16/2014 - Computational Physics Group, A.U.Th.:...

COVER PICTURE

The cover image shows the hydrogen-storage capacity of a Li-decorated (0,6) boronnanotube, which is obtained by rolling up a boron-double-ring sheet. On p. 3453, Y.Liu et al. describe the use of density functional theory to reveal several novel boronnanostructures based on the boron double ring.

NEWSSpotlights on our sister journals 3422 – 3425

16/2014

Most of the articles in this issue have already appeared online on wileyonlinelibrary.com.See www.chemphyschem.org under EarlyView�.

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� 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2014, 15, 3407 – 3417 3407

http://dx.doi.org/10.1002/cphc.201402418


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Further masthead information follows directly after theTable of Contents.

CHEMPHYSCHEMMASTHEAD

CONCEPTS

J. Li,* M. C. Lemme, M. �stling

3427 – 3434

Inkjet Printing of 2D LayeredMaterials

You can print anything these days: Asimple and general solvent exchangetechnology is introduced for inkjetprinting of 2D layered materials. Thetechnology addresses the critical chal-lenges and improves the manufacturingefficiency and product quality. Excellentjetting performance, ideal printing pat-terns and a variety of promising applica-tions for inkjet printing of 2D layeredmaterials are demonstrated.

COMMUNICATIONS

A. R. Patel,* N. Cludts, M. D. Bin Sintang,B. Lewille, A. Lesaffer, K. Dewettinck

3435 – 3439

Polysaccharide-Based OleogelsPrepared with an Emulsion-TemplatedApproach

Well gel: Oleogels (containing>97 wt % liquid oil) are prepared byusing a polysaccharide-based emulsionas a template. The obtained oleogel hasa unique microstructure and interestingrheological properties, including a highgel strength, shear sensitivity, good thix-otropic recovery, and good thermosta-bility.

S. Alam, C. Anand, K. S. Lakhi, J.-H. Choy,W. S. Cha, A. Elzhatry, S. S. Al-deyab,Y. Ohya, A. Vinu*

3440 – 3443

Highly Magnetic Nanoporous Carbon/Iron-Oxide Hybrid Materials

Fatal attraction: Size-controlled Fe2O3

nanoparticles grown in a nanoporouscarbon material with tuneable pore di-ameters are prepared and exhibitstrong, non-linear magnetic propertiesand an extremely high magneticmoment of approximately 229 emu g�1.

A. Hecht, P. Commiskey, F. Lazaridis,P. Argyrakis,* R. Kopelman*

3444 – 3446

Fractal Dimension of MicrobeadAssemblies Used for Protein Detection

A bead cluster biomarker probe usesfractal dimension analysis to quantitatemarker concentration for medical diag-nostics (see picture).


CHEMPHYSCHEMCONTENTS www.chemphyschem.org






C. M. Winterflood,* H. Ewers*

3447 – 3451

Single-Molecule LocalizationMicroscopy using mCherry

The cherry on top! Single-molecule lo-calization microscopy using standardmCherry is shown with sub-40 nm reso-lution. The wealth of well-characterizedmCherry fusion proteins can be readilyrevisited by using single-moleculesuper-resolution microscopy. Super-res-olution imaging can be done ina straightforward way eliminating theneed for external labeling or the use ofhighlighter fluorescent proteins.

ARTICLES

J. Wang, H.-Y. Zhao, Y. Liu*

3453 – 3459

Boron-Double-Ring Sheet, Fullerene,and Nanotubes: Potential HydrogenStorage Materials

The new graphene: Similar to carbon-based graphene, fullerenes, and carbonnanotubes, boron atoms can formsheets, fullerenes, and nanotubes. Here,several of these novel boron struc-tures—all based on the boron doublering—are investigated. The nanostruc-tures are interesting potential candi-dates for hydrogen storage.

S. O. Krabbenborg, J. van Weerd,M. Karperien,* P. Jonkheijm,* J. Huskens*

3460 – 3465

Locked-in Biomimetic SurfaceGradients that are Tunable in Size,Density and Functionalization

Locked-in supported lipid bilayer gra-dients are prepared that can be tunedin space, time and density in a processcontrolling lipid phase behaviour, elec-tric field and temperature. Stable gradi-ents of functional serine and biotin ter-minated lipids are shown. Covalent andnon-covalent chemical modification isused to fabricate gradients of FITC, hex-ahistidine-tagged proteins and SAv/biotin.

F. C. Maier, M. Fyta*

3466 – 3475

Type-Dependent Identification of DNANucleobases by Using Diamondoids

Diamondoid biosensor: Diamondoids,small amine-modified diamond-likecages, can probe DNA molecules andidentify the type (purine or pyrimidine)of nucleobase. Diamondoids can poten-tially be used to functionalize a biosens-ing device, scan along the DNA, and,based on the specific frontier orbitals asshown in the figure, read out the DNAnucleobases.








