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Fe^(Ⅴ)(O)(TAML)高价铁-氧反应中间体活化C-H键的机理转变的理论研究
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作者 周安然 傅志强 +2 位作者 曹萱雨 赵玉芬 王永 《Chinese Journal of Chemical Physics》 SCIE EI CAS CSCD 2022年第2期383-389,I0032-I0064,I0004,共41页
本文运用密度泛函理论对Gupta实验中脂肪族与芳香族底物C-H键氧化反应中所表现出的动力学差异进行深入的机理研究.计算表明,这种差异是山于两种底物(脂肪族的环己烷、2,3-二甲基丁烷两种底物以及芳香族的甲苯、乙苯和异内苯三种底物)C-... 本文运用密度泛函理论对Gupta实验中脂肪族与芳香族底物C-H键氧化反应中所表现出的动力学差异进行深入的机理研究.计算表明,这种差异是山于两种底物(脂肪族的环己烷、2,3-二甲基丁烷两种底物以及芳香族的甲苯、乙苯和异内苯三种底物)C-H键活化反应机理的不同所造成.对于脂肪族底物,活性反应中间体Fe^(V)(O)(TAML)进行C-H氧化是一种氢原子转移过程;而对于芳香族底物,C-H键活化则是一个质子耦合的电子转移过程,并且在过渡态具有质子转移特性,即质子耦合的电子转移过程.这种差异是由四氨基的TAML环和芳香底物的苯环之间存在的π-π相互作用产生的,具有“拉电子”效应,从而使得电子从芳香化底物转移到Fe^(V)(O)(TAML)氧化物的效率降低. 展开更多
关键词 C-H键活化 氢原子转移 质子耦合电子转移 密度泛函理论
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腹腔镜下肝右后叶切除术的体位综述
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作者 朱常琰 付志强 +3 位作者 胡玉秋 段金鑫 郑楚莲 周泉波 《中华肝脏外科手术学电子杂志》 CAS 2024年第2期231-234,共4页
进入微创外科时代以来,腹腔镜下肝右后叶切除术(LRPS)因为手术难度高,术中显露病灶困难,手术切除创面大,故较其它腹腔镜下肝叶切除术发展缓慢。手术体位的选择和Trocar孔的布局可以充分暴露术区,为手术成功提供保障。本综述总结了LRPS... 进入微创外科时代以来,腹腔镜下肝右后叶切除术(LRPS)因为手术难度高,术中显露病灶困难,手术切除创面大,故较其它腹腔镜下肝叶切除术发展缓慢。手术体位的选择和Trocar孔的布局可以充分暴露术区,为手术成功提供保障。本综述总结了LRPS不同手术体位特点和各个体位下手术时间、术中出血、术后住院时间、术后并发症的比较以及不同体位下术区暴露技巧的运用。鉴于国内还未将LRPS的手术体位标准化,笔者希望跟各位同仁分享关于LRPS下不同手术体位的经验,为各位医师选择合适的手术体位施行LRPS提供参考。 展开更多
关键词 腹腔镜 肝切除术 肝右后叶 手术体位
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Standard pancreatoduodenectomy versus extended pancreatoduodenectomy with modified retroperitoneal nerve resection in patients with pancreatic head cancer:a multicenter randomized controlled trial 被引量:4
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作者 Qing Lin Shangyou Zheng +21 位作者 Xianjun Yu Meifu Chen Yu Zhou Quanbo Zhou Chonghui Hu Jing Gu Zhongdong Xu LinWang Yimin Liu Qingyu Liu MinWang Guolin Li He Cheng Dongkai Zhou Guodong Liu zhiqiang fu Yu Long Yixiong Li Weilin Wang Renyi Qin Zhihua Li Rufu Chen 《Cancer Communications》 SCIE 2023年第2期257-275,共19页
Background:The extent of pancreatoduodenectomy for pancreatic head cancer remains controversial,and more high-level clinical evidence is needed.This study aimed to evaluate the outcome of extended pancreatoduodenectom... Background:The extent of pancreatoduodenectomy for pancreatic head cancer remains controversial,and more high-level clinical evidence is needed.This study aimed to evaluate the outcome of extended pancreatoduodenectomy(EPD)with retroperitoneal nerve resection in pancreatic head cancer.Methods:This multicenter randomized trial was performed at 6 Chinese highvolume hospitals that enrolled patients between October 3,2012,and September 21,2017.Four hundred patients with stage I or II pancreatic head cancer and without specific pancreatic cancer treatments(preoperative chemotherapy or chemoradiation)within three months were randomly assigned to undergo standard pancreatoduodenectomy(SPD)or EPD,with the latter followed by dissection of additional lymph nodes(LNs),nerves and soft tissues 270◦on the right side surrounding the superior mesenteric artery and celiac axis.The primary endpoint was overall survival(OS)by intention-to-treat(ITT).The secondary endpoints were disease-free survival(DFS),mortality,morbidity,and postoperative pain intensity.Results:TheR1 ratewas slightly lower with EPD(8.46%)thanwith SPD(12.56%).The morbidity and mortality rates were similar between the two groups.The median OS was similar in the EPD and SPD groups by ITT in the whole study cohort(23.0 vs.20.2 months,P=0.100),while the median DFS was superior in the EPD group(16.1 vs.13.2 months,P=0.031).Patients with preoperative CA19–9<200.0 U/mL had significantly improved OS and DFS with EPD(EPD vs.SPD,30.8 vs.20.9 months,P=0.009;23.4 vs.13.5 months,P<0.001).The EPD group exhibited significantly lower locoregional(16.48%vs.35.20%,P<0.001)andmesenteric LNrecurrence rates(3.98%vs.10.06%,P=0.022).The EPD group exhibited less back pain 6 months postoperation than the SPD group.Conclusions:EPD for pancreatic head cancer did not significantly improve OS,but patients with EPD treatment had significantly improved DFS.In the subgroup analysis,improvements in bothOS and DFS in the EPD armwere observed in patients with preoperative CA19–9<200.0 U/mL.EPD could be used as an effective surgical procedure for patients with pancreatic head cancer,especially those with preoperative CA19–9<200.0 U/mL. 展开更多
