Conductive wiring of immobilized photosynthetic reaction center to electrode by cytochrome C

The photosynthetic reaction center (RC) found in photosynthetic bacteria is one of the most advanced photoelectronic devices developed by nature. However, after immobilization on the electrode surface, the efficiency of electron transfer (ET) between the RC and the electrode is relatively low. This inefficiency has limited the possibility of using the RC for technological applications. Here we show that photoinduced electron transfer between the immobilized RC and a gold electrode can be increased by several tens-fold by incorporation of cytochrome c into the RC-self-assembled monolayer (SAM)-electrode complex. The effect does not depend on the initial redox state of the cytochrome and seems to be the result of the formation of a complex between the RC and the cytochrome c serving as an ET wire. This observation opens the possibility for electrochemical analysis of the special pair in the RC protein that is deeply buried inside the protein globe and is barely electrically addressable from the electrode surface.     

Polymer ultrathin films with immobilized photosynthetic reaction center proteins

Properties of mixed monolayers of lipid-photosynthetic reaction center proteins (RC) were studied and the optimum conditions for stable films fabrication were determined. The following synthetic: N-acryloylphosphatidylethanolamine (ACPE), tetracosa-11, 13-diinoic acid (TDA), pentacosa-10, 12-diinoic acid (PDA), dioctadecyldienoylphosphatidylcholine (DODL) and natural lipids: L-α-phosphatidylethanolamine (PE), L-α-phosphatidylcholine (PC) were used. The rate of polymerization of the mixed ACPE-RC and TDA-RC monolayers is lower in comparison with corresponding values for pure lipid-like monomers on air/water interface. The optical and photoelectrical measurements provide evidence for an orientation of RCs on interface. Hydrophilic H-subunit in monomeric and polymeric ACPE-RCs, and monomeric DODL-RCs monolayers is preferentially oriented towards water as in the pure RC monolayers. Opposite orientation was found with TDA-RCs and PDA-RCs films. No preferential orientation for lipid-RCs from C. aurantiacus monolayers was found because of the RCs having low assymmetry of hydrophobic subunits (M and L).     

Graphitic encapsulation of catalyst particles in carbon nanotube production

A new model is proposed for the encapsulation of catalyst metal particles by graphite layers that are obtained, for example, in low-temperature chemical vapor deposition production of carbon nanotubes (CNTs). In this model graphite layers are primarily formed from the dissolved carbon atoms in the metal-carbide particle when the particle cools. This mechanism is in good agreement with molecular dynamics simulations (which show that precipitated carbon atoms preferentially form graphite sheets instead of CNTs at low temperatures) and experimental results (e.g., encapsulated metal particles are found in low-temperature zones and CNTs in high-temperature regions of production apparatus, very small catalyst particles are generally not encapsulated, and the ratio of the number of graphitic layers to the diameter of the catalyst particle is typically 0.25 nm(-1)).     

多壁碳纳米管修饰玻碳电极测定铜离子

以多壁碳纳米管(MWCNTs)修饰玻碳电极为工作电极,采用阳极溶出线性扫描法研究了铜离子的电化学测定方法。探讨了MWCNTs修饰层数、富集电位、富集时间、溶液pH、支持电解质对峰电流的影响。实验表明,铜离子浓度在1.0×10-8~1.0×10-5mol·L-1范围内与峰电流呈良好的线性关系,检测限为2.0×10-9mol·L-1,且该电极具有良好的稳定性和抗干扰能力。     

Type 1 reaction center of photosynthetic heliobacteria

The reaction center (RC) of heliobacteria contains iron-sulfur centers as terminal electron acceptors, analogous to those of green sulfur bacteria as well as photosystem I in cyanobacteria and higher plants. Therefore, they all belong to the so-called type 1 RCs, in contrast to the type 2 RCs of purple bacteria and photosystem II containing quinone molecules. Although the architecture of the heliobacterial RC as a protein complex is still unknown, it forms a homodimer made up of two identical PshA core proteins, where two symmetrical electron transfer pathways along the C2 axis are assumed to be equally functional. Electrons are considered to be transferred from membrane-bound cytochrome c (PetJ) to a special pair P800, a chlorophyll a-like molecule A0, (a quinone molecule A1) and a [4Fe-4S] center Fx and, finally, to 2[4Fe-4S] centers FA/FB. No definite evidence has been obtained for the presence of functional quinone acceptor A1. An additional interesting point is that the electron transfer reaction from cytochrome c to P800 proceeds in a collisional mode. It is highly dependent on the temperature, ion strength and/or viscosity in a reaction medium, suggesting that a heme-binding moiety fluctuates in an aqueous phase with its amino-terminus anchored to membranes.     

