Ag60纳米颗粒[{Cl@Ag12}@Ag48(dppm)12]的结构(其中dppm=双(二苯基膦基)甲烷

本文合成一种新的双膦连接Ag₆₀纳米团簇[{Cl@Ag₁₂}@Ag₄₈(dppm)₁₂],并通过X射线晶体学进行表征. 二十面体的银处于核心位置,里面是中心氯化物组成,外面有48 个银原子/离子的包裹,顶端是12个双(二苯基膦基)甲烷(dppm)配体. 同时利用密度泛函理论对阳离子[{Cl@Ag₁₂}@Ag₄₈(dppm)₁₂]⁺进行计算,以确定该结构是否对应于核心数n=58的超原子. DFT计算的优化结构与X射线一致,但是HOMO-LUMO的能差并不能保证其超级稳定性.     

Emerging nanocomposite biomaterials as biomedical adsorbents: an overview

Abstract

Biomedicine and pharmacy identify highly important scientific fields within the present time. However, increased advancements in these sciences have influenced the identification of increased levels in environmental degradation through pollution. Pharmaceutical production has influenced increased scientific and public concern regarding the increasing rate of pollution attributed to high levels of toxicological properties within the products. Pharmaceutical compounds are not fully removed through the integration of wastewater treatment plants (WWTP). This renders pharmaceutical compounds, municipal effluents together with hospitals as the major culprits in the development of the majority of the sources that enhance environmental degradation. A wide range of the compounds have been the identified within WWTP effluents, surface water together with ground and drinking water on a global scale. All above has influenced the research development in technological field developing new ways for efficient removal of pharmaceuticals from wastewater produced from the pharmaceuticals or biomedical industries. This situation may be altered through the utilization of adsorbents. Therefore more studies have been published investigating the use of nanocomposite biomaterials for removing the pharmaceutical compounds existing in biomedical effluents.     

泥沙输运模拟综述——现状及其发展趋势

随着流体力学中数值方法的飞速发展,计算模型已经成为研究流体运动,泥沙输运和不同环境(诸如河流,湖泊及沿海地区)中相应污染物归趋过程等方面非常有吸引力的工具,在过去的30多年里,发展了许多计算水动力学/泥沙输运模型.文章追溯当前具有代表性的(一维、二维、三维)模型的发展历程,描述他们各自的特点,优势及局限,力图作为对模型方面感兴趣读者的第一指南,同时也为大家讨论模型的局限性,未来的发展趋势和研究需求方面搭建一个平台.给出了模型的表达,时空特性,水动力学和沉积物的耦合方式,处理非恒定流,推移质和悬移质,泥沙交换过程,泥沙类型(粘性或非粘性)及非均匀泥沙输运的能力.总结了不同模型的应用实例,读者可以运用这些例子作为研究模型设置,模型率定及模型验证的参考.给出了选择泥沙输运模型应遵循的原则,模型输入及率定方面存在的问题及改进的途径.探讨了现有水动力学/泥沙输运模型在处理复杂湍流,泥沙携带,流动与输沙耦合,非均匀泥沙,离散和扩散系数,河岸来沙处理等方面的局限性及改进的方向.最后,对基于多相流思想的泥沙输运模型及其它一些交叉性问题作了评述与展望.     

Feature extraction algorithms for constrained global optimization I. Mathematical foundation

Nonconvex mixed integer nonlinear programming problems arise quite frequently in engineering decision problems, in general, and in chemical process design synthesis and process scheduling applications, in particular. These problems are characterized by high dimensionality and multiple local optimal solutions. In this work, a novel approach is developed for determining the global optimum in nonlinear continuous and discrete domains. The mathematical foundations of the feature extraction algorithm are presented and the properties of the algorithm discussed in detail. The algorithm uses a partition and search strategy in which the problem domain is successively partitioned and a statistical approximation approach is used to characterize the objective function values and the constraint feasibility over a partition. Specifically, the general joint distribution function representing the objective function values is relaxed to a separable form and approximated using an expansion in terms of Bernstein functions. The coefficients of the expansion are determined by solving a small linear program. Feasibility is established by computing upper and lower bounds for the inequality constraint functions, while equality constraints are explicitly or numerically eliminated. Estimates of the volume averaged values of objective function and constraint feasibility are used to select efficient partitions for further investigation. These are refined successively so as to focus the search on the most promising decision regions. An alternative, constant resolution partitioning strategy is also developed using a suitably modified genetic search algorithm. Illustrative examples are used to demonstrate the key computational features of the method.     

