceremony at the ACS National Meeting inAtlanta in the presence of more than 1,500 students af fili-ates and faculty advisors, went to the Bridgewater StateCollege SA chapter for its “Green Machine.” The grandprize of $2,000 from Air Products & Chemicals will be usedfor the purchase of computer equipment that will benefitstudents in the chemical sciences. The Northeastern Uni-versity SA chapter will receive four Texas Instruments TI-89 Platinum Graphing Calculators as its finalist award.

Chemvention is a team competition sponsored by theACS as part of National Chemistry Week activities. SAchapters compete against each other to solve a commonproblem, using their chemical intuition to invent a device ormethod that works better and is more clever than its com -petitors. The finalists presented posters that described theirChemvention at Sci-Mix on Monday evening.Bridgewater State College

Bridgewater’s “Green Machine” is a toy designed toteach chemical principles from a green chemistry perspec -tive, and was created for children between the ages of 10and 14 years. The “Green Machine” is similar to a RubeGoldberg device in that one action directly leads to another .Each module in the “Green Machine” demonstrates separatechemical concepts, such as acid-base reactions and pH indi -cators, solubility rules, gas laws, Archimedes principle, andelectrolyte conductivity. Furthermore, the toy utilizes com -mon, inexpensive reagents typically found in the home,presents minimal hazards, and follows green chemistry prin-ciples. The “Green Machine” was displayed at “GreenChemistry Day” at the Boston Museum of Science onDecember 15, 2005. The BSC “Green Team” memberswere Lindsay McDonald, Bethany Collins, and Sarah Lane,and co-advisors Drs. Ed Brush, Cielito De Ramos-King, andFrank Gorga.

In addition to the Chemvention award, the Bridgewatergroup also received “Honorable Mention” recognition andwas awarded “Green Chemistry Affiliate” status for itsactivities in 2005. These two additional awards wereaccepted by the club’s past president, Bethany Masten.Northeastern University

This was the second year in which the NortheasternUniversity SA chapter participated in the national Chemven-tion competition. The board game for high school and gen -

eral chemistry students that was created, called “ELE-MENTS,” involved the following skills: balancing chemicalequations, connecting the names and symbols of the ele-ments, and understanding periodic trends. The game alsoincludes true/false questions that test a general knowledge ofchemistry. Players can move their pieces around the gameboard by rolling an element die and by accumulating “elec -tron” points by answering questions correctly. The North-eastern University SA chapter is made up of 60 membersfrom all five years of the cooperative education under gradu-ate program; its faculty advisor is Dr. Tom Gilbert. It alsoreceived “Honorable Mention” recognition for its 2005activities. ◆◆

(l-r): Lindsay McDonald, Bethany Collins, Sarah Lane, and Dr. Ed Brushof Bridgewater State College

(l-r) Micki Miskiv, Amy Kallmerten, Brittany Rowland, and Dr. TomGilbert of Northeastern University

Scheme of BridgewaterState’s “Green Machine”

My name is Amy Kallmerten. I am asenior chemistry major at NortheasternUniversity. I am also president of ourStudent Affiliates chapter. In the pastfour years I have seen our chapter gofrom myself and my friends (about 12people total) to its present membershipof seventy-five. Part of the fun of hav -ing a club so new is that nothing is setup for you. I have yet to receive a how-to guide for any new event, program,or issue that comes our way and that isone of the things I am most grateful for.I have been an executive officer of theclub for almost two and a half years.With every new event or program weparticipate in or put on, I find myselfwishing even more to continue toexpand both my own and the clubs’horizons in every way I can. This year,my department was generous enough tosponsor not only myself, but four othermembers of our group to attend theNational Meeting in Atlanta. I have tosay, this has been one of the best expe-riences ACS has offered me thus far.

It is amazing how a world so bigcan grow smaller every day. I didn’trealize until I attended the NationalMeeting in March how universal thecharacteristics of chemistry majors areand, more importantly, I had no ideahow much of a reality-check this expe -rience would be.

In the South, there is no such thingas a Southern accent. If I had a dollarfor every time someone chuckled backat me; “you’re from Bah-stan” I’d beon a beach somewhere instead ofpreparing for my summer finals. Thiscould be indicative of the differencesin cultures and speech no matter whereyou go, but it is a better indication ofthe many friends, acquaintances andcontacts I made at the meeting. We gotup early Sunday morning to go to the

presentation of the undergraduatedemo’s and began to interact withother student affiliates immediately.Standing out among the people we met,of course, were our beloved friendsfrom Arkansas. This interaction even-tually ended up in email exchanges andwords about next year.

Although part of me saw this as afour day break from the semester, Ihave to admit, I learned a lot at themeeting. Being president of my univer-sity’s Student Affiliates chapter, itwould be a huge understatement to sayI am only slightly excited for thisyear’s National Chemistry Week. I amonly now beginning to grasp howbroad the term chemistry is and howmany different career choices we haveupon graduation. I also would be lyingif I said I wasn’t inspired by howcharismatic people involved with ACScan be. After interacting with the Presi-dent of the ACS, I thought to myself,

who knows—maybe that will be mesomeday.

This is what I feel is the mostimportant lesson I took away from thismeeting. At events like the annual con-ferences of national organizations-It isnot always about the technical skillsyou gain. Sometimes it is about thepeople you meet and the experiencesyou take away with you. As a result ofthe emphasis on networking and groupactivities incorporated in the under-graduate program I now have aninkling I am not the only one who hascaught onto this detail. However, I ama firm believer that this is somethingevery person must learn and apply forhim or herself. Not everyone is goingto value networking, connections, andmeeting people outside your everydaygroup, but I think that as a product ofthe ACS National Meeting, this is notsomething I will put on the backburner in this lifetime. ◆◆


A Chemistry Yankee Goes SouthAn Undergraduate’s Reflections on Her First ACS National Meetingby Amy Kallmerten

Your one-stop source to career-relatedlinks in the Chemical Sciences

WWW.NESACS.ORG/CAREERS


Lyman C.NewellGrantsThe Northeastern Section of the Amer-ican Chemical Society has awardedfour Lyman C. Newell Grants for the68th Annual Summer Conference of theNew England Association of Chem-istry on Green Chemistry at Bridgewa-ter State College, in Bridgewater, MA,August 7-10, 2006. Grants of $225.00each to partially cover the cost of theconference have been awarded to thefollowing high school teachers:

Esther Hines of Lexington HighSchool in Lexington, MA

Nancy Jean Ward of East Bridge-water High School in East Bridge-water, MA

Kimberly Rebello of Bristol Ply-mouth Technical High School inTaunton, MA

Marcia Boccuzzi of Fairfield Lud-lowe High School in Trumbull, CT

The four-day conference will giveparticipants opportunities to work inthe lab and to design new activities, toview demonstrations and to discuss abroad variety of applications of GreenChemistry in academia and in industry.The program is co-sponsored byNEACT and the Department of Chem-ical Sciences at Bridgewater State Col -lege.

