砷-核酸碱基化合物的结构与性质研究-study on the structure and properties of arsenic - nucleic acid base compounds.docxVIP

AbstractThestudiesabouttheinteractionbetweenarsenicatomandnucleobasesarehelpfultoinvestigatethephysiologyprocessofarsenicatomandthemicro-mechanismofbiologicalfunctionofnucleicacids.Inthisthesis,thegroundstatestructures,harmonicvibrationalfrequencies,chargedistribution,electronaffinities,andformationenergiesforthecompoundsformedbetweenarsenicatomandfivenucleobases(adenine,guanine,cytosine,thymine,anduracil)havebeeninvestigatedsystematicallywithB3LYPmethodandDZP++basisset.TheresultrevealsthatR-As-Hform(R=nucleobasesradical)ischaracteristicgeometryofAs-nucleobaesesandtheiranions.Forneutrals,astrongassociationbetweenarsenicatomandnucleobasesisfoundandthegroundstatestructuresareR-As-H(R=nucleobasesradical)complexes.Foranions,themoststablestructuresarealsoR-As-Hforms,buttheassociationsitesofarsenicatomwiththeexceptionofAs-adeninearedifferentfromcorrespondingneutralsbecauseintramolecularAs-transferisoccurrencewhenthegroundstatestructuresofAs-nucleobaseschangefromneutraltoanion.Naturalpopulationanalysis(NPA)calculationsindicatethatmorethan80%ofextraelectronislocalizedonthearsenicatom.Threetypesofelectronaffinitypresentedinthisthesisaretheadiabaticelectronaffinity(EAad),theverticalelectronaffinity(EAvert),andtheverticaldetachmentenergy(VDE).ThecalculatedEAadvalueswithoutZPVEcorrectionfortheAs-adenine,theAs-guanine,theAs-cytosine,theAs-thymine,andtheAs-uracilare2.07eV,2.12eV,2.38eV,2.55eV,and2.52eV,respectively(ZPVEcorrectedvaluesare2.07eV,2.15eV,2.39eV,2.56eV,and2.55eV,respectively).TheEAvertvaluesarefrom1.62eVto1.98eV,andtheVDEsrangefrom2.15eVto2.74eV.Theformationenergiesofthesecomplexesareestimatedinordertoexaminerelativestabilities.Thecalculatedformationenergiesrangefrom?27.0kcal/molto?23.1kcal/mol.Itindicatesthattheinterationbetweenarsenicatomandnucleobasesisstrong.ThestabilityorderisAs-guanineAs-adenineAs-uracilAs-cytosineAs-thymine.Keywords:As-nucleobasescompounds；Groundstatestructures；Electronaffinities；Formationenergies目录第一章绪论.........................................