Cyclic Voltammograms of Ferrocene on Multi‐Walled Carbon Nanotubes (MWCNTs)‐Modified Edge Plane Pyrolytic Graphite (EPPG) Electrode in Room Temperature Ionic Liquids (RTILs) of 1‐Ethyl‐3‐Methylimidazolium Tetrafluoroborate (EMIBF4)

In this work, the electrochemical behavior of ferrocene (Fc) was investigated by cyclic voltammetry (CV) in room temperature ionic liquids (RTILs) of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄) on glass carbon (GC), edge plane pyrolytic graphite (EPPG) and multi‐walled carbon nanotube (MWCNTs)‐modified EPPG electrodes, respectively. The results demonstrated that on GC electrode, pairs of well‐defined reversible peaks were observed, while for the electrode of EPPG, the peak potential separation (ΔE_p) is obviously larger than the theoretical value of 59 mV, hinting that the electrode of EPPG is distinguished from the commonly used electrode, consistent with the previous proposition that EPPG has many “defects”. To obtain an improved electrochemical response, multi‐walled carbon nanotubes (MWCNTs) were modified on the electrode of EPPG; the increased peak current and promoted peak potential separation not only proved the existence of “defects” in MWCNTs, but also supported that “creating active points” on an electrode is the main contribution of MWCNTs. Initiating the electrochemical research of Fc on the MWCNTs‐modified EPPG electrode in RTILs and verifying the presence of “defects” on both EPPG and MWCNTs using cyclic voltammograms (CVs) of Fc obtained in RTILs of EMIBF₄, is the main contribution of this preliminary work.     

Nitrile-functionalized pyridinium ionic liquids: synthesis, characterization, and their application in carbon-carbon coupling reactions

A series of relatively low-cost ionic liquids, based on the N-butyronitrile pyridinium cation [C(3)CNpy](+), designed to improve catalyst retention, have been prepared and evaluated in Suzuki and Stille coupling reactions. Depending on the nature of the anion, these salts react with palladium chloride to form [C(3)CNpy](2)[PdCl(4)] when the anion is Cl(-) and complexes of the formula [PdCl(2)(C(3)CNpy)(2)][anion](2) when the anion is PF(6)(-), BF(4)(-), or N(SO(2)CF(3))(2)(-). The solid-state structures of [C(3)CNpy]Cl and [C(3)CNpy](2)[PdCl(4)] have been established by single-crystal X-ray diffraction. The catalytic activity of these palladium complexes following immobilization in both N-butylpyridinium and nitrile-functionalized ionic liquids has been evaluated in Suzuki and Stille coupling reactions. All of the palladium complexes show good catalytic activity, but recycling and reuse is considerably superior in the nitrile-functionalized ionic liquid. Inductive coupled plasma spectroscopy reveals that the presence of the coordinating nitrile moiety in the ionic liquid leads to a significant decrease in palladium leaching relative to simple N-alkylpyridinium ionic liquids. Palladium nanoparticles have been identified as the active catalyst in the Stille reaction and were characterized using transmission electron microscopy.     

The influence of cetyltrimethyl ammonium bromide on electrochemical properties of thyroxine reduction at carbon nanotubes modified electrode

The effect of cetyltrimethyl ammonium bromide (CTAB) on the electrochemical behaviors of thyroxine at a glassy carbon electrode (GCE) modified with single-walled carbon nanotubes (SWNTs) was investigated. At the SWNTs film-coated GCE, a well-defined oxidation peak of thyroxine at 0.78 V was obtained, but the reduction peak of thyroxine was indiscernible. When trace CTAB was added to the working solution, the reduction current could be greatly enhanced and the oxidation current remained stable. The reaction mechanisms for the reduction of thyroxine were explored by chronocoulometry. Thyroxine might form particular ion complex with CTAB via the interaction between iodine atoms on thyroxine and bromide ions in CTAB, which made the concentration of thyroxine at the surface of the modified electrode increased and the electron transfer rate enhanced. The proper mechanisms for the enhanced reduction of thyroxine in the present of CTAB were explored by several electrochemical techniques including cycle voltammetry linear sweep voltammetry and others. It was concluded that the special interactions between the thyroxine CTAB and SWNTs resulted in the increase of the reduction peak current. All results indicated that two iodine atoms on the thyroxine and four electrons were involved the reduction process which was irreversible and two iodine ions produced. In this system, the sensitive reduction peak of thyroxine at 0.3 V was employed to determine thyroxine and a low detection limit of 2x10(-8) mol/L was obtained for 2 min accumulation at 0.9 V. The SWNTs coated GCE had good stability and reproducibility.     

