Acetohydroxamic acid(AHA) is a novel saltfree reagent used for the separation of Pu and Np from U in the advanced Purex process. This paper reports the c-ray damage of AHA in HNO_3 and its radiolytic product. For 0.2 ...Acetohydroxamic acid(AHA) is a novel saltfree reagent used for the separation of Pu and Np from U in the advanced Purex process. This paper reports the c-ray damage of AHA in HNO_3 and its radiolytic product. For 0.2 mol L^(-1) AHA in 0.2–2.0 mol L^(-1) HNO_3 irradiated at a dose of 5–25 kGy, the radiolytic rate of AHA is6.63–77.5%, and it increases with the HNO_3 concentration and absorbed dose. The main radiolytic gases are N_2O and H_2, with volume fractions of(0.500–16.2) 9 10^(-2) and(1.30–11.8) 9 10^(-3), respectively, and they increase with the absorbed dose; the H_2 volume fraction decreases with increasing HNO_3 concentration. The main liquid radiolytic products are CH_3 COOH and HNO_2, and their concentrations are(3.40–19.7) 9 10^(-2) and(0.200–4.80) 9 10^(-3)-mol L^(-1), respectively, which increase with the HNO_3 concentration. Since a significant concentration of HNO_2 is present in the irradiated AHA-HNO_3 solution, a holding reductant must be used to destroy HNO_2 and stabilize Pu(Ⅲ) and Np(Ⅴ) when AHA is applied for the separation of Pu and Np from U.展开更多
We studied the reaction kinetics of dismutation for superoxide ion by copper (Ⅱ) complex of macrocycllc dioxotetramine ligand 12- ( 4' - nitro )- benzyl-1,4,7,10- tetraazacy-clotridecane-11,13-dionato copper (Ⅱ)...We studied the reaction kinetics of dismutation for superoxide ion by copper (Ⅱ) complex of macrocycllc dioxotetramine ligand 12- ( 4' - nitro )- benzyl-1,4,7,10- tetraazacy-clotridecane-11,13-dionato copper (Ⅱ) by using pulse radiolysis. The rate constants of dismutation kcat's were measured to be 1. 78×106 mor-1 . L.s-1(at pH 7. 0) and 1. 06×106 mol-1. L. s-1(at pH 7. 8). The reaction mechanism is similar to that catalyzed by super-oxide dismutase.展开更多
The dismutation kinetics of superoxide anion by copper complex of 1,4,7,10-tetranza- cyctotridecane-11,13-dione was studied by pulse radiolysis.The dismutation rate constants at various pH and concentration of complex...The dismutation kinetics of superoxide anion by copper complex of 1,4,7,10-tetranza- cyctotridecane-11,13-dione was studied by pulse radiolysis.The dismutation rate constants at various pH and concentration of complex were obtained.展开更多
A compact pulse radiolysis apparatus using a BNL-type s-band photocathode RF gun is now under development at Waseda University.The laser pulse is used for excitation of the photocathode and for generation of white lig...A compact pulse radiolysis apparatus using a BNL-type s-band photocathode RF gun is now under development at Waseda University.The laser pulse is used for excitation of the photocathode and for generation of white light,which is used for analyzing light in the pulse radiolysis.展开更多
Successful treatment of keloids has eluded the medical community since their first description. Multitudes of therapeutic options are available, but none achieves satisfactory resolution of keloids. One major stumblin...Successful treatment of keloids has eluded the medical community since their first description. Multitudes of therapeutic options are available, but none achieves satisfactory resolution of keloids. One major stumbling block is lack of understanding about their genesis. Assuming keloids are tumors, attempts have been made to treat this condition with standard radiotherapy, with dismal results. Keloidal masses are not an active biological entity. They are aggregations of cellular, hypovascular, hypoxic bundles of collagen, which are produced by atypical fibroblasts in the wounds and eventually cease production due to a hostile biological environment. Having no demonstrable inherent process of disposal of these collagen bundles, this excessive collagen tends to linger to form the bulk of keloids. The lesions eventually become symptomatic and aesthetically unacceptable, and therapeutic intervention is sought. Of all available treatments, such as post-resection radiotherapy, primary radiotherapy in selected cases and primary brachytherapy stand out above any other form of treatment. Be it brachytherapy or external beam treatment, one fundamental aspect of radiation action is the process of “radiolysis”, explaining why “radiobiological” approaches have been ineffective.展开更多
