反式共轭类碳烯CH_2CH—CHC∶LiF的构型及异构化反应

用MP2 / 6 - 31G 解析梯度方法研究了反式共轭类碳烯CH2CH—CHC∶LiF的结构 .得到 3个平衡构型和 2个异构化反应的过渡态 .计算结果表明 ,反式共轭类碳烯有两种比较稳定的平衡构型 .分析了各平衡构型的结构特点及稳定性 ,给出了各种平衡构型及过渡态结构的Mulliken集居数 ,并讨论了两种稳定构型的化学活性     

反式共轭类碳烯CH2=CH-CH=C:LiF的构型及异构化反应

用MP2／6－31G^**解析梯度方法研究了反式共轭类碳烯CH2＝CH－CH＝C：LiF的结构。得到3个平衡构型和2个异构化反应的过渡态。计算结果表明，反式共轭类碳烯有两种比较稳定的平衡构型。分析了各平衡构型的结构特点及稳定性，给出了各种平衡构型及过渡态结构的Mulliken集居数，并讨论了两种稳定构型的化学活性。     

苹果蠹蛾性信息素的合成研究进展

综述了用Wittig反应构建烯烃、炔化物还原、烯烃硼氢化、山梨酸衍生物格氏偶联、油脂的氧化-还原等方法,合成苹果蠹蛾性信息素(8E,10E-十二碳二烯-l-醇)的研究进展。并介绍了其部分类似物的合成方法。参考文献21篇。     

烯碳材料在人工肌肉领域的应用进展

随着仿生机器人、智能控制及人工智能等领域的发展,传统的机械驱动方式已无法满足相关领域对致动系统提出的柔性、高效及多源刺激响应性等要求,因此需发展新型的人工肌肉材料。以碳纳米管和石墨烯为代表的烯碳材料具有轻质、高强、高电导率和柔性等特征,在人工肌肉领域展现出了巨大的应用潜力。以烯碳材料为基元构筑宏观组装体材料,或以烯碳材料为添加相制备纳米复合材料,可在微观和宏观架起桥梁,实现烯碳材料在人工肌肉领域的应用。本文基于上述两种应用形式,综述了烯碳材料在人工肌肉领域的应用进展。首先从一维纤维和二维薄膜的烯碳人工肌肉宏观表现形态出发,介绍了既作为结构材料,又提供了响应、驱动功能的烯碳材料在人工肌肉中的应用。接着从机电性能、可编程的响应形变以及传感功能三个方向,介绍了烯碳材料作为增强赋能相在人工肌肉材料中的功能性应用。最后阐述了基于烯碳材料人工肌肉的机遇与挑战。     

毛细管气相色谱法同库仑法联合测定含烯汽油的烃族及芳烃组成

本文在使用填充柱色谱法与库仑法联合测定含烯汽油烃族组成的基础上,又使用涂以极性固定液的FFAP WCOT毛细柱分析了含烯汽油的饱和烃/烯烃及芳烃、芳烃单体烃的含量。通过芳烃单体烃的测定确定油品的碳数及准确扣除高沸点非芳烃组分在芳烃部分中的含量,使定量更加准确可靠。     

关环转换反应在天然产物合成中的应用

关环转换反应是形成碳碳双键的重要反应之一,即双烯化合物在金属碳烯催化下关环得到环烯类化合物。本文概述了关环转换反应所用催化剂体系及其在天然产物合成中的应用,内容涉及到碳环及含氧、含氮杂环天然产物的合成。     

