亚甲蓝作为光谱探针研究对-二甲氨甲基-杯[8]芳烃与DNA间的作用

亚甲蓝作为光谱探针研究对-二甲氨甲基-杯[8]芳烃与DNA间的作用;对二甲基杯[8]芳烃;小牛胸腺DNA;紫外光谱法;荧光探针     

新型磺酸盐型Gemini表面活性剂的合成及其与聚合物相互作用

以溴代正烷烃、乙二胺、1,3-丙磺内酯合成了一系列新型磺酸盐型Gemini表面活性剂(SGS-8、SGS-10、SGS-12、SGS-14);采用IR、1H NMR及元素分析等手段对合成产物进行结构表征,并研究了其表面活性,采用等温滴定微量热技术、表面张力法和稳态荧光光谱法研究了SGS-12与聚丙烯酰胺(PAM)的相互作用规律及热力学参数。结果表明,合成的产物纯度较高,具有较低的cmc值和较好的表面活性;SGS-12/PAM混合体系的表面张力曲线和芘探针在体系中微极性的变化表明,二者发生相互作用且形成混合胶束;SGS-12与PAM结合是一个由焓驱动的自发过程,△H和△S均小于0,表明相互作用力以氢键和范德华力为主,合成产物在聚丙烯酰胺分子上的平均结合数为287。     

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure,Redox Properties,and Oxidation Reactions Investigated by DFT Calculations

The electronic structure and redox properties of the highly oxidizing, isolable Ru^V?O complex [Ru^V(N₄O)(O)]²⁺, its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol^?1, respectively. The overall free energy activation barrier (ΔG^≠=25.5 kcal mol^?1) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru^III(N₄O)(HOCl)]²⁺ (ΔG=15.0 kcal mol^?1) and the substitution of HOCl by a water molecule (ΔG^≠=10.5 kcal mol^?1). For water oxidation, nucleophilic attack on Ru^V?O by water, leading to O? O bond formation, has a free energy barrier of 24.0 kcal mol^?1, the major component of which comes from the cleavage of the H? OH bond of water. Intermolecular self‐coupling of two molecules of [Ru^V(N₄O)(O)]²⁺ leads to the [(N₄O)Ru^IV? O₂? Ru^III(N₄O)]⁴⁺ complex with a calculated free energy barrier of 12.0 kcal mol^?1.     

Wrinkling and Growth Mechanism of CuO Nanowires in Thermal Oxidation of Copper Foil

We report a systematic study on wrinkling and CuO nanowires （NWs） growth in the thermal oxidation of copper foil. Copper foils with thickness of 0.5 mm were thermally oxidized in air at 500℃ for 0.5-10 h. It is found that all the samples have wrinkles and the size of the wrinkles increases with the oxidation time increasing. CuO NWs can grow on both the sidehill and hilltop of wrinkle. The CuO NWs on sidehill are longer and denser than those on hilltop. The growth direction of the CuO NWs on sidehill is not vertical to the substrate but vertical to their growth surfaces. The process of wrinkling and CuO NWs growth can be divided into three stages： undulating, voiding, and cracking. The CuO NWs on both sidehill and hilltop grow at the undulating stage. However, only the CuO NWs on sidehill grow and those on hilltop stop growing at the voiding and cracking stages because of the void in hilltop. The local electric field in a wrinkle at undulating stage was calculated, and it is found that the difference of local electric field strengths between hilltop and sidehill is small, which indicates that the predominant driving force for the diffusion of Cu ion during CuO NWs growth is internal stress.     

Effect of particle size of activated clay on the adsorption of paraquat from aqueous solution

This paper describes the effect of particle size on the process of paraquat adsorption from aqueous solution onto an activated clay surface at 25 degrees C and initial pH 11.0. Measurements of the pore properties of the clay adsorbents with three different particle sizes (0.053-0.074 mm, 0.037-0.053 mm, and <0.037 mm) were carried out. The rates and isotherms of adsorption have been also investigated by batch methods under the controlled conditions. From the experimental results obtained, the adsorption process can be well described with the pseudo-second order model and Freundlich model for adsorption kinetics and adsorption isotherm, respectively. In addition, the effect of the particle size of the clay adsorbent on the adsorption kinetics was found to be of considerable significance; namely, the rate constant (k) of paraquat adsorption by the clay adsorbent decreased with increasing particle size. It was concluded that the pore properties (i.e., surface area and total pore volume) and particle size of the clay adsorbent played a significant role in determining adsorption capacity and adsorption rate, respectively.     