Using pulse radiolysis technique, the reaction between hydroxyl radical and 7 phenylpropanoidglycosides: echinacoside, verbascoside, leucosceptoside A, martynoside, pediculariosides A, M and N which were isolated from...Using pulse radiolysis technique, the reaction between hydroxyl radical and 7 phenylpropanoidglycosides: echinacoside, verbascoside, leucosceptoside A, martynoside, pediculariosides A, M and N which were isolated from Pedicularis were examined. The rate constants of these reactions were determined by transient absorption spectra. All 7 phenylpropanoid glycosides react with hydroxyl radical at high rate constants within (0.97-1.91)×1010L · mol-1 · s-1. suggesting that they are effective hydroxyl radical scavengers. The results demonstrate that the numbers of phenolic hydroxyl groups of phenylpropanoid glycosides are directly related to their scavenging activities. The scavenging activities are likely related to o-dihydroxy group of phenylpropanoid glycosides as well.展开更多
By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal tha...By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal that attack of the oxidizing SO4- radical on Phe leads directlyto the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes -COOH and -NH2 and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.展开更多
The reactions between gatifloxacin(GFX) and various one-electron oxidants,such as ˙OH,N3˙,Br2˙ˉ,and SO4˙ˉ,have been studied by pulse radiolysis techniques.The GFX radical anion formed in the reaction of GFX with...The reactions between gatifloxacin(GFX) and various one-electron oxidants,such as ˙OH,N3˙,Br2˙ˉ,and SO4˙ˉ,have been studied by pulse radiolysis techniques.The GFX radical anion formed in the reaction of GFX with eaqˉ could either be protonated or deprotonated,and the absorption of GFX radical anion was located at 390 nm.The transient species produced by the reaction of GFX with ˙OH radical shows a broad band in the 380?600 nm region with a shoulder,while the oxidation by N3˙,SO4˙ˉ,and Br2˙ˉ results in an absorption band with λmax = 370 nm.At neutral condition(pH 7),the rate constants of GFX reacting with ˙OH,N3˙,Br2˙ˉ,SO4˙ˉ and eaqˉ are estimated to be 1.0 × 1010,3.1 × 109,2.8 × 109,3.0 × 109,and 1.8 × 1010 dm3 mol?1 s?1,respectively.From the pH dependence on the formation of electron adducts and on the rate constant of GFX with eaqˉ,the pKa of GFX radical anion is estimated to be 5.5 and 9.3.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
Repair activities of thymine radical anion by echinocoside, isolated from Pedicularis plicata. were studied using pulse radiolysis technique. The thymine radical anion was produced by the reaction of hydrated electron...Repair activities of thymine radical anion by echinocoside, isolated from Pedicularis plicata. were studied using pulse radiolysis technique. The thymine radical anion was produced by the reaction of hydrated electron with thymine. Echinocoside. one of the polyphenols of phenylpropanoid glycoside, was added to the thymine aqueous solution saturated with N2. Kinetic analysis by transient absorption spectrum showed that thymine radical anion was formed at first, and then after several decades of microseconds of pulse radiolysis. the spectrum of thymine radical anion was changed to that of echinocoside radical anion. The evidence indicated that thymine radical anion was repaired through one-electron-transfer between the DNA base radical anion and echinocoside. The rate constant of electron transfer by echinocoside was 1.45× 109 dm3 · mol1 · s 1.展开更多
