A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising path...A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising pathway.It has been demonstrated that the coupling of CO with the metal carbide can represent the early stage in the FTS process,while the related mechanism is elusive.Herein,the reactions of the CuC3H-and CuC3-cluster anions with CO have been studied by using mass spectrometry and theoretical calculations.The experimental results showed that the coupling of CO with the C3H-moiety of CuC3H can generate the exclusive ion product COC3H-.The reactivity and selectivity of this reaction of CuC3H-with CO are greatly higher than that of the reaction of CuC3-with CO,and this H-assisted C-C coupling process was rationalized by theoretical calculations.展开更多
The membrane-associated c-type cytochromes(c-Cyts) have been well known as the key enzymes mediating extracellular electron transfer to terminal electron acceptors, resulting in biogeochemical elemental transformation...The membrane-associated c-type cytochromes(c-Cyts) have been well known as the key enzymes mediating extracellular electron transfer to terminal electron acceptors, resulting in biogeochemical elemental transformation, contaminant degradation, and nutrient cycling. Although c-Cyts-mediated metal reduction or oxidation have been mainly investigated with the purified proteins of metal reducing/oxidizing bacteria, the in vivo behavior of c-Cyts is still unclear, given the difficulty in measuring the proteins of intact cells. Fortunately, the in situ spectroscopy would be ideal for measuring the reaction kinetics of c-Cyts in intact cells under noninvasive physiological conditions. It can also help the establishment of kinetic/thermodynamic models of extracellular electron transfer processes, which are essential to understand the electron transfer mechanisms at the molecular scale. This review briefly summarizes the current advances in spectral methods for examining the c-Cyts in intact cells of dissimilatory metal reducing bacteria and Fe(Ⅱ)-oxidizing bacteria.展开更多
从芫花（Daphne genkwa Sieb. et Zucc.）的干燥叶中分离出两种黄酮化合物,经化学和光谱分析,鉴定为木犀草甙（galuteolin）,系首次从本植物中分离得到;另一个结构确定为3′-羟基芫花素-5-O-β-D-葡萄糖甙（3′-hydroxygenkwanin-5-O-β...从芫花（Daphne genkwa Sieb. et Zucc.）的干燥叶中分离出两种黄酮化合物,经化学和光谱分析,鉴定为木犀草甙（galuteolin）,系首次从本植物中分离得到;另一个结构确定为3′-羟基芫花素-5-O-β-D-葡萄糖甙（3′-hydroxygenkwanin-5-O-β-D-glucoside）,定名为芜花叶甙（yuanhuanin）。讨论了芫花叶甙及其甙元羟基芫花素的13C-核磁共振谱并进行了峰的归属。展开更多
Prediction of vapor-liquid equilibrium （VLE） is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is n...Prediction of vapor-liquid equilibrium （VLE） is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is not economical. The infinite dilution activities can be used to predict VLE. However, it needs both the ends of the activities that are difficult to obtain for many systems. In the present study, a new model is proposed for correlating the frequency shift of C-H stretching band of IR spectra over the whole concentration. Investigated mixtures in- clude water/2-propanol, water/N, N-dimethylformamide （DMF）, water/methanol, water/ethanol, water/1, 4-dioxane, and water/dimethylsulfoxide （DMSO） systems. Simultaneous correlations of C--H frequency shift and VLE data are made. Furthermore, the VLE data were predicted with satisfactory results by the parameters obtained from IR spectra coupled with one ot the intinite chlution activity coefficients.展开更多
Allergic contact dermatitis is a delayed hypersensitivity reaction, which results from skin exposure to low molecular weight chemicals such as haptens. To clarify the pathogenic mechanism, electrospray ionization mass...Allergic contact dermatitis is a delayed hypersensitivity reaction, which results from skin exposure to low molecular weight chemicals such as haptens. To clarify the pathogenic mechanism, electrospray ionization mass spectrometry （ESI-MS） and hydrogen/deuterium （H/D） exchange, as well as UV spectroscopy, were applied to determine the interaction between the model protein cytochrome c （cyt c） and the hapten 2,4- dinitro-fiuorobenzene （DNFB）. The ESI-MS results demonstrate that the conformation of cyt c can change from native folded state into partially unfolded state with the increase of DNFB. The equilibrium state H/D exchange followed by ESI-MS further confirms the above results. UV spectroscopy indicates that the strong- field coordination between iron of heme （prosthetic group） and His18 or Met80 of cyt c is not obviously affected by the hapten.展开更多
We studied the first oxidation product of vitamin C, the dehydro-L-ascorbic acid dimer and characterized it by infrared and Raman spectroscopies in the solid phase. The Density functional theory was used to study its ...We studied the first oxidation product of vitamin C, the dehydro-L-ascorbic acid dimer and characterized it by infrared and Raman spectroscopies in the solid phase. The Density functional theory was used to study its structure and vibrational properties. These calculations gave us a precise knowledge of the normal modes of vibration taking into account that the molecule comprises a system of five fused rings; non planar γ-lactone and furonose rings are attached to a central dioxan ring in the twisted boat conformation. The calculated harmonic vibrational frequencies are consistent with the experimental vibrational spectra. An assignment of the observed spectral features is proposed. The shift of the band located in the infrared spectrum of the ascorbic acid from 3409 cm^-1 to 3299 cml and the remarkable increase in the band intensity at 1784 cm^-1 evidences the acid decomposition into its first product, the dehydro-L-ascorbic acid. The theoretical vibrational calculations allowed us to obtain a set of scaled force constants. The nature of the different -γ-lactone, furanose and dioxan rings and their topological properties were investigated by means of natural bond orbital and Bader＇s atoms in the molecule theory, respectively.展开更多
