The growth and thermal stability of Au clusters on a partially-reduced rutile TiO2 (110)-1 × 1 surface were investigated by high-resolution photoelectron spectroscopy using synchrotron- radiation-light. The val...The growth and thermal stability of Au clusters on a partially-reduced rutile TiO2 (110)-1 × 1 surface were investigated by high-resolution photoelectron spectroscopy using synchrotron- radiation-light. The valence-band photoelectron spectroscopy results demonstrate that the Ti^3+3d feature attenuates quickly with the initial deposition of Au clusters, implying that Au clusters nucleate at the oxygen vacancy sites. The Au4f core-level photoelectron spectroscopy results directly prove the existence of charge transfer from oxygen vacancies to Au clusters. The thermal stability of Au clusters on the partially-reduced and stoichiometric TiO2(110) surfaces was also comparatively investigated by the annealing experiments. With the same film thickness, Au clusters are more thermally stable on the partially-reduced TiO2(110) surface than on the stoichiometric TiO2(110) surface. Meanwhile, large Au nanoparticles are more thermally stable than fine Au nanoparticles.展开更多
Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 51-deoxy-5-fiuorocytidine (5'-DFCR) and 51-deoxy-5- fiuorouridine (5'- DFUR), were investigated wi...Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 51-deoxy-5-fiuorocytidine (5'-DFCR) and 51-deoxy-5- fiuorouridine (5'- DFUR), were investigated with infrared laser desorption/tunable synchrotron VUV photoionization mass spectrometry. Molecular ions (M+) with small amounts of fragments can be found for these compounds at relatively low photon energies, while more fragment ions would be produced by increasing the photon energies. (M-H2O)+, (base+H)+, (base+2H)+, (base+30)+, (base+60)+, and sugar moiety were proposed for these nucleoside drugs with similar backbones. Decomposition channels for the major fragments were discussed in detail. Moreover, ab initio calculations were introduced to study the dehydration pathways of three fluoro-nucleosides. Corresponding appearance energies for the (M-H2O)+ ions were computed.展开更多
Pyrolysis of benzene at 30 Torr was studied from 1360 K to 1820 K in this work. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to detect the pyroly- sis products such as radicals, isomer...Pyrolysis of benzene at 30 Torr was studied from 1360 K to 1820 K in this work. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to detect the pyroly- sis products such as radicals, isomers and polycyclic aromatic hydrocarbons, and measure their mole fraction profiles versus temperature. A low-pressure pyrolysis model of benzene was developed and validated by the experimental results. Rate of production analysis was performed to reveal the major reaction networks in both fuel decomposition and aromatic growth processes. It is concluded that benzene is mainly decomposed via H-abstraction reaction to produce phenyl and partly decomposed via unimolecular decomposition reac- tions to produce propargyl or phenyl. The decomposition process stops at the formation of acetylene and polyyne species like diacetylene and 1,3,5-hexatriyne due to their high thermal stabilities. Besides, the aromatic growth process in the low-pressure pyrolysis of benzene is concluded to initiate from benzene and phenyl, and is controlled by the even carbon growth mechanism due to the inhibited formation of C5 and C7 species which play important roles in the odd carbon growth mechanism.展开更多
The proton nuclear magnetic resonance spectroscopy (1H-NMR), the synchronous fluorescence spectrometry (SFS) and the ruthenium ions catalyzed oxidation (RICO) method were used to determine the chemical structure...The proton nuclear magnetic resonance spectroscopy (1H-NMR), the synchronous fluorescence spectrometry (SFS) and the ruthenium ions catalyzed oxidation (RICO) method were used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions. The results of 1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics, resins and asphaltenes units were 3.2, 5.6 and 8.2, respectively. SFS was used to investigate the distribution of aromatic rings in residue fractions, the main distribution range of aromatic rings in aromatics, resins and asphaltenes were 3 4 rings, 3--5 rings and more than 5 rings, respectively. The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids. The types and content of benzenepolycarboxylic acids, such as phthalic acid, benzenetricarboxylic acids, benzenetetracarboxylic acids, benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core. The biphenyl fraction (BIPH), the cata-condensed fraction (CATA), the peri-condensed fraction (PERI) and the condensed index (BCI) were calculated based on the benzenepolycarboxylic acids formed. The results implied that there was less biphenyl type structures in all residue fractions. The aromatics fraction was almost composed of the cata-condensed type system, and the asphaltenes fraction was wholly composed of the peri-condensed type system, while in the resins fraction co-existed the two types, herein the peri-con- densed type was predominant over the cata-condensed type. Based on the analytical results obtained in the study, the components --aromatics, resins and asphaltenes -- were given the likely structural models.展开更多
Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV cir...Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ(χ, θe, Фe) MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and (θe, Фe) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.展开更多
A protective synchronization scheme (ProSync) for the non-contiguous orthogonal frequency-division multiplexing (NC-OFDM) system is proposed in this paper, aiming to minimize the impact of cross-band interference ...A protective synchronization scheme (ProSync) for the non-contiguous orthogonal frequency-division multiplexing (NC-OFDM) system is proposed in this paper, aiming to minimize the impact of cross-band interference in opportunistic dynamic spectrum sharing networks. ProSync partly shrinks the preamble at the transmitter and exploits two multi-band filters at the receiver. By doing so, the potential interference suffered by NC-OFDM users, including both the cross-band interference and self interference, can be greatly reduced. Simulation results verify the effectiveness of ProSync, which is able to lower the carrier frequency offset (CFO) estimation error by up to 50%, compared with the traditional method.展开更多
Aiming at solving the problems such as time consuming and application limiting presented in the existing synchronous cooperative spectrum sensing schemes,a triggered asynchronous scheme based on Dempster-Shafer(D-S) t...Aiming at solving the problems such as time consuming and application limiting presented in the existing synchronous cooperative spectrum sensing schemes,a triggered asynchronous scheme based on Dempster-Shafer(D-S) theory was proposed.Sensing asynchronously,each cognitive user calculated the confidence measure functions with double threshold spectrum sensing method.When the useful report was received by the fusion center,a fusion process would be triggered.Then the sensing results were fused together based on D-S theory.The analysis and simulation results show that the proposed scheme can improve the spectrum sensing efficiency and reduce the calculation amount of the fusion center compared with the existing schemes.展开更多
A static approach method method is used to get the spectrum expression of the pulse interval modulation signal.The expression is simple,has a clear physical concept and it has been confirmed by a simultaneous experiment.
Abstract Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extra...Abstract Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extraction with methylbenzene and then divided into three parts by distillation. Gas chromatography (GC) and high-performance liquid chromatography (HPLC) were coupled with quadrupole time-of-flight mass spectrometry (Q-TOF MS) to separate and characterize organic nitrogen species in the distillates of asphaltene at molecular level. Molecular mass of compounds was mainly distributed from 150 to 600 ~t. Number of rings plus double bonds (rdb) and synchronous fluorescence spectra indicated that most of the organonitrogen compounds (NPAC) contained heterocyclic aromatic rings, including pyridines, anilines, quinolins, pyrroles, carbazoles and indoles plus various alkyl groups. Constant-wavelength synchronous fluo- rescence spectrometry (CWSFS) indicated NPAC with 2-3 rings were the main structures of organonitrogen compounds and the corresponding structural information was proposed. Some organic nitrogen isomers were separated and identified by atmospheric pressure chemical ionization (APCI) GC-Q-TOF MS and electrospray ionization (ESI) HPLC-Q-TOF MS. The methodology applied here contained chromatographic injection of the diluted sample using conventional columns sets and Data Analysis 4.2 software. Identifying molecular structures provides a foundation to understand all aspects of coal- derived asphaltene, enabling a first-principles approach to optimize resource utilization.展开更多
Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z...Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N+ (rn/z=86), C2H5NO2+ (m/z=75), C5H9+ (rn/z=-69), C4H9+ (m/z=57), and CH4N+ (m/z=30) are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05+0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.展开更多
