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
The properties of the triplet excited state of [60]fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60]fullerene-containing cyclic...The properties of the triplet excited state of [60]fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60]fullerene-containing cyclic sulphoxide showed two decay-components, which were attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60]fullerene-containing cyclic sulphoxide are also reported.展开更多
To contribute to the understanding of Eu(Ⅲ)interaction properties on hydrous alumina particles in the absence and presence of fulvic acid(FA),the complexation properties of Eu(Ⅲ)with hydrous alumina,FA and FA-alumin...To contribute to the understanding of Eu(Ⅲ)interaction properties on hydrous alumina particles in the absence and presence of fulvic acid(FA),the complexation properties of Eu(Ⅲ)with hydrous alumina,FA and FA-alumina hybrids are studied by batch and time-resolved laser fluorescence spectroscopy(TRLFS)techniques.The continuous increase in the fluorescence lifetime of Eu-alumina and Eu-FA with increasing pH indicates that the complexation is accompanied by decreasing number of hydration water in the first coordination sphere of Eu(Ⅲ).Eu(Ⅲ)is adsorbed onto alumina particles as outer-sphere surface complexes of≡(Al-O)-Eu·(OH)·7H_2O and≡(Al-O)-Eu·6H_2O at low pH values,and as inner-sphere surface complexes as≡(Al-O)_2-Eu^+·4H_2O at high pH.In FA solution,Eu(Ⅲ)forms complexes with FA as(COO)_2Eu^+(H_2O)_x and the hydration water number in the first coordination sphere decreases with pH increasing.The formation of≡COO-Eu-(O-Al≡)·4H_2O is observed on FA-alumina hybrids,suggesting the formation of strong inner-sphere surface complexes in the presence of FA.The surface complexes are also characterized by their emission spectra[the ratio of emission intensities of^5D_0→~7F_1(λ=594nm)and^5D_0→~7F_2(λ=619nm)transitions]and their fluorescence lifetime.The findings is important to understand the contribution of FA in the complexation properties of Eu(Ⅲ)on FA-alumina hybrids that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Eu(Ⅲ),or its analogue trivalent lanthanide and actinide ions in natural environment.展开更多
The femtosecond time-resolved difference absorption spectra of all-trans-b- Apo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequent...The femtosecond time-resolved difference absorption spectra of all-trans-b- Apo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequential model for the excited-state energy relaxation. With this model, we have obtained the excited-state absorption spectra and the lifetimes of the corresponding excited states both in nonpolar solvent n-hexane and polar solvent methanol. Three excited states, namely S3(170fs), S2(2.32ps) and S1(26ps) in n-hexane, and two excited states S2 (190fs) and S1(9.4ps) in methanol have been observed. The excited-state absorption spectra of all-trans-b-Apo-8′-carotenal in methanol display a red shift and broadeness, while the lifetime of S1 state becomes shorter. It is proposed that these effects are related to the presence of a carbonyl functional group that leads to the solvent effect on the excited-state energy level. At the same time, it is shown that the SVD method is a useful tool in resolving the time-resolved absorption spectra.展开更多
Objective:This study aimed to employ time‐resolved spectroscopy(TRS)to explore age‐related differences in prefrontal cortex(PFC)activity while subjects performed a working memory task.Methods:We employed TRS to meas...Objective:This study aimed to employ time‐resolved spectroscopy(TRS)to explore age‐related differences in prefrontal cortex(PFC)activity while subjects performed a working memory task.Methods:We employed TRS to measure PFC activity in ten healthy younger and ten healthy older subjects while they performed a working memory(WM)task.All subjects performed the Sternberg test(ST)in which the memory‐set size varied between one and six digits.Using TRS,we recorded changes in cerebral blood oxygenation as a measure of changes in PFC activity during the task.In order to identify left/right asymmetry of PFC activity during the working memory task,we calculated the laterality score,i.e.,Δoxy‐Hb(rightΔoxy‐Hb—leftΔoxy‐Hb);positive values indicate greater activity in the right PFC,while negative values indicate greater activity in the left PFC.Results:During the ST,statistical analyses showed no significant differences between the younger and older groups in accuracy for low memory‐load and high memory‐load.In high memory‐load tasks,however,older subjects were slower than younger subjects(P<0.05).We found that the younger group showed right lateral responses with a stronger right than left activation in the frontal pole,whereas the older group showed bilateral responses(P<0.05).Conclusions:The present results are consistent with the hemispheric asymmetry reduction in older adults(HAROLD)model;working memory tasks cause asymmetrical PFC activation in younger adults,while older adults tend to show reduced hemispheric lateralization.展开更多