The excited triplet of C60 or C70 is generated via either direct excitation by laser light or energy transfer from excited states of solvent to C60 and C70. The cation radical of C60 is produced either via hole transf...The excited triplet of C60 or C70 is generated via either direct excitation by laser light or energy transfer from excited states of solvent to C60 and C70. The cation radical of C60 is produced either via hole transfer from cation radical of CCl4 to C60 or via electron transfer from excited triplet of C60 to CCl4. C60 and C70 could be added to trichloromethyl radical to produce adduct radicals with different mechanisms.展开更多
The antitumor mechanism of etoposide (VP-16) is investigated using pulse radiolysis technology. The oxidizing mechanism of VP-16 is studied by sodium persulfate, and the reaction rate constant is 4.04× 109 L·...The antitumor mechanism of etoposide (VP-16) is investigated using pulse radiolysis technology. The oxidizing mechanism of VP-16 is studied by sodium persulfate, and the reaction rate constant is 4.04× 109 L· mol-1 · s-1. The electron-transfer between VP-16 and tyrosine is observed and the reaction rate constant is 1.1 - 108 L · mol-1· s-1.展开更多
One-electron oxidation of N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleoside wyosine with several oxidative radicals, has been studied by using pulse radiolysis. The transient spectra of the radical...One-electron oxidation of N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleoside wyosine with several oxidative radicals, has been studied by using pulse radiolysis. The transient spectra of the radicals dYt˙+ and dYt(-H)˙ and the pK a of the radical cation were measured. The rate constants of reactions of dYt with SO 4 ˙? and CO 3 ˙? radicals have been determined and related reaction mechanisms were discussed.展开更多
1 Introduction Radiation-inducde direct damage of DNA originates primarily from the electron-gaining and losing sites. Determining the chemical nature and distribution of these sites is obviously a central problem in ...1 Introduction Radiation-inducde direct damage of DNA originates primarily from the electron-gaining and losing sites. Determining the chemical nature and distribution of these sites is obviously a central problem in this field. At present, the most widely accepted model is T^-/G^+ dichotomy model, i. e. electrons are mainly trapped at thymine (T) and holes at guanine (G) through electron transfer along DNA chain. However, recent work showed another possible electron-gaining center: cytosine. In the mean time, the role of proton transfer in affecting the distribution of electron trapping among the DNA bases has received more展开更多
The free radical scavenging activities of puerarin towards nitrogen dioxide radicals (NO 2 ˙ ), nitric oxide radicals (NO˙) and hydroxyl radicals (OH˙) were investigated by pulse radiolysis. Puerarin reacted with (...The free radical scavenging activities of puerarin towards nitrogen dioxide radicals (NO 2 ˙ ), nitric oxide radicals (NO˙) and hydroxyl radicals (OH˙) were investigated by pulse radiolysis. Puerarin reacted with (NO 2 ˙ ) or (NO˙) to form puerarin-4-O˙ with the absorption maximum at 340 nm, but reacted with OH˙ to form at least three transient species including puerarin-2-O˙, puerarin-4-O˙ and [puerarin-OH]˙with a broad absorption spectrum band (300-750 nm). In addition, the reaction rate constants of puerarin reacting with NO 2 ˙ , and NO˙ were determined as 2.6 × 108, 1.7× 108 and 3.9 × 109 L · mol?1 · s?1, respectively.展开更多
The interactions of carotenoids (bixin, β-carotene and lycopene) with CCl3OO. in aqueous and i-propylalcohol solution saturated with air have been studied by pulse radiolysis. For bixin and β-carotene reaction produ...The interactions of carotenoids (bixin, β-carotene and lycopene) with CCl3OO. in aqueous and i-propylalcohol solution saturated with air have been studied by pulse radiolysis. For bixin and β-carotene reaction products from forming process, absorbing in the region of 650 nm, is observed with concomitant carotenoid bleaching (bixin at 500 nm, β-carotene at 450 nm). Their rate constants from forming process are 1.78 ×108 and 7.8 ×107 mol-1 · L · s-1 respectively. However, in the case of lycopene, no such a forming process of reaction as bixin and β-carotene can be observed although there is the bleaching reaction (rate constant 4 ×107 mol-1 · L · s-1). The results suggest that the carotenoid radical cation and an additional radical are produced in the case of bixin and β-carotene, whereas lycopene undergoes electron transfer with CCl3OO., forming cation radical.展开更多
