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用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程
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作者 姜润 乔泽龙 +1 位作者 许昊翔 曹达鹏 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第5期224-234,共11页
过渡金属M-N-C单原子催化剂(SACs),特别是Fe-N-C催化剂.已被认为是替代铂族金属进行氧还原反应(ORR)的最佳候选材料之一.实验研究和理论计算均表明,FeN_(4)配位结构是Fe-N-C材料的活性中心,但实验合成不可避免的构型缺陷明显影响了FeN_... 过渡金属M-N-C单原子催化剂(SACs),特别是Fe-N-C催化剂.已被认为是替代铂族金属进行氧还原反应(ORR)的最佳候选材料之一.实验研究和理论计算均表明,FeN_(4)配位结构是Fe-N-C材料的活性中心,但实验合成不可避免的构型缺陷明显影响了FeN_(4)中心的物理性质和催化活性.目前有些技术能可控地产生缺陷,这为原子级调控Fe-N-C催化剂局部结构提供可能.目前关于缺陷对Fe-N-C材料ORR活性影响的计算研究仍存在一些不足,如未考虑Fe位点的预吸附行为,没有系统考察各种缺陷结构对FeN_(4)中心的ORR活性的影响.因此,探索不同缺陷类型及其位置对ORR活性的影响,揭示缺陷Fe-N-C催化剂的结构-性能关系,对于进一步指导实验调控局部结构以获得高性能的Fe-N-C氧还原催化剂具有极其重要的意义.本文在FeN_(4)位点周围的二、三、四壳层内构建了13种含555777缺陷的Fe-N-C模型、16种含5775缺陷的Fe-N-C模型和14种含585缺陷的Fe-N-C模型,研究了缺陷对Fe-N-C材料ORR活性的影响,以及缺陷种类和位置对FeN_(4)位点ORR活性的影响.首先通过DFT计算确定了缺陷Fe-N-C材料在ORR过程中真正的活性位点结构,即当Fe-N键长>2.10Å时,Fe位点不会预吸附任何中间体,其活性中心为FeN_(4),速率决定步骤(PDS)为*OH质子化为H_(2)O(*OH+H^(+)+e^(-)→*+H_(2)O);而当Fe-N键长<2.10Å时,Fe位点会预吸附*OH物种形成Fe(OH)N_(4)活性中心,其PDS为O_(2)质子为*OOH(*+O_(2)+H^(+)+e-→*OOH).预吸附的*OH会通过调节Fe(OH)N_(4)位点(特别是Fe-dz^(2)和dyz轨道之间)和再吸附的*OH中间体之间的电子分布,降低Fe中心的吸附能力,从而提高ORR活性.也进一步揭示了Fe(dxz)-O(px)、Fe(dyz)-O(py)和Fe(dz^(2))-O(pz+s)轨道的杂化是缺陷Fe-N-C材料ORR活性的来源.为了在不进行DFT计算的情况下实现结构-性能关系的预测,基于Fe(OH)N_(4)位点的LFe-OH(Fe-OH的键长)和LFe-defect(Fe原子和缺陷的距离),建立了一个通用的仅与材料本征性能相关的结构描述符φ,该描述符可以准确和定量地预测缺陷Fe-N-C催化剂的ORR活性.研究发现,5775和585缺陷的大环毗邻Fe-N-C五边形环时通常会增加LFe-OH和LFe-defect,这显著调节了Fe-dyz轨道在费米能级上方的峰值位置,以接近最佳能级,从而提高了ORR性能.此外,提出了与Fe-N键长相关的指数α,以确认实验中是否形成主动设计的缺陷.综上,本文揭示了缺陷Fe-N-C材料的ORR活性来源,建立了一个内在的结构描述符φ,可以无需DFT计算准确预测ORR活性,为通过缺陷工程提高Fe-N-C的ORR性能提供了新思路. 展开更多
关键词 单原子催化剂 氧还原反应 缺陷工程 轨道杂化理论 预吸附 结构描述符
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CTX-Ⅰ, TRACP, ADAMTS-4 and MMPs-3 expression and their correlation with different syndromes of knee osteoarthritis
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作者 run jiang Tao Zhang +1 位作者 Jun Duan Zhen Mao 《Journal of Hainan Medical University》 2021年第23期21-25,共5页
Objective:To observe the expression of CTX-I(Ⅰcollagen C-terminal foreign body peptide)and TRACP(tartrate-resistant acid phosphatase)in different syndromes of knee osteoarthritis and their correlation with ADAMTS-4(p... Objective:To observe the expression of CTX-I(Ⅰcollagen C-terminal foreign body peptide)and TRACP(tartrate-resistant acid phosphatase)in different syndromes of knee osteoarthritis and their correlation with ADAMTS-4(polyproteoglycan enzyme-4)and MMPS-3(matrix metalloproteinase-3).Methods:A total of 98 patients diagnosed with knee osteoarthritis were enrolled from the Rehabilitation Pain Department and Rheumatology Department of Wuhan Caidian District People's Hospital.According to their syndrome types,they were divided into 40 cases of Yang deficiency and cold constipation type,28 cases of qi stagnation and blood stasis type,and 30 cases of kidney jing deficiency type.The contents of bone metabolism