The evolution of a molecular system excited above its ionization threshold depends on a number of parameters that include the nature of the excited states and their couplings to the various continua. The general natur...The evolution of a molecular system excited above its ionization threshold depends on a number of parameters that include the nature of the excited states and their couplings to the various continua. The general nature of the processes governing this evolution depends also essentially on the complexity of the molecule, more precisely on its size, density of states, and strength of the couplings among the various internal degrees of freedom. In this paper we address the question of the transition between autoionization that prevails in small molecules, and delayed ionization occurring in larger molecules or clusters. This transition is illustrated by autoionization of Na2 Rydberg states on one hand, delayed ionization in fullerene C60, and delayed detachment in small cluster anions on the other hand. All processes are studied in the case of nanosecond laser excitation, corresponding to a rather slow deposition of the internal energy.展开更多
The aim of this study was to prepare arsenic trioxide （ATO）-loaded stealth PEGylated PLGA nanoparticles （PEG-PLGA-NPs） and to assess the merits of PEG-PLGA-NPs as drug carriers for ATO delivery. PEG-PLGA copolymer...The aim of this study was to prepare arsenic trioxide （ATO）-loaded stealth PEGylated PLGA nanoparticles （PEG-PLGA-NPs） and to assess the merits of PEG-PLGA-NPs as drug carriers for ATO delivery. PEG-PLGA copolymer was synthesized with methoxypolyethyleneglycol （Mw=5000）, D, L-lactide, and glycolide by the ring-opening polymerization method. Amorphous ATO was transformed into cubic crystal form to increase its solu-bility in the organic solvent. ATO-loaded PEG-PLGA-NPs were prepared by the modified spontaneous emulsification solvent diffusion （SESD） method, and the main experimental factors influencing the characteristics of nanopar- ticles were investigated, to optimize the preparation. To confirm the escape of PEG-PLGA-NPs from phagocytosis by phagocytes, PEG-PLGA-NPs labeled rhodamine B uptake by murine peritoneal macrophages （MPM） were analyzed by flow cytometry. The results showed that the physicochemical characteristics of PEG-PLGA-NPs were affected by the type and concentration of the emulsifiers, polymer concentration, and drug concentration. ATO-loaded PEG-PLGA-NPs, with particle size of 120.8nm, zeta potential of-10.73mV, encapsulation efficiency of 73.6%, and drug loading of 1.36%, were prepared under optimal conditions. The images of transmission electron micros-copy （TEM） indicated that the optimized nanoparticles were near spherical and without aggregation or adhesion. The release experiments in vitro showed the ATO release from PEG-PLGA-NPs exhibited consequently sustained release for more than 26d, which was in accordance with Higuchi equation. The uptake of PEG-PLGA-NPs by MPM was found to decrease markedly compared to PLGA-NPs. The experimental results showed that PEG-PLGA-NPs were potential nano drug delivery carriers for ATO.展开更多
Differential scanning calorimetry(DSC)was used to investigate the thermal decomposition and thermal safety characteristics of Shuangfang-3(SF-3)gun propellant.The kinetic calculation of the DSC curve was carried out b...Differential scanning calorimetry(DSC)was used to investigate the thermal decomposition and thermal safety characteristics of Shuangfang-3(SF-3)gun propellant.The kinetic calculation of the DSC curve was carried out by Kissinger and Friedman models,and the time to the maximum rate under adiabatic conditions and the self-accelerating decomposition temperature were calculated by using the AKTS thermal analysis software in combination with the heat balance equation.The thermal history experiment was carried out to further analyze the autocatalytic properties of SF-3.The results show that the initial decomposition temperature,decomposition peak temperature,and decomposition completion temperature of SF-3 all move to the high temperature direction with the increase of heating rate,and the average decomposition heat is 1521.4 J/g.The kinetic model showcased that SF-3 has different reactions in different reaction stages,and its apparent activation energy is 168.2 kJ/mol.When the times to maximum rate under adiabatic conditions are 2.0 h,4.0 h,8.0 h,24.0 h,respectively,the corresponding temperatures are 130.7℃,124.8℃,119.2℃and 110.5℃,respectively.When the masses are 5.0 kg,15.0 kg,25.0 kg,50.0 kg,100.0 kg,respectively,the corresponding self-accelerating decomposition temperatures are 110.0℃,105.0℃,102.0℃,99.0℃and 96.0℃,respectively.As the packaging mass increases,it is more difficult to exchange the liberated heat into the surrounding environment and its safety would be further reduced.The thermal history experiment demonstrates that the thermal decomposition of SF-3 is an n-stage reaction and does not have autocatalytic properties.Therefore,the size and ventilation conditions of the sample have a certain impact on the storage stability of SF-3.In the actual production,usage,storage and transportation,sample size and ventilation conditions should be controlled,and practical and effective measures should be taken according to the actual situation.展开更多
文摘The evolution of a molecular system excited above its ionization threshold depends on a number of parameters that include the nature of the excited states and their couplings to the various continua. The general nature of the processes governing this evolution depends also essentially on the complexity of the molecule, more precisely on its size, density of states, and strength of the couplings among the various internal degrees of freedom. In this paper we address the question of the transition between autoionization that prevails in small molecules, and delayed ionization occurring in larger molecules or clusters. This transition is illustrated by autoionization of Na2 Rydberg states on one hand, delayed ionization in fullerene C60, and delayed detachment in small cluster anions on the other hand. All processes are studied in the case of nanosecond laser excitation, corresponding to a rather slow deposition of the internal energy.
