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PosterAbstracts__________________________________________1. Synthesis of a fluorinated C-glycoside of theimmunostimulatoryglycolipidKRN7000KhaleelAli,*AhmadAltiti,DavidR.MootooDepartmentofChemistry,HunterCollege

The stimulation of iNKT cells by KRN7000 1 (alsoknownasα-galactosylceramide)inducesthepotentreleaseofboth pro-inflammatory (Th1) and anti-inflammatory (Th2)cytokines. For clinical applications, KRN7000 analogues thatexhibitapolarizedresponse(i.eTh1orTh2bias)andmeasuredpotencies are required. In this context, binding of KRN7000analogs in the active immunological complex is believed toimpact on Th1/Th2 bias, and accordingly, modifications inregionsofKRN7000thatareintimatelyengagedinbindingisanactiveareaofresearch.Inparticular,theglycosideregionhasattractedmuchattentionastheC-glycosideofKRN70002hasshownhighTh1biasandpotency.Inthisvein,C-glycosideswithfluorinesubstituentsonthepseudoanomericcarbon(e.g.3), are of interest because the electrostatic andconformationalpropertiesoffluorinemayelicitnovelbindingproperties,andbyextensionuniquecytokineprofiles.Herein,we report the synthesis of fluoro-C-glycoside 3. The pivotalstep in this synthesis was the reaction of a fluorinated C-glycosylcrotyltin5andthelipidaldehyde6togiveamixture

ofdiastereomericcrotylationproducts.Thestereochemistryofthese products was assigned by NMR analysis of cyclicderivatives, and 4, the diastereomer corresponding to thestereochemistry in KRN7000, was transformed to the finalcompound3.Thekeystrategyinthese"end-games"wastheCurtius rearrangement on the acyl azide derived fromoxidative cleavage of the alkene moiety in the crotylationproduct. This synthesis is a potentially general one for C-sphingolipidswithfluorineontheethylenelinker.__________________________________________2.SelectiveinhibitionoflivercancercellproliferationandmigrationwithsnailvenompeptideTv1Prachi Anand,* Michael Lyudmer, Marouf Hossain,Jeannete Huaman, Olorunseun Ogunwobi, MandëHolfordDepartmentofChemistryandBiochemistry,HunterCollegeHepatocellularcarcinomaisthethirdleadingcauseofcancerdeaths worldwide, with over 500,000 people affected. Themost common treatment for patients with liver cancer,hepatocellular carcinoma (HCC), is chemotherapy withdoxorubicin, 5-fluorouracil or cisplatin, or targeted therapywith sorafenib. Peptidic compoundswith high specificity fortumor cells provide a route for killing cancer cells whileprotectingnormalcellsandhaveseveraladvantages,suchas

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low molecular weight, and selectivity for a specific target,organelles or cells with minimal toxicity compared tochemotherapyorradioactivetreatment.ThisworkillustratesthecytotoxicandanticancerpropertiesofTv1,asmalldisulfiderich peptide from a terebrid snail Terebra variegate. Tv1appearstoinhibitthecellproliferationviaapoptosisusingCox-2pathwayinmouselivercancerBNL1MEA.7R.1(chemicallytransformedfromnormallivercells)cells.In-vivotreatmentinallograft mouse tumor models also showed significantreduction in tumor sizes over a three week period oftreatment.Immunofluorescentco-localizationstudiesindicateTv1's mechanism of action is inhibition of TRPC6 channels,whichareoverexpressedincancercellscomparedtonormallivercells.Tv1'sinhibitionofTRPC6resultsindownregulationof Cox-2 expression and further PGE2 release, two proteinsinvolved in cell proliferation. Our results suggest theanticancerpropertyofTv1canbeexploitedtocontributetoselectiveHCCtherapy.__________________________________________3.HexagonallyOrderedNanoscaleArraysofa-HelicalBundlesDeborahA.Barkley*andJonathanG.RudickDept.ofChemistry,StonyBrookUniversitySelf-assemblyofsoftmatter intonanostructuredarrayswithperiodic,long-rangeorderiscriticalinbothbiologicalsystemsand in materials design. Peptide-dendron hybrid moleculeswhich form thermotropic liquid crystals, with long-range,periodic order and liquid-like flow, are reported. Thestructuresandself-assemblyofthesedendron-peptidehybridsdependonboth thesequenceof thepeptide,programedasalpha helix, and the anisotropic shape and amphiphilicity ofthebenzyletherdendrons.IRspectroscopyresultsshowthatthedendronizedpeptidesretainthealphahelixconformationprogrammedbythesequenceofthepeptide.Polarizedopticalmicroscope results show that alpha helix peptide-dendronhybridsdisplay liquidcrystalphases. X-rayscatteringresultsindicate that the programmed bundle stoichiometry of fourhelicesperbundleisretainedintheorganizedarrayofα-helixpeptide-dendron hybrids. This work will allow for furtherinvestigation into how the sequence of the peptide can beusedtotailorthefunctionalpropertiesofthepeptide-dendronhybrids.__________________________________________4.AsymmetricBreathingMotionsofNucleosomalDNAandtheRoleofHistoneTailsKaushikChakraborty,SharonM.LoverdeDepartmentofChemistry,CollegeofStatenIsland

