Use of alkane monolayer templates to modify the structure of alkyl ether monolayers on highly ordered pyrolytic graphite

Scanning tunneling microscopy (STM) has been used to investigate the structure of pure and mixed monolayers formed by adsorption of long-chain alkanes and/or ethers on highly ordered pyrolytic graphite. Application of a pure phenyloctane solution of simple alkanes, such as tritriacontane, CH3(CH2)31CH3, produced a monolayer within which the individual molecular axes were oriented perpendicular to the lamellar axes. In contrast, a pure solution of symmetrical long-chain ethers, such as di-n-hexadecyl ether, CH3(CH2)15O(CH2)15CH3, produced a monolayer within which the molecular axes were oriented at an angle of approximately 65 degrees relative to the lamellar axes. The compositions of the overlying solutions were then gradually changed either from pure alkanes to nearly pure ethers or from pure ethers to nearly pure alkanes. When ethers replaced alkanes in the monolayer, the ethers conformed to the orientation within the existing alkane layer, rather than adopting the characteristic orientation of pure ether monolayers. However, when alkanes were incorporated into monolayers that had been formed from pure ether solutions, the orientation of the molecules within the monolayer converted to that characteristic of pure alkanes. Alkane monolayers thus acted as templates for subsequent ether layers, but ether monolayers did not act as templates for alkane layers.     

Single enantiomer epoxides by bromomandelation of prochiral alkenes

A combination of mandelic acid and N-bromosuccinimide efficiently converts prochiral alkenes into a readily separable 1:1 mixture of the bromomandelates. The diastereomerically pure bromomandelates are then converted into a variety of enantiomerically pure products. Terminal alkenes are converted into enantiomerically pure epoxides. Cyclohexene is converted into enantiomerically pure cis-2-azidocyclohexanol and cis-2-phenylthiocyclohexanol.     

Objects of inquiry in classical chemistry: material substances

I argue in the paper that classical chemistry is a science predominantly concerned with material substances, both useful materials and pure chemical substances restricted to scientific laboratory studies. The central epistemological and methodological status of material substances corresponds with the material productivity of classical chemistry and its way of producing experimental traces. I further argue that chemist??s ??pure substances?? have a history, conceptually and materially, and I follow their conceptual history from the Paracelsian concept of purity to the modern concept of pure stoichiometric compounds. The history of the concept of ??pure substances?? shows that modern chemists?? concept of purity abstracted from usefulness rather than being opposed to it. Thus modern chemists?? interest in pure chemical substances does not presuppose a concept of pure science.     

Synthesis of Pure Silica Zeolites

Pure silica zeolite has become an important porous material in the chemical industry due to its excellent stability and hydrophobicity. However, there are still some problems in the synthesis process of pure silica zeolite, such as environmental pollution, complex operation and high cost. How to effectively and environmentally synthesize pure silica zeolite still remains a significant challenge. This review summarizes the pure silica zeolitetype frameworks that have been discovered currently, introduces the progresses achieved in the synthesis of pure silica zeolite and prospects the areas for future exploration in the synthesis and development of pure silica zeolite.     

Thermo-oxidative degradation of novel epoxy containing silicon and phosphorous nanocomposites

Modified epoxy nanocomposites containing silicon and phosphorous was prepared and compared with pure epoxy. The study of thermo-oxidative degradation of modified epoxy nanocomposites and pure epoxy has been utilized by thermal analysis. The thermal stability of modified epoxy nanocomposites is not superior to that of the pure epoxy at low temperature, however, the char yield of modified epoxy nanocomposites is higher than that of the pure epoxy at 800 °C in air atmosphere. The modified epoxy nanocomposites possess better thermal stability at high temperature range. The values of the limiting oxygen index of pure epoxy and modified epoxy nanocomposites are 24 and 32, respectively. This indicates that modified epoxy nanocomposites possesses better flame retardance.By the Kissinger’s method, the activation energies of thermo-oxidative degradation for epoxy nanocomposites are less than those of thermo-oxidative degradation for pure epoxy in first stage of thermo-oxidative degradation. However, the activation energies of thermo-oxidative degradation for epoxy nanocomposites are more than those of thermo-oxidative degradation for pure epoxy in second stage of thermo-oxidative degradation.     

