物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2014年
11期
2134-2141
,共8页
李海霞%周保昌%刘艳成%唐睿智%张鹏%李景烨%王文锋
李海霞%週保昌%劉豔成%唐睿智%張鵬%李景燁%王文鋒
리해하%주보창%류염성%당예지%장붕%리경엽%왕문봉
光化学性质%激光光解%脉冲辐解%二氟沙星%激发态
光化學性質%激光光解%脈遲輻解%二氟沙星%激髮態
광화학성질%격광광해%맥충복해%이불사성%격발태
Photochemical property%Laser flash photolysis%Pulse radiolysis%Difloxacin%Excited state
对二氟沙星在中性水溶液中的光化学性质进行了研究.在pH值为7.17的水溶液中二氟沙星的紫外吸收峰位于273 nm (摩尔消光系数ε=33000 dm3?mol-1?cm-1),323 nm (ε=15500 dm3?mol-1?cm-1),335 nm (ε=15500 dm3?mol-1?cm-1)处.荧光吸收和发射光谱均显示二氟沙星具有pH效应,其pKa(电离平衡常数)测定分别为5.9和9.8.二氟沙星的荧光量子产额较低,在pH=3.00时达到最大值,为0.06.同时对二氟沙星在中性水溶液中的激光光解和脉冲辐解进行详细研究.激光光解研究发现在水溶液中二氟沙星的三重激发态位于620 nm,其摩尔消光系数为7900 dm3?mol-1?cm-1.通过能量转移的方法得到其三重激发态的能量为263.5 kJ?mol-1,三重激发态的量子产额为0.21.在激光激发下,二氟沙星进行单光子电离其量子产额为0.02.脉冲辐解研究表明二氟沙星可以与水合电子(e-aq)及羟基自由基(?OH)快速反应,其二级反应动力学常数分别为1.72×1010和1.0×1010 dm3?mol-1?s-1.本文对二氟沙星光化学性质的研究有助于确定其光敏毒性的产生机理.
對二氟沙星在中性水溶液中的光化學性質進行瞭研究.在pH值為7.17的水溶液中二氟沙星的紫外吸收峰位于273 nm (摩爾消光繫數ε=33000 dm3?mol-1?cm-1),323 nm (ε=15500 dm3?mol-1?cm-1),335 nm (ε=15500 dm3?mol-1?cm-1)處.熒光吸收和髮射光譜均顯示二氟沙星具有pH效應,其pKa(電離平衡常數)測定分彆為5.9和9.8.二氟沙星的熒光量子產額較低,在pH=3.00時達到最大值,為0.06.同時對二氟沙星在中性水溶液中的激光光解和脈遲輻解進行詳細研究.激光光解研究髮現在水溶液中二氟沙星的三重激髮態位于620 nm,其摩爾消光繫數為7900 dm3?mol-1?cm-1.通過能量轉移的方法得到其三重激髮態的能量為263.5 kJ?mol-1,三重激髮態的量子產額為0.21.在激光激髮下,二氟沙星進行單光子電離其量子產額為0.02.脈遲輻解研究錶明二氟沙星可以與水閤電子(e-aq)及羥基自由基(?OH)快速反應,其二級反應動力學常數分彆為1.72×1010和1.0×1010 dm3?mol-1?s-1.本文對二氟沙星光化學性質的研究有助于確定其光敏毒性的產生機理.
대이불사성재중성수용액중적광화학성질진행료연구.재pH치위7.17적수용액중이불사성적자외흡수봉위우273 nm (마이소광계수ε=33000 dm3?mol-1?cm-1),323 nm (ε=15500 dm3?mol-1?cm-1),335 nm (ε=15500 dm3?mol-1?cm-1)처.형광흡수화발사광보균현시이불사성구유pH효응,기pKa(전리평형상수)측정분별위5.9화9.8.이불사성적형광양자산액교저,재pH=3.00시체도최대치,위0.06.동시대이불사성재중성수용액중적격광광해화맥충복해진행상세연구.격광광해연구발현재수용액중이불사성적삼중격발태위우620 nm,기마이소광계수위7900 dm3?mol-1?cm-1.통과능량전이적방법득도기삼중격발태적능량위263.5 kJ?mol-1,삼중격발태적양자산액위0.21.재격광격발하,이불사성진행단광자전리기양자산액위0.02.맥충복해연구표명이불사성가이여수합전자(e-aq)급간기자유기(?OH)쾌속반응,기이급반응동역학상수분별위1.72×1010화1.0×1010 dm3?mol-1?s-1.본문대이불사성광화학성질적연구유조우학정기광민독성적산생궤리.
The photochemical properties of difloxacin (DFX) were investigated in neutral aqueous solution. DFX aqueous solution showed intense absorption with one peak at 273 nm (molar absorption coefficientε=33000 dm3?mol-1?cm-1) and two other peaks at 323 and 335 nm (ε=15500 dm3?mol-1?cm-1) with the same molar absorption coefficient. Both the absorption and emission properties of DFX were pH-dependent. The acid dissociation constant (pKa) for the protonation equilibria of the ground state (5.9 and 9.8) were determined spectroscopical y. DFX fluoresces weakly, and its maximum quantum yield for fluorescence emission was 0.06 at pH 3. Laser flash photolysis and pulse radiolysis studies were carried out to characterize the transient species of DFX aqueous solution. Triplet-triplet absorption reached a maximum at 620 nm with a molar absorption coefficient of 7900 dm3?mol-1?cm-1. The energy transfer method was used to estimate the triplet energy of DFX, which was 263.5 kJ?mol-1. The quantum yield of triplet formation was determined to be 0.21. Furthermore, DFX showed monophotonic photoionization with a quantum yield of 0.02. Pulse radiolysis indicated that DFX could react with e-aq and?OH, and the bimolecular rate constants for these reactions were 1.72×1010 and 1.0×1010 dm3?mol-1?s-1, respectively. It is expected that this research may be helpful in determining the phototoxicity mechanism of DFX.