Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-ec...Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-economic synthesis.Undoubtedly,selectively activating and transforming multiple inert chemical bonds is an even more intriguing and demanding task in synthetic chemistry.However,due to its inherent complexity and extreme challenges,this endeavour is rarely accomplished.We report a copper-mediated complete cleavage and selective transformation of multiple inert chemical bonds of three easily available feedstocks,i.e.,a sp^(2)C—H bond in indoles,three sp^(3)C—H bonds and one C—N bond in a methyl carbon atom in TMEDA,and the C≡N triple bond in CH_(3)CN.This reaction proceeds via tandem carbon and nitrogen atom transfer,and allows for the direct and efficient cyanation of indoles,presenting a simple and direct alternative for synthesizing 3-cyanoindoles.展开更多
Using a combination of the Monte Carlo models of fast electrons, of molecular ions （N＋） and of atomic species （N^＋, Nf）, the influence of the discharge pressure （P） and voltage （Vc） on the energy distributio...Using a combination of the Monte Carlo models of fast electrons, of molecular ions （N＋） and of atomic species （N^＋, Nf）, the influence of the discharge pressure （P） and voltage （Vc） on the energy distributions of fast atomic species （N^＋, Nf） produced by e^--N2s and N2^＋- N2s dissociation reactions at the cathode in a nitrogen dc glow discharge was investigated. Both the angular distributions and the density distributions along the radius of the species （N^＋, Nf） produced by the two dissociations at the cathode were calculated. The results show that： （1） there is an optimum discharge condition for P and Vc in order to obtain the species （N^＋, Nf） at the cathode with high a density and energy, （2） when the voltage is above 800 V, the species （N^＋, Nf） bombarding the cathode are mainly produced by the N^＋-N2s dissociation, whereas when the voltage is below 300 V, they are mainly produced by the e-N2s dissociation, and （3） at high Voltages the incident angles of a considerable number of Nf into the cathode are quite small. The density of the species （N^＋ Nf） at the cathode increases with the voltage, and when the pressure goes up to about 133 Pa, it decreases with the increasing pressure.展开更多
Interference effects on the photoionization cross sections between two neighbouring atoms are considered based on the coherent scattering of the ionized electrons by the two nuclei when their separation is less than o...Interference effects on the photoionization cross sections between two neighbouring atoms are considered based on the coherent scattering of the ionized electrons by the two nuclei when their separation is less than or comparable to the de Broglie wave length of the ionized electrons. As an example, the single atomic nitrogen ionization cross section and the total cross sections of two nitrogen atoms with coherently added photoionization amplitudes are calculated from the threshold to about А （1 А=0.1 nm） of the photon energy. The photoionization cross sections of atomic nitrogen are obtained by using the close-coupling R-matrix method. In the calculation 19 states are included. The ionization energy of the atomic nitrogen and the photoionization cross sections agree well with the experimental results. Based on the R-matrix results of atomic nitrogen, the interference effects between two neighbouring nitrogen atoms are obtained. It is shown that the interference effects are considerable when electrons are ionized just above the threshold, even for the separations between the two atoms are larger than two times of the bond length of N2 molecules. Therefore, in hot and dense samples, effects caused by the coherent interference between the neighbours are expected to be observable for the total photoionization cross sections.展开更多
Using compounds modified by the isotopes carbon-13 and nitrogen-15 helps conduct research in various fields of science, such as medicine, pharmacology, pharmacokinetics, metabolism, agriculture, and others. In the cas...Using compounds modified by the isotopes carbon-13 and nitrogen-15 helps conduct research in various fields of science, such as medicine, pharmacology, pharmacokinetics, metabolism, agriculture, and others. In the case of the availability of reliable, express, and cheap methods, the area of their use will gradually expand. A determination of the atomic fraction of the isotopes carbon-13 and nitrogen-15 directly in glycine, leucine, isoleucine, and alanine is proposed;the modification concerns all centers or one or more identical carbon and nitrogen centers separately, as well as both isotopes at the same time. There are defined mass lines of the mass spectrum of each amino acid, through which the isotopic content of carbon and nitrogen is calculated. The processes that must be taken into account for the determination of the isotopic content are also established. Isotopic analysis of these compounds until now was carried out by transforming them into carbon oxide, dioxide, and molecular nitrogen, and determination of their content in individual centers was impossible.展开更多
