Microenvironmental control of photochemica reactions Ⅱ.Fluorescence quenching of naphthalene and 1,3-di-(a-naphthyl)propane by RNA and bases in aqueous methanol

(整期优先)网络出版时间:1990-04-14
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Thefluorescencequenchingofnaphthalene(2)and1,3-di(α-naphthyl)propane(1)byRNAandbasesinmethanol-water(v:v=1:1)binarysolventsinthepresenceorabsenceofcyclodex-trin(CD)hasbeeninvestigated.Theresultsshowthatboththemonomerandexcimerfluorescenceof1canbequenchedbythesequenchers.Thequenchingandratesdependonthequencherandtem-perature.Itisshownthatthereisacriticaltemperature(Tc)foreachquencher.BelowTc,theexcimerfluorescencespectrashowvibrationalstructuresandtheStern-Volmerplotsarestraightlines(forura-cilandcytosine);whileabovetheTc,thevibrationalstructuresdisappearandtheStern-Volmerplotsdeviatefromlinearityandcurveupward.Theformerisastaticprocess;whilethelatterisamixtureofbothstaticanddynamicprocesses.Theadditionofα-CDhasnoeffectonthefinestructure,whereasβ-CDpreventstheappearanceofthisstructureefficiently.Thequenchingratesbothforthemonomerandexcimerof1bybasesexceptcytosineinthepresenceofβ-CDatambienttemperaturearenotchanged;thequenchingoffluorescenceof1byRNAinthepresenceofβ-CD,however,ishindered.Time-resolvedfluorescencestudyshowsthattheexcimerfinestructuresappearfromthezerotime.Theintensityoffinestructuresdependonthefractionofwater(φ)inbinarysolvents,anditisindependentofthepHvalueofthesolvents.ItissuggestedthatbasesandRNAinducedaggregates(perhapsmicrocrystal)areformed,inwhichthemotionofmolecules1islimited.