The effects of solvent preoxidation on inhibited chemiluminescence of pyrogallol oxidation in flow injection analysis and liquid chromatography

A new extension of chemiluminescence technique using pre-oxidation of a carrier solvent before the conventional inhibited chemiluminescence detection is presented in this study. The method is based on the modification of the oxidation chemistry of pyrogallol upon contact with a flow stream consisting of an organic solvent in mixture with an aqueous solution of a soft oxidant. The final response was found to depend on the kind of solvent and the oxidant/pre-oxidant mixture employed for the oxidation of pyrogallol and the solvent, respectively. By selecting the appropriate combination two detection modalities with increased sensitivity can be achieved. The first is based on the enhancement of the analytes signal through intensification of their scavenging effect on pyrogallol oxidation and the second on the enhancement of signal above the emission induced during the pyrogallol oxidation. Various combinations of organic solvents, oxidizing and pre-oxidizing mixtures were examined for their response in inhibited chemiluminescence measurements yielding very interesting results. The analytical utility of this new technique to the improvement of previous analytical methods as well as to the development of new procedures employing flow injection analysis is demonstrated. Furthermore, the application of the proposed method in combination with liquid chromatographic analysis is also presented.     

Development and validation of a liquid chromatography-electrosprayionization mass spectrometric method for the determination of dexamethasone in sheep plasma

A quantitative liquid chromatographic-electrospray ionization mass spectrometric method for the determination of dexamethasone in sheep plasma has been developed and validated. The samples were extracted using solid-phase extraction cartridges with mixed reversed-phase materials (oasis-HLB). The chromatographic separation was performed on a reversed-phase XTerrra MS C₁₈ column ( mm; 5 μm) using a mobile phase consisting of 65% methanol in water containing 0.1% (v/v) formic acid, pumped at a flow rate of 0.30 ml min⁻¹. The analyte was detected after positive electrospray ionization using selected ion monitoring (SIM) mode. The probe heater temperature was set at 260 °C, the capillary voltage was set at 3.5 kV and the source block voltage (AQA_max) was set at 30 V. The method was fully validated. Calibration graphs were linear (r better than 0.998, n=11), in concentration ranges 6-1000 ng ml⁻¹ for dexamethasone. The intra- and inter-day RSD values were less than 24.1% (n=6). The limits of detection and quantitation for dexamethasone were found to be 1 and 6 ng ml⁻¹, respectively. The efficiency of the solid phase extraction procedure was found to be 92.4% for dexamethasone. The method was further applied to a pilot kinetic study in order to assess the main pharmacokinetic parameters of dexamethasone in sheep.     

Low-temperature brewing by freeze-dried immobilized cells

We propose a novel biocatalyst in brewing. A cryotolerant strain of Saccharomyces cerevisiae was immobilized on delignified cellulosic material followed by freeze-drying of the immobilized cells without the use of any cryoprotectant. The freeze-dried immobilized biocatalyst was used in repeatedbatch fermentation of wort and showed reduced fermentation time and increased productivities as compared with free freeze-dried cells (FFDCs). It also demonstrated suitability for low-temperature brewing (5 and 0°C). The fermentation time in repeated-batch fermentations at 15°C was 1.5–2 d for a period of 13 mo, showing a high operational stability of the system. At 0°C the freeze-dried immobilized biocatalyst showed a 2- to 3.5-fold decrease in fermentation time in comparison with FFDCs. Polyphenol contents, bitterness, and diacetyl concentration were lower in beers produced by freezedried immobilized cells as compared with FFDCs. At 0°C polyphenols were 40% lower than at 15°C. Higher alcohols were reduced and ethyl acetate increased in comparison with FFDCs. Amyl alcohols at 0°C were lower than half of their content at 15°C, while ethyl acetate was 31 mg/L at 0°C and 18 mg/L at 15°C. These data justify the improved aroma and taste of beers produced by freeze-dried immobilized biocatalyst mainly at low temperatures.     