indexes,ADAMTS-4 and MMPS-3 in different syndromes of the three groups were compared.Correlation of bone metabolism indexes with ADAMTS-4 and MMPS-3.Results:There were statistically significant differences in the contents of CTX-I,TRACP,ADAMTS-4 and MMPS-3 among three groups with different syndromes(P<0.05).There was a positive correlation between CTX-I,TRACP,ADAMTS-4 and MMPS-3(P<0.05).The syndrome of qi stagnation and blood stasis was positively correlated with TRACP and ADAMTS-4,and negatively correlated with MMPS-3(P<0.05).The renal essence deficiency syndrome was positively correlated with CTX-I,ADAMTS-4 and MMPS-3(P<0.05).Bone metabolic indexes(CTX-I,TRACP)were positively correlated with ADAMTS-4 and MMPS-3(P<0.05).Conclusion:Different syndromes of knee osteoarthritis are correlated with bone metabolism indexes,ADAMTS-4 and MMPS-3,which can provide a certain objective basis for clinical TCM syndrome differentiation and classification。 展开更多
关键词 Knee osteoarthritis TCM syndrome Bone metabolism ADAMTS-4 Correlation study
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Clinical observation of electroacupuncture"Tongmin Point"combined with heat-sensitive moxibustion on knee osteoarthritis and its influence on blood lipid level and ADAMTS-4
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作者 Zhen Mao run jiang +3 位作者 Yong-Hong Liu Jun Duan Jian-Chao Fan Hong-Xing Zhang 《Journal of Hainan Medical University》 2021年第16期12-17,共6页
Objective:To observe the clinical effect of electroacupuncture"Tongmin point"combined with heat-sensitive moxibustion on knee osteoarthritis and its effect on blood lipid level,polyprotein polysaccharide enz... Objective:To observe the clinical effect of electroacupuncture"Tongmin point"combined with heat-sensitive moxibustion on knee osteoarthritis and its effect on blood lipid level,polyprotein polysaccharide enzyme-4(a disintegrin and metalloprotease with thrombospondin motifs,ADAMTS-4,matrix metalloproteinase-3(matrix metalloproteinase-3,);and MMPs-3)Impact.Methods:80 patients were randomly divided into two groups,40 cases per group,Treatment and control groups,The treatment group was given electroacupuncture combined with heat-sensitive moxibustion,Six times a week,Continuous treatment for 4 weeks;The control group was given intraarticular sodium hyaluronate,Once a week,continuous treatment for 4 weeks.Results:During the treatment period,Visual analogue scale visual analogue scale,VAS)show a downward trend,Intra-group comparisons,Differences were statistically significant(P<0.05);After 2 weeks of treatment,4 weeks of treatment and 2 weeks of follow-up,All the scores in the treatment group were lower than those in the control group(P<0.05).After treatment in two groups(The Western Ontario and Mc Master Universities Osteoarthritis Index,)of osteoarthritis index,University of Western Ontario WOMAC)The scores of each item decreased significantly,treatment group