杯芳烃对铁的配位及其超分子化学研究进展

介绍了近年来杯芳烃对铁的配位及其超分子化学的研究进展,讨论了杯芳烃对铁的配位结构及其超分子作用机理.并对\"杯芳烃-铁\"配位及其超分子化学的研究动向作了展望.     

Electrochemical myoglobin biosensor based on carbon ionic liquid electrode modified with Fe3O4@SiO2 microsphere

In this paper, a Fe₃O₄@SiO₂ core-shell structure microsphere was synthesized and used to investigate the direct electron transfer of myoglobin (Mb) with a 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the substrate electrode. The mixture of Mb and Fe₃O₄@SiO₂ microsphere could form an organic–inorganic composite, which was immobilized on the surface of CILE with a chitosan (CS) film. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared on CS/Mb-Fe₃O₄@SiO₂/CILE with the formal peak potential (E ^0′) located at ?0.31 V (vs. saturated calomel electrode), which was corresponded to the electroactive center of Mb heme Fe(III)/Fe(II) redox couples. Direct electrochemical behaviors of Mb in CS-Fe₃O₄@SiO₂ composite film were carefully investigated with the electrochemical parameters calculated. The CS/Mb-Fe₃O₄@SiO₂/CILE showed good electrocatalytic behaviors to the reduction of trichloroacetic acid in the concentration range from 0.2 to 11.0 mmol L^?1 with the detection limit of 0.18 mmol L^?1 (3σ). Based on CS/Mb-Fe₃O₄@SiO₂/CILE, a new third-generation reagentless electrochemical biosensor was constructed with higher sensitivity and reproducibility.     

Adsorptive removal of La(III) from aqueous solutions with 8-hydroxyquinoline immobilized GMZ bentonite

Due to the low permeability, high swelling capacity and good retardation properties, bentonite has been considered as the main component of buffer/backfill material for high level radioactive wastes repository all over the world. The adsorptions of metal ion were widely investigated recently. In this presentation, we provide an easy-to-use method to immobilize 8-hydroxyquinoline onto the surface of bentonite for the use of adsorption studies of La(III) from the aqueous solution. The effects of various parameters such as contact time, pH of the solution, ionic strength and metal ion concentration on the adsorption were investigated by the batch experiments. The biggest adsorption capacity is 41.7 mg/g, higher than the value reported by our previous work which is performed by the raw bentonite. Langmuir isotherm fits the experimental data well and the adsorption follows pseudo-second-order kinetic model. In summary, 8-hydroxyquinoline immobilized GMZ bentonite is an effective adsorbent for the removal of La(III) from aqueous solutions.     

Tough nanocomposite hydrogels from cellulose nanocrystals/poly(acrylamide) clusters: influence of the charge density,aspect ratio and surface coating with PEG

Cellulose-derived materials are usually characterized by sophisticated structures, leading to unique and multiple functions, which have been a source of inspiration for the fabrication of a wide variety of nanocomposites. Cellulose nanocrystals/poly(acrylamide) (CNCs/PAM) nanocomposite hydrogels were synthesized via in situ polymerization in the CNC suspension. The cellulose from pulp fiber under different sulfuric acid hydrolysis conditions, examined by conductometric titration and transmission electron microscopy, was applied to study how the effects of the surface charge and aspect ratio affect CNCs’ mechanical reinforcement in nanocomposites. The results indicated that the higher surface charge concentration resulted in better dispersibility in aqueous suspension, leading to a more efficient energy dissipation process. The CNC reinforcement behavior followed the percolation model where the greater aspect ratio of CNC contributed to higher mechanical properties. The preferential adsorption of poly(ethylene glycol) (PEG) on the CNC surface was characterized by zeta potential measurements where the fracture strength and fracture elongation of nanocomposites decreased with increasing PEG concentration. The adsorption of PEG on the CNC surface occupied the active sites for polymer chain propagation, which hindered the PAM cross-linking effect on the CNC surface and decreased the cross-linking density of the network.     

Synthesis,structure and characterization of the trinuclear copper (I) complex [Cu3(μ3-Br)2(dppm)3]Br

The novel trinuclear copper(I) complex [Cu₃(μ₃,-Br)₂(dppm)₃]Br has been obtained by reaction of bis(diphenyl-phosphino)methane (dppm) with cupric bromide. The title complex was characterized by single-crystal X-ray analysis, elemental analysis, molecular weight determination, ³¹P NMR and its conductivity was also measured. The [ Cu₃ (dppm)₃ Br₂ ]⁺ cation consists of a triangular array of copper atoms, with dppm ligands (Ph₂ PCH₂ PPh₂) bridging each edge of the triangle and two triply bridging Br groups bound to the two faces of the Cu₃ unit. Crystallographic data: monoclinic, space group P2₁/c, a = 1.4739(4), b = l.7708(5), c = 2.8395(8) nm, β= 97.16(3)°, V = 7.353nm³, Z = 4, F(000)= 3296, D_calc, = 1.472 g/cm³, μ = 26.478 cm^?1, R=0.06, R_W = 0.08, 4654 reflections observed with I3≥(I).     

