Low-Field NMR Relaxation Analysis of High-Pressure Ethane Adsorption in Mesoporous Silicas

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) ¹H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25–50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g⁻¹ of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis.     

萃取分光光度法测定水和硫酸中的硒

本文提出一种测定硒的分光光度法。在酸性介质中，四价硒氧化Ｉ成为Ｉ３，Ｉ３－和结晶紫形成的离子缔合物用二甲苯萃取，进行分光光度测定。硒的检出限是０．０５μｇ／ｍＬ。用磷酸和ＥＤＴＡ消除Ｆｅ＾３＋，Ｐｂ＾２＋，Ｈｇ＾２＋等离子的干扰影响。本法可不和硫酸中四价硒。     

A facile approach to surface graft vinyl acetate onto polyolefin articles

A facile and environment friendly approach was developed to graft vinyl acetate (VAc) onto plastic articles in an aqueous solution using tert‐butyl alcohol (TBA) as a compatiblizer and benzoyl peroxide (BPO) as an initiator. In a novel setup, excessive monomer suspended in a water phase, VAc could be conveniently grafted on the model substrate of low‐density polyethylene (LDPE) film and the graft percentage (GP) could be developed up to 7.3%. Reaction temperature could increase GP significantly, while adding monomer over a critical volume did not influence GP. By adding some paradioxybenzene, i.e. 0.06–0.08% in VAc phase, homopolymer PVAc could be avoided practically, while graft polymerization proceeded favorably in aqueous solutions. It was proved by attenuated total reflection‐infrared (ATR‐IR) spectroscopy that grafted VAc was located mainly at the surface of the LDPE film and hydrophilic nature of both grafted and alcoholyzed films were improved via contact angle measurements. Copyright © 2004 John Wiley & Sons, Ltd.     

Rigid rod anchored to infinite membrane

We investigate the shape deformation of an infinite membrane anchored by a rigid rod. The density profile of the rod is calculated by the self-consistent-field theory and the shape of the membrane is predicted by the Helfrich membrane elasticity theory [W. Helfrich, Z. Naturforsch. 28c, 693 (1973)]. It is found that the membrane bends away from the rigid rod when the interaction between the rod and the membrane is repulsive or weakly attractive (adsorption). However, the pulled height of the membrane at first increases and then decreases with the increase of the adsorption strength. Compared to a Gaussian chain with the same length, the rigid rod covers much larger area of the membrane, whereas exerts less local entropic pressure on the membrane. An evident gap is found between the membrane and the rigid rod because the membrane's curvature has to be continuous. These behaviors are compared with that of the flexible-polymer-anchored membranes studied by previous Monte Carlo simulations and theoretical analysis. It is straightforward to extend this method to more complicated and real biological systems, such as infinite membrane/multiple chains, protein inclusion, or systems with phase separation.     

Automated,continuous, and dynamic speciation of urinary arsenic in the bladder of living organisms using microdialysis sampling coupled on-line with high performance liquid chromatography and hydride generation atomic absorption spectrometry

An on-line and fully automated method was developed for the continuous and dynamic in vivo monitoring of four arsenic species [arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)] in urine of living organisms. In this method a microdialysis sampling technique was employed to couple on-line with high performance liquid chromatography (HPLC) and hydride generation atomic absorption spectrometry (HGAAS). Dialysates perfused through implanted microdialysis probes were collected with a sample loop of an on-line injector for direct and automated injection into HPLC system hyphenated with HGAAS. The saline (0.9% NaCl) solution was perfused at the rate of 1 microl min(-1) through the microdialysis probe and the dialysate was loaded into 50 microl of sample loop. The separation conditions were optimally selected to be in phosphate buffer solution at a pH 5.2 with a flow rate of 1.2 ml min(-1). The effluent from the HPLC was first mixed on-line at the exit of the column with HCl (1 M) solution and then mixed with a NaBH4 (0.2% m/v) solution. Based on the optimal conditions obtained, linear ranges of 2.5-50 ng ml(-1) for AsIII and 6.75-100 ng ml(-1) for the other three arsenic species were obtained. Detection limits of 1.00, 2.18, 1.03 and 2.17 ng ml(-1) were obtained for AsIII, DMA, MMA and AsV, respectively. Typical precision values of 3.4% (AsIII), 5.4% (DMA), 3.6% (MMA) and 7.5% (AsV) were obtained, respectively, at a 25 ng ml(-1) level. Recoveries close to 100%, relative to an aqueous standard, were observed for each species. The average in vivo recoveries of AsIII, DMA, MMA and AsV in rat bladder urine were 56+/-5%, 60+/-9%, 49+/-3% and 55+/-7%, respectively. The use of an on-line microdialysis-HPLC-HGAAS system permitted the determination of four urinary arsenic species in the bladder of an anesthetized rat with a temporal resolution of 50 min sampling.     

超细粉Pb0.75Ca0.25[(Ni1/3Nb2/3)0.08Ti0.912Mn0.008]O3的制备与表征

报道了用化学共沉淀法制备掺杂Ca、Ni、Nb、Mn钛酸铅超细陶瓷粉末的方法。制得的粉料化学式为:Pb_0.75Ca_0.25[(Ni_1/3Nb_2/3)_0.08Ti_0.912Mn_0.008]O₃,粒径小于0.1μm,所有的掺杂元素均能定量掺入。     

硝酸钆低水合物的制备及表征

本文用两种方法制得硝酸钆的低水合物Gd(NO_3)_3·5H_2O、Gd(NO_3)_3·3.5H_2O,其中Gd(NO_3)_3·3.5H_2O是文献中尚未报道的 ,给出了它们的M.P.和X-衍射特征值。     

硼酸溶液中氯柱硼镁石的溶解及相转化动力学

对氯柱硼镁石（2MgO•2B2O3•MgCl2•14H2O）在4.5％H3BO3水溶液40 ℃的溶解及相转化过程进行了动力学研究.对不同时间取出的液相的化学分析及不同阶段分离固相的鉴定结果表明,该复盐在溶解阶段出现与前所报导不同的同步溶解，最终产物是库水硼镁石（2MgO•3B2O3•15H2O）.提出了库水硼镁石的形成条件和溶解及相转化动力学机理，利用单纯形优化法配合Runge-Kutta微分方程组数值解法对实验数据进行处理，给出了转化结晶动力学方程.     

Total synthesis of methyl protodioscin: a potent agent with antitumor activity

Methyl protodioscin (1), otherwise known as 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-d-glucopyranosyl]-26-O-[beta-D-glucopyranosyl]-22-methoxy-25(R)-furost-5-ene-3 beta,26-diol, has been synthesized for the first time from diosgenin through nine steps in an overall yield of 7.8%.     

An aldol approach to the total synthesis of (+)-brefeldin A

A convergent selective route to (+)-brefeldin A (BFA) and 7-epi-BFA was developed, with the crucial C-4/C-5 stereogenic centers were established using Crimmins asymmetric aldolization.