Etoposide的氧化还原反应: 脉冲辐解和激光光解研究

首次用脉冲辐解时间分辨方法研究了etoposide(VP16)在水溶液中与N~3^.,(SCN)~2^.^-和e~a~q^-之间发生的单电子氧化还原反应,测定了VP16的阴离子自由基、脱质子中性自由基的特征吸收谱;测得VP16与e~a~q^-,N~3^.,(SCN)~2^.^-的绝对反应速率常数分别为2.7×10^9,3.2×10^9和2.5×10^8dm^3.mol^-^1.s^-^1。研究表明,水溶液中的VP16可为248nm激光光电离,光电离的瞬态产物为阳离子自由基及脱质子中性自由基,并且测定了其酸碱电离的pK值。测得SO~4^.^-自由基单电子氧化VP16的反应速率常数为2.8×10^9dm^3.mol^-^1.s^-^1。     

Photosensitized oxidation of tryptophan and tyrosine by aromatic ketones: A laser flash photolysis study

Photochemical processes of benzophenone (BP) and xanthone (XT) with tryptophan (TrpH) and tyrosine (TyrOH) were studied using the laser flash photolysis technique.It has been observed that the triplet state of BP and XT reacted with TrpH and TyrOH by hydrogen transfer with the formation of BP and XT ketyl radicals and oxidized radicals of TrpY and TyrOY.The related rate constants of these reactions were determined in this paper.The free energy changes (G) of these reactions suggested that the proposed hydrogen transfer mechanism was thermodynamically feasible.These results provide theoretical foundation for further studying structural effects on the photochemical behaviors of proteins with triplet state BP and XT.     

Laser flash photolysis of carboxymethylcellulose in an aqueous solution

Laser flash photolysis with excitation at 248 nm was used to study photochemically derived changes of carboxymethylcellulose (CMC) in aqueous solutions. Transient absorption spectra of solutions after photolysis revealed a broad band with a maximum of approximately 720 nm, which could be ascribed to the signal of the hydrated electron. The interaction of the hydrated electron with CMC was slow (<10⁷ dm³ mol^?1 s^?1), but the OH radical, formed by the decomposition of H₂O₂, reacted with CMC at a high rate constant (9.5–11.0 × 10⁸ dm³ mol^?1 s^?1). The rate constant of the reactions of CMC with hydroxyl radicals depended on the conformation of the macromolecules, which was determined by the pH of the solution. Transient absorption was recorded at a wavelength shorter than 370 nm for CMC solutions photolyzed in the presence of H₂O₂. As a result of OH attack, long‐lived radicals were formed on CMC. The recombination of macroradicals led to the formation of crosslinking bonds between side‐chain groups, and as a result of it an insoluble gel arose in low‐pH solutions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 505–518, 2005     

水相中四氯化碳的激光闪光光解研究

利用激光闪光光解技术研究了水相中四氯化碳光分解和光氧化的微观机制,并且指证了水相中四氯化碳受光激发所产生的瞬态光谱中的一些瞬态物种的特征吸收峰。并对这些瞬态物种的行为和归宿进行了研究。研究表明在248nm激光作用下,四氯化碳受光激发将分解为CCl~3^.自由基和Cl^.自由基。CCl~3^.自由基在无氧/有氧条件下的反应途径是不同的:在无氧条件下CCl~3^.自由基将进行偶合反应生成更难于降解的C~2Cl~6;而在有氧条件下CCl~3^.自由基则与O~2反应生成CCl~3O~2^.自由基,而CCl~3O~2^.自由基最终转变为COCl~2,这意味着光氧化能够有效地降解CCl~4。Cl^.自由基基本上不受氧气存在的影响,其归宿是与水分子发生电荷转移反应。     

Characterization of the transient species generated by the photoionization of Berberine: A laser flash photolysis study

Using 266 nm laser flash photolysis it has been demonstrated that Berberine (BBR) in aqueous solution is ionized via a mono-photonic process giving a hydrated electron, anion radical that formed by hydrated electron react with steady state of BBR, and neutral radical that formed from rapid deprotonation of the radical cation of BBR. The quantum yield of photoionization is determined to be 0.03 at room temperature with KI solution used as a reference. Furthermore utilizing pH changing method and the SO₄⁻ radical oxidation method, the assignment of radical cation of BBR was further confirmed, the pK_a value of it was calculated, and the related set up rate constant was also determined.     