The Lyman C. Newell Grantscommemorate a former chair of theNortheastern Section who was a distin-guished chemist, teacher, and historianof chemistry. For many years he waschair of the Chemistry Department atBoston University. Lyman Newellserved as the first president of NEACTfrom 1889 to 1900 and expressed acontinuing interest in training chem-istry students throughout his longcareer. His efforts are continued bygrants that bear his name. ◆◆

ACSDesignatesHistoricalChemicalLandmark Development of baking powderreceives historical recognitionBy Morton Z. Hoffman The discovery of baking powder —which made baking easier, quicker andmore reliable — was designated aNational Historic Chemical Landmarkin a special ceremony in East Provi-dence, R.I., on June 12. The ACSsponsors the Landmarks program,which is open for nominations fromlocal sections. Much of the credit forthis recognition of a Rhode Islandlandmark can be given to ProfessorMartin Saltzman of Providence Col-lege.

In the mid-19th century, EbenHorsford, a chemist at Harvard Univer-sity, devised a unique mixture of bicar -bonate of soda (baking soda) andcalcium acid phosphate, which henamed “yeast powder” and later calledbaking powder. In the presence ofwater, the mixture releases carbondioxide, which leavens biscuits, cook-ies and quick breads. To prevent a pre-mature chemical reaction, Horsfordintroduced starch to keep the mixturedry.

Horsford and his business partner,George Wilson, established the Rum-ford Chemical Works in East Provi-dence in the 1850s to market bakingpowder. Rumford Baking Powder wasmarketed for decades using the for-mula first devised by Horsford in the1850s and refined in the 1860s.

Ann Nalley, ACS President, pre-sented a commemorative bronzeplaque to Nancy Moore, president ofthe East Providence Historical Society,sponsor of the designation ceremony,

and Colin Kane of Peregrine LLC, areal estate development firm that isrestoring the old Rumford ChemicalWorks on the corner of Newman andGreenwood Avenues in the Rumfordsection of East Providence.

Eben Norton Horsford was born inupstate New York in 1818, attendedRensselaer Polytechnic Institute andreceived his formal education in chem-istry in Germany, where he studied fortwo years with the noted chemist, Jus-tus von Liebig. In 1847 he returned tothe United States to assume the Rum-ford Professorship at Harvard, a chairendowed by Benjamin Thompson, thephysicist who fled the American Revo-lution and who eventually becameCount Rumford of the Holy RomanEmpire. When Horsford and Wilsonbegan their chemical plant, Horsfordchose the name Rumford, after hisHarvard chair. ◆◆

Save theDate!The 5th Annual New EnglandEnvironmental ResearchSymposiumSaturday, November 11, 20069:00 AM – 3:00 PMBridgewater State CollegeUndergraduate and graduate studentresearch posters in all environmentaldisciplines are welcome. Please email Ed Br ush([email protected]) to add yourname to our email distribution list. Aformal “Call for Abstracts” will besent electronically in mid-September.◆◆


Although there are amazing thingsgoing on all the time, we rarely stop tothink and notice them. Recently, ayoung lady, while taking informationfor a subscription over the phone,casually asked me what I teach. Onhearing that I teach chemistry, I heardthe so often repeated phrase, “ Oh, Iwas never good at chemistry.” I hadheard such amazements at chemistryamong the general public before, but Ihad really never given any seriousthought to what it exactly meant. Mostof the time, I took it as a conversationpoint, or a compliment at the most.

During this latest conversation onthis topic, suddenly, it came to my real-ization that everybody was good atchemistry, for without being good atchemistry, no one could survive. Afterall, proper and adequate chemistry is atthe heart of the life of all kinds, notjust humans. And not just the life butsheer existence of everything, be itrock or the rocket, is good and depend-ent on chemistry. I know, I know -

those who say they are not good atchemistry, they mean they do notunderstand it well, not that they reallyare not good at chemistry. That is thepoint. Even humans do not realize thatevery one of them is a really goodchemist, albeit subconsciously.

So, it basically boils down to theunderstanding of the chemistry, whichis difficult, and consequently distinctfor different people. But the idea that“everything is good at chemistry”remains, and only the understandingdiffers. Thus if we understand thechemistry of anything well we willhave the same good understanding ofchemistry. This should remove all thenotions of a superiority complexamong various types of chemists, ana -lytical (most major departments aretrying to eliminate it!), bio (NIH is itsis biggest supporter!), organic (badname, with too many environmentallyunfriendly synthetic chemicals; in dan-ger of being replaced with green chem-istry), inorganic (most students cannot

get excited by it, for too long now), andphysical (too dependent on physicists,who seem to have lost clues to matter).

The major advantage we aschemists have is the understanding.This idea has become ingrained in peo-ple so much so that it has become ajournalistic and political jargon – goodchemistry between two leaders, etc.What do we as chemists make of thesereferences? It probably refers to a goodunderstanding between two individu-als. It is the understanding, stupid!

We understand this world byobserving all the matters (remember,chemistry is defined as the study ofmatter), primarily using five sensoryfaculties. Of course, there is muchknown information on the chemistry ofsensory perception, though we still aresubstantially far from complete under-standing of these reactions. So, weneed instruments of all kinds to get tothe bottom of some of these processes.To make an instrument, we use ourprimitive understanding of tools todesign and build parts, assemble them,and make measurements to analyzeand understand.

Since nothing is perfect in thisworld, efficiency at every level is lessthan one, and ultimate efficiency is aproduct of efficiencies of all the steps.Assuming 0.9 for efficiency (beingquite generous) of every step (part,process, design, analysis, understand-ing, etc.), and 24 steps in examining anitem (no, I am not talking about Marsthough Hubble), the ultimate under-standing remains only 0.08. This is ter-rible way to develop an understanding,and the results are everywhere to see –from Osama bin Laden to Geor geBush.

Where does this lead us then? Myanswer: commonsense. That is non-sense, you say: How could chemistry,being such a sophisticated source ofunderstanding, have anything seriousto do with commonsense?