was better than the control group(P<0.05).After four weeks of treatment,(Total cholesterol,)Total cholesterol TC,triglycerides(Triglyceride,);and TG,LDL(Low density lipoprotein,);and LDL-C)A decrease in content,High density lipoprotein High density lipoprotein,HDL-C)Increased content,and the improvement was better than that of the control group(P<0.05).After treatment,the ADAMTS-4,MMPs-3 content decreased,Intergroup comparisons,Differences were statistically significant(P<0.05);The effective rate in the treatment group was 87.5%,The control rate was 60%,treatment group was more effective(P<0.05).Conclusions:Electroacupuncture"Tongmin point"combined with heat-sensitive moxibustion can obviously improve the symptoms of knee osteoarthritis patients,Regulate blood lipids,High security,It is worth popularizing in clinic. 展开更多
关键词 ELECTROACUPUNCTURE Tongmin point Thermosensitive moxibustion Clinical observation ADAMTS-4
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Effect of Jianpi Liqi recipe on diabetic dyspepsia and its effect on blood lipid level
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作者 Zhen Mao Cheng-Hong Zheng +1 位作者 run jiang Pai-Di Xu 《Journal of Hainan Medical University》 2021年第14期30-36,共7页
Objective:To observe the clinical effect of Jianpi Liqi Decoction on diabetic gastroparesis.Methods:80 patients were randomly divided into 2 groups,Treatment and control groups,40 cases per group,The treatment group u... Objective:To observe the clinical effect of Jianpi Liqi Decoction on diabetic gastroparesis.Methods:80 patients were randomly divided into 2 groups,Treatment and control groups,40 cases per group,The treatment group used Jianpi Liqi recipe,One dose a day,Take it twice,Six times a week,For 4 weeks;Control group with mosapride citrate,5 mg,each Three times a day,Take continuously for 4 weeks.Observe the two groups before treatment,2 weeks after treatment,4 weeks after treatment,Subjective symptoms(early satiety,abdominal distention,upper abdomen burning,upper abdomen pain)score;Before and after treatment,The contents of FBG,2 hPG,HbA1c,TC,GAS,MLT in the two groups.Results:The scores of early satiety,abdominal distention,burning sensation of upper abdomen and pain of upper abdomen were decreased,Intra-group comparisons,Differences were statistically significant(P<0.05);After treatment,the gastric emptying rate increased in both groups,A more significant increase in the treatment group(P<0.05);Treatment group after treatment TC,TG,LDL-C decreased more significantly(P<0.05);After treatment,the GAS,MLT content of both groups increased significantly,Intergroup comparisons,and the difference was statistically significant(P<0.05).Conclusion:Jianpi Liqi Decoction is effective in treating Diabetic gastroparesis,High security,it is worth clinical use. 展开更多
关键词 Diabetic dyspepsia Jianpi Liqi prescription Clinical observation Randomized controlled