磺胺甲恶唑在二硫化钼纳米片修饰电极上的电化学行为

采用了研磨后超声和离心分离方法制备了二硫化钼纳米片,通过原子力显微镜(AFM)和扫描电子显微镜(SEM)对不同离心速度分离的二硫化钼纳米片进行了表征。使用循环伏安法(CV)和差分脉冲伏安法(DPV)在磺胺甲恶唑溶液中对二硫化钼纳米片修饰的玻碳电极进行了电化学行为研究。结果显示,磺胺甲恶唑在二硫化钼修饰电极的循环伏安图上有一对氧化还原峰。其峰电流值与扫描速度的平方根成正比,是扩散控制过程。DPV扫描结果显示,磺胺甲恶唑的峰电流与其浓度之间存在着明显的线性关系。研磨超声方法制备出的二硫化钼纳米片层材料在电极上能够加速电子的转移和传输,从而有效提高峰电流值,为进一步研制准确测定磺胺甲恶唑电化学传感器提供了一种可选择的材料和电化学分析方法。     

色谱法在三氯半乳蔗糖合成中的应用

采用薄层色谱和柱色谱法，选择优化展开体系，有效地分析了三氯半乳蔗糖中间体2，3，6，3′，4′-五氧乙酰蔗糖混合物，并证实该混合物中杂质为三苯甲醇，为三氯半乳蔗糖的合成研究取得了重要发现。     

Novel approach to synthesizing hydrophobically associating copolymer using template copolymerization: the synthesis and behaviors of acrylamide and 4-(omega-propenoyloxyethoxy) benzoic acid copolymer

Hydrophobically associating copolymers of acrylamide (AM) with a small amount of 4-(omega-propenoyloxyethoxy) benzoic acid (PEBA, <2.5%) were synthesized by template copolymerization in the presence of poly(allylammonium chloride) (PAAC) as a template in an aqueous medium. These template copolymers exhibited remarkable thickening properties due to the effective hydrophobic association, which were similar to those copolymers with a multiblock structure obtained by the micellar process. The pH of the reaction medium and the molecular weight of the template strongly influenced the thickening properties of the products. In the experimental range, the higher the PEBA content, the larger the thickening capacity of these hydrophobic copolymers. The aggregate behaviors of these copolymers were studied by fluorescence, transmission electron microscopy (TEM), and light scattering techniques. The apparent critical interpolymer aggregate concentration (cac) of the copolymer solution was about 0.5 g/dL. As the concentration of the copolymer became higher than the cac, the aggregates changed their morphology from small hollow spheres to big flower-shaped aggregates. All the above results indicated that the template copolymerization gave access to a very simple and powerful means for the preparation of hydrophobically associating copolymers and other functional polymer materials.     

Co-C bond dissociation energy and reaction volume change of 2',5'-dideoxyadenosylcobalamin studied by laser-induced time-resolved photoacoustic calorimetry

Time resolved photoacoustic calorimetry (PAC) was applied to a study of the photolysis of a coenzyme B(12) analog 2',5'-dideoxyadenosylcobalamin, which lacks an -OH group at the 2' position of ribofuranose ring. In aqueous solution, we report for the first time the quantum yield Phi(d) (0.25+/-0.02), Co-C bond dissociation energy (BDE; 31.8+/-2.5 kcal mol(-1)) and reaction volume change deltaV(R) (6.5+/-0.5 ml mol(-1)) due to conformation changes of the corrin ring and its side chains accompanying the cleavage of the Co-C bond. These values for the analog are very similar to those for the natural cofactor. Based our results and previous studies, a possible explanation for the similarity in their structure and properties versus the large difference in their enzymatic activity is discussed.     

Liquefaction of corn stover and preparation of polyester from the liquefied polyol

This research investigated a novel process to prepare polyester from corn stover through liquefaction and crosslinking processes. First, corn stover was liquefied in organic solvents (90 wt% ethylene glycol and 10 wt% ethylene carbonate) with catalysts at moderate temperature under atmospheric pressure. The effect of liquefaction temperature, biomass content, and type of catalyst, such H₂SO₄, HCl, H₃PO₄, and ZnCl₂, was evaluated. Higher liquefaction yield was achieved in 2 wt% sulfuric acid, 1/4 (w/w) stover to liquefying reagent ratio; 160°C temperature, in 2h. The liquefied corn stover was rich in polyols, which can be directly used as feedstock for making polymers without further separation or purification. Second, polyester was made from the liquefied corn stover by crosslinking with multifunctional carboxylic acids and/or cyclic acid anhydrides. The tensile strength of polyester is about 5 MPa and the elongation is around 35%. The polyester is stable in cold water and organic solvents and readily biodegradable as indicated by 82% weight loss when buried in damp soil for 10 mo. The results indicate that this novel polyester could be used for the biodegradable garden mulch film production.     

A novel microwave dielectric ceramic Ca2Zn4Ti16O38: Preparation and dielectric properties

A novel microwave dielectric powder with composition of Ca₂Zn₄Ti₁₆O₃₈ was synthesized through a citrate sol-gel process. The development of crystalline phases with heat-treating temperature for the gel derived powders was evaluated by using thermo-gravimetric analysis and X-ray powder diffraction analysis techniques. The pure phase of Ca₂Zn₄Ti₁₆O₃₈ with crichtonite crystal structure was obtained at relatively low temperature of 1000 °C. The synthesized powder has high reactivity and the dense ceramics with single crystalline phase were obtained at low sintering temperature of 1100 °C. Impedance spectroscopy and microwave dielectric measurements on sintered samples showed the present compound to be a modest dielectric insulator with excellent dielectric properties of ε_r∼47-49, Qf value ∼27,800-31,600 GHz and τ_f∼+45 to +50 ppm/°C. It shows comparable microwave dielectric properties to other moderate-permittivity microwave dielectrics, but much lower sintering temperature of 1100 °C.