Let us try. In order to understandanything, it seems the best way is to

Chemistry of UnderstandingBal Ram Singh, Department of Chemistry and Biochemistry, University of Massachusetts Dartmouth

Continued on page 24

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New England Association of Chemistry Teachers

The 68th Annual NEACT Summer ConferenceAugust 7-10, 2006

Bridgewater State CollegeBridgewater, Massachusetts

Topic: Green ChemistryWorkshops

“Hands on” Teaching MaterialsInformal discussion time with participants and speakers

Modern, air-conditioned accommodationsContinuing Education Credits available for Mass,

Conn and RI teachers

Keynote SpeakersUMass Lowell’s John Warner

Pfizer’s “Buzz” CueACS’s GCI (Green Chemistry Institute): Kathryn Parent

NEACT and NEACS Scholarships availableProgram details will be posted at: www.neact.orgRegistration information will be available soon

Approximate cost for entire conference is about $300 per participant

contact Kathy Siok, Registrar-Treasurer at [email protected]


October 22, 2006 – Wellesley College Science CenterPhyllis A. Brauner Memorial Lecture by Dr. Bassam Shakhashiri

Dr. Bassam Shakhashiri is a Professor of Chemistry at the University of Wisconsin-Madisonand is the William T. Evjue Distinguished Chair for the Wisconsin Idea. Professor Shakhashirihas captivated audiences with his scientific demonstrations at a variety of locations includingBoston’s Museum of Science, the National Academy of Sciences and the Smithsonian’sNational Air and Space Museum in Washington.

Room 277, 11 am – 12 pm and 2 pm – 3 pm The Sunday presentations are free and open to the public. Tickets are available on a first come,first serve basis though reservations are recommended. To reserve tickets, please contact Mar -ilou Cashman either via email [email protected] (preferred) or by phone 1-800-872-2054before October 19, 2006. Tickets will be available for pick-up outside of the Science Center onthe 22nd. Parking is free. For directions to Wellesley College, please visit http://www.welles-ley.edu/Admin/travel.html. While at Wellesley, a visit to the arboretum and greenhouses(which are open to the public) is a must. For more information, visit http://www.wellesley.edu/FOH/greenhouse.html.

Kicking off National Chemistry Week 2006 festivitiesJoin us in a variety of hands-on activities related to the yearly theme. Taking place from 10 am– 3:30 pm on October 22, 2006 inside of the Wellesley Science Center for more information,please visit www.nesacs.org.

October 28, 2006Boston Children’s Museum

NCW volunteers will be on-hand to perform demonstrations and assist in hands-on activitiesrelated to the yearly theme.

Museum of Science, BostonNCW volunteers will be on-hand to perform demonstrations and assist in hands-on activitiesrelated to the yearly theme.

October 22 – 28, 2006K-12 students participate in the NCW poster competition. Grades 9-12 may participate in thepuzzle contest as well. See www.nesacs.org for detailed information.

National Chemistry Week EventsCelebrating

Your Home – It’s All Built on Chemistry!!

We all have our approaches to stayingabreast in our fields. One of the signifi-cant benefits of our society member-ship is receiving journals containingcutting edge research in chemistry andrelated fields. For years I have sub-scribed to JACS and perused the grow-ing literature and knowledge base. Butwhat do we do with journals that pub-lish more than 10,000 pages of texteach year?

One practice I used in the past wasProject Bookshare; a project run by theInternational division of the ACS todonate personal subscription journalsto libraries in needy countries through -out the world. We all, for the mostpart, have access to libraries of jour-nals so archiving is not necessary formost of us. However, Project Book-share ended in early 2006.

With the end of Project Bookshare,I had to research other approaches todonate my journals. I was not going tojust toss them out! We are planning atrip to Argentina this year and thoughtthis might be an interesting way tomake a good contact with someonethere who we might know and visit.

By “googling” <chemistry andArgentina>, a search returned 27 mil-lion hits. The leading hit was a reviewon the history of chemistry in Argentinaby Professor Maximo Baron. Profes-sor Baron is at Facultad de CiênciasExactas y Naturales, Universidad deBelgrano in Buenos Aires, Argentina.Not only is he Titular Member ofIUPAC’s Macromolecular Division

Committee and Secretary of the Com-mission on Macromolecular Nomen-clature but he also chairs the group thatacquires journals for the Argentinenation’s universities. I emailed Max-imo to learn if he would be interestedin a donation of my back issues.

Dr. Baron indicated that he wasvery happy to help me donate my jour -nals, “for apart from my work inresearch and teaching at the Universityof Belgrano, for a number of years Iam Director of the Library of theArgentine Chemical Society AQA(www>.aqa.org.ar). With great effortwe have managed to keep up withsome journals. In the golden days wedid this by exchange but, Alas! Nolonger. Now hard cash is required andthis is something we have little accessto. So we have to resort to donationsand gifts.” “For some time the ACSBook Share Program was of greathelp… Therefore, if you would like toconsider donating JACS and the Jour-nal of the Electrochemical Society wewould be more than happy to acceptthem.”

“Also if you know of any col-league that has the same “problem”please feel free to let us know. Do notfear the possibility of duplicationsbecause for some time we have beenacting as a clearing house for otherLibraries in the country that are willingto accept donations and do not haveaccess to donors. The transportationcosts can be handled at this end.”

On June 3, 2006 I shipped six M-bags of journals containing about sixtypounds each to Argentina. It will takeabout six weeks for the highly prizedjournals to arrive in Buenos Aires.

At this point, I also ask Northeast-ern Section members: Do you have aninterest in sharing your personal orcorporate journals with Argentina?This will be good for you (doing theright thing for the right reason, andgetting a tax deduction), good for the


Brian P.Coppola toReceive2006 NorrisAwardBrian P. Coppola, Professor of Chem-istry at the University of Michigan, hasbeen selected as the recipient of the2006 James Flack Norris Award forOutstanding Achievement in theTeaching of Chemistry. The award willbe presented on Thursday, November16, 2006. The award is made annuallyby the Northeastern Section of theAmerican Chemical Society to recog-nize an individual whose dedicationand excellence in the teaching ofchemistry have had wide-rangingeffects on the profession.

Coppola received his B.S. degreefrom the University of New Hamp-shire-Durham in 1978, and his Ph.D.from the University of Wisconsin-Madison in 1984. First taking a facultyappointment at the University of Wis-consin-Whitewater during the laterstages of his graduate work, he movedto the University of Michigan as a vis -iting assistant professor in 1986. Hewas appointed as a lecturer in 1987,and then as an Associate Professorwith tenure in 1997; he was promotedto Full Professor in 2002. He currentlyserves as the Associate Chair for Cur-riculum and Faculty Affairs in theDepartment of Chemistry.

