The assembling of a coating of time-resolved fluorescent chelator BSPDA ( abbreviated for 4, 7-bis ( sulfhydrylphenyl)-1, 10-phenanthroline-2, 9-dicarboxylic acid) onto a nano-gold layer was demonstrated. First, B...The assembling of a coating of time-resolved fluorescent chelator BSPDA ( abbreviated for 4, 7-bis ( sulfhydrylphenyl)-1, 10-phenanthroline-2, 9-dicarboxylic acid) onto a nano-gold layer was demonstrated. First, BSPDA was synthesized by simple procedures, and then an approach was developed to immobilize BSPDA onto the nano-gold layer deposited on a silane modified glass substrate, whereby europium ion (Ⅲ, Eu^3+ ) was captured and released owing to the interactive process of complexation and dissociation between BSPDA functionalized coating and Eu^3+ solution. The fluorescence spectra and related lifetimes were determined. Also, the BSPDA functionalized coating's specific complexation with Eu^3+ on the BSPDA assembly layer and the nonspecific adsorption of Eu^3+ on the nano-gold layer were compared. These results allowed a selective complexation of Eu^3+ by assembling a BSPDA chelating layer on the nano-gold layer; thus, a tunable time-resolved fluorescent layer was covalently attached, The results of the nanoparticle assembling and probing (or labeling) processes to specific bio-systems were very interesting and had significant implications to time-resolved-fluorescence-based detection on biosensor surfaces such as DNA chip and to arrayed light display devices.展开更多
One of the technical bottlenecks of traditional laser-induced breakdown spectroscopy(LIBS) is the difficulty in quantitative detection caused by the matrix effect. To troubleshoot this problem,this paper investigated ...One of the technical bottlenecks of traditional laser-induced breakdown spectroscopy(LIBS) is the difficulty in quantitative detection caused by the matrix effect. To troubleshoot this problem,this paper investigated a combination of time-resolved LIBS and convolutional neural networks(CNNs) to improve K determination in soil. The time-resolved LIBS contained the information of both wavelength and time dimension. The spectra of wavelength dimension showed the characteristic emission lines of elements, and those of time dimension presented the plasma decay trend. The one-dimensional data of LIBS intensity from the emission line at 766.49 nm were extracted and correlated with the K concentration, showing a poor correlation of R_c^2?=?0.0967, which is caused by the matrix effect of heterogeneous soil. For the wavelength dimension, the two-dimensional data of traditional integrated LIBS were extracted and analyzed by an artificial neural network(ANN), showing R_v^2?=?0.6318 and the root mean square error of validation(RMSEV)?=?0.6234. For the time dimension, the two-dimensional data of time-decay LIBS were extracted and analyzed by ANN, showing R_v^2?=?0.7366 and RMSEV?=?0.7855.These higher determination coefficients reveal that both the non-K emission lines of wavelength dimension and the spectral decay of time dimension could assist in quantitative detection of K.However, due to limited calibration samples, the two-dimensional models presented over-fitting.The three-dimensional data of time-resolved LIBS were analyzed by CNNs, which extracted and integrated the information of both the wavelength and time dimension, showing the R_v^2?=?0.9968 and RMSEV?=?0.0785. CNN analysis of time-resolved LIBS is capable of improving the determination of K in soil.展开更多
In the femtosecond laser-produced Cu-plasma, the transient transition dynamics that the excited state 5s4D7/2 via electron-ion recombination transfers to 4p4F9/20 (465.11 nm, Λ1 line) and 4p4D7/20 (529.25 nm, Λ2 ...In the femtosecond laser-produced Cu-plasma, the transient transition dynamics that the excited state 5s4D7/2 via electron-ion recombination transfers to 4p4F9/20 (465.11 nm, Λ1 line) and 4p4D7/20 (529.25 nm, Λ2 line) states are investigated by using the time-resolved spectroscopy. The occupation number and relevant lifetime of the excited state 5s4D7/2, the temporal evolutions of spectral intensities for Λ1 line and Λ2 line emissions are demonstrated to be in direct proportion to the employed laser intensity, which reveals the transient features of transition dynamics clearly differing from that resulted in the traditional collision excitation. Furthermore, some unique characteristics for Λ1 and Λ2 transitions stemming from electron-ion recombination are examined in detail.展开更多
A new europium complex is descried as a time-resolved luminescence-based sensor for fluoride anion. The sensor is selective even in the presence of intensive background fluorescence.
