Synthesis of Enantiomerically Pure 1,2,3,4‐Tetrahydro‐β‐carbolines and N‐Acyl‐1‐aryl Ethylamines by Rhodium‐Catalyzed Hydrogenation

The rhodium‐catalyzed asymmetric hydrogenation of different enamides, in particular, dihydro‐β‐carboline derivates, was investigated in the presence of chiral phosphorus ligands. Enantioselectivities of up to 99 % ee were obtained after ligand screening and optimization of the reaction conditions. The scope and limitation of the catalysts were shown in the synthesis of optically active tetrahydro‐β‐carbolines and other benchmark N‐acyl‐1‐aryl ethylamines.     

Square Wave Anodic Stripping Voltammetric Determination of Hg(II) with N1-Hydroxy-N1,N2-diphenylbenzamidine Modified Carbon Paste Electrode

Mercury is a highly toxic metal, of which even small doses (<200 ng mL⁻¹) can cause serious problems for humans, plants, animals and microorganisms, including marine species and freshwater organisms. Hence, a simple, fast, highly selective and sensitive and accurate method for the detection of mercury in the environmental, clinical or biological samples is necessary. A new, sensitive and selective method for the determination of Hg(II) with 5 % N¹-hydroxy-N¹,N²-diphenylbenzamidine modified carbon paste electrode has been developed. Hg(II) was accumulated for 210 s on the surface of the modified electrode using 0.1 M CH₃COONa of pH 7 at −0.8 V vs Ag/AgCl, followed by electrochemical stripping with SWASV in 0.1 M NH₄Cl at pH 4. The linear range is 0.02–10 μM Hg(II) with limit of detection of 1.28 nM. The method has RSDs of 3.7 %. The method was applied for the determination Hg(II) in five types of water samples. The recoveries were in the range 97.8–103 %. The proposed method was found to be highly selective and sensitive and has many attractive features compared to previous reports such as low cost, simplicity of electrode preparation, long term stability, fast response, easy renewable ability, and reasonable short accumulation time.     

Lack of effect of oral supplementation with antioxidants on cholesterol oxidation product concentration of human plasma,as revealed by an improved gas chromatography method

A gas chromatographic method was successfully applied to determine cholesterol oxidation products (COPs) in human plasma. The linearity, precision, recovery and sensitivity of the method were determined. Oral supplementation with a combination of vitamin E (800 IU), C (1 g) and β-carotene (24 mg), given for 21 days to 21 patients, did not significantly decrease plasma COP content. No correlations (n = 26) were found between initial plasma COP content and the following parameters: age, body mass index, plasma content of α-tocopherol, cholesterol, high-density lipoprotein cholesterol and triglycerides, and fat, natural antioxidant and oxidized lipid intake. Differences in plasma COP content between type 2 diabetic (n = 6) and nondiabetic (n = 20) patients were not statistically significant. The results from this study lead us to hypothesize that the nonenzymatic oxidation of cholesterol in plasma is negligible compared to COPs originating from the diet. This article also includes a comprehensive review of the drawbacks of the analytical methods of COP determination in plasma and serum.     

尿样中铀同位素的ICP-MS快速测量技术研究

核事故状态下的应急处理,要求对环境介质中的放射性核素进行快速分析。尿样中铀同位素测量作为内照射剂量评价的主要手段,其分析效率越高,则对核事故中涉铀人员的安全救治越及时、有效。而尿样中其它无机离子是铀含量的106倍,导致ICP-MS测量过程中尿盐堵塞进样毛细管。为降低样品的含盐量并获得较好的检测结果,本文对样品预处理过程进行优化。采用先加热氧化去除有机物,再进行1～10倍稀释后测试样品的铀同位素丰度及浓度。结果表明：将25 mL样品稀释至100 mL后效果最佳,分析方法不确定度为5.4 %,回收率95 %~105 %。     

Synthesis of highly dispersed,block copolymer‐grafted TiO2 nanoparticles within neat block copolymer films

The objective of the study is to formulate exclusive block copolymer (BCP) nanocomposites by dispersing bcp end‐grafted nanoparticles (bcp‐g‐nps) of PMMA‐b‐PS‐g‐TiO₂ within PS‐b‐PMMA matrix. PMMA‐b‐PS‐g‐TiO₂ is synthesized using a “grafting‐to” approach and characterized by XPS and TGA to establish that the copolymer chains were bonded to NPs. Good dispersion of bcp‐g‐nps in PMMA and PS‐PMMA bcp films is observed, in contrast to poor dispersion in PS films. In PS‐PMMA films, the compatible and identical bcp nature of the end‐grafted polymer, and large NP size caused it to span across entire PS‐PMMA domains. Poor and good dispersion in PS and PMMA matrices, respectively, can be rationalized by the fact that NPs interactions are driven by the PMMA at the outer corona of the bcp‐g‐nps. Developing bcp‐g‐nps as a strategic route to preparation of highly dispersed high permittivity NPs like titanium dioxide (TiO₂) in bcp matrix can have important ramifications for energy storage devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 468–478     