Brian Coppola has been veryactive with the American ChemicalSociety as well as other professionalorganizations. He participated in anACS Task Force on Minority Faculty inthe Chemical Academic Community.He currently serves on the ACS Soci-ety Committee on Science, and hasbeen a member of the ACS Committeeon Professional Relations, the ACSCouncil, as well as having served a 10-year term as Councilor for the HuronValley local section of the ACS. He has

also served on a number of editorialadvisory boards, including those of theJournal of Science Education andTechnology, the International Journalof Science Education, The ChemicalEducator, and the Journal of CollegeScience Teaching. Brian has receivednumerous awards, fellowships, andgrants as well, all of which speak to hisexpertise in and love of teaching. ◆◆

Argentine ChemistsReceive Journal DonationsBy Dan Eustace

continued on page 20


IntroductionCrystal growth in organisms such as sea urchins and

brittle stars is highly regulated yielding structures of aston -ishing complexity. Such control over crystallization has yetto be routinely reproduced in the laboratory. Organismscontrol mineral growth using special assemblies of biologi -cal macromolecules.1, 2 Over the past 20 years, extensiveresearch involved the control over growth and orientation ofcalcite crystals.3 Calcite is attractive because it has a rela -tively simple structure, its precipitation has been extensivelystudied, and it is frequently found with specifically con-trolled orientations in nature.2 In the laboratory, micropat-terned,4 self-assembled monolayers (SAM) ofalkanethiolates on gold5 have been used as substrates to con-trol calcite nucleation.2, 6-8 Microcontact printed (µCP)SAMs have provided the most effective templating agentsresulting in previously unmatched control over the crystal -lization of calcite.1 Calcite showed a tendency to nucleateon carboxy- and sulfate-terminated regions of monolayers,while methyl- and hydroxy-terminated regions of the mono -layers prohibited nucleation.2

Micropatterned SAMs of alkanethiolates on gold mayprove useful for understanding the operative crystal growthmechanism involved in other biologically relevant crystalsystems, for example, calcium oxalate monohydrate (COM),Figure 1, the main inorganic component in 70-80% of allkidney stones. 9, 10 Kidney stone formation is one of themost common examples of pathological crystallization inthe body. Of the three calcium oxalate forms; mono-, di-,and tri-hydrate, COM is the most thermodynamically stable,and the nucleation, growth, and kinetics of COM crystalliza-tion has been studied at length.11, 12 Although COM has beenstudied in the context of its pathogenic nature, the mecha -nism of kidney stone formation remains elusive.

The direct role of urinary constituents such as largemacromolecules or metabolic byproducts in the inhibition orpromotion of COM and consequently kidney stone forma -tion is currently a topic of interest. 9, 13 Real-time, atomicforce microscopy studies of COM growth mechanisms inthe presence of citrate ions and the protein osteopontin invitro support the importance of anionic molecules in theinhibition and promotion of COM growth, respectively.14-16

Polyaspartate has been also found to inhibit COM growth. 17,

18 µCP SAMs simulate macromolecules whose surfaces arerich with anionic functional groups.

SAMs can be prepared easily by submer ging an appro-priate substrate in a solution containing a ligand with theform (Y(CH2)nX). The anchoring group, Y, is reactive to thesubstrate’s surface and is the major limiting factor for theself-assembly of monolayers, as some groups bind selec-

tively to certain substrates. The surface properties can bemanipulated by modifying the head group, X. SAMs ofalkanethiolates (CH3(CH2)nS-) form most readily on gold

and silver4 and is believed to occur with a loss of dihydro -gen.5 The sulfur atoms at the end of the alkanethiolate forma uniform ordered layer on the (111) plane of gold. Thechains extend from the surface tilted at approximately 30ºfrom the normal, and adopt a trans-configuration to maxi-mize the van der Waals interactions between the methylenegroups, Figure 2.4

Further control over the nucleation site on a surface of aSAM can be controlled via µCP. A patterned elastomericpolydimethylsiloxane (PDMS) stamp is “inked” with analkanethiol in ethanol solution of a primary functionality.All of the ethanol must be evaporated so as to preventspreading of the alkanethiol molecules across the substrate’sentire surface. The stamp is turned over and pressed gentlyagainst the surface of a gold substrate so that the alkanethiolink transfers onto the regions of the gold that make contactwith the stamp. Subsequent interaction with an alkanethiolof secondary functionality permits the patterning of SAMs

Summer Scholar ReportTemplating the Growth of Calcium Oxalate Monohydrate on Gold via Microcontact Printing Tania M. Cabrera, Leigh M. Friguglietti, Richard W. Gurney Department of Chemistry, Simmons College, Boston, MA 02115.

Figure 1. (a) COM crystals with a characteristic coffin shape.(b) Twinning along the (-101) plane is also commonly observed.

Figure 2. Idealized representation of SAM of alkanethioates ongold. Mercaptohexadecanoic acid (left) mercaptohexadecane(right) on gold.


having two different functionalities. A contact time ofaround 0.3 seconds forms a highly ordered monolayer of analkanethiol on a gold substrate. 4 The process of µCP isquick, reasonably simple, and generates a minimal amountof waste.19

Here, we present methods of controlling COM nucle -ation, density and growth using SAMs. Ability to specifi-cally control location of nucleating crystals has applicationsin further studying growth promotion and inhibition of thesepathogenic crystals. Micropatterning techniques wereemployed using SAMs of alkanethiolates on gold to tem-plate COM growth. Careful control over calcium oxalatecrystal growth could lead to improved research over thispathogenic crystal’s growth and consequently, its growthinhibition. Materials

Gold-coated glass slides (1.0” x 3” x 0.04” with 5 nmof titanium and 100 nm of gold) were purchased from EMFCorporation (Ithaca, NY). Organic impurities wereremoved from the surface of the gold coated and glass slidesusing an UVO-Cleaner® Model No. 42, Jelight Company,Inc. (Irvine, CA). Microposit S1813 positive photoresistfrom Shipley was deposited using a spin coater ModelP6700, Specialty Coating Systems, Inc. (Indianapolis, IN).Microposit MF-319 developer was purchased from Rohmand Haas. Sylgard 184 silicon elastomer kit was purchasedfrom Robert McEwon Company (DOW Corning).Nanogauge reference calibration grating (10 µm, z 20 nm)from Ted Pella, Inc. Square 400 mesh Cu TEM grids fromElectron Microscopy Sciences.

Differential interference contrast images were collectedwith a Leica DMLM reflected light microscope and cap-tured with a Diagnostic Instruments Spot digital camera.Scanning Electron Microscopy (SEM) measurements wereperformed on a JEOL JSM5510-LV Scanning ElectronMicroscope operating at 2 kV. Ultrapure water wasobtained from a Barnstead NANOpure Diamond Life Sci-ence (UV/UF) filtration and ion-exchange system (resistiv -ity of 18.2 MW•cm.)

