目的探讨乙型肝炎病毒(HBV)相关性肝癌患者血清共刺激分子B7-H3(B7-H3)、白细胞介素-21(IL-21)以及表观扩散系数(ADC)与患者病情严重程度的关系。方法选取2016年3月至2018年3月在我院治疗的HBV相关性肝癌患者94例,同时选取慢性乙型肝炎...目的探讨乙型肝炎病毒(HBV)相关性肝癌患者血清共刺激分子B7-H3(B7-H3)、白细胞介素-21(IL-21)以及表观扩散系数(ADC)与患者病情严重程度的关系。方法选取2016年3月至2018年3月在我院治疗的HBV相关性肝癌患者94例,同时选取慢性乙型肝炎患者56例,乙型肝炎肝硬化60例以及健康志愿者70例作为对照,检测各受试者B7-H3和IL-21水平,同时采用MRI测量ADC。结果肝癌患者B7-H3水平为(240.02±27.81)ng/mL,明显高于健康者、慢性乙型肝炎和乙型肝炎肝硬化患者(P<0.05);肝癌患者IL-21水平为(2340.14±221.28)pg/mL,明显高于健康者(P<0.05),而与慢性乙型肝炎、乙型肝炎肝硬化患者比较差异无统计学意义(P>0.05);肝癌ADC值为(0.82±0.08)10-3 mm 2/s,明显高于健康者、慢性乙型肝炎和乙型肝炎肝硬化患者(P<0.05);Ⅲ~Ⅳ期肝癌患者血清B7-H3水平为(244.20±30.22)ng/mL,明显高于Ⅰ~Ⅱ期患者(P<0.05);HBV DNA阳性患者IL-21水平为(2401.45±231.20)pg/mL,明显高于HBV DNA阴性患者(P<0.05);Ⅲ~Ⅳ期性患者ADC值为(0.80±0.09)10-3 mm 2/s,明显低于Ⅰ~Ⅱ期患者,差异比较有统计学意义(P<0.05);B7-H3、IL-21与HBV DNA无相关性(P>0.05)。结论HBV相关性肝癌患者B7-H3、IL-21水平明显升高,B7-H3和ADC值可能与临床分期有关,而IL-21与HBV DNA复制水平高低无关。展开更多
The potential energy profile of the reaction between the atomic oxygen radical anion and acetonitrile has been mapped at the G3MP2B3 level of theory. Geometries of the reactants, products, intermediate complexes, and ...The potential energy profile of the reaction between the atomic oxygen radical anion and acetonitrile has been mapped at the G3MP2B3 level of theory. Geometries of the reactants, products, intermediate complexes, and transition states involved in this reaction have been optimized at the （U）B3LYP/6-31＋G（d,p） level, and then their accurate relative energies have been improved using the G3MP2B3 method. The potential energy profile is confirmed via intrinsic reaction coordinate calculations of transition states. Four possible production channels are examined respectively, as H＋ transfer, H-atom transfer, H2＋ transfer, and bi- molecular nucleophilic substitution （SN2） reaction pathways. Based on present calculations, the H2＋ transfer reaction is major among these four channels, which agrees with previous experimental conclusions.展开更多
The crystal structure of the title compound, diethyl 4,5-di（thienyl）-3,6-bis（trime- thylsilyl）phthalate （C26H3404S2Si2, Mr = 530.83）, has been determined by single-crystal X-ray diffraction. The crystal belongs ...The crystal structure of the title compound, diethyl 4,5-di（thienyl）-3,6-bis（trime- thylsilyl）phthalate （C26H3404S2Si2, Mr = 530.83）, has been determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pccn with a = 43.008（5）, b = 10.9000（12）, c = 11.9357（14） A, V= 5595.3（11） A3, Z = 8, F（000） = 2256, Dc= 1.260 mg/m3, p = 0.305 mm-1, T = 113（2） K, S = 1.090, R = 0.0413 and wR = 0.0969 for 5952 observed reflections with 1 〉 2o（/）. The benzene ring system is planar and makes dihedral angles of 63.7（2） and 72.5（4） with the two thienyl rings A （C（23）-C（26）, S（2）） and B （C（19）-C（22）, S（1））, respectively. The UV-vis absorption and fluorescence of the title compound were discussed. The molecular structure of the title compound has been optimized using DFT method at the B3LYP/6-31G（d） level. The computational results showed that the optimized geometer parameters are consistent well with the experiment data. The vertical ionization potential, vertical electron affinity and frontier orbitals were also discussed.展开更多
Density functional calculations have been used to study the mechanism of 1-phenyl-1-（3-pyridyl）ethene hydroformylation using rhodium catalyst.Our calculations reveal that the rate-determining step is the oxidative a...Density functional calculations have been used to study the mechanism of 1-phenyl-1-（3-pyridyl）ethene hydroformylation using rhodium catalyst.Our calculations reveal that the rate-determining step is the oxidative addition of hydrogen molecule and the preferred path is the one involving ts3ans for the lowest activation free-energy （ΔrGa）,63.8 kJ/mol.This reaction is demonstrated to be strong exothermic by-96.6 kJ/mol of branched products and-98.2 kJ/mol of linear products.And the predominant product is the linear 3-phenyl-3-（3-pyridal）propanal （pr-ns） determined by both thermodynamics and kinetics.These results are in agreement with the practicality experimental studies.展开更多
Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LY...Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step III exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-1-phenyl-1-propanone spontaneously, resulting in the need of 2 mol BH3 in the reaction.展开更多
文摘目的探讨乙型肝炎病毒(HBV)相关性肝癌患者血清共刺激分子B7-H3(B7-H3)、白细胞介素-21(IL-21)以及表观扩散系数(ADC)与患者病情严重程度的关系。方法选取2016年3月至2018年3月在我院治疗的HBV相关性肝癌患者94例,同时选取慢性乙型肝炎患者56例,乙型肝炎肝硬化60例以及健康志愿者70例作为对照,检测各受试者B7-H3和IL-21水平,同时采用MRI测量ADC。结果肝癌患者B7-H3水平为(240.02±27.81)ng/mL,明显高于健康者、慢性乙型肝炎和乙型肝炎肝硬化患者(P<0.05);肝癌患者IL-21水平为(2340.14±221.28)pg/mL,明显高于健康者(P<0.05),而与慢性乙型肝炎、乙型肝炎肝硬化患者比较差异无统计学意义(P>0.05);肝癌ADC值为(0.82±0.08)10-3 mm 2/s,明显高于健康者、慢性乙型肝炎和乙型肝炎肝硬化患者(P<0.05);Ⅲ~Ⅳ期肝癌患者血清B7-H3水平为(244.20±30.22)ng/mL,明显高于Ⅰ~Ⅱ期患者(P<0.05);HBV DNA阳性患者IL-21水平为(2401.45±231.20)pg/mL,明显高于HBV DNA阴性患者(P<0.05);Ⅲ~Ⅳ期性患者ADC值为(0.80±0.09)10-3 mm 2/s,明显低于Ⅰ~Ⅱ期患者,差异比较有统计学意义(P<0.05);B7-H3、IL-21与HBV DNA无相关性(P>0.05)。结论HBV相关性肝癌患者B7-H3、IL-21水平明显升高,B7-H3和ADC值可能与临床分期有关,而IL-21与HBV DNA复制水平高低无关。
文摘The potential energy profile of the reaction between the atomic oxygen radical anion and acetonitrile has been mapped at the G3MP2B3 level of theory. Geometries of the reactants, products, intermediate complexes, and transition states involved in this reaction have been optimized at the （U）B3LYP/6-31＋G（d,p） level, and then their accurate relative energies have been improved using the G3MP2B3 method. The potential energy profile is confirmed via intrinsic reaction coordinate calculations of transition states. Four possible production channels are examined respectively, as H＋ transfer, H-atom transfer, H2＋ transfer, and bi- molecular nucleophilic substitution （SN2） reaction pathways. Based on present calculations, the H2＋ transfer reaction is major among these four channels, which agrees with previous experimental conclusions.
基金supported by the National Natural Science Foundation of China(No.21102099)
文摘The crystal structure of the title compound, diethyl 4,5-di（thienyl）-3,6-bis（trime- thylsilyl）phthalate （C26H3404S2Si2, Mr = 530.83）, has been determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pccn with a = 43.008（5）, b = 10.9000（12）, c = 11.9357（14） A, V= 5595.3（11） A3, Z = 8, F（000） = 2256, Dc= 1.260 mg/m3, p = 0.305 mm-1, T = 113（2） K, S = 1.090, R = 0.0413 and wR = 0.0969 for 5952 observed reflections with 1 〉 2o（/）. The benzene ring system is planar and makes dihedral angles of 63.7（2） and 72.5（4） with the two thienyl rings A （C（23）-C（26）, S（2）） and B （C（19）-C（22）, S（1））, respectively. The UV-vis absorption and fluorescence of the title compound were discussed. The molecular structure of the title compound has been optimized using DFT method at the B3LYP/6-31G（d） level. The computational results showed that the optimized geometer parameters are consistent well with the experiment data. The vertical ionization potential, vertical electron affinity and frontier orbitals were also discussed.
基金Supported by the Education Commission of Chongqing (kj070809)Chongqing Normal University (06XLY018)crosswise project of Sichuan Normal University
文摘Density functional calculations have been used to study the mechanism of 1-phenyl-1-（3-pyridyl）ethene hydroformylation using rhodium catalyst.Our calculations reveal that the rate-determining step is the oxidative addition of hydrogen molecule and the preferred path is the one involving ts3ans for the lowest activation free-energy （ΔrGa）,63.8 kJ/mol.This reaction is demonstrated to be strong exothermic by-96.6 kJ/mol of branched products and-98.2 kJ/mol of linear products.And the predominant product is the linear 3-phenyl-3-（3-pyridal）propanal （pr-ns） determined by both thermodynamics and kinetics.These results are in agreement with the practicality experimental studies.
基金Project supported by the Research Foundation of Suzhou University (Q3109306)
文摘Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step III exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-1-phenyl-1-propanone spontaneously, resulting in the need of 2 mol BH3 in the reaction.