Mixed electric-magnetic second-order nonlinear optical response of helicenes

The mixed electric-magnetic second-order nonlinear optical responses of oriented films of helicenes have been computed ab initio using the random phase approximation method and compared to the pure electric-dipole counterpart. It turns out that the mixed electric-magnetic responses can be of the same order of magnitude as the pure electric-dipole counterpart when there is no donor/acceptor (D/A) substituent or these D/A pairs are weak, i.e., when the pure electric-dipole response is small. When adding strong D/A substituents, the pure electric-dipole response increases substantially and much more than its mixed electric-magnetic counterpart. Consequently, the ratio between the mixed electric-magnetic and pure electric responses decreases. Although there is no general rule, the mixed responses evolve as a function of substitution quasi similarly to the pure electric contribution. This study confirms therefore the possibility of tuning the mixed electric-magnetic response by employing appropriate chiral molecules.     

Studies on cellulose acetate-carboxylated polysulfone blend ultrafiltration membranes--Part I

Hydrophilic polysulfone ultrafiltration (UF) membranes were prepared from blends of cellulose acetate with carboxylated polysulfone of 0.14 degree of carboxylation. The effects of blend polymer composition on compaction, pure water flux, water content and membrane hydraulic resistance (R_m), have been investigated to evaluate the performance of the membranes. The performance of the blend membranes of various blend polymer compositions were compared with that of membranes prepared from pure cellulose acetate and blends of cellulose acetate and pure polysulfone. The hydrophilic cellulose acetate-carboxylated polysulfone blend UF membranes showed better performance compared to membranes prepared from pure cellulose acetate and blends of cellulose acetate and pure polysulfone.     

Preparation of optically pure α-trifluoromethyl-α-amino acids from N-tosyl-2-trifluoromethyl-2-alkyloxycarbonyl aziridine

The preparation of optically pure α-trifluoromethyl-α-amino acids from N-tosyl-2-trifluoromethyl-2-alkyloxycarbonylaziridine is described. Optically pure aziridine was prepared with a 60% yield via three steps from optically pure 2,3-epoxy-1,1,1-trifluoropropane (TFPO). Ring-opening reactions of the aziridine with a variety of nucleophiles and subsequent deprotection of the N-tosyl moieties gave the optically pure β-substituted-α-trifluoromethyl-α-amino acids in moderate to good yields (up to 85%) without racemization at the quaternary stereogenic center of the amino acid.     

Multi‐component analysis: blind extraction of pure components mass spectra using sparse component analysis

The paper presents sparse component analysis (SCA)‐based blind decomposition of the mixtures of mass spectra into pure components, wherein the number of mixtures is less than number of pure components. Standard solutions of the related blind source separation (BSS) problem that are published in the open literature require the number of mixtures to be greater than or equal to the unknown number of pure components. Specifically, we have demonstrated experimentally the capability of the SCA to blindly extract five pure components mass spectra from two mixtures only. Two approaches to SCA are tested: the first one based on ?₁ norm minimization implemented through linear programming and the second one implemented through multilayer hierarchical alternating least square nonnegative matrix factorization with sparseness constraints imposed on pure components spectra. In contrast to many existing blind decomposition methods no a priori information about the number of pure components is required. It is estimated from the mixtures using robust data clustering algorithm together with pure components concentration matrix. Proposed methodology can be implemented as a part of software packages used for the analysis of mass spectra and identification of chemical compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Generation and reactions of α-trifluoromethyl stabilized aziridinyl anion, a general synthetic precursor for stereospecific construction of α-amino-α-trifluoromethylated quaternary carbon

Optically pure α-trifluoromethylated aziridinyl anions react with various electrophiles to give the corresponding optically pure 2-trifluoromethyl-2-substituted aziridines, which are general synthetic precursors for optically pure α-amino-α-trifluoromethylated compounds, such as trifluoromethylated α/β-amino acids, in good yields.     

1,1'-Binaphthyl-2,2'-diyl phosphoroselenoyl chloride as a chiral molecular tool for the preparation of enantiomerically pure alcohols and amines

Enantiomerically pure phosphoroselenoyl chloride bearing a binaphthyl group was synthesized. This phosphoroselenoyl chloride was used to discriminate and resolve simple secondary alcohols. Stereospecific conversions of diastereomerically pure phosphoroselenoic acid esters, obtained by reaction of the chloride with simple secondary alcohols, to enantiomerically pure alcohols and amines were also achieved.     