Calcium chloride (anhydrous), sodium chloride, hexa-nes used as received from Fisher Scientific. HEPES buf fer(N-2-hydroxyethylpiperazine-N’-2-ethanesulfonic acid),potassium oxalate monohydrate (99%), ethyl alcohol (200proof), 1-hexadecanethiol (92%), 16-mercaptohexadecanoicacid (90%), and 11-mercapto-1-undecanol (97%) were usedas received from Aldrich Chemical Company. Acrylic des-iccator cabinet (with 4 shelves), Fisherbrand plain glassmicroslides (3” x 1”) from Fisher Scientific. Fixed pointdiamond tipped scriber was used to cut glass slides(McMaster & Carr).Methods1. Preparation of A Master

A plain glass slide was cut into 1” squares using a dia -mond tipped scriber. The slide was placed in an UVO-Cleaner® for five minutes, rinsed with ethanol, washed with

Ultrapure water before drying with compressed nitrogen.The slide was spin coated with 0.150 mL of MicropositS1813 positive photoresist at 500 rpm for 20 seconds.Using forceps, the slide was removed from the spin-coaterand warmed on a 100ºC hot-plate (2 min.), Scheme 1a. Asquare 400 mesh Cu TEM grid was gently placed on thesurface of the photoresist-coated slide, covered with a sec -ond 1” glass slide, and placed in the UVO-Cleaner® for oneminute to polymerize the areas of the slide not protected bythe TEM grid. The slide was gently swirled in 10 mL ofMicroposit MF-319 developer in a small beaker for 5 min -utes. Upon careful removal from the developer solution, theslide was rinsed with Ultrapure water and dried with com -pressed nitrogen, Scheme 1b. The Master was affixed in aglass Petri dish with Epoxy resin.


Photolithography: Positive photoresist is spin-coated onto aclean glass slide. (Step A). A 400 mesh copper TEM grid isplaced on top of the photoresist layer and the entire assembly isexposed to UV light. A developer is then used to wash away allareas that were exposed to light. The waffle pattern of the TEMgrid remains on the slide. (Step B). PDMS Stamps: The slidemade from photolithography is glued to a Petri dish, and coveredwith an elastomeric polymer. After the polymer hardens, thepolymer can be cut out of the dish using an Exacto knife (StepC). Microcontact Printing a SAM pattern onto gold: A 1mMsolution of HS(CH2)15CO2H is evaporated onto the stamp (StepD), then placed on gold-coated slide for 10 seconds and sliderinsed with ethanol (Step E). Slide is submerged in aHS(CH2)15CH3 for 1 minute and rinsed with ethanol. (Step F).Growing Calcium Oxalate Crystals: The slide is then placedupside down on two PDMS stands affixed to a Petri dish. TheCOM growth solution is poured into the Petri dish until contact ismade between the solution and the gold slide. The slide isallowed to sit for 24 hours while COM crystals nucleate andgrow.

Scheme 1.


2. Preparation of a PDMS StampSylgard 184 elastomeric polymer was measured into a

vial on a balance using a scupula. Curing agent was thenadded to the polymer to produce a 10:1 ratio of polymer tocuring agent. Using the wooden end of a cotton swab, thepolymer and curing agent were mixed together until it had awhite, frothy appearance. The mixture was then poured intothe Petri dish containing the previously prepared Master.The entire assembly was allowed to sit at room temperatureuntil the bubbles rose, and then placed in a 70º oven for 45minutes, or until the polymer firmed. The assembly wasthen allowed to cool. Using an exacto knife, the polymeraround the master was cut and gently pulled out of the Petridish, Scheme 1c. Any excess polymer was trimmed offusing a razor blade.3. Microcontact Printing (µCP)

Gold-coated glass slides were cut into 1 x 2.5 cm rec -tangles using a diamond-tipped scriber. Each slide wasplaced in an UVO-Cleaner® for five minutes, rinsed withethanol, washed with Ultrapure water before drying withcompressed nitrogen. One drop of a 1mM solution of 16-mercaptohexadecanoic acid in ethanol was placed onto thepatterned side of a PDMS stamp so that the small patternedarea was covered, and the ethanol was allowed to evaporatecompletely, thereby coating the pattern with 16-mercapto-hexadecanoic acid, Scheme 1d. The stamp was turned overand placed into contact with a gold-coated slide. Gentlepressure was initially applied and the assembly was leftuntouched for one minute. The stamp was removed usingforceps, the gold slide was rinsed with ethanol (200 proof)and dried with compressed nitrogen, Scheme 1e. The entireslide was submerged in a 1mM solution of 16-mercapto-hexadecane in ethanol for one minute to backfill the car-boxyl pattern. After a minute, the slide was rinsed withethanol, dried with compressed nitrogen, Scheme 1f, andimmediately used for crystal growth studies, Scheme 1g.4. Growing Calcium Oxalate Crystals on a PatternedSurface

To prepare a crystal growth chamber , cured PDMS wascut into two thin strips (~4 cm long x 8mm wide) and gluedabout 1 inch apart in a Petri dish using epoxy . A patternedstamp was turned gold-side-down and placed between thePDMS supports. A typical calcium oxalate growth solutionwas prepared according to the following procedure: X mLof a 10 mM calcium chloride solution was added to a 250mL volumetric flask containing a Y mL of buffer solution(0.15 M NaCl and 0.01 M HEPES buf fer in Ultrapure watertitrated with NaOH to produce the desired pH (6.8 – 8.2))with vigorous shaking before introducing Z mL of a 10 mMsodium oxalate solution to the flask. {Crystal growth solu -tions for initial ion concentration studies: [Ca 2+]=[C2O4

-2]=4 x 10-4 mM (X=Z=2, Y=46); 6 x 10-4 mM, (X=Z=3, Y=44);8 x 10-4 mM (X=Z=4, Y=42); 1 x 10-3 mM (X=Z=5, Y=40).

The effect of increasing ion concentrations of [Ca2+] and[C2O4

-2] on COM nucleation density at pH 7.5:[Ca2+]=[C2O4

-2]= 7 x 10-4 mM, (X=Z=3.5, Y=43); 7.5 x 10-4

mM, (X=Z=3.75, Y=42.5); 8 x 10-4 mM, (X=Z=4, Y=42);8.50 x 10-4 mM, (X=Z=4.25, Y=41.5); 9 x 10-4 mM,(X=Z=4.5, Y=41).} The solution was poured into the Petridish that contained the gold slide (up-side-down), andplaced in a closed acrylic desiccator cabinet at ambient tem -perature and pressure for 24 hours, Scheme, 1g. 5. Harvesting and Visualizing Slides

After 24 hours, the Petri dishes were removed from thedesiccator, and submerged in a beaker containing an Ultra -pure water layer below a layer of hexanes. The slide wasrinsed in the water layer, slowly pulled through the hexaneslayer, and placed face up on a KimW ipe. Once completelydry, the slide was viewed using the Leica DMLM micro -scope operating in the differential interference contrastreflectance (DIC) mode. Patterned areas could be easilylocated by breathing on the slide, causing air to condenseon the hydrophilic carboxyl-terminated regions.Results/Discussion