This paper reported the effect of the weak damage in the Al0.25Ga0.75As/GaAs epitaxial layer induced by 0.8 MeV Si ions implantation with ion dose from 1×1014 to 5×1015 cm-2. The Raman spectra measured on th...This paper reported the effect of the weak damage in the Al0.25Ga0.75As/GaAs epitaxial layer induced by 0.8 MeV Si ions implantation with ion dose from 1×1014 to 5×1015 cm-2. The Raman spectra measured on these samples showed that there were two kinds of phonon modes existing in the epitaxial Al0.25Ga0.75As films. The strains induced in the implanted layer and the corresponding lattice parameters were also evaluated as a function of the implanted dose. In addition, the Rutherford backscattering spectrometry/channeling (RBS/C) was also measured on these samples. These two measurement techniques all confirmed that the implantation only induced weak damage in the material.展开更多
The automorphism group of the Toeplitz C^*- algebra, J(C^1), generated by Toeplitz op-erators with C^1-symbols on Dirichlet space D is discussed; the K0, K1-groups and the first cohomology group of J(C^1) are compute...The automorphism group of the Toeplitz C^*- algebra, J(C^1), generated by Toeplitz op-erators with C^1-symbols on Dirichlet space D is discussed; the K0, K1-groups and the first cohomology group of J(C^1) are computed. In addition, the author proves that the spectra of Toeplitz operators with C^1-symbols are always connected, and discusses the algebraic prop-erties of Toeplitz operators.In particular, it is proved that there is no nontrivial selfadjoint Toeplitz operator on D and Tψ^* = Tψ^- if and only if Tψ is a scalar operator.展开更多
Ta/NiOx/Ni81Fe19/Ta multilayers were prepared by rf reactive and dc magnetron sputtering.The exchange coupling field (Hex) and the coercivity (Hc) of NiOx/Ni81Fe19 as a function of the ratio of Ar to O2 during the dep...Ta/NiOx/Ni81Fe19/Ta multilayers were prepared by rf reactive and dc magnetron sputtering.The exchange coupling field (Hex) and the coercivity (Hc) of NiOx/Ni81Fe19 as a function of the ratio of Ar to O2 during the deposition process were studied.The composition and chemical states at the interface region of NiOx/NiFe were also investigated using the X-ray photoelectron spectroscopy (XPS) and peak decomposition technique.The results show that the ratio of Ar to O2 has great effect on the nickel chemical states in NiOx film.When the ratio of Ar to O2 is equal to 7 and the argon sputtering pressure is 0.57 Pa,the x value is approximately 1 and the valence of nickel is +2.At this point,NiOx is antiferromagnetic NiO and the corresponding Hex is the largest.As the ratio of Ar/O2 deviates from 7,the exchange coupling field (Hex) will decrease due to the presence of magnetic impurities such as Ni+3 or metallic Ni at the interface region of NiOx/NiFe,while the coercivity (Hc) will increase due to the metallic Ni.XPS studies also show that there are two thermodynamically favorable reactions at the NiO/NiFe interface: NiO+Fe=Ni+FeO and 3NiO+2Fe=3Ni+Fe2O3.These interface reaction products are magnetic impurities at the interface region of NiO/NiFe.It is believed that these magnetic impurities would have effect on the exchange coupling field (Hex) and the coercivity (Hc) of NiO/NiFe.展开更多
The 4N1K peptide,which is derived from the C-terminal domain of thrombospondin-1(TSP-1),is usually used as a functional mimic peptide for TSP-1.Knowledge about the interaction force of 4N1K/CD47 is important in explai...The 4N1K peptide,which is derived from the C-terminal domain of thrombospondin-1(TSP-1),is usually used as a functional mimic peptide for TSP-1.Knowledge about the interaction force of 4N1K/CD47 is important in explaining how TSP-1 affects the biological effect of CD47.Here we used a single-molecule force spectroscopy(SMFS)technique to explore the interaction of 4N1K/CD47 on both normal and oxidative human red blood cells(h RBCs)at single-molecule level.There was no interaction force between 4N1K and CD47 on normal h RBCs;however,we did find 4N1K-bound CD47 on oxidative h RBCs.We also detected interaction forces for 4N1K/CD47ex(extracellular domain of human CD47),and 4N1K/oxidative CD47ex.The interaction forces of 4N1K/CD47ex were almost consistent with those of 4N1K/oxidative CD47ex at the same loading rate.These results suggest that the conformational change of CD47 is critical for 4N1K-CD47 interaction on oxidative h RBCs.展开更多
基金supported by the National Natural Science Foundation of China(No.21773254)the Youth Innovation Promotion Association Chinese Academy of Sciences(No.2016030)。
文摘A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising pathway.It has been demonstrated that the coupling of CO with the metal carbide can represent the early stage in the FTS process,while the related mechanism is elusive.Herein,the reactions of the CuC3H-and CuC3-cluster anions with CO have been studied by using mass spectrometry and theoretical calculations.The experimental results showed that the coupling of CO with the C3H-moiety of CuC3H can generate the exclusive ion product COC3H-.The reactivity and selectivity of this reaction of CuC3H-with CO are greatly higher than that of the reaction of CuC3-with CO,and this H-assisted C-C coupling process was rationalized by theoretical calculations.