Pharmacokinetic study of free mangiferin in rats by microdialysis coupled with microbore high-performance liquid chromatography and tandem mass spectrometry

Mangiferin (2-beta-D-glucopyranosyl-1,3,6,7-tetrahydroxyxanthen-9-one) has been isolated from the herbal root of Anemarrhena asphodeloides Bung showing antioxidative, antiviral, and anticancer effect. An in vivo microdialysis sampling method coupled to microbore high-performance liquid chromatography (HPLC) was employed for continuous monitoring of free mangiferin in rat blood. Microdialysis probes were inserted into the jugular vein/right atrium and brain striatum of Sprague-Dawley rats, and mangiferin at doses of 10, 30 or 100 mg/kg were then administered via the femoral vein. Dialysates were collected every 10 min and injected directly into a microbore HPLC system. Mangiferin was separated by a reversed-phase C18 microbore column (150 x 1 mm) from dialysate within 10 min. The mobile phase consisted of acetonitrile-0.05% phosphoric acid-tetrahydrofuran (10:75:15, v/v/v) with a flow-rate of 0.05 ml/min. The wavelength of the UV detector was set at 257 nm. The limit of quantification for mangiferin was 0.05 microg/ml and in vivo recovery of mangiferin at concentrations of 1, 5 and 10 microg/ml was in range of 37.7-39.8%. The results indicate that the pharmacokinetics of mangiferin at doses of 10-30 mg/kg reveals a linear relation, while doses of 30-100 mg/kg show a nonlinear pharmacokinetic phenomenon. Mangiferin was undetectable in brain dialysate. The proposed method provides a technique for rapid and sensitive analysis of free mangiferin in rat blood and further application in pharmacokinetic study. Furthermore, the metabolites of mangiferin in the rat bile were confirmed by LC electrospray ionization (ESI) tandem mass spectrometry (MS-MS).     

A new route to alumoxane gel: a versatile precursor to gamma-alumina and alumina-based ceramic oxides

We present a new route for the preparation of gamma-alumina and YAG nanoparticles. Metal salts of ethylhexanoic acids provide good solubility in hydrocarbon solvents and allow efficient ultrasonication. The sonication product is an alumioxane gel, which can reversibly collapse and reform, depending on the solvent used. The dried gel nanoparticles are calcined at temperatures significantly lower than those used in conventional syntheses, resulting in gamma-alumina nanoparticles. This is due to the complete mixing of elements at the atomic level and the small size of the formed nanoparticles.     

Controlling the optimum surfactants concentrations for dispersing carbon nanofibers in aqueous solution

As a new nano-scale functional material, it is necessary to achieve a uniform distribution in the composites for gaining the CNFs’ excellent reinforcing effect. In this paper, CNFs were purified by the method of high temperature annealing treatment. Six surfactants, methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), sodium dodecyl sulfate (SDS), dodecylamine (DDA), N, N-dimethyl formamide (DMF) and cetyltrimethyl ammonium bromide (CTAB) were used individually and combinatorially in a certain concentration to disperse the CNFs in aqueous solution. To achieve a good dispersion of the CNFs, a method utilizing ultrasonic processing was employed. The CNFs treated by the method of high temperature annealing treatment were characterized by differential thermal analysis (DTA) and thermogravimetry analysis (TGA), and the ultrasonication-driven dispersion of CNFs in aqueous solutions were monitored by UVvis spectroscopy and transmission electron microscopy (TEM). The experiments reveal that the method of high temperature annealing treatment purified the CNFs and the maximum achievable dispersion of CNFs corresponds to the maximum UV absorbance of the solution. All results show that the surfactants mixture of MC and SDS in a certain concentration of 0.4 and 2.0 g/L has the maximum dispersion effect on CNFs in aqueous solution, the optimum concentration ratio of MC, SDS, and CNFs was 2: 10: 1.