聚吡咯／多壁碳纳米管修饰电极对多巴胺的测定

制备了聚吡咯/多壁碳纳米管(PPy/MWNT)复合膜修饰电极。研究了神经递质多巴胺(DA)在该修饰电极上的电化学行为。实验表明,PPy/MWNT复合膜修饰电极对DA的电催化作用优于PPy修饰电极。在pH=4.10的0.2mol/L醋酸-醋酸钠缓冲溶液中,DA在该修饰电极上的CV曲线于0.31V和0.28V处出现一对灵敏的氧化还原峰,峰电位差△Ep比裸玻碳电极降低58mV,比PPy修饰电极降低28mV,峰电流显著增加。氧化峰电流ipa与DA浓度在1.0×10-4~7.8×10-8mol/L范围内呈良好的线性关系,线性回归方程为ip(μA)=0.2512 1.2300C(×10-5mol/L),相关系数r=0.9992,检出限为3.9×10-8mol/L。常见物质对DA的检测无干扰,DA注射液样品检测回收率为94%~104%。     

多壁碳纳米管阵列电极的循环伏安行为

用化学气相沉积法在多孔氧化铝模板中沉积有序碳纳米管阵列并制成电极.由循环伏安法实验得知,扩散控制电位下的电活性离子难以常规的扩散速度到达碳纳米管的内壁深处,绝大部分的碳纳米管内壁面积在这样的实验条件下未能充分利用,但临近管口处的一部分内壁对扩散有一定的贡献.对于电极/电解质界面的双电层电容而言,碳纳米管的所有内壁都有所贡献,其电容量可达68.7mF*cm-2(表观面积),表明碳纳米管电极具有制作超级电容器的重要应用价值.     

Amperometric biosensing of glutamate using carbon nanotube based electrode

Amperometric biosensing of glutamate using nanobiocomposite derived from multiwall carbon nanotube (CNT), biopolymer chitosan (CHIT), redox mediator meldola’s blue (MDB) and glutamate dehydrogenase (GlDH) is described. The CNT composite electrode shows a reversible voltammetric response for the redox reaction of MDB at −0.15 V; the composite electrode efficiently mediates the oxidation of NADH at −0.07 V, which is 630 mV less positive than that on an unmodified glassy carbon (GC) electrode. The CNTs in the composite electrode facilitates the mediated electron transfer for the oxidation of NADH. The CNT composite electrode is highly sensitive (5.9 ± 1.52 nA/μM) towards NADH and it could detect as low as 0.5 μM of NADH in neutral pH. The CNT composite electrode is highly stable and does not undergo deactivation by the oxidation products. The electrode does not suffer from the interference due to other anionic electroactive compounds such as ascorbate (AA) and urate (UA). Separate voltammetric peaks have been observed for NADH, AA and UA, allowing the individual or simultaneous determination of these bioanalytes. The glutamate biosensor was developed by combining the electrocatalytic activity of the composite film and GlDH. The enzymatically generated NADH was electrocatalytically detected using the biocomposite electrode. Glutamate has been successfully detected at −0.1 V without any interference. The biosensor is highly sensitive, stable and shows linear response. The sensitivity and the limit of detection of the biosensor was 0.71 ± 0.08 nA/μM and 2 μM, respectively.     

Voltammetric determination of disinfectants at multiwalled carbon nanotube modified glassy carbon electrode

The voltammetric method for simultaneous determination of some disinfectants at glassy carbon electrode modified with multiwalled carbon nanotubes is presented. The examined compounds are: 2-phenylphenol, 4-chloro-3-methylphenol, triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol and 2-mercaptobenzothiazole. The measurements has been performed using cyclic voltammetry and differential pulse voltammetry in Britton-Robinson buffers as supporting electrolytes. The modification of electrode surface with multiwalled carbon nanotubes enhances the peak current. It is possible to measure mixtures of two compounds (2-phenylphenol and 2-mercaptobenzothiazole, 4-chloro-3-methylphenol and 2-mercaptobenzothiazole, triclosan and 2-mercaptobenzothiazole) in the solution of pH 9.9, which provides the best separation of oxidation peaks.     

Reversible electrochemistry of DNA on multi-walled carbon nanotube modified electrode

Calf thymus DNA was electrochemically oxidized at a multi-walled carbon nanotube modified electrode. The potentials for DNA oxidation at pH 7.0 were 0.71 and 0.81 V versus SCE, corresponding to the oxidation of guanine and adenine residues, respectively. The initial 6e-oxidation of adenine, observed in the first scan, resulted a quasi-reversible 2e-redox process of the oxidation product in the following scans.     

