In energy-dispersive X-ray fluorescence spectroscopy,the estimation of the pulse amplitude determines the accuracy of the spectrum measurement.The error generated by the amplitude estimation of the pulse output distor...In energy-dispersive X-ray fluorescence spectroscopy,the estimation of the pulse amplitude determines the accuracy of the spectrum measurement.The error generated by the amplitude estimation of the pulse output distorted by the measurement system leads to false peaks in the measured spectrum.To eliminate these false peaks and achieve an accurate estimation of the distorted pulse amplitude,a composite neural network model is proposed,which embeds long and short-term memory(LSTM)into the UNet structure.The UNet network realizes the fusion of pulse sequence features and the LSTM model realizes pulse amplitude estimation.The model is trained using simulated pulse datasets with different amplitudes and distortion times.For the pulse height estimation,the average relative error of the trained model on the test set was approximately 0.64%,which is 27.37% lower than that of the traditional trapezoidal shaping algorithm.Offline processing of a standard iron source further validated the pulse height estimation performance of the UNet-LSTM model.After estimating the amplitude of the distorted pulses using the model,the false peak area was reduced by approximately 91% over the full spectrum and was corrected to the characteristic peak region of interest(ROI).The corrected peak area accounted for approximately 1.32%of the characteristic peak ROI area.The results indicate that the model can accurately estimate the height of distorted pulses and has substantial corrective effects on false peaks.展开更多
Based on previous laser-induced fluorescence excitation spectroscopy work, the vibrational constants of neutral FeS in the X5 △ electronic state were obtained by directly mapping the ground-state vibrational levels u...Based on previous laser-induced fluorescence excitation spectroscopy work, the vibrational constants of neutral FeS in the X5 △ electronic state were obtained by directly mapping the ground-state vibrational levels up to v＂=3 using conventional laser-induced dispersed fluorescence spectroscopy. The vibrational frequency of FeS（X5 △） （518±5 cm-1） agrees well with that reported in a recent PES measurement （520±30 cm-1） [J. Phys. Chem. A 107, 2821 （2003）] which is the only one prior experimental vibrational frequency value for the 5 △ state of FeS. Careful comparisons of our experimental results and those documented in the literature （mainly from theoretical predictions） suggest that the ground state of FeS is 5 △ state.展开更多
The white-rot fungus, Phanerochaete chrysosporium (P. chrysosporium), was inoculated during different phases of agricultural waste composting, and its effect on the fluorescence spectroscopy characteristics of humic a...The white-rot fungus, Phanerochaete chrysosporium (P. chrysosporium), was inoculated during different phases of agricultural waste composting, and its effect on the fluorescence spectroscopy characteristics of humic acid (HA) was studied. The results show that the emission spectra have a sharp peak at 400 nm and a broad shoulder with the maximum centered at 460 nm. The excitation spectra have two peaks and exhibit red shift (shift to longer wavelengths) at 470 nm. The synchronous scan spectra present a number of peaks and shoulders, and the peaks at shorter wavelengths disappear gradually and form a shoulder. At the final stage of composting, the fluorescence spectra have similar shapes, but the fluorescence intensities decrease. P. chrysosporium increases the degree of aromatization and polymerization of HA when it is inoculated during the second fermentation phase, while it does not produce an obvious change on the humification degree of HA when it is inoculated during the first fermentation phase. Compared with the fluorescence spectroscopy characteristics of HA from soil, the structure of HA from compost is simpler and the activity is higher.展开更多
Photodissociation of oxygen from oxymyoglobin（oxyMb） was investigated by means of fluorescence spectroscopy. One of the most important findings of the photodissociation of oxyMb was the discovery of two processes wh...Photodissociation of oxygen from oxymyoglobin（oxyMb） was investigated by means of fluorescence spectroscopy. One of the most important findings of the photodissociation of oxyMb was the discovery of two processes which were affected by excitation intensity, temperature, solvent viscosity, and excitation wavelength. Process I（PI） corresponded to oxygen escaping from the binding site at ferrous heme iron atom within the porphyrin ring into the heme pocket, whereas process II（PII） was ascribed to oxygen escaping from the heme pocket into the solvent. To elucidate this interesting phenomenon, we proposed a model that oxygen encountered two barriers on its way from the binding site at the ferrous heme iron to the solvent. Reversibility and wavelength sensitivity of the photodissociation were also observed.展开更多
Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluoresce...Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.展开更多
The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolut...The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolution of instantaneous emission dipole moment obtained by femtosecond transient fluorescence spectroscopy, we presented a real-time characterization of the solvent-induced SBCT dynamics in an octupolar triphenylamine derivative. While the emission dipole moment of the octupolar trimer in weakly polar toluene changes little during the excited-state relaxation, it exhibits a fast reduction in a few picoseconds in strongly polar tetrahydrofuran. In comparison with the uorescence dynamics of dipolar monomer, we deduced that the emitting state of the octupolar trimer in strongly polar solvent, which undergoes solvent-induced structural uctuation, changes from exciton-coupled octupolar to excitation localized dipolar symmetry. In weakly polar solvent, the octupolar symmetry of the trimer is largely preserved during the solvation stabilization.展开更多
<div style="text-align:justify;"> Peanut oil oxidation was to monitor and quantify combining synchronous fluorescence spectroscopy and chemometrics. Peanut oil was subjected to an accelerated oxidation...<div style="text-align:justify;"> Peanut oil oxidation was to monitor and quantify combining synchronous fluorescence spectroscopy and chemometrics. Peanut oil was subjected to an accelerated oxidation testing. The spectral and related chemical indicators were caught during oxidation induce testing. Fluorescence spectra were gained for each sample with simultaneous excitation from 200 to 800 nm and the offsets (Δλ) of 10 to 180 nm during the oxidation process. The results showed the induce period (IP) of the peanut oil was 16.45 h. Parallel factor analysis (PARAFAC) was performed to select the best Δλ interval of 70 nm, which spectral data was the most suitable for interval partial least square (iPLS) and synergy interval PLS (siPLS) modeling and forecast. The study presented all interval selection methods had the better results than the global spectrum modelling. iPLS reached the best into 10 intervals with a ratio of prediction to deviation (RPD) of 2.10. siPLS that separated the whole spectrum into 15 intervals and combined the third intervals (282 to 320 nm, 362 to 400 nm, and 761 to 800 nm) had a ratio of RPD of 2.26. The results showed the optimal siPLS model performed a little better than iPLS. The established model lying on interval selection could improve the prediction accuracy. It could provide a quick, accurate method to monitor oil oxidation process. </div>展开更多
A model HA-type polymer of para-benzoquinone synthetic humic acid (SHA) and its complexes with copper, iron and manganese metal ions were studied using atomic force microscopy (AFM). Natural humic acids (HA) and synth...A model HA-type polymer of para-benzoquinone synthetic humic acid (SHA) and its complexes with copper, iron and manganese metal ions were studied using atomic force microscopy (AFM). Natural humic acids (HA) and synthetic humic acids (SHA) were examined by fluorescence spectroscopy, which indicated similarity of SHA and HA spectra. The AFM images of SHA and its complexes revealed variable morphologies, such as small spheres, aggregates and a sponge-like structure. The SHA complexes displayed morphologies similar to those of natural HA. The presence of copper, iron and manganese ions led to the formation of aggregate-type structures in an apparent arrangement of smaller SHA particles.展开更多
The characterization of the algae Anabaena cylindrical solution with Fe(III)was investigated using fluorescence emission and synchronous-scan spectroscopy.The ranges ofconcentrations of algae and Fe(III)in aqueous sol...The characterization of the algae Anabaena cylindrical solution with Fe(III)was investigated using fluorescence emission and synchronous-scan spectroscopy.The ranges ofconcentrations of algae and Fe(III)in aqueous solutions were 5.0 X 10~7-2.5 X10^8 cell/L and 10-60mu mol/L,respectively.The effective characterization method used was synchronous-scanfluorescence spectroscopy(SFS).The wavelength difference(triangle open lambda)of 90 nm wasmaintained between excitation wavelength(lambda_(ex))and emissionwavelength(lambda_(em)).The peakwas observed at about lambda_(ex)236 nm/lambda_(em)326 nm for synchronous-scan fluorescencespectroscopy.The fluorescence quenching in system of algae-Fe(III)-HA was studied usingsynchronous-scan spectroscopy forthe first time,Fe(III)was clearly the effective quencher.Therelationship between I_0/I(quenching efficiency)and c(concentration of Fe(III).added)was alinear correlation for the algae solution with Fe(III).Also,Aldrich humic acid(HA)was found tobe an effective quencher.展开更多