Microwave-Assisted Green Synthesis of Gold Nanoparticles Using Olibanum Gum (Boswellia serrate) and its Catalytic Reduction of 4-Nitrophenol and Hexacyanoferrate (III) by Sodium Borohydride

In this work we report straightforward, an economically viable, one-step microwave-assisted green synthesis of well stabilized gold nanoparticles (AuNPs) by reducing chloroauric acid with natural water soluble olibanum gum (Boswellia serrate). The olibanum gum acts as a dual role of reducing and capping agent for synthesis of AuNPs. The formation of AuNPs was confirmed using UV–Vis spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and electron diffraction. The results indicated that the synthesized NPs were well dispersed and spherical in shape had an average diameter of 3 ± 2 nm. The reaction parameters significantly affected the formation of NPs, as the concentration of gum and irradiation time increases the formation of NPs particles increases and size of particles are reduced. In addition, it has been shown that these olibanum gum capped AuNPs functioned as effective homogeneous catalyst for the reduction of two model reactions hexacyanoferrate(III) and 4-nitrophenol by sodium borohydride. The kinetic investigations were carried out at different amount of AuNPs and different temperatures.     

Choice of item pricing feedback schemes for multiple unit reverse combinatorial auctions

Recently, interest in combinatorial auctions has extended to include trade in multiple units of heterogeneous items. Combinatorial bidding is complex and iterative auctions are used to allow bidders to sequentially express their preferences with the aid of auction market information provided in the form of price feedbacks. There are different competing designs for the provision of item price feedbacks; however, most of these have not been thoroughly studied for multiple unit combinatorial auctions. This paper focuses on addressing this gap by evaluating several feedback schemes or algorithms in the context of multiple unit auctions. We numerically evaluate these algorithms under different scenarios that vary in bidder package selection strategies and in the degree of competition. We observe that auction outcomes are best when bidders use a naïve bidding strategy and competition is strong. Performance deteriorates significantly when bidders strategically select packages to maximize their profit. Finally, the performances of some algorithms are more sensitive to strategic bidding than others.     

Relationship between 1H chemical shifts of deuterated pyridinium ions and Brønsted acid strength of solid acids

Deuterated pyridine (pyridine-d5) is one of the NMR probe molecules widely used for determination of acid strength of solid catalysts. However, the correlation between the 1H chemical shift of adsorbed pyridine-d5 and the Br?nsted acid strength of solid acids has rarely been investigated. Here, an 8T zeolite model with different Si-H bond lengths is used to represent the Br?nsted acid sites with different strengths (from weak, strong, to superacid) and to predict the pyridine adsorption structure as well as the 1H chemical shift. The theoretical calculation suggests that a smaller 1H chemical shift of the pyridinium ions on the solid acids indicates a stronger acid strength. On the basis of the results of theoretical calculations, a linear correlation between the pyridine-d5 1H chemical shift and the proton affinity (PA) of the Br?nsted acid site has been derived. In combination with the available 1H MAS NMR experimental data, we conclude that pyridine-d5 can be used as a scale to characterize the solid acid strength.     

A global optimization method for the design of space trajectories

The problem of optimally designing a trajectory for a space mission is considered in this paper. Actual mission design is a complex, multi-disciplinary and multi-objective activity with relevant economic implications. In this paper we will consider some simplified models proposed by the European Space Agency as test problems for global optimization (GTOP database). We show that many trajectory optimization problems can be quite efficiently solved by means of relatively simple global optimization techniques relying on standard methods for local optimization. We show in this paper that our approach has been able to find trajectories which in many cases outperform those already known. We also conjecture that this problem displays a “funnel structure” similar, in some sense, to that of molecular optimization problems.     

Calorimetric study of calcium aluminate cement blended with flue gas desulfurization gypsum

The use of by-product gypsum is an important alternative in concrete design. In present experiment, conduction calorimetry was applied to investigate the early hydration of calcium aluminate cement (CAC)/flue gas desulfurization (FGD) gypsum paste, supplemented with the determination of setting times and analysis of hydrates by X-ray diffraction (XRD). It was found that different profiles of heat evolution rate were presented depending on the CAC/FGD gypsum ratio. Two distinct exothermic peaks, associating with CAC hydration and ettringite formation respectively, appeared when the FGD gypsum content was less than 20%. Hydrate barrier mechanism was introduced to explain the difference in induction periods of the pastes with or without FGD gypsum. It is concluded that the blending of FGD gypsum accelerates the hydration of CAC for the quick formation of ettringite and generates greater hydration heat from per gram of pure CAC for the high exothermic effect of ettringite formation. The dissolution and diffusion of gypsum plays an important role of reacting controller during the hydrations of the pastes with FGD gypsum. The modified hydration process and mechanism in this case is well visualized by means of calorimetry.