Effects of pretreatments and modifiers on electrochemical properties of carbon paste electrodes

The electrochemical properties of carbon paste electrodes (CPEs), including unmodified and modified with protein and polycations, were investigated by impedance spectroscopy (IS) using ferricyanide and ferrocene monocarboxylic acid (FcMA) as redox probes. Various electrochemical pretreatments were applied to the unmodified CPE. The heterogeneous charge transfer rate constant of ferro/ferricyanide couple is enhanced by 2 to 10 times compared with that obtained at untreated electrodes. It was found that for ferricyanide the more suitable pretreatments are successive cyclic voltammetric scans, cathodization and a square wave-like stepping rather than high-potential anodization. However, the pretreatment only exhibits a slight effect on the kinetics of FcMA. At the CPEs containing modifier, the electron transfer rate of the redox couple depends more on the pH of electrolyte solution if ferro/ferricyanide is used. The results can be explained by the differently charged states of the CPEs that were caused by the protonation or deprotonation of the modifiers in various pH solutions and demonstrate the importance of the electrostatic interaction on the kinetics of the highly polar species such as ferricyanide. The different adsorptive behavior of ferricyanide and FcMA is also discussed.     

Using NaCl particles as porogen to prepare a highly adsorbent chitosan membranes

Macroporous chitosan membranes were prepared by using NaCl particles porogen and genipin as cross-linking agent. For characterization and sorption behavior comparison, other genipin cross-linked chitosan membranes were prepared by either freeze drying or by using silica particles as porogen. The mean pore diameter, the porosity, the crystallinity index (CrI) as well as the effect of the drying procedures of these chitosan membranes were examined. NaCl reduced the CrI of the chitosan membrane. The oven drying (OD) procedure decreased the mean pore diameter, the porosity, and increased the CrI of the chitosan membranes when compared with the vacuum drying (VD) procedure. The heat treatment of chitosan membrane in aqueous NaOH to attract silica porogen increased the CrI of the membrane. Under the same conditions, the membranes prepared with NaCl had better sorption performance on RR 189 and Cu²⁺ than other membranes. The maximum sorption capacity (q_e) reached 1836.17 mg RR 189/g chitosan and 151.98 mg Cu²⁺/g chitosan. The pore diameter (d_pore) of the membranes was much larger than the diameter of the adsorbate molecules (d_adsorbate), such that the ratio of d_pore/d_adsorbate had little influence on q_e. The porosity and the amorphous extent of the membranes were almost the same on q_e. When using tyrosinase catalyzing, the hydrocaffeic acid (HCA) grafted on the NaCl treated chitosan membrane was almost 10 times more than on chitosan beads. The chitosan membrane prepared with NaCl can be used as a good adsorbent with high loading capacity for implanting molecules (such as ligands, enzymes, etc.) on.     

Fine characterization of the ethylene and ethane sorption in poly(amide 12-block-tetramethylenoxide) copolymer/AgBF4 membranes

Ethylene/ethane sorption characteristics were determined for dry Pebax™ (poly(amide 12-block-tetramethylenoxide) copolymer)/AgBF₄ membranes by using an electronic microbalance. The membranes containing 0.7 and 22 wt.% AgBF₄ showed a dual-mode sorption isotherm. The ethane isotherms for all the membranes were of the Henry-type, which is the normal sorption for gases in rubbery polymers. The abnormal presence of Langmuir sorption sites only for ethylene in the rubbery copolymer, never reported sofar, is attributed to the silver-based specific complexation sites. The silver salt which dissolved in limited amounts in the rubbery copolymer had a much smaller Langmuir sorption capacity than the salt that crystallized in the copolymer. The sorption kinetics indicate that the crystallized salt did adsorb slowly ethylene according to a zeroth-order kinetics, but not ethane. The gas uptake kinetics resulting from a step of the pressure surrounding the copolymer exhibited one stage for ethane but two stages for ethylene. For the latter, there was first a fast Fickian sorption stage, then a drift of the zeroth-order sorption of ethylene on salt crystals, which contributes for a large part to the total uptake. The zeroth-order sorption suggests that the sorbed ethylene amount in the second-stage is independent of the crystal-surface coverage. The value of the Fickian diffusion coefficient calculated by fitting the kinetics with a solution of the second Fick’s law was 5 × 10⁻¹² m²/s for both ethylene (the first stage) and ethane, and is typical for small organic compounds in a rubbery material.     

Construction of vicinal quaternary carbon atoms by Ireland ester Claisen rearrangement: total synthesis of (±)-herbertenolide, (±)-herberteneacetal, (±)-herbertene-1,14-diol and (±)-herbertene-1,15-diol

Efficient total syntheses of the herbertane sesquiterpene title compounds have been accomplished employing an Ireland ester Claisen rearrangement and ring-closing metathesis reaction sequence based strategy for the construction of two stereogenic vicinal quaternary carbon atoms on a cyclopentane.     

壳聚糖/聚乙烯醇共混超细纤维的制备及紫外光交联研究

用静电纺丝法制备壳聚糖/聚乙烯醇的共混超细纤维,采用扫描电镜考察了纺丝液浓度、共混物配比、喷丝口内径对纤维形貌的影响.此外,为减少壳聚糖/聚乙烯醇纤维膜的溶胀变形,在上述体系中加入可光交联的单体二缩三乙二醇双甲基丙烯酸酯(TEGDMA)、引发剂2-羟基-2-甲基-1苯基丙酮(1173),对电纺纤维进行紫外光交联.结果表明,当壳聚糖与聚乙烯醇质量比为8:2的共混体系中加入占混合溶液质量分数4%的TEGDMA、0.12%的1173作为交联剂时,所得的无纺布纤维直径比较均一,平均约为200 nm,经光交联处理后其耐水性能得到提高.     