The most important packing unit of DNA in theeukaryoticcellisthenucleosome[1].Itundergoeslarge-scalestructural re-arrangements during different cell cycles [1,2].Forexample,thedisassemblyofthenucleosomeisoneofthekeystepsforDNAreplication,whereasreassemblyoccursafterreplication.Thus,conformationaldynamicsofthenucleosomeiscrucialfordifferentDNAmetabolicprocesses.Weperformthree different sets of atomistic molecular dynamics (MD)simulationsofthenucleosomecoreparticleatvaryingdegrees

of salt conditions for a total of 0.7microseconds simulationtime. We find that the conformational dynamics of thenucleosomal DNA tails are oppositely correlated from eachotherduringtheinitialbreathingmotions. Furthermore,thestrengthof the interactionof thenucleosomalDNAtailwiththe neighboring H2A histone tail modulates theconformational state of the nucleosomal DNA tail. Withincreasingsaltconcentration,thedegreeofasymmetryintheconformationofthenucleosomalDNAtailsdecreasesasbothtails tend to unwrap. This direct correlation between theasymmetricbreathingmotionsof theDNAtailsandtheH2Ahistone tails, and its decrease at higher salt concentrations,may play a significant role in the molecular pathway ofunwrapping.[1]McGinty.R.K,Tan.S.ChemicalReviews115,2255(2015) [2]Müller.M.M,Muir.T.W.ChemicalReviews115,2296(2015).__________________________________________5. Characterization of the hydrophobic collapse ofpolystyreneinwaterusingfreeenergytechniquesMihaelaDrenscko,*SharonM.LoverdeDepartmentofPhysicsandChemistry,CollegeofStatenIsland

We characterize the hydrophobic collapse of singlepolystyrene chains in water using molecular dynamicssimulations. Specifically,we calculate the potential ofmeanforce for the collapseof a single polystyrene chain inwaterusing metadynamics, comparing the results between allatomisticwithcoarse-grained(CG)molecularsimulation.Wenext explore the scaling behavior of the collapsed globularshapeattheminimumenergyconfiguration,characterizedbythe radius of gyration, as a function of chain length. Theexponentisclosetoonethird,consistentwiththatpredictedforapolymerchaininbadsolvent.Wealsoexplorethescalingbehavior of the solvent accessible surface area (SASA) as afunctionofchainlength,findingasimilarexponentforbothallatomisticandCGsimulations.Furthermore,calculationofthelocal water density as a function of chain length near theminimum energy configuration suggests that intermediatechain lengths are more likely to form dewetted states, ascomparedtoshorterorlongerchainlengths.__________________________________________6. Foldable Supramolecular Block Copolymers viaDirectionalandOrthogonalAssemblyElizabethElacqua*andMarcusWeckDepartmentofChemistry,NewYorkUniversitySupramolecular multiblock copolymers comprised of well-definedtelechelicbuildingblocksareengineeredviamultiplecontrolled polymerization techniques in concert withfunctional initiators and/or terminators. Helical motifs,formed via reversible addition-fragmentation chain-transfer(RAFT) or anionic polymerization are assembled with coil-forming and/or sheet-featuring blocks obtained via atom-transfer radical polymerization (ATRP) or ring-openingmetathesispolymerization(ROMP).Interpolymerorthogonalhydrogen bonding and/or metal-coordination then achievesdynamicmultiblockarchitecturesfeaturinghybridtopologiesofcoils,helices,and/orp-stackedsheetsthat,onabasiclevel,