Thylakoid membrane preparations of super high-yield hybrid rice (Oryza sativa L.), Liangyoupeijiu (P9) and Shanyou 63 (SH 63) were used for investigating its spectral and time properties by using picosecond time-resol...Thylakoid membrane preparations of super high-yield hybrid rice (Oryza sativa L.), Liangyoupeijiu (P9) and Shanyou 63 (SH 63) were used for investigating its spectral and time properties by using picosecond time-resolved fluorescence spectrum measuring system. The thylakoid membrane preparations of P9 and SH 63 were excited by an Ar+ laser with a pulse width of 120 ps, repetition rate of 4 MHz and wavelength of 514 nm. The time constants of the excited energy transfer in these two varieties at flowering stage and grain filling stage were calculated from the experimental data. Based on the comparative studies of the time and spectral properties of the excited fluorescence in these ultrafast dynamic experiments the following was found: at both the flowering stage and grain filling stage, the speed of the excitation energy transfer, in photosystem was faster than that in photosystem II in P9 variety; and the speed of the excitation energy transfer at grain filling stage was faster than those at flowering stage for both rice varieties; the experiments also implied that the components and assembly of pigments in SH 63, but not in P9, changed during the process from flowering stage to grain filling stage for in these two rice varieties.展开更多
Ⅰ. INTRODUCTIONPhotodynamic therapy (PDT) which utilizes hematoporphyrin derivative (HpD) as a photosensitizing drug has increasingly being used for the local treatment of malignant tumors. The success of this method...Ⅰ. INTRODUCTIONPhotodynamic therapy (PDT) which utilizes hematoporphyrin derivative (HpD) as a photosensitizing drug has increasingly being used for the local treatment of malignant tumors. The success of this method is attributed to the ability of HpD to accumulate to展开更多
Single-particle microbeam as a powerful tool can open a research field to find answers to many enigmas in radiobiology. A single-particle microbeam facility has been constructed at the Key Laboratory of Ion Beam Bioen...Single-particle microbeam as a powerful tool can open a research field to find answers to many enigmas in radiobiology. A single-particle microbeam facility has been constructed at the Key Laboratory of Ion Beam Bioengineering (LIBB), Chinese Academy of Sciences (CAS), China. However there has been less research activities in this field concerning the original process of the interaction between low-energy ions and complicated organisms. To address this challenge, an in situ multi-dimensional quantitative fluorescence microscopy system combined with the CAS-LIBB single-particle microbeam II endstation is proposed. In this article, the rationale, logistics and development of many aspects of the proposed system are discussed.展开更多
The fluorescence kinetics of 1,6-diphenyl-1,3,5-hexatriene (DPH) dissolved in cyclohexane was investigated as a function of temperature, concentration and 355 nm excitation pulse energy. At concentrations above 2.5 μ...The fluorescence kinetics of 1,6-diphenyl-1,3,5-hexatriene (DPH) dissolved in cyclohexane was investigated as a function of temperature, concentration and 355 nm excitation pulse energy. At concentrations above 2.5 μM and excitation energies above 1 mJ a long-lived, very intense emission, which appears within less than 5 ns and lasts up to 70 ns, is observed. During the first 50 ns the decay does not follow an exponential but rather a linear behaviour. In oxygen saturated solutions the long-lived emission is suppressed and solely short-lived fluorescence with τ 1-state and competes with the formation of DPH-O2 contact charge-transfer complexes and intersystem crossing which both quench the fluorescence. Our investigations show that even the small amount of oxygen dissolved in nitrogen saturated solutions has a distinct influence on the fluorescence kinetics of DPH.展开更多
Very recently,we have proposed that all culprit molecules of arteriosclerosis mightpossess a common and measurable inherent property,namely,a coaggregating ten-dency.Extensive kinetic measurements of these tendencies ...Very recently,we have proposed that all culprit molecules of arteriosclerosis mightpossess a common and measurable inherent property,namely,a coaggregating ten-dency.Extensive kinetic measurements of these tendencies in terms of △CAgC valueshave led to a new and surprising observation,i.e.,the cholesteryl ester with a longsaturated 18-carbon chain(CE-18)actually has a much smaller tendency towardcoaggregation than that of the ester with a“short”8-carbon chain(CE-8).Thisstate of affairs has been coined as the“chain-foldability effect”,i.e.,the 18-carbon展开更多