4-n-壬基酚的激光闪光光解和紫外光降解

采用266nm激光闪光光解瞬态吸收光谱和254nm紫外光降解,研究了乙腈及乙腈-水混合溶液中4-n-壬基酚（4-n-NP）的各种光解行为,考察了不同物理化学体系对4-n-NP光解行为的影响规律.实验发现,在266nm激光闪光光解下,4-n-NP既发生光电离又发生光激发,获得了4-n-NP光电离生成的阳离子自由基,以及光激发生成的激发三重态的瞬态特征吸收谱.由S2O82-光分解产生的SO4·-可快速氧化4-n-NP,测得反应速率常数为2.85×109M-1s-1,判定4-n-NP阳离子自由基在pH高于2.2条件下会转变成脱质子中性自由基.研究发现,使用254nm紫外光直接降解4-n-NP比较困难,UV结合添加H2O2可提高其降解效率,UV结合添加K2S2O8可极大提高4-n-NP降解效率,3.5min的光照即可使1×10-4M的4-n-NP完全降解.本文就4-n-NP在各种条件下的光解机理进行了探讨,为此类具有生物激素效应的非离子表面活性剂光降解奠定了基础.     

Study of radical generated from coumarin dye-sensitized photo-initiator systems in high-speed photopolymer coating layers using laser flash photolysis

Radical generation from photoinitiation systems containing carbonylbiscoumarin dye with a radical-generating reagent, 3,3′-carbonylbis[7-(diethylamino)-2H-1-benzopyran-2-one] (KCD-DA), with 2,2′-bis(2-chloro-phenyl)-4,4′5,5′-tetraphenyl-1, 1′-bi-1H-imidazole (BI) in a poly(methyl methacrylate) film has been investigated by laser flash photolysis using a total reflection cell. Imidazolyl radical (Im·) was predominantly generated from carbonylbiscoumarin triplet-sensi-­tized decomposition of BI, the quantum yield, Φ^o_Im· of Im· at an infinite concentration of BI was measured, Φ^o_Im· = 1.3. The high quantum yield, Φ^o_Im·, implies an efficient KCD-DA triplet-sensitized photoinitiation system containing BI. Copyright © 1998 John Wiley & Sons, Ltd.     

Photophysical properties of gatifloxacin in aqueous solution by laser flash photolysis and pulse radiolysis

GFX in water, at pH 7.0, shows intense absorption bands with peaks at 284 and 333 nm, (ε=24,670 and 12,670 M⁻¹ cm⁻¹). Both the absorption and emission properties of GFX were pH-dependent; the pK_a values for the protonation equilibria of the ground state (5.7 and 8.9) and excited singlet state (3.6 and 7.5) of GFX were determined spectroscopically. GFX fluoresces weakly, with a maximum quantum yield for fluorescence emission (0.06) at pH 4.7. A series of experiments were performed to characterize the transient species of GFX in aqueous solution using laser flash photolysis and pulse radiolysis. GFX undergoes monophotonic photoionization with a quantum yield of 0.16 on a 355 nm laser excitation. This process leads to the formation of a long-lived cation radical with a maximum absorption at 380 nm. Triplet-triplet absorption had maximum absorption at 510 nm. The reaction of GFX with one-electron oxidant N₃• was investigated and the bimolecular rate constant was determined to be 3.1×10⁹ M⁻¹ s⁻¹.     

