Electrostatic effect on electron transfer between cytochrome b5 and cytochrome c

The binding and electron transfer between wild type, E44A, E56A, E44/56A, E44/48/56A/D60Aand F35Y variants of cytochrome b5 and cytochrome c were studied. When mixed with cytochrome c, the cytochrome b5E44/48/56A/D60A did not show the typical UV-vis difference spectrum of absorption, indicating that the alteration ofthe surface electrostatic potential obviously influenced the spectrum. The electron transfer rates of wild type cytochromeb5, its variants and cytochrome e at different temperature and ionic strength exhibited an order of F35Y > wild type >E56A > E44A > E44/48/56A/D60A. The enthalpy and entropy of the reaction did not change obviously, suggestingthat the mutation did not significantly disturb the electron transfer conformation. The investigation of electron transfer rateconstants at different ionic strength demonstrated that electrostatic interaction obviously affected the electron transfer pro-cess. The significant difference of Cyt b5 F35Y and E44/48/56A/D60A from the wild type protein further confirmed thegreat importance of the electrostatic interaction in the protein electron transfer.     

铀酰离子-细胞色素b_5复合物的分子动力学模拟

铀酰离子(UO_2~(2+))的生物学毒性是由于它能与蛋白质形成稳定的复合物而破坏了蛋白的正常功能。通过使用分子建模和分子动力学(molecular dynamics,MD)模拟,对铀酰离子-细胞色素b_5复合物(UO_2~(2+)-cyt b_5)进行了结构预测。模拟结构显示,UO_2~(2+)通过配位和氢键作用结合到Cyt b_5中谷氨酸Glu37和Glu43,导致Cyt b_5的动力学行为发生轻微改变,而对蛋白整体结构几乎不产生影响。这些现象与Cyt b_5的体内形成以及作为电子传递蛋白的生物功能紧密相联。这些原子水平上理论信息的获得,为铀酰离子的毒性机制,尤其是涉及Cyt b_5的细胞凋亡,提供了深刻内涵。     

Electrostatic orientation during electron transfer between flavodoxin and cytochrome c

Various studies have shown that reaction rates between reversibly binding electron transfer proteins depend strongly on solution ionic strength. These observations suggest that intermolecular electrostatic interactions are important in facilitating the formation of a productive reaction complex. A recently examined system involves the reduction of vertebrate cytochrome c by bacterial flavodoxin. Although this is a nonphysiological reaction, it proceeds with rates typical for natural partners and is similarly inhibited at high ionic strengths. Here we describe computational studies which examine the role of electrostatics in the formation of a putative reaction complex between flavodoxin and cytochrome c. The results suggest that electrostatic interactions preorient the molecules before they make physical contact, facilitating the formation of an optimal reaction complex.     

Preparation and characterization of some surface negatively charged residue mutants of cytochrome b5

Site-directed mutagenesis was used to obtain seven variants of tryptic fragment of bovine liver cytochrome b_m5 (cyt b₅), in which the negatively charged residues around the heme exposed edge of cyt b₅ were replaced by hydrophobic amino acid alanine. Double-site mutants, triple-site mutants and even quadruple-site mutants were obtained. DNA sequencing and molecular weight measurements of the mutant proteins both confirmed that these site-directed mutagenesises were successfully performed. Spectroelectrochemistry of these mutant proteins revealed that the apparent redox potentials of these mutant proteins caused a positive shift of 2–10 mV. The global structure of these mutant proteins did not show much difference from that of the wild type cyt b₅, providing a solid base for the further study on the roles of the proteins’ surface charges.     

Assignment of Soret MLCT band of reduced form of copper binuclear cluster in cytochrome c oxidase film

Low concentration of dithionite results in the reduction of Cu-Cn binuclear and heine a active sites of the cytochrome c oxidase thin solid film immersed in the acidic phosphate buffer, but Fe-Cu binuclear center keeps in the oxidation state. It manifests as a negative peak at 426 nm and a positive one at -408 nln in the difference spectra induced by dithionite. The former implies decrease of the oxidized form of heme a center, that is, Fea^3 →Fea^2 . And the latter results from the contribution of metal-ligand charge transfer (MLCT) transition in the reduced binuclear Cu-Cu cluster, rather than from that of heine a center. This stronger Soret MLCT band must be helpful to overcoming the difficulty in distinguishing the weaker copper sign from the stronger one of iron when studying copper-iron protein.     