We have prepared and characterized atomically well-defined model systems for ceria-supported Pt-Co core-shell catalysts. Pt@Co and Co@Pt core-shell nanostructures were grown on well-ordered CeO2(111) films on Cu(111) ...We have prepared and characterized atomically well-defined model systems for ceria-supported Pt-Co core-shell catalysts. Pt@Co and Co@Pt core-shell nanostructures were grown on well-ordered CeO2(111) films on Cu(111) by physical vapour deposition of Pt and Co metals in ultrahigh vacuum and investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The deposition of Co onto CeO2(111) yields CoCeO2(111) solid solution at low Co coverage(0.5 ML), followed by the growth of metallic Co nanoparticles at higher Co coverages. Both Pt@Co and Co@Pt model structures are stable against sintering in the temperature range between 300 and 500 K. After annealing at 500 K, the Pt@Co nanostructure contains nearly pure Co-shell while the Pt-shell in the Co@Pt is partially covered by metallic Co. Above 550 K, the re-ordering in the near surface regions yields a subsurface Pt-Co alloy and Pt-rich shells in both Pt@Co and Co@Pt nanostructures. In the case of Co@Pt nanoparticles, the chemical ordering in the near surface region depends on the initial thickness of the deposited Pt-shell. Annealing of the Co@Pt nanostructures in the presence of O2 triggers the decomposition of Pt-Co alloy along with the oxidation of Co, regardless of the thickness of the initial Pt-shell. Progressive oxidation of Co coupled with adsorbate-induced Co segregation leads to the formation of thick CoO layers on the surfaces of the supported Co@Pt nanostructures. This process is accompanied by the disintegration of the CeO2(111) film and encapsulation of oxidized Co@Pt nanostructures by CeO2 upon annealing in O2 above 550 K. Notably, during oxidation and reduction cycles with O2 and H2 at different temperatures, the changes in the structure and chemical composition of supported Co@Pt nanostructures were driven mainly by oxidation while reduction treatments had little effect regardless of the initial thickness of the Pt-shell.展开更多
Measure synchronization in coupled Hamiltonian systems is a novel synchronization phenomenon. The measure synchronization on symplectic map is observed numerically, for identical coupled systems with different paramet...Measure synchronization in coupled Hamiltonian systems is a novel synchronization phenomenon. The measure synchronization on symplectic map is observed numerically, for identical coupled systems with different parameters. We have found the properties of the characteristic frequency and the amplitude of phase locking in regular motion when the measure synchronization of coupled systems is obtained. The relations between the change of the largest Lyapunov exponent and the course of phase desynchronization are also discussed in coupled systems, some useful results are obtained. A new approach is proposed for describing the measure synchronization of coupled systems numerically,which is advantage in judging the measure synchronization, especially for the coupled systems in nonregular region.展开更多
The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 speci...The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency (PIE) spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane,i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.展开更多
A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as ...A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports. The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.展开更多
The binding of (-)-epigallocatechin-3-O-gallate (EGCG) to bovine serum albumin (BSA) were investigated for the first time with spectral methods, including fluorescence and absorption spectrometry under simulativ...The binding of (-)-epigallocatechin-3-O-gallate (EGCG) to bovine serum albumin (BSA) were investigated for the first time with spectral methods, including fluorescence and absorption spectrometry under simulative physiological conditions. A strong fluorescence quenching reaction of EGCG to BSA was observed. It was proved that the fluorescence quenching of BSA by addition of EGCG was a result of the formation of EGCG-BSA complex. The binding constant K and the number of binding sites n were determined at physiological conditions and three different temperatures with fluorescence quenching method. The binding distance R and transfer efficiency E between BSA and EGCG were also obtained according to Forster theory of non-radiation energy transfer. The effects of Al^3+, Cu^2+, Mg^2+ and Fe^2+ on the binding constant between EGCG and BSA were studied at 298 K. The effect of EGCG on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy. PACS. 21. 10. Dr; 32. 50. +d; 32. 30. Jc; 82.80. Dx展开更多
The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at...The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at 267 Pa. About 20 products and intermediates, containing major species H2, HCN, C2H2, C5H3N, C4H2, and C3H3N, were identified by near-threshold measurements of photoionization mass spectra and their mole fractions vs. temperatures were estimated. The major reaction pathways are analyzed based on the experimental observations.展开更多