S-benzoyl O-ethyl xanthate as a new photoinitiator: Photopolymerization and laser flash photolysis studies

A new sulfur-containing photoinitiator, S-benzoyl O-ethyl xanthate ( 2 ) has been prepared and used for the photopolymerization of methyl methacrylate (MMA). The photoinitiation property of 2 has been examined by conventional polymerization methods and nanosecond laser flash photolysis studies. Upon 308 nm laser pulse excitation, 2 gave rise to transients with absorption maxima at 350 and 650 nm, assigned to the benzoyl radical ( 3 ) and (ethoxythiocarbonyl)thiyl radical ( 4 ), respectively, on the basis of their quenching by nitroxy radicals and spectral similarity to analogous species, reported in the literature. © 1993 John Wiley & Sons, Inc.     

Diffuse reflectance laser flash photolysis of adsorbed molecules

Recent progress which allows laser flash photolysis investigation of opaque materials by using diffuse reflectance from analysing sources for the detection of laser induced transient species is described. Experimental details of nanosecond and picosecond diffuse reflectance laser photolysis systems are presented and methods of analysis of data are discussed. The potential of the technique for studying elementary reactions at interfaces is demonstrated with particular reference to bimolecular reactions of (a) the triplet state of acridine adsorbed on various porous silica surfaces and (b) ion-electron recombination following multi-photon ionisation of diphenyl polyenes adsorbed on γ-alumina. The mechanisms of formation and decay of these transient adsorbed species are discussed.     

Laser flash photolysis generation and kinetic studies of corrole-manganese(V)-oxo intermediates

Corrole-manganese(V)-oxo intermediates were produced by laser flash photolysis of the corresponding corrole-manganese(IV) chlorate complexes, and the kinetics of their decay reactions in CH2Cl2 and their reactions with organic reductants were studied. The corrole ligands studied were 5,10,15-tris(pentafluorophenyl)corrole (H3TPFC), 5,10,15-triphenylcorrole (H3TPC), and 5,15-bis(pentafluorophenyl)-10-(p-methoxyphenyl)corrole (H3BPFMC). In self-decay reactions and in reactions with substrates, the order of reactivity of (Cor)Mn(V)(O) was TPC > BPFMC > TPFC, which is inverted from that expected based on the electron-demand of the ligands. The rates of reactions of (Cor)Mn(V)(O) were dependent on the concentration of the oxidant and other manganese species, with increasing concentrations of various manganese species resulting in decreasing rates of reactions, and the apparent rate constant for reaction of (TPFC)Mn(V)(O) with triphenylamine was found to display fractional order with respect to the manganese-oxo species. The kinetic results are consistent in part with a reaction model involving disproportionation of (Cor)Mn(V)(O) to give (Cor)Mn(IV) and (Cor)Mn(VI)(O) species, the latter of which is the active oxidant. Alternatively, the results are consistent with oxidation by (Cor)Mn(V)(O) which is reversibly sequestered in non-reactive complexes by various manganese species.     

Triplet states of humic acids studied by laser flash photolysis using different excitation wavelengths

The spectra and kinetics of short-lived intermediates formed from aqueous (0.1 N NaOH) solutions of the natural mixture of humic and fulvic acids (HFA) were studied by laser flash photolysis using excitation wavelengths of 337, 390, 470, and 520 nm. Laser photolysis of HFA with light of 520 and 470 nm results in the formation of triplet excited states (T_HFA) characterized by the broad absorption spectrum with a maximum near 630 nm and lifetimes of 0.15 ms in deoxygenated solutions. The formation of two types of T_HFA with lifetimes of 0.1 and 2 ms and absorption spectra with maxima at 570 nm is observed under photolysis with light of 337 and 390 nm. The estimation of quantum yields of T_HFA gives 1 and 0.3% under photolysis with excitation wavelengths of 337 and 520 nm, respectively. The rate constants of T_HFA quenching by molecular oxygen are equal to (7—8)·10⁸ L mol^–1 s^–1.     