Others have suggested that the most cost-ef fective wayto create a master is through photolithography. A photore-sist-coated, glass-slide (Scheme 1a) is masked with amicron-scaled pattern printed onto transparent celluloidfilm. A copper TEM grid with 30 µm square features willalso suffice. The square patterns etched into photoresistupon development (Scheme 1b) and the stamp created fromthe master using an elastomeric polymer were visualized viaDIC microscopy (Scheme 1c, Figure 3). 1 drop of a 1 mM

ethanolic (absolute) solution of mercaptohexadecane wasplaced on the stamp and the ethanol was allowed to evapo -rate (Scheme 1d) before the stamp was placed in contactwith the gold slide (Scheme 1e). The image of the TEMgrid with mercaptohexadecane (30µm waffle) was visual-ized by SEM, Figure 4. Gold substrates with 30 mm squareislands of mercaptohexadecanoic acid monolayers in a waf -

Summer ScholarContinued from page 15

Figure 3. A DIC micrograph of a PDMS stamp with a 30 µmwaffle pattern. The 30 x 30 µm squares are raised relative to thebackground image.


fle grid (TEM) pattern surrounded by mercaptohexadecanemonolayer were prepared via the micropatterning technique(Scheme 1e,f). The micropatterned slides were placedupside down on PDMS stands af fixed in clean Petri dishes.Calcium oxalate growth solution was poured into a Petridish, Scheme 1g.

Initial ion concentration studies ([Ca2+]=[C2O4-2]= 4 x

10-4 mM, 6 x 10-4 mM, 8 x 10-4 mM, 1 x 10-3 mM), firstdemonstrated the templating abilities of the micropatternedSAMs on COM., Figure 5. Lower concentrations ([Ca 2+] =[C2O4

-2] = 4 x 10-4 mM, 6 x 10-4 mM) were not saturatedenough in calcium and oxalate ions to nucleate COM crys -tals within a 24 hour incubation period. Water vapor selec-tively condensing onto -CO2H terminated regions ensuredsuccessful µCP technique, Figure 5a,b. [Ca2+] and [C2O4

-2]concentration equal to 8 x 10-4 mM, produced multipleCOM nucleations in the 30µm square, Figure 5c. [Ca2+] and[C2O4

-2] concentrations above 1 x 10 -3 mM resulted in over-nucleation such that the 30µm square was completely cov-ered with COM crystals, producing a 30 by 30µm COMaggregate, Figure 5d.

The aforementioned ion concentration studies led to

more specific testing within the range of [Ca 2+] = [C2O4-2] =

7 x 10 -4 mM to 9 x 10 -4 mM. As ion concentrationincreased, nucleation density also increased, Figure 6.Qualitative evidence shows that increasing the ion concen -tration also decreases the size of COM crystals. At the low-est concentration necessary to produce COM nucleations,density of COM crystals was still too high to be useful incrystal growth studies. Changing the ion concentrationalone was not enough to produce single COM cof fins in thedesired patterned regions. Varying the pH of HEPES buf feralso had no noticeable effect on COM nucleation or COMdensity, Figure 7. Working within the effective range ofHEPES buffer (6.8 - 8.2 pH) resulted in little to no changeover COM nucleation and growth.

In an attempt to decrease nucleation density of COMcrystals, and thereby potentially increase crystal size, con -centration of mercaptohexadecanoic acid per 30µm squarewas decreased by forming mixed monolayers with varying



Figure 4. Patterned SAM of hexadecanethiol on gold imagedusing SEM. Imaging electrons penetrate the areas with the SEMat a slower rate than the solely gold terminated surface andappear lighter in contrast.

Figure 5. DIC micrographs of micropatterned COM crystals.The dashed lines outline the geometry of the printed regions ofthe SAM: 30 x 30 µm squares of HS(CH2)15CO2H surrounded bya HS(CH2)15CH3 supported on a gold surface. In the absence ofcrystal growth, water vapor condensing selectively within theHS(CH2)15CO2H regions aids in the visualization of the pattern(a,b). Initial ion concentration studies (a) [Ca2+]=[C2O4

-2]= 4 x 10-

4 mM, (b) [Ca2+]=[C2O4-2]= 6 x 10-4 mM, (c) [Ca2+]=[C2O4

-2]=8 x10-4 mM, (d) [Ca2+]=[C2O4

-2]= 1 x 10-3 mM, first demonstratedthe templating abilities of the micropatterned SAM’s.

Figure 6. The effect of increasing ion concentrations of [Ca2+] and [C2O4-2] on COM nucleation density at pH 7.5 on a SAM: 30 x 30 µm

squares of HS(CH2)15CO2H surrounded by HS(CH2)15CH3 supported on a gold surface. (a) [Ca2+]=[C2O4-2]= 7 x 10-4 mM, (b)

[Ca2+]=[C2O4-2]= 7.5 x 10-4 mM, (c) [Ca2+]=[C2O4

-2]=8 x 10-4 mM, (d) [Ca2+]=[C2O4-2]= 8.50 x 10-4 mM, (e) [Ca2+]=[C2O4

-2]= 9 x 10-4

mM.


Summer Scholar

Figure 7. The effect of increasing pH on COM nucleation density with fixed ion concentrations [Ca2+]=[C2O4-2]=

7.5 x 10-4 mM on a SAM: 30 x 30 µm squares of HS(CH2)15CO2H surrounded by HS(CH2)15CH3 supported on a goldsurface. DIC micrographs of templated COM crystal growth at (a) pH = 6.8, (b) pH = 7.3, (c) pH 7.8, (d) pH 8.2.

Figure 8. DIC micrographs of COM crystals ([Ca2+]=[C2O4-2]= 7.5 x 10-4 mM, pH = 7.7) nucleating on templates of

mixed SAMs: (a) 30 x 30 µm squares of 100% HS(CH2)15CO2H surrounded by HS(CH2)15CH3; (b) 30 x 30 µmsquares of 50% HS(CH2)15CO2H : 50% HS(CH2)15CH3 surrounded by HS(CH2)15CH3; (c) 30 x 30 µm squares of25% HS(CH2)15CO2H : 75% HS(CH2)15CH3 surrounded by HS(CH2)15CH3 supported on a gold surface.

Figure 9: DIC micrographs of COM crystals ([Ca2+]=[C2O4-2]= 7.5 x 10-4 mM, pH = 7.7) nucleating on templates of

mixed SAMs: 30 x 30 µm squares of 25% HS(CH2)15CO2H : 75% HS(CH2)15CH3 surrounded by HS(CH2)15CH3supported on a gold surface grown over (a) 24 hours, (b) 48 hours. Increasing the time in growth solution increasednucleation density without affecting the average size of the COM crystals.