关键词 disease-free survival EXTENDED lymph nodes nerve resection overall survival pancreatic head cancer PANCREATODUODENECTOMY STANDARD
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QSAR模型应用域的表征方法 被引量:6
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作者 王中钰 陈景文 +1 位作者 傅志强 李雪花 《科学通报》 EI CAS CSCD 北大核心 2022年第3期255-266,共12页
定量构效关系(QSAR)模型是填补化学品环境安全数据空缺的重要工具.QSAR模型需要明确定义的应用域,才能合理地用于化学品管理.本文回顾了应用域的3种概念:描述符域、结构域和机理域.基于案例,重点介绍了基于分子指纹与相似性度量指标而... 定量构效关系(QSAR)模型是填补化学品环境安全数据空缺的重要工具.QSAR模型需要明确定义的应用域,才能合理地用于化学品管理.本文回顾了应用域的3种概念:描述符域、结构域和机理域.基于案例,重点介绍了基于分子指纹与相似性度量指标而计算结构域的方法、结构域的特点和优势.讨论了结构-活性地貌(structure-activity landscape)中呈现的活性悬崖(activity cliffs)现象及其成因.为了更好地理解描述符的适用性,解释QSAR机制及合理选择应用域的表征方法,有必要认识预测终点(endpoint)本质上所描述的系统,该系统复杂性和空间异质性,以及预测终点是否考察了系统行为的涌现. 展开更多
关键词 定量构效关系(QSAR) 应用域 描述符 活性悬崖 结构-活性地貌
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环境新污染物治理与化学品环境风险防控的系统工程 被引量:15
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作者 王佳钰 王中钰 +4 位作者 陈景文 刘文佳 崔蕴晗 傅志强 宋国宝 《科学通报》 EI CAS CSCD 北大核心 2022年第3期267-277,共11页
重视新污染物治理,是我国进入新发展阶段生态文明建设的必然要求.本文介绍了新污染物的概念、来源和特性,指出化学品管理不当及其环境释放是新污染物的主要来源.治理新污染物,需要分析化学品在人类社会子系统、新污染物在自然环境子系... 重视新污染物治理,是我国进入新发展阶段生态文明建设的必然要求.本文介绍了新污染物的概念、来源和特性,指出化学品管理不当及其环境释放是新污染物的主要来源.治理新污染物,需要分析化学品在人类社会子系统、新污染物在自然环境子系统中的源-流-汇;揭示化学品和新污染物对人类社会、生态系统、无机环境系统及各层次子系统造成的影响.以物质流分析、生命周期评价、计算毒理学、绿色化学等现代科技手段为核心要素的环境系统工程方法,有助于新污染物治理和化学品风险管理.物质流分析、生命周期评价可以追踪化学品在社会经济系统中循环流动的源-流-汇,进而定量其产生的潜在环境影响.计算毒理学通过计算机模型系统性地预测释放到环境中的化学污染物的分布和归趋,评估人类和生态物种暴露于新污染物的途径和水平,以及特定暴露条件下,化学污染物对人体和生态物种的有害影响.绿色化学则要求在开发全链条中减少有害原料使用和废物排放,并产出低危害性或无害的化学品.上述环境系统工程技术体系支撑化学品风险的源头防控,进一步结合过程控制和末端治理技术,有望实现对新污染物的有效治理. 展开更多
关键词 新污染物 化学品 风险防控 环境系统工程 源头预防
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Assessment of nomadic rice-duck complex ecosystem on energy and economy 被引量:5
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作者 Huabin Zheng Huang Huang +3 位作者 Diqin Li Xumeng Li zhiqiang fu Can Chen 《Ecological Processes》 SCIE EI 2014年第1期43-50,共8页
Introduction:Modern intensive rice production has brought a large amount of environmental pollution and do not guarantee the safety of rice quality.Thus,to improve the farmer's rice production model to reduce agro... Introduction:Modern intensive rice production has brought a large amount of environmental pollution and do not guarantee the safety of rice quality.Thus,to improve the farmer's rice production model to reduce agro-chemicals is of great importance to decrease pollution and to guarantee the security of food quality.Here,our experiments illustrated that nomadic rice-duck complex ecosystem(RD)could reduce energy input and increase both energy output and the values of the product safety index based on energy(PSI).Results:According to the results of our experiments,RD and rice monoculture production system(RM)were-0.6 and-0.78,respectively,which indicated that the safety potential of products in RD was higher than that of RM.Protein yield based on RD was significantly higher than that of RM.The output/input,gross income,and net income of RD were 15.26%,39.51%,and 44.80%,respectively,higher than that of RM;the data suggest that the economic benefits of RD were greater than that of RM.Conclusions:Consequently,as an intermediate-type technology,RD could become a feasible alternative that could reduce agro-chemical application rate without decreasing rice yield and increasing labor intensity.Furthermore,as an inheritance and development of the Chinese farming culture,RD is a classic Chinese farming technology withstanding more than 700 years of tests. 展开更多
关键词 ENERGY ECONOMY Intermediate-type technology Traditional farming technology in China PSI
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Microstructure and Mechanical Behavior of FeNiCoCr and FeNiCoCrMn High-Entropy Alloys Fabricated by Powder Metallurgy 被引量:3
