以Fe3+/Cu2+为氧化剂,绿色氧化苯偶姻合成了苯偶酰,研究了铜盐、铵盐和硝酸盐的类型及其用量对反应的影响,讨论了可能的反应的机理.结果表明:以10 mmol苯偶姻为原料,2 mL 2%的Cu(OAc)2溶液为氧化剂,10 mmol硝酸铵为助剂,14 mL冰醋酸为溶...以Fe3+/Cu2+为氧化剂,绿色氧化苯偶姻合成了苯偶酰,研究了铜盐、铵盐和硝酸盐的类型及其用量对反应的影响,讨论了可能的反应的机理.结果表明:以10 mmol苯偶姻为原料,2 mL 2%的Cu(OAc)2溶液为氧化剂,10 mmol硝酸铵为助剂,14 mL冰醋酸为溶剂,添加1 g FeCl3.6H2O,回流温度下反应时间可从90 min减少至60 min,苯偶酰的收率高达98.4%,其结构经红外光谱、元素分析等进行了表征.展开更多
针对乙醇液相氧化羰基化合成反应工艺,筛选出CuBr2/DMA(N,N-二甲基乙酰胺)均相催化体系,考察了催化剂组分配比对催化活性、时间对氧化羰基化反应的影响,以及CuBr2/DMA催化剂体系的循环使用性能。结果表明,该催化剂体系表现出良好的氧化...针对乙醇液相氧化羰基化合成反应工艺,筛选出CuBr2/DMA(N,N-二甲基乙酰胺)均相催化体系,考察了催化剂组分配比对催化活性、时间对氧化羰基化反应的影响,以及CuBr2/DMA催化剂体系的循环使用性能。结果表明,该催化剂体系表现出良好的氧化羰基化催化活性,当CuBr2在DMA溶剂中浓度为0.3 g mL 1,反应时间为2.5 h时,乙醇的转化率达到36.2%,催化剂循环性能良好。XRD表征显示,开始加入CuBr2催化剂中Cu(II)为催化主体,催化过程中Cu(Ⅱ)被还原为Cu(I);循环试验中起催化活性的物质是Cu(I),且CuBr在溶剂DMA中表现出与CuBr2相当的稳定特性。通过气相色谱及气-质联用对液相产物分析表明,产物分别是碳酸二乙酯、甲酸乙酯、乙酸乙酯和丙酸乙酯,并在此基础上探讨了产物形成和可能的催化机理。展开更多
Direct transformation of ethanol to ethyl acetate was investigated on a series of Cu（ZrO2）/SiO2 catalysts. Inductively coupled plasma（ICP）, surface area analysis, X-ray diffraction（XRD）, H2-temperature programme...Direct transformation of ethanol to ethyl acetate was investigated on a series of Cu（ZrO2）/SiO2 catalysts. Inductively coupled plasma（ICP）, surface area analysis, X-ray diffraction（XRD）, H2-temperature programmed reduc- tion（H2-TPR）, X-ray photoelectron spectroscopy（XPS）, NH3-temperature programmed desorption（NH3-TPD） and Fourier transform-infrared spectroscopy（FTIR） techniques were used to characterize the catalysts. The results reveal that ZrO2 can improve the dispersion of copper species and increase the acidity of the Cu（ZrO2）/SiO2 catalysts. The Cu0 is responsible for ethanol dehydrogenation to acetaldehyde, and both the Lewis acid and Bronsted acid sites were in favor of the selectivity to ethyl acetate. The synergistic effect of Cu0 and an appropriate amount of acidic sites played an important role in the production of ethyl acetate.展开更多
In this study, arsenic trioxide(ATO) was encapsulated in liposomes via copper acetate(Cu(OAc)2) gradients and high entrapment efficiency of over 80% was obtained. The average particle size and the zeta-potential of th...In this study, arsenic trioxide(ATO) was encapsulated in liposomes via copper acetate(Cu(OAc)2) gradients and high entrapment efficiency of over 80% was obtained. The average particle size and the zeta-potential of the liposomes were detected to be 115.1 ± 29.1 nm and-21.97 ± 0.6 m V, respectively. The TEM images showed rod-like precipitates in the inner aqueous phase, which was supposed be due to the formation of insoluble ATO–Cu complex.The in vitro drug release of ATO–Cu liposomes exhibited a sustained release over 72 h, and the release rates decreased with the increase of the p H of release media. Pharmacokinetic and tissue distribution studies of ATO liposomes showed significantly reduced plasma clearance rate, increased AUC0–12h and T1/2, and improved tumor distribution of As compared to iv administration of ATO solution. The anti-tumor effect of ATO loaded liposomes to S180 tumor-bearing mice was significantly improved with a tumor inhibition rate of 61.2%,meanwhile the toxicity of encapsulated ATO was greatly decreased. In conclusion, ATO can be effectively encapsulated into liposomes by remote loading method via Cu(OAc)2 gradients;the co-administration of ATO and Cu(Ⅱ) via liposomal formulation may find wide applications in the treatment of various tumors.展开更多
A series of silver modified Cu/SiO2 catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol.The influence of additive‘Ag’on the structural evo...A series of silver modified Cu/SiO2 catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol.The influence of additive‘Ag’on the structural evolution of catalyst was systematically studied by several characterization techniques,such as N2 adsorption–desorption,N2O titration,PXRD,FTIR,in-situ FTIR,H2-TPR,H2-TPD,XPS and TEM.Results showed that incorporation of a small amount of Ag could enhance the structural stability,and the strong interaction between Cu and Ag species was conducive to increase the dispersion of copper species and create a suitable Cu+/(Cu0+Cu+)ratio,which was proposed to be responsible for the improved catalytic activity.The maximum conversion of MA(94.1%)and selectivity of ethanol(91.3%)over optimized Cu-0.5 Ag/SiO2 and 120 h on stream without deactivation under optimal conditions demonstrates its excellent stability.展开更多