Y. Hao, H. Tian, J. Cong, W. Yang, I. Bora,L. Sun, G. Boschloo,* A. Hagfeldt

3476 – 3483

Triphenylamine Groups ImproveBlocking Behavior of PhenoxazineDyes in Cobalt-Electrolyte-Based Dye-Sensitized Solar Cells

Anything but sunblock: Triphenyla-mine groups give a good blockingeffect in phenoxazine dyes for cobaltelectrolyte-based dye-sensitized solarcells.

M. J. J. Coenen, T. Khoury, M. J. Crossley,B. L. M. Hendriksen, J. A. A. W. Elemans,*S. Speller

3484 – 3488

Nanostructuring of Self-AssembledPorphyrin Networks at a Solid/LiquidInterface: Local Manipulation underGlobal Control

Ground control to Major Tom: Globalcontrol over the self-assembly of tet-raundecyl metal porphyrins into a mono-layer at a solid/liquid interface is gov-erned by the concentration and compo-sition of the supernatant solution. Sub-sequent manipulation by nanoshavingwith a scanning tunneling microscopytip creates monolayer defects, whichcan mediate a decrease or increase inlocal surface density, or the insertion ofa second species of the same shape.

F. Holzmeier, M. Lang, P. Hemberger,*I. Fischer*

3489 – 3492

Improved Ionization Energies for theTwo Isomers of PhenylpropargylRadical

More flux, better signal! In an imagingphotoelectron photoion coincidencestudy (iPEPICO) the two isomeric C9H7

radicals, 1-phenylpropargyl (1PPR) and3-phenylpropargyl (3PPR), are reinvesti-gated, and improved ionization energiesand threshold photoelectron spectra areobtained.

C. Trujillo, G. S�nchez-Sanz,* I. Alkorta,J. Elguero

3493 – 3501

A Computational Study on 3-Azonia-,3-Phosphonia-, and 3-Arsonia-spiro[2.2]pentanes and Related Three-Membered Heterocycles

Heterocyclic spiropentanes: The strainand relative stability of heterocyclicspiro ACHTUNGTRENNUNG[2.2]pentane cations with N, P, andAs as spiro atoms are studied theoreti-cally. In addition, their interaction withthe chloride and 3-boranuidaspiro-ACHTUNGTRENNUNG[2.2]pentane anions (see picture) are in-vestigated.








B. Maity, A. Chatterjee, S. A. Ahmed,D. Seth*

3502 – 3514

Supramolecular Interactions ofNonsteroidal Anti-inflammatory Drugin Nanochannels of MolecularContainers: A Spectroscopic,Thermogravimetric and MicroscopicInvestigation

Be my guest! Supramolecular host–guest complexation between the non-steroidal anti-inflammatory drug indo-methacin and the nanochannels of dif-ferent cyclodextrin molecular containerswere investigated.

P. Giridhar, B. Weidenfeller,S. Zein El Abedin, F. Endres*

3515 – 3522

Electrodeposition and MagneticCharacterization of Iron and Iron–Silicon Alloys from the Ionic Liquid1-Butyl-1-methylpyrrolidiniumTrifluoromethylsulfonate

Knocking down the wall: Cyclic vol-tammetry of FeCl2 + SiCl4 in [Py1,4]TfO isperformed, and an investigation intothe microstructure and magnetic prop-erties of electrodeposited FeSi alloys ispresented.

L. Pengxia, Z. Du, D. Wang,* Z. Yang,*H. Sheng, S. Liang, H. Cao, W. He,H. Yang*

3523 – 3529

Optoelectronic and Self-assemblyProperties of Porphyrin Derivativeswith Click Chemistry Modification

A series of functionalized porphyrinmolecules containing electron-rich al-kynes, synthesized by means of the So-nogashira coupling reaction, are furthermodified by reacting the ethynyl groups

with click reagents through a formal[2+2] click reaction. Through a phase-exchange self-assembly method, highlyorganized morphologies are observedby scanning electron microscopy.

F. Chen,* H. Zhu, M. Forsyth

3530 – 3535

Modelling Ion-Pair Geometries andDynamics in a 1-Ethyl-1-methylpyrrolidinium-Based Ion-Conductive Crystal

Going through the motions: Tempera-ture-dependent cation motions are pre-dicted in different plastic crystals phases(see picture). Pseudorotation in the pyr-rolidine ring is first expected to involvea phase IV to III transition. The partial

rotation from one local minimum to an-other presents next-level dynamics. Thefree rotation of the cation is activatedas the temperature increases, whichmay be accompanied by reorientationof the ethyl group.








