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《化学进展》2016,(Z2)
基于有机小分子多级自组装形成的超分子凝胶,由于其潜在的应用前景越来越受到人们的关注。合理设计凝胶因子并实现在适当的溶剂中自组装形成纤维状结构,对于分子识别和自组装来说都有一定挑战。三萜化合物具有独特的手性骨架结构,是一类重要的生物活性天然产物,在消炎、降血脂、保肝护肾、抗菌、抗肿瘤、抗真菌等方面有着重要的药用价值。近年来,基于独特的手性刚性骨架和具有多个可修饰位点的特点,此类化合物的聚集性质和在超分子组装方面的应用已经引起关注。本文总结了未经修饰的五环三萜化合物的聚集组装性质和基于此类骨架的功能分子在超分子凝胶方面的研究,并介绍了此类超分子凝胶潜在的应用。结果表明,发展基于此类天然产物骨架的超分子组装体,不仅为超分子凝胶的研究引入新的构筑基元,并且能够达到阐述生物活性分子之间相互作用力以及充分利用自然界资源创造新材料的目的。 相似文献
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天然产物结构复杂,生理活性独特,常被用作先导化合物,经过结构修饰和改造,发展为具有重要药用价值的化合物,在保障人类健康方面发挥重要的作用.近年来,具有独特立体结构、多修饰位点、良好生物相容性和生物活性的天然产物作为构筑单元,已应用到基于分子自组装的有机功能材料研究领域中.介绍以天然甾体、三萜、肽、糖等为结构骨架,设计合成的功能分子在有机凝胶方面的研究现状及其潜在的应用. 相似文献
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手性组装材料作为一种新型功能复合材料,已经引起众多科学研究领域的广泛关注,尤其是其在对映体分离方面的潜在应用成为当前的研究热点。本文首先从手性来源角度对手性组装材料的构建机制进行了分类探讨,包括手性诱导、手性放大、手性传递和手性转录4个主要途径,其中具有手性的多孔金属有机骨架、纳米笼是基于手性诱导和手性传递机制构建的组装材料,手性凝胶的形成是基于手性放大机制,而手性转录机制主要用于手性多孔无机材料、螺旋纳米结构的构建。其次,介绍了手性组装材料的对映体识别功能,主要针对金属有机骨架化合物(MOFs)、手性凝胶和纳米笼三类手性组装材料在对映体分离中的应用进行了综述。阐述了天然生物大分子DNA的手性自组装特性及其对对映体的立体选择性识别功能,并介绍了DNA螺旋组装结构在手性等离子材料、非对称催化剂设计等方面的应用。最后,归纳了金属有机骨架化合物、手性凝胶、纳米笼和DNA等手性组装材料各自的优势,并对DNA在手性拆分领域的应用前景进行了展望。 相似文献
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超分子凝胶通过形成三维空间网络结构将溶剂液体相固定化,是一类重要的软物质材料。由于超分子凝胶能快速形成,自组装形成的纳米结构均一、可调,且可大规模制备,因此成为超分子化学、纳米技术以及材料科学研究的重要研究方向之一,并在诸多领域得到广泛的功能研究和应用拓展,如在材料模板、光电开关、药物释放、分子识别和超分子催化等方面已有大量研究报道。由于超分子凝胶具有固-液相可逆转变、可控组装等特性,成为了超分子手性和分子手性研究的重要载体。近年来超分子凝胶在超分子手性催化、手性分子识别等方面取得了一系列重要突破,为超分子凝胶功能应用开辟了新的空间,为手性科学研究提供了新的手段和方法。 相似文献
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超分子手性普遍存在于自然界和生命体内,可通过分子在非共价键作用下有序排列形成,对生命科学、药物化学及材料科学的发展起着重要的作用。天然产物来源广泛,具有独特的立体结构和多手性中心,由于其分子手性可以在组装过程中随着分子的有序堆积得到传递和放大,形成超分子手性结构,因此是一类优良的超分子手性构筑基元。研究天然产物的手性自组装,不仅可以拓展其在超分子化学中的应用,还能深化人们对自然界和生命体中手性现象的理解。本文总结了近年来甾体、三萜、氨基酸、糖等天然产物小分子化合物在超分子手性自组装方面的研究进展及其未来的发展前景。 相似文献
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作为一类经典的软物质材料,超分子凝胶在催化、化学传感、药物释放等许多领域展示了广泛的应用前景.最近人们研究发现,在基元砌块中引入金属特别是过渡金属之后,所形成的有机金属凝胶在光电材料、催化、磁性等方面具有独特的物理化学性质.近年来,电中性铂炔基元因其独特的线性结构、易合成及丰富的光物理性质在超分子化学及材料科学中被广泛应用.总结了基于中性铂炔基元的超分子有机金属凝胶的构筑及其功能研究进展,主要包括以苯撑共轭结构为核心骨架的铂炔有机金属凝胶以及官能团修饰的铂炔有机金属凝胶. 相似文献
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超分子凝胶作为一种重要的软物质材料,在构建多重刺激响应性、光电功能,以及生物相容材料等功能软物质方面表现出了独特的优越性。超分子凝胶在形成过程中往往得到比较均一的纳米结构,且具有结构多样性;而另一方面,超分子凝胶的构筑单元大部分是手性分子,超分子凝胶也是实现手性在超分子层次/纳米层次表达的重要途径,尤其是手性传递、手性放大、不对称催化方面,同时超分子凝胶也是构筑手性纳米结构的重要手段。本文主要对超分子凝胶形成中的纳米结构以及形貌的多样性和超分子手性进行介绍,并展望该领域未来的发展方向。 相似文献
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Triptycenes are an intriguing class of organic molecules with several unusual characteristics, such as a propeller-like shape, saddle-like cavities around a symmetrical scaffold, a rigid π-framework. They have been extensively studied and proposed as key synthons for a variety of applications in supramolecular chemistry and materials science. When decorated with an appropriate substitution pattern, triptycenes can be chiral, and, similarly to other popular chiral π-extended synthons, can express chirality robustly, efficiently, and with relevance to chiroptical spectroscopies. This minireview highlights and encompasses recent advances in the synthesis of chiral triptycenes and in their introduction as molecular scaffolds for the assembly of functional supramolecular materials. 相似文献
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Dr. Xiang Zhao Edward T. Nguyen Anh N. Hong Prof. Pingyun Feng Prof. Xianhui Bu 《Angewandte Chemie (International ed. in English)》2018,57(24):7101-7105
Homochiral metal–organic frameworks (MOFs) are an important class of chiral solids with potential applications in chiral recognition; however, relatively few are available. Of great importance is the availability of low‐cost, racemization‐resistant, and versatile enantiopure building blocks. Among chiral building blocks, d ‐camphoric acid is highly prolific, yet, its trans‐isomer, l ‐isocamphoric acid, has remained unknown in the entire field of solid‐state materials. Its rich yet totally untapped synthetic and structural chemistry has now been investigated through the synthesis of a large family of homochiral metal isocamphorates. The first observation of diastereoisomerism in isostructural MOFs is presented. Isocamphorate has a powerful ability to create framework topologies unexpected from common inorganic building blocks, and isocamphoric acid should allow access to hundreds of new homochiral materials. 相似文献
