简介：Emissionquenchingof[Ru(bpy)2(4,4’-dcbpy)](PF6)2(1)bybenzenamine,4-[2-[5-[4-[4-dimethylamino]phenyl]-4,5-di-hydro-1-phenyl-1H-pyrazol-3-yl]-ethenyl]-N,N-dimetyl(2)or1,5-diphenyl-3-(2-phenothiazine)-2-pyrazoline(3)wasobserved.Measurementsoftheemissiondecayof1beforeandafteradditionof2or3bysinglephotoncountingtechniquecon-finnedtheobservations.Theemissionquenchingof1by2or3wassubmittedtoStern-Volmerequation.Itwascalculatedthatthequenchingrateconstants(kq)are5.5×109(mol/L)-1s-1for2and4.0×109(mol/L)-1s-1for3,respectively.Theseresultsindicatedacharacterofdynamicquenchingprocess.Thesinglet-stateof2or3wasalsoquenchedby1.ThequenchingbehaviorsdidnotconformtotheStern-Volmerequationandinvolvedbothstaticanddynamicquenchingprocesses.Theapparentquenchingrateconstant(kapp)wascalculatedtobe3×109(mol/L)-1fortheinteractionofexcited2with1,and1.2×109(mol/L)-1forthatofexcited3wit

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简介：Thereactionofelectron-deficientcyclopropanederivatives,cis-1-methoxycarbonyl-2-aryl-6,6-dimethyl-5,7dioxospiro[2,5]octa-4,8-dioneswithbenzoylmethylenetriphenylarsorane(2)andmethoxycarbonylmethylenetriphenylarsorane(4)wasfoundtoformcis,trans-l-methoxycarbonyl-2-aryl-3-benzoyl-7,7-dimethyl-6,8-dioxospiro[3,5]nona-5,9-dione(3a-3e)andtrans,cis,trans-5-[2'-methoxycarbonyl-2'-(triphenylarsoranylidene)acetyl]-6oxo-3-aryl-tetrahydro-pyran-2,4-dicarboxylicaciddimethylesters(5a-5c)respectivelywithhighstereoselectivity.Thepossiblereactionmechanismsfortheformationofthedifferentproductswerealsoorooosed.

简介：KF的电子关联精力的计算结果并且(KF)2被报导。lsK2，lsF2和内部核心关联的可转移性在两K，K+，KF和FK和F完成，F-，KF系统分别地被调查。到KF系统的K和F部件的关联精力贡献是计算的。由把简单评价计划用于强壮的离子的复合KF的关联精力的计算并且(KF)2，如此的一个强大的计划不能仅仅到达化学精确性而且几乎不需要很少计算工作，这被显示出。

简介：ＥＬＥＣＴＲＯＮ　ＴＲＡＮＳＦＥＲ　ＢＥＴＷＥＥＮ　Ｅｕ３＋　ＡＮＤ　Ｃｅ３＋　ＩＮ　ＳｒＭｇＦ４　ＭＡＴＲＩＸＥＬＥＣＴＲＯＮＴＲＡＮＳＦＥＲＢＥＴＷＥＥＮＥｕ３＋ＡＮＤＣｅ３＋ＩＮＳｒＭｇＦ４ＭＡＴＲＩＸ￥ＹｉｎｇＷＵ；Ｃｈ...

简介：Concerningthetheoreticalestimationofinternalreorganizationenergycontributedbythetortionalmotionbetweenbiphenylandbiphenylanionradical,directcalculationofself-exchangeelectrontransferreactionwasinvestigated.Withtheintroductionofaproperaveragebondlengthandangleparameters,amultiplesteprelaxationNelsonmethodwasdevelopedtodealwiththetorsionalreorganizationenergyλt.pwithanapproximationofλt,1wasachieved.Theresultsof0.140and0.125eVoftorsionalreorganizationenergyforacross-reactionatthelevelsof4-31GandHP/DZP,respectively,areingoodagreenmentwiththevalueof0.13eVobtainedbyMilleretal.fromtheratemeasurements.ThisimpliestheefficiencyandvalidityofoourmethodtoestimatethereorganizationenergycontributedbypuretorisonalmotionofBp.

简介：ＳｔｕｄｉｅｓｏｎｔｈｅＥｌｅｃｔｒｏｎＴｒａｎｓｆｅｒＣｅｎｔｅｒｓｏｆＡｍｉｎｏＯｘｉｄａｓｅＩｍｍｏｂｉｌｉｚｅｄｏｎＳｅｌｆ┐ＡｓｅｍｂｌｙＭｏｎｏｌａｙｅｒＵｓｉｎｇＥｌｅｃｔｒｏｃｈｅｍｉｃａｌＭｅｔｈｏｄｓ＊ＬＩＪｉｎｇ－ｈｏｎｇ，ＣＨ...

