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BookofAbstracts,3rdEuropeanCrystallographySchool(ECS3)Sept25-Oct2,2016,Bol,Croatia

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ECS3

3rd European Crystallography School

ECS3 Book of Abstracts

Bol, Croatia, 25 Sept – 02 Oct, 2016


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ECS3DiamondSponsor

ECS3SponsorsandDonors

ImpressumPUBLISHER:CroatianAssociationofCrystallographers,Bijenička54,HR-10000Zagreb,Croatia,VAT:HR47378791658PRODUCTION:Zagreb,2016EDITORS:JasminkaPopovićandAleksandarVišnjevacCOVERILLUSTRATION:ZoranŠtefanić


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Thisbookisprotectedbycopyright.Nopartofit(exceptbriefexcerpts)maybereproducedwithoutawrittenpermissionofthepublisher.

ContentsEffectofstructuralandmicrostructuralfeaturesontheperformanceofCoMn2O4asanodematerialinlithiumionbatteries;M.Bijelić.................................................................................................1Onemolecule,fourcolours:remarkablebehaviourof2,3-thieno(bis)imidebasedmoleculewhichpresentsfourdifferentpolymorphswithdramaticdifferentemissions;ChiaraCappuccino.................................................................................................................................................................2Crystalengineeringofnewcrystalformsofvenlafaxine;FlorianaSpinelli..................................3OptimizingphysicochemicalpropertiesofanaturalantioxidantandgeroprotectorL-carnosine;OleksiiShemchuk..............................................................................................................................4Improvementofmodelqualitybyrejectionofnon-ismorphousframesusingCC1/2andthedataprocessinguserinterfaceXDSGUI;GretaAssmann........................................................................5Deprotonationinducedassemblyofbulkysilanetriols;KristijanKrekić........................................6ComputationalstudyofthesubstratespecificityofmonoamineoxidaseB;AleksandraMaršavelski.................................................................................................................................................................7Thefirstcrystalstructureofplantaminoacyl-tRNAsynthetase:seryl-tRNAsynthetasefromArabidopsisthaliana;IvanaKekez....................................................................................................................8RNA-bindingpropertiesofthearchaealSm-likeproteinfromHaloarculamarismortui;NataliaLekontseva..................................................................................................................................................9Polymorphismofnoveldoublecomplexsalt[CoC2O4(NH3)4][Fe(C2O4)2(OH2)2]∙2H2O;AlenBjelopetrović............................................................................................................................................................10Diffractioneffectsofnanostructuredaluminumoxides;DmitriyA.Yatsenko............................11LithiumlocalisationandquantificationbyquantitativeelectrondiffractiontomographyinnewAVPO4F(A=Li,K)cathodematerialsforhighpowerrechargeablebatteries;OlesiaKarakulina.................................................................................................................................................................12ExploitingIRMOF-9porosityasnanoconfinedenvironmentforthesynthesisofSi,TiandZroxideaggregates;StefanoCanossa.................................................................................................................13BacteroidesthetaiotaomicrondipeptidylpeptidaseIIIcomplexeswithsyntheticsubstrates;MarkoTomin............................................................................................................................................................14Theactivesitestructureofmanganese-containingBrassicarapaauxin-amidohydrolaseBrILL2;MarinaGrabarBranilović..................................................................................................................15HybridPerovskiteSolarCells:Activelayerdepositionmethodsandparameterinfluences;Andrei-GabrielTomulescu.................................................................................................................................16Structurefeaturesof(R0.95Bi0.05)Fe3(BO3)4(R=Gd,Y)singlecrystalsinthetemperaturerange30–295K;EkaterinaSmirnova...........................................................................................................17AnewroutetoNaOsO3post-perovskite;SephiraRiva..........................................................................18


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Synthesesandcrystallographicalstudyof2-acetylpyridine-aminoguanidineanditscopper(II)complexes;MirjanaM.Radanović............................................................................................19StructuralstudiesofdipeptidylpeptidaseIIIfromCaldithrixabyssi;IgorSabljić.....................20CocrystalstructuressosimilarevenRietveldisconfused;VeronikaSladkova..........................21Synthesis,characterizationandcrystalstructuresof2-benzothiazolylhydrazones;RobertKatava..........................................................................................................................................................................22Synchrotronpowderdiffractionmethods;R.Svetogorov....................................................................23Photocatalyticallyactivetitaniathinfilmsandpowders;BoštjanŽener......................................24CrystalPackingofAgomelatineinItsVariousSolidForms;EliškaSkořepová...........................25Versatilecoordinationbehaviorof2,6-diacetylpyridinebis(S-methylisothiosemicarbazone)intransitionmetalcomplexes;MarkoV.Rodić.........................................................................................26Cocrystalscreeningoftrospiumchloridebasedonshapeandpolarsurfaceofparticipatingcomponents;MartinBabor................................................................................................................................27Rutheniumcomplexeswithphosphineligands;MatijaUršič.............................................................283-pyrrolinehydrates:insitucrystallizationandstructuralinvestigations;PatrykRzepiński........................................................................................................................................................................................29Crystallographicstudyofcyclohexanohemicucurbit[n]urilsandtheircomplexes;SandraKaabel..........................................................................................................................................................................30Transferabilityofselectedsupramolecularsynthonsfromorganictometal-organicsystems;MladenBorovina.................................................................................................................................31Theoximemoietyinmetal-organicsystems:Thecadmium(II)studycase;IvanKodrin......32Structuralandstabilitystudiesofsodiumformatemonoperhydrate;NorahS.Alsaiari.......33Theinvestigationofbondingandnon-bondinginteractionsinflatlandmetalcomplexes;FatimahAlqahtani.................................................................................................................................................34X-raymicrostructuralcharacterizationofgelatin/hydroxyapatitescaffoldsforosteochondraldefectrepair;StellaGraziaPastore.................................................................................35CombinedX-rayPowderDiffractionDataandQuantum-ChemicalCalculationsinEXPO2014;FlavioFanelli...................................................................................................................................36HighcapacityLi-richcathodematerials;RongHao................................................................................37UsingtheCambridgeStructuralDatabase(CSD)forEducation;CarolineJ.E.Davies..............38DevelopmentofroomtemperatureserialcrystallographyatESRF,ID13;AnastasyaShilova........................................................................................................................................................................................39Polarizationofthetransferredelectrondensityofaprotein-ligandcomplextowardimprovingenthalpycalculationsbasedonmultipolarelectrostatics;ThéoLeduc...................40PurinenucleosidephosphorylasefrombacteriumHelicobacterpylori:Cloning,Expression,PurificationandCrystallisation;KarolinaGucunski...............................................................................41MgAl2O4nanoparticlesfromthermaldecompositionofmetal-triethanolaminecomplexes:theeffectofcalcinationtemperaturesandsamariumcontentonluminescencecharacteristic;WorawatWattanathana.......................................................................................................42


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Spectroscopic,thermogravimetricandx-raystudyofcopperandcobaltcomplexeswith2-pyrazinecarboxylicacid;GrzegorzŚwiderski............................................................................................43Spectroscopic,X-rayandthermogravimetricstudyofzinc2-pyrazinecarboxylate;RenataŚwisłocka...................................................................................................................................................................44Thecrystalstructureofcalciumcomplexof2,5-dihydroxybenzoicacid(gentisicacid):synthesis,XRD,XRDP,spectroscopic(IR,Raman,NMR)andbiologicalstudies;MonikaKalinowska................................................................................................................................................................45Spectroscopicandcrystallographicstudyofselectedphenoliccompounds;WłodzimierzLewandowski...........................................................................................................................................................46Interplaybetweenstructure,microstructureandmagneticpropertiesoftheCoMn2O4spinelmaterial;MartinaVrankić.....................................................................................................................47Tavorite-typematerialsatthepositiveelectrodeofLithium-ionbatteries;EdouardBoivin........................................................................................................................................................................................48Coordination-modulationassistedstepwiseliquidphaseepitaxialgrowthsofmetal-organicframeworkthin-filmsonquartzcrystalmicrobalance(QCM)substrates;SuttipongWannapaiboon........................................................................................................................................................49Crystalandmolecularstructuresofcrystalformsofmemantiniumhydrogenmaleate;MihaelaTuksar........................................................................................................................................................50AdvancesinimagingofsmallvirusparticlesatanX-raylaser;BenediktJ.Daurer................51Metal-HydrideOrganicFrameworks:synthesisandstructure;SanjaBurazer.........................52RacematesandOpticalActivity;RomainGautier....................................................................................53Studyingtheroleofdefectsinlepidocrocitenanorods;YuliaTrushkina.....................................54Forcefieldpredictionofareversaltransitioninmolecularcrystals;BrahimiKhadidja........55RietveldrefinementofXRD-CTdata;DorotaMatras.............................................................................56Formationofporouscoordinationpolymersusingzinc-nitrileinteraction;SalimgereyAdilov..........................................................................................................................................................................57Theuseofsupramolecularchemistryconceptstodesignandassemblenovelmoleculararrangements;RolaAlaeq..................................................................................................................................58SupermolecularinteractionofManganeseSchiffbasecomplexes;MonaS.Binkadem.........59Canwepredictthejumpingofcrystals?Thecaseofoxitropiumsalts;LidijaAndrošDubraja........................................................................................................................................................................................60Theroleofaminoacidsassimplemodelsoforganicmatrixmoleculesparticipatingincalciumcarbonatebiomineralization;LaraŠtajner................................................................................61Theinfluenceoffluorinatedphosphine’son[XAuPR3]structures;ArijAddaraidi...................62SpatiallyresolvedX-raydiffractionofMosobamboorevealstissue-specificmicrofibrilangledistribution;PatrikAhvenainen..........................................................................................................63

3DGrainmappingforcontinuousneutronsources;M.Raventos…………………………………..64HighPressureX-RayDiffractionoftheParamagneticCompoundUPd2Sn;DanielAntonio..65BinaryandTernaryCu(II),Mn(II),VO(II)andFe(III)ComplexesofDoxycylinewith


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PolypyridylLigands:Synthesis,CharacterizationandBiologicalApplications;OlufunsoO.Abosede......................................................................................................................................................................66


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EffectofstructuralandmicrostructuralfeaturesontheperformanceofCoMn2O4asanodematerialinlithiumionbatteriesM.Bijelic1,J.Popović2,XiangLiu3,A.B.Djurišić3,A.M.C.Ng3,4,X.Liu3,Q.Sun3,M.H.Xie3,C.Suchomski5,Ž.Skoko11PhysicsDepartment,FacultyofScience,Bijeničkac.32,Zagreb,Croatia,[email protected],RuđerBoškovićInstitute,Bijeničkac.54,Zagreb,Croatia3DepartmentofPhysics,UniversityofHongKong,PokfulamRoad,HongKong4DepartmentofPhysics,SouthUniversityofScienceandTechnologyofChina,Shenzhen,China5InstituteofNanotechnology,KarlsruheInstituteofTechnology,Leopoldshafen,Germany

Cobalt-dimanganate samples were prepared by the precipitation route at RT. Additionally,samples were thermally treated at T=300-500 °C. Structural investigation using XRPD andRaman spectroscopy have been carried out in order to correlate specific structural features

with preparation conditions and furthermorewithelectrochemical properties. Changes in unit-cell asfunctionof temperaturewere calculated; observeddecrease is inconsistent with simple spinel-typeexchange of Co2+ by Mn3+ on the tetrahedral site,andviceversaontheoctahedralsite.Basedonthe

Raman spectroscopy an alternativestructural model: IV[Co2+1-xMn2+x]VI[Co3+xMn3+2-x]O4 has beenproposed. Rietveld refinement showedincrease of M-O distances withintetrahedra, caused by thermally enhancedsubstitution of Co2+by larger Mn2+ cationsat A-site. Consequently, octahedral B-sitebecomes partially occupied by Co3+on theaccountofthetransferredMncations.In all samples, initial capacity drops ascommonlyobserved inhighcapacitymetaloxide materials. However, after a certainnumber of cycles specific capacity increasesagain. Among all samples, thermally treatedfrom 100-500 oC, highest specific capacitiesare observed for sample thermally treated athighesttemperature(500oC)despiteitslargeparticle size. Thus, contrary to the commonassumptionthatnanostructuringoftheanodematerial improves the battery performance,sampleswiththelargestparticlesizesexhibitexcellentperformancewithacapacityretentionof104%after1000cycles(comparedtothe2ndcycle)1.1.M.Bijelić,X,Liu,Q.Sun,A.Djurišić,M.iXie,A.M.C.Ng,C.Suchomski,I.Djerdj,Ž.Skoko&J.Popović,LongcyclelifeofCoMn2O4lithiumionbatteryanodeswithhighcrystallinityJ.Mater.Chem.A,2015,3,14759

S1 S2

S3 S4

S4


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Onemolecule,fourcolours:remarkablebehaviourof2,3-thieno(bis)imidebasedmoleculewhichpresentsfourdifferentpolymorphswithdramaticdifferentemissions

ChiaraCappuccino1,LuciaMaini2,ManuelaMelucci31DepartmentofChemistry,MolecularEngineeringgroup,UniversityofBologna,viaSelmi2,Bologna,Italy;E-mail:[email protected],MolecularEngineeringgroup,UniversityofBologna,viaSelmi2,Bologna,Italy3ConsiglioNazionaledelleRicerche,ISOF,viaPieroGobetti101,Bologna,Italy2,3-Thieno(bis)imide (TBI)basedmaterialsareemergingasvaluablemolecularmaterials forapplication in organic electronics thanks to their ambipolar charge transport propertiescombinedtotunableelectroluminescence.Thisnewclassofmaterialsisbeingtestedasactivelayerinthinfilmsorganicdevices,suchasambipolarlightemittingtransistors(OLETs),field-effecttransistors(OFETs)andbothasdonorandacceptorsinphotovoltaiccells(OPV).These molecules often present different crystalline modifications which show differentphotophisycal properties. One of thesemolecules, namedNTA1, shows a strong tendency toform different polymorphs. Until now we have observed at least four different crystallinephases, each one characterized by a particular colour, emission under UV light and crystalsmorphology(Figure1).FormIIandFormIIIshowsgreenandredemissionrespectivelyandtheirstructurewasdeterminedbysinglecrystalx-raysdiffraction.FormIandformIVshowsyellowandorangeemission,andtheirpowderpatternareclearlydifferentformthepreviousform.PhasetransitionfromIàIVhasbeenobservedinvariabletemperatureXRPDcollectedatPSI. Themain interaction that drives the crystallization of Form II and III is thep-stackingbetweenthearomaticcoresofthemolecules,formingchannelspossiblysuitableforthechargetransport.The formIIIseemstobe themostappropriate for thecharge transportdue to thepackingofthemoleculesthatformcolumnarstacklinkedtogetherthroughp-pinteraction.The thermal behaviour was also investigated with hot-stage microscopy and DSC; it wasobserved that the forms I, II and III, obtainedbydifferent typesof crystallization, convert informIVuponthermalannealing;thesolid-statetransitionisclearlyvisibleduetoavariationinthecoloroftheemissionunderUVlight.

Figure1:schemeofpolymorphismofNTA

1M.Zambianchi,L.Favaretto,M.Durso,C.Bettini,A.Zanelli,I.Manet,M.Gazzano,L.Maini,D.Gentili,S.Toffanin,F.Gallino,M.Muccini,M.Cavallini,andM.Melucci,(2015).J.Mater.Chem.C.3,121.


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CrystalengineeringofnewcrystalformsofvenlafaxineFlorianaSpinelli,1DarioBraga,1FabriziaGrepioni,1LauraChelazzi,2M.R.Chierotti3andElenaDichiarante41DipartimentodiChimica“G.Ciamician”,UniversitàdiBologna,ViaSelmi2,40126,Bologna,Italy;E-mail:[email protected]“UgoSchiff”,UniversitàdiFirenze,ViadellaLastruccia3,50019,SestoFiorentino(FI),Italy3DipartimentodiChimica,UniversitàdiTorino,ViaP.Giuria5,10125,Torino,Italy4PolyCrystalLine,ViaF.S.Fabri,127/1,40059,Medicina(BO),ItalySolid state chemistry and powder diffractionmethods have been attracting the attention ofmanyresearchersandindustriesinthepharmaceuticalfield, inwhichtheaspectofdiscoveryanddevelopment of new solid forms ofAPIs is particularly important. Co-crystallization canprovide a different strategy to obtain new active pharmaceutical ingredients by altering thechemical and physical properties (solubility, dissolution rate, thermal stability, etc) ofmolecularsolidformswithoutalteringthechemicalentityoftheAPI.The goal of this project has been the preparation of multicomponent crystals, in our casemolecular salts, between the antidepressant venlafaxine and Pharmacopeia accepted acids,their solid-state characterization by X-ray diffraction methods, and the optimization of thesolid-stateproductsfortabletinganddissolutionpropertiesanalysis.Themechanochemicalaswellasthesolutionreactionbetweenvenlafaxineandoxalic,fumaric,coumaric,ferulicandsalicylicacidsleadstoprotonationoftheaminogroupandformationofthecorresponding1:1molecularsalts.Theuseofmechanochemistryisanattractiveroute1toproducenewcrystalformsofAPIs,whichmayhelpinreducingproblemsrelatedtotheuseoflargeamountsofsolvents.2In the solid state chemistry there are often problems due to: i) crystallization ofmulticomponent crystals, ii) products obtained by mechanochemistry. In cases in whichsuitablecrystalsforsinglecrystalX-raydiffractionarenotobtained,powderdiffractionismorethanasimplefinger-printcharacterizationtechnique,butcanrepresentthesolutionforthesekindofproblems.

Figure1.Crystalstructureoftheantidepressantvenlafaxine.

1JamesS.L.,AdamsC.J.,BolmC.,BragaD.,CollierP.,FriscicT.,GrepioniF.,HarrisK.D.M.,HyettG.,JonesW.,KrebsA.,MackJ.,MainiL.,OrpenA.G.,ParkinI.P.,ShearouseW.C.,SteedJ.W.AndWaddellD.C.(2012).Chem.Soc.Rev.41,413-447.2BragaD.,MainiL.,GrepioniF.(2013).Chem.Soc.Rev.42,7638-7648.


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OptimizingphysicochemicalpropertiesofanaturalantioxidantandgeroprotectorL-carnosineOleksiiShemchuk,1FabriziaGrepioni,1TeresaDuarte211DepartmentofChemistry,MolecularEngineeringgroup,UniversityofBologna,viaSelmi2,Bologna,Italy;E-mail:[email protected]−CentrodeQuímicaEstrutural,InstitutoSuperiorTecnico,UniversidadedeLisboa,1049-001Lisboa,PortugalThe issue of “Healthy Ageing” has become a significant challenge because of the continuouspopulation ageing, and increasing life expectancy is accompanied by a higher danger ofdevelopment of age-associated diseases. For this reason, the increasing interest in naturalantioxidants is not surprising. The antioxidant L-carnosine, a dipeptide of amino acids β-alanineandL-histidine,isbeinginvestigatedforitspropertiesasgeroprotector,asitseemstohaveaneffectinreducingtheriskofdevelopmentofageing-relateddiseases.Nowadaysdesign,formulation and characterization of multiple crystal forms (salts, co-crystals, solvates andpolymorphs) are widely studied areas in the broad field of crystal engineering, as multiplecrystal forms of molecules of pharmaceutical interest represent a way to modify/improvephysicochemical properties and to satisfy the criteria of patentability, i.e. novelty,nonobviousnessandutility.

NH

O

OHO

H2N

NHN

NHN

NH

O

OO

NH3+

Fig. 3.1.3 L-carnosine: zwitter-ionic form

L-carnosine(left)anditszwitterionicform(right)

Arangeoforganicacidswere testedaspossibleco-formers in thereactionwithL-carnosine.NinenewmolecularsaltswerethuspreparedbyreactionwithGRASorganicacids.Obtainingthemolecular salts in a crystalline form turned out to be quite a challenge; theywere thencharacterizedviabothdiffractionandthermalmethods.Thestructuresof6of themcouldbedeterminedbyusingX-rayPowderDiffraction(XRPD).


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Improvementofmodelqualitybyrejectionofnon-ismorphousframesusingCC1/2andthedataprocessinguserinterfaceXDSGUIGretaAssmann1, Wolfgang Brehm1, and Kay Diederichs11 Department of Biology, University of Konstanz, Universitätsstr. 10, 78464 Konstanz;Germany [email protected] XDSGUI isa lightweightGUI(graphicaluser interface) forXDSthatsupportsbothnoviceandexperienced users to obtain high-quality data processing results. The program enables XDSdataprocessingwithoutthecommand-lineandsuppliesadditionalgraphicalinformation,inauser-modifiableway. Graphical evaluationwith XDSGUI of SBDG reference data sets (SNX17FERMdomain,5partialmergeddata sets)1demonstrates that applying the𝛥𝐶𝐶# $method2tosingleframesofonedataseteasilydetectssinglenon-isomorphousframes,whichcanoccurbecauseofradiationdamageorexperimentalsetuprelatederrors,e.g.Rejectionofthesenon-isomorphous frames for every partial data set and reprocessing with XDSGUI and XSCALEshowedimproveddatastatisticssuchasincreasedCC1/23,andincreasedinternalcorrelationofthe merged data sets. Moreover, comparison with the previously published model4 by thecorrelation coefficient of calculated (Fcalc2) and observed intensities (Fobs2) showed animprovedcorrelationafterrejectionoftheidentifiednon-isomorphousframes.CC1/2thereforecorrectlypredictsnon-isomorphismandtheagreementofdataandmodel.1MeyerP.A.etal.(2016).Nat.Commun.7,10882.2Assmann G.,Brehm W., Diederichs K. (2016). J.Appl.Cryst. 49, 1021-1028.3 Karplus P. A. , Diederichs K. (2012). Science 336, 1030-1.0334Stiegler A. L., Zhang R., Liu W., Boggon T. J. (2014). J.Biol.Chem. 289, 25362-25373.


