Electrochemically instantaneous reduction of conducting polyaniline-coated latex particles dispersed in acidic solution

A cathodic voltammetric wave was observed in an aqueous suspension of mono-dispersed, spherical polyaniline-coated polystyrene particles, whereas no anodic wave was detected. This irreversibility was common to particles with eight different diameters ranging from 0.2 to 7.5 μm. Such irreversibility cannot be found at polyaniline-coated electrodes, and thus is a property of the dispersion of polyaniline latex. The reduction current was controlled by diffusion of dispersed particles. The reduction, being the conversion from the electrical conducting state to the resistive one, should begin at a point of contact between the conducting particle and the electrode in order to be propagated to the whole particle rapidly. In contrast, the oxidation proceeds slowly with the propagation of conducting zone, during which Brownian motion lets the particle detach from the electrode. The number of loaded aniline units per particle, determined by weight analysis, ranged from 6 × 10⁶ (Ø 0.2 μm) to 3 × 10¹¹ (Ø 7.5 μm) and was proportional to 2.9 powers of the particle diameter. The diffusion-controlled current of the cathodic wave was proportional to 2.4 powers of the diameter. The difference in these powers, 0.5, agreed with a theoretical estimation of the diffusion-controlled current, the diffusion coefficient for which was given by the Stokes-Einstein equation.     

耐温黄胞胶铬冻胶调堵剂室内研制

从黄胞胶（XC）在水溶液中的性质出发（溶液增粘性，假塑性，耐酸碱性，盐对构象转变的影响，降解性等），设计了黄胞胶铬冻胶的基本配方：0．6％XC＋0．15％Na2Cr2O7 0.45%NaHSO3 0.1%甲醛液（杀菌剂）＋0．01％热稳定剂，在基本配方的基础上考察了每一组分用量的变化对XC／C r^3 成胶体系85℃或80℃时成胶时间，冻胶强度（承载质量），冻胶稳定性（7天脱水率）的影响，表明基本配方即为最佳配方，各组分用量可在一定范围内变化，配方中还应包含pH调节性，该调堵剂可用于85℃以下地层。     

New soluble unsaturated polyketone derived from diarylidenecycloalketone: synthesis and optical and electrochemical properties of π-conjugated poly(diarylidenecyclohexanone) with long side chains

A new type of unsaturated polyketone having cyclohexanone moiety in a π-conjugated main chain was prepared by polycondensation between 2,6-bis(4-bromobenzylidene)cyclohexanone and 2,5-dihexyloxy-p-phenylene diboric ester in the presence of Pd(PPh₃)₄. The polymer had good solubility in common organic solvents. Analysis by gel permeation chromatography (GPC; polystyrene standards) showed that the polymer had M_n and M_w values of 7800 and 18?200, respectively. The polymer exhibited a [η] value of 0.70 dl g⁻¹ in benzene at 30 °C. The chloroform solution of the polymer showed an UV-Vis peak at 392 nm, and the PL spectrum gave a peak at 533 nm. DSC exhibited that the polymer had a T_g of 85 °C. The DSC data, observation with a polarizing microscope, X-ray diffraction data and UV-Vis data of the obtained polymer showed a phase transition above 200 °C. TGA showed that the polymer had good thermal stability with 5 wt% loss temperature of 407 °C under N₂. Electrochemical oxidation (or p-doping) of the polymer started at about 0.7 V vs. Ag/AgNO₃ and gave a peak at 1.06 V vs. Ag/AgNO₃ with a color change of the film from yellow to deep red. The color change was followed by UV-Vis spectroscopy. The corresponding p-dedoping peak appeared at 0.58 V vs. Ag/AgNO₃.     

Mechanism of NO decomposition over Cu-ZSM-5

In the preceding Letter Shelef [1] has proposed a mechanism for NO decomposition involving coordinatively unsaturated Cu²⁺ sites on which NO molecules are chemisorbed in the gem-dinitrosyl form. At reaction temperature this complex is supposed to decompose into N₂ and O₂ without involving a redox process. That such a process is feasible has been pointed out by Moser [2]. Shelef cited several reasons in support of this view and others that have led him to think that a cyclic redox mechanism is not operative. These arguments are countered herein and some new data are presented showing the infrared spectra of surface species recorded under in situ reaction conditions.On leave from Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1525 Budapest, Hungary.     