The piperonal electron affinity was studied using pulse radiolysis technique. The electron transfer reaction process between piperonal and anthraquinone-2-sulfate was observed in the pH 7 phosphoric acid salt buffer. ...The piperonal electron affinity was studied using pulse radiolysis technique. The electron transfer reaction process between piperonal and anthraquinone-2-sulfate was observed in the pH 7 phosphoric acid salt buffer. The transient absorption spectra of electron transfer re-action between piperonal and anthraquinone-2-sulfate were obtained, and the initial proof of the electron transfer between electron donor and acceptor was provided directly. The one-electron reduction potential of piperonal was determined to be ?0.457 V.展开更多
The mechanisms of reactions between CC13OO? radical and quercetin, rutin and epigallocatechin gallate (EGCG) have been studied using pulse radiolytic technique. It is suggested that the electron transfer reaction is t...The mechanisms of reactions between CC13OO? radical and quercetin, rutin and epigallocatechin gallate (EGCG) have been studied using pulse radiolytic technique. It is suggested that the electron transfer reaction is the main reaction between CC13OO? radical and rutin, EGCG, but there are two main pathways for the reaction of CC13OO? radical with quercetin, one is the electron transfer reaction, the other is addition reaction. The reaction rate constants were determined. It is proved that quercetin and rutin are better CC13OO? radical scavengers than EGCG.展开更多
Based on pulse radiolysis of aqueous solutions of two salicylic acid derivatives including ethyl salicylate and benzylsalicylate the transient absorption spectra and the rate constants of hydroxyl radical with salicyl...Based on pulse radiolysis of aqueous solutions of two salicylic acid derivatives including ethyl salicylate and benzylsalicylate the transient absorption spectra and the rate constants of hydroxyl radical with salicylic acid derivatives were determined for the first time. The results indicated that ethyl salicylate and benzylsalicylate have efficient activities to scavenge hydroxyl radical.展开更多
The oxidative splitting process of cis-syn 1,3-dimethyluracil cyclobutane dimer (DMUD) in aqueous solution was investigated using pulse radiolysis technique. The results indicated that DMUD can be splitted into 1,3-...The oxidative splitting process of cis-syn 1,3-dimethyluracil cyclobutane dimer (DMUD) in aqueous solution was investigated using pulse radiolysis technique. The results indicated that DMUD can be splitted into 1,3-dimethyluracil (DMU) by OH radicals (OH ·) and Br_2 radical anions (Br ·-_2), but not by azide radicals (N ·_3). The oxidative mechanisms that an H-abstracted from DMUD for OH · oxidative splitting and an electron transfer from DMUD to Br ·-_2, were suggested. Related kinetic parameters were determined.展开更多
文摘Acetohydroxamic acid(AHA) is a novel saltfree reagent used for the separation of Pu and Np from U in the advanced Purex process. This paper reports the c-ray damage of AHA in HNO_3 and its radiolytic product. For 0.2 mol L^(-1) AHA in 0.2–2.0 mol L^(-1) HNO_3 irradiated at a dose of 5–25 kGy, the radiolytic rate of AHA is6.63–77.5%, and it increases with the HNO_3 concentration and absorbed dose. The main radiolytic gases are N_2O and H_2, with volume fractions of(0.500–16.2) 9 10^(-2) and(1.30–11.8) 9 10^(-3), respectively, and they increase with the absorbed dose; the H_2 volume fraction decreases with increasing HNO_3 concentration. The main liquid radiolytic products are CH_3 COOH and HNO_2, and their concentrations are(3.40–19.7) 9 10^(-2) and(0.200–4.80) 9 10^(-3)-mol L^(-1), respectively, which increase with the HNO_3 concentration. Since a significant concentration of HNO_2 is present in the irradiated AHA-HNO_3 solution, a holding reductant must be used to destroy HNO_2 and stabilize Pu(Ⅲ) and Np(Ⅴ) when AHA is applied for the separation of Pu and Np from U.
