The potential energy surface of O（^1D）＋C2H5Cl reaction was studied using QCISD（T）/6- 311＋＋G（d,p）//MP2/6-31G（d,p） method. The calculations reveal an insertion-elimination mechanism. The insertion reaction o...The potential energy surface of O（^1D）＋C2H5Cl reaction was studied using QCISD（T）/6- 311＋＋G（d,p）//MP2/6-31G（d,p） method. The calculations reveal an insertion-elimination mechanism. The insertion reaction of O（^1D） and C2H5Cl produces two energy-rich intermediates, IM1 and IM2, which subsequently decompose into various products. The calculations of the branching ratios of various products formed through the two intermediates were carried out using RRKM （Rice-Ramsperger-Kassel-Marcus） theory at the collision energies of 0, 20.9, 41.8, 62.7, 83.6, 104.5, and 125.4 kJ/mol. HCl is the main decomposition product for IM1; CH2OH is the main decomposition product for IM2. Since IM1 is more stable than IM2, HCl is probably the main product of the O（^1D）＋C2H5Cl reaction.展开更多
The BMPPT (4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione)was synthesized from BMPP. Its m.p. is 106-108℃. The results of the element analysis are as follows: C, 68.51%, H, 4.51%, N, 9.26%, S, 11.47%, wh...The BMPPT (4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione)was synthesized from BMPP. Its m.p. is 106-108℃. The results of the element analysis are as follows: C, 68.51%, H, 4.51%, N, 9.26%, S, 11.47%, which are in conformity with the theoretical value (C, 69.15%, H, 4.76%, N, 9.52%, S, 10.90%). The solvent extraction of Th4+ from nitric acid solution by BMPPT in benzene was studied. The extraction ability of BMPPT is not so high as that of its parent (BMPP). The Th4+ distribution ratio (DTh) increases with the increasing pH of the aqueous phase, and pH1/2 for Th4+ was 3.2 ([BMPPT]=0.10 mol/L). When the pH increases, the distribution ratio of Th4+ increases linearly with the slope of 1 .59. When the concentration of BMPPT increases, the distribution ratio of Th4+ increases rapidly. The lgDTh-lg[BMPPT] is linear with the slope of 1.42 and the extraction mechanism is the cation ion-exchange.展开更多
The formaidehyde-free finishing agent 4,5-di-hydroxy-1,3-dimethy1-2-imidazolidinone(DMeDHEU)was prepared by the reaction of 1,3-dimethylurea and glyoxal.The reaction rate and equilib-rium conversion in relation to pH ...The formaidehyde-free finishing agent 4,5-di-hydroxy-1,3-dimethy1-2-imidazolidinone(DMeDHEU)was prepared by the reaction of 1,3-dimethylurea and glyoxal.The reaction rate and equilib-rium conversion in relation to pH value,molar ratio,temperature and catalyst were studied.The conversionto DMeDHEU,catalyzed with citric acid/anhydrousNaAc,reached 95% in 6 hours at 40℃, pH 5.5 andmolar ratio 1.2.展开更多
目的以Meta分析的方法定量评估HER-2/neu基因扩增/或表达增强状态与上皮性卵巢癌患者手术后的中位生存期和5年生存率的关联性。方法检索、筛选1989年以来所有论述HER-2/neu状态与患者预后关系的中、英文回顾性研究文献。在Ludwig中心符...目的以Meta分析的方法定量评估HER-2/neu基因扩增/或表达增强状态与上皮性卵巢癌患者手术后的中位生存期和5年生存率的关联性。方法检索、筛选1989年以来所有论述HER-2/neu状态与患者预后关系的中、英文回顾性研究文献。在Ludwig中心符号轶(Centered signed rank)和DerSimonian-Laird等方法基础上对各研究提供的生存数据进行统计分析。结果共纳入25篇文献,3251例患者。HER-2/neu表达率为27.1%[95%CI(0,54.8%)],与病理分期、分型和分级无关。HER-2/neu阳性者中位生存期平均减少0.65年,5年生存率下降[HR=1.22,95%CI(1.09,1.36)]。亚组分析显示,HER-2/neu蛋白表达与预后关系最明确,强阳性者5年内死亡风险增加,且对铂类化疗药物的反应性减低。结论在妇科肿瘤临床中,将HER-2/neu作为常规的病理指标使用,有助于进行合理的预后评估,并制定个体化化疗方案。展开更多
WT5”BZ] To study the molecular mechanism of the stimulatory effect of low dose radiation(LDR) on T cell activation. [WT5”BX]Methods.[WT5”BZ] Thymocytes from Kunming mice exposed to whole body irradiation(WBI) with ...WT5”BZ] To study the molecular mechanism of the stimulatory effect of low dose radiation(LDR) on T cell activation. [WT5”BX]Methods.[WT5”BZ] Thymocytes from Kunming mice exposed to whole body irradiation(WBI) with different doses of X rays were analyzed for the changes in signal molecules of the phospholipase C phosphatidylinositol biphosphate(PLC IP2) and G protein adenylate cyclase(AC) pathways. [WT5”BX]Results.