The synthesis of chromenes, chromanes, coumarins and related heterocycles via tandem reactions of salicylic aldehydes or salicylic imines with alpha,beta-unsaturated compounds

The tandem reactions of salicylic aldehydes or salicylic imines with alpha,beta-unsaturated compounds have only been studied systematically in recent years. These tandem reactions provide an easy access to a variety of heterocycles, such as chromanes, chromenes, coumarins and tetrahydroxanthenones, many of which are synthetic useful intermediates.     

Enantio‐ and Diastereoselective Access to Distant Stereocenters Embedded within Tetrahydroxanthenes: Utilizing ortho‐Quinone Methides as Reactive Intermediates in Asymmetric Brønsted Acid Catalysis

A protocol for the highly enantioselective synthesis of 9‐substituted tetrahydroxanthenones by means of asymmetric Brønsted acid catalysis has been developed. A chiral binol‐based N‐triflyphosphoramide was found to promote the in situ generation of ortho‐quinone methides and their subsequent reaction with 1,3‐cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio‐ and diastereoselective Brønsted acid catalyzed desymmetrization of 5‐monosubstituted 1,3‐dicarbonyl substrates with ortho‐quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.     

Static fatigue fracture of polyethylene: A morphological analysis

The fracture properties of a number of high-density polyethylenes were evaluated and related to their morphology. The resistance to initiation of fracture is related to the resistance to voiding of the materials and the rate of coalescence of voids. The propensity of the materials to void has been shown to be related to the size of the amorphous region. The resistance to propagation of the fracture is also related to the above factors as well as the ease of stretching and rupture of fibrils. The ease of fibril formation has been shown to be related to the degree of perfection of the crystallites.     

DataCite and DOI names for research data

The publication of research data is still not a widespread practice in many disciplines. The lack of acceptance of data as scientific output equal to scientific articles, and the lack of suitable infrastructures for the storage of data make it difficult to publish and cite data independently. The global consortium DataCite was established in 2009 to overcome the challenges of data citation. The aim of the consortium is to establish easy access to data, to increase the acceptance of data publication and to support data archiving. The use of Digital Object Identifiers (DOI) provides an easy method to access and re-use research data. The DOI facilitates the citation of data and therefore increases the availability and acknowledgement of research data.     

成都经济生态区大气降尘中镉赋存形态的研究

采用Tessier连续提取法对成都经济生态区不同区域的24个大气降尘样中镉的赋存形态进行了研究。研究结果表明,大气降尘中的镉主要以残留态形态存在;各形态镉在总镉中所占百分比含量由大到小排列顺序依次是:残留态,碳酸盐结合态,交换态,铁锰结合态,有机结合态;交换态镉、碳酸盐结合态镉这两种具有较高生物有效性的形态镉在总镉中所占的平均百分比含量分别是6.420%和8.917%;铁锰氧化物结合态、有机结合态、残留态镉这三种形态镉生物有效性很低,分别在总镉中所占的平均百分比含量分别是3.419%、2.365%和78.907%。通过分析可得出,汽油和煤的燃烧以及工厂排放镉能加大城市大气降尘的镉污染。     

Determination of phenols and phenates in disinfectant formulations by liquid chromatography with UV detection: collaborative study

Fourteen collaborating laboratories assayed o-phenylphenol (OPP), p-t-amylphenol (PTAP), and o-benzyl-p-chlorophenol (OBPCP) in formulated products, both ready-to-use and concentrates, by RP-HPLC. The actives in the samples ranged from 0.03 to 11% OPP, 0.06 to 4% PTAP, and 0.07 to 10% OBPCP either in free forms or as salts. Seven blind duplicates were analyzed. The samples were diluted/extracted with acidified methanol, filtered, and analyzed by LC on a C18 column using gradient elution and UV detection at 285 nm. The concentration of the active ingredients was calculated from a standard curve. Each laboratory weighed each test sample twice within a single analytical run. The data were analyzed using all 14 laboratory results, with appropriate statistical tests to detect outliers. The repeatability RSDs ranged from 0.98 to 3.40% for the free phenols, and 1.26 to 2.51% for the salts. The reproducibility RSDs ranged from 5.31 to 7.80% for the free phenols, and 5.50 to 8.67% for the salts. The HorRat ranged from 0.86 to 2.17 for the free phenols, and 1.54 to 2.72 for the salts.     