C. H. C. Janssen, A. S�nchez,M. N. Kobrak*

3536 – 3543

Selective Extraction of Metal Ions fromAqueous Phase to Ionic Liquids: ANovel Thermodynamic Approach toSeparations

Pick and choose: The selective extrac-tion of metals from aqueous mixtureshas generally relied on the use of selec-tive ionophores. An alternative strategyis presented that exploits a recently de-veloped approach to extraction into anionic liquid phase, and shows thata high degree of control over selectivitycan be obtained by tuning the relativeconcentrations of extraction agents.

S. Mandal, J. Kuchlyan, D. Banik,S. Ghosh, C. Banerjee, V. Khorwal,N. Sarkar*

3544 – 3553

Ultrafast FRET to Study SpontaneousMicelle-to-Vesicle Transitions in anAqueous Mixed Surface-Active Ionic-Liquid SystemIn a jiffy! Spontaneous micelle–vesicle

transitions in a mixed surface-activeionic-liquid system are of interest, be-cause of the advantageous properties ofamphiphilic ionic liquids compared with

conventional surfactants. In addition todetailed characterization, how ultrafastfluorescence resonance energy transfer(FRET) can be used to probe such transi-tions is discussed.

S. Pan, D. Moreno, G. Merino,*P. K. Chattaraj*

3554 – 3564

Stability of Noble-Gas-Bound SiH3+

Clusters

A noble cause: The stability of noblegas (Ng)-bound SiH3

+ clusters is ex-plored by ab initio computations. SiH3

+

can bind Ng atoms effectively. The Si�Xe/Rn bonds are covalent in nature.

Both the �I (inductive) effect of the Xatoms and X!Si p-backbonding havedecisive roles in the Ng binding abilityof SiX3

+ (X = F, Cl, Br).

J. M. Clough, R. P. Sijbesma*

3565 – 3571

Dioxetane Scission ProductsUnchanged by Mechanical Force

Illuminating mechanoluminescence:Dioxetane-based force-induced lightemission from polymers is a powerfulnew way to characterize polymer be-havior under stress. Here we reveal thatthe dioxetane is broken mechanicallyinto products almost identical to thoseformed by heating at elevated tempera-tures (see figure). Excited- and ground-state degeneracy is thought to playa critical role in regulating the outcomeof the mechanical scission process.








F. Melin, M. R. Noor, E. Pardieu,F. Boulmedais, F. Banhart, G. Cecchini,T. Soulimane, P. Hellwig*

3572 – 3579

Investigating the Thermostability ofSuccinate: Quinone OxidoreductaseEnzymes by Direct Electrochemistry atSWNTs-Modified Electrodes and FTIRSpectroscopy

Achieving thermostability: Compara-tive studies of the succinate: quinonereductases from mesophilic bacteriumEscherichia coli and thermophilic bacteri-um Thermus thermophilus by using elec-trochemistry and infrared spectroscopyallow a discussion of the possible struc-tural factors that contribute to the tem-perature-dependent activity of the stud-ied bacteria (see figure).

P. Weerachanchai, Y. Wong, K. H. Lim,T. T. Y. Tan, J.-M. Lee*

3580 – 3591

Determination of SolubilityParameters of Ionic Liquids and IonicLiquid/Solvent Mixtures from IntrinsicViscosity

Viewing the Mix in 3D: The solvationpower of ionic liquids and ionic liquid/solvent mixtures was studied by usingan intrinsic viscosity method that al-lowed the determination of Hildebrandand Hansen solubility parameters, inparticular, dispersion, polar and hydro-gen-bonding solubility parameters.These partial solubility parameters canbe visualized as coordinates in a 3D dia-gram, allowing illustration of the misci-bility of different materials.

E. M. Kosower,* G. Borz, I. Goldberg,N. Ermakov

3592 – 3597

N-Methyl-trimethylacetamide in ThinFilms Displays Infrared Spectra ofp-Helices, with Visible Static andDynamic Growth Phases, and thena b-Sheet

Growth spurt: Increasing the size of theacyl group in a simple peptide model(N-methyl-acylamide) favors the forma-tion of more open helices such as thep-helix. Sudden changes in spectroscop-ic data reveal that a crystalline p-helixcan be formed, and a succession of fur-ther changes leads to a quasiplanar p-form. Independently, a planar b-sheetform is also obtained.

E. M. Kosower,* G. Borz

3598 – 3607

N-Alkylacylamides in Thin FilmsDisplay Infrared Spectra of 310-, a-,and p-Helices with Visible Static andDynamic Growth Phases

Decline and fall of the Helical empire:Infrared spectroscopy of peptidemodels reveals helix formation relevantto the behavior of biological molecules.Remarkable properties are demonstrat-ed to belong to minimal peptide oligo-mers that are held together by hydro-gen bonds alone, that is, a new speciesis identified in the pantheon of peptideforms.








