By means of HAAKE RS105L cone and plate rheometer the concentrated solution, including viscous flow activation energy, non-Newtonian index, structural viscosity index and relaxation time of the PMIA solution were stud...By means of HAAKE RS105L cone and plate rheometer the concentrated solution, including viscous flow activation energy, non-Newtonian index, structural viscosity index and relaxation time of the PMIA solution were studied. The effect of concentration and temperature of the solution and molecular weight of the polymer on its non-Newtonian behavior was investigated. The results showed that PMIA concentrated solution prepared via low temperature condensation was of non-Newtonian fluid. With the decrease of temperature, increase of solution concentration and PMIA molecular weight, the deviation of the solution from Newtonian behavior decreased. The molecular weight of the polymer and the concentration of the solution affected the non- Newtonian behavior mete intensively.展开更多
Amino acid neurotransmitters facilitate the transmission of nerve messages across the synapses and play essential roles in the control and regulation of a variety of functions in the central and peripheral nervous sys...Amino acid neurotransmitters facilitate the transmission of nerve messages across the synapses and play essential roles in the control and regulation of a variety of functions in the central and peripheral nervous system. In this study, we developed a sensitive and efficient method using high-performance liquid chromatography （HPLC） with fluorescence detection for the assay of five important amino acid n After derivatization with o-phthaldialdehyde （OPA）, aspartate （Asp）, glutamic acid （Glu）, glycine （Gly）, taurine （Tau） and ）,-aminobutyric acid （GABA） were simultaneously detected in the presence of the internal standard homoserine （Hse）. Precise separation of these five amino acids was achieved using isocratic elution within 24 min. Good linearity was found over the concentration range with correlation coefficients （r2） not less than 0.9998. The limit of detection （LOD） values were no more than 10 nmol/L. The intra- and inter-day reproducibility was adequate with the relative standard deviation （RSD） of 10.5% or below. This method has also been applied to the analysis of amino acids in the substantia nigra and striatum samples obtained from C57BL/6 mice.展开更多
In this work, we report the first CASPT2//CASSCF study of the mechanism of the photodecarboxylation of N-phthaloylglycine. The charge transfer excited state S CT （ 1∏∏＊） is initially populated upon irradiation at...In this work, we report the first CASPT2//CASSCF study of the mechanism of the photodecarboxylation of N-phthaloylglycine. The charge transfer excited state S CT （ 1∏∏＊） is initially populated upon irradiation at 266 nm. As a result of a fast internal conversion to the lowest excited singlet state S CT-N （ 1∏∏＊）, this state becomes a favorable precursor state for proton transfer, which triggers decarboxylation. Actually, the excited state intramolecular proton transfer （ESIPT） and decarboxylation processes proceed in an asynchronous concerted way. The ESIPT process is accomplished in the S CT-N （ 1∏∏＊） state, but the CO 2 molecule is finally formed in the ground state via the S CT /S 0 conical intersection. Azomethine ylide is formed in the ground state as a complex with CO 2 . A barrier of ~15 kcal/mol indicates that azomethine ylide is stable in the ground state, which is consistent with the experimental findings. This work provides mechanistic details about the formation of azomethine ylide by photoreaction of N-phthaloylglycine.展开更多
文摘By means of HAAKE RS105L cone and plate rheometer the concentrated solution, including viscous flow activation energy, non-Newtonian index, structural viscosity index and relaxation time of the PMIA solution were studied. The effect of concentration and temperature of the solution and molecular weight of the polymer on its non-Newtonian behavior was investigated. The results showed that PMIA concentrated solution prepared via low temperature condensation was of non-Newtonian fluid. With the decrease of temperature, increase of solution concentration and PMIA molecular weight, the deviation of the solution from Newtonian behavior decreased. The molecular weight of the polymer and the concentration of the solution affected the non- Newtonian behavior mete intensively.
文摘Amino acid neurotransmitters facilitate the transmission of nerve messages across the synapses and play essential roles in the control and regulation of a variety of functions in the central and peripheral nervous system. In this study, we developed a sensitive and efficient method using high-performance liquid chromatography （HPLC） with fluorescence detection for the assay of five important amino acid n After derivatization with o-phthaldialdehyde （OPA）, aspartate （Asp）, glutamic acid （Glu）, glycine （Gly）, taurine （Tau） and ）,-aminobutyric acid （GABA） were simultaneously detected in the presence of the internal standard homoserine （Hse）. Precise separation of these five amino acids was achieved using isocratic elution within 24 min. Good linearity was found over the concentration range with correlation coefficients （r2） not less than 0.9998. The limit of detection （LOD） values were no more than 10 nmol/L. The intra- and inter-day reproducibility was adequate with the relative standard deviation （RSD） of 10.5% or below. This method has also been applied to the analysis of amino acids in the substantia nigra and striatum samples obtained from C57BL/6 mice.
基金supported by the National Natural Science Foundation of China (21033002)the National Basic Research Program of China(2011CB808503)
文摘In this work, we report the first CASPT2//CASSCF study of the mechanism of the photodecarboxylation of N-phthaloylglycine. The charge transfer excited state S CT （ 1∏∏＊） is initially populated upon irradiation at 266 nm. As a result of a fast internal conversion to the lowest excited singlet state S CT-N （ 1∏∏＊）, this state becomes a favorable precursor state for proton transfer, which triggers decarboxylation. Actually, the excited state intramolecular proton transfer （ESIPT） and decarboxylation processes proceed in an asynchronous concerted way. The ESIPT process is accomplished in the S CT-N （ 1∏∏＊） state, but the CO 2 molecule is finally formed in the ground state via the S CT /S 0 conical intersection. Azomethine ylide is formed in the ground state as a complex with CO 2 . A barrier of ~15 kcal/mol indicates that azomethine ylide is stable in the ground state, which is consistent with the experimental findings. This work provides mechanistic details about the formation of azomethine ylide by photoreaction of N-phthaloylglycine.
