用胆甾型苯并—15—冠—5气相色谱固定相分离乳酸和乳酸乙酯光学异构体

胆甾型苯并－１５－冠－５（简称ＣＨ－Ｂ－１５－Ｃ－５）在不同温度范围内的相态不同，在同一温 度范围内因处理方式不同而物性亦相去甚远，用其作成的ＧＣ固定相兼具气固色谱（ＧＳＣ）、 普通气液色谱（ＧＬＣ）和冠醚液晶气液色谱（ＣＬ－ＧＬＣ）多种功能。用该固定相在不同条件下对 乳酸和乳酸乙酯光学异构体混合物的分高效果进行了比较研究，并探讨了手性拆分机理。     

Synthesis and properties of side-chain liquid crystalline polymers grafted with chiral dimers containing cholesteryl groups

ABSTRACT

Two series of novel side-chain liquid crystal (LC) polysiloxanes grafted with chiral liquid crystalline dimers containing cholesteryl mesogens were synthesised. The chemical structure and LC properties of comonomers and polymers were characterised by FTIR, ¹H-NMR, DSC, TGA, POM and XRD. M₁ and M₂ were chiral nematic (N*) dimers, and M₃ was an achiral LC monomer displaying nematic mesophase in a narrow mesomorphic temperature range, while the copolymers exhibited N* mesophase whose mesomorphic temperature ranges were much wider than those of the comonomers. Moreover, the glass transition temperatures and isotropization temperatures of the polymers all decreased with decreasing the dimer components. Reflection spectra showed that P_a series tend to attain wide-band selective reflection at long wavelengths, while P_b series were more potential at short wavelengths with narrow bandwidths. Decreasing the dimer components led the wavelength of the selective reflection to blue shift, which was an abnormal phenomenon in chiral mixture system.     

Separation of Photosynthetic Pigments by High-performance Liquid Chromatography: Comparison of Column Performance,Mobile Phase,and Temperature

High-performance liquid chromatography (HPLC) has been commonly used as method of separating and identifying photosynthetic pigments such as chlorophylls and carotenoids because of such advantages as speed, high resolution and sensitivity. In this technique, high separation relies largely on the type of column material. This study compared the efficiency of five reverse-phase columns, C8, C18, C18 monolithic, π-NAP, and cholester, for separation of photosynthetic pigments at several fixed conditions of mobile phase and temperature. This investigation also analysed the parameters of Δt_R and t_R ratio for selected pigments and resolution for structural isomers, such as α- and β-carotene. Among above columns tested, cholester column is suitable for separation of pigments not only for a broad range of polarity, but also for hydrophobic pigments in a simple mobile phase. This finding can help in the selection of column and HPLC parameters in separating photosynthetic pigments.     

具有刚性液晶元侧基的嵌段共聚物PHEMAChol-b-PBLG的合成及自组装研究

以胆固醇和谷氨酸苄酯为主要出发原料,采用可逆加成-断裂链转移(RAFT)自由基聚合、氨基酸环内酸酐(NCA)开环聚合(ROP)以及"点击化学"(click chemistry)组合方法,设计、合成了系列具有刚性液晶元侧基的聚甲基丙烯酸羟乙酯胆固醇碳酸酯-嵌段-聚谷氨酸苄酯(PHEMAChol-b-PBLG),并通过核磁共振(NMR)、红外光谱(FTIR)、凝胶渗透色谱(GPC)和静态光散射(SLS)对其化学结构进行了表征.运用热重分析仪(TGA)、热台偏光显微镜(POM)和示差扫描量热仪(DSC)研究了系列共聚物的热稳定性、液晶相结构及相转变行为,并通过固体红外、13C固体核磁共振(13C CP/MAS)和X射线衍射仪(XRD)研究了PBLG均聚物及系列嵌段共聚物中聚氨基酸多肽链段的二级结构.研究结果表明,系列嵌段共聚物均具有良好的热稳定性,表现为近似向列相的液晶织构,PBLG链段趋于呈刚直棒状的α-螺旋构型,且其多肽链段越长,二级结构越规整.进一步采用圆二色谱(CD)和透射电镜(TEM)对系列嵌段共聚物在四氢呋喃溶液中的二级结构及自组装行为进行了研究,制备得到纺锤形自组装聚集体和大复合胶束,并通过变性酸三氟乙酸的引入实现对嵌段共聚物中PBLG的二级结构及相应自组装聚集体形貌的有效调控.     

