Solvation of uranyl(II), europium(III) and europium(II) cations in "basic" room-temperature ionic liquids: a theoretical study

We report a molecular dynamics study of the solvation of UO2(2+), Eu3+ and Eu2+ ions in two "basic" (Lewis acidity) room-temperature ionic liquids (IL) composed of the 1-ethyl-3-methylimidazolium cation (EMI+) and a mixture of AlCl4- and Cl- anions, in which the Cl-/AlCl4- ratio is about 1 and 3, respectively. The study reveals the importance of the [UO2Cl4]2- species, which spontaneously form during most simulations, and that the first solvation shell of europium is filled with Cl- and AlCl4- ions embedded in a cationic EMI+ shell. The stability of the [UO2Cl4]2- and [Eu(III)Cl6]3- complexes is supported by quantum mechanical calculations, according to which the uranyl and europium cations intrinsically prefer Cl- to the AlCl4- ion. In the gas phase, however, [Eu(III)Cl6]3- and [Eu(II)Cl6]4- complexes are predicted to be metastable and to lose two to three Cl- ions. This contrasts with the results of simulations of complexes in ILs, in which the "solvation" of the europium complexes increases with the number of coordinated chlorides, leading to an equilibrium between different chloro species. The behavior of the hydrated [Eu(OH2)8]3+ complex is considered in the basic liquids; the complex exchanges H2O molecules with Cl- ions to form mixed [EuCl3(OH2)4] and [EuCl4(OH2)3]- complexes. The results of the simulations allow us to better understand the microscopic nature and solvation of lanthanide and actinide complexes in "basic" ionic liquids.     

High-level expression of soluble human β-defensin-2 fused with green fluorescent protein in Escherichia coli cell-free system

Human β-defensin-2 (hBD2), a small cationic peptide, exhibits a broad range of antimicrobial activity and does not acquire any microbial resistance. To produce this uneasily detectable, degradable, and toxic polypeptide efficiently, an alternative approach based on the Escherichia coli cell-free biosynthesis system was proposed. The approach implies that a polypeptide of interest is synthesized as a fusion protein linked to a green fluorescent protein (GFP) through a cleavable spacer. With batch-mode operation, a significant amount of hBD2 fused with GFP (0.25 mg/mL) can be expressed in this cell-free system. The productivity of the fusion protein can be improved up to 1.2 mg/mL by employing a continuous-exchange cell-free system. Furthermore, the GFP moiety provides directly visible and quantitative monitoring of the polypeptide synthesis, and the product is soluble and stable. This work will be helpful in allowing the rapid and visible expression of other similar defensins using an in vitro cell-free system.     

Green Chemistry and Modern Technology

The basic principles, approaches, and early achievements of green chemistry are considered. The definition of green chemistry as a branch of chemistry that studies the laws of passing of chemical reactions and the properties of substances participating in such reactions, with the aim of acquiring basic knowledge that provides a basis for designing chemical technologies that eliminate (sharply curtail) the use and production of materials that pose a risk to the environment.     

Sonogashira反应研究的最新进展

对Sonogashira反应的最新研究进展作了综述. 详细地介绍了Sonogashira 反应的最新优化、联串化、绿色化以及非Pd催化的Sonogashira反应等, 同时还综述了Sonogashira反应的机理研究.     

SDS胶束对孔雀绿褪色反应的影响

研究了十二烷基硫酸钠（SDS）表而活性剂胶束和预胶束对孔雀绿褪色可逆反应的影响，建立了1－1型可逆反应的胶束催化模型和预胶束催化模型，获得了胶束相中正逆反应的速率常数和预胶束的平均聚集数．结果表明，SDS胶束和预胶束对正反应有禁阻作用，而对逆反应有催化作用．     

Oxidation of crystal violet and malachite green in aqueous solutions — a kinetic spectrophotometric study