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DeprotonationinducedassemblyofbulkysilanetriolsKristijanKrekić,1DanielČasandRudolfPietschnig1InstitutfürChemieundCINSaT,UniversitätKassel,HeinrichPlett-Straße40,34132Kassel,Deutschland;E-mail:[email protected] formation and structural characterization of the first dilithium salt of atetrahydroxydisiloxane, [DmpSi(OH)OLi]2O (3), was recently reported (Dmp = 2,6-dimesitylphenyl).1Thesolidstatestructurerevealsthepresenceofadimericmotifwheretwodisiloxaneunitsare linkedby coordinating lithiumatomswhichdiffers from those found forthe sodium1 (4) andpotassium4analogs.Thearrangement imposedby the cluster formationleads to diastereomeric silicon atoms exhibiting (R,S) configuration in the solid state. Inaddition, the intermediatesofthereaction,monolithiatedanddilithiatedsilanetriolscouldbeidentified.

Thehydrogenbondacceptorguidedself-assemblyofsilanetriolswith4,4’-bipyridineleadstoinfinitecolumnsofcofaciallyarrangedπ-stacksasevidencedbyX-raydata.2Variationofthesilanetriol (DMP or t-Bu) reveals a subtle balance between hydrogen bonding and π-interactionswhichbyproper choiceof the substituentmay foster eitherdominanthydrogenbondingordominantπ-interaction.

The authorswould like to thank the PhD networks SHINE (EU-ITN) and FreCheMaterie(AustrianBMWF)forfinancialsupport.WealsoaregratefultotheEU-COSTnetworkCM1302“SmartInorganicPolymers”(SIPs).

OH

SiR OH

OH

OH

SiDMP O

OH

Si

OH

OH

DMP

OLi

SiDMP O

OH

Si

OH

OLi

DMP

OH

SiDMP O

OH

Si

ONa

OH

DMP

NaOHn-BuLi

BPY

OH

SiR OH

OH

NN

1

2

3 4

5

THF

n-BuLi

THF, -78 °C

Figure1.Preparationof3,4and5.

1Čas,D.,Hurkes,N.,Spirk,S.,Belaj,F.,Bruhn,C.,Rechberger,G.N.&Pietschnig,R.(2015).DaltonTrans.44,12818.2Krekić,K.,Hurkes,N.,Bruhn,C.,Belaj,F.&Pietschnig,R.(2016).Z.Anorg.Allg.Chem.642,302.3Pietschnig,R.Merz,K.(2004),Organometallics,23,1373.


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ComputationalstudyofthesubstratespecificityofmonoamineoxidaseBAleksandraMaršavelski,1RobertVianello11ComputationalOrganicChemistryandBiochemistryGroup,RuđerBoškovićInstitute,Bijeničkacesta54,HR-10000Zagreb,Croatia;E-mail:[email protected] plays an important role in the human body and is involved inmore than twentydifferentphysiologicalprocesses.Duetohistaminepotentphysiologicalactivity,itsdegradationhas to be carefully regulated to avoid adverse reactions. The major routes of histamineinactivation inmammals includemonoamineoxidaseB (MAOB) anddiamineoxidase (DAO)enzymes. The fact that MAO B metabolizes only N-methylhistamine while DAO prefershistamine1-2,pinpointstheirremarkableselectivitytowardstwocompoundsthatdifferonlyinonemethyl group. Themechanismof enzyme catalysis and specificity are usually elucidatedfromthedifferencesinmechanisticaspectsofenzymaticreactionsforeachpossiblesubstrate,which provide unambiguous quantitative information about the thermodynamics and thekineticsofreactionpathways.Unfortunately,mechanisticstudiesarenotalwaysexperimentallyapproachable.Therefore,weutilizeda combinationofmoleculardynamics (MD)simulations,MM-PBSA binding free energy calculations and quantum mechanical cluster approach toaddresssubstratespecificityandmechanismofMAOBcatalysis.Wehaveidentifiedfavourablehydrophobic interactions betweenmethyl group of theN-methylhistamine substrate and thehydrophobicsidechainsoftheenzymebindingsitethatkeepsubstrateanchoredandproperlyoriented for theenzymaticreaction.Sincehistamine isdeprivedofmethylgroup itcannotbeproperly anchored and rotates within the active site, which results in non-productiveorientationforthereaction.Quantum-chemicalmechanisticanalysiswithintheclustermodelof the enzyme revealed higher activation parameters for histamine relative to its N-methylcounterpart,thusaidinginrationalizingthementionedselectivity.Inspectionofthecalculatedfree-energy profiles (Figure 1.) convincingly shows that MAO B selectivity for the N-methylhistamineoverhistamine isaresultof twosynergisticeffects: loweractivationbarrierandmorefavourablereactionthermodynamics.Moreover,reactionpathwayobtainedfromQMcalculationsisconsistentwithrecentlyproposedhydridemechanismofMAOBmechanismofcatalysis3-4.

Figure1.Free-energyprofilesfortheMAOBcatalyzeddegradationofN-methylhistamine(left)andhistamine(right)1Edmondson,D.E.,Binda,C.,Wang,J.,Upadhyay,A.K.&Mattevi,A.(2009).Biochemistry.48,4220.2Ochiai,Y.,Itoh,K.,Sakurai,E.,Adachi,M.&Tanaka,Y.(2006).BiolPharmBull.29,2362.3Vianello,R.,Repic,M.&Mavri,J.(2012)EurJOrgChem.2012,7057.4Repic,M.,Vianello,R.,Purg,M.,Duarte,F.,Bauer,P.,Kamerlin,S.C.L.&Mavri,J.(2014).Proteins.82,3347.


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Thefirstcrystalstructureofplantaminoacyl-tRNAsynthetase:seryl-tRNAsynthetasefromArabidopsisthalianaIvanaKekez1,KekezMario2,Gruić-SovuljIta2,Rokov-PlavecJasmina2,Matković-ČalogovićDubravka11DivisionofGeneralandInorganicChemistry,DepartmentofChemistry,FacultyofScience,UniversityofZagreb,Horvatovac102a,Zagreb,Croatia;E-mail:[email protected],DepartmentofChemistry,FacultyofScience,UniversityofZagreb,Horvatovac102a,Zagreb

Seryl-tRNAsynthetase(SerRS)playsanessentialroleinthetranslationprocessbycovalentattachment of serine to its cognate tRNASer. Most SerRS enzymes belong to the so calledbacterialtypethatisfoundinmostarchea,bacteriaandeukaryotes.Asmallnumberofenzymesfound in methanogenic archea show structural and mechanistic differences and can beclassified as methanogenic type1. Moreover higher eukaryotic SerRS, like human SerRS,possesses two types of additional insertions: Insertion I (G75-N97) and Insertion II (K253-N261)locatedinthetRNAbindingdomainandinthecatalyticcore,respectively2.Untilnowthecrystal structure of human SerRS, as well as of several prokaryotic systems and lowereukaryotes,havebeenstudiedbyX-raycrystallographywhilenocrystallographicstructureofanyplantSerRSisknowntodate.

In order to clarify the structural and functional properties of plant SerRS (pSerRS) weperformed cloning, purification, crystallization and X-ray analysis. Plate-like crystals wereprepared by the sitting drop vapor diffusion method using an automated crystallizationplatform(Oryx8robot).DiffractiondataweremeasuredattheXRD1beamline(Elettra,Trieste,Italy)andwerecollectedtotheresolutionof2.8Å.ThecrystalsbelongtothemonoclinicspacegroupC2. The structure of pSerRS was solved by the molecular replacement method whilefurthermodelbuildingandrefinementisinprogress.1Bilokapić,S.,Maier,T.,Ahel,D.,Gruić-Sovulj,I.,Söll,D.,Weygand-Đurašević,I.&Ban,N.(2006).EMBOJ.25,2498-2509.2Xiaoling,X.,Yi,S.&Xiang-Lei,Y.(2013).Structure.21,2078-2086.


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RNA-bindingpropertiesofthearchaealSm-likeproteinfromHaloarculamarismortuiNataliaLekontseva,EkaterinaNikonova,AlisaMikhaylina,VitalyBalobanov,MariaNemchinova,SvetlanaTishchenkoandAlexeyNikulinInstituteofProteinResearchRAS,Pushchino,Russia;E-mail:natalja-lekontseva@rambler.ruTheSmandSm-likeproteinsarewidelydistributedamongbacteria,archaeaandeukarya.TheyaredefinedbytheabilitytoadopttheSmfold,whichiscomprisedofa5-strandedβ-sheetandanN-terminalα-helix.TheyareparticipatedinmanyprocessesconnectedwithRNA-processingor regulation of gene expression. Bacterial Lsm protein Hfq act as an RNA chaperone tofacilitate interaction between regulatory RNA and mRNA, eukaryotic Sm/Lsm proteins aremainly scaffold proteins of spliceosomes and telomerases, but the role of Lsm proteins inarchaeaisexploredpoorly.Inourwork,theRNA-bindingabilityofarchaealSm-likeproteinfromHaloarculamarismortuihasbeenstudiedbyX-raycrystallographyandbyfluorescentmeasurements.Earlierwehavedemonstratedthatitispossibletodeterminesingle-strandedRNA-bindingsitesontheproteinsurface using a soaking procedure followed by structure determination of the obtainednucleotide–proteincomplexes1.The SmAPH.marismortuiprotein was isolated and purified. Crystals of the protein and itscomplexeswithribonucleotideswereobtained.Usingourcrystallographicapproach,wehavedetermined potential single-stranded RNA-binding sites on the protein surface. In addition,AMPaffinitytotheproteinhasbeendeterminedbymeasuringoffluorescencechangesduringtitrationoftheAMP-MANTsolutionbytheprotein.ThisworkwassupportedbyRussianScientificFoundation(project14-14-00496).1Murina,V.N.,Lekontseva,N.V.,Nikulin,A.D.(2013).ActaCryst.D69,1504-1513.


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Polymorphismofnoveldoublecomplexsalt[CoC2O4(NH3)4][Fe(C2O4)2(OH2)2]∙2H2OAlenBjelopetrović,KristianNakić,MirtaRubčić,MarinaCindrićUniversityofZagreb,FacultyofScience,[email protected] Doublecomplexsaltsareclassofchemicalcompoundsinwhichbothcationandanionarecomplexeswiththeirownelectriccharge.Oneofmanyapplicationsofthesecompoundsisasprecursorsinpreparationofvariousbimetallicoxideswhichcanbeusedascatalizatorsduetotheir distinctive structures and properties.1 It has been known that their thermaldecomposition,whichcanbeaccompaniedwithreduction, results inhomogenousmixtureofmetalsand/ortheiroxides.2

Novel double complex salt described with formula [CoC2O4(NH3)4][Fe(C2O4)2(OH2)2] ∙2H2Owaspreparedbyreactionof[CoC2O4(NH3)4]NO3∙H2OwithK3[Fe(C2O4)3]∙3H2Oundervarious reaction conditions,molar ratios and concentrations of reactants. Depending on thereactionconditions,itwaspossibletoisolatetwopolymorphs.Molecularandcrystalstructureof both polymorphswas determined using single-crystal X-ray diffraction. Both polymorphswere further characterizedbymeansof IR-spectroscopy, thermal analysis andpowderX-raydiffractionmethod.1S. Parres-Esclapez, M. J. Illan-Gomez, C. Salinas-Martinez de Lecea, and A. Bueno-Lopez, Appl. Catalysis B:Environmental,96,(2010);370-378.2S. V. Komogortsev, R. S. Iskhakov, A. A. Zimin, E. Yu. Filatov, S. V. Korenev, Yu. V. Shubin,N. A. Chizhik, G. Yu.Yurkin,andE.V.Eremin,AppliedPhysicsLetters103,(2013)152404.


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DiffractioneffectsofnanostructuredaluminumoxidesDmitriyA.Yatsenko1,2andSergeyV.Tsybulya1,21NovosibirskStateUniversity,PirogovaStreet2,630090Novosibirsk,Russia;E-mail:[email protected],SBRAS,Pr.Lavrentieva5,630090Novosibirsk,Russia

Nanocrystalline materials are of considerable interest because particle morphology to

affectphysicochemicalproperties.Investigationoftherelationshipbetweenproperties,atomicstructureandnanostructureofmaterialsisanactualproblem.

So various nanostructures of aluminum oxides can be obtained depending on thepreparation conditions. The difference betweenmorphology of the structures is revealed bymicroscopyanddiffractioninvestigations[1].Thiscanappearasanisotropicbroadeningofthediffractionpeaks,redistributionoftheintensitiesorappearanceofdiffusescattering.

Interpretation of nanostructures involves identifying specific shape/size of primarynanocrystallitesandidentificationtheirtypeofcoherentordering.Theobjectiveofthisworkistheillustrationofpossibilitiesofthediffractionmethodforresearchofnanostructuredsystems.

ThemethodbasedontheDebyeequation[2]isknownintheliteratureasDebyeFunctionAnalysis (DFA) [3]. It is full-profile method which is applicable for any an arbitrary atomscollection,andthereforecanbeusedforcrystallinematerialsornano-structuredobjects.Forthispurposestheapproachesaredevelopedbasedonpreviouslysubmittedprogram[4]. It ispublic-domainsoftwareandavailableonthewebsite:www.sourceforge.net/projects/dianna.

ThisworkissupportedbyRussianScienceFoundationprojectN14-23-00037.

1Tsybulya,S.V.&Kryukova,G.N.(2008).Phys.Rev.77,024112.2Debye,P.(1915).ZerstreuungvonRöntgenstrahlen.AnnalenderPhysik,351,ZerstreuungvonRöntgenstrahlen3Tsybulya,S.V.&Yatsenko,D.A.(2012).JournalofStructuralChemistry.53,S150-S165.4Yatsenko,D.A.&Tsybulya,S.V.(2012).BulletinoftheRussianAcademyofSciences:Physics.76,382-384.


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LithiumlocalisationandquantificationbyquantitativeelectrondiffractiontomographyinnewAVPO4F(A=Li,K)cathodematerialsforhighpowerrechargeablebatteries

OlesiaKarakulina1,StanislavFedotov2,NellieKhasanova2,EvgenyAntipov2,ArtemAbakumov1,2,3,JokeHadermann1;E-mail:[email protected],UniversityofAntwerp,Antwerp,Belgium;2DepartmentofChemistry,LomonosovMoscowStateUniversity,Moscow,Russia3SkoltechCenterforElectrochemicalEnergyStorage,SkolkovoInstituteofScienceandTechnology,Moscow,Russia

We synthesized new Li0.70K0.12VPO4F fluorophosphate using ion exchange. This methodallows obtaining Li cathode materials that are isostructural to Na or K analogues and thatcannotbeobtainedbydirectsynthesisduetothermodynamicreasons.Insuchstructures,thealkalimetal resides in the channels of the framework and canbe easily deintercalateduponchargethereafterLicanbeinsertedupondischarge.

The initial KVPO4F fluorophosphate has a KTiOPO4 type structure, with a 3D system ofcontinuousspatialcavitiesandtwopotassiumpositions[1].InordertoobtaintheLianalogue,potassiumisextractedbychargingupto5.0VvsLi/Li+.

Thecrystalstructurewasdeterminedbyselectedareaelectrondiffractionandquantitativeelectron diffraction tomography (EDT), which can obtain diffraction data from submicroncrystals (100-200nm). This allowedus to solve and refine the structure of the charged anddischargedmaterials,whereas bulk diffractionmethods are hindered by the presence of theobligatoryextraphases,suchascarbon,whichneededforafunctioningbattery.

Potassiumwasnotfullydeintercalated(17%left)anditremainsintheK2site,whereastheK1 site is not occupied. At the same time, the structure changes from noncentrosymmetric(Pna21)tocentrosymmetric(Pnan).

Afterlithiation,theK2siteissharedbyKandLibutK1siteisstillempty.LiisfoundinanewLi3positionthatwas locatedbytheuseofdifferenceFouriermapscalculatedfromEDTdata.ThisLi3has[4+2]coordinationwithfourshort1.99−2.14ÅLi3−Obonds.BothLisitesreside in the channels along the b axis, which results in a row of Li atomswith alternatingoccupancy.TheLi3position can accept only0.5Li and it is fully occupied.The rest 0.2Li ispresent in theK2site. It canbeconcluded thatLiprefers to reside in the sitewith thecloseoxygenenvironmentinsteadoftheK1andK2sitesthataresurroundedbyoxygenandfluorineata2.7-2.9Ådistance.

J.Hadermann,O.M.KarakulinaandA.M.AbakumovacknowledgesupportfromFWOundergrantG040116N.S.S.FedotovacknowledgessupportfromRFBR(grant16-33-00211mol_a).

1S.S.Fedotov,N.R.Khasanova,A.S.Samarin,O.A.Drozhzhin,D.Batuk,O.M.Karakulina,J.Hadermann,A.M.Abakumov,E.V.Antipov(2016),Chem.Mater.28,411.


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ExploitingIRMOF-9porosityasnanoconfinedenvironmentforthesynthesisofSi,TiandZroxideaggregatesStefanoCanossa,1PaoloPelagatti,1ClaudiaGraiff,1GiovanniPredieri,1andAlessiaBacchi11DepartmentofChemistry,UniversityofParma,ParcoAreaScienze17A,Parma,ItalyE-mail:[email protected] ordered porosity ofMetalOrganic Frameworks is commonly acknowledged as themostimportant feature inmaking these crystalline solids verypopular amongmanifold classes offunctionalmaterials.Theirusageas trappinghost towards several classesof guest species isindeedoften themain topic in the research field concerning their applications.Furthermore,thecrystallinityofthesesolidscaninprincipleallowstructuralinformationtobeacquiredonthesituationofthetrappedspecies,ifwithanydegreeoforder,bymeansofX-rayanalyses.Inthepresentresearch,IRMOF-91,aZincandbiphenyl-4,4’-dicarboxylatebasedMOF,hasbeenusedtotrapmolecularprecursorsforsilica,zirconiaandtitaniaparticles,theperspectivebeingto trigger the hydrolysis of precursor and synthesize the final material in a nanoconfinedenvironment.While the structural characterization of the guests and of their final productsseemedahard task toachievedue to the lossofashort-rangeorder, theirpresenceseemtoinfluencethebehaviouroftheMOFwithtemperaturechangings.Forexample,crystalssoakedinTiisopropoxydeandthenexposedtotheairforafewminutesseemtoretaintheirsymmetryandstructuralpropertiesaftercoolingitdownto100K,whereasspecimens soaked in tetraethyl orthosilicate (TEOS) exhibit, with the temperature drop, asymmetry breakage typical of the starting solid (Figure 1). This is reasonably due to theformation in the MOF cavities of a structured titania aggregate which prevent theconformationalfreedomofthecrystals.Furtherstudiesareneededtodefinethenatureofsuchphasesandtheirstructuralfeatures.

Figure 1. Different structural behaviour of the IRMOF-9 after soaking in two different liquidprecursors(TEOSandTiisopropoxyde),asobservedbycollectingthesinglecrystalXRDdataat100K.1Yaghi,O.M.,etal.(2002).Science.295,pp469-472.


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BacteroidesthetaiotaomicrondipeptidylpeptidaseIIIcomplexeswithsyntheticsubstratesMarkoTomin,1SanjaTomić,11RuđerBoškovićInstitute,Bijeničkacesta54,10000Zagreb;E-mail:[email protected] peptidase III isolated from Bacteroides thetaiotaomicron is a two-domain zincexopeptidase from the M49 family. Members of this family, characterized by HEXXGH andEEXR(K)AE(D)motifs,cleavedipeptidylresiduesfromtheN-terminusoftheirsubstrates.ThisconservedregioncontainstwoHisresiduesthatcoordinatetheZnionalongwithGlu449andGlu476. The BtDPP3 crystal structure1 shows two domains separated by a cleft, stronglyresemblingthehumanDPP3despitethelowsequenceidentity(~23%). In thisworkwe performed docking of synthetic substrates Arg-Arg-2-naphtylamide andLys-Ala-2-naphtylamide in thewild-typeDPPIIIand itsC450Smutant inordertounderstandenzyme-ligand interactions. The starting structures were prepared from the human DPPIII-RRNAcomplexusedinpreviousstudies2.Complexsimulationswereperformedoverthecourseof200nsusingff12sbandff14sbforcefields.Theseforcefieldswereselectedbasedontheirgood performance in conformational studies of both human and bacterial DPPIII. Specialemphasis has beenplaced on the zinc ion coordination flexibility, since the existing data forhumanDPP3suggeststhehighplasticityoftheZn2+coordination3. Ourresultsareinqualitativeagreementwithavailablekineticdata4andrepresentagoodstartingpointforfurtherQM/MMstudiesnecessarytoelucidatethemechanismofthebacterialDPPIII.

1.Sabljić,I.,internalcorrespondence2.Tomić,A.,Berynskyy,M.,Wade,R.C.,Tomić,S.(2015).Mol.BioSyst.,11,pp.3068-3080.3.Tomić,A.,Tomić,S.(2014).Daltontrans.,43,pp.15503-14.4.Vukelić,B.,Salopek-Sondi,B.,Špoljarić,J.,Sabljić,I.,Meštrović,N.,Agić,D.,Abramić,M.(2012).Biol.Chem.393,pp.37-46.


