共查询到20条相似文献,搜索用时 859 毫秒
1.
Ren Y Kan WH Henderson MA Bomben PG Berlinguette CP Thangadurai V Baumgartner T 《Journal of the American Chemical Society》2011,133(42):17014-17026
A series of new amphiphilic phosphonium materials that combine the electronic features of phospholes with self-assembly features of lipids were synthesized. Variable concentration/temperature and 2D NMR studies suggested that the systems undergo intramolecular conformation changes between a "closed" and "open" form that are triggered by intermolecular interactions. The amphiphilic features of the phospholium species also induce liquid crystalline and soft crystal phase behavior in the solid state, which was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature powder X-ray diffraction (VT-PXRD). The studies revealed that both conjugated backbones and counteranions work together to organize the systems into different morphologies (liquid crystal/soft crystal). Dithieno[3,2-b:2',3'-d]phosphole-based compounds exhibit enhanced emission in the solid state and at low temperature in solution due to aggregation-induced enhanced emission (AIEE). Photoinduced electron transfer (PET) induced via the alkoxybenzyl group at the phosphonium center in the fused-ring systems can be effectively suppressed through intermolecular charge transfer (ICT) processes within the main scaffold of a nonfused system, which was confirmed by static and dynamic fluorescence spectroscopy. The dynamic features of these new materials also endow the systems with external-stimuli responsive photophysical properties that can be triggered by temperature and/or mechanical forces. 相似文献
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Xiao-Yun Yan Dr. Zhiwei Lin Prof. Wei Zhang Hui Xu Qing-Yun Guo Yuchu Liu Jiancheng Luo Xian-You Liu Prof. Rongchun Zhang Jiahao Huang Tong Liu Zebin Su Ruimeng Zhang Shuailin Zhang Prof. Tianbo Liu Prof. Stephen Z. D. Cheng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5264-5272
How biomembranes are self-organized to perform their functions remains a pivotal issue in biological and chemical science. Understanding the self-assembly principles of lipid-like molecules hence becomes crucial. Herein, we report the mesostructural evolution of amphiphilic sphere-rod conjugates (giant lipids), and study the roles of geometric parameters (head–tail ratio and cross-sectional area) during this course. As a prototype system, giant lipids resemble natural lipidic molecules by capturing their essential features. The self-assembly behavior of two categories of giant lipids (I-shape and T-shape, a total of 8 molecules) is demonstrated. A rich variety of mesostructures is constructed in solution state and their molecular packing models are rationally understood. Giant lipids recast the phase behavior of natural lipids to a certain degree and the abundant self-assembled morphologies reveal distinct physiochemical behaviors when geometric parameters deviate from natural analogues. 相似文献
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In this review, we examine the interaction of nucleic acids with cell-like structures based on liquid–liquid phase separation of charged molecules (complex coacervation) and amphiphilic self-assembly (lipid vesicles). We discuss the mechanisms of their assembly and describe how they can be used as models for origin of life studies and for understanding two recently-described phenomena in modern cells: membrane-free organelles and exosomes. Hybrid cells with increased structural complexity are highlighted and we then briefly explore how strategies based on electrostatic and hydrophobic assembly can be used for designing and synthesizing delivery agents for therapeutic nucleic acids. While the physical mechanisms of self-assembly vary, both strategies provide viable routes for generating minimal compartmentalized systems, modeling cellular pathways, and for rational design of new synthetic cells for technological applications. 相似文献
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Self-assembly of inorganic nanoparticle vesicles and tubules driven by tethered linear block copolymers 总被引:1,自引:0,他引:1
Controllable self-assembly of nanoscale building blocks into larger specific structures provides an effective route for the fabrication of new materials with unique optical, electronic, and magnetic properties. The ability of nanoparticles (NPs) to self-assemble like molecules is opening new research frontiers in nanoscience and nanotechnology. We present a new class of amphiphilic "colloidal molecules" (ACMs) composed of inorganic NPs tethered with amphiphilic linear block copolymers (BCPs). Driven by the conformational changes of tethered BCP chains, such ACMs can self-assemble into well-defined vesicular and tubular nanostructures comprising a monolayer shell of hexagonally packed NPs in selective solvents. The morphologies and geometries of these assemblies can be controlled by the size of NPs and molecular weight of BCPs. Our approach also allows us to control the interparticle distance, thus fine-tuning the plasmonic properties of the assemblies of metal NPs. This strategy provides a general means to design new building blocks for assembling novel functional materials and devices. 相似文献
