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 techn...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.展开更多
The transient absorption spectra and kinetics of excited triplet state of anthraquinone derivatives 2-anthraquinonesulfonatesodium (AQS) and 2-deoxythymidine (dT) have been investigated in CH3CN-H2O (97:3) using the t...The transient absorption spectra and kinetics of excited triplet state of anthraquinone derivatives 2-anthraquinonesulfonatesodium (AQS) and 2-deoxythymidine (dT) have been investigated in CH3CN-H2O (97:3) using the time-resolved laser flash photolysis technique (KrF, 248 nm). The absorption spectra of dT radical cation and the radical anion of AQS have been observed. From dynamic and thermodyrnamic analysis, the mechanism of this transient reaction has been initially analysed.展开更多
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 photolytical...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.展开更多
Photoinduced chemical reactions of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF_6]) were studied by laser photolysis at a wavelength of 266 nm.Excited triplet state ~3[bmim]^+ was observed,radical cation...Photoinduced chemical reactions of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF_6]) were studied by laser photolysis at a wavelength of 266 nm.Excited triplet state ~3[bmim]^+ was observed,radical cation [bmim]^(2+) and neutral [bmim] radical via photoionization were also formed.Energy transfer from ~3[bmim]^+ toβ-carotene was confirmed.Oxidation via one electron transfer from TMPD to ~3[bmim]^+ was also observed and the rate constant was determined to be 1.2×10.5 L.mol^(-1).s^(-1).The reaction of [bmim][PF_6] with hydrated electron (e_(aq)) was confirmed by laser photolysis in aqueous solution.展开更多
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 photoionization of etoposide and podophyllotoxin h...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 photoionization 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.展开更多
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 transfe...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.展开更多
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 re...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.展开更多
Fullerols of C 60 and of C 70 \ [C 60 (OH)\-\%n\%, C 70 (OH)\-\%m\%], water\|soluble fullerene derivatives, unlike some other fullerene derivatives (such as C 60 (C\-4H\-6O), C 60 (C\-3H\-7N) and C 60 [C(COOEt)\-2]\-\...Fullerols of C 60 and of C 70 \ [C 60 (OH)\-\%n\%, C 70 (OH)\-\%m\%], water\|soluble fullerene derivatives, unlike some other fullerene derivatives (such as C 60 (C\-4H\-6O), C 60 (C\-3H\-7N) and C 60 [C(COOEt)\-2]\-\%x\%), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser. The quantum yields of formation of hydrated electron ( Φ e - ) are determined to be 0.08 and 0.11 for fullerols of C 60 and of C 70 respectively at room temperature (ca. 15℃) with KI solution used as reference. By laser flash photolysis and oxidation of sulfate radical anion SO -· \-4, the fullerol radical cation or neutral radical of C 60 is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C 70 are observed for the first time.展开更多
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...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.展开更多
The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized acc...The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments. The intermediates recorded were assigned to the excited triplet state of tryptophan, the radicals of tryptophan and tyrosine. The excited triplet state of tryptophan produced via a triplet-triplet excitation transfer and the radicals arising from electron transfer reaction has been identified. Neither electron transfer nor energy transfer between triplet acetone and phenylalanine can occur in photolysis of phenylalanine aqueous solution which contains acetone. Furthermore, triplet acetone-induced radical transformation: Trp/N-Tyr→Trp-Tyr/O was observed directly in photolysis of dipeptide (Trp-Tyr) aqueous solution containing acetone, and the transformation resulting from intramolecular electron transfer was suggested.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.21173002） and the Anhui Provincial Natural Science Foundation, China （No.1308085MB20）.
文摘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.
文摘The transient absorption spectra and kinetics of excited triplet state of anthraquinone derivatives 2-anthraquinonesulfonatesodium (AQS) and 2-deoxythymidine (dT) have been investigated in CH3CN-H2O (97:3) using the time-resolved laser flash photolysis technique (KrF, 248 nm). The absorption spectra of dT radical cation and the radical anion of AQS have been observed. From dynamic and thermodyrnamic analysis, the mechanism of this transient reaction has been initially analysed.
文摘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.
基金Supported by National Natural Science Foundation of China(20573130,20673137)
文摘Photoinduced chemical reactions of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF_6]) were studied by laser photolysis at a wavelength of 266 nm.Excited triplet state ~3[bmim]^+ was observed,radical cation [bmim]^(2+) and neutral [bmim] radical via photoionization were also formed.Energy transfer from ~3[bmim]^+ toβ-carotene was confirmed.Oxidation via one electron transfer from TMPD to ~3[bmim]^+ was also observed and the rate constant was determined to be 1.2×10.5 L.mol^(-1).s^(-1).The reaction of [bmim][PF_6] with hydrated electron (e_(aq)) was confirmed by laser photolysis in aqueous solution.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 39700029).
文摘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 photoionization 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.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 0 710 12 ) ,ResearchFundfortheYoungTeacherPro gramofHigherEducationofChina (No .2 0 0 0 6 5 )andtheNaturalScienceFoundationofGuangdongProvince (No .0 0 0 70 0 )
文摘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.
基金Project supported by the National Natural Science Foundation of China （No. 10675158）.
文摘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.
文摘Fullerols of C 60 and of C 70 \ [C 60 (OH)\-\%n\%, C 70 (OH)\-\%m\%], water\|soluble fullerene derivatives, unlike some other fullerene derivatives (such as C 60 (C\-4H\-6O), C 60 (C\-3H\-7N) and C 60 [C(COOEt)\-2]\-\%x\%), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser. The quantum yields of formation of hydrated electron ( Φ e - ) are determined to be 0.08 and 0.11 for fullerols of C 60 and of C 70 respectively at room temperature (ca. 15℃) with KI solution used as reference. By laser flash photolysis and oxidation of sulfate radical anion SO -· \-4, the fullerol radical cation or neutral radical of C 60 is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C 70 are observed for the first time.
基金supported by the National Natural Science Foundation of China (21173252)
文摘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.
基金Project supported by the China Postdoctoral Science Foundation.
文摘The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments. The intermediates recorded were assigned to the excited triplet state of tryptophan, the radicals of tryptophan and tyrosine. The excited triplet state of tryptophan produced via a triplet-triplet excitation transfer and the radicals arising from electron transfer reaction has been identified. Neither electron transfer nor energy transfer between triplet acetone and phenylalanine can occur in photolysis of phenylalanine aqueous solution which contains acetone. Furthermore, triplet acetone-induced radical transformation: Trp/N-Tyr→Trp-Tyr/O was observed directly in photolysis of dipeptide (Trp-Tyr) aqueous solution containing acetone, and the transformation resulting from intramolecular electron transfer was suggested.