文摘We studied the reaction kinetics of dismutation for superoxide ion by copper (Ⅱ) complex of macrocycllc dioxotetramine ligand 12- ( 4' - nitro )- benzyl-1,4,7,10- tetraazacy-clotridecane-11,13-dionato copper (Ⅱ) by using pulse radiolysis. The rate constants of dismutation kcat's were measured to be 1. 78×106 mor-1 . L.s-1(at pH 7. 0) and 1. 06×106 mol-1. L. s-1(at pH 7. 8). The reaction mechanism is similar to that catalyzed by super-oxide dismutase.
文摘The dismutation kinetics of superoxide anion by copper complex of 1,4,7,10-tetranza- cyctotridecane-11,13-dione was studied by pulse radiolysis.The dismutation rate constants at various pH and concentration of complex were obtained.
文摘A compact pulse radiolysis apparatus using a BNL-type s-band photocathode RF gun is now under development at Waseda University.The laser pulse is used for excitation of the photocathode and for generation of white light,which is used for analyzing light in the pulse radiolysis.
文摘Successful treatment of keloids has eluded the medical community since their first description. Multitudes of therapeutic options are available, but none achieves satisfactory resolution of keloids. One major stumbling block is lack of understanding about their genesis. Assuming keloids are tumors, attempts have been made to treat this condition with standard radiotherapy, with dismal results. Keloidal masses are not an active biological entity. They are aggregations of cellular, hypovascular, hypoxic bundles of collagen, which are produced by atypical fibroblasts in the wounds and eventually cease production due to a hostile biological environment. Having no demonstrable inherent process of disposal of these collagen bundles, this excessive collagen tends to linger to form the bulk of keloids. The lesions eventually become symptomatic and aesthetically unacceptable, and therapeutic intervention is sought. Of all available treatments, such as post-resection radiotherapy, primary radiotherapy in selected cases and primary brachytherapy stand out above any other form of treatment. Be it brachytherapy or external beam treatment, one fundamental aspect of radiation action is the process of “radiolysis”, explaining why “radiobiological” approaches have been ineffective.
基金Project partly supported by the National Natural Science Foundation of China and partly by Open Laboratory of Radiation Chemistry, the Chinese Academy of Sciences.
文摘Using pulse radiolysis technique, the reaction between hydroxyl radical and 7 phenylpropanoidglycosides: echinacoside, verbascoside, leucosceptoside A, martynoside, pediculariosides A, M and N which were isolated from Pedicularis were examined. The rate constants of these reactions were determined by transient absorption spectra. All 7 phenylpropanoid glycosides react with hydroxyl radical at high rate constants within (0.97-1.91)×1010L · mol-1 · s-1. suggesting that they are effective hydroxyl radical scavengers. The results demonstrate that the numbers of phenolic hydroxyl groups of phenylpropanoid glycosides are directly related to their scavenging activities. The scavenging activities are likely related to o-dihydroxy group of phenylpropanoid glycosides as well.
基金S. J. Zhang thanks Professor K. Bobrowski for his instructive discussion concerning this work. This work was supported by the National Natural Science Foundation of China (Grant No. 39800036).
文摘By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal that attack of the oxidizing SO4- radical on Phe leads directlyto the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes -COOH and -NH2 and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.