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采用Monte Carlo模拟方法研究了溶剂尺寸对ABA两亲性三嵌段共聚物在选择性溶剂中自组装行为的影响。模拟结果表明,溶剂尺寸是决定共聚物聚集形态的重要因素之一。随着溶剂尺寸的增大,嵌段共聚物自组装所形成的胶束可以发生从球状到棒状再到囊泡状的转变。通过对各组分的相互作用对数随溶剂尺寸变化曲线的分析发现,增大溶剂尺寸会使溶剂的溶解性变差,由此引发体系中的一系列形态转变。此外,通过对体系自组装形貌结构相图的分析发现,增大溶剂尺寸或增加疏水作用同减小亲水作用对于自组装形态的改变具有同等效果。 相似文献
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Future nanoscale soft matter design will be guided to a large extent by the teachings of amphiphile (lipid or surfactant) self-assembly. Ordered nanostructured lyotropic liquid crystalline mesophases may form in select mixtures of amphiphile and solvent. To reproducibly engineer the low energy amphiphile self-assembly of materials for the future, we must first learn the design principles. In this critical review we discuss the evolution of these design rules and in particular discuss recent key findings regarding (i) what drives amphiphile self-assembly, (ii) what governs the self-assembly structures that are formed, and (iii) how can amphiphile self-assembly materials be used to enhance product formulations, including drug delivery vehicles, medical imaging contrast agents, and integral membrane protein crystallisation media. We focus upon the generation of 'dilutable' lyotropic liquid crystal phases with two- and three-dimensional geometries from amphiphilic small molecules (225 references). 相似文献
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In this work, we used lattice Monte Carlo simulations and theoretical model calculations to show how the self-assembly of adsorbed amphiphilic molecules is affected by the local curvature of solid surfaces. It is found that, beyond a critical curvature value, solid surface geometry governs the spatial ordering of aggregates and may induce the morphological transitions. The simulation results show how the curvature of solid surfaces modulates the distribution of aggregates: the anisotropy in local curvature along and perpendicular to the cylindrical surfaces tends to generate orientationally ordered cylindrical micelles. To account for the morphological transitions induced by the local curvature of solid surfaces, we constructed a theoretical model which includes the Helfrich bending energy, the deformation energy of aggregates induced by solid surfaces, and the adsorption energy. The model calculations indicate that on highly curved solid surfaces the bending energy for bilayer structure sharply increases with surface curvature, which in turn induces the morphological transition from bilayer to cylindrical structure. Our results suggest that the local curvature provides a means of controlling the spatial organization of amphiphilic molecules. 相似文献
8.
Recently, cyclodextrins (CDs) were found to play important yet complicated (or even apparently opposite sometimes) roles in self-assembly systems of amphiphiles or surfactants. Herein, we try to review and clarify the versatility of CDs in surfactant assembly systems by 1) classifying the roles played by CDs into two groups (modulator and building unit) and four subgroups (destructive and constructive modulators, amphiphilic and unamphiphilic building units), 2) comparing these subgroups, and 3) analyzing mechanisms. As a modulator, although CDs by themselves do not participate into the final surfactant aggregates, they can greatly affect the aggregates in two ways. In most cases CDs will destroy the aggregates by depleting surfactant molecules from the aggregates (destructive), or in certain cases CDs can promote the aggregates to grow by selectively removing the less-aggregatable surfactant molecules from the aggregates (constructive). As an amphiphilic building unit, CDs can be chemically (by chemical bonds) or physically (by host–guest interaction) attached to a hydrophobic moiety, and the resultant compounds act as classic amphiphiles. As an unamphiphilic building unit, CD/surfactant complexes or even CDs on their own can assemble into aggregates in an unconventional, unamphiphilic manner driven by CD–CD H-bonds. Moreover, special emphasis is put on two recently appeared aspects: the constructive modulator and unamphiphilic building unit. 相似文献
9.
Hans v. Berlepsch Kai Ludwig Boris Schade Rainer Haag Christoph Böttcher 《Advances in colloid and interface science》2014
The self-assembly of amphiphilic molecules into fibrous structures has been the subject of numerous studies over past decades due to various current and promising technical applications. Although very different in their head group chemistry many natural as well as synthetic amphiphilic compounds derived from carbohydrates, carbocyanine dyes, or amino acids tend to form fibrous structures by molecular self-assembly in water predominantly twisted ribbons or tubes. Often a transition between these assembly structures is observed, which is a phenomenon already theoretically approached by Wolfgang Helfrich and still focus point in current research. With the development of suitable sample preparation and electron optical imaging techniques, cryogenic transmission electron microscopy (cryo-TEM) in combination with three-dimensional (3D) reconstruction techniques has become a particular popular direct characterization technique for supramolecular assemblies in general. Here we review the recent progress in deriving precise structural information from cryo-TEM data of particularly fibrous structures preferably in three dimensions. 相似文献
10.
