胆固醇分子印迹聚合物的制备及其选择性吸附

随着人们生活水平的逐步提高,因人体内胆固醇过高所产生的疾病呈逐年增加的趋势.近年来的研究表明,胆固醇分子印迹聚合物对胆固醇具有良好的选择性吸附能力.将胆固醇分子印迹聚合物作为胆固醇的识别剂,提取食品中的胆固醇和治疔胆固醇有关的疾病,展现出了良好的应用前景.本文分别从胆固醇分子印迹聚合物的制备方法、识别机理、提高选择性识别途径以及新的印迹方法等方面进行了综述.     

Efficient Non-Fullerene Organic Solar Cells Based on a Wide-Bandgap Polymer Donor Containing an Alkylthiophenyl-Substituted Benzodithiophene Moiety

Two wide-bandgap polymer donors containing an alkylthiophenyl substituted benzo[1,2-b : 4,5-b′]dithiophene moiety, namely PTZPO and PTZPS, were designed and synthesized. Both polymers exhibit relatively wide optical bandgap of 1.95 V with similar absorption profiles. The polymer PTZPS with alkylthiophenyl substituted benzo[1,2-b : 4,5-b′]dithiophene units showed enhanced light-harvesting capabilities, leading to improved short-circuit current densities. The PTZPS : ITIC film shows more appreciable film morphology and phase separation than the film composed of a blend of ITIC with alkoxyl substitutions containing copolymer PTZPO, which facilitates exciton dissociation and charge transport. The PTZPS : ITIC-based non-fullerene organic solar cells show clearly improved short-circuit current density and an impressively high power conversion efficiency of more than 11 %. These observations demonstrate the great promise of using PTZPS as electron-donating materials for high-performance non-fullerene organic solar cells.     

Selective adsorption of D- and L-phenylalanine on molecularly-imprinted polymerized organogels formed using polymerizable gelator N-octadecyl maleamic acid

The polymerizable gelator N-octadecyl maleamic acid (ODMA) can self-assemble in selected polymerizable organic solvents, such as 2-hydroxyethyl methacrylate (HEMA) and methylacrylic acid (MAA) to form thermally stable polymerizable organogels. A mixture consisting of HEMA and MAA as the monomer and functional monomer, PEG dimethacrylates (PEG200DMA) as the crosslinker, BOC-L-phenylalanine (BPA) or L-phenylalanine ethyl ester (PEE) as the chiral templates, was gelatinized by ODMA firstly and subsequently polymerized by in situ UV irradiation or thermal initiation. The molecularly imprinted polymerized organogels were obtained after the removal of the templates through ethanol extraction. Selective adsorption of D- and L-phenylalanine was performed on the polymerized organogels. The results indicate rather high adsorption efficiency obtained for L-phenylalanine compared with that for D-phenylalanine, which was found to be dependent on the concentrations of ODMA, content of template, and the method of polymerization. Herein, the concentration of ODMA in the organogels played an important role for the adsorption efficiency of D- and L-phenylalanine.     

用雅可比-傅里叶矩进行图像描述

提出了雅可比—傅里叶矩,它是用雅可比多项式作为径向函数,用傅里叶因子作为角向函数构造而成的,是广义正交傅里叶—梅林矩。经过归一化处理后的雅克比—傅立叶矩具有平移、尺度、旋转、灰度多畸不变性。从归一化图像重建误差、噪声灵敏度等方面对雅可比—傅里叶矩的图像描述能力进行了研究,结果显示雅可比—傅里叶矩在各种参量选择的情况下,具有良好的图像描述和抗噪声能力,是一个优良的图像特征。以前的研究多为单纯构建某一个函数,而现在将其扩展为构建一个函数族,开阔了矩描述量的研究视野。     

α-Branched amines through radical coupling with 2-azaallyl anions,redox active esters and alkenes

α-Branched amines are fundamental building blocks in a variety of natural products and pharmaceuticals. Herein is reported a unique cascade reaction that enables the preparation of α-branched amines bearing aryl or alkyl groups at the β- or γ-positions. The cascade is initiated by reduction of redox active esters to alkyl radicals. The resulting alkyl radicals are trapped by styrene derivatives, leading to benzylic radicals. The persistent 2-azaallyl radicals and benzylic radicals are proposed to undergo a radical–radical coupling leading to functionalized amine products. Evidence is provided that the role of the nickel catalyst is to promote formation of the alkyl radical from the redox active ester and not promote the C–C bond formation. The synthetic method introduced herein tolerates a variety of imines and redox active esters, allowing for efficient construction of amine building blocks.

