气相色谱法同步测定煤基油品的硫分布和沸点分布

应用火焰光度检测器与氢焰检测器偶联技术，通过对模拟蒸馏法的拓展，利用气相色谱仪同步测定了煤基油品的硫分布、沸点分布和总硫含量。结果表明：油品测定的准确性和重复性均较好，沸点分布、硫分布和总硫含量的最大相对标准偏差分别为0．47％、1．01％和2．51％。本方法需要样品量小，操作简便，比较适合于实验室煤基油品的分析研究。     

Theoretical study of nitric oxide adsorption on Au clusters

The adsorption properties of NO molecule on anionic, cationic, and neutral Au(n) clusters (n=1-6) are studied using the density functional theory with the generalized gradient approximation, and with the hybrid functional. For anionic and cationic clusters, the charge transfer between the Au clusters and NO molecule and the corresponding weakening and elongation of the N-O bond are essential factors of the adsorption. The neutral Au clusters have also remarkable adsorption ability to NO molecule. The adsorption energies of NO on the cationic clusters are generally greater than those on the neutral and anionic clusters.     

CeO2担载Cu纳米粒子电催化CO2还原产乙烯：CeO2不同暴露晶面对催化性能的影响

Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO₂, the primary greenhouse gas. Notably, the concentration of CO₂ in the atmosphere is increasing annually at an astounding rate. Electrochemical CO₂ reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO₂ emissions. Despite the steady progress in the selective generation of C₁ products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C₂H₄) has a higher energy density than do C₁ species and is an important industrial feedstock in high demand. However, the conversion of CO₂ to C₂H₄ is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C₂H₄ by taking advantage of the prominent interaction of Cu with shape-controlled CeO₂ nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO₂. The overall ECR Faradaic efficiency (FE) over Cu/CeO₂(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO₂(100) (FE ≈ 51.5%) and Cu/CeO₂(111) (FE ≈ 48.4%) in 0.1 mol·L^-1 KHCO₃ solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO₂(100), CeO₂(110), and CeO₂(111). In particular, the FE toward C₂H₄ formation and the partial current density increased in the sequence Cu/CeO₂(111) < Cu/CeO₂(100) < Cu/CeO₂(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO₂(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO₂(100) and Cu/CeO₂(111) were FE_C2H4 ≈ 31.8% and FE_C2H4 ≈ 29.6%, respectively. The C₂H₄ selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C₂H₄ remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO₂(110) to yield C₂H₄ was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO₂ but also remarkably stabilized Cu⁺, thereby boosting the ECR to produce C₂H₄. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering.     

Two new megastigmane O-glucopyranosides from the leaves of Broussonetia papyrifera

Two new megastigmane O-glucopyranosides,named (2R,3R,5R,6S,9R)-3-hydroxy-5,6-epoxy-β-ionol-2-O-β-D-glucopyrano- side(1) and (2R,3R,5R,6S,9R)-3-hydroxyl-5,6-epoxy-acety-β-ionol-2-O-β-D-glucopyranoside(2) together with six known mega- stigmanes,were isolated from the leaves of Broussonetia papyrifera (Linn.) Vent.Their structures were established by chemical methods and spectroscopic techniques including 2D NMR.     

Rapid simultaneous determination of four anthracene derivatives using a single non-linear variable-angle synchronous fluorescence spectrum

A rapid, simple and inexpensive spectrofluorimetric method has been developed for the simultaneous identification and quantification of anthracene (ANT), 9,10-dimethylanthracene (DIM), 2-aminoanthracene (AMI) and dibenz[ah]anthracene (DIB). A well-resolved spectrum for the mixture of these four compounds is obtained based on a single non-linear variable-angle synchronous scanning. The linear concentration ranges are 10-1,000, 5-500, 50-1,000 and 10-200 ng mL(-1) for ANT, DIM, AMI and DIB, respectively, at lambdaex/lambdaem = 358/380, 399/408, 414/465 and 298/394 nm, respectively. The analyses are performed in cyclohexane. Recoveries of 90.0-111.0% in synthetic mixtures are obtained. The detection limits are 2.0 ng mL(-1) for DIM, 2.7 ng mL(-1) for ANT, 15.8 ng mL(-1) for AMI and 4.2 ng mL(-1) for DIB. The method has also been applied to several real water samples with satisfactory results.     