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聚合物接枝纳米粒子两亲性分子在溶液中自组装行为的模拟研究 被引量:4
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作者 李青霄 王铮 +2 位作者 尹玉华 蒋润 李宝会 《高分子学报》 SCIE CAS CSCD 北大核心 2018年第10期1351-1358,共8页
利用布朗动力学模拟方法,研究了聚合物接枝纳米粒子组成的两亲性分子在溶液中的自组装行为.这种两亲性分子可通过自组装形成多种结构.考察了两亲性分子浓度、疏溶剂纳米粒子直径、聚合物链和纳米粒子之间的相互作用、聚合物链的链长以... 利用布朗动力学模拟方法,研究了聚合物接枝纳米粒子组成的两亲性分子在溶液中的自组装行为.这种两亲性分子可通过自组装形成多种结构.考察了两亲性分子浓度、疏溶剂纳米粒子直径、聚合物链和纳米粒子之间的相互作用、聚合物链的链长以及溶剂性质对组装结构的影响.构建了随不同参数变化的形态相图.我们观察到2种囊泡形成路径,并且通过控制两亲性分子浓度,能实现2种路径之间的转变,并将本研究的模拟结果与已报道的相关实验观测和模拟结果做了比较. 展开更多
关键词 聚合物接枝纳米粒子两亲性分子 自组装 溶液 囊泡形成路径
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接枝点分布对ABA三嵌段共聚物刷自组装形态的影响 被引量:1
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作者 徐纪华 陈印启 +3 位作者 尹玉华 蒋润 王铮 李宝会 《高分子学报》 SCIE CAS CSCD 北大核心 2020年第6期632-640,I0005,共10页
采用模拟退火方法研究了接枝点分布对ABA三嵌段共聚物刷在选择性溶剂中自组装形态的影响,其中溶剂对A单体为不良溶剂,对B单体为良溶剂.主要以高接枝密度体系为例,研究了均匀接枝、区域随机接枝和全随机接枝时共聚物刷聚集体的形态,分别... 采用模拟退火方法研究了接枝点分布对ABA三嵌段共聚物刷在选择性溶剂中自组装形态的影响,其中溶剂对A单体为不良溶剂,对B单体为良溶剂.主要以高接枝密度体系为例,研究了均匀接枝、区域随机接枝和全随机接枝时共聚物刷聚集体的形态,分别构建了3种接枝方式下体系的相图,并考察了接枝点分布对ABA三嵌段共聚物刷形态的影响机制.研究表明3种接枝方式下,ABA三嵌段共聚物刷体系形成相图大致相同,并且单层A聚集体结构与双层A聚集体结构在相图中的分界线相同;接枝点分布主要对底部的A富集层胶束形态产生影响,而对顶层胶束形态影响很小.在随机接枝时,接枝点的密度涨落导致底层A聚集体不易形成较规则的形态,其长程有序性较低. 展开更多
关键词 三嵌段共聚物刷 模拟退火 自组装 接枝点
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MMP-2在眼组织中的表达与检测 被引量:1
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作者 蒋润 周激波 《中华眼视光学与视觉科学杂志》 CAS CSCD 2021年第4期312-316,共5页
基质金属蛋白酶-2(MMP-2)是基质金属蛋白酶(MMPs)家族中的一员,它的异常表达近年来被证明与多种疾病的发生发展有关,其在眼科疾病中起着重要作用。现笔者对MMP-2在眼组织中的表达、检测以及在眼病中的作用进行总结。
关键词 基质金属蛋白酶 基质金属蛋白酶-2 近视 青光眼 黄斑变性 白内障
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ABA三嵌段共聚物在油/水乳化液滴中自组装行为的Monte Carlo模拟研究 被引量:2
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作者 郑玲飞 王铮 +2 位作者 尹玉华 蒋润 李宝会 《高分子学报》 SCIE CAS CSCD 北大核心 2019年第9期915-924,I0002,共11页
采用Monte Carlo方法,研究了溶剂蒸发条件下对称ABA三嵌段共聚物在油/水乳化液滴中的自组装行为,并与AB双嵌段共聚物体系的模拟结果进行了比较.构建了随表面活性剂浓度(φ)和B嵌段体积分数(fB)变化的相图;观察到无孔粒子、闭孔粒子、开... 采用Monte Carlo方法,研究了溶剂蒸发条件下对称ABA三嵌段共聚物在油/水乳化液滴中的自组装行为,并与AB双嵌段共聚物体系的模拟结果进行了比较.构建了随表面活性剂浓度(φ)和B嵌段体积分数(fB)变化的相图;观察到无孔粒子、闭孔粒子、开孔粒子、胶囊和胶束等形态,以及不同fB下bridge链的比例随φ的变化.研究表明,当fB≤1/2时,随着φ的增大,体系出现从无孔粒子到闭孔粒子再到开孔粒子的形态转变;当fB>1/2时,在较大的φ区间范围内形成胶束.上述形态中bridge链的比例均远小于对应的体相值.由于链构象的影响,当fB≤1/2时,ABA三嵌段共聚物体系中没有出现胶囊结构,这与AB双嵌段共聚物体系不同.相同形态粒子的比表面积大致落在相同的p区间内,表明粒子的形态很大程度上决定了其比表面积;而通过计算粒子的形成能,证实体系中的表面活性剂是多孔粒子形成的关键.这些均与AB双嵌段共聚物体系相同. 展开更多
关键词 ABA三嵌段共聚物 自组装 表面活性剂 乳化液滴 多孔粒子
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循环溶剂退火条件下柱状相组成的两嵌段共聚物薄膜自组装行为的模拟研究 被引量:1
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作者 胡卨俊 郝金龙 +3 位作者 王铮 尹玉华 蒋润 李宝会 《高分子学报》 SCIE CAS CSCD 北大核心 2021年第10期1379-1389,共11页
采用蒙特卡洛模拟研究了体相形成柱状相的两嵌段共聚物薄膜在循环溶剂退火条件下的自组装行为.结果表明,在循环溶剂退火条件下,溶剂蒸发速率、溶剂选择性和有效薄膜厚度与柱状相周期的匹配性都会影响形成垂直柱状结构的表面选择性窗口(... 采用蒙特卡洛模拟研究了体相形成柱状相的两嵌段共聚物薄膜在循环溶剂退火条件下的自组装行为.结果表明,在循环溶剂退火条件下,溶剂蒸发速率、溶剂选择性和有效薄膜厚度与柱状相周期的匹配性都会影响形成垂直柱状结构的表面选择性窗口(β窗口).当溶剂蒸发速率在一定范围内时,β窗口随蒸发速率的增大而增大.溶剂对长嵌段的选择性越强,形成垂直柱状结构的β窗口越宽.当溶胀比约为1.5时的薄膜厚度与柱状相周期不匹配时更利于形成垂直柱状结构.通过对链节均方位移曲线的分析发现,在循环溶剂退火条件下高分子链节在垂直方向的扩散始终快于平行方向,因此链节优先沿垂直方向聚集,从而促进了垂直柱状结构的形成.循环溶剂退火条件下,β窗口比溶剂退火条件下的宽,同时大幅度减少了退火时间. 展开更多
