基于分子钳化合物的手性识别研究进展

手性是自然界中广泛存在的现象,设计合成新型人工受体模拟生物体内的分子识别已经成为生物有机化学和超分子化学等领域富于挑战性的课题之一.分子钳类人工受体结构易于修饰,在手性识别和检测中具有广泛的应用前景,本文对近年来合成的分子钳人工受体以及应用光谱、色谱和质谱等检测手段对其手性识别性能的研究进行了总结,并对分子钳人工受体的发展前景作出了展望.     

分子钳人工受体研究进展

分子识别是生物体系的基本特征, 并在生命活动中起中心作用. 利用合成的人工受体与适当底物间的分子识别以建立化学模型或化学仿生体系对生命过程中的分子识别现象进行模拟研究是生物有机化学和超分子化学前沿富于挑战的课题之一. 按照不同的隔离基, 综述了分子钳人工受体的研究进展.     

“分子钳”人工受体的研究进展

本文综述了分子钳人工受体近年来在分子识别领域中的新进展     

氨基甲酸酯型石胆酸分子裂缝的微波合成

利用人工受体与适当底物间的分子识别以建立仿生模型的研究已成为生物有机化学的前沿领域之一。作为一类新型的人工受体,分子裂缝近年来在分子识别、生物传感、外消旋体的拆分、分子器件等领域引起越来越多的关注[1-3]。胆甾因其具有刚性的凹面结构和固有的手性,是构筑钳形人工     

新型脱氧胆酸钳形阴离子受体的设计合成及其对阴离子的识别性能研究

具有对阴离子选择性识别的人工受体的设计合成是生物有机化学和超分子化学前沿富于挑战性的领域之一[1].在许多识别阴离子的人工受体化合物中,脲和硫脲衍生物是重要的中性受体化合物之一.     

新型鹅去氧胆酸分子裂缝的设计合成

分子识别是生物体系的基本特征,并在生命活动中起中心作用。生物酶高效专一地催化生化反应,抗体与抗原的结合,蛋白质分子与DNA序列的相互作用等都源于精确的分子识别[1,2]。利用合成的人工受体与适当底物之间的分子识别以建立仿生仿酶模型的研究,已成为生物有机化学前沿富有挑战性的领域。分子裂缝作为一类新型的人工受体,以其灵活的结构以及易于将功能团聚集在受体与底物结合的活性部位上等优点,引起了人们的广泛关注[3-5]。胆甾因其具有刚性的凹面结构和天然的手性,是构筑分子裂缝人工受体的理想结构单元。我们曾报道3α-OH和7α-OH同…     

脱氧胆酸手性分子钳的微波合成及其对中性分子的识别性能研究

在微波辐射条件下,以脱氧胆酸甲酯为间隔基,高产率合成了5个脱氧胆酸手性分子钳人工受体,其结构经IR,1HNMR,MS及元素分析确证。用差紫外光谱法测定了其对中性分子的识别性能。实验结果表明,这类分子钳人工受体对所考察的客体分子有良好的识别作用,主客体间形成1∶1型主客体配合物,受体5d对苯胺的结合常数高达14171.39 M-1。     

芳杂环类多重氢键分子钳人工受体研究新进展

氢键是分子识别的重要推动力之一.综述了芳杂环类多重氢键分子钳人工受体研究进展.     

杯芳烃类受体的分子识别作用研究进展

综述了杯芳烃类人工受体的分子识别作用的研究进展。主要介绍通过非共价键作用引起的识别-配合与识别-催化作用。     

囊泡表面分子间通讯交流体系的构建: 利用受体的分子识别行为调控酶的活性

在人工双层膜囊泡表面, 构建了一个通过人工受体的分子识别行为控制酶反应活性的超分子体系. 体系以生物体细胞信号转导系统为模拟原型, 由作为受体的烷基胺、被受体识别的信号分子吡哆醛衍生物、乳酸脱氢酶、受体和酶之间的媒介物Cu^2＋以及作为体系载体的合成肽脂囊泡五个成分构成．通过UV-vis光谱法及动态光散射测定对体系进行了评价, 结果表明: 随着受体疏水参数增大, 其对信号分子的识别能力增强, 二者呈良好的线性关系; 通过信号分子与囊泡表面静电相互作用的研究表明信号分子具有选择性; 媒介物与信号分子–受体可形成化学计量比为1∶2的配合物, 其形成能力比媒介物与酶的结合能力更强．作为结论, 体系中烷基胺受体对磷酸吡哆醛信号分子的识别有效控制了处于囊泡表面的乳酸脱氢酶的活性．     

甘脲类分子胶囊受体合成方法的研究进展

甘脲类分子胶囊是一类独特的由非共价键弱相互作用力组装而成的人工受体, 在分子识别、自组装、分子微反应器、智能材料等方面得到了广泛而深入的研究. 系统综述了网球型(Tennis ball)、垒球型(Softball)、足球型(Football)及圆盘型(Jelly Doughnut)等分子胶囊的合成方法.     