We review the technique and research of the ultrahigh spatiotemporal resolved spectroscopy and its applications in the field of the ultrafast dynamics of mesoscopic systems and nanomaterials. Combining femtosecond tim...We review the technique and research of the ultrahigh spatiotemporal resolved spectroscopy and its applications in the field of the ultrafast dynamics of mesoscopic systems and nanomaterials. Combining femtosecond time-resolved spectroscopy and scanning near-field optical microscopy (SNOM),we can obtain the spectra with ultrahigh temporal and spatial resolutions simultaneously. Some problems in doing so are discussed. Then we show the important applications of the ultrahigh spatiotemporal resolved spectroscopy with a few typical examples.展开更多
Adsorption and oxidation of ethylene glyco(EG) on Pt(100) electrode were studied by in situ timeresolved FTIRS (TRFTIRS). The TRFTIR spectra recordedat 0.10 V illustrate that an IR band appears near 2050 cm?at t > ...Adsorption and oxidation of ethylene glyco(EG) on Pt(100) electrode were studied by in situ timeresolved FTIRS (TRFTIRS). The TRFTIR spectra recordedat 0.10 V illustrate that an IR band appears near 2050 cm?at t > 5 s, corresponding to linearly bonded CO formed indissociative adsorption of EG. The TRFTIR results haveconfirmed also that CO species are distributed uniformly onPt(100) surface. Another band appears near 2342 cm?1 at > 70 s, associating with IR absorption of CO2 produced inthe direct oxidation of EG. With the increase of electrodepotential, the direct oxidation of EG becomes gradually themain reaction. When the potential is above 0.40 V, the oxidation of EG occurs mainly via the reactive intermediates, i.especies containing –COOH determined by in situ TRFTIRS.展开更多
A variant of all-resonant CARS named electronic-resonant enhancement CARS(ERE-CARS) is applied to measure the methanol-water solution concentration at room temperature.The measurements are performed using the ERE-CARS...A variant of all-resonant CARS named electronic-resonant enhancement CARS(ERE-CARS) is applied to measure the methanol-water solution concentration at room temperature.The measurements are performed using the ERE-CARS signal of the Raman vibrations near the C-H stretching modes(at 2835 and 2942 cm 1) in methanol.By changing the timing(t>0) of the laser pulses of this non-degenerate four wave mixing technique,the concentration information based on the vibrational dynamics of the C-H bonds can be successfully detected as the frequency-spread dephasing rate during the first few hundred fs in the ERE-CARS signal with high sensitivity and accuracy.Femtosecond time-resolved ERE-CARS technique is applied to the concentration analysis of a mixture of the organic solution.This investigation indicates that femtosecond time-resolved ERE-CARS technique might be a powerful tool for real-time detection for solution concentration of different liquids.展开更多
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.
文摘The properties of the triplet excited state of [60]fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60]fullerene-containing cyclic sulphoxide showed two decay-components, which were attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60]fullerene-containing cyclic sulphoxide are also reported.
基金Financial supports from the National Natural Science Foundation of China(21225730,91326202 and 21577032)the Fundamental Research Funds for the Central Universities(JB2015001)+1 种基金Kunlun scholarship of Qinghai province,the priority Academic program development of Jiangsu Higher Education Institutionsthe Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions are acknowledged
文摘To contribute to the understanding of Eu(Ⅲ)interaction properties on hydrous alumina particles in the absence and presence of fulvic acid(FA),the complexation properties of Eu(Ⅲ)with hydrous alumina,FA and FA-alumina hybrids are studied by batch and time-resolved laser fluorescence spectroscopy(TRLFS)techniques.The continuous increase in the fluorescence lifetime of Eu-alumina and Eu-FA with increasing pH indicates that the complexation is accompanied by decreasing number of hydration water in the first coordination sphere of Eu(Ⅲ).Eu(Ⅲ)is adsorbed onto alumina particles as outer-sphere surface complexes of≡(Al-O)-Eu·(OH)·7H_2O and≡(Al-O)-Eu·6H_2O at low pH values,and as inner-sphere surface complexes as≡(Al-O)_2-Eu^+·4H_2O at high pH.In FA solution,Eu(Ⅲ)forms complexes with FA as(COO)_2Eu^+(H_2O)_x and the hydration water number in the first coordination sphere decreases with pH increasing.The formation of≡COO-Eu-(O-Al≡)·4H_2O is observed on FA-alumina hybrids,suggesting the formation of strong inner-sphere surface complexes in the presence of FA.The surface complexes are also characterized by their emission spectra[the ratio of emission intensities of^5D_0→~7F_1(λ=594nm)and^5D_0→~7F_2(λ=619nm)transitions]and their fluorescence lifetime.The findings is important to understand the contribution of FA in the complexation properties of Eu(Ⅲ)on FA-alumina hybrids that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Eu(Ⅲ),or its analogue trivalent lanthanide and actinide ions in natural environment.