环氧丙烯酸酯的紫外光固化

制备了适于配制紫外光固化涂料的环氧丙烯酸酯，研究了反应温度、阻聚剂、催化剂等因素对环氧树脂与丙烯酸反应的影响；讨论了反应机理和动力学；并利用红外光谱观察了产物的紫外光固化行为。季铵盐能有效地催化环氧树脂和丙烯酸的反应，当其用量为０．６％～１．２％时，在９０～１１０℃反应４．５～８小时后，环氧基转化率大于９７％。由此配制的光固化涂料经紫外光辐照能快速固化。     

Potential distribution around a charged spherical colloidal particle in a medium containing its counterions and a small amount of added salts

A theory is developed for the potential distribution around a charged spherical colloidal particle carrying ionized groups on the particle surface in a medium containing its counterions (i.e., counterions produced from dissociation of the particle surface groups) and a small amount of added salts on the basis of the theory of Imai and Oosawa. Numerical solutions to the Poisson–Boltzmann equation for the potential distribution are obtained for the case of dilute (but not infinitely dilute) particle suspensions of volume fraction 1 for a1 (where is the Debye–Hückel parameter and a is the particle radius). Here we have taken into account the effects of (i) counterions from the particle surface groups, and (ii) the finite particle volume fraction. These effects, which are usually neglected in the conventional Poisson–Boltzmann equation, are found to be important. It is found that, as in the case of completely salt-free media, there is a certain critical value of the particle charge (which is the same as that for the completely salt-free case). When the particle charge is lower than the critical value, the potential is given by a Coulomb potential. If the particle charge is higher than the critical value, then counterions are accumulated in the vicinity of the particle surface (counterion condensation) and the potential becomes less dependent on the particle charge. The above behaviors can be observed even for the case where the electrolyte concentration is higher than the concentration of counterions from the particle surface groups, if the conditions 1 and a1are both satisfied.     

Ce(IV) ion initiated graft polymerization of glycidylmethacrylate onto a demineralized bone matrix: effect of reaction parameters

Studies on chemical modification of demineralized bone matrix (DBM) have opened new arenas in the field of clinical orthopedics owing to its potential osteoinductivity with desired chemical functionality. To widen its usage to biomolecular delivery, graft polymerization of glycidylmethacrylate onto DBM was carried out by a free-radical initiating process using ceric ammonium nitrate as an initiator. The evidence of the grafting reaction was examined by chemical analysis using Fourier transform IR spectroscopy. The grafting condition was standardized by regulating the reaction parameters such as the concentrations of the backbone, the monomer and the initiator, the polymerization temperature and time. The optimum polymerization temperature and time to have the maximum grafting yield were 40 °C and 3 h, respectively. The percentage of grafting and the percentage of grafting efficiency were determined as a function of the reaction parameters, and both were found to increasing initially and thereafter decrease in most of the cases. The grafting results are discussed in a detailed fashion and a reaction mechanism is proposed.     

粘度法预测聚乙二醇/壳聚糖体系的相容性

甲壳素在自然界的含量很大，仅次于纤维素，是一种颇具应用潜力的天然高分子．可由甲壳素经脱酸基化制得壳聚糖．由于其分子中存在氨基，因此能溶解干酸性水溶液中，并以聚电解质的形式存在，近来用壳聚糖制得的纤维膜应用于药物、食品等的分离和纯化、污水的处理，分离效果好，且不带入任何化学杂质．在壳聚糖纤维膜制作及与纤维的混纺过程中，都要探讨它与其它相应高聚物的相容性[1]．我们以相容的壳聚糖（chitosan）／聚乙二醇（PEG）体系为例，采用粘度法讨论其分子间的相互作用，并预测它们的相容性．壳聚糖的基本结构为1实验部分1.1…     

An ion-imprinted silica-supported organic-inorganic hybrid sorbent prepared by a surface imprinting technique combined with a polysaccharide incorporated sol-gel process for selective separation of cadmium(II) from aqueous solution

Ion-imprinting concept and polysaccharide incorporated sol-gel process were applied to the preparation of a new silica-supported organic-inorganic hybrid sorbent for selective separation of Cd(II) from aqueous solution. In the prepared shell/core composite sorbent, covalently surface coating on the supporting silica gel was achieved by using a Cd(II)-imprinting sol-gel process starting from an inorganic precursor, γ-glycidoxypropyltrimethoxysiloxane (GPTMS), and a functional biopolymer, chitosan (CS). The sorbent was prepared through self-hydrolysis of GPTMS, self-condensation and co-condensation of silanol groups (Si-OH) from siloxane and silica gel surface, in combination with in situ covalent cross-linking of CS with partial amine shielded by Cd(II) complexation. Extraction of the imprinting molecules left a predetermined arrangement of ligands and tailored binding pockets for Cd(II). The prepared sorbent was characterized by using X-ray energy dispersion spectroscopy (EDX), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Batch experiments were conducted to study the sorption performance by removal of Cd(II) when present singly or in binary system, an aqueous Cd(II) and Zn(II) mixture. The ion-imprinted composite sorbent offered a fast kinetics for the sorption of Cd(II) and the maximum capacity was 1.14 mmol g⁻¹. The uptake capacity of the imprinted sorbent and the selectivity coefficient were much higher than that of the non-imprinted sorbent. The imprinted sorbent exhibited high reusability. The prepared functional sorbent was shown to be promising for the preconcentration of cadmium in environmental and biological samples.