Electron Transfer Reaction Between Desoxyadenosine and Triplet 2-Methyl-1,4-naphthaquinone:A Laser Photolysis Study

Introduction Electron transfer oxidation of DNA by triplet artificial photonuclease reveals a bright prospect of its application in biology and medicine. Both molecular orbital calculation and laser experiments have indicated that the homo guanine sequence should be the final localization site of photoexcited hole via long range migration within DNA. However, the direct observation of the produced ion pairs of biomolecules especially the stabilized radical cation DNA or its components is hampered by the overwhelming transient absorption of protonated radical anion of photosensitizers, such as 2-methyl-1,4-naphthaguinonel （MQ）.

Laser Flash Photolysis Mechanism of Anthraquinone-2-Sodium Sulfonate in Pyridine Ionic Liquid/Water Mixed System

The photochemical reaction process of anthraquinone-2-sodium sulfonate （AQS） in the mixture of water （H2O） and N-butylpyridinium tetrafluoroborate （[BPy] [BF4]） was studied using the laser flash photolysis technique. Experimental results show that the excited triplet of AQS （3AQS＊） could react rapidly with H2O and the transient absorption spectra greatly changed by increasing the volume fraction of the ionic liquid （VIL） in [BPy][BF4]/H2O mixtures. The absorbance at 510 nm increased gradually with increasing VIL when 0〈VIL〈0.1. By contrast, the absorbance decreased gradually when VIL〉0.1. Otherwise, the absorbance of the band near 380 nm steadily increased. The apparent kinetic parameters of transient species B and ^3AQS＊ are obtained approximately. 3AQS＊ abstracting hydrogen from [BPy]＋ was also explored. It was deduced that the 350-420 nm band was the superposition of the peaks of 3AQS＊ and AQSH＇. The two reactions of 3AQS＊ with [BPy][BF4] and H2O are a pair of competitive reactions. We also concluded that the entire reaction processes slow down in the case of high [BPy] [BF4] concentrations.

Temperature-dependent Kinetics on Laser Induced Photolysis of Aqueous CS_2-HONO Solutions

A laser photolysis/transient absorption technique has been employed to investigate the photolysis kinetics of aqueous CS2-HONO solutions at 355 nm. Spectral analysis shows that CS2OH will react with HONO to form CS2OH-HONO. Temperature dependent rate coefficients for the reaction are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 273-313 K （units are L·mol^-1·s^-1）： In k = （31.6±0.6）-{（4.1±0.2）×10^3/T}, and the activation energy in unit of kJ.molA is 32.47 with the temperature accuracy 0.2 K.

pH Dependence of Photochemical Kinetics of Thioxanthen-9-one from Nanosecond Time-resolved Laser Flash Photolysis

pH dependent uorescence emission of a thioxanthone-based probe has been re-ported recently.The potential deter-minant factors of pH dependence may provide important clues to design novel thioxanthone-based probes in the fu-ture.pH dependence of photochemical kinetics of thioxanthone itself was inves-tigated in this work using nanosecond time-resolved laser ash photolysis.The nanosecond time-resolved transient absorption spectra and kinetics of TX in aqueous acetonitrile were recorded,as well as for a model reaction system including TX with diphenylamine(DPA)as a co-initiator.Besides the well-known absorption peak of ^(3)TX*,other peaks at 417,518,673 and 780 nm,have been reliably attributed to major intermediates in the overall reaction between TX and DPA with photolysis,which has been con rmed to occur along a multistep process.In the strong acidic solution(pH≈3.0),TX and protonated TX ions(TXH^(+))coexist due to protonated equilibrium.Consequently,high proton concentration promotes the predominant decay pathway after photolysis from electron transfer to proton affnity.Subsequently,the di erent primary products,^(3)TXH^(+*)or TX^(·-),proceed di erent secondary reaction channels.In addition,within the wide pH range from weak acid(pH=5.0)to alkaline solution(pH=13.0),the overall reaction mechanism and rates do not show visible changes.