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Theactivesitestructureofmanganese-containingBrassicarapaauxin-amidohydrolaseBrILL2MarinaGrabarBranilovića,AnaSmolkob,FilipŠupljikac,BrankaSalopek-Sondib,IvoPiantanidac,andSanjaTomićaaRuđerBoškoivćInstitute,DivisionofPhysicalChemistry,Bijenička54,Zagreb,CroatiabRuđerBoškoivćInstitute,DivisionofMolecularBiology,Bijenička54,Zagreb,CroatiacRuđerBoškoivćInstitute,DivisionofOrganicChemistryandBiochemistry,Bijenička54,Zagreb,CroatiaAuxin-amidohydrolasefromBrassicarapa(Br),BrILL2,belongstotheM20Dmetallopeptidasesubfamily, related to the amidohydrolase superfamily (M20) of enzymes which hydrolyze anumber of different substrates, including amino acids, sugars, nucleic acids, andorganophosphateesters.1BrILL2iscatalyticallythemostefficientauxin-amidohydrolasefromBr,playingakeyroleinhomeostasisoftheplanthormoneauxininawaytohydrolasesaminoacidconjugates(AACs)ofauxins(IAA,IBA,IPA).Alargeconcentrationoffreeauxins,ofwhichthemostcommonisindole-3-aceticacid(IAA),istoxicforplants,soonlyabout5%ofthetotalconcentrationofauxinmoleculesinplantsisinthefree(active)form,whiletherestisstoredininactive forms,mostly as aminoacidand sugar conjugates.2 Inorder tohydrolyze theamidebond of amino acid conjugated auxins (inactive, storage forms), and release the free auxin,BrILLneedsmanganese.3Theaimofourresearchwastodeterminenumberofthemanganeseions,Mn2+,intheenzymeactivesite,andtheinfluenceofCystoSermutationsontheproteinstructure and activity. In order to fulfil this aim we conducted an interdisciplinary studycombiningdifferentexperimental andcomputational approaches:biochemical, spectroscopic,calorimetricandcomputational.1Seibert,C.M.,Raushel,F.M.(2005).Biochemistry,44,6383–6391.2Ludwig-Müller,J.(2011).JournalofExperimentalBotany,62(6),1757-1773.3Savić,B.,Tomić,S.,Magnus,V.,Gruden,K.,Barle,K.,Grenković,R.,Ludwig-Müller,J.,Salopek-Sondi,B.(2009).Plant&CellPhysiology,50(9),1587-1599.


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HybridPerovskiteSolarCells:ActivelayerdepositionmethodsandparameterinfluencesAndrei-GabrielTomulescu1,VioricaStancu1,CristinaBesleagaStan1,MarianSima1,Liliana-MarinelaTrinca1,GeorgeStan1,AurelianCatalinGalca1,LucianPintilie1andIoanaPintilie11NationalInstituteofMaterialsPhysics,Romania;E-mail:[email protected]

In this century the population of the world has risen by 21%. This coupled with the

increasing energy consummation per capita has determined an increase of green houseemissionscausedbyconventionalenergysources.Onesolutiontothisevergrowingproblemistheuseof environmentally friendly energy sources like solar cells.Research in this fieldhasbeengoingonformorethan35years,newtypesofphotovoltaicstructuresbeendevelopedinacontinuousefforttoimproveefficientlyandcost.

Hybridperovskitesolarcellsareatypeofphotovoltaicdevicesthathavegatheredalotofattentioninrecentyears,havingattainedamaximumefficiencyof20,8%inonly4years.1AnhalidehybridperovskitewiththegeneralformulaMPbX3(whereMisaorganicionandXisI,Br orCl) is the activematerial of thedevice. Its excellent light absorbingproperties and thepossibilityofsynthesisbywetchemistrymakesthistypeofmaterialveryinterestingforhighefficiency–lowcostsolutions.CH3NH3PbI3andCH3NH3PbI3-xClxarethemostusedperovskitesbecauseoftheirband-gapandelectron-holediffusionlengths2,aone-steportwo-stepmethodbeingemployedforthedepositionoftheactivelayer.3-5Thekeyparametersandvulnerabilitiesof each method will be discussed in this study, additional post and during depositiontreatmentsbeingalsoaddressed.Becauseofthedegradationofthistypeofsolarcellahighlightofthepossiblemechanisms,sitesandsolutionswillbeproduced.1Bi,D.,Tress,W.,Dar,M.I.,etal.(2016).SciAdv.2(1),pp.-2Stranks,S.D.,Eperon,G.E.,Grancini,G.,etal.(2013).Science.342(6156),pp.341-3443Zheng,L.,Zhang,D.,Ma,Y.,etal.(2015).DaltonTans.44(23),pp.10582-105934Im,J.H.,Kim,H.S.&Park,N.G.(2014).APLMat.2(8),pp.-5Zhao,Y.&Zhu,K.(2014).J.Phys.Chem.Lett.5(23),pp.4175-4186


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Structurefeaturesof(R0.95Bi0.05)Fe3(BO3)4(R=Gd,Y)singlecrystalsinthetemperaturerange30–295KEkaterinaSmirnova,1OlgaAlekseeva,1IgorVerin,1AlexanderDudka,1VladimirArtemov,1KirillFrolov,1IgorLyubutin11ShubnikovInstituteofCrystallography,RussianAcademyofSciences,Moscow,Russia;E-mail:[email protected]

Rare-earth iron borates RFe3(BO3)4 (R=Y, REE) attract considerable attention due to theirstructural and magnetic behavior.1 Iron borates reveal a cascade of phase transitions:structural,magnetic,spin-reorientation.2-5Varietyoftheirpropertiesiscausedbythepresenceoftwomagneticsubsystems:Feionsandrareearthions.ThemainstructurefeatureofthesecompoundsisthepresenceofhelicalchainsalongcaxisformedbyFeatoms.Structuralphasetransitions occur in some of them at 88–450 K reducing R32 symmetry to P3121. Manyquestionsconcerningthestructure-propertiesrelationshipsofRFe3(BO3)4arestillnotclarified.The low-temperature crystal structure, lattice parameters and atomic positions for manycrystalsofthisfamilyandalsothehigh-temperaturestructureforsomeofthemhasnotbeenstudiedyet.Inthepresentworkthestructuresof(R0.95Bi0.05)Fe3(BO3)4(R=Gd,Y)singlecrystalshavebeenstudied.TheBiatomsweredetectedinthestructuresbyenergy-dispersiveX-rayanalysis.Unitcell parameters have been measured over the 295–30 K range using the Huber-5042diffractometer equipped with point detector and a Displex DE-202 helium cryostat (APDCryogenics). With temperature decreasing the unit-cell parameters a and b ofGd0.95Bi0.05Fe3(BO3)4preservetheirvaluesuntilTstr=155Kandthenthevaluesreduceabruptlyindicating the structural transition R32→P3121. After that the values decrease withtemperaturedecreasingfrom155Kto30K.ThereisnophasetransitionforY0.95Bi0.05Fe3(BO3)4(P3121 sp.gr.) in this temperature range. The cparameterdecreases for both crystals from295K to 80K and then its value increases with a smooth decrease of a,b parameters andvolume. X-ray diffractionmeasurements at 293K, 90K and 30Kwere carried out using theXcalibur CCD (Rigaku Oxford Diffraction) with CryoJetHT (Oxford Instruments) open-flowcoolerandHuberdiffractometers.ThecalibrationoftheCryoJetHTcoolerwasperformed.Thecrystal structures have been refined using the JANA20066 and ASTRA7 programs. At roomtemperaturetheGd0.95Bi0.05Fe3(BO3)4crystalshaveR32sp.gr.,theY0.95Bi0.05Fe3(BO3)4–P3121sp.gr.At90Kand30KbothcompoundsbelongstoP3121sp.gr.ThereisonetypeofFeatomsinR32whereas there are two independent positions inP3121.Upon lowering the temperaturefrom 293 to 30 K the distortions of theR(Bi)O6, FeO6 и B(2)O3 coordination polyhedra areobserved forbothcrystals.TheFe1–Fe1distances in thehelicalchainsalongc axisdecrease,the Fe2–Fe2 distances increase, the angles Fe–O–Fe change nonuniformly. The shortestdistances between3 chains inab plane become reduced, themost distant distances expand.TheexistanceoftwoFecrystallographicpositionsmightleadtoemergenceoftwomagneticFepositions below theNeel temperature. The distortions in the crystal structure can affect themagneticproperties.ThestudywassupportedbytheRFBR(pr.no.14-02-00483)andpr.NSh-6617-2016-5.

1Vasiliev,A.N.&Popova,E.A.(2006).LowTemp.Phys.32,7352Levitin,R.Z.,Popova,E.A.,Chtsherbov,R.M.(2004).JETPLett.79(9),423–4263Fausti,D.,Nugroho,A.A.,vanLoosdrecht,P.H.M.(2006).Phys.Rev.74,0244034Kharlamova,S.A.,Ovchinnikov,S.G.,Balaev,A.D.(2005).JETPLett.101(6),1098–11055Rebbouh,L.,Desautels,R.D.,Ritter.C.(2011).Phys.Rev.83,1404066Petricek,V.,Dusek,M.&Palatinus,L.(2014).Z.Kristallogr.229(5),345–3527Dudka,A.(2007).J.Appl.Cryst.40,602–608.


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AnewroutetoNaOsO3post-perovskiteSephiraRiva,1WilsonA.Crichton,2andSerenaMargadonna11CollegeofEngineering,SwanseaUniversity,BayCampus,SA18EN,Swansea,UK2ESRF-TheEuropeanSynchrotron,71avenuedesMartyrs,Grenoble38000,FranceE-mail:[email protected]

The study of electronic and magnetic responses of 5d compounds is at the centre of aconsiderableresearcheffortduetotheirfascinatingpropertieswhichmakethemsuitableforspintronics and other advanced electronic technologies. In particular, several Na-Os oxidessystems(e.g.Na2OsO4,Na3OsO6,Na5OsO6)havebeenextensivelystudied,whileothers,suchasNaOsO3,havebeenonlybrieflydescribed.AllthesecompoundsbelongtotheKSbO3-typefamilyand combine certain structuralmotifs (cP, (Pn3) and (Im3) symmetries)withgreat chemicalvariability.Theyarethereforeidealtoexplorenewsyntheticprotocolsthatcanexploitchangesinoxidationstateandbulk chemistry toproducenovelphases.The recent identificationofaperovskite phase in NaOsO3 has generated quite some interest, as it displays a continuousmetal-insulator transition driven by 3D antiferromagnetic order. However, the synthesis israther complex and should cope with the requirements of increasing the oxidation state ofosmium from IV to V, avoiding the production of toxic OsO4 and being held in a generallyreducinghighpressureassembly.

In this work, the perovskite-phase (pv) of NaOsO3 wassynthesized under high-pressureand high-temperature. Theformationofpost-perovskitephase(ppv)hasbeen investigated insituusing large-volume multi-anvilpress installed at the ID06LVPbeam-line, ESRF. The pv to ppvtransitionoccursat16.35GPaand1135 K (see figure). Quenched to ambient conditions, the ppv’s lattice dimensions can beindexed and refined in the Cmcm space group with a = 2.8323(3), b = 10.6927(14), c =7.3345(7)ÅandV=222.12(4)Å3.

Twodifferentsyntheticrouteswereexplored.1Firstly,ppvNaOsO3wasproducedfromtheGdFeO3-type pv phase of NaOsO3, even though all the structural criteria commonly used topredict such a transition were not fulfilled (values of tilting angle, tolerance factor andpolyhedralvolumeratiowerewelloutsideestablishedboundaries).2Thesecondrouteincludesa production of the ppv phase from an assemblage which did not contain any perovskite-structured compound. Indeed, the growthof pv as a precursor or indicator to ppv appearedcounterproductive,requiringapressure10GPahighertoinitiatetransformation.

Thisworksuggests thatppvcanbeobtained inothercompoundsandchemistrieswheregeneralizedrulesbasedonpvmaynotapply,orwherenopv isknown.Rather,pvformationmayevenmaskandhinderotherlessextremechemicalpathwaystoppvphases.1Crichton,W.A.,Yusenko,K.V.,Riva,S.,Mazzali,F.&Margadonna,S.(2016).Inorg.Chem.Comm.-Submitted.2Bernal,F.B.,Yusenko,K.V.,Sottmann,J.,Drathen,C.,Guignard,J.,Løvvik,O.M.,Crichton,W.A.&Margadonna,S.(2014).Inorg.Chem.52,12205-12214.

6

Figure:TransitionfrompvtoppvinNaOsO3,occurringat1100Kand16GPawithrapidonset.Theppvphaseisquenchableandrecoverable.


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Synthesesandcrystallographicalstudyof2-acetylpyridine-aminoguanidineanditscopper(II)complexesMirjanaM.Radanović,LjiljanaS.Vojinović-Ješić,MarkoV.Rodić,VukadinM.LeovacFacultyofSciences,UniversityofNoviSad,TrgDositejaObradovića3,21000NoviSad,Serbia;E-mail:[email protected]

The survey of Schiff bases of non-substituted and substituted aminoguanidine inCambridgeStructuraldatabase1revealed77structureswith54differentcarbonylcompounds.However, the number of structurally characterized complexeswith these Schiff bases is stillsmall. Themostnumerous are complexes of copper(II)withpyridoxilidene aminoguanidine2andsalicylideneaminoguanidine.3

Having inmind the recognizedbiological importanceof aminoguanidine and its Schiffbasesaswellastheirinterestingcoordinationbehaviorwefounditimportanttoexaminethesynthesesandcharacteristicsofcopper(II)complexeswiththeSchiffbaseofaminoguanidineand2-acetylpyridine.

Dichlorideandsulfatesaltsoftheligand2-acetylpyridine-aminoguanidinewereisolatedin the formof single crystals, thus the first structural data on this ligand are described. Thereaction ofwarm aqueous solution of the appropriate Cu(II) salt andmethanolic solution ofdichloride ligand in molar ratio 1:1 resulted in formation of green single crystals of thecomplexes. Ligands and the complexes are characterized by IR spectra, conductometricmeasurements and X-ray analysis. In these complexes chelate ligand is coordinated in itsneutral form in a tridentate N3-coordination mode, via pyridine, azomethine and iminonitrogenofaminoguanidine fragment.Cu(II) issituated inamoderatelyorseverelydistortedsquare-pyramidal surroundings (the distortion from the ideal geometry is described by τ5parameter4).Thecompound[CuLCl2] (Fig.a)was isolated in twopolymorphic forms,both inmonoclinicsystemandP21/cspacegroup.However,theircrystalstructuresgreatlydiffer.Theasymmetric unit of the other complex (Fig. b) contains two [CuL(Cl)MeOH]+cations and twoNO3− anions arranged in a peculiar way so that [CuL(Cl)MeOH]NO3 subunits are pseudo-symmetrically related by non-crystallographic two-fold rotation axis. Common fragmentsencountered in the structures were compared by r.m.s. overlay calculations as well as half-normalprobabilityplots.

Fig.Molecularstructuresofthecomplexes[CuLCl2](a)and[CuL(Cl)MeOH]NO3(b).1Allen,F.H.(2002)ActaCrystallogr.,B58,380-388.2Lalović,M.M.,Vojinović-Ješić,Lj.S., Jovanović,Lj.S.,Leovac,V.M.,Češljević,V.I.,Divjaković,V. (2012)Inorg.Chim.Acta.388157-162.3Vojinović-Ješić,Lj.S.,Radanović,M.M.,Rodić,M.V.,Jovanović,Lj.S.,Češljević,V.I.,Joksović,M.D.(2014)Polyhedron8090-96.4Addison,A.W.,Rao,T.N.,Reedijk,J.,Rijn,J.,Verschoor,G.C.(1984).J.Chem.Soc.DaltonTrans.1349-1356.


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Figure1.HumanDPPIIIvs.CaDPPIII

StructuralstudiesofdipeptidylpeptidaseIIIfromCaldithrixabyssiIgorSabljić1,KarlGruber2,PeterMacheroux3,MarijaAbramić4andMarijaLuić11DivisionofPhysicalChemistry,RuđerBoškovićInstitute,Zagreb,Croatia;E-mail:[email protected],UniversityofGraz,Graz,Austria3InstituteofBiochemistry,GrazUniversityofTechnology,Graz,Austria4DivisionofOrganicChemistryandBiochemistry,RuđerBoškovićInstitute,Zagreb,CroatiaDipeptidylpeptidaseIII(DPPIII),azincpeptidaseoftheM49family,isacytosolicenzymewidelydistributedamongeukaryoticandprokaryoticorganisms.Currently,threecrystalstructuresareavailableintheproteindatabank(PDB):thehumanenzyme,freeandasacomplexwithtynorphin1,aswellasyeastenzyme2.Thebindingofinhibitorsinducesalargedomainmotionfromsocalledopentoclosedconformation.Uptonow,thereisnostructuralinformationonprokaryoticDPPIII.We have been studying DPP III from thebacterium Caldithrix abyssi (Ca), whichinhabits hydrothermal vents. The gene encoding CaDPPIII was heterologously expressed inEscherichia coli and the generated protein was purified using affinity and size exclusionchromatography. Using diverse crystallization screens, first crystals were obtained andcrystallisation conditionswere optimised. A datasetwas collected up to 2.3 Å at the ElettraSincrotroneTrieste, Italyatawavelength foranomalousscatteringof thezincatom(1.27Å).Unfortunately, scattering was too weak for the structure to be solved using the single-wavelengthanomalousdispersionofthezincatom.Also,alleffortstosolvethestructureusingmolecular replacementwere unsuccessful. Therefore, selenomethionine-labelled proteinwasprepared, and crystals were grown under similar conditions as for wild-type protein. Thecrystalstructurewassolvedusingmulti-wavelengthanomalousdispersionofseleniumatoms.CaDPP III crystallized in thespacegroupP212121withonemolecule in theasymmetricunit.TheoveralltopologyofCaDPPIIIisverysimilartothefoldforothermembersoftheM49familywithtwostructuraldomainsseparatedbyacleft.However, incomparisontothestructureoftheyeastandhumanenzyme,CaDPPIIIadoptsaconformationbetweenthe(fully)openandclosedstructure(Fig.1).AsCaDPPIIIis179aminoacidsshorterthenhumanprotein,itlacksalargepartof the lowerdomain.The loopbetweenthetwoconservedzincbindingmotives inthe upper domain is 36 amino acids shorter and does not contain the ETGE motif, that issupposedlyresponsibleforthebindingofhumanDPPIIItoKeap1,arepressorproteinfromtheKeap1-Nrf2signallingpathway.1. G.A.Bezerra,E.Dobrovetsky,R.Viertlmayr,A.Dong,A.Binter,M.Abramic,P.Macheroux,S.Dhe-PaganonandK.Gruber,Proc.Natl.Acad.Sci.U.S.A.109(2012)6525-6530.2. P.K.Baral,N.Jajčanin-Jozić,S.Deller,P.Macheroux,M.AbramićandK.Gruber,J.Biol.Chem.283(2008)22316-22324.


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CocrystalstructuressosimilarevenRietveldisconfusedVeronikaSladkova,1,2EliskaSkorepova,1,2OndrejDammer,2andBohumilKratochvil11DepartmentofSolidStateChemistry,UniversityofChemistryandTechnologyPrague,Technicka5,16628,Prague6,CzechRepublicE-mail:[email protected],Zentivak.s.,UKabelovny130,10237,Prague,CzechRepublic

Ivabradinehydrochloride(IVAHCl)isanactivepharmaceuticalingredient(API)indicatedfor the symptomatic treatment of chronic stable angina pectoris and chronic heart failure.Ivabradine hydrochloride exhibits extensive polymorphism: there are more than twentypolymorphsof IVAHCldescribed inpatent literature.Also,othersaltsof ivabradine(oxalate,adipate,citrateetc.)areunderpatentprotection.

WeconcludedthatIVAHClcouldalsobepronetoaccommodateacoformer,thusprovidinga cocrystal. We performed a cocrystal screening and identified two cocrystals: ivabradinehydrochloride (S)-mandelic acid1:1 (IClSM) and ivabradinehydrochloride (R)-mandelic acid1:1 (IClRM).The cocrystal structureswere successfully determined from single crystal X-raydiffractiondataandthematerialswerecharacterizedbyothersolidstateanalyticaltechniques,suchasX-raypowderdiffraction(XRPD),solidstateNMRspectroscopyandDSC.

Asapartof thecharacterization,wewondered,whichcocrystal structurewaspreferred.To decide, we let IVA HClmature in the slurries with excess of racemicmandelic acid. TheresultingsolidsweremeasuredbyXRPDbothonflatSiholderandincapillary(Bragg-BrentanoandDebye-Scherrerconfigurations)andthephasequantificationof thepowderpatternswasdonebyRietveldrefinementinJana2006andHighScorePlussoftware.However,thesimilarityof the two structures of IClSM and IClRM (similar unit cell parameters and overall crystalpacking) resulted in the algorithm getting confused during the refinement. The limits of theRietveldfitinthisparticularexamplewillbediscussed.


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Synthesis,characterizationandcrystalstructuresof2-benzothiazolylhydrazones.RobertKatavaandGordanaPavlovićDepartmentofAppliedChemistry,FacultyofTextileTechnology,UniversityofZagreb,PrilazbarunaFilipovića28a,HR-10000Zagreb,Croatia;E-mail:[email protected]

2-benzothiazolylhydrazonesrepresentanimportantclassofheterocycliccompoundswithdiverse pharmacological activities such as: antitumor, antimicrobial, antidiabetic,anticonvulsant and anti-inflammatory. 1, 2 Reactions of 2-hydrazinobenzothiazole andarenecarbaldehydes afforded four 2-benzothiazolylhydrazones of general formulas:Bzt−NH−N=C6H4‒X and Bzt−NH−N=C10H6‒Y (Bzt=benzothiazolyl, X = 2‒OH (1),Y=2‒OCH3(2),4‒OCH3(3),6‒OCH3(4).

Preparedcompoundsarecharacterizedonthebasisofelementalanalysis,IRspectroscopy,TGAmeasurements,powderdiffractionmethod,singlecrystalX-raydiffractionmethodand1HNMR spectral studies. Both amino 2 – 4 and imino 1 tautomeric forms of prepared2-benzothiazolylhydrazones are found, leading to different supramolecular architecture oftheircrystalstructuresandareaccountablefordifferentbiologicalactivity.3Theaminoformofcompound 2 enables assembling of molecules into 2D infinite chains of𝑅$$(8)and𝑅$$(6)hydrogenbondedringsviaN−H···NandC−H···O intermolecularhydrogenbonds,respectively(Fig.1a.). The chains are crossover connectedvia π∙∙∙π stacking interactionsbetweenphenyland thiazolyl rings of neighbouring chains. The imino form of1 shapes infinite helical C(4)chainviaN−H···Nhydrogenbondsbetween thiazolyl –NHgroupand thehydrazonenitrogenatom,supplementedbyπ∙∙∙πinteractions(Fig1b.).

Fig.1.Supramolecularassemblyofcompounds2(a)and1(b).