关键词 嵌段共聚物 循环溶剂退火 取向 柱状相
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溶剂对嵌段共聚物AB/均聚物C共混体系增容效果的模拟研究
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作者 刘志瑶 王铮 +2 位作者 尹玉华 蒋润 李宝会 《高分子学报》 SCIE CAS CSCD 北大核心 2019年第11期1229-1237,共9页
采用模拟退火方法研究了两嵌段共聚物AB/均聚物C共混体系在溶液中的相行为.关注于C与A/B为排斥作用时溶剂对它们的增容作用.考察了溶剂的加入量(以聚合物链节的浓度Φ表征)、加入C的体积分数f_c、C与AB的链长比X、C与AB排斥作用、溶剂S... 采用模拟退火方法研究了两嵌段共聚物AB/均聚物C共混体系在溶液中的相行为.关注于C与A/B为排斥作用时溶剂对它们的增容作用.考察了溶剂的加入量(以聚合物链节的浓度Φ表征)、加入C的体积分数f_c、C与AB的链长比X、C与AB排斥作用、溶剂S与C吸引作用强度等对体系相容性及组装行为的影响.构建了作为Φ和f_c的函数的形态相图.研究表明,当X小于0.5,且C与A/B间的排斥作用不是很强时,加入强亲A/C的溶剂能够提高体系的相容性.并获得了层状相、连通相、层中柱状相、核壳柱状相等相结构,其中层中柱状相是纯两嵌段共聚物体系中没有的结构.在高Φ值的体系中,C分布在A/B的界面上;在低Φ值的体系中,C分布在A相区中.研究表明,X越小,C与A、B嵌段的接触数越大,均聚物越容易与两嵌段共聚物相容;X越大,加入少量的均聚物体系就发生宏观相分离,且增加B/C间的排斥作用会降低体系的相容性.体系形态结构的转变以及微相分离到宏观相分离的转变都是体系的能量与熵之间竞争的结果.溶液体系中宏观相分离与熔体时的不同,溶液中部分C链节在AB的界面上以减小AB的接触,而熔体时全部的C链节均与AB宏观相分离. 展开更多
关键词 嵌段共聚物 均聚物 共混 溶剂 增容
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Morphological transformations of diblock copolymers in binary solvents: A simulation study
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作者 Zheng Wang Yuhua Yin +1 位作者 run jiang Baohui Li 《Frontiers of physics》 SCIE CSCD 2017年第6期97-108,共12页
Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on th... Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on the morphological transformation depending on the fraction of the selective solvent Cs2, the concentration of the polymer Cp, and the polymers-solvent interactions εij (i = A, B; j = S1, S2). Morphology diagrams are constructed as functions of Cp, Cs2, and/or εAs2. The copolymer morpho- logical sequence from dissolved → sphere → rod → ring/cage → vesicle is obtained upon increasing Cs2 at a fixed Cv. This morphology sequence is consistent with previous experimental observations. It is found that the selectivity of the selective solvent affects the self-assembled microstructure signifi- cantly. In particular, when tile interaction εBS2 is negative, aggregates of stacked lamellae dominate the diagram. The mechanisms of aggregate transformation and the formation of stacked lamellar ag- gregates are discussed by analyzing variations of the average contact numbers of the A or B monomers with monomers and with molecules of the two types of solvent, as well as the mean square end-to-end distances of chains. It is found that the basic morphological sequence of spheres to rods to vesicles and the stacked lamellar aggregates result from competition between the interfacial energy and the chain conformational entropy. Analysis of the vesicle structure reveals that the vesicle size increases with increasing Cp or with decreasing Cs2, but remains almost unchanged with variations in εAS2. 展开更多
关键词 SELF-ASSEMBLY diblock copolymers binary solvents morphological transformation simulated annealing
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