TIME-RESOLVED IR STUDIES OF UV LASER FLASH PHOTOLYSIS OF W(CO)_6 IN C_6H_(12)-CCl_4 AND CCl_4 SOLUTION

Time-resolved IR absorption spectroscopy has been used to atudy the photochemistry of W(CO)_6 in cyclohexane, carbon tetrachloride, and the mixture of carbon tetrachloride and cyelohexane. The reastion of photolytically generated W(CO)_5. C_6H_(12) with CCl_4 was investigated. An intermediate with a lifetime of about 0.5ms, presumably attributed as W(GO)_5.CCl_4, was first observed.

Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

Pentachlorophenol, a widespread environmental pollutant that is possibly carcinogenic to humans, is metabolically oxidized to tetrachloroquinone （TCBQ） which can result in DNA damage. We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases （thymine and uracil） upon UVA （355 ran） excitation using the technique of nanosecond time-resolved laser flash photolysis. It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ＊, which are highly reactive towards thymine or uracil and undergo two parallel reactions, the hydrogen abstraction and electron transfer, leading to the observed photoproducts of TCBQH. and TCBQ.- in transient absorption spectra. The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards. By characterizing the photochemical hydrogen abstraction and electron transfer reactions, our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

Photophysical Properties and Photoinduced Electron Transfer between [60] Fullerene-Containing Cyclic Sulphoxide [C_(60)-C_6H_8SO] and Tetrathiafulvalene (TTF) by Laser Flash Photolysis

Photoinduced electron transfer (PET) processes between C 60-C 6H 8SO and Tetrathiafulvalene (TTF) have been studied by nanosecond laser photolysis. Quantum yields (Φ et) and rate constants of electron transfer (k et) from TTF to excited triplet state of fullerene-containing cyclic sulphoxide in benzonitrile (BN) have been evaluated by observing the transient absorption bands in the NIR region. With the decay of excited triplet state of fullerene-containing cyclic sulphoxide, the rise of radical anion of fullerene-containing cyclic sulphoxide is observed.

Determination of Astaxanthin and Canthaxanthin Triplet Properties in Different Polarities of the Solvent by Laser Flash Photolysis

Triplet-triplet extinction coefficients for astaxanthin （I） and canthaxanthin （II） in different deaerated polarity solutions of MeCN and benzene were evaluated by laser flash photolysis at 298 K in the spectral region from 350 to 650 nm by energy transfer method, employing 2-acetonaphthone as sensitizer. The triplet-triplet extinction coeffi- cients in MeCN and benzene were different in terms of the carotenoid present. The maximum triplet-triplet extinc- tion coefficient was 0.1-1.7 ×10^5 L·mol^-1·cm^-1 in different solvents. The rate constants of triplet decay were I： 1.25×10^10 L·mol^-1·s^-1, II： 1.12×10^10 L·mol^-1·s^-1 in MeCN; and I： 1.75×10^10 L·mol^-1, II： 3.27×10^10 L·mol^-1·s^-1 in benzene. The bimolecular rate constants of energy transfer from triplet excited 2-acetonaphthone to carotenoids were determined from the linear regression of the decay rate constant of 2-acetonaphthone triplet at varying carotenoid concentrations. The triplet lifetimes of ^3AST^＊ and 3CAN^＊ in different solvents were also determined. The results indicated that triplet energy transfer was nearly diffusion-controlled.