基金Supported by the Special Funds for Major State Basic Research Program of China (973 Program, No.2007CB935800)theNational High Technology Research and Development Program of China (863 Program, No.2004AA215162).
文摘The aim of this study was to prepare arsenic trioxide （ATO）-loaded stealth PEGylated PLGA nanoparticles （PEG-PLGA-NPs） and to assess the merits of PEG-PLGA-NPs as drug carriers for ATO delivery. PEG-PLGA copolymer was synthesized with methoxypolyethyleneglycol （Mw=5000）, D, L-lactide, and glycolide by the ring-opening polymerization method. Amorphous ATO was transformed into cubic crystal form to increase its solu-bility in the organic solvent. ATO-loaded PEG-PLGA-NPs were prepared by the modified spontaneous emulsification solvent diffusion （SESD） method, and the main experimental factors influencing the characteristics of nanopar- ticles were investigated, to optimize the preparation. To confirm the escape of PEG-PLGA-NPs from phagocytosis by phagocytes, PEG-PLGA-NPs labeled rhodamine B uptake by murine peritoneal macrophages （MPM） were analyzed by flow cytometry. The results showed that the physicochemical characteristics of PEG-PLGA-NPs were affected by the type and concentration of the emulsifiers, polymer concentration, and drug concentration. ATO-loaded PEG-PLGA-NPs, with particle size of 120.8nm, zeta potential of-10.73mV, encapsulation efficiency of 73.6%, and drug loading of 1.36%, were prepared under optimal conditions. The images of transmission electron micros-copy （TEM） indicated that the optimized nanoparticles were near spherical and without aggregation or adhesion. The release experiments in vitro showed the ATO release from PEG-PLGA-NPs exhibited consequently sustained release for more than 26d, which was in accordance with Higuchi equation. The uptake of PEG-PLGA-NPs by MPM was found to decrease markedly compared to PLGA-NPs. The experimental results showed that PEG-PLGA-NPs were potential nano drug delivery carriers for ATO.
基金Key Research and Development Project of Shanxi Province(No.201903D121028)。
文摘Differential scanning calorimetry(DSC)was used to investigate the thermal decomposition and thermal safety characteristics of Shuangfang-3(SF-3)gun propellant.The kinetic calculation of the DSC curve was carried out by Kissinger and Friedman models,and the time to the maximum rate under adiabatic conditions and the self-accelerating decomposition temperature were calculated by using the AKTS thermal analysis software in combination with the heat balance equation.The thermal history experiment was carried out to further analyze the autocatalytic properties of SF-3.The results show that the initial decomposition temperature,decomposition peak temperature,and decomposition completion temperature of SF-3 all move to the high temperature direction with the increase of heating rate,and the average decomposition heat is 1521.4 J/g.The kinetic model showcased that SF-3 has different reactions in different reaction stages,and its apparent activation energy is 168.2 kJ/mol.When the times to maximum rate under adiabatic conditions are 2.0 h,4.0 h,8.0 h,24.0 h,respectively,the corresponding temperatures are 130.7℃,124.8℃,119.2℃and 110.5℃,respectively.When the masses are 5.0 kg,15.0 kg,25.0 kg,50.0 kg,100.0 kg,respectively,the corresponding self-accelerating decomposition temperatures are 110.0℃,105.0℃,102.0℃,99.0℃and 96.0℃,respectively.As the packaging mass increases,it is more difficult to exchange the liberated heat into the surrounding environment and its safety would be further reduced.The thermal history experiment demonstrates that the thermal decomposition of SF-3 is an n-stage reaction and does not have autocatalytic properties.Therefore,the size and ventilation conditions of the sample have a certain impact on the storage stability of SF-3.In the actual production,usage,storage and transportation,sample size and ventilation conditions should be controlled,and practical and effective measures should be taken according to the actual situation.