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mimicproteinstructuralmotifsinfullysyntheticsystems.Theintrinsicpropertiesofeachblock(e.g.,circulardichroismandfluorescence)remainunaffectedinthewakeofself-assembly.Thisstrategytodevelopcomplexsyntheticpolymerscaffoldsfromfunctionalbuildingblocksissignificantinafieldstrivingto produce architectures reminiscent of biosynthesis, whileproviding a linear and facile path towards the design ofsynthetic architectures structurally reminiscent of naturalsystems.__________________________________________7. Structure and Chirality of SupramolecularNanostructureswithPeptide-DrugAmphiphilesMyungshimKang,*KaushikChakraborty,HonggangCui,SharonLoverdeDepartmentofChemistry,CollegeofStatenIslandSupramolecular nanostructures of peptide-drug amphiphilesholdagreatpotentialindrugdeliveryapplications[Cheethamet al., J. Am. Chem. Soc. 135, 2907 (2013)]. Specificintermolecularinteractionsandimpactofanauxiliarysegmentonthechiralassemblyremainpoorlyunderstood.Wereporton the formation of the self-assembled nanostructurescomposedofdrugamphiphiles(DAs)containingthearomaticdrugcamptothecin(CPT)usingatomisticmoleculardynamicssimulations.Oursimulationsshowthatπ-πstackingbetweenplanar CPTs can act like an anchor in the early stage of theaggregation,whilethehydrogenbondingnetworkscomeintoplayatarelativelylaterstage.ChangesinthenumberofCPTdrugs attached to eachDA shift the intermolecular packing,resulting in the morphological changes to the nanotube,compared to the nanofilament reported earlier [Kang et al.,Macromolecules49(3),994(2016)].Wefindthatπ-πstackingbetweenCPTsmediates thechirality inboth supramolecularnanofilament and nanotube, as well as the well-expectedintermolecularhydrogenbondingnetworkbetweenpeptides.Characterization of solvation structure and dynamics insideandoutside of the nanotube finds thatwater inside theDAnanotubesdiffusesslowerthanbulkwater,butfasterthanthesurface water. The results provide useful insights on therationaldesignoffunctionalsupramolecularassemblies.__________________________________________8.ThermoresponsiveProteinEngineeredHydrogelforDrugDeliveryPriya Katyal,* Qingyun Tian, Chuanju Liu, Jin KimMontclareDepartment of Chemical and Biomedical Engineering, NewYorkUniversityProtein-based biomaterials offer several advantages oversyntheticmaterials,owingtotheiruniquestimulusresponsiveproperties,biocompatibilityandmodularnature.Ourlabhassuccessfullydevelopedproteinblockpolymersthatconsistofelastin like polypeptide (E) and the coiled-coil domain ofcartilage oligomeric matrix protein (C). While both E and Chaveself-assemblingproperties,Chasauniquecharacteristicto self assemble into a homopentameric structure with ahydrophobic core. Our protein block polymer, EC has beenpreviously shown to bind and release small hydrophobic

molecules;here,weexpandtheversatilityofEC,andexploredits potential in delivering protein therapeutics. Preliminaryresults demonstrate that E5C, a construct consisting of fiverepeats of E and one C domain, is capable of forming ahydrogelatphysiologicaltemperature,makingitanexcellentcandidate for injectable biomaterials. These hydrogels areusedtoencapsulateamodelprotein,BSAanda therapeuticprotein,progranulin(PGRN),knowntohaveanti-inflammatoryandchondroprotectiveeffectsinpost-traumaticosteoarthritis(PTOA) patients. Further studies are underway to study therelease profile of these proteins using the engineeredhydrogels.__________________________________________9.Kinetic and chemical encodingof catalytic peptideassemblypathwaysMohitKumar,*NicoleIng,AllonHochbaumandReinV.UlijnCUNYAdvancedScienceResearchCenterOne key feature of biological systems is the existence ofchemicallyfueled,transientstructureandfunction,liketheon-demand formation/degradation of tubulin, actin fibers etc.Thishasinspiredasurgeinrecentresearchtowardstemporalcontrol of nanostructures, which is achieved by using (bio-)catalysis to activate building blocks and thereby driveassembly. In this regard, potential for design of activesupramolecular nanostructures based on peptidenanotechnology is increasinglyappreciated.Theobjectiveofthiswork is demonstration of transient nanostructureswithtunablelifetimesandchirality.Thisisachievedbysystematicbiocatalytic exchange of amino acid sequences in dynamicdipeptideslinkedtoanaphthalenediimide(NDI)basedorganicsemiconductor. Our results show a novel design of peptideconjugatefortransientcontrolovertheirchirality,wheretheresultanthelicityofself-assemblyisencodedbythechemicalnatureoftheaminoacidsequence.Primaryrequisiteofsuchtransient assembly is a coordinated competition between afastassemblyreactionandaslowdisassemblyprocess.Thus,we designed a bifunctional peptide conjugate, with tworeactivesiteshavingdifferentialreactionratesateitherend,leadingtotransientfunction.WesynthesizedNDIderivative,whichisconjugatedoneitherend,withtyrosinemethylestersofoppositechirality,resulting inamesochirality(symmetricmolecule). Due to stereoselective preference of enzymeaction,weobservedafastreactiononlyattheterminalwithL-chirality, resulting in symmetry breaking with evolution ofdesired helical assembly within hours. Further, very slowenzymatic reaction at the non-preferredD-chirality terminalresults in loss of both molecular asymmetry andsupramolecular chirality in two weeks. Thus, we observeformation of transient chiral nanostructure, where systemautonomously evolves from racemic to helical to racemicassembly over time with evolving nanostructures likenanofibers and tubes. Importantly, diverse outcomes likeachiral, transient and permanent chirality could be encodedinto the amino acid sequence. Such an active system withspectrumoffunctionalresponsetovariousaminoacidscould