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作者 Chenliang Chu Weiping Chen +3 位作者 Zhen Chen Zhenfei Jiang Hao Wang zhiqiang fu 《Acta Metallurgica Sinica(English Letters)》 SCIE EI CAS CSCD 2021年第4期445-454,共10页
The present work reports a systematic investigation on phase evolution,microstructure and microstructure-property relationship of two typical face-centered cubic(FCC)structured high-entropy alloys(HEAs),FeNiCoCr and F... The present work reports a systematic investigation on phase evolution,microstructure and microstructure-property relationship of two typical face-centered cubic(FCC)structured high-entropy alloys(HEAs),FeNiCoCr and FeNiCoCrMn,prepared via mechanical alloying(MA)followed by spark plasma sintering(SPS).Following 50 h of MA,the two HEAs consisted of a mixture of FCC and body-centered cubic phases.Following SPS,the bulk FeNiCoCr alloy showed a primary FCC phase with a small amount of Cr_(23)C_(6) and Cr_(2)O_(3) contaminants,while the bulk FeNiCoCrMn alloy was composed of a primary FCC phase with some(Cr,Mn)23C6 and MnCr_(2)O_(4) contaminants.The average grain size of the primary FCC phase in the bulk FeNiCoCr alloy was~416 nm,while that of the primary FCC phase in the bulk FeNiCoCrMn alloy was~547 nm.The yield strength,compressive strength and strain-to-failure of the bulk FeNiCoCr alloy are 1525 MPa,1987 MPa and 24.4%,respectively,whereas those of the bulk FeNiCoCrMn alloy are 1329 MPa,1761 MPa and 21.9%,respectively.It suggests that the bulk FeNiCoCrMn exhibited lower strength and plasticity in comparison with the bulk FeNiCoCr alloy.Clearly,the smaller grain size of the primary FCC phase in the FeNiCoCr alloy is mainly responsible for the better mechanical performance. 展开更多
关键词 High-entropy alloy Mechanical alloying MICROSTRUCTURE Strengthening CONTAMINANTS
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Genome assembly and transcriptome analysis provide insights into the antischistosome mechanism of Microtus fortis 被引量:1
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作者 Hong Li Zhen Wang +16 位作者 Shumei Chai Xiong Bai Guohui Ding Yuanyuan Li Junyi Li Qingyu Xiao Benpeng Miao Weili Lin Jie Feng Mingyue Huang Cheng Gao Bin Li Wei Hu Jiaojiao Lin zhiqiang fu Jianyun Xie Yixue Li 《Journal of Genetics and Genomics》 SCIE CAS CSCD 2020年第12期743-755,共13页
Microtus fortis is the only mammalian host that exhibits intrinsic resistance against Schistosoma japonicum infection.However,the underlying molecular mechanisms of this resistance are not yet known.Here,we perform th... Microtus fortis is the only mammalian host that exhibits intrinsic resistance against Schistosoma japonicum infection.However,the underlying molecular mechanisms of this resistance are not yet known.Here,we perform the first de novo genome assembly of M.fortis,comprehensive gene annotation analysis,and evolution analysis.Furthermore,we compare the recovery rate of schistosomes,pathological changes,and liver transcriptomes between M.fortis and mice at different time points after infection.We observe that the time and type of immune response in M.fortis are different from those in mice.M.fortis activates immune and inflammatory responses on the 10th day post infection,such as leukocyte extravasation,antibody activation,Fc-gamma receptor-mediated phagocytosis,and the interferon signaling cascade,which play important roles in preventing the development of schistosomes.In contrast,an intense immune response occurrs in mice at the late stages of infection and could not eliminate schistosomes.Infected mice suffer severe pathological injury and continuous decreases in cell cycle,lipid metabolism,and other functions.Our findings offer new insights into the intrinsic resistance mechanism of M.fortis against schistosome infection.The genome sequence also provides the basis for future studies of other important traits in M.fortis. 展开更多
关键词 Genome assembly Microtus fortis SCHISTOSOME IMMUNE TRANSCRIPTOME
