目的:探讨EMSY基因表达水平和多态性与早期卵巢上皮癌患者预后的关系。方法:选取118例早期卵巢上皮癌患者(研究组)及63例良性妇科肿瘤患者(对照组),采用逆转录-聚合酶链反应(RT-PCR)分析EMSY m RNA,PCR-限制性片段长度多态性(RFLP)检测4...目的:探讨EMSY基因表达水平和多态性与早期卵巢上皮癌患者预后的关系。方法:选取118例早期卵巢上皮癌患者(研究组)及63例良性妇科肿瘤患者(对照组),采用逆转录-聚合酶链反应(RT-PCR)分析EMSY m RNA,PCR-限制性片段长度多态性(RFLP)检测421+242A>G位点多态性,并进一步分析EMSY基因表达水平及多态性与预后的关系。结果:RT-PCR检测显示,研究组EMSY m RNA和乳腺癌易感基因2(BRCA2)m RNA相对表达量高于对照组,差异有统计学意义(t=33.592,P=0.000;t=25.046,P=0.000)。年龄、绝经情况、国际妇产科联盟(FIGO)分期、分化程度、病理类型、术后化疗及术后复发与EMSY mRNA表达水平相关(均P<0.05)。研究组EMSY基因421+242A>G位点3种基因型和2种等位基因分布频率与对照组比较差异有统计学意义(均P<0.05)。EMSY基因421+242A>G位点GG基因型总生存期、疾病无进展生存期与AA基因型比较差异有统计学意义(Log-rank χ~2=7.482,P=0.006;Log-rank χ~2=8.406,P=0.004)。EMSY mRNA高表达是影响患者总生存期的危险因素(OR=2.322,95%CI:1.277～5.031,P=0.027),AA基因型是影响患者疾病无进展生存期的危险因素(OR=1.882,95%CI:1.192～4.323,P=0.039)。结论:初步研究证实EMSY基因表达水平及421+242A>G位点多态性与早期卵巢上皮癌预后有关。展开更多
A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic effic...A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).展开更多
Tailoring the electronic metal-support interaction(EMSI)has attracted considerable interests as one of the most efficient approaches to improve both the activity and stability of metal catalysts in heterogeneous catal...Tailoring the electronic metal-support interaction(EMSI)has attracted considerable interests as one of the most efficient approaches to improve both the activity and stability of metal catalysts in heterogeneous catalysis.In this viewpoint,we illustrate the methodology and relevant fundamentals on the disentanglement,characterization,and interpretation of EMSI.Under the choice of monometallic catalyst over inert support,a combination of optimal experiment design,multimodal techniques,in situ characterization,with a comprehensive understanding of the underlying measurement protocols is highly desirable for a reliable determination of EMSI.Accordingly,not only the d-band filling but also d-band energy within the EMSI should be taken into consideration for providing general principles to guide the electron-promoting catalytic reaction.展开更多
CO oxidation has been studied for more than a century;however,molecular-level understanding of its activation protocol and related intermediates remains elusive.Here,we present a unified mechanistic and kinetic pictur...CO oxidation has been studied for more than a century;however,molecular-level understanding of its activation protocol and related intermediates remains elusive.Here,we present a unified mechanistic and kinetic picture of various electronic metal-support interactions within platinum-carbon catalysts via in situ spectroscopic/kinetic analyses and multi-scale simulations.Transient kinetic analysis and molecular dynamics simulations with a reactive force field provided a quantitative description of the competition between the oxygen association and oxygen dissociation mechanisms tuned by the interfacial charge distribution and CO coverage.Steady-state isotopic transient kinetic analysis and density functional theory calculations revealed a simultaneous shift in the rate-determining step(RDS)from O_(2)^(*)dissociation to O^(*)and CO^(*)and O_(2)^(*)and CO^(*)association.A de novo strategy from the interfacial charge distribution to the reaction mechanism,kinetics/thermodynamics of RDS,and,ultimately,catalytic performance was developed to quantitatively map the above CO activation mechanism with an order-of-magnitude increase in reactivity.The proposed catalytic picture and de novo strategy are expected to prompt the development of theories and methodologies for heterogeneous catalysis.展开更多