双吲哚烯类受体对氨基酸的比色识别作用

设计合成了一系列3,3′-双吲哚烯类受体分子,应用紫外-可见吸收光谱研究了该类受体对二十种天然氨基酸分子的识别作用. 结果表明,在乙腈-水溶液中,双吲哚烯受体分子可以通过其氢键受体位点的质子化作用比色识别天冬氨酸、谷氨酸等酸性氨基酸;而硝基取代的双吲哚烯受体分子则通过其氢键供体位点的去质子化作用比色识别精氨酸、赖氨酸等碱性氨基酸. 在乙腈-水的中性缓冲溶液体系中,硝基取代的双吲哚烯类受体分子通过与巯基发生亲核加成反应高选择性比色识别半胱氨酸和同型半胱氨酸.     

氨基酸及其衍生物的手性识别研究进展

本文综述了近年来开拓的多种人工受体模型对氨基酸及其衍生物的对映选择性识别性能，并做了相互比较，从中总结出手性识别的几个基本原则，预期了其应用前景。     

Opportunities to improve selectivity of determining oxidoreductase substrate using artificial receptors

The review considers the prospects of using molecular recognition by artificial receptors (macro-cyclic compounds and molecularly imprinted polymers) to create sensors for the determination of biologically active compounds, i.e., substrates of oxidoreductases, in samples with complex matrices. The data on the production, properties, and application of complexes of the indicated artificial receptors with the analytes, i.e., organic compounds of different classes, for analytical purposes have been systemized for the first time. Special attention is focused on the discussion of approaches that ensure the specificity of the receptor due to molecular recognition.     

Interactions with aromatic rings in chemical and biological recognition

Intermolecular interactions involving aromatic rings are key processes in both chemical and biological recognition. Their understanding is essential for rational drug design and lead optimization in medicinal chemistry. Different approaches-biological studies, molecular recognition studies with artificial receptors, crystallographic database mining, gas-phase studies, and theoretical calculations-are pursued to generate a profound understanding of the structural and energetic parameters of individual recognition modes involving aromatic rings. This review attempts to combine and summarize the knowledge gained from these investigations. The review focuses mainly on examples with biological relevance since one of its aims it to enhance the knowledge of molecular recognition forces that is essential for drug development.     

Molecular recognition of carbohydrates by artificial receptors: systematic studies towards recognition motifs for carbohydrates

The synthesis and binding properties for carbohydrates of several artificial, acyclic receptors containing two or three heterocyclic recognition units covalently attached to a phenyl spacer is described. These host molecules having uncharged hydrogen-bonding sites were used in a systematic study towards the evaluation of recognition motifs for carbohydrates. A novel effective, acyclic hydrogen-bonding receptor possessing naphthyridine-amide moieties as heterocyclic recognition units has been developed.     

合成受体的分子识别

系统地总结了我们近年来在超分子化学研究中的一些工作进展,着重介绍了一些合成受体(环糊精,冠醚,杯芳烃)的分子识别和组装研究。     

Nanoscale substrate recognition by porphyrin dendrimers with patched structures

Dendrimer technology has enabled us to build macromolecules with nanosized defined structures. By introducing unsymmetrical patched structures in dendrimers, sophisticated artificial receptors exhibiting nanoscale substrate recognition can be obtained. In this review article, our recent studies on molecular recognition by porphyrin dendrimers with patched structures are summarized. Three topics are presented: (1) oligopeptide-patched dendrimers as a nanoscale receptor of cytochrome c protein; (2) pocket dendrimers as a nanoscale receptor for bimolecular guest accommodation; and (3) energy transfer in unsymmetrical dendrimers. These dendrimers nicely mimic proteins and enzymes, and also act as photofunctional artificial receptors, in which porphyrin’s strong photoabsorption and intense fluorescence signals can respond sensitively to the substrate binding.     

Cooperation between artificial receptors and supramolecular hydrogels for sensing and discriminating phosphate derivatives

This study has successfully demonstrated that the cooperative action of artificial receptors with semi-wet supramolecular hydrogels may produce a unique and efficient molecular recognition device not only for the simple sensing of phosphate derivatives, but also for discriminating among phosphate derivatives. We directly observed by confocal laser scanning microscopy that fluorescent artificial receptors can dynamically change the location between the aqueous cavity and the hydrophobic fibers upon guest-binding under semi-wet conditions provided by the supramolecular hydrogel. On the basis of such a guest-dependent dynamic redistribution of the receptor molecules, a sophisticated means for molecular recognition of phosphate derivatives can be rationally designed in the hydrogel matrix. That is, the elaborate utilization of the hydrophobic fibrous domains, as well as the water-rich hydrophilic cavities, enables us to establish three distinct signal transduction modes for phosphate sensing: the use of (i) a photoinduced electron transfer type of chemosensor, (ii) an environmentally sensitive probe, and (iii) an artificial receptor displaying a fluorescence resonance energy transfer type of fluorescent signal change. Thus, one can selectively sense and discriminate the various phosphate derivatives, such as phosphate, phospho-tyrosine, phenyl phosphate, and adenosine triphosphate, using a fluorescence wavelength shift and a seesaw type of ratiometric fluorescence change, as well as a simple fluorescence intensity change. It is also shown that an array of the miniaturized hydrogel is promising for the rapid and high-throughput sensing of these phosphate derivatives.