BACKGROUND Wilson disease(WD)is a progressive,potentially fatal degenerative disease affecting the liver and central nervous system.Given its low prevalence,collecting data on large cohorts of patients with WD is chal...BACKGROUND Wilson disease(WD)is a progressive,potentially fatal degenerative disease affecting the liver and central nervous system.Given its low prevalence,collecting data on large cohorts of patients with WD is challenging.Comprehensive insur-ance claims databases provide powerful tools to collect retrospective data on large numbers of patients with rare diseases.AIM To describe patients with WD in the United States,their treatment and clinical outcome,using a large insurance claims database.METHODS This retrospective,longitudinal study was performed in the Clarivate Real-World Data Product database.All patients with≥2 claims associated with an Interna-tional Classification of Diseases 10(ICD-10)diagnostic code for WD(E83.01)between 2016 and 2021 were included and followed until death or study end.Patients were divided into two groups by whether or not they were documented to have received a specific treatment for WD.Clinical manifestations,hospital-isations,liver transplantation and death were documented.RESULTS Overall,5376 patients with an ICD-10 diagnostic code for WD were identified.The mean age at inclusion was 41.2 years and 52.0%were men.A specific WD treatment was documented for 885 patients(15.1%),although the number of patients taking zinc salts may be underestimated due to over the counter purchase.At inclusion,the mean age of patients with a documented treatment was 36.6±17.8 years vs 42.2±19.6 years in those without a documented treatment.During follow-up,273 patients(5.1%)died.Compared with the American general population,the standardised mortality ratio was 2.19.The proportion of patients with a documented WD-specific treatment who died during follow-up was 4.0%and the mean age at death 52.7 years.CONCLUSION Patients treated for WD in the United States had an excess early mortality compared with the American population.These findings indicate that there is a significant unmet need for effective treatment for WD in the United States.展开更多
采用浸渍法制备铜金属氧化物改性活性炭吸附剂,采用同步热重差热分析（TG/DTA）、比表面分析（N2-BET）和X线光电子能谱（XPS）分析,考察吸附剂的净化性能。研究结果表明：最佳焙烧温度为300℃,最优体积空速为600 h 1;铜金属氧化物改性...采用浸渍法制备铜金属氧化物改性活性炭吸附剂,采用同步热重差热分析（TG/DTA）、比表面分析（N2-BET）和X线光电子能谱（XPS）分析,考察吸附剂的净化性能。研究结果表明：最佳焙烧温度为300℃,最优体积空速为600 h 1;铜金属氧化物改性能显著增加活性炭对HCN的吸附性能,孔径为0.74~1.98 nm的微孔对HCN的吸附贡献较大,改性活性炭在325℃以内保持较优的热稳定性,CuO是吸附剂的主要活性组分,吸附HCN后,HCN被催化氧化分解为NH3,吸附剂的失活可能是HCN在脱除过程中生成的CuCN填充和覆盖了活性炭的微孔。展开更多
This paper addressed the efect of copper acetate on the combustion characteristics of anthracite depending on the fractional composition of fuel and additive introduction method.Anthracite was impregnated with 5 wt%of...This paper addressed the efect of copper acetate on the combustion characteristics of anthracite depending on the fractional composition of fuel and additive introduction method.Anthracite was impregnated with 5 wt%of Cu(CH_(3)COO)_(2)by mechanical mixing and incipient wetness impregnation.Four anthracite samples of diferent fraction with d<0.1 mm,d=0.1-0.5 mm,d=0.5-1.0 mm,and d=1.0-2.0 mm were compared.According to EDX mapping,incipient wetness impregnation provides a higher dispersion of the additive and its uniform distribution in the sample.The ignition and combustion characteristics of the modifed anthracite samples were studied by thermal analysis and high-speed video recording of the processes in a combustion chamber(at heating medium temperature of 800℃).It was found that copper acetate increases anthracite reactivity,which was evidenced by decreased onset temperature of combustion(ΔT_(i))by 35-190℃and reduced ignition delay time(Δτ_(i))by 2.1-5.4 s.Copper acetate reduces fuel underburning(on average by 70%)in the ash residue of anthracite and decreases the amount of CO and NO_(x)in gas-phase products(on average by 18.5%and 20.8%,respectively).The mechanism for activation of anthracite combustion by copper acetate is proposed.展开更多
文摘以Fe3+/Cu2+为氧化剂,绿色氧化苯偶姻合成了苯偶酰,研究了铜盐、铵盐和硝酸盐的类型及其用量对反应的影响,讨论了可能的反应的机理.结果表明:以10 mmol苯偶姻为原料,2 mL 2%的Cu(OAc)2溶液为氧化剂,10 mmol硝酸铵为助剂,14 mL冰醋酸为溶剂,添加1 g FeCl3.6H2O,回流温度下反应时间可从90 min减少至60 min,苯偶酰的收率高达98.4%,其结构经红外光谱、元素分析等进行了表征.
