The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfacta...The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.展开更多
In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides her...In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.展开更多
Hydroformylation of 1-dodecene was studied in a biphasic systemusing water-soluble rhodium complex [RhCl(CO)(TPPTS)_2] as catalystin the presence of cetyl trimethyl ammonium bromide as surfactant toenhance the reactio...Hydroformylation of 1-dodecene was studied in a biphasic systemusing water-soluble rhodium complex [RhCl(CO)(TPPTS)_2] as catalystin the presence of cetyl trimethyl ammonium bromide as surfactant toenhance the reaction rate. Efforts were devoted to improve theperformance of hydroformylation by exploring reactor configurationwhich enhanced the mixing, dispersion and interphase mass transfer.Experiments were carried out in a 0.5 L autoclave at the totalpressure of 1.1 Mpa and temperature from 363 K to 373 K.展开更多
The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HR...The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.展开更多
The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved...The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.展开更多
Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pil...Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pilot plant with continuous mixingreactingseparatingrecycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquidliquid settling phase separator, was introduced as an alternative. The results showed that the continuous fast mixing and separation of ionic liquid catalyst from reactant mixture could be synchronously accomplished within a wider flow rate ratio range of the recycling reaction mixture to the ionic liquid catalyst. The recycling of chloroaluminate ionic liquid was realized. ICPAES detection results of Al content in the reactants proves that in-situ Al compensation to the reaction system may be an important choice to prolong the stable running time of moisture-sensitive ionic liquid BMIMClAlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.展开更多
目的探索酮还原酶家族1成员C3(aldo-keto reductase family 1 member C3,AKR1C3)对乳腺癌恶性细胞生物学行为的干预作用及对程序性细胞死亡蛋白/程序性死亡-配体1(programmed cell death protein1/programmed death-ligand1,PD-1/PD-L)...目的探索酮还原酶家族1成员C3(aldo-keto reductase family 1 member C3,AKR1C3)对乳腺癌恶性细胞生物学行为的干预作用及对程序性细胞死亡蛋白/程序性死亡-配体1(programmed cell death protein1/programmed death-ligand1,PD-1/PD-L)通路的影响。方法把MCF-7人乳腺癌细胞中NC组和AKR1C3组分别转染空质粒和AKR1C3质粒,采用MTT法检测转染后24 h、48 h、72 h细胞活力;采用流式细胞技术测定各组细胞的存活率以及早期、晚期凋亡比例;通过Transwell实验对各组细胞的迁移和侵袭能力进行检测;通过Western blot检测各组细胞PD-1、PD-L1、蛋白激酶B(protein kinase b,AKT)蛋白表达水平。使用C57BL/6小鼠构建荷瘤模型,将采用人乳腺癌MCF-7细胞转染NC质粒和AKR1C3质粒进行细胞荷瘤,每3 d测量瘤体积,持续21 d,绘制两组小鼠肿瘤生长曲线,并于实验终点测量肿瘤质量。结果相较于NC组,AKR1C3组细胞活力降低(P<0.05),并且具有时间依赖效应(P<0.05),迁移和侵袭能力降低(P<0.05),早期凋亡和晚期凋亡比例升高(P<0.05),PD-1、PD-L1、AKT蛋白表达水平降低(P<0.05)。动物实验表明,AKR1C3组小鼠肿瘤体积降低,肿瘤质量下降(P<0.05)。结论AKR1C3可以抑制人乳腺癌细胞恶性生物学行为,抑制PD-1/PDL1信号通路蛋白表达。展开更多
文摘The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.
文摘In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.
基金the National Natural Science Foundation of China (No. 29792074) and SINOPEC.
文摘Hydroformylation of 1-dodecene was studied in a biphasic systemusing water-soluble rhodium complex [RhCl(CO)(TPPTS)_2] as catalystin the presence of cetyl trimethyl ammonium bromide as surfactant toenhance the reaction rate. Efforts were devoted to improve theperformance of hydroformylation by exploring reactor configurationwhich enhanced the mixing, dispersion and interphase mass transfer.Experiments were carried out in a 0.5 L autoclave at the totalpressure of 1.1 Mpa and temperature from 363 K to 373 K.
基金We thank the National Basic Research Project of China(G2000048008)for the financial support.
文摘The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.
文摘The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.
基金State Key Fundamental Research Program (No.G2000048006)
文摘Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pilot plant with continuous mixingreactingseparatingrecycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquidliquid settling phase separator, was introduced as an alternative. The results showed that the continuous fast mixing and separation of ionic liquid catalyst from reactant mixture could be synchronously accomplished within a wider flow rate ratio range of the recycling reaction mixture to the ionic liquid catalyst. The recycling of chloroaluminate ionic liquid was realized. ICPAES detection results of Al content in the reactants proves that in-situ Al compensation to the reaction system may be an important choice to prolong the stable running time of moisture-sensitive ionic liquid BMIMClAlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.
