Voltammetric studies of microcrystalline C60 adhered to a carbon electrode surface and placed in contact with aqueous electrolyte containing potassium ions

The reduction of microcrystalline C₆₀ fullerene, adhered at a carbon electrode and immersed in aqueous electrolyte, has been studied under various voltammetric conditions. This work reports mainly the voltammetric studies carried out principally in electrolyte containing potassium ions. Comparison of adherence techniques, such as solvent casting and mechanical transfer methods, are made to assess if the type of adhered techniques has any significant influence on the observed electrochemistry. The solvent casting method is found to produce three peaks in the potential for C₆₀^0/n- redox couple as compared to a single and large peak produced when a mechanical transfer technique is employed. When the reduction potential of microcrystalline C₆₀ in the presence of K⁺ is compared with other cations, such as Li, Na, Rb and Cs, it is observed that the shift of reduction potential follows the change in the hydration energy in the order Cs>Rb>K>Na>Li. In a mixed electrolyte study of CsCl/KCl, the reduction potential and peak shape of C₆₀^0/n- redox couple during cyclic voltammetry is observed to change with concentration of the cations and the observed electrochemistry can be attributed to a cation-exchange mechanism. The reduction of C₆₀ is irreversible in aqueous electrolyte containing alkaline cations as the re-oxidation process does not produce any observed electro-activity. Evidence of the formation of a passive coating of K _n C₆₀ fulleride, which does not appear to undergo dissolution is obtained under cyclic voltametric conditions. This coating remains electrochemically active in the presence of tetrabutylammonium ions in acetonitrile. Scan rate, chronocoulometric, and scanning electron microscopic studies provide evidence of the presence of a surface process involving solid–solid transformation.     

Carbon dioxide reduction under visible light: a comparison of cadmium sulfide and titania photocatalysts

1. Download : Download high-res image (135KB)
2. Download : Download full-size image

     

ITSTUDIES ON THE EFFECT OF UREA ON THE COMPATIBILITY OF PMMA/PVC MIXTURES IN DMF BY A DILUTE- SOLUTION VISCOMETRY METHOD

The interaction between poly(methymethacrylate) (PMMA) and poly(vinyl chloride) (PVC) has been studied indilute urea solutions of dimethylformamide (DMF) at 28℃ using a dilute solution viscometry method. The results show thatthe polymer mixtures are compatible in DMF solution in the absence of urea. The influence of urea addition on the degree ofcompatibility of the polymer mixtures has been studied in terms of the compatibility parameters (△b_m and △[η]_m). It wasfound that the compatibility of the polymer mixtures is decreased with increasing urea addition, passing through a minimumat 0.5 M urea.     

盐类和温度对非离子型表面活性剂溶液粘度的影响

研究在各种盐类存在下,温度对非离子表面活性剂(OP类)溶液粘度的影响,发现相对粘度的对数值与1/T呈线性关系,从直线的斜率可得活化自由能ΔG′。由热力学关系式可计算粘性流体的活化焓ΔII′和活化熵ΔS′。用所得热力学函数对胶束型态的转化进行了讨论。     

Synthesis of functionalized rab GTPases by a combination of solution- or solid-phase lipopeptide synthesis with expressed protein ligation

Prenylated proteins with non-native functionalities are generally very difficult to obtain by recombinant or enzymatic means. The semisynthesis of preparative amounts of prenylated Rab guanosine triphosphatases (GTPases) from recombinant proteins and synthetic prenylated peptides depends largely on the availability of functionalised prenylated peptides corresponding to the proteins' native structure or modifications thereof. Here, we describe and compare solution-phase and solid-phase strategies for the generation of peptides corresponding to the prenylated C terminus of Rab7 GTPase. The solid-phase with utilisation of a hydrazide linker emerges as the more favourable approach. It allows a fast and practical synthesis of pure peptides and gives a high degree of flexibility in their modification. To facilitate the analysis of semisynthetic proteins, the synthesised peptides were equipped with a fluorescent group. Using the described approach, we introduced fluorophores at several different positions of the Rab7 C terminus. The position of the incorporated fluorescent groups in the peptides did not influence the protein-ligation reaction, as the generated peptides could be ligated onto thioester-tagged Rab7. However, it was found that the positioning of the fluorescent group had an influence on the functionality of the Rab7 proteins; analysis of the interaction of the semisynthetic Rab7 proteins with REP (Rab escort protein) and GDI (guanosine diphosphate dissociation inhibitor) molecules revealed that modification of the peptide side chains or of the C-terminal isoprenoid did not significantly interfere with complex formation. However, functionalisation of the C terminus was found to have an adverse effect on complex formation and stability, possibly reflecting low structural flexibility of the Rab GDI/REP molecules in the vicinity of the lipid-binding site.     

