超分子砌块间苯二酚杯芳烃的研究进展

间苯二酚杯芳烃是一类以间苯二酚为单元的杯芳烃, 作为新一代超分子砌块, 在分子催化、分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用, 已成为当今化学研究的新热点. 综述了间苯二酚杯芳烃的功能化修饰及其应用新进展.     

一类新型超分子主体——硫代杯芳烃的研究进展

硫代杯芳烃是一类以硫原子取代桥联亚甲基的新型杯芳烃, 作为新一代超分子砌块, 在分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用, 已成为当今超分子化学研究的新热点. 综述了硫代杯芳烃及其衍生物的合成、功能化修饰及应用方面的研究进展.     

杯芳烃的功能化修饰及其在分子识别中的应用

本文综述了近几年杯芳烃类人工受体在功能化修饰方面的研究进展, 主要讨论了新型功能化衍生物的合成及其超分子识别功能的应用。     

硫杂杯[4]芳烃化学修饰的研究进展

硫杂杯[4]芳烃是由S原子取代经典杯芳烃中的桥联亚甲基而成的大环化合物,在分子识别、多核金属配合物、化学传感器等方面有广泛的应用.对硫杂杯[4]芳烃的化学修饰进行综述,有助于新型功能化硫杂杯芳烃衍生物的研究.     

杯吡咯和杂杯吡咯的结构、合成与应用

杯吡咯以其特殊的结构和优异性能, 在主客体化学尤其是分子识别等方面的应用前景已备受关注, 合成新型功能化杯吡咯及其衍生物已成为超分子化学领域的研究热点之一. 近年来通过引入新型芳烃基体合成了结构和性能多样的杂杯吡咯. 主要介绍了功能化的杯吡咯和杂杯吡咯的结构、合成及其在分子识别等领域的应用.     

杯芳烃吡啶衍生物作为液膜载体对金属离子的选择传质

超分子化学主要研究以非共价键弱相互作用力结合的分子聚集体体系,分别识别作为超分子化学的基础,是目前研究的热点.冠状化合物、天然和修饰环糊精以及环番等主体的分子识别已被广泛研究,而杯芳烃等人工合成受体体系的分子识别研究还相对有限.杯芳烃,正如环糊精一样,起源于19世纪,但直到70年代末,Gutsche对其大小可调的空腔产生兴趣,设想可以用来作为广泛的人工酶模型,对其合成方法进行了深入研究,优化出合成路线,可以方便地制备较大量的价廉样品,从而启动了杯芳烃化学的发展[1].......     

杯芳烃-卟啉化合物的合成及性质

杯芳烃和卟啉通过共价键连结或者分子间作用力聚集形成的杯芳烃-卟啉化合物在分子识别、分子催化、分子自组装等方面有潜在的用途. 本工作综述了杯芳烃-卟啉化合物的合成及性质.     

新型大环超分子化学:从杂杯芳烃到冠芳烃——纪念黄志镗先生诞辰90周年

本文介绍了杂杯芳烃和冠芳烃的研究起源,总结了杂杯芳烃和冠芳烃的设计与合成、构象和大环空腔结构特征,展示了杂杯芳烃和冠芳烃的分子识别和组装性质,概述了杂杯芳烃和冠芳烃在功能材料的制备中的应用,展望了大环超分子化学未来的发展方向。     

手性杯芳烃及其超分子手性

杯芳烃是由苯酚单元通过亚甲基连接而成的空腔型分子,具有衍生位点多,构象丰富等特点,被称为第三代主体分子。在分子层次,依手性因素的结构特点不同,可将手性杯芳烃分为具有手性亚单元的杯芳烃、固有手性杯芳烃和桥手性杯芳烃。在超分子层次,杯芳烃自身或杯芳烃与其他分子或离子在溶液中、晶态中或二维表面可通过非共价键力形成多种拓扑结构的纳米手性聚集体。研究手性杯芳烃和基于杯芳烃的超分子手性组装体的合成、结构和性能,不仅在理解手性起源、手性结构等方面具有理论意义,而且有望获得以分子识别为基础的手性传感器、手性催化剂、手性分离材料、手性载体和手性纳米材料。本文综述近十年来有代表性的分子手性杯芳烃和以杯芳烃为组分的超分子手性聚集体的设计、合成、结构和功能。着重展示杯芳烃骨架在形成新颖分子手性和超分子手性上的优势,以及杯芳烃单元在实现特定功能如手性识别时发挥的作用。相信随着杯芳烃合成技术和杯芳烃超分子设计的发展,必将进一步发挥杯芳烃的结构优势,涌现出更多性能优异的手性杯芳烃功能分子和超分子手性杯芳烃功能材料。     