文摘针对乙醇液相氧化羰基化合成反应工艺,筛选出CuBr2/DMA(N,N-二甲基乙酰胺)均相催化体系,考察了催化剂组分配比对催化活性、时间对氧化羰基化反应的影响,以及CuBr2/DMA催化剂体系的循环使用性能。结果表明,该催化剂体系表现出良好的氧化羰基化催化活性,当CuBr2在DMA溶剂中浓度为0.3 g mL 1,反应时间为2.5 h时,乙醇的转化率达到36.2%,催化剂循环性能良好。XRD表征显示,开始加入CuBr2催化剂中Cu(II)为催化主体,催化过程中Cu(Ⅱ)被还原为Cu(I);循环试验中起催化活性的物质是Cu(I),且CuBr在溶剂DMA中表现出与CuBr2相当的稳定特性。通过气相色谱及气-质联用对液相产物分析表明,产物分别是碳酸二乙酯、甲酸乙酯、乙酸乙酯和丙酸乙酯,并在此基础上探讨了产物形成和可能的催化机理。
基金Supported by the Natural Science Foundation of Science and Technology Department of Jilin Province, China（No.20130101015JC）, the Open Project Supported by State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University, China （No.2012-15）, and the Innovation Project of Frontiers of Science and New Interdiscipline of Jilin University, China.
文摘Direct transformation of ethanol to ethyl acetate was investigated on a series of Cu（ZrO2）/SiO2 catalysts. Inductively coupled plasma（ICP）, surface area analysis, X-ray diffraction（XRD）, H2-temperature programmed reduc- tion（H2-TPR）, X-ray photoelectron spectroscopy（XPS）, NH3-temperature programmed desorption（NH3-TPD） and Fourier transform-infrared spectroscopy（FTIR） techniques were used to characterize the catalysts. The results reveal that ZrO2 can improve the dispersion of copper species and increase the acidity of the Cu（ZrO2）/SiO2 catalysts. The Cu0 is responsible for ethanol dehydrogenation to acetaldehyde, and both the Lewis acid and Bronsted acid sites were in favor of the selectivity to ethyl acetate. The synergistic effect of Cu0 and an appropriate amount of acidic sites played an important role in the production of ethyl acetate.
基金Research Grant from Liaoning Province Office of EducationChina(No.L2014395)+1 种基金the Natural Science Foundation of Liaoning Province(No.201602711)Supporting Program for Young Researchers from Sheyang Pharmaceutical University。
文摘In this study, arsenic trioxide(ATO) was encapsulated in liposomes via copper acetate(Cu(OAc)2) gradients and high entrapment efficiency of over 80% was obtained. The average particle size and the zeta-potential of the liposomes were detected to be 115.1 ± 29.1 nm and-21.97 ± 0.6 m V, respectively. The TEM images showed rod-like precipitates in the inner aqueous phase, which was supposed be due to the formation of insoluble ATO–Cu complex.The in vitro drug release of ATO–Cu liposomes exhibited a sustained release over 72 h, and the release rates decreased with the increase of the p H of release media. Pharmacokinetic and tissue distribution studies of ATO liposomes showed significantly reduced plasma clearance rate, increased AUC0–12h and T1/2, and improved tumor distribution of As compared to iv administration of ATO solution. The anti-tumor effect of ATO loaded liposomes to S180 tumor-bearing mice was significantly improved with a tumor inhibition rate of 61.2%,meanwhile the toxicity of encapsulated ATO was greatly decreased. In conclusion, ATO can be effectively encapsulated into liposomes by remote loading method via Cu(OAc)2 gradients;the co-administration of ATO and Cu(Ⅱ) via liposomal formulation may find wide applications in the treatment of various tumors.