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pavethewayforpeptide-encodednanotechnology.__________________________________________10. Force Feedback Controls Motor Activity andMechanical Properties of Self-Assembling BranchedActinNetworksTai-De Li,* Peter Bieling, Dyche Mullins, Daniel A.FletcherCUNYAdvancedScienceResearchCenterBranched actin networks-created by the Arp2/3 complex,cappingprotein,andanucleationpromotingfactor-generateandtransmitforcesrequiredformanycellularprocesses,buttheirresponsetoforceispoorlyunderstood.Toaddressthis,weassembledbranchedactinnetworksinvitrofrompurifiedcomponentsandusedsimultaneousfluorescenceandatomicforcemicroscopytoquantifytheirmolecularcompositionandmaterial properties under various forces. Remarkably,mechanical loading of these self-assembling materialsincreasestheirdensity,power,andefficiency.Microscopically,increased density reflects increased filament number andaltered geometry but no change in average length.Macroscopically,increaseddensityenhancesnetworkstiffnessandresistancetomechanicalfailurebeyondthoseofisotropicactinnetworks.Theseeffectsendowbranchedactinnetworkswith memory of their mechanical history that shapes theirmaterial properties and motor activity. This work revealsintrinsic force feedback mechanisms by which mechanicalresistance makes self-assembling actin networks stiffer,stronger,andmorepowerful.__________________________________________11.Biological Characterizationof Tv1VenomPeptideforHepatocellularCarcinomaTherapyMichael Lyudmer,* Marouf Hossain, Prachi Anand,OlorunseunOgunwobi,MandëHolfordDepartmentofChemistry,HunterCollege

Compelling experimental evidence supports theassumptionthatpharmacologicalinhibitionofionchannelsortheir regulators is an effectivemethod to counteract tumorgrowth,preventmetastasisandovercometherapyresistanceof tumor cells. Compared to traditional cancer treatments,such as chemotherapy or radioactive treatment, peptidiccompounds with high specificity for cancer cells are anefficient means of preventing metastasis while protectingnormal cells. Venomous peptides are generally antagoniststhat can selectively inhibit the function of cell membranechannelsandreceptors.Here,weexaminedthecytotoxicandantiproliferative properties of a small disulfide rich peptide,Tv1, from venomous terebrid snail, Terebra variegata.Cytotoxicityassaysonmouselivernormalandcancercelllinesindicated Tv1 is lethal to tumor cells. In cell westernsperformedonnormalandtumormouseandhumanlivercelllinesidentifiedsubtypesofTRPCandTRPV,whicharepartofthefamilyofTransientReceptorPotential(TRP)channels,asthepotentialmoleculartargetsofTv1.Comparedtostandardlivercancertherapiesdoxorubicinandsorafenib,Tv1ismuchmorespecificforlivertumorsandresultedinfewernormalcelldeath.Takentogether,ourfindingsillustratethepotentialof

using venom snail peptides to target ion channels in cancertreatment.__________________________________________12.Activity-assistedself-assemblyofcolloidalparticlesStewartMallory*andAngeloCacciutoDepartmentofChemistry,ColumbiaUniversity

Weoutlineabasicstrategyofhowself-propulsioncanbeusedtoimprovetheyieldofatypicalcolloidalself-assemblyprocess. The success of this approach is predicated on thethoughtfuldesignofthecolloidalbuildingblockaswellashowself-propulsionisendowedtotheparticle.Aslongasasetofcriteriaaresatisfied,itispossibletosignificantlyincreasetherate of self-assembly, and greatly expand the window inparameterspacewhereself-assemblycanoccur.__________________________________________13. Effect of Nucleotide State on the ProtofilamentConformationofTubulinOctamersAnjela Manandhar,* Myungshim Kang and Sharon M.LoverdeDepartmentofChemistry,CollegeofStatenIsland

Microtubules (MTs) are cytosolic filaments vital formultiple cellular processes such as cell division, cellularmorphologyandcellulartrafficking.Atthemolecularlevel,thedynamicinstability(randomgrowthandshrinkage)oftheMTisdrivenbythehydrolysisstateofGTPintheβsubunitofthetubulin dimers at the MT end. Here, we use large-scalemolecular dynamics simulations and normal mode analysis(NMA)tocharacterizetheeffectofasingleGTPcaplayerontubulin octamers composed by two neighboringprotofilaments.Weutilizerecenthigh-resolutionstructuresofdynamic MTs by Nogales et al. [Cell 157, 1117 (2014)] tosimulatebothaGDPoctamerandanoctamerwithasingleGTPcaplayer.Weanalyzemultiplereplicasoflong-timeatomisticmoleculardynamics(~2μssimulationtime)ofboththeGDPoctamer and the octamer with a single GTP cap layer.Furthermore,usingNMA,wecalculatemechanicalpropertiessuch as flexural rigidity (kf), persistence length (lp), bendingmodulus (Yf), stretching rigidity (ks) and stretchingmodulus(Ys)of both octamers, averaging over multiple replicas.Moreover, we next incorporate the negatively charged C-terminal tails, characterizing their effect on protofilamentconformationandMTstabilityatvaryingsaltconcentrations.We propose that both the lateral and longitudinal contactsbetween PFs, as well as the phosphorylation state of thenucleotide, play cooperative roles in determiningprotofilament conformation and, therefore, the dynamicstabilityoftheMT.__________________________________________14. Anti-reflective and anti-soiling properties ofsuperhydrophobicnano-coatingsonsolarglassIllya Nayshevsky,* Gil Barahman, Qianfeng Xu, AlanLyonsDepartmentofChemistry,CollegeofStatenIslandTheelectricaloutputofphotovoltaicsolarpanelsislimitedbyseveral factors including reflectionsat theair-glass interface