Total internal reflection fluorescence spectroscopy (TIRF) and synchronous scanning technique were combined to study the adsorption behavior of the meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS) at the glass-water...Total internal reflection fluorescence spectroscopy (TIRF) and synchronous scanning technique were combined to study the adsorption behavior of the meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS) at the glass-water interface without any surfactant. The pH dependence of synchronous fluorescence signal at the interface was analyzed. Both unprotonated (TPPS4-) and diprotonated (H2TPPS2-) forms of TPPS were observed at the interface. But the interface favored the adsorption of. The apparent estimated pKa2 value shifted from 5.00 in the bulk solution to 2.7 at the interface. STIRF provides a good technique to study multi-component systems at the interface.展开更多
In the heterogeneous wireless networks of the next generation, a large number of different radio access technologies will be integrated into a common network. This paper considers optimizing the utilization of spectru...In the heterogeneous wireless networks of the next generation, a large number of different radio access technologies will be integrated into a common network. This paper considers optimizing the utilization of spectrum resource in heterogeneous environment consisting two different networks: wireless local area network (WLAN) and time division-synchronous code division multiple access (TD-SCDMA) network. An optimal joint spectrum borrowing scheme maximizing overall network revenue is proposed with quality of service (QoS) constraints over both the WLAN and the TD-SCDMA cellular networks. Simulation results illustrate that system revenue earned in the proposed joint spectrum borrowing scheme is significantly larger than the case when individual networks are optimized independently.展开更多
Nitroxoline is a wide spectrum antibacterial and is one of the most important urinary antiseptics.The interaction between nitroxoline and human serum albumin(HSA)has been investigated systematically by fluorescence sp...Nitroxoline is a wide spectrum antibacterial and is one of the most important urinary antiseptics.The interaction between nitroxoline and human serum albumin(HSA)has been investigated systematically by fluorescence spectroscopy,synchronous fluorescence,three-dimensional fluorescence,CD spectroscopy and UV-Vis absorption spectroscopy.The results indicated that the quenching of HSA by nitroxoline was static.The corresponding thermodynamic parameters △H,△S and △G calculated according to van’t Hoff equation revealed that the intermolecular forces acting between nitroxoline and HSA were mainly hydrogen bonding and van der Waals forces.The conformational changes in the interaction were studied by synchronous fluorescence,CD spectroscopy and three-dimensional fluorescence spectra which showed changes in the microenvironment and conformation of HSA.展开更多
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20773113 and No.20803072), the Hundred Talent Program of Chinese Academy of Sciences, the MOE Program for Changjiang Scholars and Innovative Research Team (No.IRT0756), and the MPG-CAS Partner-group Program.
文摘The growth and thermal stability of Au clusters on a partially-reduced rutile TiO2 (110)-1 × 1 surface were investigated by high-resolution photoelectron spectroscopy using synchrotron- radiation-light. The valence-band photoelectron spectroscopy results demonstrate that the Ti^3+3d feature attenuates quickly with the initial deposition of Au clusters, implying that Au clusters nucleate at the oxygen vacancy sites. The Au4f core-level photoelectron spectroscopy results directly prove the existence of charge transfer from oxygen vacancies to Au clusters. The thermal stability of Au clusters on the partially-reduced and stoichiometric TiO2(110) surfaces was also comparatively investigated by the annealing experiments. With the same film thickness, Au clusters are more thermally stable on the partially-reduced TiO2(110) surface than on the stoichiometric TiO2(110) surface. Meanwhile, large Au nanoparticles are more thermally stable than fine Au nanoparticles.
文摘Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 51-deoxy-5-fiuorocytidine (5'-DFCR) and 51-deoxy-5- fiuorouridine (5'- DFUR), were investigated with infrared laser desorption/tunable synchrotron VUV photoionization mass spectrometry. Molecular ions (M+) with small amounts of fragments can be found for these compounds at relatively low photon energies, while more fragment ions would be produced by increasing the photon energies. (M-H2O)+, (base+H)+, (base+2H)+, (base+30)+, (base+60)+, and sugar moiety were proposed for these nucleoside drugs with similar backbones. Decomposition channels for the major fragments were discussed in detail. Moreover, ab initio calculations were introduced to study the dehydration pathways of three fluoro-nucleosides. Corresponding appearance energies for the (M-H2O)+ ions were computed.
基金This work is supported by the National Natu- ral Science Foundation of China (No.51106146 and No.51036007), China Postdoctoral Science Foundation (No.20100480047 and No.201104326), Chinese Univer- sities Scientific Fund (No.WK2310000010), and Chinese Academy of Sciences.