基金funded by the National Natural Science Foundations of China(41522105 and 41571130052)Guangdong Natural Science Funds for Distinguished Young Scholar(2014A030306041)Special Support Program(2016)
文摘The membrane-associated c-type cytochromes(c-Cyts) have been well known as the key enzymes mediating extracellular electron transfer to terminal electron acceptors, resulting in biogeochemical elemental transformation, contaminant degradation, and nutrient cycling. Although c-Cyts-mediated metal reduction or oxidation have been mainly investigated with the purified proteins of metal reducing/oxidizing bacteria, the in vivo behavior of c-Cyts is still unclear, given the difficulty in measuring the proteins of intact cells. Fortunately, the in situ spectroscopy would be ideal for measuring the reaction kinetics of c-Cyts in intact cells under noninvasive physiological conditions. It can also help the establishment of kinetic/thermodynamic models of extracellular electron transfer processes, which are essential to understand the electron transfer mechanisms at the molecular scale. This review briefly summarizes the current advances in spectral methods for examining the c-Cyts in intact cells of dissimilatory metal reducing bacteria and Fe(Ⅱ)-oxidizing bacteria.
文摘从芫花（Daphne genkwa Sieb. et Zucc.）的干燥叶中分离出两种黄酮化合物,经化学和光谱分析,鉴定为木犀草甙（galuteolin）,系首次从本植物中分离得到;另一个结构确定为3′-羟基芫花素-5-O-β-D-葡萄糖甙（3′-hydroxygenkwanin-5-O-β-D-glucoside）,定名为芜花叶甙（yuanhuanin）。讨论了芫花叶甙及其甙元羟基芫花素的13C-核磁共振谱并进行了峰的归属。
基金Supported by the National Natural Science Foundation of China (No.20573093 and No.20434020).
文摘Prediction of vapor-liquid equilibrium （VLE） is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is not economical. The infinite dilution activities can be used to predict VLE. However, it needs both the ends of the activities that are difficult to obtain for many systems. In the present study, a new model is proposed for correlating the frequency shift of C-H stretching band of IR spectra over the whole concentration. Investigated mixtures in- clude water/2-propanol, water/N, N-dimethylformamide （DMF）, water/methanol, water/ethanol, water/1, 4-dioxane, and water/dimethylsulfoxide （DMSO） systems. Simultaneous correlations of C--H frequency shift and VLE data are made. Furthermore, the VLE data were predicted with satisfactory results by the parameters obtained from IR spectra coupled with one ot the intinite chlution activity coefficients.
基金This work was supported by the National Natural Science Foundation of China （No.20473020）.
文摘Allergic contact dermatitis is a delayed hypersensitivity reaction, which results from skin exposure to low molecular weight chemicals such as haptens. To clarify the pathogenic mechanism, electrospray ionization mass spectrometry （ESI-MS） and hydrogen/deuterium （H/D） exchange, as well as UV spectroscopy, were applied to determine the interaction between the model protein cytochrome c （cyt c） and the hapten 2,4- dinitro-fiuorobenzene （DNFB）. The ESI-MS results demonstrate that the conformation of cyt c can change from native folded state into partially unfolded state with the increase of DNFB. The equilibrium state H/D exchange followed by ESI-MS further confirms the above results. UV spectroscopy indicates that the strong- field coordination between iron of heme （prosthetic group） and His18 or Met80 of cyt c is not obviously affected by the hapten.
