高凝固点原油与一般原油300℃以前组分的碳数分布特性比较

用气相色谱和色－质联用以对高凝固点（约42℃）原油及一般原油300℃以前组分的碳数分布情况作了分析和比较，并使用氧化铝多孔层空心毛细管柱分离了原油中石油气的低碳数组分，效果良好。     

Perovskites-like composites for CO2 photoreduction into hydrocarbon fuels

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Structural modification and antitumor activity of antimicrobial peptide HYL

HYL derived from the venom of the solitary bee Hylaeus signatus (Hymenoptera: Colletidae) is an α-helical antimicrobial peptide with 16 residues. To explore whether HYL can be applied in anti-tumor therapy, we synthesized HYL and further modified its structure by using a solid-phase synthesis method, and then evaluated their antitumor activities. Firstly, we identified the key residues of HYL by alanine scanning strategy, and then a series of stapled peptides were synthesized by hydrocarbon stapling strategy without destroying the key residues. All the stapled peptides of HYL showed significant improvement not only in α-helicity, but also in antitumor activity and protease resistance when compared to the parent peptide HYL. The results showed that hydrophobicity and amphiphilicity are important factors affecting the antitumor activity of HYL, and the stapling strategy can significantly affect the proteolytic stability and helicity of HYL. What's more, we find that the stapled peptides HYL-14, HYL-16 and HYL-18 show a promising prospect for novel anti-tumor drug development.     

The identification of irradiated seasoned filefish (Thamnaconus modestus) by different analytical methods

Dried seasoned filefish (Thamnaconus modestus) was irradiated at 0–10 kGy and the identification of irradiation treatment was investigated by analyzing the characteristics of thermoluminescence (TL), hydrocarbon (HC), and 2-alkylacyclobutanone (2-ACB). The TL (TL₁), glow curve of the irradiated samples peaked at approximately 150 °C with high intensity, but that of the non-irradiated samples peaked at about 300 °C with little intensity, thus making it possible to discriminate between irradiated and non-irradiated samples. Moreover, TL ratio (TL₁/TL₂), through normalization steps, enhanced the reliability of the TL₁ results. Six kinds of HCs and three kinds of 2-ACBs quantitatively determined for the samples linearly increased in proportion to irradiation doses. In particular, two HCs like 1-hexadecane and 1,7-hexadecadine, and three ACBs, such as 2-dodecylcyclobutanone, 2-(5′-tetradeceyl)cyclobutanone, and 2-tetradecylcyclobutanone, were identified only in the irradiated samples as radiation-induced markers.     

Design and synthesis of water-soluble bioconjugatable trans-AB-porphyrins

Three free base porphyrins have been prepared that bear a polar and facially encumbering 2,4,6-tris-(carboxymethoxy)phenyl motif at one meso (5-) position. The only other substituent (15-position) comprises phenyl, formyl, or p-aminophenyl. The porphyrins exhibit solubility in water (or aqueous buffer solutions) at pH ≥7 and concentrations >1 mM at room temperature. The concise syntheses, water solubility, and bioconjugatable handle make these porphyrin constructs suitable for biological applications.     

Enumeration of conjugated hydrocarbons: Hollow hexagons revisited

The numbers of nonisomorphic hollow hexagons are expressed in terms of a generating function.     