基金supported by the National Natural Science Foundation of China (21173252)
文摘The reactions between gatifloxacin(GFX) and various one-electron oxidants,such as ˙OH,N3˙,Br2˙ˉ,and SO4˙ˉ,have been studied by pulse radiolysis techniques.The GFX radical anion formed in the reaction of GFX with eaqˉ could either be protonated or deprotonated,and the absorption of GFX radical anion was located at 390 nm.The transient species produced by the reaction of GFX with ˙OH radical shows a broad band in the 380?600 nm region with a shoulder,while the oxidation by N3˙,SO4˙ˉ,and Br2˙ˉ results in an absorption band with λmax = 370 nm.At neutral condition(pH 7),the rate constants of GFX reacting with ˙OH,N3˙,Br2˙ˉ,SO4˙ˉ and eaqˉ are estimated to be 1.0 × 1010,3.1 × 109,2.8 × 109,3.0 × 109,and 1.8 × 1010 dm3 mol?1 s?1,respectively.From the pH dependence on the formation of electron adducts and on the rate constant of GFX with eaqˉ,the pKa of GFX radical anion is estimated to be 5.5 and 9.3.
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Project supported by the National Natural Science Foundation of China, Doctoral Programme of State Education Commission and Open Laboratory of Radiation Chemistry,the Chinese Academy of Sciences.
文摘Repair activities of thymine radical anion by echinocoside, isolated from Pedicularis plicata. were studied using pulse radiolysis technique. The thymine radical anion was produced by the reaction of hydrated electron with thymine. Echinocoside. one of the polyphenols of phenylpropanoid glycoside, was added to the thymine aqueous solution saturated with N2. Kinetic analysis by transient absorption spectrum showed that thymine radical anion was formed at first, and then after several decades of microseconds of pulse radiolysis. the spectrum of thymine radical anion was changed to that of echinocoside radical anion. The evidence indicated that thymine radical anion was repaired through one-electron-transfer between the DNA base radical anion and echinocoside. The rate constant of electron transfer by echinocoside was 1.45× 109 dm3 · mol1 · s 1.
文摘The excited triplet of C60 or C70 is generated via either direct excitation by laser light or energy transfer from excited states of solvent to C60 and C70. The cation radical of C60 is produced either via hole transfer from cation radical of CCl4 to C60 or via electron transfer from excited triplet of C60 to CCl4. C60 and C70 could be added to trichloromethyl radical to produce adduct radicals with different mechanisms.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 39700029).
文摘The antitumor mechanism of etoposide (VP-16) is investigated using pulse radiolysis technology. The oxidizing mechanism of VP-16 is studied by sodium persulfate, and the reaction rate constant is 4.04× 109 L· mol-1 · s-1. The electron-transfer between VP-16 and tyrosine is observed and the reaction rate constant is 1.1 - 108 L · mol-1· s-1.
基金supported by the National Natural Science Foundation of China(Grant No.20072025)Promoted Research Programs of Chinese Academy of Sciences.
文摘One-electron oxidation of N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleoside wyosine with several oxidative radicals, has been studied by using pulse radiolysis. The transient spectra of the radicals dYt˙+ and dYt(-H)˙ and the pK a of the radical cation were measured. The rate constants of reactions of dYt with SO 4 ˙? and CO 3 ˙? radicals have been determined and related reaction mechanisms were discussed.
