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聚苯胺用作乙醇脱氢反应中的电子传递介质 被引量:1
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作者 穆绍林 杨一飞 《物理化学学报》 SCIE CAS CSCD 北大核心 2000年第9期830-834,共5页
The aniline solution containing nicotinamide adenine dinucleotide(NAD+ )was electrolyzed. Polyaniline film with NAD+ formed on the platinum thin plate. The thickness of the film was controlled by the charge consumed... The aniline solution containing nicotinamide adenine dinucleotide(NAD+ )was electrolyzed. Polyaniline film with NAD+ formed on the platinum thin plate. The thickness of the film was controlled by the charge consumed in the electrolysis, which was 0.006 C in this case. This electrode, used as an anode, was immersed in the solution containing aniline.A second film formed on this electrode during the electrolysis. The charge passed during the second electrolysis was 0.016 C. Alcohol dehydrogenase(ADH) was immobilized on the polyaniline film based on the isoelectric point of ADH and the doping principle of conducting polymers. The enzyme electrode has a good bioelectrochemical response to ethanol in the absence of a homogeneous mediator. The optimum pH, apparent Michaelis- Menten constant and optimum temperature of ADH immobilized in polyaniline film are 7.83, 7.5 mmol· dm- 3, and 30.6 ℃ , respectively.The activation energy of the enzyme- catalyzed reaction is 33.5 kJ· mol- 1. The response current of the enzyme electrode increases linearly with increasing concentration of ethanol below 2.4 mmol· dm- 3.This enzyme electrode can be used to determine the concentration of ethanol. 展开更多
关键词 脱氢酶聚苯胺 电子传递介质 乙醇 脱氢反应
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电荷分离和转移调控光催化剂稳定的Pickering乳液用于光-酶偶联催化
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作者 刘嘉立 戴慧聪 +3 位作者 刘鑫 任亦起 王茂弟 杨启华 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第2期114-122,共9页
人类社会可持续发展面临的能源紧缺和环境污染等问题迫切需要化工生产向绿色、低碳转型.酶催化反应因具有高活性、高选择性、专一性和低能耗等优点,在化工和制药行业得到了广泛应用.其中,氧化还原酶催化反应是还原醇类、胺类、酮类、酸... 人类社会可持续发展面临的能源紧缺和环境污染等问题迫切需要化工生产向绿色、低碳转型.酶催化反应因具有高活性、高选择性、专一性和低能耗等优点,在化工和制药行业得到了广泛应用.其中,氧化还原酶催化反应是还原醇类、胺类、酮类、酸类和无机底物的有效方法,该类反应通常需要采用还原型辅酶NAD(P)(H)作为还原剂,而NAD(P)(H)的昂贵价格严重制约了酶催化反应的工业化发展.受自然界中光合作用启发,光催化辅酶再生技术通过将酶催化与光催化技术耦合,旨在常温常压的温和反应条件下利用太阳能实现化学品的高效、绿色合成.迄今为止,虽然已有多种类型的光催化剂被用于光催化NAD(P)H再生,但电荷分离效率低、电子/质子转移效率低、有机底物在水溶液中的溶解度低以及酶失活等仍是光-酶偶联系统亟待解决的问题.针对酶失活的问题,研究人员通过Pickering乳液催化技术利用固体颗粒直接乳化两相体系,进而构建高效的生物催化反应体系,提高催化反应效率.Pickering乳液中固体乳化剂吸附在水油界面形成的稳固空间壳层不仅可以将酶限域,而且可以像在细胞中一样为酶提供合适的微环境和足够的自由度.另外,Pickering乳液的高反应界面也可以解决底物在反应相中溶解度低的问题,实现类似细胞的功能和长期连续流动的生物催化,是构建仿生微反应器的理想平台.本文采用电子传递介质固载化界面活性复合光催化剂为固体乳化剂,ADH和NAD+为生物催化单元,开发了一种基于Pickering乳液的人工光-酶偶联体系.针对光敏剂中电荷分离和转移以及光敏剂向NAD(P)H的电子转移效率低等问题,光催化体系采用溶胶凝胶法制备了具有异质结结构的共价聚合物-氧化钛复合材料光催化剂.共价聚合物和氧化钛之间的高界面面积有效地提高了电荷分离效率,共价聚合物含量优化后的光催化剂在可见光下NADH再生的TOF值可达5.5 mmol·g^(-1)·h^(-1),是对应纳米共价聚合物与无定形氧化钛物理混合物的27.5倍.随后进一步将电子传递介质[Cp^(*)Rh(bpy)H_(2)O]^(2+)(简称M)通过嫁接法固载到光催化剂上,电子传递距离的缩短和场效应有效促进了电荷分离以及光生电子从光催化剂到电子传递介质的传递,同时解决了电子传递介质回收繁琐和酶失活的问题.得到的光催化剂在可见光下催化NADH再生反应的TOF值为2.4 mmol·g^(-1)·h^(-1),远高于其对应的物理混合物.最后分别以长碳链硅烷修饰后具有界面活性的光催化剂为固体乳化剂,辅酶、酶以及牺牲剂为水相,正己烷及底物正丁醛为油相制备了光催化反应与酶催化反应偶联的Pickering乳液人工光-酶偶联体系.可见光下Pickering乳液有效催化还原正丁醛,在6 h内累积生成了16.1 mmol·L^(-1)的丁醇,相当于NADH再生循环14次.综上,本文以制备具有异质结结构的高效复合光催化剂为切入点,理性设计出了高效Pickering乳液光-酶偶联体系,为构建高效的光-酶偶联体系,缓解能源和环境危机、实现碳减排提供了一种有效策略. 展开更多
关键词 光催化 NADH再生 聚合物 电子传递介质 Pickering乳液
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Biogeochemistry of methanogenesis with a specific emphasis on the mineral-facilitating effects
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作者 Yahai Lu Wei Zhang 《Acta Geochimica》 EI CAS CSCD 2017年第3期379-384,共6页
The Earth surface contains various oxic and anoxic environments. The later include natural wetlands,river and lake sediments, paddy field soils and landfills. In the last few decades, the biogeochemical cycle of carbo... The Earth surface contains various oxic and anoxic environments. The later include natural wetlands,river and lake sediments, paddy field soils and landfills. In the last few decades, the biogeochemical cycle of carbon in anoxic environments, which leads to the production and emission of methane, a potent greenhouse gas in the atmosphere, has drawn great attentions from both scientific and public sectors. New organisms and mechanisms involved in methanogenesis and carbon cycling have been uncovered. Interspecies electron transfer is considered as a crucial step in methanogenesis in anoxic environments.Electron-carrying mediators, like H_2 and formate, are known to play the key role in electron transfer. Recently, it has been found that in addition to the conventional electron transfer via chemical mediators, direct interspecies electron transfer(DIET) can occur. In this Review, we describe the ecology and biogeochemistry of methanogenesis and highlight the effect of microbe-mineral interaction on microbial syntrophy. Recent advances in the study of DIET may pave the way towards a mechanistic understanding of methanogenesis and the influence of microbe-mineral interaction on this process. 展开更多
关键词 SYNTROPHY METHANOGENESIS Direct interspecies electron transfer MAGNETITE Wetland Paddy fields
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