High resolution laser induced fluorescence, spectra of IrN in the spectral region between 394 and 520 nm were recorded using laser vaporization/reaction free jet expansion and laser induced fluorescence spectroscopy. ...High resolution laser induced fluorescence, spectra of IrN in the spectral region between 394 and 520 nm were recorded using laser vaporization/reaction free jet expansion and laser induced fluorescence spectroscopy. Seven new vibronic transition bands were observed and analyzed. Two Ω=1 and five Ω=0 new states were identified. Least squares fit of rotationally resolved transition lines yielded accurate molecular constants for the upper states. Spectra of isotopic molecules were observed, which provided confirmation for the vibrational assignment. Comparison of the observed electronic states of IrB, IrC, and IrN provides a good understanding of the chemical bonding of this group of molecules.展开更多
A rapid method of determination of BaP in various environmental samples,using synchronous fluorescence spectroscopy scanning in defined range of dual-wavelengths(SFDW)is described in this paper.
The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for pH ranges of 1-8.5 and an initial Eu concentration (C Eu) of 2×10 -4 M. The sorption rate...The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for pH ranges of 1-8.5 and an initial Eu concentration (C Eu) of 2×10 -4 M. The sorption rate of Eu was initially low, but significantly increased at pH>4. The sorption density of Eu species on a silica surface was ～1.58×10 -7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at pH=～5.8. The sorbed Eu species at pH<6 is aquo Eu 3+, which is sorbed onto silica-water interfaces as an outer-sphere complex at pH<5, but may be sorbed as an inner-sphere bidentate complex at 5<pH<6, due to the decrease of N H 2O to ～6 at pH=6. At pH=6-8.5, Eu(OH)+ 2, Eu(CO 3)+ and Eu(CO 3)- 2 formed in the solutions, and Eu(CO 3)+ is dominant at pH=～7.5. These ions may be sorbed onto silica-water interfaces as inner-sphere bidentate complexes.展开更多
Quality of soil humic substances and compost quality was assessed using different techniques of fluorescence spectroscopy. Emission, excitation, synchronous and emission-excitation matrix help us to characterize diffe...Quality of soil humic substances and compost quality was assessed using different techniques of fluorescence spectroscopy. Emission, excitation, synchronous and emission-excitation matrix help us to characterize different fluorophores in humic substances molecule. Content of stabile carbon forms in soil was assessed by humic substances fractionation. Content of labile water extractable carbon and nitrogen was determined by analyzer Shimadzu TOC-VCSH with chemo-luminescent detection in infrared spectral region. Results showed that compost amendment caused changes in both stabile （recalcitrant） and labile carbon content. Humic substances isolated from compost consist mainly of simple structural components of wide molecular heterogeneity and low molecular weight. Humification degree and content of conjugated fluorophores in compost was lower compared with stabile soil humic substances. The last contained more conjugated aromatic π-electron systems with electron-withdrawing functional groups, which are responsible for the fluorescence shift to lower energy levels or longer wavelengths.展开更多
The interactions of bovine serum albumin （BSA） with three structurally related isoflavonoids, genistein, puerarin and daidzein, were studied under physiological conditions by fluorescence spectroscopic technique. Th...The interactions of bovine serum albumin （BSA） with three structurally related isoflavonoids, genistein, puerarin and daidzein, were studied under physiological conditions by fluorescence spectroscopic technique. The quenching mechanism of these compounds with BSA was suggested as static quenching and the binding constants were determined at different temperatures based on the fluorescence quenching results. The transfer efficiency of energy and distance between the acceptor and BSA were investigated on the basis of the mechanism of the Forster energy transference. According to the thermodynamic parameters it has been suggested that the acting force be mainly hydrophobic force. The comparison of binding potency of the three isoflavonoids to BSA showed that the substitution by 5-OH and 8-Glc could enhance the binding affinity. All these obtained in the work can make us better understand the mode of the action and pharmacological activities of the isoflavonoids.展开更多