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Dr. Md. Nasim Khan Prof. Dr. Thomas Wirth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(24):7059-7068
Triptycenes have been established as unique scaffolds because of their backbone π-structure with a propeller-like shape and saddle-like cavities. They are some of the key organic molecules that have been extensively studied in polymer chemistry, in supramolecular chemistry and in material science. Triptycenes become chiral molecules when substituents are unsymmetrically attached in at least two of their different aromatic rings. This Minireview highlights the chirality of triptycenes from basics to an advanced stage for the development of functional molecules. 相似文献
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以甘草酸分子为印迹分子,N-异丙基丙烯酰胺作为温度响应性单体,和甲基丙烯酸共同为甘草酸的吸附性单体,在大量交联剂存在下,N-甲基吡咯烷酮中经自由基模板聚合,制备了一种热敏性印迹凝胶,对水凝胶的热收缩动力学进行了表征;用红外光谱证实了甘草酸分子与单体分子间的相互作用,以旁证其模板作用的存在:同时还与没有模板作用所合成的同种凝胶作了实施对比,发现模板聚合所得的水凝胶可以富集水溶液中的甘草酸,并对它表现出特殊的选择性分离作用,分配系数约为非模板聚合水凝胶的11倍。 相似文献
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氨基酸桥联手性双卟啉的二阶非线性光学性质研究 总被引:4,自引:0,他引:4
采用半经验量子化学PM3方法对系列氨基酸桥联双卟啉1, 2, 3, 4及其锌配合物进行了几何结构优化, 并用TDHF/PM3方法计算了其静态二阶非线性光学系数. 计算结果表明, L型-氨基酸桥联双卟啉及其锌配合物具有右手螺旋结构特征. 在电偶极近似下, 不同手性氨基酸侧链基团R对分子的总体二阶非线性光学系数β和βHRS的影响不大, 但对二阶非线性光学系数的手性分量βxyz却有显著影响. βxyz与螺旋结构参数r2ζ/L4成正比关系, 符合手性分子二阶非线性光学响应的单电子螺旋模型理论. β张量分析表明, 此类分子表现为以八极为主、 偶极为辅的多极分子, 卟啉环与锌离子的配位有利于增加二阶非线性光学响应的偶极分量和手性分量βxyz. 相似文献
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Fabrication of chiral materials and revealing the mechanisms involved in their formation are crucial issues in scientific research. The combination of cooperative self-assembly routes and the chiral templating process favors the formation of inorganic chiral materials with highly ordered mesostructures. This tutorial review highlights the recent research on chiral mesoporous silica (CMS) of hierarchical helical constructions transcribed from organic templates. The rules and mechanisms involved in the synthesis of CMS and related materials, especially the novel expression of chirality and imprinting of helical micellar superstructure by the functional groups immobilized on the mesopore surface, provide us with a deeper insight into the chiral self-assembly process and new strategies for the design and application of chiral materials. This review is addressed to researchers and students interested in chiral chemistry, supramolecular chemistry and mesoporous materials (53 references). 相似文献
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Dinesh N. Nadimetla Mohammad Al Kobaisi Sandesh T. Bugde Sheshanath V. Bhosale 《Chemical record (New York, N.Y.)》2020,20(8):793-819
The design and synthesis of achiral organic functional molecules which can assemble into a chiral with selective handedness in the absence of chiral substances is an important in understanding the role chirality plays within these systems. In this review, we described general approaches towards supramolecular chiral molecules the synthesis and self‐assembly of achiral molecule to active chiral molecules to investigate controlled supramolecular chiral nanostructures with their photoluminescent properties for rapid, sensitive and selective detection of analytes of choice. Various small molecules have been discussed for achiral to chiral along with induction of chirality and controlled chiral helical structures in detail. We discussed few examples where stimuli used to control the chirality such as temperature, pH etc. Finally, we will also explore on the photo responsive helicity properties of the aggregation induced emission active molecule such as tetraphenylethene conjugates. 相似文献