IN a previous paper, we have studied the energy transfer mechanism among the PBS-thy-lakoid complex in detail by using steady-state spectra and deconvolution techniques. The ex-perimental results indicated that the en...IN a previous paper, we have studied the energy transfer mechanism among the PBS-thy-lakoid complex in detail by using steady-state spectra and deconvolution techniques. The ex-perimental results indicated that the energy transfer from PBS to two reaction centers of PS Ⅰand PS Ⅱ were parallel, and confirmed the model which was suggested by Mullineaxu.展开更多
Triple exciplex formed between polyacenaphthalene and terephthalic dimethylester (TDE) has been studied by means of the steady-state and time-resolved fluorescence spectra. The theoretical model of the triple exciplex...Triple exciplex formed between polyacenaphthalene and terephthalic dimethylester (TDE) has been studied by means of the steady-state and time-resolved fluorescence spectra. The theoretical model of the triple exciplex formation for a flexible polymer chain in a dilute solution has been proposed. The fluorescence decays of the monomer, the exciplex and the triple exciplex obey a double exponential rule in the pbotophysical processes of the triple exciplex formation. The association rate constant of the exciplex formation is k_3=6.0×10~9s^(-1)(mol/L)^(-1); the association rate constant of the triple exciplex formation is k_6=5.2×10~7s^(-1). A mechanism for the triple exciplex formation from the exciplex to the triple exciplex has been proved through the noncrystal films corresponding to the same concentrations of the solution systems and the fluorescence lifetimes of the intramolecular excimer.展开更多
An intramolecular excimer of poly(2- vinyl) naphthalene was formed by non-adjacentchromophores interaction, then a triple exciplex was formed by interaction with the acceptormolecule further in dilute solution. The li...An intramolecular excimer of poly(2- vinyl) naphthalene was formed by non-adjacentchromophores interaction, then a triple exciplex was formed by interaction with the acceptormolecule further in dilute solution. The lifetime of the intramolecular excimer of poly(2-vinyl) naphthalene, τ_2 = 18.83 ns and the rate constant for the triple exciplex formation,k_7 = 4. 18× 10~9 (mol/L)^(-1)s^(-1), under diffusion-control were measured. An excimer or anexciplex could be an intermediate of the triple exciplex formation. A theoretical model ofthe triple exciplex formation is proposed.展开更多
基金Project supported by the National Natural Science Foundation of China (20505020) the Natural Science Foundation ofGuangdong Province (06300086) +2 种基金 China Postdoctoral Science Foundation (20060390202) Scientific Research Fund ofHunan Provincial Education Department (05C508) Skeleton Youth Faculty Programof Hunan Higher Educational School
文摘The assembling of a coating of time-resolved fluorescent chelator BSPDA ( abbreviated for 4, 7-bis ( sulfhydrylphenyl)-1, 10-phenanthroline-2, 9-dicarboxylic acid) onto a nano-gold layer was demonstrated. First, BSPDA was synthesized by simple procedures, and then an approach was developed to immobilize BSPDA onto the nano-gold layer deposited on a silane modified glass substrate, whereby europium ion (Ⅲ, Eu^3+ ) was captured and released owing to the interactive process of complexation and dissociation between BSPDA functionalized coating and Eu^3+ solution. The fluorescence spectra and related lifetimes were determined. Also, the BSPDA functionalized coating's specific complexation with Eu^3+ on the BSPDA assembly layer and the nonspecific adsorption of Eu^3+ on the nano-gold layer were compared. These results allowed a selective complexation of Eu^3+ by assembling a BSPDA chelating layer on the nano-gold layer; thus, a tunable time-resolved fluorescent layer was covalently attached, The results of the nanoparticle assembling and probing (or labeling) processes to specific bio-systems were very interesting and had significant implications to time-resolved-fluorescence-based detection on biosensor surfaces such as DNA chip and to arrayed light display devices.