Poly(methacrylic acid)‐bound dihydroxybenzene units: Redox polymers

Poly(methacrylic acid) (PMAA) was functionalized with a hydroquinone/catechol under the reaction conditions of Minisci. Optimum conditions for maximum functionalization (52%) were found to be as follows: [benzoquinone]/[PMAA] ratio, 0.75; reaction time, 3 h; temperature, 75°C; and a nitrogen atmosphere. Redox properties of hydroquinone/catechol‐modified PMAA (PMAA‐HQ) were evaluated by their midpotentials potentiometrically estimated to be 898 mV at 20°C. At 35°C, a two‐stage oxidation was observed with a midpotential of 1000 mV. These midpotentials were found to be higher than those of hydroquinone, catechol, and a 1 : 1 hydroquinone‐catechol mixture, under the same conditions of potentiometric titration. Under the modification reaction conditions, the modified PMAA underwent severe degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 954–961, 2006     

添加剂对全钒液流电池电解液稳定性的影响

为获得更高浓度、更稳定的钒电池阳极电解液,在钒离子硫酸溶液中分别加入了硫酸钾、硫酸钠、硫酸锌、尿素、柠檬酸、柠檬酸钠、柠檬酸三钠和EDTA,并恒温在43℃保存。利用电位滴定分别测定钒离子硫酸溶液恒温保存1和30 d后的钒离子浓度。结果表明,硫酸钾、硫酸钠、硫酸锌、尿素等添加剂可以使钒离子硫酸溶液更稳定,而柠檬酸、柠檬酸钠、柠檬酸三钠和EDTA不适合做添加剂。     

Pt/CrCeAlO催化剂对二氯甲烷的催化氧化性能

催化氧化是消除挥发性有机废气的有效手段,而二氯甲烷是含氯有机废气的代表性化合物。采用沉淀法制备了不同CrO_x含量的CrCeAlO催化剂,并用浸渍法制备了Pt/CrCeAlO催化剂,将其用于二氯甲烷催化氧化。结果表明,催化剂均表现出较好的活性,Cr_0.03Ce_0.05Al_0.95O₂催化剂在390 ℃时即可完全氧化二氯甲烷。而负载Pt后的催化剂活性明显提高,2.0Pt/Cr_0.03Ce_0.05Al₀.₉₅O₂催化剂表现出最好的活性,在340 ℃条件下,转化率即达100%。采用XRD、SEM、TEM、H₂-TPR和NH3-TPD对催化剂进行表征,表明催化剂的活性主要受其表面酸性和氧化还原性的影响,表面酸性位提供二氯甲烷化学吸附位,而催化剂表面氧化还原性则有利于反应中氧物种的活化。催化剂中添加Pt后,由于Pt、CeO₂ 和 CrO_x物种间的相互作用而增强了催化剂的氧化还原性,从而进一步促进了反应活性的提高。     

Gold‐Catalyzed Redox Synthesis of Imidazo[1,2‐a]pyridines using Pyridine N‐Oxide and Alkynes

A mild, catalytic, atom economical synthesis of imidazo[1,2‐a]pyridines has been developed: catalytic dichloro(2‐pyridinecarboxylato)gold [PicAuCl₂] in the presence of an acid produces a range of imidazo[1,2‐a]pyridines in good yields starting from alkynes and 2‐aminopyridine N‐oxides. This strategy is mild and foreseen to be of particular use for the installation of stereogenic centers adjacent to the imidazo[1,2‐a]pyridine ring without loss of enantiomeric excess.

     

The staying power of adhesion-associated antioxidant activity in Mytilus californianus

The California mussel, Mytilus californianus, adheres in the highly oxidizing intertidal zone with a fibrous holdfast called the byssus using 3, 4-dihydroxyphenyl-l-alanine (DOPA)-containing adhesive proteins. DOPA is susceptible to oxidation in seawater and, upon oxidation, loses adhesion. Successful mussel adhesion thus depends critically on controlling oxidation and reduction. To explore how mussels regulate redox during their functional adhesive lifetime, we tracked extractable protein concentration, DOPA content and antioxidant activity in byssal plaques over time. In seawater, DOPA content and antioxidant activity in the byssus persisted much longer than expected—50% of extractable DOPA and 30% of extractable antioxidant activity remained after 20 days. Antioxidant activity was located at the plaque–substrate interface, demonstrating that antioxidant activity keeps DOPA reduced for durable and dynamic adhesion. We also correlated antioxidant activity to cysteine and DOPA side chains of mussel foot proteins (mfps), suggesting that mussels use both cysteine and DOPA redox reservoirs for controlling interfacial chemistry. These data are discussed in the context of the biomaterial structure and properties of the marine mussel byssus.