STUDY ON STYRENE-BUTADIENE BLOCK COPOLYMER FOR THE MODIFICATI0N OF TIRE TREAD

This paper mainly deals with the design and synthesis of a novel styrene-butadieneblock copolymer. When this copolymer is used in the tread portion of tyres, it can improvewet skid resistance and reduce rolling resistance without sacrificing its general physical-mechanical properties. The visco-elastic curve of tire tread using the novel copolymer asits rubber portion was showed. Reactivity ratios for two monomers in the polymerizingsystem were calculated. The diagrams of differelitial, integral and finite difference calculithroughout the whole molecular chain were presented. The influence of the micro- andmacro-structure of the copolymer chain on wet skid resistance and rolling resistance wasdiscussed     

四氟乙烯-乙烯溶液沉淀聚合

本文编制了一个简易计算机程序,测定了氟氯烷溶液沉淀聚合体系中四氟乙烯-乙烯共聚竞聚率:40℃:γC_2H_4=0.156±0.001,γC_2F_4=0.022±0.01670℃:γC_2H_4=0.197±0.001,γC_2F_4=0.055±0.020在此聚合体系中,聚合温度和共聚物组成比对链的规整性都有明显影响。当乙烯在45～55mol%范围内时,共聚物的IR随组成比而变化,利用此规律可简便地测定共聚物的组成比。     

丙烯酸甲酯/4-丙烯酰胺基-2,2,6,6-四甲基哌啶光共聚合体系的竞聚率和序列分布研究

以丙烯酸甲酯(MA,M1)和4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP,M2)溶液光共聚合体系为研究对象,采用1H-NMR手段测定了MA/AATP共聚物的组成,用Mayo-Lewis积分法和扩展Kelen-Tüdos方法计算的竞聚率分别为0.88相似文献   

Rheology of polystyrene solutions around the coil overlapping concentration: A phenomenological description of stresses in simple shear flow

Linear viscoelasticity behavior is described with the sum of two terms for polystyrene solutions in tricresyl phosphate around the coil overlapping concentration (K. Osaki, T. Inoue, & T. Uematsu, J Polym Sci Part B: Polym Phys 2001, 39, 211). One is a Rouse–Zimm (RZ) term represented by the Zimm theory with arbitrarily chosen values of the hydrodynamic interaction parameter and the longest relaxation time (τ_RZ). The other (the L term) consists of a relaxation mode with a single relaxation time (τ_L > τ_RZ) and a high‐frequency limiting modulus proportional to the square of the concentration. In this study, we describe the viscosity (η) and first normal stress coefficient (Ψ₁) in steady shear with simple formulas. The stress due to the L term is assumed to be given by a Kaye, Bernstein, Kearsley, and Zapas (K‐BKZ) equation with the damping function h(γ) = (1 + 0.2γ²)^?1/2, where γ is the magnitude of shear. Contributions to η and Ψ₁ from the RZ term are derived from the RZ model, in which the relaxation time in steady flow is given by τ_st = τ + (τ_RZ ? τ)/(1 + 0.35τ_RZ γ˙) instead of τ_RZ. Here, γ˙ is the rate of shear, and τ is the τ_RZ value at the infinite dilution limit. η and Ψ₁ at various concentrations for two polystyrene samples (with molecular weights of 2890 and 8420 kg mol^?1) are well described with parameters derived from dynamic viscoelasticity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1038–1045, 2002     

Binding of hexacyanoferrate(II) by aliphatic amines in aqueous solution

The stability of hexacyanoferrate(II)-amine(methylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine) was determined potentiometrically. Species Fe(CN)₆(A)H _j ^(j–4) (A=amine) are formed in all the systems investigated, with j=1...n+2 (n=number of aminogroups). Some other complexes Fe(CN)₆(A)_iH_j (with i>1) were also found. The stability of these complexes is fairly high: the full protonated amine species, show for the reaction Fe(CN)₆ ^4- + H_nAⁿ⁺ = Fe(CN)₆(A)H_n ^(n-4) an equilibrium constant given by logK=0.686+2.10n. Factors affecting the stability are discussed in comparison with similar systems, together with the importance of interferences.