1Ćaleta,I.,Kralj,M.,Marjanović,M.,Bertosa,B.,Tomić,S.,Pavlović,G.,Pavelić,K.andKarminski-Zamola,G.(2009).J.Med.Chem.52,1744-1756.2Lindgren,E.B.,deBrito,M.A.,Vasconselos,T.R.A.,deMorales,M.O.,Montenegro,R.C.,Yoneda, J.D.andLeal,K.Z.(2014).Eur.J.Med.Chem.86,12-16.3Nogueira,A.F.,Vasconcelos,T.R.A.,Wardell,J.L.andWardell,S.M.S.V.(2011).Z.Kristallogr.226,846-860.


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Synchrotronpowderdiffractionmethods

R.Svetogorova,Y.Zubavichusa,A.Ryazanova,b,E.Semenova,R.Flukigerc,L.BotturacaNationalResearchCenter“KurchatovInstitute”,Moscow,RussiabNationalResearchNuclearUniversity“MEPhI”,Moscow,RussiaCERN,Geneve,SwitzerlandE-mail:[email protected]

Powderdiffractionwithsynchrotronradiationhasampleopportunitiesforthestudyofthestructural features of various materials. One of the modern task in is to investigatemicrostructural changes occurring in low-temperature superconductors under irradiationbyhigh-energy particles. Nb-based materials (Nb3Sn, NbTi) are now widely used to fabricatemagnetic coils for generating strong and superstrong magnetic fields in various largeexperimentalfacilities,forexamplethemodernizationprojectofLargeHadronCollider(CERN,Switzerland) involves the use of Nb3Sn as a superconducting material of magnetic systems,whichmakesitnecessarytoexaminethechangesinitspropertiesafterirradiationbybeamsoffastparticles(protons). As it is known from the literature [1] the superconducting property changes of Nb3Snunder the influenceofradiationareprimarilyassociatedwithchanges in itsstructureand inparticularwith theappearanceofantisiteradiationdefects,whenapartofNbatomsgoes totheSnatomicpositionsandviceversa.ThepresentworkisdedicatedtothestudyofappearingofantisitedefectsintheNb3Snsamplesunderirradiationbyfastprotons. Samples for the studywereprovidedby a groupofRenéFlückiger (CERN, Switzerland).Irradiationbyfastprotonswithanenergyof12.8MeVatroomtemperaturewascarriedoutatthecyclotronU-150NRC“Kurchatovinstitute”.MeasurementsusingX-raydiffractioninnormaland resonant modes were carried out at the "Structural Materials science" beamline atKurchatovsynchrotronradiationsource.[1] R. D. Blaugher, R. E. Hein, J. E. Cox and R. M.Waterstrat, "Atomic ordering and superconductivity in A-15compounds,"JournalofLowTemperaturePhysics,vol.1,no.6,pp.539-561,1969.


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PhotocatalyticallyactivetitaniathinfilmsandpowdersBoštjanŽener,1PetraHorvat,2,3RomanaCercKorošec11 Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1000Ljubljana,Slovenia;E-mail:bostjan.zener@fkkt.uni-lj.si2LaboratoryforPolymerChemistryandtechnology,NationalInstituteofChemistry,Hajdrihova19,1000Ljubljana,Slovenia3JozefStefanInternationalPostgraduateSchool,Jamovacesta39,1000Ljubljana,SloveniaTiO2hasbeenincreasinglyusedasaphotocatalystindifferentenvironmentalapplicationsandsolarcellmanufacture1.Heterogeneousphotocatalyticoxidationisapromisingtechniqueforthecompleteoxidationoforganicpollutants.TheUVlightexciteselectronsofthephotocatalystfromthevalencebandintotheconductionband,andtheresultingelectron/holepairscanthenmigratetothesurfaceandinitiateredoxreactionwithadsorbedorganics2.TiO2photocatalysthasbeen investigated inapowdered form(inasuspension),andsupportedasa thin filmonvarioussubstrates.ThelatterformhasbecomeabetteroptionasTiO2inslurryorsuspensionhastogothroughseparationofdispersedparticlesafterthetreatment3.Thin filmsandcorrespondingxerogelswerepreparedbyparticulate sol-gel route fromTiCl4precursor and stabilized by sulphuric or hydrochloric acid. Organic polymer hydroxypropylcellulose was added to control the porosity of the prepared samples. A transparent sol isformedafterhydrolysisoftheprecursor,whichcanbecoatedonthesubstratesandthermallytreatedathighertemperaturestopromotecrystallizationofanatasephase.Adegreeofthermaltreatmentisveryimportantstepinthepreparationofefficientthinfilmorpowders. Not only the crystalline phase (anatase, rutile, brookite), but also the size of theanatasegrainsdeterminesthepropertiesofthematerial.Twooppositeeffectswereobservedasparticlediameterdecreases:1)specificsurfaceareaofthematerialincreasedand2)inthesemiconducting material recombination rate of photo-induced electron-hole pairs decreasesduetofasterarrivaltothereactionsiteonthesurface.Ontheotherhand,thereisanincreaseinthebandgapwithdecreaseintheparticlesizemeaningthatshorterwavelengthisneededforexcitation. X-raydiffractionisindispensabletechniquefordeterminingthecrystallinephaseobtainedafter various thermalprocessing aswell fordetermining the sizeof thenano-grains. For thelatter,Scherrerequationwasused.Photocalyticefficiencyofthinfilmsandpowders,thermallytreated to a different degree, was determined from the rate of methy-stearate degradationduringUV-lightirradiation.1Addamo,M.,Bellardita,M.,DiPaola,A.,Palmisano,L.,(2006)Chem.Commun.,47,4943.2Bischoff,B.L.,Anderson,M.A.,(1995),Chem.Mater.,7,1772.3Hidaka,H.,Shimura,T.,Ajisaka,K.,Horikoshi,S.,Zhao,J.,Serphone,N.,(1997),J.Photochem.Photobio.A:Chem.,109,165.


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CrystalPackingofAgomelatineinItsVariousSolidFormsEliškaSkořepováa,MichalHušáka,LuděkRidvanb,JanRohlíčekcaDepartmentofSolidStateChemistry,UniversityofChemistryandTechnologyPrague,Technicka5,Prague6,CzechRepublicbSolidStateDevelopment,Zentivak.s.,UKabelovny130,Prague10,CzechRepublicc Institute of Physics of the Czech Academy of Sciences, Na Slovance 2, 182 21 Praha 8, CzechRepubliceliska.skorepova@vscht.czOneofthemaintasksofpharmaceuticalsolidstatechemistryisthesearchfornewsolidforms,as they can offer advantageous physico-chemical properties important in the final drugformulation.Crystalstructuresolutionoffersinvaluableinformationaboutmanypropertiesofthesaidmaterials.Ourmodelcompoundisagomelatine,amelatonergicantidepressant.Itcanformmanydifferentphases.Wehavedescribedseveralsaltsandco-crystals.Asthenumberofcrystalstructuresofthiscompoundrises,itisbecomingdifficulttoeasilycompareallofthemand find their similarities and differences. We would like to present the comparison ofmolecularpackingofagomelatinebytwomethods.Oneofthesoftwareusedisbeingdevelopedby our group. A new approach is introduced for comparison of molecular packing and foridentifyingidenticalcrystalstructuremotifs.Thesimilarityiscalculatedfromasimpleformulaincluding intermolecular distances and relative orientations of molecules inside the finitemolecular cluster. The other software is the Crystal Packing Similarity tool in theMaterialsmoduleofMercury.Frombothapproaches,asimilaritytreediagramisthefinalresult.Thetreediagram is used for a clear analysis of similarity in crystal packing of structures of onecompound.Itcancomparethecrystalpackingofonlythelargestmoleculeinthestructure(inour case agomelatine). Therefore, it can be easily used to analyze a family of polymorphs,hydrates,solvates,saltsandco-crystals.Besidethedifferenceinthecalculationitself,themaindifference between the two types of software is the convenience for the user. While theconstructionofatreediagrambasedondatacalculatedinMercurytakesatleasthours(first,severalseparatecalculationsarerun,thentheresultscanbeprocessedbytheusertoaformofadiagram),ourapproach ismuch fasterandmoreuser-friendly,because the treediagram isgeneratedautomatically.This work was supported by the Grant Agency of Czech Republic, Grant no.106/14/03636Sand received financial support from specific university research (MSMT No20/2016).


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Versatilecoordinationbehaviorof2,6-diacetylpyridinebis(S-methylisothiosemicarbazone)intransitionmetalcomplexesMarkoV.Rodić,VukadinM.Leovac,LjiljanaS.Vojinović-JešićFacultyofSciences,UniversityofNoviSad,TrgDositejaObradovića3,21000NoviSad,Serbia;E-mail:[email protected]

Thiosemicarbazones (tsc) are important class of S-donor ligands1. Their transition- and

non-transitionmetalcomplexeshavebeenstudiedformanyyears,mainlyduetovidespectrumof theirbiological activity.TheirS-alkylatedderivatives—isothiosemicarbazones (itsc)—havebeenlessstudied,althoughtheyshowinterestingstructuralandelectrochemicalfeatures.Asarule, isothiosemicarbazones are coordinated through the azomethine and isothioamidenitrogenatoms.However,2,6-diacetylpyridinebis(S-methylisothiosemicarbazone)(H2L)isoneoftherareexampleswhichshowsseveralcaseswherethisruleisnotobeyed.

Several complexes with this ligand are known,2–4 five of which are structurallycharacterized: [Mn(H2L)(NCS)MeOH]NCS (1), [Fe(HL)(N3)2] (2), [Ni(HL)I] (3), [Cu(H2L)Cl2Py](4)and[CuII2(H2L)2Br10CuI6](5).Herewepresentcrystalstructuresoftwocoppercomplexeswiththisligandoftheformula[Cu(H2L)(ClO4)2]·Me2CO(6)and[Cu(H2L)(ClO4)2](7)wheretwonovelcoordinationmodesareobserved.

Hitherto observed coordination modes of H2L are summarized as follows (Fig.).Symmetricalpentadentate (N5) coordinationmode inneutralandmonodeprotonated form isobservedin1and2,whiletridentate(N3)coordinationmodeisfoundin4.Incomplexes3and7 very unusual coordination of one isothiosemicarbazide moiety through the hydrazinenitrogen atom only is found, which leads to formation of six-membered metallocycle andunsymmetrical tetradentate (N4) coordination. In complex 6 an unsymmetrical tetradentate(N4) coordination mode in a different way is achieved, while in the complex 5 the uniquepentadentatecoordination(N4S)occurs,withadditionalinvolvementofalkylatedsulfuratom.Itappearsthatcoordinationofterminalisothioamidegroupscanbeavoidedbyintroducingco-ligands with good donor capabilities; that coordination of alkylated sulfur atom is possiblewhenacceptorsaresoftPearsonacids.

Fig.Summaryof2,6-diacetylpyridinebis(S-methylisothiosemicarbazone)coordinationmodes

1 Lobana,T.S.,Sharma,R.,Bawa,G.&Khanna,S.(2009).Coord.Chem.Rev.253,977.2 Leovac,V.M.,Divjaković,V.,Češljević,V.I.&Fazlić,R.(2003).J.Serb.Chem.Soc.68,425;Leovac,V.M.,Ivegeš,E.,

Češljević,V.I.,Divjaković,V.&Klement,U.(1997).J.Serb.Chem.Soc.62,837.3 Leovac,V.M.,Bogdanović,G.A.,Češljević,V.I.&Divjaković,V.(2000).ActaCryst.C56,936.4 Rodić,M.V.,Leovac,V.M.&Vojinović-Ješić,Lj.S.(2015).ActaCryst.A71,s446.


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CocrystalscreeningoftrospiumchloridebasedonshapeandpolarsurfaceofparticipatingcomponentsMartinBabor,1JanCejka,1EliskaSkorepova11DepartmentofSolidStateChemistry,UniversityofChemistryandTechnologyPrague,CzechRepublicTechnicka516628Praha6;E-mail:[email protected]

Trospiumchloride(TCl)isadrugusedtotreaturgeincontinenceandfrequenturination.Structuresoffiveco-crystalsofTClwithvariousco-formers(glutaricacid,salicylicacid,oxalicacid, adipic acid and urea) were published. Twenty one coformers were selected for thecocrystal screening. Selection of these coformers was based on shape and polar surfacesimilaritybetweenthecoformersandTCl1.Asthecocrystallizationscreeningtechnique,slowevaporation of solution from three different solvents was used. In this work, single-crystal(SXRD) and powder X-ray diffraction (PXRD) were used for structure characterization andphaseanalysis.ThesolidsobtainedfromthescreeningwereanalyzedbyPXRDand24uniquepowderpatternswereobserved,representingnewsolidphases.FiveofthesenewphasesweresuccessfullysolvedfromSXRDorPXRD.Twoofthedeterminedstructureswerecocrystals:TClcocrystal with benzoic acid and a co-crystal with aminobenzoic acid. The other threedetermined structureswere a novel polymorphs or solvates of the coformers: diazastilbenemonohydrate, cholic acid ethanol solvate and the new polymorph of methyl-4-hydroxybenzoate.

Fig.1:asymmetricunitcellofcocrystaltrospiumchlorideandbenzoicacid

1Fábián,L.(2009).CrystalGrowthandDesign9.3,1436-1443.


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RutheniumcomplexeswithphosphineligandsMatijaUršič,TanjaLipec,AntonMeden,IztokTurelFacultyofChemistryandChemistryTechnology,UniversityofLjubljana,Večnapot113,SI-1000Ljubljana,Slovenija;E-mail:[email protected]

Chemotherapyisoneofthemostwidelyusedtherapies forthetreatmentofcancer,with

cisplatin as one of the most commonly used drugs. However, its severe side effects haveencouraged research of metal-based drugs with improved properties. In recent years,ruthenium-based complexes have emerged as promising agents with anti-tumor and anti-metastaticproperties.1Oneofthenewestclassesoforganorutheniumagentsarebasedonthephosphine ligand pta, which was originally introduced to increase solubility. The originalcompounds containing this ligand, prepared byDyson et al., have been shown to have goodanti-metastaticproperties.2

In our previous research we have reported the synthesis, physico-chemicalcharacterization and biological evaluation of organoruthenium complexes with diketonateligandsandthemonodentatephosphineligandpta.Oneofthemaindiscoverieswasthechangein the mode of action based on the introduction of pta, which is probably owed by therestistance tohydrolysis thatptabrings.3Buildingon this research,more complexesbearingptaligandhavebeensynthesizedandtheirstructuresdeterminedbysinglecrystaldiffraction.Saidcomplexeswill furtherbebiologicallyevaluated inabid toelucidate themodeofactionandthestructure-activityrelationshipofthecomplexes.1Ang,W.H.&Dyson,P.J.(2006).Eur.J.Inorg.Chem.,20,4003-4018.2Murray,B.S.,Babak,M.V.,Hartinger,C.G.,&Dyson,P.J.(2016).Coord.Chem.Rev.305,86-114.3Seršen,S.,Kljun,J.,Kryeziu,K.,Panchuk,R.,Alte,B.,Körner,W.,Heffeter,P.,Berger,W.&Turel,I.(2015).J.Med.Chem.58(9),3984-3996


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3-pyrrolinehydrates:insitucrystallizationandstructuralinvestigationsPatrykRzepiński,ŁukaszDobrzycki,MichałK.Cyrański,RolandBoeseTheCzochralskiLaboratoryofAdvancedCrystalEngineering,FacultyofChemistry,UniversityofWarsaw,ŻwirkiiWigury101,PL-02-089Warsaw,Poland,E-mail:[email protected](2,5-dihydropyrrole,C4H7N)isacyclicamine,liquidatambientconditions.Usingthe in situ crystallization technique1 assisted by IR laser focused radiationwe obtained twohydratesof3-pyrroline(three-andhexahydrate)presentedinthefigurebellow.Thetrihydratecrystallizes inP21/c spacegroup (V=690Å3)withH2Omolecules forming layers.TheaminemoleculesareattachedtotheselayersviaN∙∙∙Ohydrogenbonds.ThehexahydratebelongingtoP21/m space group (V=538 Å3) contains 3D network of interacting watermolecules. In thestructure the amine molecules are incorporated to this network thus the hexahydrate isexample of semiclathrate2. This structure is isostructural with hexahydrate of pyrrolidine3 -saturated analogue of 3-pyrroline. Contrary to the pyrrolidine hexahydrate however,correspondingstructurewith3-pyrroline,doesnotundergoorder-disorderphasetransition.Inallpresentedstructurescontaining3-pyrrolinewatermoleculesaredisorderedwhatmanifestsin alternative positions of hydrogen atoms similarly like in the hexagonal ice Ih crystalstructure.

Crystalpackingdiagramsof3-pyrrolinehydrates

TheworkwassupportedbyFacultyofChemistryYoungResearcherGrant(DSM110200).References1BoeseR.,Z.Kristallogr.,2014,229,595.2FowlerD.L.,LoebensteinW.V.,PallD.B.,KrausC.A.,J.Am.Chem.Soc.,1940,62,1.3Dobrzycki.Ł,TaraszewskaP.BoeseR.CyrańskiM.K.,CrystalGrowth&Design,2015,15,4804.


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Crystallographicstudyofcyclohexanohemicucurbit[n]urilsandtheircomplexesSandraKaabel,1,2MadliTrunin,1FilipTopić,2KariRissanen2andRiinaAav11Department of Chemistry, TallinnUniversity of Technology, Akadeemia tee 15, Tallinn, 12618,Estonia;E-mail:[email protected] of Jyvaskyla, Department of Chemistry, Nanoscience Center, P.O. Box. 35, FI-40014UniversityofJyvaskyla,FinlandCucurbit[n]urils (CB[n]) are a versatile family of macrocyclic molecules, which consist ofreoccurring monomers, giving the core CB[n] a range of inherent symmetry elements. Ourgroup has focussed on cyclohexanohemicucurbit[n]urils (cycHC[n]), by synthesising andcharacterising chiral (all-R,R) or (all-S,S)-cycHC[6] and (all-R,R)-cycHC[8].1,2 In a dynamicsystem,wheremultipleproductsareobtained,singlecrystalX-raydiffractioncanbeavaluabletool for structure elucidation. A new macrocycle i-(all-R,S)-cycHC[6] with one invertedmonomerwasobtained,which introducesan interestingcrystallographicproblem(Figure1).Theoverallshapeofthemacrocycledeviatesso littleasaresultof thismodification, thattheobtained chloroform solvate of i-(all-R,S)-cycHC[6] is isostructural to the solvate of thepreviouslyknown(all-R,S)-cycHC[6]3.The inversioncentre in thecentreof thecycle rendersthe inverted monomer in i-(all-R,S)-cycHC[6] disordered between two symmetry-relatedpositions, so that structure elucidation becomes inconclusive between a single-invertedproductanda1:1mixtureofdoublyinvertedandunmodified(all-R,S)-cycHC[6].Asimilarcasewas recently confronted by Ayhan et al., 4 where the disorder in the crystal structure ofhydroxylated CB[n] prevents an unequivocal assignment of the structures as mono-,dihydroxylated or unmodified cucurbiturils. Isostructural set of crystal structures was alsoobtainedinoureffortstogaininsightintothebindingofanionicguestsby(all-R,R)-cycHC[8].Theanionboundwithinthecavityof thecycHC[8]doesnotsignificantlychangetheshapeofthe host and the packing is thus directedmainly by the counter cations. Interestingly, usingstructurallysimilartetrabutylammonium(TBA)and–phosphonium(TBP)saltsgavecrystalsintheorthorhombic spacegroupP212121ormonoclinic spacegroupP21 respectively.The latterwere in all cases found to imitate the higher Laue symmetry as a result of twinning bypseudomerohedry.

Figure1:ThepossibleinterpretationsofthedisorderedX-raystructureofi-(all-R,S)-cycHC[6]1Aav,R.;Shmatova,E.;Reile,I.;Borissova,M.;Topić,F.;Rissanen,K.(2013)Org.Lett.15(14),3786–3789.2Prigorchenko,E.;Öeren,M.;Kaabel,S.;Fomitšenko,M.;Reile,I.;Järving,I.;Tamm,T.;Topić,F.;Rissanen,K.;Aav,R.(2015)Chem.Commun.(Camb).51(54),10921–10924.3Li,Y.;Li,L.;Zhu,Y.;Meng,X.;Wu,A.(2009)Cryst.GrowthDes.9(10),4255–4257.4Ayhan,M.M.;Karoui,H.;Hardy,M.;Rockenbauer,A.;Charles,L.;Rosas,R.;Udachin,K.;Tordo,P.;Bardelang,D.;Ouari,O.(2015)J.Am.Chem.Soc.137(32),10238–10245.


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Transferabilityofselectedsupramolecularsynthonsfromorganictometal-organicsystemsMladenBorovina,IvanKodrin,andMarijanaĐakovićDepartment of Chemistry, Faculty of Science, Univeristy of Zagreb, Horvatovac 102a Zagreb,Croatia;E-mail:[email protected]

Directedsupramolecularinteractions(suchashydrogenandhalogenbonds)haveproventobeinvaluabletoolsinthefieldofcrystalengineering.Insimplesystemsitispossibletopredicttheformation of supramolecular synthons when using these types of interactions. Problemsconcerning synthonpredictionarise inmore complicated systemswheremultiple competingdonor and acceptor sites are present. If we want to harness specific interactions in suchsystems,without relyingonchance, ameansofpredicting the interactionmotifsneeds tobedeveloped.Oneapproachisusingtherelativestrengthsofdonorsandacceptorstopredicttheinteractionsbetweenthemandageneralrulewasproposedthatthebestdonorswillinteractwiththebestacceptors.1Thismethodofpredictionhasshownmeritbutmeasuringthe“strength”ofdonorsandacceptorsstillremainedaproblem.Electrostaticpotentialmapsmappedontotaldensitysurfaces obtained via quantum-mechanical calculations offered an elegant solution fordonor/acceptor strength assessment. It was shown that in purely organic systems themoleculestendtointeractsothatthebesthydrogenbonddonor(ESPmaxima)pairsupwiththebestacceptor(ESPminima).2Hereweoptedtotesttransferabilityofselectedsupramolecularsynthonsformorganicsystemsto metal-organic environment, where additional competing acceptor sites are necessarilypresent.Wefocusourattentiontothosesynthonsthathavealreadyproventoberobustandreliable in purely organic systems. For this purpose we prepared a series of β-diketonatocomplexes of Co2+, Ni2+ and Cu2+ with simple and rigid heterocyclic ligands bearingfunctionalities capable of forming self-complementary and directional interactions with HBdonors and acceptors being directly attached to the heterocyclic systems. Complexes weresynthesizedbysolutionmethodsandsolventassistedgrinding.Singlecrystalswereobtainedeither by slow evaporation from mother liquor or by liquid diffusion methods. Crystalstructures were determined by single crystal X-ray diffraction experiments and DFTcalculationswereperformedtoassessthecapacityofacceptorsanddonorspresentinthem.Ourresultshaveshownthatselectedsynthonsweretransferabletothemetal-organicsystemofourchoicedespiteofthepresenceofadditionalcompetingacceptorsites,andfollowingthebest-donor/best-acceptorconceptfromorganicsystems.

