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