For the first time, absolute densities of atomic nitrogen in its ground state (N4S) have been measured in hot dry and humid air plasma columns under post-discharge regime. The determination of space-resolved absolute ...For the first time, absolute densities of atomic nitrogen in its ground state (N4S) have been measured in hot dry and humid air plasma columns under post-discharge regime. The determination of space-resolved absolute densities leads to obtain the dissociation degrees of molecular nitrogen in the plasma. The hot plasmas are generated inside an upstream gas-conditioning cell at 600 mbar when the air gas flow is directly injected at 10 slm in a microwave resonant cavity (2.45 GHz, 1 kW) placed in the downstream side. Density measurements based on laser induced fluorescence spectroscopy with two-photon excitation (TALIF), are more particularly performed along the radial and axial positions of the plasma column. Calibration of TALIF signals is performed in situ (i.e. in the same gas-conditioning cell but without plasma) using an air gas mixture containing krypton. Optical emission spectroscopy is considered to estimate the rotational gas temperature by adding a small amount of H2 in dry air to better detect OH (A-X) spectra. The rotational temperatures in humid air plasma column (50% of humidity) are larger than those of dry air plasma column by practically 30% near the nozzle of resonant cavity on the axis of the plasma column. This is partly due to attachment heating processes initiated by water vapor. A maximum of the measured absolute nitrogen density is also observed near the nozzle which is also larger for humid air plasma column. The obtained dissociation degrees of molecular nitrogen in both dry and humid air plasma along the air plasma column are lower than the cases where only thermodynamic equilibrium is assumed. This is characteristic of the absence of chemical and energetic equilibria not yet reached in the air plasma column dominated by recombination processes.展开更多
The aim of this study is to investigate the biological effects of ion beams on pollen. Pollen grains of Cedrus deodara were implanted with 30 keV nitrogen ion beams at doses ranging from 1 × 10^15 ions/cm^2 to 15...The aim of this study is to investigate the biological effects of ion beams on pollen. Pollen grains of Cedrus deodara were implanted with 30 keV nitrogen ion beams at doses ranging from 1 × 10^15 ions/cm^2 to 15 × 10^15 ions/cm^2. The effects of N^＋ implantation on the pollen exine substructure were examined using an atomic force microscope （AFM）, and the structure and morphology of pollen and pollen tubes were observed using a laser scanning confocal microscope （LSCM）. AFM observations distinctly revealed the erosion of the pollen exine caused by N^＋ implantation in the micrometer to nanometer range. Typical results showed that the erosion degree was linearly proportional to the ion dose. Pollen germination experiments in vitro indicated that N^＋ implantation within a certain dose range increased the rate of pollen germination. The main abnormal phenomena in pollen tubes were also analyzed. Our results suggest that low energy ion implantation with suitable energy and dosage can be used to break the pollen wall to induce a transfer of exogenous DNA into the pollen without any damage to the cytoplasm and nuclei of the pollen. The present study suggests that a combination of the method of ion-beam-induced gene transfer and the pollen-tube pathway method （PTPW） would be a new plant transformation method.展开更多
In this paper, an N-doped titanium oxide （TiO2） photocatalyst is deposited by a plasma-enhanced atomic layer deposition （PEALD） system through the in-situ doping method. X-ray photoelectron spectroscopy （XPS） an...In this paper, an N-doped titanium oxide （TiO2） photocatalyst is deposited by a plasma-enhanced atomic layer deposition （PEALD） system through the in-situ doping method. X-ray photoelectron spectroscopy （XPS） analysis indicates that substitutional nitrogen atoms （-395.9 eV） with 1 atom% are effectively doped into TiO2 films. UV-VIS spectrometry shows that the in-situ nitrogen doping method indeed enhances the visible-activity of TiO2 films in the 425-550 nm range, and the results of the performance tests of the N-doped TiO2 films also imply that the photocatalysis activity is improved by in-situ doping. The in-situ doping mechanism of the N-doped TiO2 film is suggested according to the XPS results and the typical atomic layer deposition process.展开更多
基金support from the National Natural Science Foundation of China(Grant Nos.22378106,21878072,21706058,and 22002169)the Natural Science Foundation of Hunan Province(Grant No.2020JJ2011)the China Postdoctoral Science Foundation(No.2019M662774).