杯芳烃化学的研究

杯芳烃作为超分子化学研究中一类重要的人工合成受体分子已受到广泛的关注,在化学、生物以及材料领域内显示出巨大的研究和应用前景。本文首先综述了杯芳烃在分子识别、模拟酶及分子自组装等方面的最新研究进展,然后介绍了作者从事杯芳烃研究十余年所取得的成果。     

Tuning the release rate of volatile molecules by pore surface engineering in metal-organic frameworks

Encapsulation and controlled release of volatile molecules such as fragrances in a designed manner is important but challenging for the flavor and fragrance industry. Here, we report the tuning release of volatile molecules by postsynthetic modification of an amine-terminated metal-organic framework(MOF) MIL-101-NH_2. By amidation, we obtained three MIL-101 MOFs, the trimethylacetamideterminated TC-MIL-101, the benzamide-terminated BC-MIL-101, and the oxalic acid monoamideterminated OC-MIL-101. All the MOFs can efficiently encapsulate volatile molecules. Moreover, we demonstrate that the release profile of volatiles can be widely tuned to sustain the release in several days to months and even over a year using different modified MIL-101 MOFs. We show that the release profiles are correlated with the binding energies between the guest volatiles and pores in MOFs. The pore diffusion and the synergistic transport are the rate-limiting step of the guest molecules from the modified MOFs.     

杯芳烃化学传感器的研究进展

杯芳烃衍生化得到不同结构和功能基团的主体分子。通过主客体分子作用可包结、螯合客体分子,并可作为敏感材料应用在离子选择电极、离子敏感场效应管、离子光导膜、压电晶体等各种类型的化学传感器上,用于离子和中性分子的识别和检测。     

水杨酸分子印迹膜电化学传感器的制备

以水杨酸为模板分子,采用循环伏安法电聚合形成聚吡咯膜,以固定电位过氧化法去除印迹分子,制备了水杨酸分子印迹膜电极.本印迹电极能促进水杨酸电氧化过程,有效地避免结构类似物(如苯甲酸)对其测定的干扰.循环伏安法用于电化学检测,当富集时间为10 min,磷酸盐缓冲溶液的pH=6.86 时,在1.0×10-6～2.0×10-3 mol/L浓度范围内,水杨酸氧化峰电流与其浓度呈良好的线性关系,检出限为0.8 μmol/L, 用分子印迹膜电极对加标样品进行分析,回收率为94.6%～103.4%.     

Surface functionalization chemistries on highly sensitive silica-based sensor chips

The surfaces of silica-based sensor chips, designed for evanescent-field-coupled waveguide-mode sensors, were functionalized using various surface chemistries. The immobilization of molecular entities on the functionalized silica surfaces was monitored using various microscopic techniques (scanning electron, fluorescence, and atomic force microscopies). Further, gold nanoparticle-based signal enhancement analyses were performed with protein conjugation on different functionalized surfaces using a waveguide-mode sensor. Based on these analyses, the sensor surfaces modified with glutaraldehyde (Glu) and carbonyldiimidazole were found to be good for molecules of different sizes. In addition, it can be inferred that the Glu-modified surface may be suitable for small molecules with diameters around 5 nm owing to its surface roughness. The modified surface with carbonyldiimidazole is suitable for the direct immobilization of larger molecules especially for biomolecular assemblies without intermediate chemical modifications.     

Separation of proteins on surface-modified poly(dimethylsiloxane) microfluidic devices

Separation and detection of proteins have been realized on nonionic surfactant-modified poly(dimethylsiloxane) (PDMS) microfabricated devices with end-column amperometric detection. The hydrophobic PDMS channels are turned into hydrophilic ones after being modified with Brij35 and facilitate the separation of proteins. The coating can remarkably reduce the adsorption of large protein molecules and is stable in the range of pH 6-12. The detection of proteins in such channels needs less rinsing time and thus efficiency is raised. Even large molecules of proteins can also be detected with better reproducibility and enhanced plate numbers. The relative standard deviation (RSD) of the migration time for glucose oxidase (GOD) is 2.2% (n = 19). Separation of GOD and myoglobin has been developed in modified channels. Predominant operational variables, such as the coating conditions, the concentration of surfactant and buffer, are studied in detail.     