1Etter,M.C.(1990).Acc.Chem.Res.23,120-1262Aakeroy,C.B.,Wijethunga,T.K.&Desper,J.(2015).NewJ.Chem.39,822-828


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ThisworkhasbeenfullysupportedbyCroatianScienceFoundationundertheprojectUIP-11-2013-1809Theoximemoietyinmetal-organicsystems:Thecadmium(II)studycaseIvanKodrin,VedranBarbarićandMarijanaĐakovićDepartmentofChemistry,FacultyofScience,UniversityofZagreb,Horvatovac102a,HR-10000,Zagreb,E-mail:[email protected]

Theway inwhichmolecules interact to formhighly-ordered 3D structures is one of themost interestingquestions inmaterialssciencetoday.Understandingtherelativelyweakandreversible interactionsbetweenmoleculescangiveusagreatopportunitytotargetadesiredphysical property. The time and effort invested in research of intermolecular interactions inorganicsystemsexceedsthatspentonstudyingtheirmetal-organiccounterparts.Thequestioniswhetherthesupramolecularsynthons,alreadyprovenasrobustandreliableinthedesignoforganic systems, can play the same/similar role in the supramolecular metal-containingarchitectures?

Our research is mainly focused on the idea of transferability of same or alikesupramolecularmotifsfromorganictometal-organicsystems.Herewehavefoundtheoximemoiety a promising supramolecular connector for that purpose due to its easily achievedtunability.1Tobeusedasaconnectorformetal-organicbuildingblocks,wefirstlyequippedtheoximemoietywiththepyridylbackbonetoprovideitwithcoordinatingpowerthusleavingtheoxime functionality unaffected and ready to form the same type of interactions as in pureorganic systems. Furthermore, we opted for CdX2 systems as these are known to form 1-Dpolymeric structures and consequently reduce the dimensionality of supramolecularinteractionsthatneedstobecontrolled.

Hirshfeld surface analysis anddetailed computational study, in addition to our structuredeterminationresultscomplementedbydatamining,allowedustogetadditionalinsightintointermolecular interactions responsible for the assembly of 1-D building blocks andtransferabilityoftheoximemotifstothesesystems.Furthermore,bycomparisonofmolecularelectrostatic potential (MEP)maps and the calculated interaction energies between pairs ofmolecules we were able to identify the most prominent interactions. A set of tentativeguidelinesaboutthedesignofalikestructuresemergedandtheirvalidityshouldbeaddressedinfuturestudiesonothermetal-containingsystems.

1Aakeroy,C.B.,Sinha,A.S.,Epa,K.N.,Chopade,P.D.,Smith,M.M.&Desper,J.(2013).Cryst.GrowthDes.13,2687–2695.


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ThisworkhasbeenfullysupportedbyCroatianScienceFoundationundertheprojectUIP-11-2013-1809.Structuralandstabilitystudiesofsodiumformatemonoperhydrate

NorahS.AlsaiariandRobinG.PritchardSchoolofChemistry,UniversityofManchester,M139Pl,E.mail:[email protected] crystal structure of a novel solid state hydrogen peroxide carrier, sodium formatemonoperhydrate,hasbeendeterminedandcomparedtoothersodiumoxysaltperhydrates.Itsdecomposition under ambient conditions has been studied using PXRD, showingdeperhydration to be the main mode of decomposition. At higher temperatures, TGA/DSCmeasurements showed that the title compound was completely transformed to anhydroussodiumcarbonateinanexothermicoxidationreactionat100°C.


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Theinvestigationofbondingandnon-bondinginteractionsinflatlandmetalcomplexesFatimahAlqahtani,RobinPritchardandAlanBrisdonSchoolofChemistry,ManchesterUniversity,M139PL,e-mail:[email protected] is interesting toobserve that anumberof themolecules that are crucial for life inour3Dworldarethemselvesplanare.g.theDNAbasesandheme.Thefocusofmyresearchwillbetostudythestructuresofplanarcompoundscontainingπ-systems.

2,4,6-Tris(2-pyridyl)-1,3,5-triazine(tptz)isabulkyheterocyclicorganiccompoundcomposedofthree2-pyridylringsanda1,3,5-triazineringwithanextendedconjugatedπsystem,Figure1.Ithasbeenshownthattptzisaplanarmoleculewithlargestabilizingπsystems.Asaresultof theaforementionedfeaturesof tptz, itdrawsmuchof theattentionamongthepolypyridylligands.Thetptzligandisbelievedtobestabletowardsnucleophilicattackandhasbeenfoundtoformmetalcomplexesinwhichthetptzactsapproximatelyasaplanartridentateligand.Ithas, therefore, been used as an analytical reagent for various metal ions. The tptz metalcomplexescontinuetobethesubjectofextensiveresearchduetotheirbiologicalactivityandtheirphysical,magneticandphotoluminescenceproperties.

Theprojectpresents the synthesize and structural characterisationof three illustratednoveltptz metal complexes, [Cu(tptz)Cl20.5(CH3OH)](1), [Ni(tptz)Cl2(CH3OH)](2) and[Cr(tptz)Cl3(CH3OH)](3).Solid-statestructuresoftheabovecomplexeshavebeendeterminedby single-crystal X-ray diffraction as a primary technique. The research has been started bylooking through Cambridge Crystallographic Database (CSD) for similar structures to becompared.Theresearchwilllookatthestereochemistryaroundthemetalcentre;alsoitwillbeinterestingtoobservethetypeofnon-bondedinteractionsthatcanoccurwithextendedplanararomaticsystems.

thetptzligand complex1 complex2 complex3


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X-raymicrostructuralcharacterizationofgelatin/hydroxyapatitescaffoldsforosteochondraldefectrepairStellaGraziaPastore1,DavideAltamura1,MariaGraziaRaucci2,DritanSiliqi1,FabioDePascalis3,MicheleNacucchi3&CinziaGiannini11InstituteofCrystallography(IC),NationalResearchCouncil,Bari,Italy.E-mail:[email protected],CompositesandBiomaterials(IPCB),Naples,Italy3ItalianNationalAgencyforNewTechnologies,EnergyandSustainableEconomicDevelopment(ENEA),Brindisi,ItalyAn osteochondral defect is a damage affecting the articular cartilage and the underlying(subchondral)bone.Severaleffortshavebeenmadeaimingatovercomingtraditionalclinicalmethodsforthetreatmentofboneandcartilageinjuries.Promisingresultshavebeenobtainedwith the tissue engineering approach by developing scaffolds that mime the osteochondraltissue.Herea3Dosteochondralscaffoldmadeofagradientofhydroxyapatite(HA)at30wt%embedded into a bovine gelatin matrix, fabricated by an in situ sol-gel synthesis1 ischaracterized by two different techniques exploiting X-ray radiation, with table-top setups:micro-tomography (micro-CT) and microdiffraction.2,3 MicroCT characterizes the materialmicrostructure in the three dimensions at the micron scale spatial resolution, whereasmicrodiffraction allows to have a combined structural/morphological information on theatomicandnanoscalestructure,withhundredmicronsspatialresolution.Thecombinationofthesetwotechniquesallowsacompletestructuralcharacterizationofthescaffold,determiningtheHAcrystallinephaseintothegelatinandconfirmingthepresenceofaHAgradientacrossthelongitudinalaxisofthescaffold.1Raucci,M.G.,Guarino,V.&Ambrosio,L.(2010).Comp.Sci.Tech.70,1861-1868.2Landis,E.D.&Keane,D.T.(2010).Mater.Charact.61,1305-1316.3Giannini,C.,Siliqi,D.,Ladisa,M.,Altamura,D.,Diaz,A.,Beraudi,A.,Sibillano,T.,DeCaro,L.,Stea,S.,Baruffaldi,F.&Bunk,O.(2014).J.Appl.Cryst.47,110-117.


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CombinedX-rayPowderDiffractionDataandQuantum-ChemicalCalculationsinEXPO2014FlavioFanelli,1,2CorradoCuocci,1AureliaFalcicchio1,AngelaAltomare1,FulvioCiriaco31InstituteofCrystallography(IC),NationalResearchCouncil,Bari,Italy;E-mail:[email protected]–DrugScience,Bari,Italy3DepartmentofChemistry,Bari,Italy Quantum-chemical calculationshavebeensuccessfullyused to complement theexperimentalX-raypowderdiffraction(XRPD)dataatseveralstagesofthestructuresolutionprocess:(1)Tooptimize the molecular geometry in the gas phase to obtain accurate starting molecularstructuresuitableforstructuresolutionbyrealspacemethods.Inthisstagedifferentlevelsoftheory are applied: molecular mechanics, semi-empirical methods, Hartree-Fock methods,density functional theory (DFT). (2)Tominimize theenergyof crystal structureandprovidereasonablebondlengthsandanglestoinputintotheRietveldrefinementaschemicalrestraints.Calculations are performed using plane wave DFT with dispersion correction (DFT-D). (3)BecauseitisdifficulttoaccuratelylocatethepositionsofHatomsfromtheXRPDdata,energyoptimizationprovides themost reasonable approach to computeoptimalpositions for theHatomsasthefinalstep,withunitcellandnon-HatomicpositionsfixedtothoseestablishedbyRietveldrefinement1.(4)ToclarifyanambiguityconcerningtheorientationoffunctionalgroupthatcouldnotbedistinguishedonthebasisoftheXRPDdataalone2.(5)GeometryoptimizationwithDFT-Dapproach in thesolidstatehasbeenapplied torefine thecrystalstructurewhenRietveldrefinementyieldedinaccuratemoleculargeometry,providingresultswhoseaccuracyis comparable to that of single-crystal refinement3. (6) To assess the correctness ofexperimentalorganiccrystalstructures4.EXPO20145providescrystallographerswithtools tomake theoretical molecular calculations feasible: (a) Preparing input files and readingmoleculargeometry fromoutput filesofawidevarietyof computational chemistrypackages(GAMESS, NWCHEM, GAUSSIAN, and others)6-8. (b) Optimizing the geometry ofmolecule bymolecularmechanicsusingOpenBabel'sforcefields9.(c)Providinggraphical interfacetorunsemi-empiricalquantumcalculationbyMOPAC10.(d)InputfileforDFT-Dcanalsobeproduced.1BhardwajR.M.,JohnstonB.F.,OswaldI.D.H.andFlorenceA.J.(2013)ActaCryst.,C69,1273.2NaelapääK.,vandeStreekJ.,RantanenJ.andBondA.D.(2012)J.Pharm.Sci.,,101(11),4214.3SmrcokL.,MachP.andLeBailA.(2013)ActaCryst.,,B69,395.4vandeStreekJ.andNeumannM.A.(2010)ActaCryst.,,B66,544.5AltomareA.,CuocciC.,GiacovazzoC.,MoliterniA.,RizziR.,CorrieroN.andFalcicchioA.(2013)J.Appl.Cryst.,46,1231.6SchmidtM.W.,BaldridgeK.K.,BoatzJ.A.,ElbertS.T.,GordonM.S.,JensenJ.H.,KosekiS.,MatsunagaN.,NguyenK.A.,SuS.,WindusT.L.,DupuisM.,MontgomeryJ.A.(1993)J.Comput.Chem.,14,1347.7ValievM.,BylaskaE.J.,GovindN.,KowalskiK.,StraatsmaT.P.,vanDamH.J.J.,WangD.,NieplochaJ.,ApraE.,WindusT.L.,deJongW.A.(2010)Comput.Phys.Commun.,181,1477.9O’BoyleN.M.,BanckM.,JamesC.A.,MorleyC.,VandermeerschT.,HutchisonG.R.(2011)JCheminf.,3,1.


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HighcapacityLi-richcathodematerialsRongHao,KunLuo,MatthewRobertsandPeterBruceDepartmentofMaterials,UniversityofOxford,Oxford,Oxfordshire,OX13PH,UK

The need for better batteries has never been greater. In the application of electrical vehicle,automotivemanufacturersrequirelithiumbatterieswithmoreadvancedperformancethanitisnow.Lithiumbatteriesmayalsoplayacriticalroleinde-carbonizationoftheelectricitygrid.Lithium rich layered cathodes, which offer increased capacity and higher operation voltage,have,forseveralyears,beenregardedasthenextmajoradvance,buttheyarestillchallengedbyproblemssuchirreversiblefirstcyclecapacity,voltagefadeoncyclingrelatedtochangesinthestructure.Recentlyimportantworkhasbeencarriedouttobetterunderstandtheoriginofthehighcapacityandthevoltagefade.In this contribution we shall present a new sol-gel synthesis for compositions such asLi1.2Mn0.54Ni0.13Co0.13O2anddiscusstheirlimitationsandoperation.Thecyclingstabilityofthematerialisextremelygoodwithacapacityof~250mAhg-1maintainedafter100cycles.

Figure1.Loadcurveandcyclabilitydataofsol-gelpreparedLi1.2Mn0.54Ni0.13Co0.13O2atarateof50mAhg-1


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UsingtheCambridgeStructuralDatabase(CSD)forEducationCarolineJ.E.Davies,1AmyA.Sarjeant,2MatthewP.Lightfoot,1andSuzannaC.Ward11TheCambridgeCrystallographicDataCentre,12UnionRoad,Cambridge,CB21EZ,UK;E-mail:[email protected],PiscatawayNJ08854,US.The Cambridge Structural Database (CSD) contains over 800,000 small molecule crystalstructures, curated and maintained by the Cambridge Crystallographic Data Centre (CCDC).The CSD is the go-to resource for structural chemists worldwide and can also serve as aresourceforeducatorsteachingbothcrystallographyandchemistry. TheCSDprovidesthreedimensional structures and a wealth of statistical information about symmetry, packing,coordination environments, bond distributions, and intermolecular interactions. We canillustrateahugevarietyofchemicalandcrystallographicprinciplesusingtheinformationintheCSD.ThisposterwillfocusonthewayseducatorscanusecrystalstructuredataandCSDtoolsintheclassroom to augment the learning experiences of students in schools and universitiesworldwide.


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DevelopmentofroomtemperatureserialcrystallographyatESRF,ID13AnastasyaShilova,1ManfredBurghammer21ESRF,France,Grenoble,6rueJulesHorowitzE-mail:[email protected],GhentUniversity,BelgiumStructuredeterminationofmembraneproteinsremainsoneofthecriticalstepstobemasteredbefore achieving breakthroughs in life science andmedicine. This ismainly due to intrinsicproblemswithgrowingstablecrystals,whicharesuitableforstructureanalysisusingstandardX-ray crystallography techniques. But recent developments of serial crystallography at thesynchrotrons,suchasnewsamplemountingsystems1,2,ultra-fastdetectors(EIGER),anintense,small X-ray beam and computational infrastructure to process the large volume of data, aremaking itpossible to collect a largenumberof short exposures in situ frommicrocrystals atroom-temperature.One of themethods to develop serial crystallography of membrane proteins is lipidic cubicphase(LCP)microjet-basedserialmillisecondcrystallographyatthirdgenerationsynchrotrons,similar toserial femtosecondcrystallography(SFX)atX-ray freeelectron lasers(XFELs).Themain advantages of the method are: crystal injection using LCP-jets combined with amicrofocus beamline allows diffraction data to be collected at room temperature, withoutcrystal freezing and difficult crystal handling steps (such as mounting crystals in a loop);thousandsofcrystalscanbescreenedinashorttimeandwithlessthanamilligramofprotein;microfocusbeamsat storageringsourcesarewidelyavailableand finally themethod iswellsuitedfortime-resolveddiffractionstudiesonthemicrosecondtomillisecondtimescale.TheLCP-jet method has been recently demonstrated by solving a structure of the light-drivenproton-pumpbacterio-rhodopsinataresolutionof2.4Å2.Another innovation is to perform serial crystallography at room-temperature usingCrystalDirect plates thatwere created atHTX-lab in EMBL, Grenoble3. These plates allow togrow crystals on very thin films that can then be excised with a laser beam to recover thecrystallinematerial.Duetotheirdesign,CrystalDirectplatesallowtocollectdiffractiondatain-situwithverylowbackground.CrystalDirectsystemsofferalotofadvantages,likeabsenceofthe mechanical stress for the crystals (as no tools enter the crystallization drop), fullautomationof the crystal-harvestingprocess, availability to know in advance all positions ofthecrystals,systematictestingthelargenumbersofcrystals.Alternative approach is based on scanning micro-crystals, which are deposited on solidsupports 1. First successful results have already been obtained usingmicro-crystals. Futurepossibilitiesforoptimization,includinghumiditycontrolledgassampleenvironments,andthepotentialofroomtemperaturescanningserialcrystallographyforobservingmacro-moleculardynamicswillbediscussed.1N.Coquelleetall.Raster-scanningserialproteincrystallographyusingmicro-andnano-focusedsynchrotronbeamsActaCrystallographyD2015May1;71(Pt5):1184–11962P.Noglyetall.LipidiccubicphaseserialmillisecondcrystallographyusingsynchrotronradiationDOI:10.1107/S20522525140264873Marquez,J.A.,Cipriani,F.(2014)CrystalDirect:anovelapproachforautomatedcrystalharvestingbasedonphotoablationofthinfilms.Methodsinmolecularbiology1091,197-203


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Polarizationofthetransferredelectrondensityofaprotein-ligandcomplextowardimprovingenthalpycalculationsbasedonmultipolarelectrostatics.ThéoLEDUC,1ChristianJELSCH,2CristianIORDACHE,2andBenoitGUILLOT,21CRM2,UniversitédeLorraine,BP70232boulevarddesAiguillettes,54506Vandoeuvre-lès-Nancy;E-mail:[email protected],UniversitédeLorraine,BP70232boulevarddesAiguillettes,54506Vandoeuvre-lès-NancyThescopeofthisworkistoassessthetransferofmultipolarelectrondensityonproteinstructurestoextrapolatesomeoftheirproperties,heretherigid-bodyinteractionenergybetweenmembersofaprotein-ligandco-crystalintheabsenceofsolvent.Thetransferablemultipolarparametersoriginatefromhighlyaccuratechargedensitystudiesoforganicsmallmoleculesstructures.Theseparametersdon'ttakeintoaccounttheinhomogeneouselectricfieldsfoundinproteins.Howeveritisbelievedthatatomicpolarizationcontributesignificantlytotheelectrostaticinteractioninsuchproteinligandcomplexes.Hence,toaccounttheselocalinfluencesatthedipolelevel,weusedtheJ.Applequist1andB.T.Thole2formalismallowingthedeterminationofinduceddipolesoneachatominresponsetoanexternalelectricfield.Thoseinduced dipoles are then included3 in the electrostatic contribution of the protein-ligandinteractionenergy.Sincethismethodusesa3n²matrixinversionfornatomsincludedinthepolarizationprocess,theuseofCoupledPolarizationmatrixInversionandIteration(CPII)4isneeded to obtain polarization of the whole protein in a reasonable time. CPII is based onsplittingtheproteininsmallerregions,allowingfastmatricesinversions,beforere-evaluationof the external electric field induced on each region. This process is iterated until induceddipole moments reach numerical stability (under a given threshold). Atomic polarizabilitiesand screening factors are parameters inherent to the interacting dipole formalism1,2. To fitthem, along with compatible van der Waals parameters, we use a custom database, whereIsothermalTitrationCalorimetry (ITC)experiments results found in the literaturearepairedwith the most relevant Protein Data Bank structures (n=58 couples). The choice of ITC ismotivated by the access to experimental binding enthalpies,which are expected to bemoreclosely related to the calculated contribution (sumof electrostatics andvanderWaals) thaninhibitionordissociationconstants.PolarizabilitiesandatomicvanderWaalsparameters fornon-organic atoms were taken from the literature. To avoid statistical bias, the database isstratifiedoncrystallographicprecision(evaluatedbytheirDiffractionPrecisionIndex5),ligandstructurecategoriesandsequencehomology.1Applequist,J.,Carl,J.R.&Fung,J.K.(1972).J.Am.Chem.Soc.94,2952.2Thole,B.T.(1981).Chem.Phys.59,341.3Coppens,P.,X-RayChargeDensitiesandChemicalBonding(1997).IUCrOxfordUniversityPress.Ch.7,142-164.4Xie,W.,Pu,J.&Gao,J.(2009).J.Phys.Chem.A.113,2109-2116.5Cruickshank,D.W.J.(1998).Act.Cryst.Sec.D.55,583-601.