Hybridized particle swarm algorithm for adaptive structure training of multilayer feed-forward neural network: QSAR studies of bioactivity of organic compounds

The multilayer feed-forward ANN is an important modeling technique used in QSAR studying. The training of ANN is usually carried out only to optimize the weights of the neural network and without paying attention to the network topology. Some other strategies used to train ANN are, first, to discover an optimum structure of the network, and then to find weights for an already defined structure. These methods tend to converge to local optima, and may also lead to overfitting. In this article, a hybridized particle swarm optimization (PSO) approach was applied to the neural network structure training (HPSONN). The continuous version of PSO was used for the weight training of ANN, and the modified discrete PSO was applied to find appropriate the network architecture. The network structure and connectivity are trained simultaneously. The two versions of PSO can jointly search the global optimal ANN architecture and weights. A new objective function is formulated to determine the appropriate network architecture and optimum value of the weights. The proposed HPSONN algorithm was used to predict carcinogenic potency of aromatic amines and biological activity of a series of distamycin and distamycin-like derivatives. The results were compared to those obtained by PSO and GA training in which the network architecture was kept fixed. The comparison demonstrated that the HPSONN is a useful tool for training ANN, which converges quickly towards the optimal position, and can avoid overfitting in some extent.     

Electrochemistry of the bis(1,4,7-triazacyclodecane) cobalt(III) complex and its role in the catalytic reduction of hydrogen

The electrochemistry of the bis(1,4,7-triazacyclodecane) cobalt(III) complex at a mercury electrode, HMDE, in aqueous Britton–Robinson buffer solutions was investigated using cyclic voltammetry, double-potential-step chronoamperometry and chronocoulometry. The cyclic voltammetric data were analyzed by digital simulation to confirm and to measure the heterogeneous and homogeneous parameters for the suggested electrode mechanism. Generally, the complex is electrochemically reduced giving rise to two cyclic voltammetric waves. The first wave is a diffusion-controlled reversible wave. It is assigned to the stable Co(III)/Co(II) redox couple. The second one is found to be irreversible and corresponding to a reduction of Co(II) to Co(I) species. The monovalent cobalt, highly unstable, is rapidly protonated, and then forms cobalt hydride. The hydride decomposes to hydrogen molecules and regenerates Co(II) species following a disproportionation pathway. The overall reduction mechanism is concluded to be an EECC kinetics.     

Explicit finite difference simulations for accelerating cross diffusion flow over a perpendicular shield with parabolic motion

The heat transfer phenomenon subject to thermos-diffusion effects convey important applications in the heating processes, extrusion systems, chemical processes and various engineering systems. The objective of current work is to observe the contribution of Soret and Dufour effects in oscillating shield for cross diffusion flow. The perpendicular shield with oscillating motion induced the flow. The magnitude of oscillations is assumed to be small so that laminar flow due to oscillating shield has been resulted. The motivations for addressing the thermos-diffusion phenomenon due to oscillating of shield are due to applications in oscillatory pumps, moving surface, metal detectors, power systems etc. The dimensionless problem is obtained via introducing the appropriate set of variables. The numerical outcomes are suggested by using the most interesting explicit finite difference scheme. The physical illustration for flow parameters is presented. Moreover, the aspect of physical quantities involving the flow are graphically reported.     

铜基催化剂的制备方法对草酸二乙酯加氢反应的影响

草酸二乙酯加氢性成乙二醇的反应过程中，所用的铜基催化剂是由Ｃｕ（ＮＯ３）２与硅溶胶凝法制得的。本文考察了该催化剂的ＴＰＲ特性，结果表明，随着催化剂中Ｃｕ／ＳｉＯ２值的增大，其ＴＰＲ主峰ＴＭ峰温有所升高，这意味着催化剂的还原温度随Ｃｕ／ＳｉＯ２值的增大而提高。用ＸＲＤ和ＸＰＳ等手段对该催化剂还原后铜的含量及价态进行了考察，表明用胶凝法制备的铜基催化剂，还原后存在Ｃｕ＾ｏ和Ｃｕ＾＋两种价态。结合活性评     

Studies of the Rate Constant of l-DOPA Oxidation and Decarboxylation by HPLC

The objective of current investigation was to study the degradation behavior of l-DOPA under different conditions by high performance liquid chromatography (HPLC), and to develop and validate a stability-indicating HPLC method. The developed RP-HPLC method was validated with respect to linearity, accuracy, precision and specificity. Oxidation was found to occur in alkaline and to some extent in thermal conditions, while the drug was stable when incubated at acidic conditions and under photolytic stress. The oxidation of l-DOPA was observed to follow first-order kinetics. The degradation rate constants and half-life were calculated. The cytotoxicity and enzymatic degradation of l-DOPA was examined using the human intestinal epithelial Caco-2 cells. The drug was rapidly decarboxylated by aromatic amino acid decarboxylase to dopamine. The conversion of l-DOPA to dopamine was dose- and time-dependent.     