Laser flash photolysis and pulse radiolysis study on chemical activity of VP-16 and podophyllotoxin

Time-resolved laser flash photolysis and pulse radiolysis have been used to study the chemical activity of podophyllotoxin(PPT) and etoposide(VP-16). The mechanism of photoioniza-tion of etoposide and podophyllotoxin has been confirmed and illustrated. It is demonstrated that VP-16 and PPT in aqueous solution can be photoionized at 248 nm to give hydrated electron and neutral radical resulting from rapid deprotonation of radical cation of VP-16 and PPT. The quantum yield for the photoionization of VP-16 and PPT with single-photo is 0.21 and 0.61, respectively. In addition, they can react with hydrated electron, hydrogen radical and hydroxyl radical. This will give chemists some advice on synthesizing new derivatives of podophyllotoxin in cancer treatment.     

Study on the hydrogen donating abilities of benzofuranones as chain-breaking antioxidants using laser flash photolysis technique

The hydrogen donation kinetics of four 3-aryl-benzofuranones with different chemical structures toward tert-butoxyl radicals were studied using laser flash photolysis (LFP) technique. The rate constants of hydrogen reactions, which can be used to evaluate the hydrogen donating abilities of 3-aryl-benzofuranones toward radicals, were obtained. The results showed that the position of substituted methyl group has a very important effect on the hydrogen donating ability of benzofuranone toward tert-butoxyl radicals, i.e. if the methyl group is on 2′-position, the hydrogen donation of 3-aryl-benzofuranone toward tert-butoxyl radicals will be prevented and the hydrogen donating ability will be weakened.     

Laser flash photolysis of fluorinated aryl azides in neutral and acidic solutions

Laser flash photolysis of perfluoro-4-biphenyl azide andN-propyl-4-azido-2,3,5,6-tetrafluorobenzylamide in acetonitrile, water-acetonitrile mixtures, and HCl-containing solutions was studied. The absorption spectra of primary intermediates, singlet arylnitrenes(2a(S) and2b(S), respectively), were recorded. The absolute rate constants of their intersystem crossing in MeCN were measured, and the corresponding Arrhenius parameters were found from the temperature dependences of the rate constants of isomerization of singlet arylnitrenes2a(S) and2b(S) to azirines. Protonation of singlet arylnitrenes2a(S) and2b(S) was observed, the rate constants of their protonation were measured, and the transient absorption spectra of arylnitrenium ions were recorded. It was shown by quantum-chemical calculations (the hybrid B3LYP method) that the arylnitrenium ions that formed have the singlet ground state and the singlet-triplet gap is ∼20 kcal mol⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 49–54, January, 2000.     

Laser flash photolysis of fluorinated aryl azides in neutral and acidic solutions

Laser flash photolysis of perfluoro-4-biphenyl azide andN-propyl-4-azido-2,3,5,6-tetrafluorobenzylamide in acetonitrile, water-acetonitrile mixtures, and HCl-containing solutions was studied. The absorption spectra of primary intermediates, singlet arylnitrenes(2a(S) and2b(S), respectively), were recorded. The absolute rate constants of their intersystem crossing in MeCN were measured, and the corresponding Arrhenius parameters were found from the temperature dependences of the rate constants of isomerization of singlet arylnitrenes2a(S) and2b(S) to azirines. Protonation of singlet arylnitrenes2a(S) and2b(S) was observed, the rate constants of their protonation were measured, and the transient absorption spectra of arylnitrenium ions were recorded. It was shown by quantum-chemical calculations (the hybrid B3LYP method) that the arylnitrenium ions that formed have the singlet ground state and the singlet-triplet gap is ∼20 kcal mol⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 49–54, January, 2000.     