Nephrotoxicity assessments of benzo(a)pyrene during zebrafish embryogenesis

Benzo(a)pyrene is a chemical produced during the process of making fried, roasted, and smoked foods. It remains unclear whether benzo(a)pyrene affects the early development of human organs. In this study, we used the transgenic zebrafish line Tg(wt1b:GFP) as a model to assess benzo(a)pyrene-induced kidney malformation. By soaking zebrafish embryos in benzo(a)pyrene at various doses (2, 20, and 200 ppb), only a minor effect on the survival rate was detected (0 ppb: 97.8 ± 1.9 %; 2–200 ppb: 89.1 ± 5.8–91.5 ± 8.3 %). However, benzo(a)pyrene significantly affected the development of the kidney (malformation rates ranges from 50.0 ± 3.5 to 77.4 ± 5.3 %). Various abnormalities, such as unusual curving of pronephric tubes, swollen glomerulus, and incomplete development of pronephric ducts, were observed. This study provides a rapid and effective protocol for the evaluation of the notable effects of benzo(a)pyrene on embryonic kidney development.     

Efficient electrochemical incineration of phenol on activated carbon fiber as a new type of particulates

The feasibility of activated carbon fibers (ACFs) used as a new type of particle electrodes in 3-dimensional (3D) electrode for the electrochemical degradation of phenol wastewater was investigated for the first time. The surface morphology, textual properties and electrochemical behaviors of ACF were studied by scanning electron microscopy (SEM), N₂-BET sorption and cyclic voltammograms (CVs), respectively. Compared with the commercialized granular activated carbon (GAC), ACF particle electrodes exhibited higher electrochemical oxidation performance on the mineralization of target pollutant. The identification of intermediates indicated most of oxidation products were adsorbed onto the ACFs. The detection of hydrogen peroxide and hydroxyl radicals in the reaction system suggested that the reaction mechanism was direct anodic oxidation of pollutant on ACFs if the cathode did not contact the ACFs. The operative parameters including initial concentration of substrate, applied current density and the initial aqueous pH have been scientifically studied in search of the optimum condition. Based upon the obtained results, the ACFs longevity was tested in solution at pH 2.0, revealing relatively high electrooxidation capacity and long catalyst lifetime of ACFs in acid solution.     

Cyclodextrin-Modified Gold Nanoparticle Capillary Electrochromatography with Online Sample Stacking for Simultaneous and Sensitive Determination of Aminobenzoic Acid Isomers

A newly-developed method of complete separation and sensitive determination of o-, m-, and p-aminobenzoic acid isomers was achieved by combining open-tubular columns for capillary electrochromatography (OT-CEC) and online sample stacking. In this study, spherical gold nanoparticles were modified by a covalent attachment of mono-6-thio-β-cyclodextrin, and OT-CEC was formed by immobilizing cyclodextrin-modified gold nanoparticles (CD-AuNP) on prederivatized 3-mercaptopropyl-trimethoxysilane fused-silica capillaries. Based on the theory of moving chemical reaction boundary, effects of several important factors such as the pH and concentration of running buffer and the conditions of stacking analytes were optimized. The optimized separations were carried out in 58 mmol/L HAc buffer at pH 3.0 using a capillary coated with CD-AuNP, while the optimized concentration was carried out in 50 mmol/L disodium hydrogen phosphate (pH 9.5). The linear ranges for m-, p-, and o-aminobenzoic acid were from 5.0 × 10^?4–0.1, 5.0 × 10^?4–0.1 and 1.0 × 10^?4–0.1 mmol/L, respectively. And the detection limits (S/N = 3) were as low as 8.22 × 10^?5, 8.21 × 10^?5, and 3.76 × 10^?5 mmol/L for m-, p-, and o-aminobenzoic acid, respectively. The run-to-run, day-to-day, and column-to-column reproducibilities of migration time were satisfactory with relative standard deviation values of less than 4.5 % in all cases. This method was successfully used in determining procaine hydrochloride injection sample with recoveries in the range of 96.1–106.6 % and relative standard deviations less than 5.0 %.     

六方稀土氧化物水化和碳酸化产物的振动光谱研究

六方稀土氧化物在空气中极易水化和碳酸化。测定并讨论了光谱纯粉晶ＲＥ２Ｏ３（ＲＥ＝ Ｌａ ,Ｐｒ,Ｎｄ） 样品的Ｒａｍａｎ 光谱、红外光谱及粉晶Ｘ 射线衍射谱。结果表明, 其水化产物为ＲＥ（ＯＨ）３ , 碳酸化产物主要为六方双氧单碳酸盐ＲＥ２Ｏ３ＣＯ３ 以及少量的单氧双碳酸盐ＲＥ２Ｏ（ＣＯ３）２ 和四方ＲＥ２Ｏ２ＣＯ３ 。