Effect of bovine serum albumin(BSA)on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)(PEO-PPO-PEO)block copolymers was investigated using pyrene fluore...Effect of bovine serum albumin(BSA)on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)(PEO-PPO-PEO)block copolymers was investigated using pyrene fluorescence spectroscopy.The critical micellization temperature(CMT)of pluronics in aqueous solution was increased by the addition of BSA.A closed association model was used to obtain the standard free energies(△DG^(0)),enthalpies(△DH^(0)),and entropies(△DS^(0))of micellization.The standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA content.The more PPO component in the pluronic polymer,the higher the changed values of micellization enthalpy and entropy.The hydrophobic part of the pluronics,PPO,was responsible for the interaction between pluronics and BSA.Hydrophobic interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA,which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.展开更多
The fluorescence spectra of synthetic food dyes of sunset yellow and tartrazine are analyzed. The fluorescence peak wavelengths of sunset yellow and tartrazine are 576 and 569 nm, respectively, while the fluorescence ...The fluorescence spectra of synthetic food dyes of sunset yellow and tartrazine are analyzed. The fluorescence peak wavelengths of sunset yellow and tartrazine are 576 and 569 nm, respectively, while the fluorescence spectra widths are 480-750 and 500 750 nm induced by ultraviolet light between 310-400 nm. The fluorescence spectra of sunset yellow overlap heavily with those of tartrazine, so it is difficult to distinguish them. Based on the principle of radial basis function neural network, a neural network is obtained from the training of the 14 groups of experimental data. The results show that the species of sunset yellow and tartrazine could be recognized accurately. This method has potential applications in other synthetic food dyes detection and food safety inspection.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
Single molecule techniques emerge as powerful and quantitative approaches for scientific investigations in last decades. Among them, single molecule fluorescence spectroscopy （SMFS） is able to non-invasively charact...Single molecule techniques emerge as powerful and quantitative approaches for scientific investigations in last decades. Among them, single molecule fluorescence spectroscopy （SMFS） is able to non-invasively characterize and track samples at the molecular level. Here, applications of SMFS to fundamental biological questions have been briefly summarized in catalogues of single-molecule counting, distance measurements, force sensors, molecular tracking, and ultrafast dynamics. In these SMFS applications, statistics and physical laws are utilized to quantitatively analyze the behaviors of biomolecules in cellular signaling pathways and the mechanisms of biological functions. This not only deepens our understanding of bio-systems, but also provides a fresh angle to those fundamental questions, leading to a more quantitative thinking in life science.展开更多
Igneous and sedimentary rocks contain an amount of natural radioactivity (NORM). U-238, Th-232 and their decay products, and K-40 are important sources of gamma-radiation. Knowledge of the radionuclide content of rock...Igneous and sedimentary rocks contain an amount of natural radioactivity (NORM). U-238, Th-232 and their decay products, and K-40 are important sources of gamma-radiation. Knowledge of the radionuclide content of rocks is necessary to estimate the exposure of the population to the radiation. Many types of rocks are used in building and industries, thus the radiation detection is important, it provides a baseline map of levels of the radioactivity in the study region. The purpose of this study is to evaluate the activity concentrations of the natural radionuclides (U-238 (Ra-226), Th-232 and K-40) and the fallout nuclide (Cs-137) (if found) in thirty samples of igneous and sedimentary rocks of Al-Atawilah (Al-Baha). The samples were collected and prepared during 2018/2019, and analyzed with a good experimental instrument (High energy resolution γ-ray spectroscopy with HPGe detector), also these rock samples were analyzed with X-ray fluorescence to subdivided these rocks based on the major oxides proportions contained of each sample. The mean activity concentrations of naturally radionuclides were found in the igneous rock samples varied depending on the type of the igneous rock. For sedimentary rock samples, the activity concentrations were found high for quartz sandstone sample, which may be due to its high proportion of SiO<sub>2</sub> and K<sub>2</sub>O. The estimated mean values of absorbed dose rate are within the permissible limit value. The findings indicate high dose level values in granite (rhyolite) and most of diorite (andesite) igneous rock samples while gabbro (basalt) igneous rock samples (except for one sample) record low levels of dose rate. All sedimentary rock samples have low dose rate (except for the quartz sand-stone sample).展开更多