Study on electron transfer of fluorescent probe lumichrome and nucleic acid by laser flash photolysis

Laser flash photolysis (LFP) of lumichrome (LC) has been studied upon laser excitation at 355 nm. The transient absorption spectra of LC in aqueous solution displayed two bands at 380 nm and 540–700 nm for the triplet ³LC, and a wide band at 430–530 nm for the radical anion LC^.. The triplet-state lifetime was measured up to 12 μs. It was found that the self-quenching of ³LC by the ground state of LC occurred to produce LC^. during LFP. The transient spectra of LC in the presence of electron-donating triphenylamine (TPA), nucleosides and nucleic acids showed that the absorbance of ³LC was strongly quenched by these substrates and the formation of LC^. was enhanced in a great extent simultaneously. The bimolecular quenching kinetics were studied and the rate constants of ³LC by a series of quenchers, including TPA, LC, nucleosides and nucleic acids were determined to be 10⁸–10⁹ M⁻¹ s⁻¹. The photo-induced electron-transfer mechanism for these processes involving the triplet ³LC was proposed.     

Kinetics of hydrated electron reactions with phosphate anions: a laser photolysis study

The decay kinetics of hydrated electron (e_aq ⁻) formed upon photolysis of aqueous solutions of sodium pyrene-1,3,6,8-tetrasulfonate at λ = 337 nm in the presence of phosphate anions (up to 2 mol L⁻¹) was studied by nanosecond laser-pulse photolysis in a wide range of pH (3.5–10) and ionic strength (I, up to 2 mol L⁻¹) values. At high pH values, where the HPO₄ ²⁻ ions dominate, the e_aq ⁻ decay kinetics depends only slightly on phosphate concentration (rate constant for the reaction is at most 2·10⁵ L mol⁻¹ s⁻¹). The H₂PO₄ ⁻ ions react with e_aq ⁻ at a rate constant of 2.8·10⁶ L mol⁻¹ s⁻¹ (I = 0), which increases linearly with the parameter in accordance with the Debye-Hückel theory. The rate constant for quenching of e_aq ⁻ by H₃PO₄ at pH ≤ 4 decreases linearly with the parameter due to the secondary salt effect and equals 1.6·10⁹ L mol⁻¹ s⁻¹ at I = 0. The logarithm of the rate constant for quenching of e_aq ⁻ by phosphates is linearly related to the number of the O-H bonds in the phosphate molecule. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1277–1280, July, 2007.     

C-O-bond cleavage of esters with a naphthyl group in the higher triplet excited state during two-color two-laser flash photolysis

A C-O-bond cleavage of esters having a naphthyl group, NpCO-OR and RCO-ONp (Np=alpha- and beta-naphthyl ((alpha)Np and (beta)Np, respectively), R=Ph and Me), was found during the two-color two-laser flash photolysis in acetonitrile. The C-O-bond cleavage occurred when NpCO-OR and RCO-ONp were excited to the singlet excited states (S1). On the other hand, no reaction occurred from the lowest triplet excited states (T1). When NpCO-OR(T1) and RCO-ONp(T1) were excited to the higher triplet excited states (Tn) using the second laser during the two-color two-laser flash photolysis, the C-O-bond cleavage occurred. The C-O-bond cleavage quantum yield (Phi) was estimated from the plots of the T1-state esters disappeared within a laser flash versus the second laser intensities. The C-O-bond cleavage in (beta)NpCO-OPh(Tn) occurred more efficiently than in (alpha)NpCO-OPh(Tn) and that in PhCO-O(beta)Np(Tn) occurred more efficiently than in PhCO-O(alpha)Np(Tn). The Phi value for ester with Ph and beta-Np groups was larger than that for ester with Ph and alpha-Np groups. The Phi value for MeCO-O(alpha)Np(Tn) was similar to those for PhCO-ONp(Tn), while that for MeCO-O(beta)Np(Tn) was much smaller than those for PhCO-ONp(Tn) and MeCO-O(alpha)Np(Tn). On the other hand, no C-O-bond cleavage was observed in NpCO-OMe(Tn). The Phi value depended on the characters of the groups (Np, Ph, and Me) on the ester. Whether R is Ph or Me with or without pi electron, respectively, is important for the C-O-bond cleavage. In other words, electronic delocalization of the T(n) state including Np and ester groups is necessary for the occurrence of the C-O-bond cleavage in NpCO-OR(Tn) and RCO-ONp(Tn).