简介：明确的表达以前由作者介绍了因为库仑积分被概括到另外的二中心的积分，除了交换积分。在这个框架以内，分子的积分与递归地评估的著名不完全的gamma功能和这些功能有关仔细以一些新功能被表示。在混合积分的情况中产生的特刊被处理，并且结果与在文学发现的相比。

简介：Asasuccessiveworkofourpreviouspaper,^1theelectrontransfermatrixelement(Vrp)intheoxidationofthesimplifiedmodelmoleculeofα-aminocarbon-centeredradicalbyO2hasbeeninvestigatedwithabinitiocalculationatthelevelofUHF/6-31G**.Basedontheoptimizedgeometriesofthereactgantandtheion-paircomplexobtainedpreviously,thereactionheatandtheiunerreorganizationenergyhavebeenobtainedbyconstructingthepotentialenergycurvesofreactantandproductstatesconsideringthesolventeffectwiththeconductor-likescreeningmodel(COSMO).ThesolventreorganizationenergyhasbeenestimatedusingLippert-Matagarelationship.ThecalculatedresultsshowthatthevalueofVrpisseveraltimeslargerthanthatofRT,whichmeansthatthemodelreactionisanadiabaticone.Theoreticalinvestigationindicatesthatthesolventeffectonthedirectelectrontransfer(ET)processofoxidationofα-aminocarbon-centeredradicalbyoxygenisremarkable.

简介：ThelaserphotolysisofN-diisopropylphosphoryltryptophyltyrosinedipeptidemethylester(N-DiPP-TrpH-TyrOH)hasbeencarriedoututilizingaKrF(248nm)laser.ThedirectintramolecularETbetweenTrpH+residueandTyrOHresiduewasdetectedfirstandtheETbetweenTrpandTyrOHbecameslow.Itwassuggestedthatphosphorylgroupstabilizeneighbourradicalofaromaticringbyhyperconjugation.IncombinationwithcomputermodelingweobtainedthekineticparametersoftheETandprovedthatphosphorylgroupstookpartintheprocessofET.Theresultsshouldbesignificantforbiologicalsystemsinceeverybiologicalprocessinvolvesthephosphorylationornonphosphorylation.

简介：Dibromobiphenylreactedwithcynomethylanioninammoniaunderirradiationtoformnucleophilicbis-substitutedproductinhighyieldwithoutsubstantialmonosubstitutedproduct.Quantumyieldsfortheformationsofbis-andmonosubstitutedproductswerefoundtobe85.6and2.3×10-6respectively,whilethecorrespondingpseudo-first-orderrateswere6.9×10-3and5.2×10-10mol.L-1.S-1.Blockupthepossibleelectrontransferof4-brome-4’-cyanomethylbiphenylylradicalanionto4-cyanometbyl-biphenylylradicalandbromineion.

简介：ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｒｅｃｅｎｔｄｉｓｃｏｖｅｒｙｏｆａｃｌａｓｓｏｆｃａｒｂｏｎｃｏｎｔａｉｎｉｎｇｍｏｌｅｃｕｌｅｓｋｎｏｗｎａｓｔｈｅｆｕｌｅｒｅｎｅｓｈａｓｐｒｏｄｕｃｅｄａｓｅｒｉｅｓｏｆｍａｔｅｒｉａｌｓｗｉｔｈａｗｉｄｅｒａｎ...

简介：Anumberofnaphthalenedonorcompoundsthatpossessanadamantanaminebindingmoietyandan(OCH2CH2)n(nn1,2,3,4,6,8)spacerweresynthesized.Thefluorescencequenchingbetweenthesedonorsubstratesandmono-6-O-p-nitrobenzoyl-β-cyclodextrin(pNBCD)andmono-6-O-m-nitrobenzoyl-β-cyclodextrin(mNBCD)wasstudiedindetail.Itwasfoundthatveryefficientfluorescencequenchingcouldoccurinthesesupramolecularsystems.Thisquenchingwasattributedtothephotoinducedelectrontransferinsidethesupramolecularassemblybetweenthenaphthalenedonorsandcyclodextrinacceptors.DetailedStern-VolmerconstantsweremeasuredandtheywerepartitionedintodynamicStern-Volmerquenchingconstantsandstaticbindingconstants.Itwasdemonstratedthatthebindingconstantsbetweenallthenaphthalenecompoundsandcyclodextrinsarethesameastheypossessthesamebindingsite,i.e.,adamantanamine.