Figure 10. Representative DIC micrographs of COM crystals nucleating on templates of SAMs: 30 x 30 µm squaresof HS(CH2)11OH surrounded by HS(CH2)15CH3 supported on a gold surface grown over 24 hours. Varying the ionconcentration ([Ca2+]=[C2O4

-2]= 7 x 10-4 mM, [Ca2+]=[C2O4-2]= 7.5 x 10-4 mM, [Ca2+]=[C2O4

-2]=8 x 10-4 mM) andpH = 6.8 to 8.2 had little effect on nucleation density.


ratios of mercaptohexadecanoic acid to mercaptohexade-cane. The mixed monolayer study may also more closelyapproximate the surface of a biological macromolecule,which is not often a two-dimensional crystalline interface ofsingle functionality as is prepared via a SAM of mercapto -hexadecanoic acid. As the ratio of mercaptohexadecanoicacid to mercaptohexadecane was decreased, nucleation den -sity dramatically decreased. Not only did the average num -ber of crystals per growth region decrease, but the averagecrystal size also decreased, contrary to our original hypothe -sis, Figure 8. Further attempts to increase crystal size bypermitting growth to continue for 48 hours did not lead toincreased crystal size, but simply increased nucleation den -sity, Figure 9.

Terminal SAM functional groups have been shown tohave a profound effect on the nucleation, size, and orienta -tion of calcite. 2, 6 SAMs of hydroxy-terminated alkanethiolshad a similar effect as methyl-terminated SAMs on calcitegrowth. In an attempt to lower COM nucleation density,mercaptoundecanol was patterned onto the gold surface andthe pattern was backfilled with mercaptohexadecane. Themercaptoundecanol templated COM growth such that nucle-ation density was lowered, and crystal size was increased,Figure 10. Conclusion

µCP SAMs of w-functionalized alkanethiolates on goldare effective templating agents for the growth of COM.COM crystals nucleate on carboxyl terminated µCP SAMpatterns regardless of ion concentrations, once a critical con-centration is reached, and regardless of pH, within the effec-tive range of the HEPES buffer. The µCP carboxylterminated patterned SAMs appeared to be ineffective incontrolling the orientation of the COM crystals and relativeratios of twinned COM crystals formed. Evidence of thedi- and tri-hydrate forms of calcium oxalate was also notobserved.

While the surface of biological macromolecules impor -tant in kidney stone formation and inhibition are rich inanionic functionality, a SAM, which can be approximatedby a two-dimensional crystalline slice of a long-chained car-boxylic acid crystal may not serve as an appropriate mimic.Mixed µCP SAMs of mercaptohexadecane and mercapto-hexadecanoic acid with varying ratios may better model thesurface of biological macromolecules by both decreasingthe anionic functionality and by forming more disorderedinterfaces with the growth solution. These mixed µCPSAMs appear to nucleate lower densities of COM, while atthe same time decreasing average crystal size. Longergrowth periods did not increase crystal size, but served todecrease the effectiveness of the templating surface as COMnuclei formed on the surface without regard for the func -tionality of the micropattern. Complete alteration of the ter -minal alkanethiolate functional group to a hydroxyl

terminated thiol, had a significant effect on both the nucle-ation density and size of the COM crystals within the nor -mal 24-hour incubation period.

These studies provide the impetus to synthesize othernon-commercially available w-functionalized alkanethio-lates to further study COM nucleation and growth by µCPSAMs.References1. Aizenberg, J., Templated crystallization of calcite on pat-

terned self-assembled monolayers. Materials Research Soci-ety Symposium Proceedings 2000, 620, (Morphology andDynamics of Crystal Surfaces in Complex Molecular Sys-tems), M4 1 1-M4 1 11.

2. Aizenberg, J.; Black, A. J.; Whitesides, G. M., OrientedGrowth of Calcite Controlled by Self-Assembled Monolayersof Functionalized Alkanethiols Supported on Gold and Silver.Journal of the American Chemical Society 1999, 121, (18),4500-4509.

3. Addadi, L.; Weiner, S., Biomineralization: Crystals, asymme-try and life. Nature (London, United Kingdom) 2001, 411,(6839), 753, 755.

4. Xia, Y.; Whitesides, G. M., Soft lithography. Annual Reviewof Materials Science 1998, 28, 153-184.

5. Whitesides, G. M.; Gorman, C. B., Self-assembled monolay -ers: models for organic surface chemistry. Handbook of Sur-face Imaging and Visualization 1995, 713-32.

6. Aizenberg, J.; Black, A. J.; Whitesides, G. M., Control ofcrystal nucleation by patterned self-assembled monolayers.Nature (London) 1999, 398, (6727), 495-498.

7. Han, Y.-J.; Aizenberg, J., Face-selective nucleation of calciteon self-assembled monolayers of alkanethiols: Effect of theparity of the alkyl chain. Angewandte Chemie, InternationalEdition 2003, 42, (31), 3668-3670.

8. Aizenberg, J.; Han, Y.-J., Self-assembled monolayers as high-definition templates for inorganic crystallization. Abstracts ofPapers, 225th ACS National Meeting, New Orleans, LA,United States, March 23-27, 2003 2003, COLL-554.

9. Han, I.-S.; Nakagawa, Y.; Park, J.-W.; Suh, M.-H.; Suh, S.-I.;Shin, S.-W.; Ahn, S.-Y.; Choe, B.-K., FKBP-12 exhibits aninhibitory activity on calcium oxalate crystal growth in vitro.Journal of Korean Medical Science 2002, 17, (1), 41-48.

10.Girija, E. K.; Latha, S. C.; Kalkura, S. N.; Subramanian, C.;Ramasamy, P., Crystallization and microhardness of calciumoxalate monohydrate. Materials Chemistry and Physics 1998,52, (3), 253-257.

11.Gardner, G. L., Nucleation and crystal growth of calciumoxalate trihydrate. Journal of Crystal Growth 1975, 30, (2),158-68.

12.Nancollas, G. H.; Gardner, G. L., Kinetics of crystal growthof calcium oxalate monohydrate. Journal of Crystal Growth1974, 21, (2), 267-76.

13.Shiraga, H.; Min, W.; VanDusen, W. J.; Clayman, M. D.;Miner, D.; Terrell, C. H.; Sherbotie, J. R.; Foreman, J. W.;Przysiecki, C.; et al., Inhibition of calcium oxalate crystalgrowth in vitro by uropontin: another member of the asparticacid-rich protein superfamily. Proceedings of the NationalAcademy of Sciences of the United States of America 1992,89, (1), 426-30.




Grace L. Priest (1914-2005)Grace L. Priest, retired chief physicalchemist of the Materials Research Lab-oratory, U.S. Army Materials ResearchAgency, Watertown Arsenal, in Massa-chusetts, died on October 20, 2005, atthe age of 91.

She was born June 30, 1914 inManchester by the Sea, Massachusetts,as Grace L. Ernst.