SAPO-34催化剂上甲醇制烯烃诱导期反应

甲醇制烯烃(MTO)是典型的自催化过程,包含诱导期反应.在诱导期反应中,甲醇转化生成的烃池物种在分子筛催化剂上积累,形成含有活性中心的烃池,从而进一步促进和加快更多烃池物种的生成.作为MTO反应的活性中间体,研究分子筛上烃池物种及其演变,对于理解MTO反应机理以及C1化学中第一个C-C键的生成具有重要意义.本文采用SAPO-34分子筛催化剂,对较低温度下流化床反应器中MTO诱导期反应进行研究,获得了诱导期反应的数据.通过HF溶解分子筛骨架的方法,检测各阶段存留在SAPO-34分子筛催化剂中的有机物种,分析了分子筛催化剂上烃池物种的积累和演变、烃池的形成以及烃池物种与催化剂失活之间的关系,并结合诱导期反应数据进一步讨论了MTO诱导期反应的动力学.研究发现,与ZSM-5分子筛类似,SAPO-34分子筛上的MTO诱导期反应对温度非常敏感.诱导期证实可分为三个反应阶段:初始反应阶段(最初C-C键生成阶段)、第二阶段(烃池物种的生成和积累阶段)及第三阶段(自催化反应阶段).这表明SAPO-34分子筛上MTO反应中烃池机理的重要性.然而,由于烃池物种和烃池机理的复杂性,在缺乏动力学研究的情况下,很难将诱导期反应三个阶段与反应机理进行明确的关联.因此,我们分别讨论了诱导期反应三个阶段的动力学,并计算了各阶段的表观活化能.动力学研究表明,与ZSM-5不同的是,在SAPO-34上的MTO诱导期反应中,初始反应阶段表观活化能较低,反应进行相对容易;而自催化反应阶段的活化能较高,反应进行相对困难.这主要是SAPO-34与ZSM-5分子筛的结构差异所致.SAPO-34分子筛因具有CHA结构而导致的扩散限制和空间约束,使得在第一阶段初始活性物种的生成和积累相对容易;但是在自催化反应阶段,不具活性的金刚烷类物质开始生成,并随着反应的进行在所有积碳物种所占的比例逐渐升高,导致其在自催化反应阶段(第三阶段)的活化能高于烃池物种的生成和积累阶段(第二阶段).对于HZSM-5催化剂上的MTO诱导期反应,由于MFI结构所产生的扩散限制和空间约束低于CHA结构,在第一阶段初始活性物种的积累相对困难,导致其初始阶段的表观活化能高于SAPO-34催化剂;但是随着反应的进行,活性物种在HZSM-5催化剂上不断积累,导致自催化反应阶段的进行相对比较容易.然而,对于SAPO-34分子筛上MTO诱导期反应,随着反应时间的推移,催化剂上积累的活性物种和非活性物种同时增多,而且由于SAPO-34结构特点而引起的扩散限制,大部分物种均保留在SAPO-34分子筛的笼中.分子筛中活性物种能提高反应活性,相应地,非活性物种则会抑制反应活性.因此,SAPO-34分子筛上甲醇转化诱导期反应活化能反映的是活性物种和非活性物种之间的竞争关系.     

A novel method of determining hard-core radius and roughness factor for organic mixtures

The translational–rotational coupling factor or the roughness factor coefficient introduced by Chandler has been evaluated for a number of organic mixtures containing hydrocarbons from their shear viscosity. The hard-core radius and hence the radial distribution function at contact, required in such an evaluation is obtained through a novel method. Its variation with temperature and concentration is discussed. With the available shear viscosity measurements, the roughness factor is also calculated and analyzed.     

索尔库里盆地侏罗系烃源岩有机地球化学特征

在油气勘探中,烃源岩的研究占有重要组成部分。侏罗系烃源岩在索尔库里盆地主体部位广泛分布,面积3 875.7km~2,最大厚度300 m以上,分布在盆地中南部。对索尔库里盆地侏罗系烃源岩样品进行有机地球化学分析。通过研究生物标记化合物来分析有机质的类型、成熟度和沉积环境。结果表明:研究样品中饱和烃馏分含量较高,在33%~75%之间。烃源岩样品Pr/Ph分布范围在0.49~0.99之间,说明其具有还原沉积环境;三环萜烷/霍烷分布范围为0.27~2.64,r-/0.5C_(31)丰度平均值为0.34,具有明显的淡水沉积环境特征。样品规则甾烷均呈C_(27) C_(28) C_(29)的V字型分布,认为烃源岩以偏腐泥混合型母质为主。藿烷与甾烷的成熟度参数存在差异,说明了烃源岩可能受到微生物降解作用。因此,对索尔库里盆地侏罗系烃源岩的研究,为以后该区的油气勘探提供一定的科学依据。     

Solvation molar enthalpies and heat capacities of n-alkanes and n-alkylbenzenes on stationary phases of wide-ranging polarity

A comparison of the most usual gas chromatographic methods for the calculation of partial molar enthalpies of solvation (Δ(sol)H(o)) has been carried out. Those methods based on the fitting of lnV(g) or ln(k/T) vs. 1/T and ln(k/T) vs. (1/T and the temperature arrangement, T(a)) are the most adequate ones for obtaining Δ(sol)H(o) values. However, the latter is the only reliable option for Δ(sol)H(o) estimation when commercial WCOT capillary columns are used, since in this case the estimation of some variables involved in the V(g) determination is less accurate or even impossible. Consequently, in this paper, Δ(sol)H(o) obtained from ln(k/T) vs. (1/T+T(a)) fitting at 373.15 and 298.15K for n-alkanes and n-alkylbenzenes on 12 commercial capillary columns coated with stationary phases covering the 203-3608 McReynolds polarity range are reported. Moreover, molar heat capacities of solvation at constant pressure (Δ(sol)C(p)(o)) have also been calculated using this method. A clear influence on Δ(sol)H(o) of the type and content of the substitution group in the stationary phase was observed. In addition, a linear relationship of Δ(sol)C(p)(o) with the van der Waals volume of the n-alkanes and the temperature gradient of density of the stationary phase was found. The effect of the size of the hydrocarbon on both thermodynamic variables was also investigated.