基金supported by the Open Project of Guangxi Key Laboratory of Nuclear Physics and Nuclear Technology(No.NLK2022-05)the Central Government Guidance Funds for Local Scientific and Technological Development,China(No.Guike ZY22096024)+5 种基金the Sichuan Natural Science Youth Fund Project(No.2023NSFSC1366)Key R&D Projects of Sichuan Provincial Department of Science and Technology(No.2023YFG0287)the Open Research Fund of National Engineering Research Center for Agro-Ecological Big Data Analysis&Application,Anhui University(No.AE202209)the National Natural Science Youth Foundation of China(No.12305214)the Vanadium and Titanium Resource Comprehensive Utilization Key Laboratory of Sichuan Province(No.2023FTSZ03)the Key Laboratory of Interior Layout optimization and Security,Institutions of Higher Education of Sichuan Province(No.2023SNKJ-01)。
文摘In energy-dispersive X-ray fluorescence spectroscopy,the estimation of the pulse amplitude determines the accuracy of the spectrum measurement.The error generated by the amplitude estimation of the pulse output distorted by the measurement system leads to false peaks in the measured spectrum.To eliminate these false peaks and achieve an accurate estimation of the distorted pulse amplitude,a composite neural network model is proposed,which embeds long and short-term memory(LSTM)into the UNet structure.The UNet network realizes the fusion of pulse sequence features and the LSTM model realizes pulse amplitude estimation.The model is trained using simulated pulse datasets with different amplitudes and distortion times.For the pulse height estimation,the average relative error of the trained model on the test set was approximately 0.64%,which is 27.37% lower than that of the traditional trapezoidal shaping algorithm.Offline processing of a standard iron source further validated the pulse height estimation performance of the UNet-LSTM model.After estimating the amplitude of the distorted pulses using the model,the false peak area was reduced by approximately 91% over the full spectrum and was corrected to the characteristic peak region of interest(ROI).The corrected peak area accounted for approximately 1.32%of the characteristic peak ROI area.The results indicate that the model can accurately estimate the height of distorted pulses and has substantial corrective effects on false peaks.
基金Acknowledgment： This work was supported by the National Natural Science Foundation of China （No.20673107 and No.20873133）, the National Basic Research Program of China （No.2007CB815203 and No.2010CB923302）, the Chinese Academy of Sciences （No.KJCX2-YW-N24）, and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education of China.
文摘Based on previous laser-induced fluorescence excitation spectroscopy work, the vibrational constants of neutral FeS in the X5 △ electronic state were obtained by directly mapping the ground-state vibrational levels up to v＂=3 using conventional laser-induced dispersed fluorescence spectroscopy. The vibrational frequency of FeS（X5 △） （518±5 cm-1） agrees well with that reported in a recent PES measurement （520±30 cm-1） [J. Phys. Chem. A 107, 2821 （2003）] which is the only one prior experimental vibrational frequency value for the 5 △ state of FeS. Careful comparisons of our experimental results and those documented in the literature （mainly from theoretical predictions） suggest that the ground state of FeS is 5 △ state.
基金Project(2005CB724203) supported by the Major State Basic Research and Development Program of ChinaProject(IRT0719) supported by the Program for Changjiang Scholars and Innovative Research Team in University of China+1 种基金Projects(50608029,50808073) supported by the National Natural Science Foundation of ChinaProject(2007185) supported by the Environmental Protection Technology Research Program of Hunan Province,China
文摘The white-rot fungus, Phanerochaete chrysosporium (P. chrysosporium), was inoculated during different phases of agricultural waste composting, and its effect on the fluorescence spectroscopy characteristics of humic acid (HA) was studied. The results show that the emission spectra have a sharp peak at 400 nm and a broad shoulder with the maximum centered at 460 nm. The excitation spectra have two peaks and exhibit red shift (shift to longer wavelengths) at 470 nm. The synchronous scan spectra present a number of peaks and shoulders, and the peaks at shorter wavelengths disappear gradually and form a shoulder. At the final stage of composting, the fluorescence spectra have similar shapes, but the fluorescence intensities decrease. P. chrysosporium increases the degree of aromatization and polymerization of HA when it is inoculated during the second fermentation phase, while it does not produce an obvious change on the humification degree of HA when it is inoculated during the first fermentation phase. Compared with the fluorescence spectroscopy characteristics of HA from soil, the structure of HA from compost is simpler and the activity is higher.