文摘Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-economic synthesis.Undoubtedly,selectively activating and transforming multiple inert chemical bonds is an even more intriguing and demanding task in synthetic chemistry.However,due to its inherent complexity and extreme challenges,this endeavour is rarely accomplished.We report a copper-mediated complete cleavage and selective transformation of multiple inert chemical bonds of three easily available feedstocks,i.e.,a sp^(2)C—H bond in indoles,three sp^(3)C—H bonds and one C—N bond in a methyl carbon atom in TMEDA,and the C≡N triple bond in CH_(3)CN.This reaction proceeds via tandem carbon and nitrogen atom transfer,and allows for the direct and efficient cyanation of indoles,presenting a simple and direct alternative for synthesizing 3-cyanoindoles.
基金supported by the Natural Science Foundation of Hebei Province,China(No.A2006000123)
文摘Using a combination of the Monte Carlo models of fast electrons, of molecular ions （N＋） and of atomic species （N^＋, Nf）, the influence of the discharge pressure （P） and voltage （Vc） on the energy distributions of fast atomic species （N^＋, Nf） produced by e^--N2s and N2^＋- N2s dissociation reactions at the cathode in a nitrogen dc glow discharge was investigated. Both the angular distributions and the density distributions along the radius of the species （N^＋, Nf） produced by the two dissociations at the cathode were calculated. The results show that： （1） there is an optimum discharge condition for P and Vc in order to obtain the species （N^＋, Nf） at the cathode with high a density and energy, （2） when the voltage is above 800 V, the species （N^＋, Nf） bombarding the cathode are mainly produced by the N^＋-N2s dissociation, whereas when the voltage is below 300 V, they are mainly produced by the e-N2s dissociation, and （3） at high Voltages the incident angles of a considerable number of Nf into the cathode are quite small. The density of the species （N^＋ Nf） at the cathode increases with the voltage, and when the pressure goes up to about 133 Pa, it decreases with the increasing pressure.
基金Project supported by the National Natural Science Foundation of China (Grant No 10734140)the National Basic Research Program of China (Grant No 2007CB815105)
文摘Interference effects on the photoionization cross sections between two neighbouring atoms are considered based on the coherent scattering of the ionized electrons by the two nuclei when their separation is less than or comparable to the de Broglie wave length of the ionized electrons. As an example, the single atomic nitrogen ionization cross section and the total cross sections of two nitrogen atoms with coherently added photoionization amplitudes are calculated from the threshold to about А （1 А=0.1 nm） of the photon energy. The photoionization cross sections of atomic nitrogen are obtained by using the close-coupling R-matrix method. In the calculation 19 states are included. The ionization energy of the atomic nitrogen and the photoionization cross sections agree well with the experimental results. Based on the R-matrix results of atomic nitrogen, the interference effects between two neighbouring nitrogen atoms are obtained. It is shown that the interference effects are considerable when electrons are ionized just above the threshold, even for the separations between the two atoms are larger than two times of the bond length of N2 molecules. Therefore, in hot and dense samples, effects caused by the coherent interference between the neighbours are expected to be observable for the total photoionization cross sections.
文摘Using compounds modified by the isotopes carbon-13 and nitrogen-15 helps conduct research in various fields of science, such as medicine, pharmacology, pharmacokinetics, metabolism, agriculture, and others. In the case of the availability of reliable, express, and cheap methods, the area of their use will gradually expand. A determination of the atomic fraction of the isotopes carbon-13 and nitrogen-15 directly in glycine, leucine, isoleucine, and alanine is proposed;the modification concerns all centers or one or more identical carbon and nitrogen centers separately, as well as both isotopes at the same time. There are defined mass lines of the mass spectrum of each amino acid, through which the isotopic content of carbon and nitrogen is calculated. The processes that must be taken into account for the determination of the isotopic content are also established. Isotopic analysis of these compounds until now was carried out by transforming them into carbon oxide, dioxide, and molecular nitrogen, and determination of their content in individual centers was impossible.
