The effect of the conformation on the spin multiplicity of the ground state and the stability of the ground state were investigated for m-phenylene type of biradicals by means of comparative study with DFT, CASSCF and...The effect of the conformation on the spin multiplicity of the ground state and the stability of the ground state were investigated for m-phenylene type of biradicals by means of comparative study with DFT, CASSCF and AM1-CI approaches. It was found that AM1-CI approach is reliable in dealing with the stability of the high-spin ground state with the change of conformation; DFT method can give the reasonable results of the spin density of the high-spin state. Furthermore, when one or two radical centers are twisted sufficiently out of the conjugation with the benzene ring, m-phenylene turns into weak ferromagnetic and weak antiferromagnetic coupling units, respectively.展开更多
Novel stable high-spin molecules possessing three different arranging fashions were designed with —^＊N—S— as a spin-containing （SC） fragment, an aromatic group, such as benzene （ 1 ）, pyridine （2）, pyridazi...Novel stable high-spin molecules possessing three different arranging fashions were designed with —^＊N—S— as a spin-containing （SC） fragment, an aromatic group, such as benzene （ 1 ）, pyridine （2）, pyridazine （3） , pyrimidine （4）, pyrazine （5） or triazine （6） as end groups （EG）, and phenyl as a ferromagnetic coupling （FC） unit. The effects of different EG on the spin multiplicities of the ground states and their stabilities were investigated by means of the AM1-CI approach. All the investigated molecules corresponded to the FC and possessed high-spin ground states. The spin on the two atoms of the SC fragment was not in agreement with the delocalization results in the specific stability of —^＊N—S—. In those molecules, the stabilities of the triplet states decreased when the distance between the atoms of central SC fragments （—N—） increased. The stabilities of the triplet states of compounds 1a-n, 1b-n and 1c-n, with heterocycles as EG were higher than those of the triplet states of those compounds with phenyl as EG. Furthermore, the stahilities of the triplet states of the compounds with pyrimidine and triazine as EG were higher than those with pyridine, pyridazine or pyrasine as EG.展开更多
Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as ben...Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of - · N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m -phenyl can improve ferromagnetic coupling, while the heteroatom lying in o -phenyl or p -phenyl is not in favor of the ferromagnetic coupling.展开更多
Astrocytes can release increased levels of brain-derived neurotrophic factor during cerebral ischemia, but it is unclear whether brain-derived neurotrophic factor affects y-aminobutyric acid type A receptor function i...Astrocytes can release increased levels of brain-derived neurotrophic factor during cerebral ischemia, but it is unclear whether brain-derived neurotrophic factor affects y-aminobutyric acid type A receptor function in normal neurons. Results from this study demonstrated that y-aminobutyric acid at 100 pmol/L concentration raised the intracellular calcium level in neurons treated with medium from cultured hypoxic astrocytes, and the rise in calcium level could be inhibited by y-aminobutyric acid type A receptor antagonist bicuculline or brain-derived neurotrophic factor receptor antagonist k252a, y-aminobutyric acid type A-gated current induced by 100 IJmol/L y-aminobutyric acid was in an inward direction in physiological conditions, but shifted to the outward direction in neurons when treated with the medium from cultured hypoxic astrocytes, and this effect could be inhibited by k252a. The reverse potential was shifted leftward to -93 mV, which could be inhibited by k252a and Na＋-K＋-CI cotransporter inhibitor bumetanide. Brain-derived neurotrophic factor was released from hypoxic astrocytes at a high level. It shifted the reverse potential of y-aminobutyric acid type A-gated currents leftward in normal neurons by enhancing the function of Na＋-K＋-CI- cotransporter, and caused y-aminobutyric acid to exert an excitatory effect by activating y-aminobutyric acid type A receptor.展开更多
The development of facile and rapid quantification of biologically active biomolecules such as isotretitoin in therapeutic drugs contained in many generic formu- lations is necessary for determining their efficiency a...The development of facile and rapid quantification of biologically active biomolecules such as isotretitoin in therapeutic drugs contained in many generic formu- lations is necessary for determining their efficiency and their quality to improve the human health care. Isotretritoin finds its applications in the maintenance of epithelial tissues. Different processes to date such as normal phase HPLC, or gas chromatrography am- ong others are able to separate and quantify isote- troin. However, the extraction is quite complex and in the case of HPLC, the analysis requires long retention times. In such context, an isocratic reversed- phase high-performance liquid chromatography (HP- LC) technique coupled with an UV-vis detector is described here for easy separation and quantification of 13-cis-retinoic (isotretinoin) from soft gelatin capsule formulations. The isotretinoin was extracted from three different commercial drug samples with tetrahydrofuran (THF) solvent by a procedure that can be completed in less than 10 minutes. Subsequent separation and quantification were accomplished in less than 5 minutes under isocratic reversed-phase conditions on a Lichrospher RP18 column and a mobile phase consisting of 0.01% TFA/acetonitrile (15/85, v/v) at a flow rate of 1.0 mL/min. Isotretoin was detected for the three samples via its UV-vis absorbance at 342 nm. The method was validated and the results showed good linearity, precision and accuracy for sensitive and selective quantitative determination of isotretinoin in the different pharmaceutical formulations. We found that the average isotretinoin content in two of the three commercial pro- ducts fell outside the 90-110% United States Pha- rmacopeia specifications. Consequently, the facile extraction and the precise method for the biomole- cule quantification open up tremendous possibilities in improving the quality control of drugs which can exist as different generic brands.展开更多
基金Supported by the National Natural Science Foundation of China( No.2 980 4 0 0 2,2 0 2 74 0 0 6 ) ,FokYing-TungEducationFoundation( No.710 13) and Foundation of Northeast Normal University( No.1114 34)
文摘The effect of the conformation on the spin multiplicity of the ground state and the stability of the ground state were investigated for m-phenylene type of biradicals by means of comparative study with DFT, CASSCF and AM1-CI approaches. It was found that AM1-CI approach is reliable in dealing with the stability of the high-spin ground state with the change of conformation; DFT method can give the reasonable results of the spin density of the high-spin state. Furthermore, when one or two radical centers are twisted sufficiently out of the conjugation with the benzene ring, m-phenylene turns into weak ferromagnetic and weak antiferromagnetic coupling units, respectively.