How surface tension of surfactant solutions influences the characteristics of sprays produced by hydraulic nozzles used for pesticide application

The sprays produced by hydraulic agricultural nozzles are influenced by the surface tension of the spray liquid, but models of spray formation relate only to pure liquids with constant surface tension. The way surfactant solutions affect spray formation is studied by investigating sprays of pure liquids compared with a range of surfactant solutions. Some surfactants caused changes in the appearance of the liquid sheet produced by the nozzles, which did not occur with pure liquids, and smaller spray drop sizes than pure liquids, suggesting that other surface properties may also be important.     

Regio- and stereoselective synthesis of Z-vinylic tellurides from propargylic alcohols: a route to chiral Z-enynes

tert-Butyldimethylsilyl ethers of propargylic alcohols are hydrotellurated regioselectively to give 1,2-Z-vinylic tellurides. Enantiomerically pure propargylic alcohols give enantiomerically pure vinylic tellurides, which are coupled with alkynes under Pd catalysis to give enantiomerically pure allylic enynols.     

乳化结晶法制精蒽新工艺的研究

研究了用乳化结晶法从粗蒽制精蒽的新工艺，考察了溶剂种类、乳化剂种类、乳化剂用量、水／粗蒽质量比、助剂加入量以及结晶终温等因素对精蒽质量的收率的影响，实验结果表明：以糖醛作溶剂，米唑啉物Ｓｐａｎ２０复合型乳化剂，经一次乳化结晶得得精蒽纯度大于９５％，符合国家一级精蒽标准，蒽收率大于８０％。     

水-甲醇体系的Monte Carlo分子膜拟

本文应用Monte Carlo分子膜拟方法对水、甲醇水-甲醇的1:1混合物、甲醇无限稀释时的水溶液和水无限稀释时的甲醇溶液等五个体系进行了研究。采用TIP分子位能函数, 得到了上述体系的热力学性质、原子径向分布函数、分子氢键配位数分布。并以Monte Carlo分子模拟获得的结构函数与X射线衍射实验结果进行了比较。     

Synthesis of enantiomerically pure analogues of the meta-substituted aniline antibiotics

A practical route is described for the preparation of enantiomerically pure analogues of the meta-substituted aniline antibiotics. Starting with enantiomerically pure anilinide, photooxygenation, reduction and diastereoselective Weitz-Scheffer epoxidation protocols provide enantiomerically pure analogues of the meta-substituted aniline antibiotics in three steps.     

Enantiospecific synthesis of norcoronamic acids

The synthesis of enantiomerically pure norcoronamic acids, starting from enantiomerically pure 1,2-propanediols, is described.     

微波－气相－热压法分解高纯铂的研究

本文研究了微波气相热压法新技术分解高纯铂在密闭的聚四氟乙烯高压罐中，以微波瞬间加热混合酸产生的高压、纯净蒸气分解金属铂，此法避免了酸中杂质的沾污以制备供高纯铂分析的试液，提高了痕量杂质分析的准确度和降低检测限     

Temperature‐Controlled Bidirectional Enantioselectivity in a Dynamic Catalyst for Asymmetric Hydrogenation

Asymmetric catalysis using enantiomerically pure catalysts is one of the most widely used methods for the preparation of enantiomerically pure compounds. The separate synthesis of both enantiomerically pure compounds requires tedious and time‐consuming preparation of both enantiomerically pure catalysts or chiral separation of the racemic products. Here, we report a stereochemically flexible diastereomeric rhodium(I) catalyst for asymmetric hydrogenations of prochiral (Z)‐α‐acetamidocinnamates and α‐substituted acrylates, which changes its enantioselectivity depending on the temperature to produce each enantiomerically pure compound in high yield with constant high enantioselectivity over time. The same axially chiral rhodium(I) catalyst produces (R)‐phenylalanine derivatives in enantiomeric ratios of up to 87:13 (R/S) at low temperature and up to 3:97 (R/S) of the corresponding S enantiomers after re‐equilibration of the same catalyst at elevated temperature.     

用逆向神经元模型从两维混和谱中提取纯组分两维光谱

提出一种少输入、多输出节点的逆向神经元模型.当训练样本数大于模型输入节点数时,可以得到唯一的神经元模型权重.所求得的权重是混合物中组分的纯光谱.将蒽、菲、芘混合物的荧光激发-发射光谱中提取的纯光谱与实验谱作了比较,并分别作为广义减秩法的校准预报未知混合物的浓度.结果表明所求得的谱比实验谱更适合于作校准.对于蒽、菲、芘、平均预报百分误差从7.0%、8.5%、7.8%分别下降到2.3%、5.0%、3.5%.