A mild method for the construction of α-branched amine derivatives is presented. SET processes between the Ni catalyst, redox active esters and 2-azaallyl anions generate azaallyl radicals and alkyl radicals that functionalize the alkenes.     

胆固醇分子印迹聚合有机凝胶的制备及其选择性吸附研究

以N-十八烷基马来酰胺酸(ODMA)为凝胶剂,在甲基丙烯酸β-羟乙酯、甲基丙烯酸、聚乙二醇二甲基丙烯酸酯和模板分子3-胆固醇酰氧基丙酸(COPA)混合物中自组装形成稳定的超分子有机凝胶,经UV原位光聚合,乙腈提取模板分子制备了胆固醇非共价印迹聚合有机凝胶.吸附实验在水/THF中进行.结果显示胆固醇非共价印迹聚合有机凝胶...     

Synthesis of Benzofuran Derivatives through Cascade Radical Cyclization/Intermolecular Coupling of 2‐Azaallyls

Benzofurans are among the most popular structural units in bioactive natural products, however, the synthesis of such structures by radical cyclization cascade reactions is rare. Herein, we report a mild and broadly applicable method for the construction of complex benzofurylethylamine derivatives through a unique radical cyclization cascade mechanism. Single‐electron transfer (SET) from 2‐azaallyl anions to 2‐iodo aryl allenyl ethers initiates a radical cyclization that is followed by intermolecular radical–radical coupling. This expedient approach enables the synthesis of a range of polycyclic benzofurans that would otherwise be difficult to prepare.     

Nickel-catalyzed enantioselective vinylation of aryl 2-azaallyl anions

A unique enantioselective nickel-catalyzed vinylation of 2-azaallyl anions is advanced for the first time. This method affords diverse vinyl aryl methyl amines with high enantioselectivities, which are frequently occurring scaffolds in natural products and medications. This C–H functionalization method can also be extended to the synthesis of enantioenriched 1,3-diamine derivatives by employing suitably elaborated vinyl bromides. Key to the success of this process is the identification of a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, all of which favor an anionic vinylation route over a background radical reaction. A telescoped gram scale synthesis and a product derivatization study confirmed the scalability and synthetic potential of this method.

A unique enantioselective Ni-catalyzed vinylation of 2-azaallyl anions is advanced. This method affords vinyl aryl methyl amine or 1,3-diamine derivatives with high enantioselectivities, which are frequently occurring scaffolds in medications.     

Formation mechanism of supramolecular hydrogels in the presence of L-phenylalanine derivative as a hydrogelator

A novel chiral hydrogelator, L-phenylalanine derivative can self-assemble in aqueous media at different pH values to form supramolecular hydrogels. The images of the FE-SEM indicate that different aggregates of TC(18)PheBu in morphology were formed, which further lead to the formation of spherical crystallites as observed by polarized optical microscope (POM). The FT-IR spectra of the supramolecular hydrogels reveal that intermolecular hydrogen-bonding and hydrophobic interactions are the driving forces for the self-assembly of TC(18)PheBu. Fluorescence spectra of TC(18)PheBu in aqueous solutions in the presence of pyrene as a probe further confirm the importance of hydrophobic interactions for the self-assembly. The circular dichroism (CD) spectra of TC(18)PheBu in supramolecular hydrogels in the presence of KF indicate that the hydrogen-bonding interaction can be disrupted by fluoride ions, which further confirm the importance of hydrogen bonding for the self-assembly of TC(18)PheBu.     

聚合有机凝胶印迹膜对D-和L-苯丙氨酸的选择性吸附

以1-甲基-2,4-二(N’-十八烷脲基)苯为凝胶剂,以液体单体丙烯酸-2-乙基己酯、甲基丙烯酸甲酯、二甲基丙烯酸聚乙二醇(200)酯以及模版分子和光敏引发剂的混合物为溶剂,研究表明,这种二烷基脲型凝胶剂在这些单体混合物中可进行超分子自组装,形成互相缠绕的具有纳米尺寸的纤维状聚集体,最终导致这些单体混合物首先形成稳定的超分子有机凝胶。然后经UV光引发聚合,经乙醇抽提凝胶剂聚集体和模板分子,制备了一种新型分子印迹的聚合有机凝胶薄膜。探讨了不同凝胶剂浓度、模板分子浓度、单体混合物配比所制备的印迹聚合有机凝胶薄膜对D-和L-苯丙氨酸吸附效率的影响。结果表明所制备的印迹聚合超分子凝胶对L-苯丙氨酸吸附效率约为对D-苯丙氨酸吸附效率的3～4倍,表现出明显的选择性吸附性。