基金Supported by the National Natural Science Foundation of Chana(Nos. 29804002, 20274006) and Tianjin Polytechnic Univer-sity Item(Nos. 029307, 029302).
文摘Novel stable high-spin molecules possessing three different arranging fashions were designed with —^＊N—S— as a spin-containing （SC） fragment, an aromatic group, such as benzene （ 1 ）, pyridine （2）, pyridazine （3） , pyrimidine （4）, pyrazine （5） or triazine （6） as end groups （EG）, and phenyl as a ferromagnetic coupling （FC） unit. The effects of different EG on the spin multiplicities of the ground states and their stabilities were investigated by means of the AM1-CI approach. All the investigated molecules corresponded to the FC and possessed high-spin ground states. The spin on the two atoms of the SC fragment was not in agreement with the delocalization results in the specific stability of —^＊N—S—. In those molecules, the stabilities of the triplet states decreased when the distance between the atoms of central SC fragments （—N—） increased. The stabilities of the triplet states of compounds 1a-n, 1b-n and 1c-n, with heterocycles as EG were higher than those of the triplet states of those compounds with phenyl as EG. Furthermore, the stahilities of the triplet states of the compounds with pyrimidine and triazine as EG were higher than those with pyridine, pyridazine or pyrasine as EG.
基金Supported by the National Natural Science Foundation of China( No.2 980 4 0 0 2,2 0 2 74 0 0 6 ) ,FokYingTungEducationFoundation( No.710 13) and Foundation of Northeast Normal University( No.1114 34)
文摘Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of - · N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m -phenyl can improve ferromagnetic coupling, while the heteroatom lying in o -phenyl or p -phenyl is not in favor of the ferromagnetic coupling.
基金the National Natural Science Foundation of China, No. 30471657
文摘Astrocytes can release increased levels of brain-derived neurotrophic factor during cerebral ischemia, but it is unclear whether brain-derived neurotrophic factor affects y-aminobutyric acid type A receptor function in normal neurons. Results from this study demonstrated that y-aminobutyric acid at 100 pmol/L concentration raised the intracellular calcium level in neurons treated with medium from cultured hypoxic astrocytes, and the rise in calcium level could be inhibited by y-aminobutyric acid type A receptor antagonist bicuculline or brain-derived neurotrophic factor receptor antagonist k252a, y-aminobutyric acid type A-gated current induced by 100 IJmol/L y-aminobutyric acid was in an inward direction in physiological conditions, but shifted to the outward direction in neurons when treated with the medium from cultured hypoxic astrocytes, and this effect could be inhibited by k252a. The reverse potential was shifted leftward to -93 mV, which could be inhibited by k252a and Na＋-K＋-CI cotransporter inhibitor bumetanide. Brain-derived neurotrophic factor was released from hypoxic astrocytes at a high level. It shifted the reverse potential of y-aminobutyric acid type A-gated currents leftward in normal neurons by enhancing the function of Na＋-K＋-CI- cotransporter, and caused y-aminobutyric acid to exert an excitatory effect by activating y-aminobutyric acid type A receptor.
文摘The development of facile and rapid quantification of biologically active biomolecules such as isotretitoin in therapeutic drugs contained in many generic formu- lations is necessary for determining their efficiency and their quality to improve the human health care. Isotretritoin finds its applications in the maintenance of epithelial tissues. Different processes to date such as normal phase HPLC, or gas chromatrography am- ong others are able to separate and quantify isote- troin. However, the extraction is quite complex and in the case of HPLC, the analysis requires long retention times. In such context, an isocratic reversed- phase high-performance liquid chromatography (HP- LC) technique coupled with an UV-vis detector is described here for easy separation and quantification of 13-cis-retinoic (isotretinoin) from soft gelatin capsule formulations. The isotretinoin was extracted from three different commercial drug samples with tetrahydrofuran (THF) solvent by a procedure that can be completed in less than 10 minutes. Subsequent separation and quantification were accomplished in less than 5 minutes under isocratic reversed-phase conditions on a Lichrospher RP18 column and a mobile phase consisting of 0.01% TFA/acetonitrile (15/85, v/v) at a flow rate of 1.0 mL/min. Isotretoin was detected for the three samples via its UV-vis absorbance at 342 nm. The method was validated and the results showed good linearity, precision and accuracy for sensitive and selective quantitative determination of isotretinoin in the different pharmaceutical formulations. We found that the average isotretinoin content in two of the three commercial pro- ducts fell outside the 90-110% United States Pha- rmacopeia specifications. Consequently, the facile extraction and the precise method for the biomole- cule quantification open up tremendous possibilities in improving the quality control of drugs which can exist as different generic brands.