燃煤电厂电除尘PM10和PM2.5的排放控制I:电除尘选型及工业应用

 针对电除尘细颗粒物(PM_2.5)排放控制,提出利用电除尘指数指导电除尘本体和电源设计选型技术的原理和方法,并介绍电除尘改造的应用案例.通过优化电除尘指数、采用三相高压电源开展电除尘改造和选型.通过电除尘和脱硫塔除雾器的同步改造,可以实现烟囱出口颗粒物排放浓度低于5 mg/m³,同时,PM_2.5 (直径2.5 μm 以下的颗粒物)排放浓度低于2.5 mg/m³.示范工程还表明当电除尘器出口PM₁₀(直径10 μm 以下的颗粒物)排放在6~30 mg/m³时,PM_2.5占PM₁₀比例为6%至20%;当PM₁₀排放在5~15 mg/m³时,PM_2.5排放可低于2.5 mg/m³.     

细胞色素c在硅基有序介孔材料SBA-15上直接电化学行为

用水热法合成了硅基有序介孔分子材料SBA-15,研究了细胞色c(Cyt c)在SBA-15修饰玻碳(GC)电极表面的直接电化学行为.结果表明,在pH 7.0磷酸缓冲溶液中(PBS),细胞色素c在SBA-15修饰电极表面表现出一对准可逆的氧化还原峰,电位差ΔE为87 mV,式电位E0′为0.275 V,峰电流的大小与循环伏安扫描速度成正比,说明细胞色素c在电极表面过程是受表面控制.固定在电极上的细胞色素c能促进过氧化氢的催化还原,显示出较高的亲和力,为过氧化氢传感器的研制提供理论依据.     

燃煤电厂电除尘PM10和PM2.5的排放控制IV:采用二维PIV 除尘

 利用粒子成像测速法(PIV)和电子低压冲击仪(ELPI),研究实验室规模的电除尘器(ESP)内电场强度、电晕放电功率和气流场等因素对PM₁₀(粒径小于10 μm 的颗粒物)分级收尘效率.电除尘器为线-板式电极结构,其中板-板间距为200 mm,高电压电极为单根或双根.实验颗粒物采用艾灸烟作为示踪粒子,气体流量85 m³/h,颗粒物初始质量浓度33 mg/m³左右.实验结果表明,随着电场强度或电晕放电功率的增加,在高压电晕极线周围气流场从有规律的单个涡旋发展为相互作用的多个涡旋,优化电晕放电离子风分布是提高PM₁₀收集效率和降低电耗的关键.从颗粒物个数浓度、外加电场或电晕放电功率看,可将电除尘器性能以电场强度为3 kV/cm 为界分为2 个区域.当电场强度低于3 kV/cm 时,分级除尘效率随着电场强度或电除尘指数的增加而增加.然而,当电场强度远大于3 kV/cm 时,收尘效率基本不变或降低.     

细胞色素C在电沉积PAMAM-HA修饰电极上的电化学行为

采用双电位阶跃法在铂电极上电沉积制备聚酰胺胺一羟基磷灰石复合涂层,研究了细胞色素C在复合涂层修饰的铂电极上的电化学行为,循环伏安测量结果表明,细胞色素C在修饰电极上呈现一对氧化还原电流峰,表现为扩散控制的准可逆的电子转移过程、重点探讨了涂层的厚度对促进细胞色素C电子传递的影响．对电化学交流阻抗谱的测试结果进行了相关的电化学参数的拟合,讨论了该修饰电极促进细胞色素C电子传递可能的机制．     

Investigation of electron transfer across the ice/liquid interface by scanning electro- chemical microscopy

Charge transfer across a liquid/liquid (L/L) interface is not only related to chemical sensors, drug delivery and phase transfer catalysis, but also significant for mimicking biological membranes[1—3]. The thermodynamics, kinetics and mechanism regarding of this type of heterogeneous transfer process have been intensively investigated in the past three decades. An external potential is usually applied to polarizing the interface in the case of conventional electrochemistry at L/L interfaces.…     

燃煤电厂电除尘PM10和PM2.5的排放控制II:电除尘电源改造与PM10和PM2.5的排放(以660 MW 机组为例)

 通过对比660 MW 燃煤锅炉电除尘改造前后细颗粒物(PM_2.5)和颗粒物(PM₁₀)的排放,讨论电除尘改造的必要性及可行性.四电场电除尘器在常规单相电源供电下,PM₁₀和PM_2.5的排放浓度分别在63 和23 mg/m³左右,总排放在75 mg/m³左右;采用三相高压电源时PM₁₀和PM_2.5的排放可控制在15 和2.5 mg/m³以下,总排放在18 mg/m³左右,PM₁₀和PM_2.5的排放分别减排76%和89%以上.     