基金Supported by the National Natural Science Foundation of China(No.20871024)the Program for Liaoning Excellent Talents in University,China(No.RC-04-10)+1 种基金the Fund of Liaoning Innovative Research Team in University,China(Nos.2006T002,2008T005,2009T003)the Plan Project of Dalian Science and Technology,China(No.2008E11SF170)
文摘Photodissociation of oxygen from oxymyoglobin（oxyMb） was investigated by means of fluorescence spectroscopy. One of the most important findings of the photodissociation of oxyMb was the discovery of two processes which were affected by excitation intensity, temperature, solvent viscosity, and excitation wavelength. Process I（PI） corresponded to oxygen escaping from the binding site at ferrous heme iron atom within the porphyrin ring into the heme pocket, whereas process II（PII） was ascribed to oxygen escaping from the heme pocket into the solvent. To elucidate this interesting phenomenon, we proposed a model that oxygen encountered two barriers on its way from the binding site at the ferrous heme iron to the solvent. Reversibility and wavelength sensitivity of the photodissociation were also observed.
文摘Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.
基金supported by the National Natural Science Foundation of China (No.21673252, No.21333012, No.21672211, and No.21773252, No.21827803)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB12020200)
文摘The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolution of instantaneous emission dipole moment obtained by femtosecond transient fluorescence spectroscopy, we presented a real-time characterization of the solvent-induced SBCT dynamics in an octupolar triphenylamine derivative. While the emission dipole moment of the octupolar trimer in weakly polar toluene changes little during the excited-state relaxation, it exhibits a fast reduction in a few picoseconds in strongly polar tetrahydrofuran. In comparison with the uorescence dynamics of dipolar monomer, we deduced that the emitting state of the octupolar trimer in strongly polar solvent, which undergoes solvent-induced structural uctuation, changes from exciton-coupled octupolar to excitation localized dipolar symmetry. In weakly polar solvent, the octupolar symmetry of the trimer is largely preserved during the solvation stabilization.
文摘<div style="text-align:justify;"> Peanut oil oxidation was to monitor and quantify combining synchronous fluorescence spectroscopy and chemometrics. Peanut oil was subjected to an accelerated oxidation testing. The spectral and related chemical indicators were caught during oxidation induce testing. Fluorescence spectra were gained for each sample with simultaneous excitation from 200 to 800 nm and the offsets (Δλ) of 10 to 180 nm during the oxidation process. The results showed the induce period (IP) of the peanut oil was 16.45 h. Parallel factor analysis (PARAFAC) was performed to select the best Δλ interval of 70 nm, which spectral data was the most suitable for interval partial least square (iPLS) and synergy interval PLS (siPLS) modeling and forecast. The study presented all interval selection methods had the better results than the global spectrum modelling. iPLS reached the best into 10 intervals with a ratio of prediction to deviation (RPD) of 2.10. siPLS that separated the whole spectrum into 15 intervals and combined the third intervals (282 to 320 nm, 362 to 400 nm, and 761 to 800 nm) had a ratio of RPD of 2.26. The results showed the optimal siPLS model performed a little better than iPLS. The established model lying on interval selection could improve the prediction accuracy. It could provide a quick, accurate method to monitor oil oxidation process. </div>
基金The authors acknowledge CAPES(Coordenação de Aperfeiçoamento de Pessoal de Nível Superior)and CNPq(Conselho Nacional de Desenvolvimento Científico e Tecnológico)process 302756/2009-4 for their financial supportEMBRAPA(Empresa Brasileira de Pesqui-sa Agropecuária)for its structural support of this work
文摘A model HA-type polymer of para-benzoquinone synthetic humic acid (SHA) and its complexes with copper, iron and manganese metal ions were studied using atomic force microscopy (AFM). Natural humic acids (HA) and synthetic humic acids (SHA) were examined by fluorescence spectroscopy, which indicated similarity of SHA and HA spectra. The AFM images of SHA and its complexes revealed variable morphologies, such as small spheres, aggregates and a sponge-like structure. The SHA complexes displayed morphologies similar to those of natural HA. The presence of copper, iron and manganese ions led to the formation of aggregate-type structures in an apparent arrangement of smaller SHA particles.