烯碳材料改性有机高性能纤维：制备、性能及应用

有机高性能纤维是全球化纤工业的重要发展方向之一。提升现有纤维力学性能的同时研发新型结构功能一体化的纤维对提升我国在航天航空等领域的国际地位具有重要意义。以石墨烯和碳纳米管为代表的烯碳材料具备优异的力、电、热学等性能,可用于改性传统有机高性能纤维。通过制备不同物化性质的烯碳材料并设计合理的改性方式,可将烯碳材料优异的性能传递到传统纤维中,形成具备更高力、电、热学等性能的烯碳材料改性有机高性能纤维。本文首先综述了烯碳材料改性有机高性能纤维的制备方式,包括烯碳材料的分散与功能化、烯碳材料对有机高性能纤维的改性方法,阐述了烯碳材料改性有机高性能纤维的力、电、热学等性能以及烯碳材料的增强机理,进而总结了烯碳材料改性有机高性能纤维的应用,并对其现存的挑战和未来的发展做出展望。     

由富烯配体合成茂金属化合物的研究

报道了一系列富烯包括烷基取代富烯、6-氨基富烯和具有稠环结构的6-氨基苯并富烯经由去氢或加成反应合成取代二茂金属络合物;(1-二甲氨基)乙烯基环戊二烯基锂与过渡金属的络合反应在一定条件下可以发生分子内碳碳偶联及二甲基胺的消除反应,得到丙烯桥联茂金属化合物,从推导的反应历程提出该反应的反应机理;尚合成了两个新的外消旋手性化合物。     

顺式环十二碳烯的构象

用分子力学法(MMX程序)计算了15-苯基双环[10,3,0]十五碳-1(12)-烯-13-酮,其分子中环十二碳烯部分的构象为能量最低的[l_(ene)2333],与X衍射结果吻合.同时,还计算了15个顺式环十二碳烯的构象,求出了它们的能量及结构参数,讨论了影响构象稳定性的因素.     

气相色谱保留参数用于刺五加果挥发油中萜烯及萜烯氧化物的分类

根据刺五加挥发油中24个挥发性成分在5个程序升温条件下的保留时间,采用基于Levenberg-Marquardt法的软件GC_AB计算得到相应成分的气相色谱保留参数(A, B值)。通过对其中的萜烯及萜烯氧化物之间A, B关系的相关性分析,发现相同碳数的单萜烯、倍半萜烯和其氧化物分别具有良好的A-B线性相关性,但单萜烯与倍半萜烯、单萜烯与其氧化物、倍半萜烯与其氧化物的A-B关系不共线。研究表明,在中草药挥发油之类的复杂未知混合物体系的分析中,通过色谱保留参数进行萜烯及萜烯氧化物的分类是一种很有潜力的辅助定性方法。     

Characterization and identification of a "mystery" oil spill from Quebec (1999)

This paper describes a case study in which advanced chemical fingerprinting and data interpretation techniques were used to characterize the chemical compositions and determine the source of an unknown spilled oil from Quebec. On 28 February 1999, significant amounts of oil was reported on the river banks of St. Laurence River in front of a company named "Thermex" (in a town - Beauharnois, Quebec, about 50 km northwest of Montreal). The spilled oil was suspected to be released from a nearby factory. In response to this specific site investigation needs, a tiered analytical approach using GC-MS and GC-flame ionization detection was applied. A variety of diagnostic ratios of "source-specific marker" compounds, in particular isomers of biomarkers and alkylated series of polycyclic aromatic hydrocarbons within the same alkylation groups, were determined and analyzed. The hydrocarbon analysis results reveal the following: (1) the spilled oil is very "specific", and is significantly different from most crude oils in chemical composition; (2) the oil in samples come from the same source, however, the spill sample 2569 was identified to contain a small amount (approximately 10%) of diesel; (3) the spilled oil was relatively "fresh", its chemical composition has not undergone significant alteration yet; (4) the spilled oil showed unusually high concentration of the US Environmental Protection Agency priority polycyclic aromatic hydrocarbons (PAHs). The "Pyrogenic Index" values were determined to be as high as 0.11-0.13, significantly higher than crude oils (<0.010) and heavy Bunker type fuels (0.015-0.060). This indicates significant contribution of PAH composition from pyrogenic components; (5) biomarkers were also detected, but their concentrations were unusually low in comparison to most crude oils.     