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PurinenucleosidephosphorylasefrombacteriumHelicobacterpylori:Cloning,Expression,PurificationandCrystallisationKarolinaGucunski,IvanaLeščićAšler,MarijaLuićRuđerBoškovićInstitute,Bijeničkacesta54,10002Zagreb,Croatia;E-mail:[email protected] nucleoside phosphorylase (PNP) is the key enzyme in the purine salvage pathway. Itcatalyses the reversible phosphorolytic cleavage of the glycosidic bond of ribo- anddeoxyribonucleosides, in the presence of inorganic orthophosphate as a second substrate togeneratethepurinebaseandribose(deoxyribose)-1-phosphate.TherearePNPswithdifferingspecificities whiche can be divided in two main classes, low-molecular-mass homotrimersspecific forcatalysisof6-oxopurinesandmostly found ineukaryotesandsomebacteria,andhigh-molecular-mass homohexamers with broader specificity for both 6-oxo-and/or 6-aminopurinesandarecharacteristicforbacteria.1 Helicobacter pylori is a Gram-negative, microaerophilic bacterium, human pathogeninvolvedindevelopmentofmanydiseasesasgastriculcersandstomachcancer,andthereforeknownforitsabilitytocolonizehumanstomach.2StudyoftheH.pylori,duetotheevergrowinginfection rate and increase of H.pylori antibiotic resistance, is centered on understandingpathogenesisandfindingawaytoattackanderadicateH.pylori.3 Purineproduction isrequired forDNAandRNAsynthesisanddirectlyaffectsgrowthforbothprokaryioticandeukaryoticcells–H.pyloricannotsythesizepurineringsthroughdenovopathwayandhastorelyonpurineproductionthroughpurinesalvagepathway.1 Purine nucleoside phosphorylase gene deoD was isolated from genomic DNA ofHelicobacterpylori(strain26695)andamplifiedusingPhusionHigh-FidelityPCRkitwith theset of specific DNA primers for both 5' and 3' ends of the gene. Resulting plasmid pet21b-HP26695deoD, with ampicilin resistance and without purification tag,was transformed intoE.coli strain RIL+. Induction conditions for PNP expression in E.coli were optimised andevaluatedbySDS-PAGEelectrophoresysofbacterialcultratefiltrate.4PurificationofoverexpressedPNPfromthebacterialculture filtratewaspreformedbyanionexchange chromatography on Q-Sepharose FF column. Next step, which gave single proteinbandonSDS-PAGEwasaffinitychromatography,performedonSepharose-formycinAcolumn.Biochemical characterization involves, and is ongoing, kinetic studies, temperature and pHeffects on stability and activity of PNP. Crystallisation experiments with purified purinenucleosidephosphorylasefromH.pyloriareunderway.1A.Bzowskaetal.(2000),Pharmacol.Ther.88349-4252P.Malfertheineretal.(2012)CurrOpinGastroeneterol.28608-6143G.Liechtietal.(2011),J.Bacteriol.194839-8544W.P.Schraderetal.(1976),J.Biol.Chem.2514026-4032


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MgAl2O4nanoparticlesfromthermaldecompositionofmetal-triethanolaminecomplexes:theeffectofcalcinationtemperaturesandsamariumcontentonluminescencecharacteristic

WorawatWattanathana,1,2ApiratLaobuthee,2andNattamonKoonsaeng11DepartmentofChemistry,FacultyofScience,KasetsartUniversity,Bangkok10900ThailandE-mail:[email protected];[email protected],FacultyofEngineering,KasetsartUniversity,Bangkok10900Thailand

MagnesiumaluminatespinelphosphorsdopedwithSm3+(MgAl2O4:Sm3+)werepreparedby thermal decomposition of metal-triethanolamine complexes. The complexes weresynthesizedbysimplymixingtriethanolaminewithnitratesaltsinethanolicsolution.Then,theobtainedcomplexesweresubjectedtocalciningatvarioustemperature(800,900,1000,1100and1200oC) for2h.ThecalcinedpowderswerecharacterizedbyFT-IR,XRD,FE-SEM,TEM,XASandPL.XRDpatternsrevealedthatthemaincrystallinephaseofthecalcinedpowderswasMgAl2O4 spinel and no impurity phase of Sm2O3 was observed. This suggested that thesamarium ionsmight be substituted in the lattice points of theMgAl2O4 host. FT-IR spectrashowedtwopeaksofthevibrationaccordingtothelatticeofMgAl2O4,consistentwiththeXRDdata.Moreover, theXRDpeakswere alsoused to calculate the crystallite sizesby Scherrer’sequation. Itwas found that the crystallite size got larger as the calcination temperaturewasincreasedwhichwas related to the larger in particle sizes observed from FE-SEM and TEM.XANESstudyillustratedthatthesamariumionsdopedinthemagnesiumaluminatespinelwereSm3+duetothesameedgeenergyasthestandardSm2O3.Fromthephotoluminescentstudy,allthepreparedphosphorsexhibitedtheemissionpeaksat598nm(4G5/2®6H7/2)and644nm(4G5/2® 6H9/2)1, under excitation at 280 nm. These transitions were due to the electronicrelaxationof theSm3+systemso that theresultswere in linewithXANESstudy.Besides, theluminescence intensityof thepeakweredecreasedas thecalcination temperature increased.ThisobservationcanbeexplainedbyintermsofthelocalstructureofsamariumionsstudiedbyEXAFS.Thegreater thecrystallinityof theSm3+ localstructure, the lower the luminescentintensity.Therefore, inthisstudy,themaximumluminescenceintensitywasobservedforthephosphors calcined at the temperature of 800 oC. Furthermore, the optimum Sm3+concentrationwas1mol%astheluminescentintensitydidnotincreasesignificantlyforSm3+contenthigherthan1mol%.1Sharma,Y.K.,Surana,S.S.L.,Dubedi,R.P.&Joshi,V.(2005).Mater.Sci.Eng.B.119,131-135.


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Spectroscopic,thermogravimetricandx-raystudyofcopperandcobaltcomplexeswith2-pyrazinecarboxylicacidGrzegorzŚwiderski1,SławomirWojtulewski2,AgnieszkaZofiaWilczewska2andWłodzimierzLewandowski11DivisionofChemistry,BialystokUniversityofTechnology,Wiejska45EStreet,15-351Bialystok,Poland;E-mail:[email protected],UniversityofBialystok,CiolkowskiegoStreet1K,15-245Bialystok

In the frameofourpreviousworkswestudiedtheeffectofover40metalcationsontheelectronicsystem,physicochemicalandbiologicalpropertiesofdifferentligands–derivativesofbenzoicacids1-4 .Thecomplexationsofaromaticcarboxylicacidsbymetalcationschangestheelectronic chargedistributionwithinthearomaticringandthecarboxylateanion.Sofar,ourstudiesshowedthattheeffectofmetalcationontheelectronicstructureofpyridineringofpyridinecarboxylicacidsdependson thepositionofnitrogenatomwithin thecarboxylicacidstructure.Intheframeofthisworkthecomplexesof2-pyrazinecarboxylicacidwithcobaltandcooper were synthesized as well as the x-ray diffraction, spectroscopic (FT-IR) andthermogravimetric studies of obtained compounds were done. The FT-IR spectra wererecordedwithanAlfa (Bruker) spectrometerwithin the rangeof400–4000cm-1. Samples inthe solid state were measured in KBr matrix pellets and ATR technique. The products ofdehydrationanddecompositionprocessesweredeterminedfromtheTGcurves. 1Lewandowski,W.,Kalinowska,M.,Lewandowska,H.(2005).J.Inorg.Biochem.99,1407–23.2Lewandowski,W., Fuks, L., Kalinowska, M., Koczoń, P. (2003). Spectrochim.Acta.A.Mol.Biomol.Spectrosc.59,3411–20.3Koczoń,P.,Hrynaszkiewicz,T.,Świsłocka,R.,Samsonowicz,M.,Lewandowski,W.(2003).Vib.Spectrosc.33,215–22.4Świderski,G.,Wojtulewski,S.,Kalinowska,M.,Świsłocka,R.,Lewandowski,W.(2011).J.Mol.Struct.993:448–58.

Studieshavebeencarriedoutintheframeworkoftheworkno.S/WBiIŚ/1/2012andfinancedfromthefundsforscienceMNiSW.Thermogravimetric research was performed at the Center of Synthesis and AnalysisBioNanoTechnoof theUniversityofBialystok.Theequipment in theCenterof SynthesisandAnalysis BioNanoTechno of University of Bialystok was funded by the EU, project:POPW.01.03.00–20–034/09–00.


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Spectroscopic,X-rayandthermogravimetricstudyofzinc2-pyrazinecarboxylateGrzegorzŚwiderski1,RenataŚwisłocka1,SławomirWojtulewski2,AgnieszkaZofiaWilczewska2,WłodzimierzLewandowski11DivisionofChemistry,FacultyofCivilandEnvironmentalEngineering,BialystokUniversityofTechnology,Wiejska45EStreet,15-351Bialystok,Poland,[email protected],UniversityofBialystok,CiolkowskiegoStreet1K,15-245BialystokIntheframeofthisworkthecomplexof2-pyrazinecarboxylicacidwithzincwassynthesized.Thezinc2-pyrazinecarboxylatewaspreparedinwatersolutionbyaddingsodiumsaltofligandtoappropriateamountofzincchloridesat80oC,continuousstirringfortwohours(molarratioofsodiumsaltof ligands to thezincchloridewas2:1.Themixtureswere left for24hoursatroomtemperature.Afteronedayreceivedwhitecrystals.X-raydiffraction,spectroscopic(FT-IR) and thermogravimetric studies of obtained compoundwere done. X-Ray diffraction datawerecollectedat100Kandcrystalstructurewassolvedandrefined.TheFT-IRspectrawererecordedwithanAlfa (Bruker) spectrometerwithin the rangeof400–4000cm-1. Samples inthe solid state were measured in KBr matrix pellets and ATR technique. The products ofdehydration and decomposition processes were determined from the TG curves.Thermogravimetric analysis (TGA)was performed on aMettler Toledo Star TGA/DSC1 unit.Argon was used as a purge gas (20 mL•min-1). Sample were placed in aluminum pans andheatedfrom50°Cto850°Cwithaheatingrateof10ºC/min.

Fig.1.Thestructureofhydratedcomplexofzinc2-pyrazinecarboxylate.

Studieshavebeencarriedoutintheframeworkoftheworkno.S/WBiIŚ/1/2012andfinancedfromthefundsforscienceMNiSW.Thermogravimetric research was performed at the Center of Synthesis and AnalysisBioNanoTechnoof theUniversityofBialystok.Theequipment in theCenterof SynthesisandAnalysis BioNanoTechno of University of Bialystok was funded by the EU, project:POPW.01.03.00–20–034/09–00.


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Thecrystalstructureofcalciumcomplexof2,5-dihydroxybenzoicacid(gentisicacid):synthesis,XRD,XRDP,spectroscopic(IR,Raman,NMR)andbiologicalstudies

MonikaKalinowska1,LilianaMazur2,AgataJabłońska3andWłodzimierzLewandowski11DivisionofChemistry,BialystokUniversityofTechnology,Wiejska45EStreet,15-351Bialystok,Poland;E-mail:m.kalinowska@pb.edu.pl2DepartmentofGeneralandCoordinationChemistry,MariaCurie-SklodowskaUniversity,Lublin,Poland3Division of Sanitary Biology and Biotechnology, Bialystok University of Technology, Bialystok,Poland

2,5-Dihydroxybenzoicacid(gentisicacid)belongstothegroupofplantantioxidantsthatare extensively studied due to their possible application in medicine, pharmacy or foodindustry.Becausefreeradicalsareconstantlyformedinourbodyduringnormalmetabolismaswell as pathological states it is necessary to maintain the proper balance of free radicalsproductionandantioxidantdefensesystem.Theoxidativestressisconsideredamajorcauseofinflammatory,ischemicandneurologicaldiseases,anthersclerosis,differenttypesofcancerandaging process. Hence the natural nontoxic antioxidants (or their derivatives) may play animportantroleinthetherapyofthesediseases.

Thestructureandcompositionoftheresultingcomplex(Fig.1)werestudiedbysingle-crystal and powder X-ray diffraction. Single-crystal X-ray data revealed that the compoundcrystallizes in the orthorhombic space group Pbcn. The Ca(II) cation is coordinated in amonodentatefashionbytwosymmetry-relatedgentisateanionsandfivewatermolecules.Themetal ionandoneof thewatermolecules are locatedona2-fold rotationaxis.Theadjacentmonomeric units are assembled into a 3-D supramolecular framework via O-H…O hydrogenbonds.Comparisonof theexperimentalX-raydiffractionpowderpatternwith that simulatedfromsingle-crystalX-raydataconfirmedthepurityandhomogeneityofthesample.TheFT-IR,FT-Raman, UV/VIS, 1H and 13C NMR spectra of calcium 2,5-dihydroxybenzoic acid wereregistered and analyzed. Moreover the effect of calcium complex and 2,5-dihydroxybenzoicacidonbasicoxidative stressparameters, suchas thiol groupcontentand lipidperoxidationwasstudied.TheantiradicalandferricreducingpowerofthesecompoundswasmeasuredbyDPPH,ABTSandFRAPmethod.

Figure1.Molecularstructureofthecalciumcomplexof2,5-dihydroxybenzoicacid.

ThisworkwasfundedbytheNationalScienceCentre(Poland)onthebasisofthedecisionnumberDEC-2013/11/D/NZ9/02774.


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SpectroscopicandcrystallographicstudyofselectedphenoliccompoundsRenataŚwisłocka,AleksandraGolonko,GrzegorzŚwiderski,MonikaKalinowskaandWłodzimierzLewandowskiDivisionofChemistry,FacultyofCivilandEnvironmentalEngineering,BialystokUniversityofTechnology,Wiejska45E,15-351Bialystok,Poland,E-mail:[email protected]

Inourpreviouspapersweinvestigatedtheinfluenceofmetalsontheelectronicstructureofbiologically important ligands, suchas aminobenzoic andpicolinic acids aswell as chosenphenolic acids.1-3 Presently we study correlations between the molecular structure andelectronic charge distribution of compounds and biological activity of these compounds andtheir metal complexes. This research is aimed on finding new, more effective and selectivesubstances exhibiting cytostatic or antioxidative properties. The proposed approach is alsointended to reveal, if metal complexation can improve the activity and selectivity of someanticancerligands.

Theaimofthepresentwork,beingapartoftheabovementionedwidercontextresearchis:(1)tocollectcomplementarydatadescribingthemolecularstructureandelectronicchargedistribution (determining biological properties) of some chosen phenolic compounds, (2)analysis of correlations between the spectroscopic, X-ray diffraction data and quantumchemicalcalculationsdescribingthemolecularstructureofphenoliccompounds.

Inourworkweappliedthefollowingresearchmethods:vibrationalspectroscopy(FT-IR,FT-Raman),massspectrometry(MS),nuclearmagneticresonance(1HNMR,13CNMR,aswell2D), electronic absorption spectroscopy (UV-Vis), spectrofluorymetry, X-ray diffraction andquantumchemicalcalculations.

Studiedwere phenolic compounds and flavonoids comprising so called “logical series ofligands” – wherein each subsequent ligand differs from the previous one with a particularfunctional group. For example: flavone, 3-hydrokxyflavone, 3,5-dihydroxyflavone, 3,5,7-trihydroxyflavone,3,5,7,3’-tetrahydroxyflavone,quercetin.

Studieshavebeencarriedoutintheframeworkoftheworkno.S/WBiIŚ/1/2012andfinancedfromthefundsforscienceMNiSW.1Lewandowski,W.,Kalinowska,M.&Lewandowska,H.(2005).J.Inorg.Biochem.99,pp.1407-14232Świsłocka,R.,Samsonowicz,M.,Regulska,E.,&Lewandowski,W.(2006).J.Mol.Struct.792,pp.227-2383Kowczyk-Sadowy,M.,Świsłocka,R.,Lewandowska,H.,Piekut,J.&Lewandowski,W.(2015).Molecules.20,pp.3146-3169


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Interplaybetweenstructure,microstructureandmagneticpropertiesoftheCoMn2O4spinelmaterial

MartinaVrankić,1JasminkaPopović1,MarijanaJurić1,DamirPajić21RuđerBoškovićInstitute,Bijenička54,10000Zagreb,Croatia;E-mail:[email protected],FacultyofScience,UniversityofZagreb,Bijenička32,Zagreb,CroatiaComplexmetaloxides,especiallythosecrystallizinginthespinel-typefamilyAB2O4,representan important class of the functional materials, which as a result of their unique chemical,electric,magneticandmechanicalpropertieshavewiderangeofpotentialapplicationsrangingfrom energy storage and conversion to magnetism, electronics and catalysis.1 Among largenumberofdifferentspinelmaterials,cobaltmanganite(CoMn2O4)attractedgreatattentionasnew advanced anode material for lithium-ion batteries, electrocatalysts for oxygenreduction/evolutionreactionsandcatalystinCOoxidation.Majorityofrecentworkappearstobestronglyfocusedonelectrochemicalpropertiesi.e.applicationsoftheCoMn2O4oxideashighcapacityandhighperformanceanodesLiB,whilethestructuralandmagneticstudieshavebeenscarce in spite of few papers reporting on very intriguing and complex but still poorlyunderstoodmagneticbehaviour.CoMn2O4 samples were prepared by thermal decomposition of single-molecular precursor

{[Co(bpy)3][Mn2(C2O4)3]·H2O}n at variustemperature: 500, 700, 800 and 1000 °C.Rietvledstructure refinementshowed that theincreaseofdecomposition temperature causesprolongation of the octahedral bond lengthsd(Moct–O) and shortening of the tetrahedralonce, d(Mtet–O). Decrease of metal-oxygeninteratomic distances resulted from thermallyenhanced substitution of tetCo2+ by smallertetMn3+cationsatAsite(4a)ofspinelstructure.On the other hand, octahedral B site (8d)becomes partially occupied by octCo2+ as aconsequence of transferred Mn cations fromoctahedral to tetrahedral site. Changes in the

temperatureofheating,besides influencing the structural featureswithin crystal lattice, alsohad a strong impact onmicrostructural properties of prepared samples. Size-strain analysisperformedduringRietveldrefinementshowedthataveragecrystallitesizeofCoMn2O4canbeeasilytunedinrangeof8–40nm.Thetemperaturedependenceofmagnetization,M(T),ofallpreparedoxideswasmeasuredindifferentmagneticfields,inthetemperaturerange2–330K.Twomodesofmeasurementwereapplied: after cooling in zero-field (ZFC), and after cooling in magnetic field (FC) in whichmeasurementisperformedduringheating.Thefielddependencesofmagnetization,M(H), i.e.magnetichysteresisloops,weremeasuredatseveralstabletemperaturesinfieldsupto50kOe.OurresultsshowthatitispossibletoswitchbetweenthesuperparamagneticandferrimagneticbehaviourofCoMn2O4andeventotailor thecharacteristicmagnetic transitiontemperatures,i.e.theboundariesbetweenthehardandsoftmagneticbehaviour.TheworkwasfinancedbytheCroatianScienceFoundationgrantno.IP-2014-09-4079J.Hemberger,P.Lunkenheimer,R.Fichtl,H.-A.KrugvonNidda,V.TsurkanandA.Loidl,Nature,2005,434,364.


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Li,Na

Ti,V,Mn,Fe…

P,S

O,F,OH,H2O…

O

Tavorite-typematerialsatthepositiveelectrodeofLithium-ionbatteries.EdouardBOIVIN1,2,3,Jean-NoëlCHOTARD2,3,ChristianMASQUELIER2,3andLaurenceCROGUENNEC1,31LaboratoiredeRéactivitéetdeChimiedesSolides,CNRS-UMR#7314,UniversitédePicardieJulesVerne,F-80039AmiensCedex1,France.2CNRS,Univ.Bordeaux,BordeauxINP,ICMCBUPR9048,F-33600Pessac,France.3RS2E,RéseauFrançaissurleStockageElectrochimiquedel’Energie,FRCNRS3459,F-80039AmiensCedex1,France.

Polyanionic materials attract a strong interest in the field of Li-ion battery researchthankstothewiderangeofcompositions,structuresandelectrochemicalpropertiestheyoffer.Thehigherelectronegativityofthepolyanionicgroupsversusthatofoxygentendstoincrease,by inductiveeffect, thedifferenceofpotentialwith lithiumreferenceofagivenredoxcoupleversus that observed in oxides.1 Among the variety of bi- or three-dimensional frameworksavailable,Tavorite-typecompositionsAnMXO4Y(A=Li,Na;M=V,Fe,Mn,Ti…;X=P,SandY=O,F,OH,H2O)offeraveryrichcrystalchemistry.2Thisstructureischaracterizedbyoctahedralchains of transition metal cations [Y-MO4-Y]∞ bridged by corner-sharing XO4 tetrahedra, insuchawaytogenerateathreedimensionalframeworkinwhichalkalicationscandiffuseeasily.Theiroperatingpotentialistailoredasillustratedinfigure1,“playingwith”theinductiveeffectofthebridginganionYinadditiontothatoftheXO4group.

Figure1:RepresentationofTavoritestructureandworkingpotentialofTavorite-typeAMPO4Y

compositions.2

The stabilization of new Tavorite-type compositions is therefore a major issue both atpractical and fundamental levels. A combination of diffractions (SynchrotronX-ray,Neutron,andelectrondiffractions)andspectroscopies(NMR,IRandXAS)wasusedtocharacterizetheatomic layout and the microstructure, and to highlight the presence of local defects whichgreatlyaffecttheelectrochemicalproperties.Moreover,in-situoroperando(duringthebatteryoperation) experiments, using high resolution powder Synchrotron X-ray diffraction andneutron diffraction, are essential to get an in-depth understanding of the structuralmodifications involved during the alkali insertion/extraction reactions into/from the hoststructure, and to fully determine the phase diagram. The formation of alkali and/or chargeorderings, which can be highlighted by the appearance of superstructures or modulations,allowsabetterunderstandingofthetransportproperties.InthisposteraseriesofseveralnewTavoritephases(LiVPO4OH,3LiVO4F1-xOxandNaVPO4F)willbepresented.1Manthiram,A.;Goodenough,J.B.(1987).J.SolidStateChem.71,349–360.2Masquelier,C.;Croguennec,L.(2013).Chem.Rev.113,6552–6591.3Boivinetal.(2016).SubmittedtoJ.Mat.Chem.A.


