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
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
Gamma-cyclodextrin (γ-CD) was used to induce the formation of N,N-diethylaniline (DEA) exciplex in 15:85{φ=0.15)v/v EtOH-H_2O binary mixture.Measurements of the fluorescence spectra of anthracene in the presence or ...Gamma-cyclodextrin (γ-CD) was used to induce the formation of N,N-diethylaniline (DEA) exciplex in 15:85{φ=0.15)v/v EtOH-H_2O binary mixture.Measurements of the fluorescence spectra of anthracene in the presence or absence of DEA and γ-CD show that γ-CD can form 1:1:1 host/guest-Ⅰ/guest-Ⅱ inclusion complex with anthracene and DEA.展开更多
Formation and decay processes of pyrene excimer in acetonitrile have been measured by laser flash spectroscopy at 475nm,and the dependence of λ_1+λ_2 on the pyrene concentration has also been measured at 290°K....Formation and decay processes of pyrene excimer in acetonitrile have been measured by laser flash spectroscopy at 475nm,and the dependence of λ_1+λ_2 on the pyrene concentration has also been measured at 290°K.On the basis of these measurements,six rate parameters which describe the behaviour of pyrene excimer system in acetonitrile solution have been evaluated.At 355 nm laser light irradiation,the ΔG of the pyrene excimer formation in acetonitrile is evaluated to be -30.18kJ/mol. This value is quite different from the corresponding ΔG in cyclohexane (-16.72kJ/mol).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
Nanocomposites were fabricated by using a commercial two part epoxy as a matrix and multiwalled carbon nanotubes, graphite fibers and boron nitride platelets as filler materials. Multiwalled carbon nanotubes (MWCNTs) ...Nanocomposites were fabricated by using a commercial two part epoxy as a matrix and multiwalled carbon nanotubes, graphite fibers and boron nitride platelets as filler materials. Multiwalled carbon nanotubes (MWCNTs) that were produced by chemical vapor deposition were found to produce nanocomposites with better thermal diffusivity and thermal conductivity than the MWCNTs that were produced by the combustion method. Compared to the MWCNTs produced by both methods and graphite fibers, boron nitride produced nanocomposites with the highest thermal conductivity. Specific heat capacity was measured by using differential scanning calorimetry and thermal diffusivity was measured by using the laser flash.展开更多
Achieving efficient thermal management urges to exploit high-thermal-conductivity materials to satisfy the boosted demand of heat dissipation.It is critical to adopt standardized characterization protocols to evaluate...Achieving efficient thermal management urges to exploit high-thermal-conductivity materials to satisfy the boosted demand of heat dissipation.It is critical to adopt standardized characterization protocols to evaluate the intrinsic thermal conductivity of thermal management materials.However,for the most representative laser flash method,the lack of standard measurement methodology and systematic description on the thermal diffusivity and influencing factors has led to significant deviations and confusion of the thermal conduction performance in the emerging thermal management application.Here,the measurement error factors of thermal diffusivity by the common laser flash analyzer(LFA)are discussed.Taking high-thermal-conductivity graphitic film(GF)as a typical case,the key factors are analyzed to guide the measurement protocol of related carbon-based thermal management materials.The basic principle of the LFA measurement,actual pre-processing conditions,instrument parameters setting,and data analysis are elaborated for accurate measurements.Furthermore,the graphene thick films and common isotropic materials are also extended to meet various thermal measurement requirements.Based on the existing practical problems,we propose a feasible test flow to achieve a unified and standardized thermal conductivity measurement,which is beneficial to the rapid development of carbon-based thermal management materials.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
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
This paper presents an in-situ, non-contact, non-destructive "dual-wavelength laser flash Raman spectroscopy method" for measuring the thermal diffusivity. In this method, a heating pulse is used to heat the...This paper presents an in-situ, non-contact, non-destructive "dual-wavelength laser flash Raman spectroscopy method" for measuring the thermal diffusivity. In this method, a heating pulse is used to heat the sample and another pulsed laser with a different wavelength and negligible heating effect is used as a probe to measure the sample temperature changes during the heating and cooling periods from the Raman peak shifts. The sample temperature rise and fall curves are measured by changing the delay between the heating pulse and the probing pulse with the thermal diffusivity then characterized by fitting the temperature curves. The time delay between the heating and probing pulses can be precisely controlled with a minimum step of 100 ps. Hence, the temperature variation can be scanned with an ultra-high temporal resolution of up to 100 ps, which significantly improves the measurement accuracy of transient thermal parameters. The measurement accuracy of this method has been verified using a bulk material model and experiments. The measured thermal diffusivity of a silicon sample has been obtained to be 8.8×10^(-5 )m^2/s with a 3% difference between the measured value and the average result for bulk silicon in the literature which verifies the reliability and accuracy of this method.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
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
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
转镜调Q无插入损耗,是获得窄脉冲、高峰值功率输出激光的直接方式。纳秒脉冲需要使用高速转镜调Q,并精准控制电机转速与氙灯放电延时,以使激光介质上能级粒子数反转最大,获得最大激光能量输出。本文设计了以Arduino mega 2560单片机为...转镜调Q无插入损耗,是获得窄脉冲、高峰值功率输出激光的直接方式。纳秒脉冲需要使用高速转镜调Q,并精准控制电机转速与氙灯放电延时,以使激光介质上能级粒子数反转最大,获得最大激光能量输出。本文设计了以Arduino mega 2560单片机为核心的高速转镜调Q控制系统,通过精确单片机解析串口屏指令控制激光电源的充放电和高速电机启停,同时通过对转镜脉冲信号整合降频控制氙灯放电时刻,实现对延迟时间的精准控制,实现了灯泵Er,Cr:YSGG激光纳秒窄脉冲调Q输出。在5 Hz重复频率下,转镜转速为650 r/s时,获得的最高单脉冲激光能量为45.7 mJ、脉冲宽度为86.2 ns,相应的峰值功率为530.2 kW。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.
