On the Chiroptical Behavior of Conjugated Multichromophoric Compounds of a New Pseudoaromatic Class Bicolchicides and Biisocolchicides 英文参考文献.docVIP

On the Chiroptical Behavior of Conjugated Multichromophoric Compounds of a New Pseudoaromatic Class Bicolchicides and Biisocolchicides 英文参考文献.doc

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On the Chiroptical Behavior of Conjugated Multichromophoric Compounds of a New Pseudoaromatic Class Bicolchicides and Biisocolchicides 英文参考文献

OntheChiropticalBehaviorofConjugated MultichromophoricCompoundsofaNew PseudoaromaticClass:BicolchicidesandBiisocolchicides TizianaFunaioli1*,MarinoCavazza1,MaurizioZandomeneghi1,FrancescoPietra2 1DipartimentodiChimicaeChimicaIndustriale,Universita` diPisa,Pisa,Italy,2AccademiaLucchesediScienze,LettereeArti,Lucca,Italy Abstract Background:Itiswellknownthat,stemmingfromthemutualinterplaybetweenchromophores,circulardichroism(CD)isa powerfultechniquetodealwithstructuralproblems forboththesmallorganicmoleculeandthebiopolymer.However, quantitative interpretations of the spectroscopic and structural terms that give rise to the exciton couplet are usually presentedforidealcases,orafewCDbandsonlyaretakenintoaccount,overlookingtheroleofthesolventmedium. Methodology/Principal Findings: Circular dichroism and UV absorption spectra were carried out for colchicide (3 ) and isocolchicide(6),aswellastheircouplingproducts, 10,109-bicolchicide(2)and9,99-biisocolchicide(5),inbothhydrogen bondingandnonhydrogenbondingsolvents,aswellasMeCN/H2Omixtures.Adramaticcontrolbythesolventemerged, aseventinychangesinthecompositionofsolventmixtures,atca1watermolarfraction,inducedadramaticmodification oftheirCDbands.Amutarotationphenomenon-longknownforisocolchicine(8)-wasalsoobservedfor5,andcanbe attributedtotheinterconversionbetweenatropisomers(Ra,7S),(Ra,79S)-5aand(Ra,7S),(Sa,79S)-5b. Conclusions/Significance: Ourdatashowthatwithmoleculesbuiltontwostructurallyidenticalmoietieswhichembody both hydrophilic and hydrophobic groups, even tiny changes in the composition of solvent mixtures cause a dramatic modificationoftheCDbands.TheiranalysisarrivesataqualitativerationalizationoftheobservedCDcoupletsfromthe coupling of high energy transitions, while attempts at a quantitative interpretation of these phenomena through time- dependentdensityfunctionaltheoryallowedtoreproducesatisfactorilytheCDspectruminthe300–450nmregiononly. Failurewithhigherenergiesprobablyreflectscurrentlyinadequatespecif

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