Monte Carlo simulations of a coarse grained model for an athermal all-polystyrene nanocomposite system

The structure of a polystyrene matrix filled with tightly cross-linked polystyrene nanoparticles, forming an athermal nanocomposite system, is investigated by means of a Monte Carlo sampling formalism. The polymer chains are represented as random walks and the system is described through a coarse grained Hamiltonian. This approach is related to self-consistent-field theory but does not invoke a saddle point approximation and is suitable for treating large three-dimensional systems. The local structure of the polymer matrix in the vicinity of the nanoparticles is found to be different in many ways from that of the corresponding bulk, both at the segment and the chain level. The local polymer density profile near to the particle displays a maximum and the bonds develop considerable orientation parallel to the nanoparticle surface. The depletion layer thickness is also analyzed. The chains orient with their longest dimension parallel to the surface of the particles. Their intrinsic shape, as characterized by spans and principal moments of inertia, is found to be a strong function of position relative to the interface. The dispersion of many nanoparticles in the polymeric matrix leads to extension of the chains when their size is similar to the radius of the dispersed particles.     

Study on the Formation Mechanism of Oxygen-containing Groups on the Surfaces of Hypercrosslinked Polystyrenes

Davankov and Tsyurupa described a new series of hypercrosslinked polymeric networks in 19691. Owing to their high internal surface area, unique porosity, and excellent swelling feature, hypercrosslinked polymers have exhibited a good adsorption affinity t…     

先锋褐煤在水热处理过程中的结构演绎

以先锋褐煤(XF)为原料,在高压反应釜中考察了水热处理过程中褐煤的结构变化,通过13C固体核磁共振(NM R)和傅里叶变换红外光谱进行了分析表征。结果表明,在低于240℃的水热处理条件下,煤有机分子结构中的弱化学键有一定断裂,含氧官能团逐步减少;水中氢以离子形态迁移至褐煤中,处理后褐煤结构中甲基比例先增加后减少,次甲基比例由原煤的4.80%增加至XF-240的13.16%;释放的气体中主要是CO_2,烃类气体组分随处理温度的升高略有增加。当水热处理温度高于240℃时,褐煤中部分共价键开始断裂,释放的烃类气体(C1-4)由240℃时的2.13%增加至300℃时的8.59%,脂肪碳比例由XF-240的44.83%降低至XF-300的39.49%,与氧连接的碳比例由XF-240的12.57%降低至XF-300的1.49%。水热处理对褐煤的脱氧提质效果显著,300℃时氧含量降低约30%,芳香碳比例增加至60.50%,比原煤提高19%。     

Highly reusable chitosan-stabilized Fe-ZnO immobilized onto fiberglass cloth and the photocatalytic degradation properties in batch and loop reactors

The new design of the photocatalytic reactor is crucial to study for improving compatibility and scaling up the operation. A compatible loop photocatalytic reactor has been designed and used for rhodamine B decomposition. The photocatalysts were either ZnO or Fe-ZnO immobilized onto fiberglass cloth. The ZnO catalyst exhibited high crystallinity with or without Fe as the dopant. The crystallite size increased with the presence of Fe in the lattices. Most of the crystal parameters matched the standard ZnO data, and the cluster size was comparable to most reported studies. Diffuse Reflectance Spectroscopy (DRS) analysis confirmed the photon absorption shifted to the visible light range. The Fe dopant decreased the ZnO bandgap, and SEM-EDS confirmed the catalysts adhered to the fiberglass surface. The volume, thickness of the substrate solution, and reaction temperature influenced the photocatalytic-degradation rate. The photocatalytic degradation rate was higher under sunlight than ultraviolet irradiation. The reaction rate was lower in the batch reactor than in the loop reactor. The photocatalytic reaction almost completely mineralized RhB and changed the red solution to colorless. The immobilized photocatalyst has been reused more than 50 times without significantly decreasing the catalytic activity.     