文摘Pyrolysis of benzene at 30 Torr was studied from 1360 K to 1820 K in this work. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to detect the pyroly- sis products such as radicals, isomers and polycyclic aromatic hydrocarbons, and measure their mole fraction profiles versus temperature. A low-pressure pyrolysis model of benzene was developed and validated by the experimental results. Rate of production analysis was performed to reveal the major reaction networks in both fuel decomposition and aromatic growth processes. It is concluded that benzene is mainly decomposed via H-abstraction reaction to produce phenyl and partly decomposed via unimolecular decomposition reac- tions to produce propargyl or phenyl. The decomposition process stops at the formation of acetylene and polyyne species like diacetylene and 1,3,5-hexatriyne due to their high thermal stabilities. Besides, the aromatic growth process in the low-pressure pyrolysis of benzene is concluded to initiate from benzene and phenyl, and is controlled by the even carbon growth mechanism due to the inhibited formation of C5 and C7 species which play important roles in the odd carbon growth mechanism.
文摘The proton nuclear magnetic resonance spectroscopy (1H-NMR), the synchronous fluorescence spectrometry (SFS) and the ruthenium ions catalyzed oxidation (RICO) method were used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions. The results of 1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics, resins and asphaltenes units were 3.2, 5.6 and 8.2, respectively. SFS was used to investigate the distribution of aromatic rings in residue fractions, the main distribution range of aromatic rings in aromatics, resins and asphaltenes were 3 4 rings, 3--5 rings and more than 5 rings, respectively. The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids. The types and content of benzenepolycarboxylic acids, such as phthalic acid, benzenetricarboxylic acids, benzenetetracarboxylic acids, benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core. The biphenyl fraction (BIPH), the cata-condensed fraction (CATA), the peri-condensed fraction (PERI) and the condensed index (BCI) were calculated based on the benzenepolycarboxylic acids formed. The results implied that there was less biphenyl type structures in all residue fractions. The aromatics fraction was almost composed of the cata-condensed type system, and the asphaltenes fraction was wholly composed of the peri-condensed type system, while in the resins fraction co-existed the two types, herein the peri-con- densed type was predominant over the cata-condensed type. Based on the analytical results obtained in the study, the components --aromatics, resins and asphaltenes -- were given the likely structural models.
文摘Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ(χ, θe, Фe) MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and (θe, Фe) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.
文摘A protective synchronization scheme (ProSync) for the non-contiguous orthogonal frequency-division multiplexing (NC-OFDM) system is proposed in this paper, aiming to minimize the impact of cross-band interference in opportunistic dynamic spectrum sharing networks. ProSync partly shrinks the preamble at the transmitter and exploits two multi-band filters at the receiver. By doing so, the potential interference suffered by NC-OFDM users, including both the cross-band interference and self interference, can be greatly reduced. Simulation results verify the effectiveness of ProSync, which is able to lower the carrier frequency offset (CFO) estimation error by up to 50%, compared with the traditional method.
基金Science and Technology Projects of Xuzhou City,China(No.XX10A001)Jiangsu Provincial National Natural Science Foundation of China(No:BK20130199)
文摘Aiming at solving the problems such as time consuming and application limiting presented in the existing synchronous cooperative spectrum sensing schemes,a triggered asynchronous scheme based on Dempster-Shafer(D-S) theory was proposed.Sensing asynchronously,each cognitive user calculated the confidence measure functions with double threshold spectrum sensing method.When the useful report was received by the fusion center,a fusion process would be triggered.Then the sensing results were fused together based on D-S theory.The analysis and simulation results show that the proposed scheme can improve the spectrum sensing efficiency and reduce the calculation amount of the fusion center compared with the existing schemes.
文摘A static approach method method is used to get the spectrum expression of the pulse interval modulation signal.The expression is simple,has a clear physical concept and it has been confirmed by a simultaneous experiment.
基金Acknowledgements The authors gratefully acknowledge the financial support of this work by the National Natural Science Foundation of China (No. U1510122). The authors declare that the experiments comply with the current laws of China.