基金supported by National Natural Science Foundation of China (Grant No. 61505253)National Key Research and Development Plan of China (Project No. 2016YFD0200601)
文摘One of the technical bottlenecks of traditional laser-induced breakdown spectroscopy(LIBS) is the difficulty in quantitative detection caused by the matrix effect. To troubleshoot this problem,this paper investigated a combination of time-resolved LIBS and convolutional neural networks(CNNs) to improve K determination in soil. The time-resolved LIBS contained the information of both wavelength and time dimension. The spectra of wavelength dimension showed the characteristic emission lines of elements, and those of time dimension presented the plasma decay trend. The one-dimensional data of LIBS intensity from the emission line at 766.49 nm were extracted and correlated with the K concentration, showing a poor correlation of R_c^2?=?0.0967, which is caused by the matrix effect of heterogeneous soil. For the wavelength dimension, the two-dimensional data of traditional integrated LIBS were extracted and analyzed by an artificial neural network(ANN), showing R_v^2?=?0.6318 and the root mean square error of validation(RMSEV)?=?0.6234. For the time dimension, the two-dimensional data of time-decay LIBS were extracted and analyzed by ANN, showing R_v^2?=?0.7366 and RMSEV?=?0.7855.These higher determination coefficients reveal that both the non-K emission lines of wavelength dimension and the spectral decay of time dimension could assist in quantitative detection of K.However, due to limited calibration samples, the two-dimensional models presented over-fitting.The three-dimensional data of time-resolved LIBS were analyzed by CNNs, which extracted and integrated the information of both the wavelength and time dimension, showing the R_v^2?=?0.9968 and RMSEV?=?0.0785. CNN analysis of time-resolved LIBS is capable of improving the determination of K in soil.
基金Project supported by the National Natural Science Foundation of China(Grant No.51705009)the NSAF of China(Grant No.U1530153)
文摘In the femtosecond laser-produced Cu-plasma, the transient transition dynamics that the excited state 5s4D7/2 via electron-ion recombination transfers to 4p4F9/20 (465.11 nm, Λ1 line) and 4p4D7/20 (529.25 nm, Λ2 line) states are investigated by using the time-resolved spectroscopy. The occupation number and relevant lifetime of the excited state 5s4D7/2, the temporal evolutions of spectral intensities for Λ1 line and Λ2 line emissions are demonstrated to be in direct proportion to the employed laser intensity, which reveals the transient features of transition dynamics clearly differing from that resulted in the traditional collision excitation. Furthermore, some unique characteristics for Λ1 and Λ2 transitions stemming from electron-ion recombination are examined in detail.
基金the National Natural Science Foundation of China(20490210)Shanghai Sci.Tech.Comm.(03QB14006,03DZ12031 and 05DJ14004)for financial support.
文摘A new europium complex is descried as a time-resolved luminescence-based sensor for fluoride anion. The sensor is selective even in the presence of intensive background fluorescence.
文摘Thylakoid membrane preparations of super high-yield hybrid rice (Oryza sativa L.), Liangyoupeijiu (P9) and Shanyou 63 (SH 63) were used for investigating its spectral and time properties by using picosecond time-resolved fluorescence spectrum measuring system. The thylakoid membrane preparations of P9 and SH 63 were excited by an Ar+ laser with a pulse width of 120 ps, repetition rate of 4 MHz and wavelength of 514 nm. The time constants of the excited energy transfer in these two varieties at flowering stage and grain filling stage were calculated from the experimental data. Based on the comparative studies of the time and spectral properties of the excited fluorescence in these ultrafast dynamic experiments the following was found: at both the flowering stage and grain filling stage, the speed of the excitation energy transfer, in photosystem was faster than that in photosystem II in P9 variety; and the speed of the excitation energy transfer at grain filling stage was faster than those at flowering stage for both rice varieties; the experiments also implied that the components and assembly of pigments in SH 63, but not in P9, changed during the process from flowering stage to grain filling stage for in these two rice varieties.