文摘Gamma-cyclodextrin (γ-CD) was used to induce the formation of N,N-diethylaniline (DEA) exciplex in 15:85{φ=0.15)v/v EtOH-H_2O binary mixture.Measurements of the fluorescence spectra of anthracene in the presence or absence of DEA and γ-CD show that γ-CD can form 1:1:1 host/guest-Ⅰ/guest-Ⅱ inclusion complex with anthracene and DEA.
文摘Formation and decay processes of pyrene excimer in acetonitrile have been measured by laser flash spectroscopy at 475nm,and the dependence of λ_1+λ_2 on the pyrene concentration has also been measured at 290°K.On the basis of these measurements,six rate parameters which describe the behaviour of pyrene excimer system in acetonitrile solution have been evaluated.At 355 nm laser light irradiation,the ΔG of the pyrene excimer formation in acetonitrile is evaluated to be -30.18kJ/mol. This value is quite different from the corresponding ΔG in cyclohexane (-16.72kJ/mol).
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Nanocomposites were fabricated by using a commercial two part epoxy as a matrix and multiwalled carbon nanotubes, graphite fibers and boron nitride platelets as filler materials. Multiwalled carbon nanotubes (MWCNTs) that were produced by chemical vapor deposition were found to produce nanocomposites with better thermal diffusivity and thermal conductivity than the MWCNTs that were produced by the combustion method. Compared to the MWCNTs produced by both methods and graphite fibers, boron nitride produced nanocomposites with the highest thermal conductivity. Specific heat capacity was measured by using differential scanning calorimetry and thermal diffusivity was measured by using the laser flash.
基金supported by the National Natural Science Foundation of China(Nos.52272046,52090030,52090031,52122301,51973191)the Natural Science Foundation of Zhejiang Province(LR23E020003)+4 种基金Shanxi-Zheda Institute of New Materials and Chemical Engineering(2021SZ-FR004,2022SZ-TD011,2022SZ-TD012,2022SZ-TD014)Hundred Talents Program of Zhejiang University(188020*194231701/113,112300+1944223R3/003,112300+1944223R3/004)the Fundamental Research Funds for the Central Universities(Nos.226-2023-00023,226-2023-00082,2021FZZX001-17,K20200060)National Key R&D Program of China(NO.2022YFA1205300,NO.2022YFA1205301,NO.2020YFF0204400,NO.2022YFF0609801)"Pioneer"and"Leading Goose"R&D Program of Zhejiang 2023C01190。
文摘Achieving efficient thermal management urges to exploit high-thermal-conductivity materials to satisfy the boosted demand of heat dissipation.It is critical to adopt standardized characterization protocols to evaluate the intrinsic thermal conductivity of thermal management materials.However,for the most representative laser flash method,the lack of standard measurement methodology and systematic description on the thermal diffusivity and influencing factors has led to significant deviations and confusion of the thermal conduction performance in the emerging thermal management application.Here,the measurement error factors of thermal diffusivity by the common laser flash analyzer(LFA)are discussed.Taking high-thermal-conductivity graphitic film(GF)as a typical case,the key factors are analyzed to guide the measurement protocol of related carbon-based thermal management materials.The basic principle of the LFA measurement,actual pre-processing conditions,instrument parameters setting,and data analysis are elaborated for accurate measurements.Furthermore,the graphene thick films and common isotropic materials are also extended to meet various thermal measurement requirements.Based on the existing practical problems,we propose a feasible test flow to achieve a unified and standardized thermal conductivity measurement,which is beneficial to the rapid development of carbon-based thermal management materials.
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supported by the National Natural Science Foundation of China (Grant Nos. 51827807 and 51636002)
文摘This paper presents an in-situ, non-contact, non-destructive "dual-wavelength laser flash Raman spectroscopy method" for measuring the thermal diffusivity. In this method, a heating pulse is used to heat the sample and another pulsed laser with a different wavelength and negligible heating effect is used as a probe to measure the sample temperature changes during the heating and cooling periods from the Raman peak shifts. The sample temperature rise and fall curves are measured by changing the delay between the heating pulse and the probing pulse with the thermal diffusivity then characterized by fitting the temperature curves. The time delay between the heating and probing pulses can be precisely controlled with a minimum step of 100 ps. Hence, the temperature variation can be scanned with an ultra-high temporal resolution of up to 100 ps, which significantly improves the measurement accuracy of transient thermal parameters. The measurement accuracy of this method has been verified using a bulk material model and experiments. The measured thermal diffusivity of a silicon sample has been obtained to be 8.8×10^(-5 )m^2/s with a 3% difference between the measured value and the average result for bulk silicon in the literature which verifies the reliability and accuracy of this method.
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.
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 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.