J. R. Machado, A. Baniodeh, A. K. Powell,B. Luy, S. Kr�mer,* G. Guthausen*

3608 – 3613

Nuclear Magnetic ResonanceRelaxivities: Investigations ofUltrahigh-Spin Lanthanide Clustersfrom 10 MHz to 1.4 GHzNMRD on ultrahigh-spin coordinative

clusters: The nuclear magnetic reso-nance relaxivities of aqueous solutionscontaining FeIII

10DyIII10 ultrahigh-spin

cyclic coordinative clusters have beeninvestigated by using a wide range of

1H Larmor frequencies up to 1.4 GHz.These single molecule magnets showinteresting relaxivities and can be con-sidered as potential relaxation agents inhigh-field magnetic resonance imaging.

M. Nagy, D. R�cz, L. L�z�r, M. Purgel,T. Ditr�i, M. Zsuga, S. K�ki*

3614 – 3625

Solvatochromic Study of HighlyFluorescent AlkylatedIsocyanonaphthalenes, Theirp-Stacking, Hydrogen-BondingComplexation, and Quenching withPyridine

Dyeing to quench: The solvatochromicproperties of novel, effective, alkylated,aminoisocyanonaphthalene-based fluo-rophores are investigated. Their com-

plexation and special quenching withpyridine is studied in detail (see picture;1: cyclohexane, 2: cyclohexane/pyridine,3: pyridine).

Y. J. Kim, Y. R. Cheon, J. Y. Back,Y.-H. Kim,* D. S. Chung,* C. E. Park*

3626 – 3633

Naphtho[2,1-b :3,4-b’]dithiophene-based Bulk Heterojunction Solar Cells:How Molecular Structure InfluencesNanoscale Morphology andPhotovoltaic Properties

Thiophene length on the BHJ: An in-vestigation of the influence of the thio-phene-chain lengths of three NDT-

based polymers on the nanoscale mor-phologies and device performances ofthe active layers.

E. Portenkirchner,* D. Apaydin,G. Aufischer, M. Havlicek, M. White,M. C. Scharber, N. S. Sariciftci

3634 – 3638

Photoinduced Energy Transfer fromPoly(N-vinylcarbazole) toTricarbonylchloro-(2,2’-bipyridyl)rhenium(I)

CO2 snaps? The photoinduced energytransfer from poly(N-vinylcarbazole), asa donor material, to fac-(2,2’-bipyridyl)-Re(CO)3Cl, as a catalyst acceptor, is in-vestigated in terms of a potential appli-cation towards CO2 reduction. Photolu-minescence quenching experimentsreveal dynamic quenching through res-onance energy transfer in solid donor/acceptor mixtures and in solid/liquidsystems.








M. T. Pçschko, J. Schlagnitweit, G. Huber,M. Nausner, M. Hornic�kov�, H. Desvaux,*N. M�ller*

3639 – 3645

On the Tuning of High-ResolutionNMR Probes

Out of tune: Three distinctly differenttuning optima can be found for cryo-genically cooled NMR probes, depend-ing on whether pulse performance, spin

noise line shape or frequency pushingare optimized. The choice of the tuningoptimum has important consequencesfor spin dynamics.

I. Haidar, S. Lau-Truong, J. Aubard,J.-P. Renault, N. F�lidj, F. Maurel,L. Boubekeur-Lecaque*

3646 – 3654

Oxadiazole-2-thiol Adsorption on GoldNanorods: A Joint Theoretical andExperimental Study by Using SERS,XPS, and DFT

Feel the vibrations : N,S-Heterocyclicprobes on gold nanorods (GNRs) andspherical gold nanoparticles (GNPs)have distinct vibrational features, as re-vealed by surface-enhanced Ramanspectroscopy (SERS). The combinationof surface analysis and density function-al calculations on an Au20 cluster ena-bled not only the identification of thecoordination mode on the gold surface,but also the assignment of bands.

K. I. Lilova, C. I. Pearce, K. M. Rosso,A. Navrotsky*

3655 – 3662

Energetics of Spinels in the Fe�Ti�OSystem at the Nanoscale

To nano or not to nano? Assessment ofthe mixing thermodynamics and theeffect of the particle size on Fe�Tispinel oxides leads to an intriguing con-clusion about the heats of mixing onboth macro and nanoscale. The ener-getics of the nanosized spinel oxidesturn out to be predictable based onlyon knowledge of their macroscale ener-getics and surface energies, which areconsistent regardless of composition.The findings have important implica-tions for designing nanoscale spineloxides with desirable properties.







L. M. Azofra,* I. Alkorta, J. Elguero

3663 – 3670

Chiral Discrimination in Dimers ofDiphosphines PH2�PH2 and PH2�PHF

Heterochiral diphosphine dimers: Thechirodiastaltic energy of the Ra :Ra versusRa :Sa (PH2�PH2)2 dimers amounts to1.77 kJ mol�1, which indicates that theformation of the heterochiral complex isfavored.

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