文摘Ⅰ. INTRODUCTIONPhotodynamic therapy (PDT) which utilizes hematoporphyrin derivative (HpD) as a photosensitizing drug has increasingly being used for the local treatment of malignant tumors. The success of this method is attributed to the ability of HpD to accumulate to
文摘Single-particle microbeam as a powerful tool can open a research field to find answers to many enigmas in radiobiology. A single-particle microbeam facility has been constructed at the Key Laboratory of Ion Beam Bioengineering (LIBB), Chinese Academy of Sciences (CAS), China. However there has been less research activities in this field concerning the original process of the interaction between low-energy ions and complicated organisms. To address this challenge, an in situ multi-dimensional quantitative fluorescence microscopy system combined with the CAS-LIBB single-particle microbeam II endstation is proposed. In this article, the rationale, logistics and development of many aspects of the proposed system are discussed.
文摘The fluorescence kinetics of 1,6-diphenyl-1,3,5-hexatriene (DPH) dissolved in cyclohexane was investigated as a function of temperature, concentration and 355 nm excitation pulse energy. At concentrations above 2.5 μM and excitation energies above 1 mJ a long-lived, very intense emission, which appears within less than 5 ns and lasts up to 70 ns, is observed. During the first 50 ns the decay does not follow an exponential but rather a linear behaviour. In oxygen saturated solutions the long-lived emission is suppressed and solely short-lived fluorescence with τ 1-state and competes with the formation of DPH-O2 contact charge-transfer complexes and intersystem crossing which both quench the fluorescence. Our investigations show that even the small amount of oxygen dissolved in nitrogen saturated solutions has a distinct influence on the fluorescence kinetics of DPH.
基金the National Natural Science Foundation of China Laboratory of Photochemistry and PhotophysicsInstitute of Photographic Chemistry,Chinese Academy of Sciences.
文摘Very recently,we have proposed that all culprit molecules of arteriosclerosis mightpossess a common and measurable inherent property,namely,a coaggregating ten-dency.Extensive kinetic measurements of these tendencies in terms of △CAgC valueshave led to a new and surprising observation,i.e.,the cholesteryl ester with a longsaturated 18-carbon chain(CE-18)actually has a much smaller tendency towardcoaggregation than that of the ester with a“short”8-carbon chain(CE-8).Thisstate of affairs has been coined as the“chain-foldability effect”,i.e.,the 18-carbon
文摘IN a previous paper, we have studied the energy transfer mechanism among the PBS-thy-lakoid complex in detail by using steady-state spectra and deconvolution techniques. The ex-perimental results indicated that the energy transfer from PBS to two reaction centers of PS Ⅰand PS Ⅱ were parallel, and confirmed the model which was suggested by Mullineaxu.
基金Project supported by the National Natural Science Foundation of China.
文摘Triple exciplex formed between polyacenaphthalene and terephthalic dimethylester (TDE) has been studied by means of the steady-state and time-resolved fluorescence spectra. The theoretical model of the triple exciplex formation for a flexible polymer chain in a dilute solution has been proposed. The fluorescence decays of the monomer, the exciplex and the triple exciplex obey a double exponential rule in the pbotophysical processes of the triple exciplex formation. The association rate constant of the exciplex formation is k_3=6.0×10~9s^(-1)(mol/L)^(-1); the association rate constant of the triple exciplex formation is k_6=5.2×10~7s^(-1). A mechanism for the triple exciplex formation from the exciplex to the triple exciplex has been proved through the noncrystal films corresponding to the same concentrations of the solution systems and the fluorescence lifetimes of the intramolecular excimer.
文摘An intramolecular excimer of poly(2- vinyl) naphthalene was formed by non-adjacentchromophores interaction, then a triple exciplex was formed by interaction with the acceptormolecule further in dilute solution. The lifetime of the intramolecular excimer of poly(2-vinyl) naphthalene, τ_2 = 18.83 ns and the rate constant for the triple exciplex formation,k_7 = 4. 18× 10~9 (mol/L)^(-1)s^(-1), under diffusion-control were measured. An excimer or anexciplex could be an intermediate of the triple exciplex formation. A theoretical model ofthe triple exciplex formation is proposed.