Controlled radical polymerization of cholesteryl acrylate and its block copolymer with styrene via the RAFT process

Reversible addition fragmentation chain transfer (RAFT) polymerization of cholesteryl acrylate (ChA) was conducted using S-1-dodecyl-S′-(α,α′-dimethyl-α′′-acetic acid)trithiocarbonate as CTA and AIBN as initiator in toluene at 80 °C. The polymerization was investigated at two different CTA concentrations (0.025 and 0.040 M). Polymerization of ChA with CTA concentration of 0.040 M proceeds in a controlled/living manner as evidenced by linear increase of the molecular weight with conversion and narrow polymer polydispersity (PDI < 1.2). With lower initial CTA concentration, namely 0.025 M, although poly(cholesteryl acrylate) (PChA) exhibiting narrow molecular weight distributions could be synthesized, the polymerization showed relatively low control with many termination products. Chain extension polymerizations were performed starting from either the PChA or the polystyrene (PS) block, and well-defined copolymers based on ChA and styrene were prepared. Thermal properties of PChA and PS-b-PChA copolymer were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and the results showed that both PChA and PS-b-PChA are amorphous polymers. PChA begins to decompose at ca. 218 °C with maximum weight loss rate at 351 °C, while PS-b-PChA shows double weight loss rate peaks located at 345 and 415 °C, respectively.     

高压下三种脂肪酸甲酯液相导热系数的实验研究

生物柴油是新型环境友好型替代能源,其主要成分为碳数分布在C6～C24的长链脂肪酸酯.利用瞬态单丝法导热系数测量系统在272～352K温度范围内、0.1～15 MPa压力范围内对三种生物柴油组成成分壬酸甲酯、庚酸甲酯和己酸甲酯的液相导热系数进行了实验测量,并将导热系数拟合成关于温度和压力的方程,壬酸甲酯、庚酸甲酯和己酸甲...     

Synthesis of organogelling, fluoride ion-responsive, cholesteryl-based benzoxazole containing intra- and intermolecular hydrogen-bonding sites

A cholesteryl-based 2-(2′-hydroxyphenyl)benzoxazole (HPB) derivative 3 linked with an amide bond was prepared through an efficient synthetic pathway. The HPB, amide, and cholesteryl groups play important roles in constructing the supramolecular gel structure. UV-vis and fluorescence spectroscopy also showed that HPB and amide groups, which provide intra- and intermolecular hydrogen bonding, respectively, also contribute the recognition of fluoride anions.     

Fluorescence study on the coaggregating tendencies of the cholesterols --the culprits of arteriosclerosis

The coaggregating tendencies of the culprits of arteriosclerosis, the cholesteryl esters (CE-n's), have been investigated in the 40:60 V/V (Φ= 0.40) dioxane (DX)-H2O system, by using decyl pyrenyl ketone (Py-11) as the fluorescence probe. The fluorescence intensity of Py-11 decreases when coaggregation occurs between CE-n and Py-11, because of the low polarity of the microenviroment of the coaggregates. The order of the coaggregating tendencies obtained from the fluorescence data is in full agreement with that from the kinetic method, i.e., CE-ol, CE-in > CE-12 > CE-8 > CE-18 > CE-0.     

胆甾醇丙烯酸酯／甲基丙烯酸丁酯无规共聚物的研究

胆甾醇丙烯酸酯／甲基丙烯酸丁酯无规共聚物的研究李安东，宋襄玉，周恩乐（中国科学院长春应用化学研究所高分子物理开放研究实验室，长春，１３００２２）关键词胆甾醇丙烯酸酯，甲基丙烯酸丁酯，高分子液晶，相态转变近来场致显示受到极大重视［１，２］，但对含有胆甾...