文摘We studied the first oxidation product of vitamin C, the dehydro-L-ascorbic acid dimer and characterized it by infrared and Raman spectroscopies in the solid phase. The Density functional theory was used to study its structure and vibrational properties. These calculations gave us a precise knowledge of the normal modes of vibration taking into account that the molecule comprises a system of five fused rings; non planar γ-lactone and furonose rings are attached to a central dioxan ring in the twisted boat conformation. The calculated harmonic vibrational frequencies are consistent with the experimental vibrational spectra. An assignment of the observed spectral features is proposed. The shift of the band located in the infrared spectrum of the ascorbic acid from 3409 cm^-1 to 3299 cml and the remarkable increase in the band intensity at 1784 cm^-1 evidences the acid decomposition into its first product, the dehydro-L-ascorbic acid. The theoretical vibrational calculations allowed us to obtain a set of scaled force constants. The nature of the different -γ-lactone, furanose and dioxan rings and their topological properties were investigated by means of natural bond orbital and Bader＇s atoms in the molecule theory, respectively.
基金the National Natural Science Foundation of China (Grant No. 19975030) .
文摘This paper reported the effect of the weak damage in the Al0.25Ga0.75As/GaAs epitaxial layer induced by 0.8 MeV Si ions implantation with ion dose from 1×1014 to 5×1015 cm-2. The Raman spectra measured on these samples showed that there were two kinds of phonon modes existing in the epitaxial Al0.25Ga0.75As films. The strains induced in the implanted layer and the corresponding lattice parameters were also evaluated as a function of the implanted dose. In addition, the Rutherford backscattering spectrometry/channeling (RBS/C) was also measured on these samples. These two measurement techniques all confirmed that the implantation only induced weak damage in the material.
文摘The automorphism group of the Toeplitz C^*- algebra, J(C^1), generated by Toeplitz op-erators with C^1-symbols on Dirichlet space D is discussed; the K0, K1-groups and the first cohomology group of J(C^1) are computed. In addition, the author proves that the spectra of Toeplitz operators with C^1-symbols are always connected, and discusses the algebraic prop-erties of Toeplitz operators.In particular, it is proved that there is no nontrivial selfadjoint Toeplitz operator on D and Tψ^* = Tψ^- if and only if Tψ is a scalar operator.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 19890310) .
文摘Ta/NiOx/Ni81Fe19/Ta multilayers were prepared by rf reactive and dc magnetron sputtering.The exchange coupling field (Hex) and the coercivity (Hc) of NiOx/Ni81Fe19 as a function of the ratio of Ar to O2 during the deposition process were studied.The composition and chemical states at the interface region of NiOx/NiFe were also investigated using the X-ray photoelectron spectroscopy (XPS) and peak decomposition technique.The results show that the ratio of Ar to O2 has great effect on the nickel chemical states in NiOx film.When the ratio of Ar to O2 is equal to 7 and the argon sputtering pressure is 0.57 Pa,the x value is approximately 1 and the valence of nickel is +2.At this point,NiOx is antiferromagnetic NiO and the corresponding Hex is the largest.As the ratio of Ar/O2 deviates from 7,the exchange coupling field (Hex) will decrease due to the presence of magnetic impurities such as Ni+3 or metallic Ni at the interface region of NiOx/NiFe,while the coercivity (Hc) will increase due to the metallic Ni.XPS studies also show that there are two thermodynamically favorable reactions at the NiO/NiFe interface: NiO+Fe=Ni+FeO and 3NiO+2Fe=3Ni+Fe2O3.These interface reaction products are magnetic impurities at the interface region of NiO/NiFe.It is believed that these magnetic impurities would have effect on the exchange coupling field (Hex) and the coercivity (Hc) of NiO/NiFe.
基金financially supported by the National Basic Research Program of China(2011CB933600,2013CB966900)the National Natural Science Foundation of China(21373200,81273334)Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT,IRT1133)
文摘The 4N1K peptide,which is derived from the C-terminal domain of thrombospondin-1(TSP-1),is usually used as a functional mimic peptide for TSP-1.Knowledge about the interaction force of 4N1K/CD47 is important in explaining how TSP-1 affects the biological effect of CD47.Here we used a single-molecule force spectroscopy(SMFS)technique to explore the interaction of 4N1K/CD47 on both normal and oxidative human red blood cells(h RBCs)at single-molecule level.There was no interaction force between 4N1K and CD47 on normal h RBCs;however,we did find 4N1K-bound CD47 on oxidative h RBCs.We also detected interaction forces for 4N1K/CD47ex(extracellular domain of human CD47),and 4N1K/oxidative CD47ex.The interaction forces of 4N1K/CD47ex were almost consistent with those of 4N1K/oxidative CD47ex at the same loading rate.These results suggest that the conformational change of CD47 is critical for 4N1K-CD47 interaction on oxidative h RBCs.