Degradation characteristic of 4-bromdiphenyl ether in mixed solutions by electron beam irradiation

The degradation characteristic of 4-bromdiphenyl ether （BDE-4） was investigated in different solutions.The study indicates that the process of direct degradation of this compound is dependent upon the bromine and the ether bond connected to diphenyl by electron beam.laser flash photolysis was employed to determine the degradation of each species （cationic,neutral,and anionic）.From these data,intermediate products of BDE-4 degradation were shown for direct irradiationdegradation.The neutral radical was formed during the photolysis of these compounds.For all the compounds,diphenyl ether and hydroxybiphenyl were observed as common products.Reaction of the BDE-4 under electron beam was debromide.The debromide rate of BDE-4 at pH=5.5 is somewhat lower than that of BDE-4 at pH=10.0.The decomposition rate for BDE-4 is 99.8% at pH=10.0 on the dose of 14 kGy.BDE-4 from its radical could provide bromine ion into water and the cation radical of BDE-4 formed quickly recombine with hydrogen radical and formed phenyl ether.

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 stud- ied 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 Trp＂ and TyrO＇. The re- lated rate constants of these reactions were determined in this paper. The free energy changes （AG） 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.

H-Atom Transfer Reaction of Photoinduced Excited Triplet Duroquinone with Tryptophan and Tyrosine in Acetonitrile-Water and Ethylene Glycol-Water Homogeneous Solutions

Laser flash photolysis was used to investigate the photoinduced reactions of excited triplet bioquinone molecule duroquinone(DQ)with tryptophan(Trp)and tyrosine(Tyr)in acetonitrile-water(Me CN-H_(2)O)and ethylene glycol-water(EG-H_(2)O)solutions.The reaction mechanisms were analyzed and the reaction rate constants were measured based on Stern-Volmer equation.The H-atom transfer reaction from Trp(Tyr)to ^(3)DQ^(*)is dominant after the formation of^(3)DQ^(*)during the laser photolysis.For DQ and Trp in MeCN-H_(2)O and EG-H_(2)O solutions,^(3)DQ^(*)captures H-atom from Trp to generate duroquinone neutral radical DQH^(·),carboncentered tryptophan neutral radical Trp^(·)/NH and nitrogen-centered tryptophan neutral radical Trp/N^(·).For DQ and Tyr in Me CN-H_(2)O and EG-H_(2)O solutions,^(3)DQ^(*)captures H-atom from Tyr to generate duroquinone neutral radical DQH^(·) and tyrosine neutral radical Tyr/O^(·).The H-atom transfer reaction rate constant of^(3)DQ^(*)with Trp(Tyr)is on the level of 109 L·mol^(-1)·s^(-1),nearly controlled by diffusion.The reaction rate constant of^(3)DQ^(*)with Trp(Tyr)in Me CN/H_(2)O solution is larger than that in EG/H2O solution,which agrees with Stokes-Einstein relationship qualitatively.

Magnetic Field Effects on Photoreduction Reaction of 2-Methyl-1,4-Naphthoquinone in Brij 35 Micellar Solution with Additional Radical

A study was made of magnetic field effects (MFEs) on the photoreduction reaction of 2-methyl-1,4-naphthoqui- none (MNQ) in Brij 35 micellar solution containing 4-lauroylamino-TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) radical (L-R) under magnetic fields below 1.75 T by a nanosecond laser flash photolysis technique. The triplet MNQ mainly underwent the hydrogen abstraction from Brij 35 molecule to give a radical pair. The escaped radical yield increased with magnetic fields from 0 to 0.62 T and then saturated from 0.62 to 1.75 T. MFEs for both sys-tems can be explained by the relaxation mechanism. However, it was supposed that additional radical, L-R affected the MFEs mainly through enhancing the spin-spin interactions of radical pairs. The effect of the micelle size on MFEs of the studying system was also discussed.

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both3RF* and hydrated electron (eaq) formed from photoionization could be detected. Photobiological implications have been inferred on the basis of reactivity of3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF·+ was generated by oxidation of SO4 ·-radical with the aim of confirming the results of photolysis.