文摘Abstract Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extraction with methylbenzene and then divided into three parts by distillation. Gas chromatography (GC) and high-performance liquid chromatography (HPLC) were coupled with quadrupole time-of-flight mass spectrometry (Q-TOF MS) to separate and characterize organic nitrogen species in the distillates of asphaltene at molecular level. Molecular mass of compounds was mainly distributed from 150 to 600 ~t. Number of rings plus double bonds (rdb) and synchronous fluorescence spectra indicated that most of the organonitrogen compounds (NPAC) contained heterocyclic aromatic rings, including pyridines, anilines, quinolins, pyrroles, carbazoles and indoles plus various alkyl groups. Constant-wavelength synchronous fluo- rescence spectrometry (CWSFS) indicated NPAC with 2-3 rings were the main structures of organonitrogen compounds and the corresponding structural information was proposed. Some organic nitrogen isomers were separated and identified by atmospheric pressure chemical ionization (APCI) GC-Q-TOF MS and electrospray ionization (ESI) HPLC-Q-TOF MS. The methodology applied here contained chromatographic injection of the diluted sample using conventional columns sets and Data Analysis 4.2 software. Identifying molecular structures provides a foundation to understand all aspects of coal- derived asphaltene, enabling a first-principles approach to optimize resource utilization.
基金V. ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (No.10875126 and No.10979048) and the Specialized Research Fund for the Doctoral Program of Higher Education, SRF for ROCS, SEM.
文摘Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N+ (rn/z=86), C2H5NO2+ (m/z=75), C5H9+ (rn/z=-69), C4H9+ (m/z=57), and CH4N+ (m/z=30) are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05+0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.
基金funded by the European Community(FP7-NMP.2012.1.1-1 project chip CAT,Reference No.310191)by the Deutsche Forschungsgemeinschaft(DFG)within the Excellence Cluster“Engineering of Advanced Materials”in the framework of the excellence initiative+2 种基金support by the DFG is acknowledged through the Priority Program SPP 1708 and the Research Unit FOR 1878supported by structural funds under project CZ.02.1.01/0.0/0.0/16_025/0007414by the Czech Ministry of Education(grant LM2015057)。
文摘We have prepared and characterized atomically well-defined model systems for ceria-supported Pt-Co core-shell catalysts. Pt@Co and Co@Pt core-shell nanostructures were grown on well-ordered CeO2(111) films on Cu(111) by physical vapour deposition of Pt and Co metals in ultrahigh vacuum and investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The deposition of Co onto CeO2(111) yields CoCeO2(111) solid solution at low Co coverage(0.5 ML), followed by the growth of metallic Co nanoparticles at higher Co coverages. Both Pt@Co and Co@Pt model structures are stable against sintering in the temperature range between 300 and 500 K. After annealing at 500 K, the Pt@Co nanostructure contains nearly pure Co-shell while the Pt-shell in the Co@Pt is partially covered by metallic Co. Above 550 K, the re-ordering in the near surface regions yields a subsurface Pt-Co alloy and Pt-rich shells in both Pt@Co and Co@Pt nanostructures. In the case of Co@Pt nanoparticles, the chemical ordering in the near surface region depends on the initial thickness of the deposited Pt-shell. Annealing of the Co@Pt nanostructures in the presence of O2 triggers the decomposition of Pt-Co alloy along with the oxidation of Co, regardless of the thickness of the initial Pt-shell. Progressive oxidation of Co coupled with adsorbate-induced Co segregation leads to the formation of thick CoO layers on the surfaces of the supported Co@Pt nanostructures. This process is accompanied by the disintegration of the CeO2(111) film and encapsulation of oxidized Co@Pt nanostructures by CeO2 upon annealing in O2 above 550 K. Notably, during oxidation and reduction cycles with O2 and H2 at different temperatures, the changes in the structure and chemical composition of supported Co@Pt nanostructures were driven mainly by oxidation while reduction treatments had little effect regardless of the initial thickness of the Pt-shell.
基金国家重点基础研究发展计划(973计划),国家自然科学基金,the Innovation Funds for Laser Technology
文摘Measure synchronization in coupled Hamiltonian systems is a novel synchronization phenomenon. The measure synchronization on symplectic map is observed numerically, for identical coupled systems with different parameters. We have found the properties of the characteristic frequency and the amplitude of phase locking in regular motion when the measure synchronization of coupled systems is obtained. The relations between the change of the largest Lyapunov exponent and the course of phase desynchronization are also discussed in coupled systems, some useful results are obtained. A new approach is proposed for describing the measure synchronization of coupled systems numerically,which is advantage in judging the measure synchronization, especially for the coupled systems in nonregular region.
基金This work is supported by the National. Natural Science Foundation of China (No.51106146, No.51036007, No.U1232127), the China Postdoctoral Science Foundation (No.20100480047 and No.201104326), the Chinese Universities Scientific Fund (No.WK2310000010), the Anhui Science & Technology Department (No.l1040606Q49), and the Chinese Academy of Sciences.