文摘For the first time, absolute densities of atomic nitrogen in its ground state (N4S) have been measured in hot dry and humid air plasma columns under post-discharge regime. The determination of space-resolved absolute densities leads to obtain the dissociation degrees of molecular nitrogen in the plasma. The hot plasmas are generated inside an upstream gas-conditioning cell at 600 mbar when the air gas flow is directly injected at 10 slm in a microwave resonant cavity (2.45 GHz, 1 kW) placed in the downstream side. Density measurements based on laser induced fluorescence spectroscopy with two-photon excitation (TALIF), are more particularly performed along the radial and axial positions of the plasma column. Calibration of TALIF signals is performed in situ (i.e. in the same gas-conditioning cell but without plasma) using an air gas mixture containing krypton. Optical emission spectroscopy is considered to estimate the rotational gas temperature by adding a small amount of H2 in dry air to better detect OH (A-X) spectra. The rotational temperatures in humid air plasma column (50% of humidity) are larger than those of dry air plasma column by practically 30% near the nozzle of resonant cavity on the axis of the plasma column. This is partly due to attachment heating processes initiated by water vapor. A maximum of the measured absolute nitrogen density is also observed near the nozzle which is also larger for humid air plasma column. The obtained dissociation degrees of molecular nitrogen in both dry and humid air plasma along the air plasma column are lower than the cases where only thermodynamic equilibrium is assumed. This is characteristic of the absence of chemical and energetic equilibria not yet reached in the air plasma column dominated by recombination processes.
文摘The aim of this study is to investigate the biological effects of ion beams on pollen. Pollen grains of Cedrus deodara were implanted with 30 keV nitrogen ion beams at doses ranging from 1 × 10^15 ions/cm^2 to 15 × 10^15 ions/cm^2. The effects of N^＋ implantation on the pollen exine substructure were examined using an atomic force microscope （AFM）, and the structure and morphology of pollen and pollen tubes were observed using a laser scanning confocal microscope （LSCM）. AFM observations distinctly revealed the erosion of the pollen exine caused by N^＋ implantation in the micrometer to nanometer range. Typical results showed that the erosion degree was linearly proportional to the ion dose. Pollen germination experiments in vitro indicated that N^＋ implantation within a certain dose range increased the rate of pollen germination. The main abnormal phenomena in pollen tubes were also analyzed. Our results suggest that low energy ion implantation with suitable energy and dosage can be used to break the pollen wall to induce a transfer of exogenous DNA into the pollen without any damage to the cytoplasm and nuclei of the pollen. The present study suggests that a combination of the method of ion-beam-induced gene transfer and the pollen-tube pathway method （PTPW） would be a new plant transformation method.
基金supported by the National Science and Technology Major Project of China(No.2009ZX02037-003)China Postdoctoral Science Foundation(No.2011M500996)the Opening Project of Key Laboratory of Microelectronics Devices&Integrated Technology,Institute of Microelectronics,Chinese Academy of Sciences
文摘In this paper, an N-doped titanium oxide （TiO2） photocatalyst is deposited by a plasma-enhanced atomic layer deposition （PEALD） system through the in-situ doping method. X-ray photoelectron spectroscopy （XPS） analysis indicates that substitutional nitrogen atoms （-395.9 eV） with 1 atom% are effectively doped into TiO2 films. UV-VIS spectrometry shows that the in-situ nitrogen doping method indeed enhances the visible-activity of TiO2 films in the 425-550 nm range, and the results of the performance tests of the N-doped TiO2 films also imply that the photocatalysis activity is improved by in-situ doping. The in-situ doping mechanism of the N-doped TiO2 film is suggested according to the XPS results and the typical atomic layer deposition process.