基金Key Research Program of Frontier Sciences,CAS(Grant No.QYZDB-SSW-SLH 022)the National Natural Science Foundation of China-National Research Council of Thailand(NSFC NRCT,51661145012)K.C.Wong Education Foundation(GJTD 2582018-04)。
文摘A series of silver modified Cu/SiO2 catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol.The influence of additive‘Ag’on the structural evolution of catalyst was systematically studied by several characterization techniques,such as N2 adsorption–desorption,N2O titration,PXRD,FTIR,in-situ FTIR,H2-TPR,H2-TPD,XPS and TEM.Results showed that incorporation of a small amount of Ag could enhance the structural stability,and the strong interaction between Cu and Ag species was conducive to increase the dispersion of copper species and create a suitable Cu+/(Cu0+Cu+)ratio,which was proposed to be responsible for the improved catalytic activity.The maximum conversion of MA(94.1%)and selectivity of ethanol(91.3%)over optimized Cu-0.5 Ag/SiO2 and 120 h on stream without deactivation under optimal conditions demonstrates its excellent stability.
文摘BACKGROUND Wilson disease(WD)is a progressive,potentially fatal degenerative disease affecting the liver and central nervous system.Given its low prevalence,collecting data on large cohorts of patients with WD is challenging.Comprehensive insur-ance claims databases provide powerful tools to collect retrospective data on large numbers of patients with rare diseases.AIM To describe patients with WD in the United States,their treatment and clinical outcome,using a large insurance claims database.METHODS This retrospective,longitudinal study was performed in the Clarivate Real-World Data Product database.All patients with≥2 claims associated with an Interna-tional Classification of Diseases 10(ICD-10)diagnostic code for WD(E83.01)between 2016 and 2021 were included and followed until death or study end.Patients were divided into two groups by whether or not they were documented to have received a specific treatment for WD.Clinical manifestations,hospital-isations,liver transplantation and death were documented.RESULTS Overall,5376 patients with an ICD-10 diagnostic code for WD were identified.The mean age at inclusion was 41.2 years and 52.0%were men.A specific WD treatment was documented for 885 patients(15.1%),although the number of patients taking zinc salts may be underestimated due to over the counter purchase.At inclusion,the mean age of patients with a documented treatment was 36.6±17.8 years vs 42.2±19.6 years in those without a documented treatment.During follow-up,273 patients(5.1%)died.Compared with the American general population,the standardised mortality ratio was 2.19.The proportion of patients with a documented WD-specific treatment who died during follow-up was 4.0%and the mean age at death 52.7 years.CONCLUSION Patients treated for WD in the United States had an excess early mortality compared with the American population.These findings indicate that there is a significant unmet need for effective treatment for WD in the United States.
文摘采用浸渍法制备铜金属氧化物改性活性炭吸附剂,采用同步热重差热分析（TG/DTA）、比表面分析（N2-BET）和X线光电子能谱（XPS）分析,考察吸附剂的净化性能。研究结果表明：最佳焙烧温度为300℃,最优体积空速为600 h 1;铜金属氧化物改性能显著增加活性炭对HCN的吸附性能,孔径为0.74~1.98 nm的微孔对HCN的吸附贡献较大,改性活性炭在325℃以内保持较优的热稳定性,CuO是吸附剂的主要活性组分,吸附HCN后,HCN被催化氧化分解为NH3,吸附剂的失活可能是HCN在脱除过程中生成的CuCN填充和覆盖了活性炭的微孔。
文摘This paper addressed the efect of copper acetate on the combustion characteristics of anthracite depending on the fractional composition of fuel and additive introduction method.Anthracite was impregnated with 5 wt%of Cu(CH_(3)COO)_(2)by mechanical mixing and incipient wetness impregnation.Four anthracite samples of diferent fraction with d<0.1 mm,d=0.1-0.5 mm,d=0.5-1.0 mm,and d=1.0-2.0 mm were compared.According to EDX mapping,incipient wetness impregnation provides a higher dispersion of the additive and its uniform distribution in the sample.The ignition and combustion characteristics of the modifed anthracite samples were studied by thermal analysis and high-speed video recording of the processes in a combustion chamber(at heating medium temperature of 800℃).It was found that copper acetate increases anthracite reactivity,which was evidenced by decreased onset temperature of combustion(ΔT_(i))by 35-190℃and reduced ignition delay time(Δτ_(i))by 2.1-5.4 s.Copper acetate reduces fuel underburning(on average by 70%)in the ash residue of anthracite and decreases the amount of CO and NO_(x)in gas-phase products(on average by 18.5%and 20.8%,respectively).The mechanism for activation of anthracite combustion by copper acetate is proposed.