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and scattering of light by dirt on the exterior surface.Reflectionsleadtolossesofapproximately4%oftheincidentlight,whereassoilingcanresultinlossesaslargeas70%.Dustand other contaminants adhere strongly to the glass bymechanisms such as cementation that requirewashingwithmechanical abrasion. In an effort to increase the electricaloutputandthuslowerthecostsofsolarenergy,ourgrouphasdevelopednano-texturedfluoropolymercoatingsforglassthatexhibits both anti-reflective (AR) and anti-soiling (AS)properties. In this poster, we examine the optical and anti-soilingpropertiesofthesecoatings.Inparticular,weexaminethe effect of surface chemistry aswell as condensation anddryingcyclesondustaccumulationandopticaltransparency.Hydrophilicsurfacesshowvaporcondensingintoafilmwhichdistributesdustovertheentiresurfaceupondrying,resultingin greater optical losses. In contrast, hydrophobic coatedsurfaces exhibit reducedoptical losses fromdust depositiondue to a novel dust herding mechanism. On hydrophobicsurfaces the triple contact line at the solid-liquid-vaporinterface is mobile. Thus as the condensate dropletsevaporate,theydecreasesindiameter,consolidatingthedustinto discrete regions, leaving the bulk of the surfacetransparent.__________________________________________15. Nanoscopic investigations of self-assembledsupramolecular light-harvesting nanotubes andsemiconductorquantumdotsKara Ng,* Christopher W. Leishman, NikunjkumarVisaveylia,NicolasYehya,DortheM.EiseleDepartmentofChemistry,TheCityCollegeofNewYorkSelf-assembled quasi one-dimensional (quasi-1D)nanostructures of π-conjugated molecules exhibit uniqueoptoelectronicproperties,includingsharpexcitontransitions,large oscillator strengths, and high exciton mobility andphotoconductivity,andinorganicsemiconductornanocrystalssimilarly exhibit distinct non-linear optical properties. Thus,theintegrationoftheseorganicandinorganicnanomaterialsoffers the possibility of developing new photonic andoptoelectronic devices. However, to control such complexmaterialsystemsitisessentialtounderstandhowtheirvariousparts interact, and whether these interactions result incoherently shared excited states or in diffusive energytransportbetweenthem.Here,weutilizenear-fieldscanningoptical microscopy (NSOM) to investigate (1) an artificialmodel system:well-defined, thoroughly characterizedquasi-1D light-harvesting nanotubes (LHNTs) self-assembled fromcyanine dye molecules, and (2) cadmium selenide colloidalquantumdots(CdSeQDs).Thenanostructureswere isolatedfrom solution and immobilized on a solid substratewithoutaltering their supramolecular structures, then simultaneoustopographicalandopticalimageswereobtainedforindividualLHNTs and for single CdSe QDs. These results lay thegroundwork for future NSOM investigations of nanoscaleexcitationenergytransferinsupramolecularaggregatesandofresonance coupling in hybrid organic/inorganicnanostructures.

__________________________________________16. Mechanical Evolution of alpha-helical peptidelinearandstarPoly-ethyleneSeanO'Neill,*RaymondTuDepartmentofChemicalEngineering,TheCityCollegeofNewYorkWehavedesignedapeptideconjugatedpoly-ethyleneglycol(PEG)systemtoexamineintra-andinter-moleculardynamicsof gelation. The kinetics of gelation aremeasured for end-functionalized linear-andstar-architectures,whosebehaviorcorrelateswith themolecular structure and self-association.The 23-amino acid peptide sequence we designed throughsolid phase peptide synthesis is known to forma coiled-coilstructure as a function of the solution's electrolyteconcentration.ThetwotopologiesofthePEGarepeptideend-functionalized to examine formation of supramolecularassemblies.Subsequently,microrheologyisusedtoevaluatethe dynamics of self-assembly and the gelation time-scales.This study shows that the dynamics of peptide folding andassemblyforlinear-PEGconjugatedsystemsyieldapercolatednetwork,but the star-PEGconjugatedsystemsyielddiscreteassembliesandremainviscous. Theresultssuggestthatthedegreeofintra-andinter-molecularfoldingdefinesthecriticalgelbehaviorofthesupramolecularsystem.__________________________________________17.Development of IronOxideNanocages and theirapplicationsintherapeuticsandmedicalimagingAloka Paragodaarachchi, Sham Rapersaud,* HiroshiMatsuiDepartmentofChemistry,HunterCollegeIthasbeenachallengetofabricatenanoparticleslessthan15nmincomplexshapes.Wedevelopedamethodtofabricatesuch inorganic nanoparticles by controlling desorption ofatomsfromseednanocrystals.Inthesecompartments,atomicdesorption is accelerated from specific crystalline faces ofseeds based on the surface energy landscape, and thisbalancing allows one to evolve shape and structure ofinorganic nanoparticles into targeted designs. Iron oxidenanocagesweresucceeded in incorporatingdrugs insidethecavityandthecytotoxicityforcancercellswasmoreefficientlywhen the cage-shaped nanoparticles were applied as drugcarriers as compared to spherical and cubic iron oxidenanoparticles.Inthiswork,wecomparedthedrugreleaseandefficacyof ironoxidenanoparticles possessing either a cageshape(IO-NCage)orasolidsphericalshape(IO-NSP).Riluzolecytotoxicity against metastatic bone cancer cells wasenhanced three-fold with IO-NCage. The shape ofnanoparticles (ornanocages)affectedthedrugreleasepointand cellular internalization, which in turn influenced drugefficacy.Our studyprovidesevidence that the shapeof ironoxidenanoparticles has a significant impact ondrug releaseandefficacy.TheMRIactivityofironoxidenanocagesandtheeffectofshapesofnanoparticlesfordrugdeliverywillalsobediscussed. Inordertoenhancetargetingandbiodistribution,approaches such as generating nanoparticles integratedsynthetic nanoparticles and biological nano-compartments