[WT5”BZ]It was found that[Ca 2+ ] i increased in response to doses within 0 2 Gy which was most marked after 0 075 Gy and the increase was accentuated in the presence of Con A. The changes in CD3 and calcineurin(CN) expression of the thymocytes followed the same pattern as the alterations in [Ca 2+ ] i after LDR. The expression of α,β1 and β2 isoforms of protein kinase C(PKC) was all up regulated after 0 075 Gy with the increase in PKC β1 expression being most marked. The cAMP/cGMP ratio and PKA activity of the thymocytes was lowered after low dose radiation and increased after doses above 0 5 Gy in a dose dependent manner, thus giving rise to J shaped dose response curves. The Ca antagonist TMB 8 and cAMP stimulant cholera toxin suppressed the augmented thymocyte proliferation induced by LDR. [WT5”BX]Conclusion.[WT5”BZ]Data presented in the present paper suggest that activation of the PLC PIP2 signal pathway and suppression of the AC cAMP signal pathway are involved in the stimulation of the thymocytes following WBI with low dose X rays.展开更多
The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering eith...The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell.展开更多
The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reducti...The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reduction of NOx by NH3.Four different methods,namely pre-impregnation,post-impregnation,coimpregnation,and co-precipitation,were used to synthesize a series of V2 O5-WO3-TiO2-CeO2-ZrO2 catalysts.The catalysts were characterized by XRD,BET,NH3-TPD,XPS,and H2-TPR techniques.Moreover,the activity and anti-K poisoning performance were tested by an NH3-SCR model reaction.The results show that the introduction of Ce^4+and Zr^4+can improve the catalytic performance of V2O5-WO3/TiO2 catalyst,but the impregnation method cannot enhance the anti-K poisoning performance.Ce^4+and Zr^4+introduced by co-precipitation method can effectively improve the tolerance of K,which is mainly due to the incorporation of Ce^4+and Zr^4+into TiO2 lattice to form a uniform TiO2-CeO2-ZrO2 solid solution,resulting in the optimal surface acidity and redox performance,and reducing the decreases caused by Kpoisoning.Furthermore,based on the best introduction method,we further optimized the molar ratio of Ce^4+/Zr^4+,It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce^4+/Zr^4+is 2:1.展开更多
基金ACKNOWLEDGMENT This work was supported Science Foundation of China by the National Natural （No.50772107）.
文摘The potential energy surface of O（^1D）＋C2H5Cl reaction was studied using QCISD（T）/6- 311＋＋G（d,p）//MP2/6-31G（d,p） method. The calculations reveal an insertion-elimination mechanism. The insertion reaction of O（^1D） and C2H5Cl produces two energy-rich intermediates, IM1 and IM2, which subsequently decompose into various products. The calculations of the branching ratios of various products formed through the two intermediates were carried out using RRKM （Rice-Ramsperger-Kassel-Marcus） theory at the collision energies of 0, 20.9, 41.8, 62.7, 83.6, 104.5, and 125.4 kJ/mol. HCl is the main decomposition product for IM1; CH2OH is the main decomposition product for IM2. Since IM1 is more stable than IM2, HCl is probably the main product of the O（^1D）＋C2H5Cl reaction.
文摘The BMPPT (4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione)was synthesized from BMPP. Its m.p. is 106-108℃. The results of the element analysis are as follows: C, 68.51%, H, 4.51%, N, 9.26%, S, 11.47%, which are in conformity with the theoretical value (C, 69.15%, H, 4.76%, N, 9.52%, S, 10.90%). The solvent extraction of Th4+ from nitric acid solution by BMPPT in benzene was studied. The extraction ability of BMPPT is not so high as that of its parent (BMPP). The Th4+ distribution ratio (DTh) increases with the increasing pH of the aqueous phase, and pH1/2 for Th4+ was 3.2 ([BMPPT]=0.10 mol/L). When the pH increases, the distribution ratio of Th4+ increases linearly with the slope of 1 .59. When the concentration of BMPPT increases, the distribution ratio of Th4+ increases rapidly. The lgDTh-lg[BMPPT] is linear with the slope of 1.42 and the extraction mechanism is the cation ion-exchange.