基金Project supported by the National Natural Science Foundation of China
文摘1 Introduction Radiation-inducde direct damage of DNA originates primarily from the electron-gaining and losing sites. Determining the chemical nature and distribution of these sites is obviously a central problem in this field. At present, the most widely accepted model is T^-/G^+ dichotomy model, i. e. electrons are mainly trapped at thymine (T) and holes at guanine (G) through electron transfer along DNA chain. However, recent work showed another possible electron-gaining center: cytosine. In the mean time, the role of proton transfer in affecting the distribution of electron trapping among the DNA bases has received more
文摘The free radical scavenging activities of puerarin towards nitrogen dioxide radicals (NO 2 ˙ ), nitric oxide radicals (NO˙) and hydroxyl radicals (OH˙) were investigated by pulse radiolysis. Puerarin reacted with (NO 2 ˙ ) or (NO˙) to form puerarin-4-O˙ with the absorption maximum at 340 nm, but reacted with OH˙ to form at least three transient species including puerarin-2-O˙, puerarin-4-O˙ and [puerarin-OH]˙with a broad absorption spectrum band (300-750 nm). In addition, the reaction rate constants of puerarin reacting with NO 2 ˙ , and NO˙ were determined as 2.6 × 108, 1.7× 108 and 3.9 × 109 L · mol?1 · s?1, respectively.
文摘The interactions of carotenoids (bixin, β-carotene and lycopene) with CCl3OO. in aqueous and i-propylalcohol solution saturated with air have been studied by pulse radiolysis. For bixin and β-carotene reaction products from forming process, absorbing in the region of 650 nm, is observed with concomitant carotenoid bleaching (bixin at 500 nm, β-carotene at 450 nm). Their rate constants from forming process are 1.78 ×108 and 7.8 ×107 mol-1 · L · s-1 respectively. However, in the case of lycopene, no such a forming process of reaction as bixin and β-carotene can be observed although there is the bleaching reaction (rate constant 4 ×107 mol-1 · L · s-1). The results suggest that the carotenoid radical cation and an additional radical are produced in the case of bixin and β-carotene, whereas lycopene undergoes electron transfer with CCl3OO., forming cation radical.
基金supported by the National Natural Science Foundation of China(Grant No.30100035)Natural Science Foundation of Fujian(Grant No.C0510029).
文摘The piperonal electron affinity was studied using pulse radiolysis technique. The electron transfer reaction process between piperonal and anthraquinone-2-sulfate was observed in the pH 7 phosphoric acid salt buffer. The transient absorption spectra of electron transfer re-action between piperonal and anthraquinone-2-sulfate were obtained, and the initial proof of the electron transfer between electron donor and acceptor was provided directly. The one-electron reduction potential of piperonal was determined to be ?0.457 V.
基金Acknowledgements This work was supported by the Foundation of Qimingxing Program of Shanghai, China (Grant No. 99QA14034).
文摘The mechanisms of reactions between CC13OO? radical and quercetin, rutin and epigallocatechin gallate (EGCG) have been studied using pulse radiolytic technique. It is suggested that the electron transfer reaction is the main reaction between CC13OO? radical and rutin, EGCG, but there are two main pathways for the reaction of CC13OO? radical with quercetin, one is the electron transfer reaction, the other is addition reaction. The reaction rate constants were determined. It is proved that quercetin and rutin are better CC13OO? radical scavengers than EGCG.
基金Project supported by the National Natural Science Foundation of China （No. 30100035） and the Natural Science Foundation of Fujian （No. C0510029）.
文摘Based on pulse radiolysis of aqueous solutions of two salicylic acid derivatives including ethyl salicylate and benzylsalicylate the transient absorption spectra and the rate constants of hydroxyl radical with salicylic acid derivatives were determined for the first time. The results indicated that ethyl salicylate and benzylsalicylate have efficient activities to scavenge hydroxyl radical.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .30 0 0 0 0 36)andDoctoralProgrammefromtheStateEducationCom missionofChina .
文摘The oxidative splitting process of cis-syn 1,3-dimethyluracil cyclobutane dimer (DMUD) in aqueous solution was investigated using pulse radiolysis technique. The results indicated that DMUD can be splitted into 1,3-dimethyluracil (DMU) by OH radicals (OH ·) and Br_2 radical anions (Br ·-_2), but not by azide radicals (N ·_3). The oxidative mechanisms that an H-abstracted from DMUD for OH · oxidative splitting and an electron transfer from DMUD to Br ·-_2, were suggested. Related kinetic parameters were determined.