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were examined and discussed. The integration betweeninorganic nanocages and biological nano-compartmentswasalso shown to improve targeting specific cancermicroenvironmentsandbiodistributioninvivo.__________________________________________18. Controlling morphology and kinetics of MMP-9responsivenanocarriersthroughsequenceandchargedesignJiyeSon,*MariaContel,andReinUlijn.CUNYAdvancedScienceResearchCenterMatrixmetalloproteinase-9(MMP-9)isanendopeptidasethatiscrucialforregulatingmanyfunctionsinthebodythatinvolvedegradation of gelatines and collagens. However, abnormaloverexpression of MMP-9 has been associated with manydiseases, especially in cancer invasion and metastasis.Therefore, MMP-9 responsive nanomaterials provide anopportunitytospecificallytargetcellsthatoverexpressMMP-9.Wereportonthedesignof12peptideamphiphilesthatself-assemble into nanoparticles and respond to MMP-9 withvaryingkineticstodisassembleortransformintonanofibers.Wewilldemonstratehowsimplechangesinthesequenceorsurfacechargecanresultindrasticchangesintheformationoftheenzymaticproduct in termsofmorphologyandkinetics.Moving forward, the unique profiles of the peptidenanocarrierscanbeusedasadrugdeliveryplatformtoachievefinetuneddrug-releaseprofiles.__________________________________________19. The Interaction of Hydrophobic DrugCamptothecinandtheModelPhospholipidMembranesPhuK.Tang,*MyungshimKang,andSharonM.LoverdeDepartmentofChemistry,CollegeofStatenIslandThe transport of hydrophobic compounds (drugs) acrossmodel phospholipid membranes is of great interest to thepharmaceutical industry. Molecular dynamics simulationsofferauniquetooltocalculatetheinteractionenergyofthesemodelcompoundswithphospholipidmembranes.Wereporthereontheinteractionsbetweenamodelhydrophobicdrug,camptothecin (CPT) and a model phospholipid membranecomposed by 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), using all-atom molecular dynamicssimulations. CPT is a cancer drugwhich binds to the DNAtopoisomerase I ina ternarycomplex, stabilizing it, inducingapoptosis1. Specifically,we calculate thepotential ofmeanforce(PMF)interactionbetweenCPTandaPOPCmembraneusing the Adaptive Biasing Force (ABF) methodology2. Wenext compare the transfer free energy with experimentalresults reported by Selviet al. for the partitioning of CPT inoctanol/water3. Furthermore, we also characterize thepreferred angle of interaction of the CPT plane with therespect to thebilayersurface. Wenextuse theseresults tovalidate a coarse-grained model of the cancer drug CPTdevelopedbyourlaboratory,andexploreitsinteractionwithmodelcellularmembranes.__________________________________________20. Using spores of bacillus to create evaporation-