Combining combinatorial chemistry and affinity chromatography: highly selective inhibitors of human betaine: homocysteine S-methyltransferase

A new method to find novel protein targets for ligands of interest is proposed. The principle of this approach is based on affinity chromatography and combinatorial chemistry. The proteins within a crude rat liver homogenate were allowed to interact with a combinatorial library of phosphinic pseudopeptides immobilized on affinity columns. Betaine: homocysteine S-methyltransferase (BHMT) was one of the proteins that was retained and subsequently eluted from these supports. The phosphinic pseudopeptides, which served as immobilized ligands for the isolation of rat BHMT, were then tested for their ability to inhibit human recombinant BHMT in solution. The most potent inhibitor also behaved as a selective ligand for the affinity purification of BHMT from a complex media. Further optimization uncovered Val-Phe-psi[PO(2-)-CH(2)]-Leu-His-NH(2) as a potent BHMT inhibitor that has an IC(50) of about 1 microM.     

Cluster-cluster aggregation kinetics and primary particle growth of soot nanoparticles in flame by light scattering and numerical simulations

The agglomeration kinetics of growing soot generated in a diffusion atmospheric flame are here studied in situ by light scattering technique to infer cluster morphology and size (fractal dimension D(f) and radius of gyration R(g)). SEM analysis is used as a standard reference to obtain primary particle size D(P) at different residence times. The number N(P) of primary particles per aggregate and the number concentration n(A) of clusters are evaluated on the basis of the measured angular patterns of the scattered light intensity. The major finding is that the kinetics of the coagulation process that yields to the formation of chain-like aggregates by soot primary particles (size 10 to 40 nm) can be described with a constant coagulation kernel beta(c,exp)=2.37x10(-9) cm3/s (coagulation constant tau(c) approximately = 0.28 ms). This result is in nice accord with the Smoluchowski coagulation equation in the free molecular regime, and, vice versa, it is in contrast with previous studies conducted by invasive (ex situ) techniques, which claimed the evidence in flames of coagulation rates much larger than the kinetic theory predictions. Thereafter, a number of numerical simulations is implemented to compare with the experimental results on primary particle growth rate and on the process of aggregate reshaping that is observed by light scattering at later residence times. The restructuring process is conjectured to occur, for not well understood reasons, as a direct consequence of the atomic rearrangement in the solid phase carbon due to the prolonged residence time within the flame. Thus, on one side, it is shown that the numerical simulations of primary size history compare well with the values of primary size from SEM experiment with a growth rate constant of primary diameter about 1 nm/s. On the other side, the evolution of aggregate morphology is found to be predictable by the numerical simulations when the onset of a first-order "thermal" restructuring mechanism is assumed to occur in the flame at about 20 ms residence time leading to aggregates with an asymptotic fractal dimension D(f,infinity) approximately = 2.5.     

Multipurpose organically modified carbon nanotubes: from functionalization to nanotube composites

We show that covalent functionalization of carbon nanotubes (CNTs) via 1,3-dipolar cycloaddition is a powerful method for enhancing the ability to process CNTs and facilitating the preparation of hybrid composites, which is achieved solely by mixing. CNTs were functionalized with phenol groups, providing stable dispersions in a range of polar solvents, including water. Additionally, the functionalized CNTs could easily be combined with polymers and layered aluminosilicate clay minerals to give homogeneous, coherent, transparent CNT thin films and gels.