Effects on the early development of the pearl sac by cytochrome c, yolk lecithin and polyvinyplyrro

Mantle pieces ofHyriopisis cumingii was treated by three kinds of solution, These mantle pieces were inserted together with paraffin nucleuses into the connective tissue of three groups ofHyriopisis cumingii. These operated animals were cultured in a pool for a month. Several pearl sacs were put out and immersed by Bouin's solution after every five days. Sections of each animals were made by histological method. Those without treatment were in a control group. Observations of these sections showed that cytochrome c and yolk lecithin have an accelerated roles on pearl sac development and pearl layer secretion. No effects on pearl sac development by polyvinyplyrrolidone (PVP). Zheng Junying:born in May, 1966, Lecturer     

Investigation of electron transfer across the ice/liquid interface by scanning electrochemical microscopy

The study of interfacial electron transfer (ET) reaction between feericinium (Fc^ ) produced in situ in 1,2-dichloroethane (DCE) and ferrocyanide in ice matrix under low temperatures by the scanning electrochemical microscopy (SECM) is reported .Tetrabutylammonium (TBA^ ) is used as the common ion (potential -determining ion )in both phases to control the interfacial potential difference,The potential drop across the liquid/liquid interface can be quantitatively adjusted by changing the ratio of concentrations of TBA^ between beh two phases ,The apparent hetero-gencous rate constants for Fc^ reduction by Fe(CN)6^4- at the interface under different temperatures have been obtained by a best-fit analysis,where the experimental approach curves are fitted to the theoretical simulated curves.A sharp change has been observe for heterogeneous rate constants around the freezing point of the aqueous phase,which reflects the phase transition process.     

Single-sphere model for solvent reorganization energy and its application to electron transfer

Electron transfer (ET) is an elementary process in redox reactions, and it has been intensively studied for decades. The ET complexes in which the 7,7,8,8-tetra- cyanoquinodimethane (TCNQ) acts as the electron acceptor, whereas Cu, Ag, etc. as the electro…     

非晶态Ni-p合金中电子转移问题的DFT研究

根据Ni - p非晶态结构的短程有序及结构中不存在P P直接相连的实验事实 ,选择了Ni4P和Ni6 P原子簇模型 ,用B3LYP方法选用不同的基函数对其进行了高水平的量子化学计算。结果表明 ,弥散函数在研究中起着关键的作用 ,电子由P原子向Ni原子转移。没有充足的证据可以表明电子由Ni原子向P原子转移。这与实验结果相一致     

燃煤电厂电除尘PM10和PM2.5的排放控制III:电除尘电源及小分区改造与PM10和PM2.5的排放(以4×330 MW机组为例)

 讨论了4 台典型电除尘改造和细颗粒物(PM_2.5)排放控制,对四电场电除尘器通过本体小分区和电源改造实现了颗粒物(PM₁₀)和细颗粒物(PM_2.5)的超低排放控制.仅对五电场电除尘器进行电源改造,即可实现PM₁₀和PM_2.5的超低排放,电除尘出口PM₁₀和PM_2.5可分别控制在15 和2 mg/m³以下.脱硫塔对PM₁₀有较好的捕集效果,但对PM_2.5的去除几乎没有效果.电除尘振打引起的二次飞扬过程及烟气温度也影响PM₁₀和PM_2.5的排放,当烟气温度从150~160℃降低到约110℃时,电除尘出口及脱硫塔出口的PM_2.5均在2 mg/m³以下.     