drivenengineHaozhenWang*andXiChenCUNYAdvancedScienceResearchCenter

EvaporationisthedominantformofenergytransferinEarth'sclimate.Herewereportevaporation-drivenenginesthatcanpowercommontaskslikelocomotionandelectricitygeneration.Theseenginesstartandrunautonomouslywhenplacedatair-waterinterfaces,andoperateaslongastheairisnot saturated. To create these engines, we developedhygroscopy driven artificial muscles (HYDRAs) that exhibitmoisture-drivenhighactuationstrainandenergydensity.Wedesigned device architectures for HYDRA engines thatgeneratesustainedlinearoscillatorymotion(piston-like)androtarymotion (turbine-like) in the presence of evaporation.Usingtheseengines,wedemonstrateanelectricitygeneratorthatrestsonwaterwhileharvestingitsevaporationtopoweralightsource,andaminiaturecar(weighing0.1kg)thatmovesforwardasthewaterinthecarevaporates.__________________________________________21.Synthesisofself-assembledhybridnanostructuresandtheirspectroscopiccharacterizationsNikunjkumarVisaveliya,*ChristopherW.Leishman,KaraNg,NelsonTobar,NicolásYehya,andDortheM.EiseleDepartmentofChemistryandBiochemistry,,TheCityCollegeofNewYorkSelf-assembled nanomaterials formed via interfacialinteractionpresenttheinterestingpropertieswhichareusefulforwide range of applications. In general, nanoparticles arethebuildingblocksofthehierarchicalself-assemblyformationandtheypresentshighsurfacetovolumeratio.Theintegrationoforganicandinorganicnanomaterialsviaspecificinterfacialinteractionsoffersthepossibilitytocreatenoveltypeofhybridnanostructures for different uses. In our work, we aresynthesizing size, shape andmorphology-controlledmetallicnanostructureononehand,andfluorescence-activepolymernanoparticlesofdifferentshapesonotherhand. Inaddition,we are synthesizing supramolecular self-assemblingnanotubesofthecyanineaswellasporphyrindyeswhicharetherobustlight-harvestingnanostructures.Assembliesoftheplasmonic metal nanoparticles and fluorescence-activepolymer nanoparticles couple the plasmon-fluorescenceproperties. On other side, the assemblies of thesupramolecular dye aggregates andmetal nanoparticles arestimulatinghybridnanomaterialsforcoupledplasmon-excitonproperties. Furthermore, the interfacial assemblies of thepeptide/protein molecules with metal nanostructures areinteresting nanomaterials for biomedical applications. A keychallenge is to produce highly homogeneous assemblies inorder to realizeuniformperformanceduring theopticalandoptoelectronic applications. For this purpose, we utilize themicrofluidics systems due to their advantages of fast phasetransfer, efficient reactants mixing and capability of thecontinuouslyvaryingreactantscompositionintheflow.__________________________________________22. Dimeric synthetic receptor for carbohydraterecognition

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M. Fernando Bravo*1, 2, 3, Kalanidhi Palanichamy1, 2,Samuel R. Peurifoy4, Milan Schlain1, 2, Adam B.Braunschweig1,2,51CUNY Advanced Science Research Center, New York, USA.2Department of Chemistry, Hunter College, New York, USA.3DepartmentofChemistry,GraduateCenterCUNY,NewYork,USA. 4Department of Chemistry, Columbia University, USA.5Department of Biochemistry, Graduate Center CUNY, NewYork,USABy targeting the pyranosides that are prevalent on theglycocalyx, synthetic carbohydrate receptors could serve asagents for disease detection, drug delivery, or eventherapeutics1.Currently, synthetic lectinsare rarelyused forthese applications because they primarily bind only allequatorialglucosidesthatareabsentfromtheglycocalyx.Toaddress thischallenge,wehavepreviously reportedahighlyflexible synthetic carbohydrate receptor that achievedmannoside-specific binding by relying uponmultivalent andcooperative binding modes2. The major drawback of thisprevious receptor, however, is that binding has beendemonstratedonlyinchloroform.Hereinwehavedevelopedanewpyranoside receptor,1, (Figure1) that reliesuponH-bonding,C−H•••πinteractions,andconformationalflexibilitytoachievehighbindingaffinitywithC1-methoxypyranosides.Like natural glycan binding proteins, this receptor bindspyranosidesbyaccessingmultivalentinteractions,andstudiessuggest a new approach towards the biomimetic design ofsynthetic carbohydrate receptors, where conformationalflexibility and promiscuity are considered beneficial. BindingstudiesviaNMRtitrationofthecomplexwillrevealitsaffinitywhichwill have implications tomedicine and increasing ourunderstandingofbiologicalrecognition.

Figure1. a) PartialNOESY spectrum (800MHz,mixing time:

500ms)of1(0.2mM)with1equiv.MeO-β-Gal(250mM)inD2O/H2O(v/v=5/95)at283K.b)NOESYcontactsobservedforthecomplexbetweenMeO-β-Galand1(800MHz,298K,D2O,500 ms mixing time). c) A computational model of thecomplex, consistent with the NOESY data. MeO-β-Gal iscoloredred,and1isblue.NOESYcontactsarecolorcoded,anddistancesarefromthecomputationalmodel:H15-Ha(5.542Å,6.965Å)[Grey];H5-OCH3(2.516Å)[Yellow];H9-Hd(3.056Å),H8-Hd(3.708Å),H15-Hd(3.722Å),[Green].1.(a) Osborn, H.; Khan T., Oligosaccharides. Theirsynthesisandbiological roles.Oxford,UniversityPress,New York, 2000; (b) Lindhorst, T. K., Essentials ofCarbohydrate Chemistry and Biochemistry, Wiley-VCH,Weinheim,2007;(c)Garg,H.G.;Cowman,M.K.;Hales,C. A., Carbohydrate Chemistry, Biology and MedicalApplications, Elsevier, Amsterdam, 2008. 2.Rieth, S.;Miner,M.R.;Chang,C.M.;Hurlocker,B.;Braunschweig,A.,Chem.Sci.2013,4(1),357-367.__________________________________________23.4DChemicalNanolithographyD.Valles,*C.Carbonell,AWong,A.BBraunschweig