The reactions of two triphenyl methane (TPM) dyes—crystal violet (CV⁺) and malachite green (MG⁺)—with N₃^• and OH^• radicals were studied by pulse radiolytic kinetic spectrophotometry. The rate constants for the reaction of the cationic dyes (D⁺) with N₃^• are (9.0±0.6)×10⁹ and (3.0±0.2)×10⁹ dm³ mol⁻¹ s⁻¹ respectively and those for the reaction with OH^• are obtained as (8.0±0.6)×10⁹ and (1.1±0.1)×10⁹ dm³ mol⁻¹ s⁻¹ respectively. The transient spectra resulting from the oxidation of the dyes were characterized. The time-resolved spectra indicate that the reaction with OH^• radicals initially generates an adduct which subsequently dissociates to form the radical dication D^•2+. The D^•2+ species decay by further reaction with the parent dye.     

Electrochemical Preparation of Poly(Malachite Green) Film Modified Nafion‐Coated Glassy Carbon Electrode and Its Electrocatalytic Behavior Towards NADH,Dopamine and Ascorbic Acid

Poly(malachite green) film modified Nafion‐coated glassy carbon electrodes have been prepared by potentiodynamic cycling in malachite green solution. The pH of polymerisation solution has only minor effect on film formation. Electrochemical quartz crystal microbalance (EQCM) was used to monitor the growth of the poly(malachite green) film. Cyclic voltammogram of the poly(malachite green) film shows a redox couple with well‐defined peaks. The redox response of the modified electrode was found to be depending on the pH of the contacting solution. The peak potentials were shifted to a less positive region with increasing pH and the dependence of the peak potential was found to be 56 mV per pH unit. The electrocatalytic behavior of poly(malachite green) film modified Nafion‐coated glassy carbon electrodes was tested towards oxidation of NADH, dopamine, and ascorbic acid. The oxidation of dopamine and ascorbic acid occurred at less positive potential on poly(malachite green) film compared to bare glassy carbon electrode. In the case of NADH, the overpotential was reduced substantially on modified electrode. Finally, the feasibility of utilizing poly(malachite green) film electrode in analytical estimation of ascorbic acid was demonstrated in flow injection analysis.     

Stimulatory effect of red light on starch accumulation in a marine green alga,chlamydomonas sp. strain MGA161

A marine green alga,Chlamydomonas sp. strain MGA161 was cultivated under illumination of red and white lights. The growth rate under red light illumination was almost the same as that in the basic conditions under white light illumination, but red light-grown cells accumulated almost twice as much starch as white light-grown cells. Although there was a slight decrease in carbonic anhydrase activity, red light-illuminated cells had almost 2.3 times the fructose-l,6-diphos-phatase activity of white light-illuminated cells. Red light might stimulate starch accumulation by increasing the amounts of enzymes related to carbon fixation through the phytochrome system. Cells grown under red light degraded 1.6 times as much starch and produced 1.7 times as much hydrogen and 1.6 times as much ethanol compared with cells grown under white light during 12 h of dark anaerobic fermentation.     

A Simple Hydrothermal Route to Large‐Scale Synthesis of Uniform Silver Nanowires

This paper describes the preparation of uniform silver nanowires by reducing freshly prepared silver chloride with glucose at 180 °C for 18 hours in the absence of any surfactants or polymers. Scanning electron microscopy studies indicated that the silver nanowires are about 100 nm in diameter and up to 500 μm in length. High‐resolution transmission electron microscopy analyses showed that the silver nanowires grow perpendicularly to the Ag(200) plane. The silver nanowires are believed to grow through a solid–solution–solid process. Some influential factors on the growth of silver nanowires are also discussed.     

水中2-氨基-3-氰基-4-芳基-7，7-二甲基-5-氧代4H-5，6，7，8-四氢苯并[b]吡喃的洁净合成

在水溶剂中在三乙基苄基氯化铵（TEBA）存在下，取代肉桂腈与5，5-二甲基- 1，3-环已酮反应为2-氨基-3-氰基-4-芳基-7，7-二甲基-5-氧代-4H，5，6，7，8- 四氢苯并[b]吡喃提供了一种快速、方便、高效和洁净的合成方法。