Aromatic amphiphilic molecules(1) consisting of three biphenyl groups linked together with ether bonds as a rigid rod segment and poly(ethylene oxide) with the number of repeating units of 17 as a coil segment were synthesized, and their self-assembly behavior in the bulk state and aqueous solution was investigated. In bulk, molecules 1 self-assembled into 1-D lamellar structure in the solid state or smectic A phase in the liquid crystalline phase via the cooperative effects of ?-? stacking, micro-phase separation and hydrogen bond interactions. In dilute aqueous solutions, molecules 1 were observed to selfassemble into cylindrical micelles owned uniform diameter and length of hundreds of nanometers. 相似文献
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Cho EJ Kang JK Han WS Jung JH 《Langmuir : the ACS journal of surfaces and colloids》2008,24(10):5229-5232
We synthesized a tetrameric amphiphilic molecule ( 1) based on a calix[4]arene building block that self-assembled into different tunable and stable aggregation structures at different pH values in aqueous solution. The amphiphilic calix[4]arene molecule ( 1) formed a spherical structure at pH 3. However, 1 formed a hollow necklacelike structure of 500 nm diameter at pH 7. These results indicate that the self-assembled morphologies of 1 are strongly dependent on pH values. In addition, a 3D dendritic silver nanostructure was obtained by the self-assembly of 1 at pH 7. 相似文献
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Fluid-like colloidal structures are key components in nature's own functional materials and important for various applications. For instance, self-assembled structures are formed spontaneously by amphiphilic molecules in solvent, tailored by directional noncovalent intermolecular forces. These structures form the framework of cells defining their geometry and microenvironments for chemical reactions, for maintaining concentration gradients, and for nutrient exchange. Knowledge on the mechanisms at play that underlie the self-assembly of amphiphilic molecules into nanostructures in aqueous and nonaqueous solvents and their dispersion into particles can have direct implications for the rational design of new advanced and nature-inspired materials. These colloidal materials could help to deliver drug molecules and nutrients in a tailored manner to the body, or act as sustainable solvents for chemical or biotechnological processes. This contribution summarizes the recent progress in understanding the self-assembly structure formation in polar and nonpolar solvents and discusses the advances in hierarchically organized systems. Furthermore, it discusses challenges in the characterization of structure and dynamics in these biomimetic materials and highlights selected applications in the fields of drug delivery, food, and biotechnology. 相似文献
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New amphiphilic random copolymers containing hydrophobic dodecyl (C12) chain and hydrophilic L-glutamic acid were synthesized, and their self-assembly in solution as well as on the solid surfaces was investigated. The self-assembly behavior of these polymers are largely dependent on their hydrophilic and hydrophobic balances. The copolymer with a more hydrophobic alkyl chain (~90%) self-assembled into giant vesicles with a diameter of several micrometers in a mixed solvent of ethanol and water. When the hydrophobic ratio decreased to ca. 76%, the polymer self-assembled into conventional vesicles with several hundred nanometers. The giant vesicles could be fused in certain conditions, while the conventional vesicles were stable. When the content of the hydrophilic part was further increased, no organized structures were formed. On the other hand, when the copolymer solutions were directly cast on solid substrates such as silicon plates, films with organized nanostructures could also be obtained, the morphology of which depended on solvent selection. When ethanol or methanol was used, spheres were obtained. When dichloromethane was used as the solvent, honeycomb-like morphologies were obtained. These results showed that through appropriate molecular design, random copolymer could self-assemble into various organized structures, which could be regulated through the hydrophobic/hydrophilic balance and the solvents. 相似文献
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建立了含不同亲疏水粒子比的双亲性无规共聚物粗粒化模型. 采用耗散粒子动力学方法模拟了两亲性无规共聚物选择性溶剂自组装球形胶束表面的亲水性能. 模拟结果表明, 无规共聚物在选择性溶剂中自组装得到实心球形胶束, 球形胶束表面的亲水性与聚合物链亲水粒子含量、溶剂的选择性有关. 随着聚合物链所含亲水粒子增加, 球形胶束表面的亲水性增强. 球形胶束表面的亲水性随着疏水粒子与溶剂粒子间的排斥参数增大而增强, 模拟结果与实验结论一致. 该模拟方法给出的胶束微结构信息可以为双亲无规共聚物分子设计及自组装双亲胶束制备提供一定的理论指导. 相似文献
19.
In recent years, fluorescent assemblies based amphiphilic molecules have gained attention as unique and powerful materials for multiple applications that cover sensors, optoelectronics and bioimaging because of amphiphilic molecules self-assembly with outstanding flexibility and diversity spanning assembly structure from micelles, vesicles and nano-assemblies to gels. Weak and noncovalent interactions are important driving force for assemblies. The combination of the structural characteristics of self-assembly and the fluorescent properties of the fluorescent building element render the fluorescent material versatility and their easy-to-tune properties. Amphiphilic molecules can be used as building elements to co-assemble with dye molecules, aggregation-induced emission (AIE) gens, fluorescent nanoparticles and new amphiphilic molecules containing fluorescent groups can also be designed and prepared with self-assembly capability. Concomitantly, the improvement of fluorescence performance including fluorescence intensity, quantum yield, stability and controllability during assembly proved outstanding properties of fluorescence assemblies. These promising fluorescent assemblies are by far not exhaustive in construction method and mechanism explanation but foreshadow their more potential applications. Here, we will understand deeper the fluorescent assemblies and inspire future developments and applications employing this emerging fluorescence soft materials. 相似文献