胡椒碱在碳纳米管修饰电极上的电化学行为研究

研究了胡椒碱在碳纳米管修饰电极上的电化学行为,在pH为6.4的磷酸盐缓冲溶液中,胡椒碱在-1.12V(vs.SCE)处有一灵敏的还原峰.与裸电极相比,还原峰电位明显正移,峰电流显著增加,表明该修饰电极对胡椒碱的还原反应具有明显的催化作用.峰电流与胡椒碱的浓度在10-6～10-5mol/L范围内呈良好的线性关系(r=0.995),检出限为2.0×10-7mol/L.同时,计算了电荷转移数和扩散系数,考查了修饰电极的重现性,7次平行测量的RSD为4.96%.     

Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode

A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments.     

碳纳米管内P—Ylide反应的理论研究

碳纳米管空腔不仅可以改变填充到其内部分子的性质,而且对其内部的SN2取代反应有促进或抑制作用,因而被视为一种新型的“固体溶剂”．本文通过密度泛函理论研究了CH2O和PH3CH2在气相、苯溶液和碳纳米管空腔内的[2＋2]加成反应．结果表明,与气相相比,碳纳米管空腔对于[2＋2]环加成反应影响不大,这是因为所研究的[2＋2]环加成反应中,反应物并不是轴对称的,不同于SN2取代反应的一维线性排列,所以具有较大轴向极化率的碳纳米管对[2＋2]环加成反应影响较小．     

Theoretical study of the P-Ylide reaction in the carbon nanotube

Recent studies have shown that the inner phase of carbon nanotubes (CNTs) can not only change the properties of molecules inside the tube, but also enhance or restrain the S_N2 reactions. Thus, the CNTs can be considered a form of solid solvent. In this paper, we study the [2+2] cycloaddition reaction between CH₂O and PH₃CH₂ in the gas phase, benzene solution and inner phase of CNT using the density functional theory (DFT). The results indicate that the inner phase of CNT has little effect on the [2+2] cycloaddition reaction. This can be explained as that while taking the linear arrangement for S_N2 reaction, the reactants do not possess the axial symmetry for the studied [2+2] cycloaddition reaction. Therefore, although the CNT has large axial polarizability, it can exert little influence on the [2+2] cycloaddition reaction. Our studies will be helpful for further understanding of the inner phase chemistry of CNTs.     

Calorimetric approach to metabolic carbon conversion efficiency in soils

Soil carbon is the largest reservoir of organic carbon on the planet and CO₂ production by soil thus has potentially large effects on atmospheric CO₂. Carbon sequestration in soil is determined by the metabolic efficiency (substrate carbon conversion efficiency) of soil micro-organisms. That could be measured by calorespirometric methodology (parallel measurement of metabolic heat rate and CO₂ production rate) and by theoretical thermodynamic models. Carbon conversion efficiency of the glucose degradation reaction in soil is calculated from both the calorespirometric ratio of heat rate to CO₂ rate and from energy and mass balance models combined with calorimetric heat rates. Results obtained, 0.77 and 0.75, are in good agreement.     

Novel carbon nanotube composites by grafting reaction with water-compatible redox initiator system

Multi-walled carbon nanotubes were chemically functionalized with methacrylic acid and methacrylated bovine serum albumin by free radical grafting reaction to obtain novel nanocomposites. The nanotubes were synthesized by aerosol-assisted chemical vapor deposition, and then the monomers were directly grafted by the action of hydrogen peroxide/ascorbic acid redox pair which allows operating in water-compatible and eco-friendly environment without the generation of any toxic reaction by-product. A multi-technique approach was used to evaluate the effectiveness of the grafting process employing Fourier transform infrared, Raman, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analyses. Considering the high importance of methacrylate polymers and bovine serum albumin, the proposed nanocomposites could be of great applicability in biomedical and pharmaceutical fields.     

Direct electron transfer of glucose oxidase on the carbon nanotube electrode

The direct electrochemistry of redox enzymes (or proteins) has received more and more attention[1—9]. These studies developed an electrochemical basis for the investigation of enzyme structure, mechanisms of redox transformations of enzyme molecules and metabolic processes involving redox transformations. From these studies, one can also find potential appli-cations of enzymes in biotechnology. For example, if an enzyme immobilized on electrode surface is ca-pable of the direct electron tra…