Photosensitive damage of lysozyme caused by pazufloxacin and the protective effect of ferulic acid

Laser flash photolysis and sodium dodecyl sulfate-polyacrylamide gel electrophoresis(SDS-PAGE) experiments were carried out to study the photosensitive damage induced by pazufloxacin(PAX) and the protection of lysozyme(Lyso) by ferulic acid(FCA), an active antioxidant. Transient absorption spectra revealed electron transfer from Lyso and FCA to 3PAX*, with respective bimolecular reaction rate constants of 6.3×107 and 1.4×1010 dm3/(mol s). A pulse radiolysis study was also performed to investigate the formation of Lyso radical cations. Results showed that FCA effectively inhibited the cross-linking of protein induced by fluoroquinolones. Finally, a mechanism of the protective effect of FCA on Lyso was proposed.

Effects of pH and polarity on the excited states of norfloxacin and its 4′-N-acetyl derivative:a steady-state and time-resolved study

The properties of norfloxacin(NFX)and its 4?-N-acetyl derivative(ANFX)are investigated in different pH aqueous solutions and H2O-CH3CN mixed solutions,to determine the effects of pH and polarity on their ground and excited states.The triplet states of NFX and ANFX are affected more by pH than by polarity.The pH dependence of the NFX and ANFX triplet states is likely due to the different quantum yields of different protonated forms.Steady-state fluorescence,time-resolved fluorescence,and laser flash photolysis experiments at different pH values provide clear evidence of the involvement of different intramolecular charge-transfer pathways in the singlet states of NFX and ANFX.The different electron-donating capacities of 1-N,1?-N,and 4?-N under different conditions determine the major pathway.

Kinetics and mechanisms of reactions for hydrated electron with chlorinated benzenes in aqueous solution

The reactions between chlorinated benzenes （CBzs） and hydrated electron （eaq^-） were investigated by the electron beam （EB） and laser flash photolysis （LFP） experiments. Under the EB irradiation, the effects of irradiation dose, initial concentration and the number of Cl atoms on the removal efficiencies were further examined. At 10 kGy, the removal efficiencies of mono-CB, 1,3-diCB, 1,2-diCB and 1,4-diCB were 41.2%, 87.2%, 84.0%, and 84.1%, respectively. While irradiation dose was 50 kGy, the removal efficiencies increased to 47.4%, 95.8%, 95.0%, and 95.2%, respectively. Irradiation of CBzs solutions has shown that the higher the initial concentration, the lower the percentage of CBzs removal. In addition to this, the dechlorination efficiencies of 1,2-dichlorobenzene （1,2-diCB）, 1,3-dichlorobenzene （1,3-diCB） and 1,4-dichlorobenzene （1,4-diCB） were much higher than that of chlorobenzene （mono-CB）. The kinetics of the reactions was achieved with nanosecond LFP. The rate constants of second-order reaction between eaq^- with mono-CB, 1,2-diCB, 1,3-diCB and 1,4-diCB were （5.3±0.4） × 10^8, （4.76±0.1） × 10^9, （1.01±0.1） × 1010 and （3.29±0.2） × 10^9 L·mol^-1·s^-1, respectively. Density functional theory （DFT） calculations were performed to determine the optical properties of unstable CBzs anion radicals, and the main absorption peaks lied in the range of 300–550 nm. The primary reaction pathway of CBzs with eaq^- was gradual dechlorination, and the major products were Cl^- and benzene （CBzs（-Cl^-））. Furthermore, biphenyl （or chlorobiphenyl） was observed during the LFP, which was probably formed by recombination of benzene radicals.

Two-photon Dissociation Study of Carbon Disulfide in Acetonitrile at 266 nm

Using laser flash photolysis/transient absorption technique for the study of two photon photodissociation of carbon disulfide in acetonitrile solution at 266 nm, the transient UV-Vis absorption spectrum of Rydberg state CS2 （6sσg） within 240-370 nm and subsequent dissociation product CS （α^3П） with the maximum absorption at 260 nm were directly observed. The lifetime of CS （α^3П） in the nitrogen and oxygen saturated solution is also studied in our experiment.