Preliminary evaluation of interactions between selected alcoholamines and model skin sebum components

The aim was to evaluate the interaction between selected alcoholamines and components of artificial skin sebum. The rate and depth of penetration into the lipophilic bead imitating pilosebaceous unit lumen was applied for alcoholamine penetration activity assay. The activity differentiation of 0.5% aqueous alcoholamine solutions with a potential cleansing effect on the pilosebaceous unit was performed. The depth of aminomethylpropanol penetration increased from 0.080 mm after 15 min to 3.049 mm after 72 h. The depth of aminomethylpropendiol penetration increased with time from 0.148 to 4.064, respectively, of diisopropanolamine from 0.481 to 4.626, triethanolamine from 0.236 to 4.342, triisopropanolamine from 0.275 to 2.392 and trometamol from 0.338 to 4.580. The products of alcoholamines reaction with the model skin sebum are easily dispersed in water. The rate of alcoholamines reaction with the model skin sebum depends on the alcoholamine, being the highest in the case of diisopropanolamine, decreasing to minimum for triisopropanolamine. Selected alcoholamines would be applied in ex vivo and in vivo research.     

Dosimetric and spectroradiometric investigations of glass filtered solar UV

The aims of this paper were to investigate how glass-filtered UV irradiances vary with glass thickness, lamination of the glass and the effect of solar zenith angle (SZA), and to measure the glass-filtered UV exposures to different receiving planes with a newly developed UVA dosimeter. Spectroradiometric and dosimetric techniques were employed in the experimental approach. The percentage of the glass-filtered solar UV compared to the unfiltered UV ranged from 59% to 70% and was influenced to a small extent by the glass thickness and the SZA. The laminated glass transmitted 11 to 12% and the windscreen glass transmitted 2.5-2.6%. The influence of the SZA was less for the thicker glass than it was for the thinner glass. The change in transmission was less than 14% for the SZA between 48 degrees and 71 degrees. There was negligible influence due to the SZA on the glass-transmitted UV of the laminated and windscreen glass. The influence of the glass thickness in the range of 2-6 mm on the percentage transmission was less than 16%. The influences of the glass thickness and the SZA on the glass-transmitted UV have been incorporated in the use of a UVA dosimeter for the glass-transmitted UV exposures. The UVA dosimeter was employed in the field to measure the glass-filtered UV exposures to different receiving planes. The UVA dosimeter reported has the potential for personal solar UVA exposure measurements.     

多壁碳纳米管固相微萃取纤维制备及其在海水中多溴联苯测定中的应用

通过以Nation为黏合剂、不锈钢丝为涂层载体,制备了多壁碳纳米管固相微萃取纤维．该纤维的制备方法快速、简便、成本低,并具有热稳定性好（300℃）、使用寿命长（〉100次）、对多溴联苯萃取效率高等特点．研究优化了影响萃取及分离效率的解吸温度和时间、萃取时间、搅拌速度、盐度等实验条件,进行了海水中多溴联苯的测定．对一溴联苯的线性范围为0．1-5．0ng／mL,而二溴联苯、三溴联苯、四溴联苯和五溴联苯的线性范围均为0．01～5．0ng／mL．方法的检测限为0．1～0．8ng／L．在优化的条件下分别测定了0．1和1ng／mL多溴联苯的海水加标样品,回收率在91．1％～107.3％之间,相对标准偏差小于12％．该方法分析时间短、灵敏度高、操作简便,适用于水样中多溴联苯的痕量分析．     

The embedded atom model for liquid metals: Liquid gallium and bismuth

A method for calculating embedded atom potentials in liquid metals is suggested. The method uses diffraction structural data, density, bulk compression modulus, and thermal expansion coefficient close to the melting point. The method was applied to liquid gallium and bismuth at temperatures from their melting to critical points. The critical temperatures of these metals were estimated at 4940 and 4225 K. The other critical parameters were also determined. The self-diffusion coefficients were found to increase almost linearly as the temperature grew. The model allows changes in the structural characteristics of the metals when the temperature increases by several hundred kelvin units to be correctly described.     

Thermal decomposition of pentacene oxyradicals

The energetics and kinetics of the thermal decomposition of pentacene oxyradicals were studied using a combination of ab initio electronic structure theory and energy-transfer master equation modeling. The rate coefficients of pentacene oxyradical decomposition were computed for the range of 1500-2500 K and 0.01-10 atm and found to be both temperature and pressure dependent. The computational results reveal that oxyradicals with oxygen attached to the inner rings are kinetically more stable than those with oxygen attached to the outer rings. The latter decompose to produce CO at rates comparable to those of phenoxy radical, while CO is unlikely to be produced from oxyradicals with oxygen bonded to the inner rings.