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Coordination-modulationassistedstepwiseliquidphaseepitaxialgrowthsofmetal-organicframeworkthin-filmsonquartzcrystalmicrobalance(QCM)substrates

SuttipongWannapaiboon,1,2KenjiSumida,3MinTu,1KatharinaDilchert,1ShuheiFurukawa,3SusumuKitagawa,3andRolandA.Fischer21ChairofInorganicChemistryII,Ruhr-UniversityBochum,Universitätstraße150,44801,Bochum,Germany;E-mail:suttipong.wannapaiboon@rub.de2ChairofInorganicandMetal-OrganicChemistry,DepartmentofChemistry,TechnicalUniversityofMunich,Lichtenbergstraße4,85787,Garching,Germany3InstituteforIntegratedCell-MaterialSciences,KyotoUniversity,606-8302,Kyoto,KyotoPrefecture,Japan

Metal-Organic Frameworks (MOFs), or porous coordination polymers (PCPs), have beenextensively investigated during the past decade due to their outstanding porosity, chemicalmodularity and structural diversity.1 In addition to tuning of the composition ofMOFs, theirphysical form in the mesoscopic and macroscopic scales is known to uniquely affect theirproperties.ThestructuringofMOFsintwo-dimensionalsuperstructures(e.g.thinfilms)isanemerging field that has received an increased attention over the last few years due to theirpotential use inmembranes, coatings, quartz crystalmicrobalance (QCM)-based sensors andmicrocantilever-basedsensors.2AmongdiversesyntheticmethodsusedforfabricationofMOFthin films, stepwise liquid phase epitaxial growth (LPE) is one of promising methods tofabricate precise-controlled MOF thin films even at relatively low temperature. We weresuccessful to fabricate the moisture-tolerant [Zn4O(L)3]n (L= dialkyl-substituentcarboxypyrazolatederivatives)MOFson the self-assembledmonolayer (SAM)modifiedgold-coated QCM substrates. However, the observed growth behaviour is diverged from a self-terminated growth, resulting in micrometre-thick MOF films with moderately controlledcrystalline orientation.3Herein, we propose an improvement of the synthetic procedure byapplying coordination modulation (CM) technique4 into the typical LPE method, so-calledcoordination-modulation assisted stepwise liquid phase epitaxial growth (CM-LPE). Thepresence of acetic acid as amodulator plays a role in altering the coordination equilibriumbetweenmetalSBUsandorganiclinker,whichthereforeaffectsthekineticLPEgrowthofMOFthin films. Generally, the presence of modulator in the reaction retards the high degree ofnucleationattheearlystagewhereasenhancesthegrowthofthepreformednuclei intowell-definedparticles.However,thehighermoleratioofmodulatorretardsthekineticdepositionofthe MOF thin film on the substrate, resulting in less amount of deposited MOF film on thesubstrate surface. It is noted that using an optimalmole ratio ofmodulator during the LPEfabrication improves the crystallinity of the obtained MOF thin films and controls thecrystallographic orientation along the film growth direction. Moreover, the methanol totaladsorptioncapacityoftheCM-LPEfabricatedMOFfilmsissignificantlyenlargedbecauseofahigher contribution of the effectivemass (or the highly-crystalline MOF component) on theQCMsubstrate.This integratedCM-LPEmethodopens theway to fabricatehigh-qualityMOFthinfilmsonthegivensubstratesinaprecise-controlledmanner.

1Metal–OrganicFrameworks(MOFs)(2014).Chem.Soc.Rev.43,5415-6172.2Tu,M.,Wannapaiboon,S.&Fischer,R.A.(2014).Inorg.Chem.Front.1,442-463.3Wannapaiboon,S.,Tu,M.&Fischer,R.A.(2014).Adv.Funct.Mater.24,2696-2705.4Tsuruoka,T.,Furukawa,S.,Takashima,Y.,Yoshida,K., Isoda,S.&Kitagawa,S.(2009).Angew.Chem.Int.Ed.48,4739-4743.


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CrystalandmolecularstructuresofcrystalformsofmemantiniumhydrogenmaleateMihaelaTuksar,1NadaKošutić-Hulita,2AlenBjelopetrović,3*MirtaRubčić,3ErnestMeštrović11PLIVACroatiaLtd.,TAPIResearchanddevelopment,PrilazbarunaFilipovića29,10000Zagreb,Croatia;E-mail:[email protected].,GenericsResearchanddevelopment,PrilazbarunaFilipovića29,10000Zagreb,Croatia3UniversityofZagreb,FacultyofScience,DepartmentofChemistry,Horvatovac102a,10000Zagreb,Croatia*undergraduatestudent

In continuation of our study1,2 on alternative pharmaceutically acceptable salts3 ofmemantiniumchloride(drugusedforthetreatmentofAlzheimer'sdisease)twocrystalformsof memantinium hydrogenmaleate were prepared: a monohydrate form and an anhydrousform.MolecularandcrystalstructuresofbothcrystalformsweredeterminedviasinglecrystalX-raydiffraction.

WhilememantiniumhydrogenmaleatecrystallizesinamonoclinicspacegroupP21/n,itsmonohydrateformcrystallizesinanorthorhombicspacegroupAba2,havingtwotimesbiggerunitcellvolumewithrespecttotheanhydrousform(V=1668,83Å3vsV=3339,4Å3).

Both crystal structures are characterized by complex hydrogen bonded networksinvolvingprotonatedaminogroupsofmemantiniumcationsandhydrogenmaleateanions. Intheanhydrousform,eachaminogroupformsthreesomewhatcomparablehydrogenbondsofthe N–H∙∙∙O type with the surrounding hydrogenmaleate anions. In the monohydrate form,protonated amino group realizes three hydrogen bonds of the N–H∙∙∙O type, two of whichinvolvehydrogenmaleateanions,whilethethirdoneembracesawatermolecule.Moreover,thepresenceofwatermolecule,anditssimultaneousroleasahydrogenbonddonorandacceptor,resultsinagreatervarietyofhydrogenbondingmotifsinthemonohydrateformascomparedtotheanhydrousform(Figure1).

Figure1.Crystalpackinginmemantiniumhydrogenmaleate,monohydrateform,vieweddown

thea-axis.1Tuksar,M.,Žegarac,M.,Brdar,B.,Lekšić,E.,Meštrović,E.23thMeetingofChemistandChemicalEngineers,BookofAbstracts,Osijek,2013,p.117.2Tuksar,M.,Bjelopetrović,A.,JuribašićKulszar,M.,Lovković,M.,Rubčić,M.,Meštrović,E.,11thMeetingofYoungChemicalEngineers,BookofAbstracts,Zagreb,2016,p.104.


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3Stahl, P.H.,Wermuth, C.G. (Eds), Handbook of Pharmaceutical Salts: Properties, Selection and Use; VHCA andWiley-VCH,Zürich,SwitzerlandandWeinheim,Germany,2002.AdvancesinimagingofsmallvirusparticlesatanX-raylaser

BenediktJ.Daurer1andFilipeR.N.C.Maia11LaboratoryofMolecularBiophysics,DepartmentofCellandMolecularBiology,UppsalaUniversity,Husargatan3,75124Uppsala,Sweden;E-mail:[email protected]

The very short and intense pulses of recently developed X-ray lasers provide thepossibility to study the structure of non-crystalline single biomolecules and virus particlesusing coherent diffractive imaging techniques based on the principle of „diffraction beforedestruction“1. This technique has been successfully applied for 2D imaging of mimivirusparticles2,cellorganelles3andlivingcells5.However,bothforlargemacromoleculesandsmallvirusparticles themeasuredsignal intensityasof today isnot sufficient toobtainstructuresfromasingle-shotexperiment. However,thereisgreatpotentialforasuccessfulreconstructionofthethree-dimensionalstructurebycombiningmanyrandomlyorientedsingle-shotdiffractionpatternsfromasampleof reproducible particles and computationally solve the orientation problem prior to phaseretrieval6.Formimivirus,avirus500nmindiameter, thisapproachhasbeenexperimentallyprovenrecently5.Asweareapproachingsmallerparticles,e.g.virusesinthe30-100nmrange,data reduction and pre-selection of diffraction patterns becomes more challenging. Wetherefore developed fast computational methods for robust and nearly automated featureextraction (size, intensity in the beam focus, scattered intensity) based on single-shotdiffraction data of small biological particles with low signal. In this work, we present thecurrent state of small viruses imaging using an X-ray laser. Data has been collected at theCoherentX-rayImaging(CXI)beamlineattheLinacCoherentLightSource(LCLS)7.DiffractionmeasurementsofOmonorivervirus(~40nm)weretakenat5.5keVphotonenergy. Beingabletoprovidereliableinformationaboutthesizeofinjectedparticles(Figure1)and other features prior to orientation recovery and reconstruction procedures as well asproviding real-time feedback during data collection is an important step toward the aim ofrevealingtheinnerstructureofsmallviruseswithX-raylasers.

Figure1.Selectionof8diffractionhits(outof9576)showingavarietyofdifferentdiffractionpatternscollectedatCXIbeamlineofttheLCLS.Maskedvaluesareshowningray.1Neutze,R.etal.Nature406,752–757(2000).2Seibert,M.etal.Nature470,78–81(2011).3Hantke,M.etal.NaturePhotonics.8,943-949(2014).4vanderSchot,G.etal.NatureComm.6,5704(2015).5Ekeberg,T.etal.Phys.Rev.Lett.114,098102(2015).6Loh,N.-T.D.&Elser,V.,Phys.Rev.E80,026705(2009).7Emma,P.etal.,NaturePhotonics.4,641–647(2010).


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Metal-HydrideOrganicFrameworks:synthesisandstructureSanjaBurazer1,JasminkaPopović1,AntonMeden2,GregorMali3,YaroslavFilinchuk4,RadovanCerny5*1.DivisionforMaterialsPhysics,RuđerBoškovićInstitute,Bijeničkac.54,Zagreb,CroatiaE-mail:[email protected],UniversityofLjubljana,Vecnapot113,Ljubljana,Slovenia3.InstituteofChemistry,DivisionforInorganicChemistryandTechnology,Hajdrihova19,p.p.660,1001Ljubljana,Slovenia4.InstituteofCondensedMatterandNanosciences,UniversitécatholiquedeLouvain,Louvain-la-Neuve,Belgium5.LaboratoryofCrystallography,DQMP,UniversityofGeneva,CH-1211,Geneva,Switzerland

Clean and easyproduction fromwater and renewable energy classifieshydrogen as a

great candidate for energy carrier. Problem of safe and efficient storage of hydrogen can besolvedbysolidstatestorageeitherthroughchemicalbondingincrystallinecompoundsorbyphysical adsorption inporousmaterials. [1]Anovel hybridmaterials,metal-hydrideorganicframeworks(HOFs)aredesignedbyinterweavingofmolecularbuildingblocksoflight-weightcomplexhydrideswithorganiclinkers.FlexibilityoftheborohydrideanionallowsothercationcoordinationthanusuallyavailableincoordinationframeworkswhatresultswithgreatHOF’sproperties (guest-host interactions, dehydrogenation properties). Also, advantage in thisdesignispossibilitytousedirectionalanionicligandsotherthanhydridesandforthispurposeweused imidazoles and its derivatives because themetal-imidazolate-metal angle of 145° isverysimilartometal-borohydride-metalangleobservedinMg(BH4)2.[2]

Standard ball-milling procedure under inert atmosphere was used for samplepreparation. Two synthetic routeswere explored, a solvent free and liquid-assisted grindingwithdifferentsolvents (DMF,DMSO,THF,acetonitrile). [3]Chemicalsused insynthesiswereNaBH4, NaIm,MgBH4, HIm, 2-MeIm, ZnCl2 or othermetal cations as starting reactants. Firstresults on mono- and bi-metallic mixed anion (borohydride and imidazolate) frameworksbasedonZn2+andlightalkali(Li+,Na+)orearthalkali(Mg)metalcationswillbepresented.

Final products are polycrystalline and usually containing several novel crystallinephasesofuncertainchemicalcomposition,soweperformedsynchrotronhightemperaturein-situ powder diffraction measurements on prepared compounds (T-ramping). [4] Structuresolution was carried out by combining information obtained from electron density mapsprovidedbyDirectMethodsandseveraldirectspaceapproachessuchasSimulatedannealingand Parallel tempering. [5] Results on change of microstructural parameters under theinfluenceoftemperatureandresultsofNMRsolidstatemeasurementswillalsobepresented.[1] David, W. I. F., Effective hydrogen storage: a strategic chemistry challenge. Faraday Discuss. (2011) 151(HydrogenStorageMaterials),399[2]FilinchukY.,RichterB.,JensenT.R.,DmitrievV.,ChernyshovD.,HagemannH.Angew.Chem.Int.Ed.,(2011)50,11162.[3]FriščićT.,Chem.Soc.Rev.(2012)41,3493[4]CernyR.,FilinchukY.,Z.Kristallogr.(2011)226,882.[5]V.Favre-NicolinandR.Cerny,FOX,J.Appl.Cryst.,(2002)35,734AuthorsacknowledgefinancialsupportofSCOPESprojectbytheSNSF.J.PandS.BacknowledgefinancialsupportofHRZZ(Projectforeducationofnewdoctoralstudents).


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RacematesandOpticalActivityRomainGautier,1JordanM.Klingsporn,2RichardP.VanDuyne,2andKennethR.Poeppelmeier21CentreNationaldelaRechercheScientifique(CNRS)-InstitutdesMatériauxJeanRouxel,2,ruedelaHoussinière44300NantesFRANCE;E-mail:[email protected],2145SheridanRoad,EvanstonIL60208-3113,USARacemateshavebeenassumedtobeopticallyinactiveforthelast160years.Thecancelationofoppositeopticalrotationsfromleft-andright-handedenantiomers(racemates)wasdiscussedby Pasteur for tartaric acids and has never been dismissed. However, Pasteur opened aquestion:"Enest-iltoujoursainsi?C'estàl'expériencederépondre"whichcouldbetranslatedas"Is it always true?The experiments should tell us". In this poster, we will show that specificarrangementsofracemicunitsinthesolid-statecanleadtoopticalactivityandthatasmanyasone in twenty racemic compounds are potential optically active materials.1 Indeed, theenantiomers of opposite handedness can arrange into the 21 non-enantiomorphous pointgroupswhileopticalactivitycanbedescribedintheelevenenaniomorphouspoint-groupsandfournon-enantiomorphouspoint-groups(Figure1(a)).Thus,the“opticalactivity”and“Racemiccompound”groupsarenot independent.Theopticalactivity fromracemicmaterialshasbeenconfirmed by the measurement of single-crystal circular dichroism on two compoundscrystallizing in the point-groupmm2 (Figure 1(b) and (c)). In these crystal structures, thearrangementoftheseunitsisakeytobreakingthecentrosymmetryandleadstothepresenceofopticalactivity.

Figure 1. (a) The 32 crystallographic point groups and optical activity, Centrosymmetric =Black, Polar/Non chiral = Red, Chiral/Non polar = Blue, Chiral/Polar = Purple,Noncentrosymmetric/Non chiral/ Non polar = Green). Circular dichroism spectrum of (b)[Zn(bpy)3](CrO4)0.5NO36.5H2O(Ccc2),and(c)[Cu(H2O)(bpy)2]2[HfF6]2.3H2O(Pna21). 1Gautier,R.;Klingsporn,J.M.;VanDuyne,R.P.;&Poeppelmeier,K.R.(2016),NatureMaterials.doi:10.1038/nmat4628


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StudyingtheroleofdefectsinlepidocrocitenanorodsYuliaTrushkina,Cheuk-WaiTai,andGermanSalazar-AlvarezDepartmentofMaterialsandEnvironmentalChemistry,StockholmUniversity,Sweden;E-mail:[email protected]

Ironoxidenanoparticlesareinterestingfromboththefundamentalandappliedviewpointsduetotheirmagneticbehaviour.Recently, ithasbeenfoundthatdependingonthesynthesisconditionsFe3-xO4nanoparticlescanexhibitso-calledanomalousmagneticpropertiessuchasreduced saturationmagnetization compared to bulk values, emergence of exchange-couplingeffect, etc.; due to the presence of defects1. The presence of defects can thus be also ofimportanceforothertypesofiron(oxy)hydroxides.Inthisworkweinvestigatethepresenceofdefectsinlepidocrocite(γ-FeOOH)nanorods(averagedimensionsof250×10×10nm3)usingelectronmicroscopyandx-raydiffraction.Also,themagneticpropertiesofthematerialshavebeenmeasuredwithvibratingsamplemagnetometry(VSM).

From high resolution TEM data we observed clearly the presence of dislocations in the(020),(004)and(-110)planesofthestructure.ThecorrespondingBurgersvectors(magnitudeanddirectionofthelatticedistortion)are½<010>,¼<001>and½<-110>,respectively.FromGPA analysiswe saw that deformation of (020) lattice fringes is rather uniform (± 5%)andlattice distortion along deformation profile line can be ascribed to dislocations. Negativedeformationcorrespondstotheshorterlatticeparameter.Thediffuseintensity,whichcanberelated to defects (dislocations, anti-phase boundaries, etc.), was detected along <010>direction fromelectrondiffractionpatterns.Rietveld refinementofPXRDpatternusingPopaalgorithm shows an enhanced strain on (002) and (022) planes. Moreover, the magneticcharacterization indicates the presence of a ferrimagnetic component in antiferromagneticlepidocrociteandexchangebiasatlowtemperatures.1Wetterskogetal.(2013).ACSNano7,7132-7144.


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ForcefieldpredictionofareversaltransitioninmolecularcrystalsBrahimiKhadidja,1HulligerJuerg,11DepartmentofChemistryandBiochemistry,UniversityofBerne,Freiestrasse3,CH3012BerneSwitzerland;E-mail:Khadidja.brahimi@dcb.unibe.chPolarityformationisageneralgrowthfeatureofsystemsshowingunidirectionalself-assemblyof polar building blocks into a bulk state1. Channel-type inclusion compounds, singlecomponent molecular crystals, solid solutions, optically anomalous crystals, inorganic ioniccrystals,biologicaltissuesandbiomimeticcomposites investigatedexperimentallyallshoweddomainsofoppositepolaritiesintheirfinalgrownstate2.Inthisfield,molecularcrystalsmadeofdipolarorganicmoleculesgrowingintoapolarcrystalsstructurearesubjecttoundergoareversaltransitionandopenupfascinatingopportunitiesforcomputationalandexperimentalstudies.Intheframeofageneraltheoryonstochasticpolarityformation, the analytical description demonstrates that the reversal will take place in thatdirection (sectors involving the polar axis)where 1800orientational defect formation is lessendothermic3.Therefore,forcefieldcalculationsoftheenergyof1800defectformationatbothtypes of faces, i.e (hkl) and (ℎ𝑘𝑙)may allow to predictwhich side of the polar axis shouldshowreversalofmostofthedipoles.Thisbasicpropertyofmolecularcrystalsisexemplifiedbyinvestigatingrealsystemsforwhichat first we describe the structures and the representative (hkl), (ℎ𝑘𝑙) faces for whichinteraction energies are explicitly calculatedby taking into account the specific symmetryofthe lattice. Conceptually a quite simple procedure, the practical elaboration can be rathercomplicated,becauseofthepresenceofdifferentsiteswhicharesymmetryindependentatthesurfacesofdifferent(hkl)faces.The two chosen dipolar molecules are 1-chloro-4-nitrobenzonitrile and 1-bromo-4-cyanobenzonitrile.Themoleculeswereselectedassuchtoprovidegeometriesandsizeswhichdo not impose a significant surface site reconstruction (relaxation), when an 1800 reversedattachmentisconsidered.Wewill present the results of a structural and energetical analysis involving different faceswherewemaydefineadifferenceofenergywhendockingamoleculedownorup,bylookingatthevaluesofthisenergydifferencepredictiveforthepolarbehaviourofindividualfaces.Thisconfigurationalstudyhighlightsarelationshipbetweenthesymmetryofasurfaceandthereversaltransitionwhichmayoccurwhengrowthproceeds.1Hulliger,J.(2002).Chem.Eur.J.8,4579-4586.2Hulliger,J.Wüst,T.Brahimi,K.Burgener,M.Aboulfadl,H.(2013).NewJ.Chem.37,2229-2235.3Hulliger,J.Wüst,T.Brahimi,K.MartinezGarcia,J.C.(2012).Cryst.GrowthDes.12,5211-5218.


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RietveldrefinementofXRD-CTdataDorotaMatras,1SimonD.M.Jacques,1HamidR.Godini2,AndrewM.Beale3,4,RobertJ.Cernik11SchoolofMaterials,UniversityofManchester,Manchester,LancashireM139PL,UKE-mail:[email protected],[email protected],BerlinInstituteofTechnology,Strassedes17.Juni135,Sekr.KWT-9,D-10623Berlin,Germany3ResearchComplexatHarwell,Harwell,Didcot,Oxon,OX110FA,UK4DepartmentofChemistry,UniversityCollegeLondon,20GordonStreet,London,WC1H0AJ,UK The main aim of solid catalyst study is to understand the relation between catalyststructureand its function.Theanalysisof solidcatalyststructureunderoperandoconditionscanprovidetheuserwithessentialinformationaboutthecatalystactivesites1.

X-ray Diffraction Computed Tomography (XRD-CT) allows for imaging the interior of acatalyst, simultaneously providing the information about its chemical composition. Whencombined with a bright X-ray beam and state-of-the-art detectors with a fast dataacquisition/data readout, this technique can be applied to study the three-dimensionalstructureofcatalysts,underoperatingconditions2.

When analysing a diffraction pattern of a crystallinematerial containing several phases,onemay find difficulties in the phase identification, due to the peak overlap. Therefore, theRietveldrefinementshouldbeperformed,aimingtorefinethemodelstructureofthecatalyst,created by the user. In addition, for each phase presented in themodel, useful informationregarding the lattice parameter, crystallite size or finally percentage composition can beextracted.However,analysingdiffractionpatternsasafunctionofanexternalvariable,suchastemperatureorpressure, leadstobetterunderstandingofthebehaviourof thesystemunderinvestigation. This approach, called parametric refinement, in comparison with single orsequentialrefinement,resultsinhigherprecisionofrefinedparametersandgreaterstabilityofrefinementprocess3.Inaddition,itoffersapossibilitytorefinethenon-crystallographicfactors,such as temperature,which can be usefulwhen treating the space resolved data,where thepossibilityofhot-spotsformationispossible. Inthisstudy,aLa-Sr/CaOcatalyst,usedinOCMprocess(OxidativeCouplingofMethane)was studied in a packed-bed reactor. The catalyst was firstly placed in the atmosphere ofneutralgasduringthetemperatureramp(fromroomtemperatureto780°C)andtheninthemixtureofmethaneandoxygen,withdifferentmethanetooxygenratio.TheXRD-CTanalyseswereperformedatthestationID31ofESRFinGrenoble,usingamonochromaticX-raybeamof70keV.ThedatawasrefinedusingsoftwareTopas5andMATLAB.