Priest received her bachelor’sdegree in chemistry from the Univer-sity of New Hampshire in 1935 andher master’s degree from the sameinstitution in 1936. She marriedHomer F. Priest and followed him toColumbia University where he waspursuing his doctorate with Nobel Lau-reate Harold Urey. She worked in thechemistry department studying thechemistry of uranium hexafluoride.Both she and her husband wereenlisted to work on the Manhattan Pro-ject. From 1941 to 1944 she worked inthe chemistry division at the K25gaseous diffusion plant performingmaterials research to develop barriersfor the separation of uranium isotopesin the gaseous diffusion process. As aresult of her work she was recognizedas an international authority on thechemistry of uranium hexafluoride.

In 1957 she was a chemist at theU.S. Army Materials and MechanicsResearch Laboratory where she per-formed materials research and analysisof energetic materials using neutronactivation analysis. She retired as asenior chemist in 1980.

She was an avid birder and spentmany of her winter vacations inFlorida observing and photographingin the everglades. She was a lifelongmember of the MassachusettsAubudon Society, the NationalAubudon Society, the Wilderness Soci-ety, and the National Wildlife Federa-tion. An emeritus member, she joinedACS in 1941.

By Dr. John Hobbs

Carl W. Christensen (1903 –2006) Carl W. Christensen, at age 102 peace -fully passed away on Tuesday evening,February 7, 2006 in Peterborough, NH,surrounded by family and friends.

He was born in Highland Park, IL,the eldest son of Danish parents who,having second thoughts about leavingDenmark, returned there for two years,He and his parents then immigrated tothe United States where he was raisedin Spring Creek, PA. He also lived inHinsdale, IL and Beverly, MA.

He graduated as valedictorianfrom Corry High School in Corry, PAin 1921, and earned a degree in Chemi-cal Engineering from Penn State in1927. During his long career with sev -eral dvisions of Armour and Co. (laterDial) and the Shipley Co. (later Rohmand Haas) he worked in chemicalresearch and development in areas asdiverse as food chemstry, fats and oils,leather, and the breakthrough chem-istry which allowed for the productionof microchips in computers. He was amember of the American ChemicalSociety for 74 years and held over 40patents for his work.

He looked forward to the arrivalof each issue of The Nucleus

He was able to travel to Denmarkagain at the age of 90 with his daugh -ter. However, the best part of hisgolden years were spent in residence atSummerhill in Peterborough, chattingwith old friends by email, leading adaily aerobics class for fellow resi-dents. He thoroughly enjoyed life andhad a passion for learning somethingnew. Every day he considered to be agrand adventure. At the age of 101“The Old Viking” discovered a talentfor painting and eventually had a one-man show of his watercolors at Sum-merhill.

He was predeceased by his wifeand beloved soulmate of 62 years,Ruth Michell Christensen. His memoryis cherished by family and friends.

——- Karen Wells, daughter ◆◆

14.Sheng, X.; Jung, T.; Wesson, J. A.;Ward, M. D., Adhesion at calciumoxalate crystal surfaces and the effectof urinary constituents. Proceedings ofthe National Academy of Sciences ofthe United States of America 2005,102, (2), 267-272.

15.Sheng, X.; Ward Michael, D.; WessonJeffrey, A., Adhesion between mole-cules and calcium oxalate crystals:critical interactions in kidney stoneformation. Journal of the AmericanChemical Society 2003, 125, (10),2854-5.

16.Jung, T.; Sheng, X.; Choi Chang, K.;Kim, W.-S.; Wesson Jeffrey, A.; WardMichael, D., Probing crystallization ofcalcium oxalate monohydrate and therole of macromolecule additives within situ atomic force microscopy. Lang-muir : ACS journal of surfaces andcolloids 2004, 20, (20), 8587-96.

17.Sheng, X.; Ward, M. D.; Wesson, J. A.,Adhesion between Molecules and Cal-cium Oxalate Crystals: Critical Inter-actions in Kidney Stone Formation.Journal of the American ChemicalSociety 2003, 125, (10), 2854-2855.

18.Guo, S.; Ward, M. D.; Wesson, J. A.,Direct Visualization of CalciumOxalate Monohydrate Crystallizationand Dissolution with Atomic ForceMicroscopy and the Role of PolymericAdditives. Langmuir 2002, 18, (11),4284-4291.

19.Xia, Y.; Rogers, J. A.; Paul, K. E.;Whitesides, G. M., Unconventionalmethods for fabricating and patterningnanostructures. Chemical Reviews(Washington, D. C.) 1999, 99, (7),1823-1848. ◆◆


scientists in Argentina, and good forour profession.

As a starting point you may lookat the sites on:

http://www.chemistry.org/portal/resources/ACS/ACSContent/interna-tional/echangefunding020315.pdfPlease consider it. If you have interest or questions, pleasecontact me at eustacd(at)polaroid.com◆◆

Argentine ChemistsContinued from page 13

Historical Notes


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Q. Exactly, how many awards andscholarships does NESACS sponsor?

A) One b) Two c) Many

www.nesacs.org/awards

apply the least steps to maintainfidelity of the information by reducingthe loss in efficiency. The one objectthat we can understand with the leastnumber of instruments, processes,design, etc. is ourselves. The most any-one, instrument, theory, analysis, etc.can understand us is ourselves. So, it isthe self-study of self (SOS) whichcould lead to the most understanding.And, chemistry is by far the best mod -ern way to SOS, making the circle oflearning through something we all arevery good at, i.e., chemistry of self. Iknow, I know. You say, isn’t that bio-chemistry?

As a biophysical chemist, I say itis more than that. It will always bemore than anything anyone else evertells you about you. Chemistry of selfis not just interdisciplinary or centralscience; it is life to learn individuallyand infinitely. ◆◆

Chemistry ofUnderstandingContinued from page 10

Check the NESACS Homepagefor late additions:http://www.NESACS.orgNote also the Chemistry Department webpages for travel directions and updates. These include:http://chemserv.bc.edu/seminar.htmlhttp://www.bu.edu/chemistry/events/http://www.chem.brandeis.edu/colloquium.shtmlhttp://www-chem.harvard.edu/events/http://web.mit.edu/chemistry/

www.chem.neu.edu/web/calendar/index.htmlhttp://chem.tufts.edu/seminars.html [CHEM.]http://ase.tufts.edu/chemical/seminar.htm

[CHEM. ENGG.]http://www.chem.umb.edu/www.umassd.edu/cas/chemistry/seminars.cfmwww.uml.edu/Dept/Chemistry/speakers.htmlhttp://www.unh.edu/chemistry/seminars.html

Notices for the NucleusCalendar should be sent to:Sheila E Rodman 250 Kennedy Drive, Unit #403, Malden, MA 02148.E-MAIL: serodman(at)hotmail.com

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