Identification de la damascénone et de la β-damascone dans le tabac Burley

The successful identification of damascenone (I)

1 DORICENONE (trade mark of Firmenich & Cie, Geneva).

and β-damascone (III)

2 DORINONE (trade mark of Firmenich & Cia, Geneva)

in Burley tobacco oil was achieved through the use of an efficient vapour phase chromatography/mass spectrometry combination. Thus, the occurrence of β-damascone in nature and the presence of damascenone in an essential oil not related to rose oil were demonstrated.     

Essential Oil of Arischrada korolkowii from the Chatkal Mountains of Uzbekistan

The herbal parts of Arischrada korolkowii (Regel et Schmalh.) Pobed. (Lamiaceae) growing in Uzbekistan were hydrodistillated to yield 1.1% of essential oil. The essential oil was analyzed by GC/MS. Eighty eight compounds were characterized representing 98% of the essential oil with 1,8-cineole (29.3%), camphor (9.8%), -caryophyllene (8.5%), bornyl acetate (7.7%), caryophyllene oxide (7.2%), and borneol (5.6%) as the main constituents.     

Characterization,thermal properties and phase transitions of amazonian vegetable oils

Thermal profiles of buriti pulp oil (Mauritia flexuosa Mart.), tucumã pulp and kernel oils (Astrocarium vulgare Mart.), rubber seed oil (Hevea brasiliensis), passion fruit oil (Passiflora edulis) and ucuúba butter (Virola surinamensis) were analyzed by thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC). Gas chromatography and calculated iodine values were performed to determine the fatty acid profile and to measure the degree of unsaturation in these oils, respectively. The TG curves showed three steps of mass loss, which can be attributed to the degradation of polyunsaturated, monounsaturated and saturated fatty acids. The DSC crystallization and melting curves are reported and depended on the fatty acid composition. Usually, oil samples with a high degree of saturation showed crystallization and melting profiles at higher temperatures than the oils with a high degree of unsaturation. The data obtained by physicochemical analysis of oil samples were analyzed by principal component analysis and hierarchical cluster analysis to increase understanding of the data set, examining the presence or absence of natural groupings between samples.     

两种轻烃分析方法(“PTV切割反吹”和“顶空”)的对比研究

 建立了“程序升温蒸发进样器 (PTV)切割反吹”和“顶空”两种有关原油中轻烃的分析方法 ,色谱柱的使用寿命长、分析周期短 ,原油中 < ,将原油直接注入汽化室所得的分析数据较可靠 ,并对引起误差的原因进行了探讨。指出用这两种方法所获得的数据是不能合在一起作地化研究的 ) % 5 2 1%～ ( 19个地化参数的相对误差范围约为± 10个油样用两种分析方法所得 6个油区的 ,还报道了采自我国 ,并有良好的重复性。。     

Novel μ-membrane module for online determination of the free fatty acid content in the dispersed phase of oil-in-water emulsions

Monitoring the dispersed phase of an oil-in-water (O–W) emulsion by means of Fourier transform infrared (FTIR) spectroscopy is a challenging task, restricted to the continuous phase that is in contact with the FTIR probe. Nonetheless, real-time measurement and kinetic analysis by FTIR, including analysis of the dispersed, often non-polar phase containing substrates and/or products, is desirable. Enzymatic hydrolysis of sunflower oil was performed in an O–W emulsion. After separation of the oil phase by use of a newly developed μ-membrane module, infrared spectra were collected using an attenuated total reflectance (ATR) cell. Different chemometric models were calibrated using the partial least squares (PLS) algorithm. Online application of a chemometric model based on the FTIR spectra enabled real-time monitoring of free fatty acid concentrations in the oil phase.