基金Supported by the National Natural Science Foundation of China(20177017)the Scientific Research Foundation of Wuhan Environmental Pro tection Bureau
文摘The characterization of the algae Anabaena cylindrical solution with Fe(III)was investigated using fluorescence emission and synchronous-scan spectroscopy.The ranges ofconcentrations of algae and Fe(III)in aqueous solutions were 5.0 X 10~7-2.5 X10^8 cell/L and 10-60mu mol/L,respectively.The effective characterization method used was synchronous-scanfluorescence spectroscopy(SFS).The wavelength difference(triangle open lambda)of 90 nm wasmaintained between excitation wavelength(lambda_(ex))and emissionwavelength(lambda_(em)).The peakwas observed at about lambda_(ex)236 nm/lambda_(em)326 nm for synchronous-scan fluorescencespectroscopy.The fluorescence quenching in system of algae-Fe(III)-HA was studied usingsynchronous-scan spectroscopy forthe first time,Fe(III)was clearly the effective quencher.Therelationship between I_0/I(quenching efficiency)and c(concentration of Fe(III).added)was alinear correlation for the algae solution with Fe(III).Also,Aldrich humic acid(HA)was found tobe an effective quencher.
文摘High resolution laser induced fluorescence, spectra of IrN in the spectral region between 394 and 520 nm were recorded using laser vaporization/reaction free jet expansion and laser induced fluorescence spectroscopy. Seven new vibronic transition bands were observed and analyzed. Two Ω=1 and five Ω=0 new states were identified. Least squares fit of rotationally resolved transition lines yielded accurate molecular constants for the upper states. Spectra of isotopic molecules were observed, which provided confirmation for the vibrational assignment. Comparison of the observed electronic states of IrB, IrC, and IrN provides a good understanding of the chemical bonding of this group of molecules.
文摘A rapid method of determination of BaP in various environmental samples,using synchronous fluorescence spectroscopy scanning in defined range of dual-wavelengths(SFDW)is described in this paper.
文摘The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for pH ranges of 1-8.5 and an initial Eu concentration (C Eu) of 2×10 -4 M. The sorption rate of Eu was initially low, but significantly increased at pH>4. The sorption density of Eu species on a silica surface was ～1.58×10 -7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at pH=～5.8. The sorbed Eu species at pH<6 is aquo Eu 3+, which is sorbed onto silica-water interfaces as an outer-sphere complex at pH<5, but may be sorbed as an inner-sphere bidentate complex at 5<pH<6, due to the decrease of N H 2O to ～6 at pH=6. At pH=6-8.5, Eu(OH)+ 2, Eu(CO 3)+ and Eu(CO 3)- 2 formed in the solutions, and Eu(CO 3)+ is dominant at pH=～7.5. These ions may be sorbed onto silica-water interfaces as inner-sphere bidentate complexes.
文摘Quality of soil humic substances and compost quality was assessed using different techniques of fluorescence spectroscopy. Emission, excitation, synchronous and emission-excitation matrix help us to characterize different fluorophores in humic substances molecule. Content of stabile carbon forms in soil was assessed by humic substances fractionation. Content of labile water extractable carbon and nitrogen was determined by analyzer Shimadzu TOC-VCSH with chemo-luminescent detection in infrared spectral region. Results showed that compost amendment caused changes in both stabile （recalcitrant） and labile carbon content. Humic substances isolated from compost consist mainly of simple structural components of wide molecular heterogeneity and low molecular weight. Humification degree and content of conjugated fluorophores in compost was lower compared with stabile soil humic substances. The last contained more conjugated aromatic π-electron systems with electron-withdrawing functional groups, which are responsible for the fluorescence shift to lower energy levels or longer wavelengths.
基金Project supported by the Natural National Science Foundation （Nos. 20132020 and 20175026） of China and the Henan Academic Foundation of Science and Technology.