Studies of synergism for lowering dynamic interfacial tension in sodium alpha-(n-alkyl) naphthalene sulfonate/alkali/acidic oil systems

Alkylnaphthalene sulfonates with high purity were selected as model components to research synergism for lowering interfacial tension (IFT) in surfactant/alkali/acidic oil systems. The dynamic IFTs between alkylnaphthalene sulfonates with different alkyl chain length and n-decane, oleic acid model oil, or Shengli crude oil were measured. The results showed that the alkylnaphthalene sulfonates with different alkyl chain lengths had different synergism with different acidic components and their ionized acids under the same conditions. The synergism for lowering dynamic IFT in alkylnaphthalene sulfonate/alkali/acidic oil systems was controlled by alkylnaphthalene sulfonate concentration, alkyl chain length, alkali concentration, alkali type, and oleic acid concentration: optimal physicochemical conditions were necessary to the best synergism. This indicates that the synergism among added surfactant acidic components in crude oil and their ionized acids is controlled by the ratio of their interfacial concentrations.     

塔板理论对柱内和柱外浓度分布曲线的描述

使用Visual Basic和QBasic程序，分别在Excel和DOS上，在不做任何化简的情况下，对塔板理论描述的柱内和柱外组分浓度分布进行了研究。发现符合线性分配的样品组分在色谱柱内存在3种不同的浓度分布形态，在色谱柱外则都是拖尾峰形态。分析了不同分配比对柱内和柱外浓度分布曲线最高点和次高点的影响。     

羧甲基壳聚糖衍生物及其振动光谱的理论研究

用量子化学从头算STO 3G法研究了羧甲基壳聚糖及其衍生物的结构和稳定性，计算结果表明:1)壳聚糖单体经羧甲基化后，得到2种可能的产物，其中羧甲基在壳聚糖单体2位氨基上的取代产物较6位羟基上的取代产物稳定； 2)以羧甲基壳聚糖为母体经加成反应，得到羧甲基壳聚糖衍生物（2 羟基 3 丁氧基）丙基 羧甲基壳聚糖的2个异构体， 其中构型1更稳定.在优化构型的基础上，计算所得的构型1的振动光谱与实验结果相吻合.     

The 1,3-Dipolar Cycloadditions of Nitrile Oxides and Nitrile Imines to Alkyl Dicyanoacetates

The readily available alkyl dicyanoacetates 1 reacted with the 1,3-dipolar reagents arenecarbonitrile oxides 2 ′ and arenecarbonitrile imines 5 ′ to afford 1,2,4-oxadiazol and 1,2,4-triazol derivatives. The arenecarbonitrile oxides 2 ′ with electron-donating groups on the arene ring gave products 3a – d resulting from addition on both CN groups of 1 , and those with electron-withdrawing groups provided mono-adducts 4a – e (Scheme 1). Arylnitrile imines 5 ′ reacted with 1 to offer both bis- and mono-addition products (Scheme 2); the bis-adducts 8a , b possess an ester structure, whereas the mono-adducts 6a – d present a ketene-hemiacetal structure.     

Uniform hierarchical silica film with perpendicular macroporous channels and accessible ordered mesopores for biomolecule separation

Herein, we demonstrate that silica films with perpendicular macroporous channels and accessible ordered mesopores can be conveniently prepared. The hierarchical macroporous–mesoporous silica films are synthesized by using zinc oxide nanorod array as macroporous template and CTAB surfactant as mesoporous template. In basic surfactant-containing solution, ordered mesoporous silica shells homogeneously grow on the zinc oxide nanorod array. The growth of the mesostructures do not require any chemical modification for the zinc oxide nanorod, which opens a new way for preparing hierarchical silica films with perpendicular mesochannels. The prepared hierarchical macroporous–mesoporous silica films possess a uniform thickness of 2 mm, large perpendicular macropores with a length of 1.8 mm and a width of 80 nm, and accessible ordered mesopores. Separation experiment demonstrates that this macroporous–mesoporous film can effectively separate biomolecules with different sizes.