ZrAl4 C4、Zr2 Al4 C5和Zr3 Al4 C6结构、弹性和电子性质对比

采用第一性原理方法,对比研究了Zr-Al-C体系纳米层状化合物ZrAl₄C₄、Zr₂Al₄C₅和Zr₃Al₄C₆的结构、弹性和电子性质,并探寻其规律性。结果表明：从晶体结构角度分析,三种材料均可看作由(ZrC)和(Al₄C₃)两个独立单元以不同比例组合而成,可统一表示为(ZrC)_nAl₄C₃(n=1,2,3),且三者的晶格常数a值近似相等,晶格常数c随着ZrC含量的增大而变大。三种化合物弹性性质中,体模量、剪切模量、杨氏模量的大小关系满足：ZrAl₄C₄< Zr₂Al₄C₅< Zr₃Al₄C₆。通过对三者电子态密度和Mulliken布局分析得到,ZrAl₄C₄、Zr₂Al₄C₅和Zr₃Al₄C₆均具有金属键、离子键和共价键的特征,且Zr-C键强于Al-C键,从微观电子角度解释了在(ZrC)_nAl₄C₃(n=1,2,3)体系中Zr-C键含量越高则对应材料的体模量、剪切模量、杨氏模量等弹性性质越大。本文计算结果与已有实验值和理论值吻合较好。     

F修饰对SiO2@TiO2亲疏水性及光催化性能的影响

采用两步法制备了氟修饰疏水性F-SiO_2@TiO_2材料.以三乙氧基氟硅烷(TEFS)为硅源,采用后嫁接的方法在短孔道MCM-41小球表面引入F原子,再利用醇热法在F-MCM-41小球表面生长TiO_2纳米晶颗粒.利用透射电子显微镜(TEM)、X射线粉末散射(XRD)、X射线光电子能谱(XPS)、N_2气吸脱附等手段表征了材料的物相组成和表面结构.研究表明:所制备的氟修饰F-SiO_2@TiO_2纳米复合材料为核壳结构,具有较大的比表面积、较好的介孔结构及较佳的热稳定性.同时,TiO_2纳米颗粒在F-MCM-41小球表面分散均匀、结晶度高、颗粒尺寸小且均一、与F-SiO_2结合牢固.重量吸附实验和光催化实验进一步证实F修饰可抑制水的吸附有利于提高F-SiO_2@TiO_2材料的疏水性和对气相有机污染物的光催化性能.     

Acidic catalysis of microporous polyoxometalate H3PW12O40/Sio2 in acetal reaction between benzaldehyde and ethylene glycol

Microporous Keggin-type polyoxometalate material was synthesised by supporting H3PW12O40 into a silica matrix via a sol-gel technique. The silica-supported 12-tungstophosphoric acid ( H₃PW₁₂O₄₀/Sio₂ ) obtained is insoluble and readily separable porous materials with uniform micropores (0. 57 nm) and a high specific surface area (350. 5 m2/g) in oxygen-containing polar solvents. H3PW12 O4o/Si02 was characterized by infrared spectrophotometer (IR). ultraviolet-visible spectrophotometer (UV-vis). inductively coupled plasma (ICP)> thermogravimetric analysis (TGA) and Brunner-Emmett-Teller method (BET) measurements. H3PWi204o/Si02 obtained catalyzed the acetal reaction between benzaldehyde and ethylene glycol to produce 2-phenyl-l > 3-dioxolane more efficiently than the typical solid acids such as SO4 /ZrO2' Nafion-H and H-ZSM-5. Conversion was 93. 8% for benzaldehyde during the reaction period of 2 h. H₃PW₁₂O₄₀/Sio₂ kept its initial activity during three times of reuse. The initial acetal reaction follows a second-order kinetics model at 298 K.     

TiO2/SiO2/GQDs双层增透膜的制备及其在太阳能板中的应用

采用溶胶-凝胶法制备了SiO₂ 和TiO₂ 纳米溶胶,采用水热法制备了石墨烯量子点（graphene quantum dots,GQDs）。为进一步提高光伏太阳能板的透光率,设计了一种TiO₂/SiO₂/GQDs双层增透膜结构。探究了薄膜的结构、自清洁性能和增透性能,并进一步讨论了GQDs在增透性中的作用。结果表明,SiO₂-TiO₂/TiO₂-GQDs结构的双层薄膜厚度为120 nm时,太阳能板上的光透过率由未涂敷的85%增加至95%。接触角实验和室外耐环境性能实验测试表明,复合膜层接触角为10°,并具有良好的亲水性和耐环境性能。此外,户外实验结果表明,涂覆该薄膜的太阳能电板发电效率提高6%。由此说明双层增透膜可有效地提高太阳能电池板的光能利用率和使用寿命,可高效地利用太阳能。