文摘The formaidehyde-free finishing agent 4,5-di-hydroxy-1,3-dimethy1-2-imidazolidinone(DMeDHEU)was prepared by the reaction of 1,3-dimethylurea and glyoxal.The reaction rate and equilib-rium conversion in relation to pH value,molar ratio,temperature and catalyst were studied.The conversionto DMeDHEU,catalyzed with citric acid/anhydrousNaAc,reached 95% in 6 hours at 40℃, pH 5.5 andmolar ratio 1.2.
文摘目的以Meta分析的方法定量评估HER-2/neu基因扩增/或表达增强状态与上皮性卵巢癌患者手术后的中位生存期和5年生存率的关联性。方法检索、筛选1989年以来所有论述HER-2/neu状态与患者预后关系的中、英文回顾性研究文献。在Ludwig中心符号轶(Centered signed rank)和DerSimonian-Laird等方法基础上对各研究提供的生存数据进行统计分析。结果共纳入25篇文献,3251例患者。HER-2/neu表达率为27.1%[95%CI(0,54.8%)],与病理分期、分型和分级无关。HER-2/neu阳性者中位生存期平均减少0.65年,5年生存率下降[HR=1.22,95%CI(1.09,1.36)]。亚组分析显示,HER-2/neu蛋白表达与预后关系最明确,强阳性者5年内死亡风险增加,且对铂类化疗药物的反应性减低。结论在妇科肿瘤临床中,将HER-2/neu作为常规的病理指标使用,有助于进行合理的预后评估,并制定个体化化疗方案。
基金This work was supported by a grant from NSFC (No.39570188)
文摘WT5”BZ] To study the molecular mechanism of the stimulatory effect of low dose radiation(LDR) on T cell activation. [WT5”BX]Methods.[WT5”BZ] Thymocytes from Kunming mice exposed to whole body irradiation(WBI) with different doses of X rays were analyzed for the changes in signal molecules of the phospholipase C phosphatidylinositol biphosphate(PLC IP2) and G protein adenylate cyclase(AC) pathways. [WT5”BX]Results.[WT5”BZ]It was found that[Ca 2+ ] i increased in response to doses within 0 2 Gy which was most marked after 0 075 Gy and the increase was accentuated in the presence of Con A. The changes in CD3 and calcineurin(CN) expression of the thymocytes followed the same pattern as the alterations in [Ca 2+ ] i after LDR. The expression of α,β1 and β2 isoforms of protein kinase C(PKC) was all up regulated after 0 075 Gy with the increase in PKC β1 expression being most marked. The cAMP/cGMP ratio and PKA activity of the thymocytes was lowered after low dose radiation and increased after doses above 0 5 Gy in a dose dependent manner, thus giving rise to J shaped dose response curves. The Ca antagonist TMB 8 and cAMP stimulant cholera toxin suppressed the augmented thymocyte proliferation induced by LDR. [WT5”BX]Conclusion.[WT5”BZ]Data presented in the present paper suggest that activation of the PLC PIP2 signal pathway and suppression of the AC cAMP signal pathway are involved in the stimulation of the thymocytes following WBI with low dose X rays.
文摘The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell.
基金Project supported by the National Natural Science Foundation of China(21876168)the Key Projects for Common Key Technology Innovation in Key Industries in Chongqing(cstc2016zdcy-ztzx0020-01)+1 种基金Youth Innovation Promotion Association CAS(2019376)the Graduate Innovation Project of Chongqing Technology and Business University(yjscxx201803-028-22)。
文摘The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reduction of NOx by NH3.Four different methods,namely pre-impregnation,post-impregnation,coimpregnation,and co-precipitation,were used to synthesize a series of V2 O5-WO3-TiO2-CeO2-ZrO2 catalysts.The catalysts were characterized by XRD,BET,NH3-TPD,XPS,and H2-TPR techniques.Moreover,the activity and anti-K poisoning performance were tested by an NH3-SCR model reaction.The results show that the introduction of Ce^4+and Zr^4+can improve the catalytic performance of V2O5-WO3/TiO2 catalyst,but the impregnation method cannot enhance the anti-K poisoning performance.Ce^4+and Zr^4+introduced by co-precipitation method can effectively improve the tolerance of K,which is mainly due to the incorporation of Ce^4+and Zr^4+into TiO2 lattice to form a uniform TiO2-CeO2-ZrO2 solid solution,resulting in the optimal surface acidity and redox performance,and reducing the decreases caused by Kpoisoning.Furthermore,based on the best introduction method,we further optimized the molar ratio of Ce^4+/Zr^4+,It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce^4+/Zr^4+is 2:1.