Variation of saturated surface density of ovalbumin on bubble surface in continuous foam separation

The adsorption of ovalbumin (OA) onto the bubble surfaces was studied with various pHs (3.5, 4.6, 6.0 and 8.0) by a continuous foam separation technique. From the value of the saturated surface density of adsorbed OA, the variation of effective diameter (D) of an OA molecule on the bubble surface was estimated for various pHs (3.5, 4.6, 6.0 and 8.0) of the OA solutions, assuming that the cross section of the OA molecules be circular and that the OA molecules adsorb on the bubble surface in a closest packing structure. The estimated variation of D with pH was attempted to explain based on a model modified from that proposed by Pujar and Zydney. The modified model could well reproduce the variation of the effective diameter with pH; the values of D calculated on the basis of the modified model almost agreed with that estimated from the saturated surface density in the present experimental pH range. From these, conclusion was drawn that the modified model presented in this study can express the variation in the effective diameter with pH.     

Organocatalytic asymmetric transformations of modified Morita-Baylis-Hillman adducts

Chiral Lewis basic tertiary amines or phosphines can enable properly modified Morita-Baylis-Hillman (MBH) adducts to undergo asymmetric allylic substitutions with a wide range of nucleophiles. In addition, assisted by a Br?nsted base, chiral Lewis bases can also catalytically convert modified MBH adducts into allylic ylides, which can be engaged in a variety of asymmetric annulation reactions. This tutorial review will focus on such chiral Lewis base-catalysed asymmetric transformations of MBH adducts, especially those developed over the past five years, allowing for the rapid construction of densely functionalised chiral molecules with high levels of regio- and stereoselectivities.     

Biochemically functionalized silica nanoparticles

In this report, we demonstrate the biochemical modification of silica based nanoparticles. Both pure and dye-doped silica nanoparticles were prepared, and their surfaces were modified with enzymes and biocompatible chemical reagents that allow them to function as biosensors and biomarkers. The nanoparticles produced in this work are uniform in size with a 1.6% relative standard deviation. They have a pure silica surface and can thus be modified easily with many biomolecules for added biochemical functionality. Specifically, we have modified the nanoparticle surfaces with enzyme molecules (glutamate dehydrogenase (GDH) and lactate dehydrogenase (LDH)) and a biocompatible reagent for cell membrane staining. Experimental results show that the silica nanoparticles are a good biocompatible solid support for enzyme immobilization. The immobilized enzyme molecules on the nanoparticle surface have shown excellent enzymatic activity in their respective enzymatic reactions. The nanoparticle surface biochemical functionalization demonstrates the feasibility of using nanoparticles for biosensing and biomarking applications.     

尿素/乙醇胺复配增塑聚乙烯醇性能的研究

采用尿素/乙醇胺为复合增塑剂,利用流延法制备了增塑改性的PVA膜.通过FTIR法研究了尿素/乙醇胺复合体系与PVA的相互作用,采用XRD、DSC考察了增塑改性PVA膜的结晶性能和热性能.研究结果表明,乙醇胺作为尿素的良溶剂,能有效抑制尿素从PVA基体中析出.由尿素、乙醇胺组成的复合增塑剂能破坏PVA分子中的氢键作用、降低PVA的结晶度和熔点,对PVA的增塑作用显著.增塑改性后的PVA膜在水中的溶胀率(DS)下降,溶失率(S)增加.力学性能测试表明增塑改性后的PVA膜拉伸强度(TS)降低,断裂伸长率(E%)提高.含30phr尿素/乙醇胺的PVA膜的拉伸强度、断裂伸长率分别为23.89MPa和542.88%.     

Syntheses and Binding Properties of Novel Calix[4]arene Derivatives Containing Multiple Azo-groups

Introduction Calixarenes are excellent scaffolds that can bemodified by introducing various functional groups tocreate specific interactions between the host and guestmolecules. Thus, many calixarene derivatives contai-ning special functional groups, such as ester, amideand thiourea, have been synthesized and their excellentcomplexing capability for cations have also been stud-ied[1—4]. Lately, calixarene derivatives containing twoor more sorts of functional groups have attracted muchattentio…