文摘The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency (PIE) spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane,i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.
基金This work wass supported by the National Natural Science Foundation of China (No.20675074 and No.10575099).
文摘A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports. The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.
文摘The binding of (-)-epigallocatechin-3-O-gallate (EGCG) to bovine serum albumin (BSA) were investigated for the first time with spectral methods, including fluorescence and absorption spectrometry under simulative physiological conditions. A strong fluorescence quenching reaction of EGCG to BSA was observed. It was proved that the fluorescence quenching of BSA by addition of EGCG was a result of the formation of EGCG-BSA complex. The binding constant K and the number of binding sites n were determined at physiological conditions and three different temperatures with fluorescence quenching method. The binding distance R and transfer efficiency E between BSA and EGCG were also obtained according to Forster theory of non-radiation energy transfer. The effects of Al^3+, Cu^2+, Mg^2+ and Fe^2+ on the binding constant between EGCG and BSA were studied at 298 K. The effect of EGCG on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy. PACS. 21. 10. Dr; 32. 50. +d; 32. 30. Jc; 82.80. Dx
基金Ⅴ. ACKNOWLEDGMENTS This work was supported by the Chinese Academy of Sciences, the Natural Science Foundation of China (No.20533040), the National Basic Research Program of China (973) (No.2007CB815204m), and the Ministry of Science and Technology of China (No.2007DFA61310).
文摘The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at 267 Pa. About 20 products and intermediates, containing major species H2, HCN, C2H2, C5H3N, C4H2, and C3H3N, were identified by near-threshold measurements of photoionization mass spectra and their mole fractions vs. temperatures were estimated. The major reaction pathways are analyzed based on the experimental observations.
文摘Total internal reflection fluorescence spectroscopy (TIRF) and synchronous scanning technique were combined to study the adsorption behavior of the meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS) at the glass-water interface without any surfactant. The pH dependence of synchronous fluorescence signal at the interface was analyzed. Both unprotonated (TPPS4-) and diprotonated (H2TPPS2-) forms of TPPS were observed at the interface. But the interface favored the adsorption of. The apparent estimated pKa2 value shifted from 5.00 in the bulk solution to 2.7 at the interface. STIRF provides a good technique to study multi-component systems at the interface.
基金Supported by the National Natural Science Foundation of China (60832009), the Natural Sciences Foundation of Beijing (4102044), the Fundamental Research Funds for the Central Universities (BUPT2009RC019), and the National Major Prefects for Science and Technology Development (2009ZX03003-003-01).
文摘In the heterogeneous wireless networks of the next generation, a large number of different radio access technologies will be integrated into a common network. This paper considers optimizing the utilization of spectrum resource in heterogeneous environment consisting two different networks: wireless local area network (WLAN) and time division-synchronous code division multiple access (TD-SCDMA) network. An optimal joint spectrum borrowing scheme maximizing overall network revenue is proposed with quality of service (QoS) constraints over both the WLAN and the TD-SCDMA cellular networks. Simulation results illustrate that system revenue earned in the proposed joint spectrum borrowing scheme is significantly larger than the case when individual networks are optimized independently.
基金financially supported by the National Science Fund for Distinguished Young Scholars of China(21225313)the National Natural Science Foundation of China(21303126)+2 种基金Program for Changjiang Scholars and Innovative Research Team in University(IRT1030)Foundation of Hubei Educational Committee(Q20132901)Youth Science Foundation of Huanggang Normal University(2013023903)
文摘Nitroxoline is a wide spectrum antibacterial and is one of the most important urinary antiseptics.The interaction between nitroxoline and human serum albumin(HSA)has been investigated systematically by fluorescence spectroscopy,synchronous fluorescence,three-dimensional fluorescence,CD spectroscopy and UV-Vis absorption spectroscopy.The results indicated that the quenching of HSA by nitroxoline was static.The corresponding thermodynamic parameters △H,△S and △G calculated according to van’t Hoff equation revealed that the intermolecular forces acting between nitroxoline and HSA were mainly hydrogen bonding and van der Waals forces.The conformational changes in the interaction were studied by synchronous fluorescence,CD spectroscopy and three-dimensional fluorescence spectra which showed changes in the microenvironment and conformation of HSA.