文摘The interactions of bovine serum albumin （BSA） with three structurally related isoflavonoids, genistein, puerarin and daidzein, were studied under physiological conditions by fluorescence spectroscopic technique. The quenching mechanism of these compounds with BSA was suggested as static quenching and the binding constants were determined at different temperatures based on the fluorescence quenching results. The transfer efficiency of energy and distance between the acceptor and BSA were investigated on the basis of the mechanism of the Forster energy transference. According to the thermodynamic parameters it has been suggested that the acting force be mainly hydrophobic force. The comparison of binding potency of the three isoflavonoids to BSA showed that the substitution by 5-OH and 8-Glc could enhance the binding affinity. All these obtained in the work can make us better understand the mode of the action and pharmacological activities of the isoflavonoids.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.20221603,20490200 and 20273075)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education of China.
文摘Effect of bovine serum albumin(BSA)on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)(PEO-PPO-PEO)block copolymers was investigated using pyrene fluorescence spectroscopy.The critical micellization temperature(CMT)of pluronics in aqueous solution was increased by the addition of BSA.A closed association model was used to obtain the standard free energies(△DG^(0)),enthalpies(△DH^(0)),and entropies(△DS^(0))of micellization.The standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA content.The more PPO component in the pluronic polymer,the higher the changed values of micellization enthalpy and entropy.The hydrophobic part of the pluronics,PPO,was responsible for the interaction between pluronics and BSA.Hydrophobic interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA,which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.
文摘The fluorescence spectra of synthetic food dyes of sunset yellow and tartrazine are analyzed. The fluorescence peak wavelengths of sunset yellow and tartrazine are 576 and 569 nm, respectively, while the fluorescence spectra widths are 480-750 and 500 750 nm induced by ultraviolet light between 310-400 nm. The fluorescence spectra of sunset yellow overlap heavily with those of tartrazine, so it is difficult to distinguish them. Based on the principle of radial basis function neural network, a neural network is obtained from the training of the 14 groups of experimental data. The results show that the species of sunset yellow and tartrazine could be recognized accurately. This method has potential applications in other synthetic food dyes detection and food safety inspection.
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Single molecule techniques emerge as powerful and quantitative approaches for scientific investigations in last decades. Among them, single molecule fluorescence spectroscopy （SMFS） is able to non-invasively characterize and track samples at the molecular level. Here, applications of SMFS to fundamental biological questions have been briefly summarized in catalogues of single-molecule counting, distance measurements, force sensors, molecular tracking, and ultrafast dynamics. In these SMFS applications, statistics and physical laws are utilized to quantitatively analyze the behaviors of biomolecules in cellular signaling pathways and the mechanisms of biological functions. This not only deepens our understanding of bio-systems, but also provides a fresh angle to those fundamental questions, leading to a more quantitative thinking in life science.
文摘Igneous and sedimentary rocks contain an amount of natural radioactivity (NORM). U-238, Th-232 and their decay products, and K-40 are important sources of gamma-radiation. Knowledge of the radionuclide content of rocks is necessary to estimate the exposure of the population to the radiation. Many types of rocks are used in building and industries, thus the radiation detection is important, it provides a baseline map of levels of the radioactivity in the study region. The purpose of this study is to evaluate the activity concentrations of the natural radionuclides (U-238 (Ra-226), Th-232 and K-40) and the fallout nuclide (Cs-137) (if found) in thirty samples of igneous and sedimentary rocks of Al-Atawilah (Al-Baha). The samples were collected and prepared during 2018/2019, and analyzed with a good experimental instrument (High energy resolution γ-ray spectroscopy with HPGe detector), also these rock samples were analyzed with X-ray fluorescence to subdivided these rocks based on the major oxides proportions contained of each sample. The mean activity concentrations of naturally radionuclides were found in the igneous rock samples varied depending on the type of the igneous rock. For sedimentary rock samples, the activity concentrations were found high for quartz sandstone sample, which may be due to its high proportion of SiO<sub>2</sub> and K<sub>2</sub>O. The estimated mean values of absorbed dose rate are within the permissible limit value. The findings indicate high dose level values in granite (rhyolite) and most of diorite (andesite) igneous rock samples while gabbro (basalt) igneous rock samples (except for one sample) record low levels of dose rate. All sedimentary rock samples have low dose rate (except for the quartz sand-stone sample).