CUNYAdvancedScienceResearchCenterControlling the organization of biomaterials on

surfaces with nanometer resolution is of paramountimportanceforfundamentalbiological,physical,andmedicalstudies, and for the development of optical and electronicdevices.1 State of the art technologies for constructingmaterialscomposedofdelicateorganicandbiologicallyactivematterarebasedprimarilyuponink-jetprinting,pin-printing,which cannot achieve features below 10 microns, whereasconventional photolithography is expensive and destructive.By marrying massively parallel scanning-probe basednanolithography, specifically polymer-pen lithography (PPL)andbeam-penlithography(BPL),withthenewsurfaceorganicchemistry, we have developed approaches for preparingglycanarrays,2 functionalizinggraphene,3andcreatingbrushpolymer arrays.4 Recently, combining massively parallelscanning probe nanolithography, microfluidics, and brushpolymer chemistry, we have achieved 4D organicmicromanufacturing, where the four dimensions are the 3Cartesian coordinates (x,y,z) and the fourth is the chemicalcomposition of each spot in an array (Figure 1).5 This novelmaterials manufacturing approach could pave the waytowards materials with the chemical and topologicalcomplexitycommontobiologicalinterfaces.

8

Figure 1. The Road to Hyperspace Nanofabrication. Toaccomplish such 4D nanofabrication, it will be necessary toadvance nanolithography surface chemistry and 3Dcharacterization.1. Carbonell, C.; Braunschweig, A. B.;Acc. Chem. Res.2016,50,190-198.2.Bian,S.;He,J.;Schesing,K.B.;Braunschweig,A.B.;Small,2012,8,2000-2005.3.Bian,S.;Scott,A.M.;Cao,Y.;Liang, Y.; Osuna, S.; Houk, K. N.; Braunschweig, A.B.; J. Am.Chem. Soc., 2013, 135, 9240-9243. 4. Bian, S.; Zieba, S. B.;Morris,W.;Han,X.;Richter,D.C.;Brown,K.A.;Mirkin,C.A.;Braunschweig,A.B.;Chem.Sci.,2014,5,2023-2030.5.Liu,X.;Zheng, Y.; Peurifoy, S. R.; Kothari, E.; Braunschweig, A. B.;Polym.Chem.,2016,7,3229-3235.__________________________________________24.SupramolecularLightHarvestingThinFilmsAndrew Levine*1,2,3, Charles Kolodziej4, Wei-Chun Lin4,Braden Camargo3, Mehroz Ahmed3, Clemens Burda4,AdamB.Braunschweig1,2,31.PhDPrograminChemistry,CUNYGraduateCenter,3655thAve, New York, NY 10016; 2. Advanced Science ResearchCenter, City University of New York, 85 St Nicholas Terrace,New York, NY 10031; 3. Department of Chemistry, HunterCollege,695ParkAve,NewYork,NY10065;4.DepartmentofChemistry,Center forChemicalDynamicsandNanomaterialsResearch,CaseWesternReserveUniversityCleveland,OH

Organicmaterialsareincreasinglyexploredasactivecomponents in electronic, energy harvesting, and sensingapplications. Inthesesystemsnewoptoelectronicpropertiesemergefromtheinteractionsofelectrondonorandacceptorpolymers.1 However, the inability to control the donor-acceptor interface limitskeyfiguresofmerit,suchaschargeseparationandcollectionefficiency.Analternateapproachtoaddressingthischallengeinvolvesassemblingsmallmolecular

donor and acceptor compounds into precisely orderedsuperstructures via specific noncovalent bonding.2 To thisend, we have created a library composed ofdiketopyrrolopyrrole (DPP) donors and perylene bisdiimide(PDI) acceptors that assemble into hierarchicalsuperstructuresthatundergophotoinducedchargeseparationfollowing supramolecular organization (Figure). From theabilitytochemicallymodifymolecularcomponentsanddonor-acceptor pairings, we have established systematically therelationship between donor-acceptor molecular structure,frontier molecular orbitals, morphology, and emergentphotophysics.Understandingofthesesupramolecularsystemsallowsfortheirdirectintegrationintoelectronicdevices,suchassolarcells,transistors,andsensors.

Figure1. (A) LibraryofPDIelectronacceptors,DPPelectrondonors, and donor-acceptor systems, (B) fs-TA data withassignedchargetransferandseparation,and(C)TEMimageoffibersformedbycombingmDPP*anddEOPDI.1. Guzman, C. X.; Calderon, R. M. K.; Li, Z.; Yamazaki, S.;Peurifoy,S.R.;Guo,C.;Davidowski,S.K.;Mazza,M.M.A.;Han,X.; Holland, G.; Scott, A.M.; Braunschweig, A. B., ExtendedCharge Carrier Lifetimes in Hierarchical Donor–AcceptorSupramolecular Polymer Films. The Journal of PhysicalChemistryC2015,119(34),19584-19589.2.Ley,D.;Guzman,C. X.; Adolfsson, K. H.; Scott, A. M.; Braunschweig, A. B.,Cooperatively Assembling Donor–Acceptor SuperstructuresDirectEnergyIntoanEmergentChargeSeparatedState.J.Am.Chem.Soc.2014,136(22),7809-7812.__________________________________________