ThisstudyaimstopresenttheapproachofparametricrefinementofXRD-CTdataandtodemonstratetheappliedmethodologyusingtheobtainedpreliminaryresultstoexplainit.

This project has received funding from the European Union’s Horizon 2020research and innovation programme under grant agreement No 679933(MEMEREproject)

Reference:1Beale,A.M.,etal.,(2010).Coord.Chem.Rev.277-278,208–223.2Jacques,S.D.,&al.(2011).Angew.Chem.Int.Ed.50,10148-10152.3Stinton,G.W.,&EvansJ.S.O.,(2007).J.Appl.Cryst.40,87-95.


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Formationofporouscoordinationpolymersusingzinc-nitrileinteraction

ZhandosTauanov,MoldirZhanabergenovaandSalimgereyAdilovDepartmentofChemistry,NazarbayevUniversity,53KabanbayBatyrAve,Astana,RepublicofKazakhstan,;E-mail:[email protected]

Soluble host-guest coordination networks have many potential applications, such asselectiveguestremoval,anddetection.1Herewepresentnewcoordinationpolymersbasedonzinc-nitrile interaction. Porphyrin core was used as a template and its periphery wasfunctionalized with 4-cyanophenyl groups in trans fashion at two meso positions.Noncompetingarylgroupsaresituatedatremainingothertwomesopositions.Throughzinc-nitrileinteractionsitforms44-networksandformsalayeredstructure.Bychangingarylgroupsitispossibletochangesizeandelectronicenvironmentofthespacesbetweenthelayers.Thus,thesekindsofcoordinationpolymerscanbeusedforselectiveguestinclusion.2

1Suslick,K.S.;Bhyrappa,P.;Chou,J.H.;Kosal,M.E.;Nakagaki,S.;Smithenry,D.W.;Wilson,S.R.Acc.Chem.Res.2005,38,283.2Adilov,S.&Thalladi,V.R.(2007).Cryst.GrowthDes.7,481-484.


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TheuseofsupramolecularchemistryconceptstodesignandassemblenovelmoleculararrangementsRolaAlaeq,RobinPritchardSchoolofChemistry,ManchesterUniversity,M139Pl,E.mail:[email protected] order to improve crystal quality and size for magnetic measurements, Dy(III)Cl3 andEr(III)Cl3 react with di-2-pyridyl ketone (dpk) and pyrazole to give metal complexesDy3Cl3L‘3L‘‘2(1)andEr3-Cl3L‘3L‘‘2(2)inwhichL‘=py2C(OH)O-andL‘‘=py2(C3H3N2)CO-.Thecrystalstructuresof(1)and(2)havebeendeterminedbyX-raydiffraction.(1)crystallisesintherhombohedralspacegroupR-3withZ=18,a=37.901(3),b=37.901(3),c=30.9794(19)Å.(2) crystallises in the rhombohedral space group R-3 with Z=18, a= 37.7853(14),b=37.7853(14),c=30.8449(8)Å.

1-MooreD.M.,ReynoldsR.C.Jr.(1997).X-Raydiffractionandtheidentificationandanalysisofclayminerals.2ndEd.OxfordUniversityPress,NewYork.2-SkoogD.A,HollerF.J.,CrouchS.R.2007.principlesofinstrumentalanalysis.Sixthedition,ThompsonBrooks,USA


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SupermolecularinteractionofManganeseSchiffbasecomplexes.

MonaS.Binkadem,RobinPritchardSchoolofChemistry,ManchesterUniversity,M139Pl,E.mail:[email protected]]

TransitionmetalSchiffbasecomplexescontinuetobethesubjectofextensiveresearchbecauseof their catalytic roles, which includes Jacobsen catalyst, Photo system II models andwaterphoto-oxidationcatalystsandhydrogenperoxideactivators,sothatalotofresearchhasbeendirectedtowardsmodifyingthestereochemistryaroundthemetalcentre.An interesting featureof these complexes is their ability todimerise intobimetallic catalyticcores.Unpublishedwork carriedoutatManchester showscarboxylate capped,Mn(III) Schiffbasemonomersassociatingintodimersviaπ-πinteractions,and,inthesamecrystalstructure,dimersinwhichthecomplexesarelinkedviaphenoxybridges,thusdemonstratinganexquisitebalancebetweenthetwoformsofassociation.Theproposedresearchwill lookat thesupramolecular interactionsofSchiff-basemonomers,starting with the above complex, which will be studied to examine if dimer formation hastemperaturedependence.


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Canwepredictthejumpingofcrystals?Thecaseofoxitropiumsalts.LidijaAndrošDubraja,1 Tonko Dražić,1 Jasminka Popović1 and Željko Skoko2 1 Ruđer Bošković Institute, Bijenička 54, 10000 Zagreb, Croatia; E-mail: [email protected] 2Department of Physics, Faculty of Science, University of Zagreb, Croatia

Some crystals jump during the phase transition. These thermosalient crystals are biomimetic, nonpolymeric self-actuators par excellance. Yet, due to exclusivity and individuality of the phenomenon, all present investigations have not yet resulted in the full elucidation of this mechanism, let alone enabled us to predict necessary prerequisites for its existence so we aimed our research towards new materials obtained by careful modification of compounds in which the effect was noticed. It is to be expected that this exotic and unexpected effect will be extremely sensitive to subtle changes in the chemical composition (change of the anion, change of the functional groups, change of the position of the functional group inside the aromatic ring) and these investigations will enable determination of necessary chemical/structural parameters so as to arise the thermosalient effect in the system. No matter if these compounds will be thermosalient in nature, or not, comparison between original systems and their derivatives will certainly provide new and helpful insight into elucidation of thermosalient behavior and offer new guidelines in the sense of targeted fabrication of new thermosalient materials.

One of the first systematic studies of this fascinating effect, which paved a way towards its final elucidation, was conducted on the anticholinergic agent oxitropium bromide.2 It was shown that the unit-cell distortion is accompanied by a conformational change of the oxitropium cation, which triggers increased separation between the ion pairs in the lattice at nearly identical separation between the cation and the anion within each ion pair. At the molecular level, the cation acts as a molecular shuttle composed of two rigid parts (epoxy-aza-tricyclic-nonyl portion and phenyl ring) that are bridged by a flexible ester linkage. The structure of the rigid, inert aza-tricyclic portion remains practically unaffected by the temperature, suggesting a mechanism in which the large, thermally accumulated strain is transferred over the ester bridge to the phenyl ring, which rotates to trigger the phase transition.

In an attempt aimed at the targeted fabrication of thermosalient materials, a series of oxitropium salts was prepared. Oxitropium bromide was used as a starting reagent for preparation of several other oxitropium salts. Precursor compound was dissolved in minimal amount of water and the appropriate lead(II) salt was added under stirring conditions. After period of 1 h lead(II) bromide, which precipitated during the stirring, was removed by filtration. One of the prepared systems, oxitropium nitrate, showed thermosalient behaviour during observation on the hot-stage microscope and exhibited joyful jumps during heating (around 134ºC) and cooling (around 98ºC). Detailed structural (high temperature in-situ XRPD), thermal (DSC and TGA), spectroscopic (FT-IR), mechanistic and theoretical (DFT using state-of-the-art nonempirical vdW-DF-cx functional) study was conducted which revealed much information about the thermosalient effect in this system which are necessary to reach the final goal of understanding the nature and mechanism of this fascinating phenomenon.

This work is financed by the Croatian Science Foundation project IP-2014-09-7506 References 2Nath, Naba K., Panda, Manas K., Sahoo, Subash Chandra & Naumov, P. (2014). CrystEngComm. 16, 1850. 1Skoko, Ž., Zamir, S., Naumov, P. & Bernstein, J. (2010). J. Am. Chem. Soc. 132, 14191.


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TheroleofaminoacidsassimplemodelsoforganicmatrixmoleculesparticipatingincalciumcarbonatebiomineralizationLaraŠtajner,1JasminaKontrec,1BrankaNjegićDžakula,1DanielMarkLyons,2NadicaMaltarStrmečki3andDamirKralj11LaboratoryforPrecipitationProcesses,DivisionofMaterialsChemistry,RuđerBoškovićInstitute,Bijeničkac.54,Zagreb,Croatia;E-mail:[email protected],LaboratoryforMarineNanotechnologyandBiotechnology,CenterforMarineResearch,RuđerBoškovićInstitute,G.Paliaga5,Rovinj,Croatia3LaboratoryforMagneticResonances,DivisionofPhysicalChemistry,RuđerBoškovićInstitute,Bijeničkacesta54,Zagreb,CroatiaCalcium carbonate is the main inorganic component of biominerals in a wide range of invertebrate organisms and is present either as a specific polymorph (calcite or aragonite), hydrated or in an amorphous form. The calcite skeletal elements regularly contain small amounts of proteins which are either incorporated or adsorbed on the single crystals of calcite. Previously it has been shown that isolated fragments of proteins extracted from mineralised tissue, or their synthetic macromolecular analogues, exert a significant influence on the morphology and crystal structure of calcium carbonate when precipitated in the appropriate model systems.1-3 In addition, it is known that the in vitro formation of specific crystal modifications is typically determined by parameters such as temperature or initial supersaturation, as well as by the presence of inorganic or organic additives. The aim of this research is to investigate polymorphism and crystallographic distortions of the calcite lattice due to the influence of amino acids, selected as simple models of biomacromolecules supposed to be responsible for nucleation, growth and transformation of calcium carbonates in biomineralising systems. For that purpose amino acids having distinct chemical and physical properties were selected: asparagine (Asn), aspartic acid (Asp) and lysine (Lys) were chosen because of differently charged side chains, while tyrosine (Tyr) and phenylalanine (Phe), as well as serine (Ser) and alanine (Ala) have different polarity. The results of structural (FT-IR, PXRD, EPR)4 and morphological (SEM) analyses indicated an overall inhibition of calcite precipitation in the presence of all amino acids. The inhibition is probably caused by a slower transformation of initially formed vaterite into the calcite.5 Since the selected amino acids are charged under the applied experimental conditions, some surface interactions are assumed to be responsible for the observed effect. This work has been fully supported by the Croatian Science Foundation under project IP-2013-11-5055. 1 A. Adamiano et al. (2012) Chem. Eur. J 18 14367–14374. 2 B. Njegić-Džakula et al. (2013) Croat. Chem. Acta 86 39–47. 3 B. Njegić Džakula et al. (2009) Cryst. Growth Des. 9 2425–2434. 4 J. Kontrec et al. (2004) Eur. J. Inorg. Chem. 23 4579–4585. 5 D. Kralj et al. (1997) J. Cryst. Growth 177 248–257.


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Theinfluenceoffluorinatedphosphine’son[XAuPR3]structuresArijAddaraidi,AlanBrisdon,RobinPritchardSchoolofChemistry,ManchesterUniversity,M139Pl,[email protected],A series of gold(I) complexes of the type [AuX{PR3}] (where R = (m- FC6H4), (3,4,5-F3C6H2),(3,5-(CF3)2C6H3),(Ph2(C6F5),andX=Cl,Br,I)havebeenpreparedandstructurallycharacterisedby single crystal X-ray diffraction in order to investigate the presence of short Au···Au(aurophilic) interactions.Gold-Golddistances ranging from3.1273(8)Å to9.0059(6)Åwereobserved.ItisfoundthatthepresenceofshorterAu··AudistancescoincideswithmoreacuteX-Au-P angles, whilst the complexes that exhibit more linear geometry show longer Au···Audistances. While some of these complexes showed short intramolecular F-F distances andhydrogenbonding.


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SpatiallyresolvedX-raydiffractionofMosobamboorevealstissue-specificmicrofibrilangledistributionPatrikAhvenainen,1 Patrick G. Dixon,2 Aki Kallonen, 1 Heikki Suhonen, 1 Lorna J. Gibson, 2 and Kirsi Svedström1 1 Department of Physics, University of Helsinki, PO Box 64, 00014 Helsinki, Finland; E-mail: [email protected] 2 Department of Materials Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave, Cambridge, MA 02139, USA

Bamboo is a plant known for its exceptionally fast growth. Moso bamboo (Phyllostachys pubescens Mazel) is commercially the most important Chinese bamboo species and it is used as a construction material for houses, scaffolding, furniture and other objects1. The bamboo culm tissue is a composite structure of vascular bundles embedded in a parenchyma cell matrix2. In order to study the cellulose microfibril angle (MFA) distribution of these two components, a set-up3 combining X-ray diffraction (XRD) and microtomography is used (Fig. 1).

With conventional, non-localized, XRD only the average scattering pattern (Fig. 1b) could be measured and the contribution of the different tissue types cannot be resolved. With the spatially resolved XRD, enabled by the combined tomography set-up, regions-of-interest can be selected from the tomographic reconstruction slice and measured using the 200-µm wide monochromatic beam.

The tissue-selective XRD patterns show that the parenchyma cells (Fig. 1c) have weak preferred orientation whereas the vascular bundles have strong preferred orientation (Fig. 1d). The MFA distributions are compared for these two tissue types and for inner and outer parts of the bamboo culm wall.

(a) (b) (c) (d)

Figure 1: (a) Tomographic reconstruction slice of the Moso bamboo sample. The arrows indicate where the X-ray diffraction patterns shown in b-d were measured.

(b-d) Corresponding X-ray diffraction patterns. The 200-reflection of cellulose (marked with an arrow) is used to determine the microfibril angle distribution. 1 J.-H. Fu (2001) Bamboo. 22, 5 2 P.G. Dixon, L.J. Gibson (2014) J Roy Soc Interf 11, 20140321 3 J.-P. Suuronen, A. Kallonen, V. Hänninen, et al. (2014) J Appl Cryst 47, 471


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3DGrainmappingforcontinuousneutronsources

M.Raventos,1, 2 E. Lehmann,1 , C. Grünzweig1 and S. Schmidt3 1 NIAG, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland; E-mail: [email protected] 2 DQMP, University of Geneva, CH-1211 Geneva, Switzerland 3 Department of Physics, Technical University of Denmark 2800 Kgs. Lyngby, Denmark

Polycrystalline materials undergoing thermal or mechanical loading suffer deformations and damage which can modify their grain size, orientation and texture.

To obtain multigrain information from crystalline samples, 3D grain mapping is performed using

x-rays at synchrotron radiation sources.1, 2 However, the scope of this technique is limited due to the lack of penetration power inside of bulky metallic samples. S. Peetermans previously demonstrated the feasibility of such technique applied to neutrons.3

Peetermans acquired the data at the ICON beamline using two imaging detectors: one in

transmission mode and one in backscattering mode. In order to avoid spot overlap from different grains, the diffraction data was acquired with a pink beam of 4.3Å and then 3.7Å. Because Friedel pairs were used to identify the grain position, every spot had to be coupled with its pair at 180° rotation so the sample had to be rotated 360°. This experiment provided a 3D reconstruction of 12 grains from an aluminum sample. We believe the same information could be obtained with a more robust and time-efficient method.

Using white beam illumination we plan to obtain spots from all the Bragg planes at the same

time, and solve the spot overlap using image processing tools. Once the spots are segmented we can do without the Friedel pair matching by using a forward model to index the grains so that only a 90 degrees rotation is required.4 With this new method we aim to reduce the acquisition time of the diffraction data by a factor of 8, and index a larger number of grains.

Some of the scientific cases for this technique are shape memory alloys, metallic samples from

additive manufacturing, meteorites and other coarse grain samples.

1 Fu, X., Poulsen, H. F., Schmidt, S., Nielsen, S. F., Lauridsen, E. M., & Jensen, D. J. (2003). Scripta materialia. 49, 1093-1096. 2 Ludwig, W., King, A., Reischig, P., Herbig, M., Lauridsen, E. M., Schmidt, S., ... & Buffière, J. Y. (2009). Materials Science and Engineering. 524, 69-76. 3 Peetermans, S., King, A., Ludwig, W., Reischig, P., & Lehmann, E. H. (2014). Analyst. 139, 5765-5771. 4 Schmidt, S. (2014). Journal of Applied Crystallography. 47, 276-284.


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HighPressureX-RayDiffractionoftheParamagneticCompoundUPd2SnDanielAntonio,1KrzysztofGofryk21 Idaho National Laboratory, 2525 Fremont Ave. Idaho Falls, ID 83402; E-mail:[email protected],2525FremontAve.IdahoFalls,ID83402

Compounds of the form AnPd2Sn (An= Th, U, Np, and Pu) crystalize in an orthorhombicdistortion of the FCC Heusler lattice. Though they are isostructural, UPd2Sn presents verydifferentmagnetic behavior from its transuranic counterparts.1 BothNpPd2Sn and PuPd2Snorderantiferromagnetically,butUPd2Snremainsparamagneticdowntoat least80mK,eventhough neutron scatteringmeasurements show clear signs ofmagnetic coupling.2 However,reducing its Pd content by only 3% removes the orthorhombic distortion and causes anantiferromagnetictransitionat25K.3Wereportherehigh-pressureX-raydiffractionstudiesoftheparamagneticcompoundUPd2Sn,as well as new resistivity, magnetic susceptibility, and heat capacity measurements forcomparison to other AnPd2Sn-type compounds. A polycrystalline sample of UPd2Sn waspreparedbyarc-meltingand loaded inadiamondanvil cell. Its crystal structurewas refinedfrompowderX-raydataandshowedanorthorhombicsymmetrywithPnmaspacegroupanda= 9.956(4)Å b= 4.601(2)Å and c= 6.874(3)Å cell parameters at room temperature andpressure. Patterns were taken at regular intervals up to 40 GPa, showing that theorthorhombicstructureremainsuptothehighestpressure,withnosignoftheFCCstructure.Fits toaBirch-Vinetequationof stategaveavalueofB0=187.28GPa for theBulkModulus.The resistivity, magnetic susceptibility, and heat capacity data confirm UPd2Sn as aparamagnetic,non-superconducting,heavy fermionsystem. Thissets itapart fromboth theNpandPucompounds,aswellasitsnon-magneticanalogueThPd2Sn.

1Gofryk,K.etal.(2008).PhysicsB.403pp.847-8492Magnani,N.etal.(2012)J.App.Phys.111pp.07E1233Maksimov,I.etal.(2003)Phs.Rev.B.67pp.104405


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BinaryandTernaryCu(II),Mn(II),VO(II)andFe(III)ComplexesofDoxycylinewithPolypyridylLigands:Synthesis,CharacterizationandBiologicalApplications

OlufunsoO.Abosede1,JoshuaA.Obaleye2,PeterSmith3andOlusolaN.Majolagbe41DepartmentofChemicalSciences,FederalUniversityOtuoke,P.M.B.126,Yenagoa,BayelsaState,Nigeria;E-mail:[email protected];[email protected],UniversityofIlorin,P.M.B.1515,Ilorin,Nigeria3 Division of Pharmacology, Department of Medicine, University of Cape TownMedical School,Observatory7925,SouthAfrica4DepartmentofPureandAppliedBiology,LadokeAkintolaUniversityofTechnology,Ogbomoso,OyoState,NigeriaThepleiotropicpropertiesoftetracyclines,thebiologicalapplicationsoftransitionmetals,theimproved biological activities of tetracyclines upon chelation by metal ions as well as thebiologicalimportanceofpolypyridylligandshavepromptedustosynthesizesomebinaryandternarytransitionmetalcomplexesoftheantibioticdoxycylinewithpolypyridylligands.Binaryand ternary complexes of copper (II), manganese (II), iron (III) and oxovanadium (II) withdoxycyclineandpolypyridylligandsweresynthesizedandwellcharacterizedinsolidstateandinsolutionbyUV-Vis,FT-IR,EPRandESI-MS.X-raycrystalstructuresofcomplexCu(II)-doxycyclinecomplexes2and3confirmsthatoutofseveralbindingsitesdoxycyclinecoordinatesthroughtheamideoxygenandtheketooxygenofring A. Complexes 3, 4 and 5 exhibit nearly similar and moderate DNA binding constantsreflectinggroovebinding. AllcoppercomplexescleavepBR322DNAbyoxidativemechanismat significantly low concentration. Further these complexes act asMMP inhibitors similar todoxycycline.ComplexesarecytotoxictowardsMCF-7cellline,complex4beingthemostpotentwhile the complexes are more active than the chloroquine diphosphate and the drugArtesunateagainstCQ-resistantparasitesP.falciparumDd2strain.Doxycycline complexeswithmanganese (II), iron (III) and oxovanadium (II)were tested fortheir antimicrobial activities against pathogenic as well as chloroquine-sensitive andchloroquine-resistant P. Falciparum. In all cases, the complexes are more potent thandoxycycline, the parent antibiotic from which they were synthesized while some are moreactive than the chloroquine diphosphate and the drug Artesunate against CQ-resistantparasitesP.falciparumDd2strain.Theantibacterialactivitiesofsomeofthesecomplexesarecomparableandinsomecaseshigherthanthatofdoxycycline.ThecytotoxicityexperimentsofthecoppercomplexesshowthattheycanalsobeconsideredaspotentialanticanceragentsandareeffectiveasMatrixMetalloproteinase(MMP-2)inhibitors.1Abosede,O.O.,Vyas,N.A.,Singh,S.B.,Kumbhar,A.S.,Kate,A.,Kumbhar,A.A.,Khan,A.,Erxleben,A.,Smith,P.,deKock,C.,Hoffmanne,F.&Obaleye,J.A.(2016)DaltonTrans.AdvanceArticle.DOI:10.1039/C5DT04405G

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