文摘目的:探讨EMSY基因表达水平和多态性与早期卵巢上皮癌患者预后的关系。方法:选取118例早期卵巢上皮癌患者(研究组)及63例良性妇科肿瘤患者(对照组),采用逆转录-聚合酶链反应(RT-PCR)分析EMSY m RNA,PCR-限制性片段长度多态性(RFLP)检测421+242A>G位点多态性,并进一步分析EMSY基因表达水平及多态性与预后的关系。结果:RT-PCR检测显示,研究组EMSY m RNA和乳腺癌易感基因2(BRCA2)m RNA相对表达量高于对照组,差异有统计学意义(t=33.592,P=0.000;t=25.046,P=0.000)。年龄、绝经情况、国际妇产科联盟(FIGO)分期、分化程度、病理类型、术后化疗及术后复发与EMSY mRNA表达水平相关(均P<0.05)。研究组EMSY基因421+242A>G位点3种基因型和2种等位基因分布频率与对照组比较差异有统计学意义(均P<0.05)。EMSY基因421+242A>G位点GG基因型总生存期、疾病无进展生存期与AA基因型比较差异有统计学意义(Log-rank χ~2=7.482,P=0.006;Log-rank χ~2=8.406,P=0.004)。EMSY mRNA高表达是影响患者总生存期的危险因素(OR=2.322,95%CI:1.277～5.031,P=0.027),AA基因型是影响患者疾病无进展生存期的危险因素(OR=1.882,95%CI:1.192～4.323,P=0.039)。结论:初步研究证实EMSY基因表达水平及421+242A>G位点多态性与早期卵巢上皮癌预后有关。
基金supported by the Natural Scientific Foundation of China(Nos.22127803,22174110,22203050)Natural Scientific Foundation of Shandong(No.ZR2022QB002)China Postdoctoral Science Foundation(No.2020T130331)。
文摘A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).
基金financially supported by the National Key R&D Program of China (2022YFA1503503 and 2022YFA1503504)the Natural Science Foundation of China (22038003,22178100,22178101 and 22008066)+1 种基金the Innovation Program of Shanghai Municipal Education Commission,the Program of Shanghai Academic/Technology Research Leader (21XD1421000)the Shanghai Science and Technology Innovation Action Plan (22JC1403800).
文摘Tailoring the electronic metal-support interaction(EMSI)has attracted considerable interests as one of the most efficient approaches to improve both the activity and stability of metal catalysts in heterogeneous catalysis.In this viewpoint,we illustrate the methodology and relevant fundamentals on the disentanglement,characterization,and interpretation of EMSI.Under the choice of monometallic catalyst over inert support,a combination of optimal experiment design,multimodal techniques,in situ characterization,with a comprehensive understanding of the underlying measurement protocols is highly desirable for a reliable determination of EMSI.Accordingly,not only the d-band filling but also d-band energy within the EMSI should be taken into consideration for providing general principles to guide the electron-promoting catalytic reaction.
基金supported by grants from the Natural Science Foundation of China(21922803,22178100,92034301,22008066,and 21776077)the China Postdoctoral Science Foundation(BX20190116)+2 种基金the Innovation Program of Shanghai Municipal Education Commission,the Program of Shanghai Academic/Technology Research Leader(21XD1421000)111 Project of the Ministry of Education of China(B08021)BL14W1(Shanghai Synchrotron Radiation Facility)for the beam time and assistance in the experiments.
文摘CO oxidation has been studied for more than a century;however,molecular-level understanding of its activation protocol and related intermediates remains elusive.Here,we present a unified mechanistic and kinetic picture of various electronic metal-support interactions within platinum-carbon catalysts via in situ spectroscopic/kinetic analyses and multi-scale simulations.Transient kinetic analysis and molecular dynamics simulations with a reactive force field provided a quantitative description of the competition between the oxygen association and oxygen dissociation mechanisms tuned by the interfacial charge distribution and CO coverage.Steady-state isotopic transient kinetic analysis and density functional theory calculations revealed a simultaneous shift in the rate-determining step(RDS)from O_(2)^(*)dissociation to O^(*)and CO^(*)and O_(2)^(*)and CO^(*)association.A de novo strategy from the interfacial charge distribution to the reaction mechanism,kinetics/thermodynamics of RDS,and,ultimately,catalytic performance was developed to quantitatively map the above CO activation mechanism with an order-of-magnitude increase in reactivity.The proposed catalytic picture and de novo strategy are expected to prompt the development of theories and methodologies for heterogeneous catalysis.