Vitamins of the oil of the fruit ofHippophaë rhamnoides

Summary A comparative study of the chemical composition of the oil of the juice and the seed oil of the fruit ofHippophaë rhamnoides has shown that vitamins of the A group are concentrated mainly in the oil of the juice (more than 1000 mg-%) and are represented mainly by -carotene and zeaxanthin in a ratio close to 3:1.The E-group vitamins are uniformly distributed in the oil of the juice and the seed oil (more than 200 mg-%). Of the vitamins of this group, the main representatives detected were - and -tocopherols in a ratio of 2:1.The vitamins of the F group are concentrated only in the seed oil (60% of a mixture of linoleic and linolenic acids on the total fatty acids isolated from the oil, in a ratio of 1.5:1).The position of the ethylenic bond in a C_16:1 acid isolated from products of the hydrolysis of the oil of the juice in a monoenic fraction has been shown by chemical analysis. Its cis configuration was determined by IR spectroscopy, which confirms the structure of this acid as cis-hexadec-9-enoic (palmitoleic) acid. An unusually high content of the C_16:1 acid is characteristic only for the oil of the juice.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 313–317, May–June, 1978.     

Free and Glycosidically Bound Volatiles of Mentha longifolia Growing in Croatia

The glycosides of volatile compounds and the essential oil were isolated from wild Mentha longifolia. After the enzymatic hydrolysis of glycosides, fourteen volatile aglycones were identified by GC/MS. The main aglycones were eugenol, 2-phenylethanol, benzyl alcohol, lavandulol, trans- and cis-carveol, 3-octanol, and 3-hexen-1-ol. The content of aglycones was 40.85 mg kg^-1 of dried plant material. The main components of the essential oil (yield 0.93 w/w) were carvone, piperitenone oxide, limonene, and -caryophyllene. Eugenol, carveol, 3-octanol, and -terpineol were identified in the aglycones and in the essential oil.     

pH‐Induced Inversion of Water‐in‐Oil Emulsions to Oil‐in‐Water High Internal Phase Emulsions (HIPEs) Using Core Cross‐Linked Star (CCS) Polymer as Interfacial Stabilizer

A pH‐responsive core cross‐linked star (CCS) polymer containing poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) arms was used as an interfacial stabilizer for emulsions containing toluene (80 v%) and water (20 v%). In the pH range of 12.1‐9.3, ordinary water‐in‐oil emulsions were formed. Intermediate multiple emulsions of oil‐in‐water‐in‐oil and water‐in‐oil‐in‐water were formed at pH 8.6 and 7.5, respectively. Further lowering the pH resulted in the formation of gelled high internal phase emulsions of oil‐in‐water type in the pH range of 6.4‐0.6. The emulsion behavior was correlated with interfacial tension, conductivity and configuration of the CCS polymer at different pH.

     

Transport of ions through the oil phase of W(1)/O/W(2) double emulsions

Using a capillary video microscopy technique, the ion transport at liquid-liquid interfaces and through a surfactant-containing emulsion liquid membrane was visually studied by preparing a double emulsion globule within the confined space of a thin-walled, transparent, cylindrical microtube. NaCl and AgNO(3) were selected as the model reactants and were prepared to form a NaCl/AgNO(3) pair across the oil film. By observing and measuring the formed AgCl deposition, it was found that both Cl(-) and Ag(+) could transport through a thick oil film and Ag(+) was transported faster than Cl(-). Interestingly, the ion transport was significantly retarded when the oil film became extremely thin (<1 microm). The results suggested that the transport of ions mainly depends on the "reverse micelle transport" mechanism, in which reverse micelles with entrapped ions and water molecules can be formed in a thick oil film and their construction will get impeded if the oil film becomes extremely thin, leading to different ion transport rates in these two cases. The direction of ion transport depends on the direction of the osmotic pressure gradient across the oil film and the ion transport is independent of the oil film thickness in the investigated thick range. Ions with smaller Pauling radii are more easily entrapped into the formed reverse micelles and therefore will be transported faster through the oil film than bigger ions. Oil-soluble surfactants facilitate ion transport; however, too much surfactant in the oil film will slow down the ion migration. In addition, this study showed no support for the "molecular diffusion" mechanism of ion transport through oils.