文摘The femtosecond time-resolved difference absorption spectra of all-trans-b- Apo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequential model for the excited-state energy relaxation. With this model, we have obtained the excited-state absorption spectra and the lifetimes of the corresponding excited states both in nonpolar solvent n-hexane and polar solvent methanol. Three excited states, namely S3(170fs), S2(2.32ps) and S1(26ps) in n-hexane, and two excited states S2 (190fs) and S1(9.4ps) in methanol have been observed. The excited-state absorption spectra of all-trans-b-Apo-8′-carotenal in methanol display a red shift and broadeness, while the lifetime of S1 state becomes shorter. It is proposed that these effects are related to the presence of a carbonyl functional group that leads to the solvent effect on the excited-state energy level. At the same time, it is shown that the SVD method is a useful tool in resolving the time-resolved absorption spectra.
基金Supported by the Strategic Research Foundation Grant-aided Project for Private Universities(No.S1411017)a Grant-in-Aid for Exploratory Research(No.25560356)from the Ministry of Education,Culture,Sports,Sciences,and Technology of Japan
文摘Objective:This study aimed to employ time‐resolved spectroscopy(TRS)to explore age‐related differences in prefrontal cortex(PFC)activity while subjects performed a working memory task.Methods:We employed TRS to measure PFC activity in ten healthy younger and ten healthy older subjects while they performed a working memory(WM)task.All subjects performed the Sternberg test(ST)in which the memory‐set size varied between one and six digits.Using TRS,we recorded changes in cerebral blood oxygenation as a measure of changes in PFC activity during the task.In order to identify left/right asymmetry of PFC activity during the working memory task,we calculated the laterality score,i.e.,Δoxy‐Hb(rightΔoxy‐Hb—leftΔoxy‐Hb);positive values indicate greater activity in the right PFC,while negative values indicate greater activity in the left PFC.Results:During the ST,statistical analyses showed no significant differences between the younger and older groups in accuracy for low memory‐load and high memory‐load.In high memory‐load tasks,however,older subjects were slower than younger subjects(P<0.05).We found that the younger group showed right lateral responses with a stronger right than left activation in the frontal pole,whereas the older group showed bilateral responses(P<0.05).Conclusions:The present results are consistent with the hemispheric asymmetry reduction in older adults(HAROLD)model;working memory tasks cause asymmetrical PFC activation in younger adults,while older adults tend to show reduced hemispheric lateralization.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 10434020, 90501007 and 10521002)the National Basic Research Program of China (Grant No. 2007CB307001)
文摘We review the technique and research of the ultrahigh spatiotemporal resolved spectroscopy and its applications in the field of the ultrafast dynamics of mesoscopic systems and nanomaterials. Combining femtosecond time-resolved spectroscopy and scanning near-field optical microscopy (SNOM),we can obtain the spectra with ultrahigh temporal and spatial resolutions simultaneously. Some problems in doing so are discussed. Then we show the important applications of the ultrahigh spatiotemporal resolved spectroscopy with a few typical examples.
基金This work was supported by the National Natural Science Foundation of China(Gran:Nos.20373059 and 90206039)the“973"Program(Grant No.2002CB211804).
文摘Adsorption and oxidation of ethylene glyco(EG) on Pt(100) electrode were studied by in situ timeresolved FTIRS (TRFTIRS). The TRFTIR spectra recordedat 0.10 V illustrate that an IR band appears near 2050 cm?at t > 5 s, corresponding to linearly bonded CO formed indissociative adsorption of EG. The TRFTIR results haveconfirmed also that CO species are distributed uniformly onPt(100) surface. Another band appears near 2342 cm?1 at > 70 s, associating with IR absorption of CO2 produced inthe direct oxidation of EG. With the increase of electrodepotential, the direct oxidation of EG becomes gradually themain reaction. When the potential is above 0.40 V, the oxidation of EG occurs mainly via the reactive intermediates, i.especies containing –COOH determined by in situ TRFTIRS.
基金supported by the National Natural Science Foundation of China (Grant No. 61008023)the Program of Excellent at Harbin Institute of Technology
文摘A variant of all-resonant CARS named electronic-resonant enhancement CARS(ERE-CARS) is applied to measure the methanol-water solution concentration at room temperature.The measurements are performed using the ERE-CARS signal of the Raman vibrations near the C-H stretching modes(at 2835 and 2942 cm 1) in methanol.By changing the timing(t>0) of the laser pulses of this non-degenerate four wave mixing technique,the concentration information based on the vibrational dynamics of the C-H bonds can be successfully detected as the frequency-spread dephasing rate during the first few hundred fs in the ERE-CARS signal with high sensitivity and accuracy.Femtosecond time-resolved ERE-CARS technique is applied to the concentration analysis of a mixture of the organic solution.This investigation indicates that femtosecond time-resolved ERE-CARS technique might be a powerful tool for real-time detection for solution concentration of different liquids.