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Oxidation reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane(BTBPE)by CompoundⅠmodel of cytochrome P450s 被引量:2
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作者 Zhongyu Wang zhiqiang fu +1 位作者 Qi Yu Jingwen Chen 《Journal of Environmental Sciences》 SCIE EI CAS CSCD 2017年第12期11-21,共11页
Alternative brominated flame retardants(BFRs) have become prevalent as a consequence of restrictions on the use of polybrominated diphenyl ethers(PBDEs). For risk assessment of these alternatives, knowledge of the... Alternative brominated flame retardants(BFRs) have become prevalent as a consequence of restrictions on the use of polybrominated diphenyl ethers(PBDEs). For risk assessment of these alternatives, knowledge of their metabolism via cytochrome P450 enzymes is needed.We have previously proved that density functional theory(DFT) is able to predict the metabolism of PBDEs by revealing the molecular mechanisms. In the current study, the reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane and structurally similar chemicals with the Compound I model representing the active site of P450 enzymes was investigated. The DFT calculations delineated reaction pathways which lead to reasonable explanations for products that were detected by wet experiments, meanwhile intermediates which cannot be determined were also proposed. Results showed that alkyl hydrogen abstraction will lead to bis(2,4,6-tribromophenoxy)ethanol, which may undergo hydrolysis yielding2,4,6-tribromophenol, a neurotoxic compound. In addition, a general pattern of oxidation reactivity regarding the 2,4,6-tribromophenyl moiety was observed among several model compounds. Our study has provided insights for convenient evaluation of the metabolism of other structurally similar BFRs. 展开更多
关键词 1 2-Bis(2 4 6-tribromophenoxy)ethane(BTBPE) Alternative brominated flame retardants Metabolic reactivity P450 Compound
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A unified optimal planner for autonomous parking vehicle
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作者 Dequan ZENG Zhuoping YU +2 位作者 Lu XIONG Peizhi ZHANG zhiqiang fu 《Control Theory and Technology》 EI CSCD 2019年第4期346-356,共11页
In order to reduce the controlling difficulty caused by trajectory meandering and improve the adaptability to parking into regular lots,a versatile optimal planner(OP)is proposed.Taking advantage of the low speed spec... In order to reduce the controlling difficulty caused by trajectory meandering and improve the adaptability to parking into regular lots,a versatile optimal planner(OP)is proposed.Taking advantage of the low speed specificity of parking vehicle,the OP algorithm was modeled the planning problem as a convex optimization problem.Collision-free constraints were formalized into the shortest distance between convex sets by describing obstacles and autonomous vehicle as affine set.Since employing Lagrange dual function and combining KKT conditions,the collision-free constraints translated into convex functions.Taking the national standard into account,5 kinds of regular parking scenario,which contain 0°,30°,45°,60°and 90°parking lots,were designed to verify the OP algorithm.The results illustrate that it is benefit from the continuous and smooth trajectory generated by the OP method to track,keep vehicle's stability and improve ride comfort,compared with A*and hybrid A*algorithms.Moreover,the OP method has strong generality since it can ensure the success rate no less than 82%when parking planning is carried out at the start node of 369 different locations.Both of evaluation criteria,as the pear error and RMSE in x direction,y axis and Euclidean distance d,and heading deviation 6,are stable and feasible in real tests,which illustrates that the OP planner can satisfy the requirements of regular parking scenarios. 展开更多
关键词 Optimal trajectory autonomous parking vehicle regular parking lots GENERALITY convex optimization
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