多肽分子自组装

源于自然界中广泛存在的蛋白质自组装现象,近年来多肽的自组装逐渐成为材料学和生物医学等领域的研究热点.通过合理调控多肽的分子结构以及改变外界的环境,多肽分子可以利用氢键、疏水性作用、π-π堆积作用等非共价键力自发或触发地自组装形成形态与结构特异的组装体.由于多肽自身具有良好的生物相容性和可控的降解性能,利用多肽自组装技术构建的各种功能性材料在药物控制释放、组织工程支架材料以及生物矿化等领域内有着巨大的应用前景.本文总结了近年来多肽自组装研究的进展,介绍了多肽自组装技术常见的几种结构模型,概括了多肽自组装的机理,并进一步阐述多肽自组装形成的组装体形态及其在材料学和生物医学等领域里的应用.     

Recent advances in short peptide self-assembly: from rational design to novel applications

Owing to their structural simplicity and robust self-assembled nanostructures, short peptides prove to be an ideal system to explore the physical processes of self-assembly, hydrogels, semi-flexible polymers, quenched disorder, and reptation. Rational design in peptide sequences facilitates cost-effective manufacturing, but the huge number of possible peptides has imposed obstacles for their characterization to establish functional connections to the primary, secondary, and tertiary structures. This review aims to cover recent advances in the self-assembly of designed short peptides, with a focus on physical driving forces, design rules, characterization methods, and exemplar applications. Super-resolution microscopy in combination with modern image analysis have been applied to quantify the structure and dynamics of peptide hydrogels, while small-angle neutron scattering and solid-state nuclear magnetic resonance continue to provide valuable information on structures over complementary length scales. Short peptides are attractive in biomedicine and nanotechnology, e.g., as antimicrobials, anticancer agents, vehicles for controlled drug release, peptide bioelectronics, and responsive cell culture materials.     

Self-assembly and morphology control of new L-glutamic acid-based amphiphilic random copolymers: giant vesicles, vesicles, spheres, and honeycomb film

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.     

Self-assembled structures with liquid-crystalline order in aqueous solution by patterning poly(phenylene ethynylene)s

Facially amphiphilic (FA) phenylene ethynylene (PE) polymers that self-assemble in aqueous solution were studied by small-angle X-ray diffraction (SAXD) and found to self-assemble into bilayers with a fully extended backbone. The resulting bilayers have long-range liquid-crystalline order. This self-assembly is programmed into the molecule by placing polar and nonpolar groups at precise locations so that they segregate onto opposite sides of the molecular structure. The absence of FA patterning generated an amorphous sample confirming the importance of this programmed amphiphilicity in the self-assembly process. Facially amphiphilic patterning represents a new design criterion for supramolecular chemistry, illustrated here in the observation of molecular ordering into bilayers reminiscent of self-assembled structures commonly found in biology, including amphiphilic beta-sheet polypeptides and phospholipid bilayers.     

甲壳型液晶高分子的构筑、自组装及其功能化

甲壳型液晶高分子的发展很大程度上依赖于聚合物自组装的发展,而各种可设计、可预测、可调控的自组装策略的涌现,将甲壳型液晶高分子研究推向前所未有的高度,同时也极大地丰富了高分子化学与物理的内容,提升了研究水准.研究表明,侧链"甲壳效应"在调控甲壳型液晶高分子有序结构等方面有着重要作用.本综述从甲壳型液晶高分子设计合成、液晶相态调控、嵌段共聚物自组装和功能化应用等方面,总结和评述了近年来该领域国内的最新研究进展.最后,本综述总结了甲壳型液晶高分子在发展中所面临的主要问题,并对其发展趋势进行了展望.     

Morphology transformation via pH-triggered self-assembly of peptides

Three flexible peptides (P1: (C(17)H(35)CO-NH-GRGDG)(2)KG; P2: (Fmoc-GRGDG)(2)KG; P3: (CH(3)CO-NH-GRGDG)(2)KG) self-assembled to form a variety of morphologically distinct assemblies at different pHs. P1 formed nanofibers at pH 3, then self-assembled into nanospheres with pH up to 6 and further changed to lamellar structures when the pH value was further increased to 10. P2 aggregated into an entwined network structure at pH 3, and then self-assembled into well-defined nanospheres, lamellar structures, and vesicles via adjusting the pH value. However, P3 did not self-assemble into well-ordered nanostructures, presumably due to the absence of a large hydrophobic group. The varying self-assembly behaviors of the peptides at different pHs are attributed to molecular conformational changes. These self-assembled supramolecular materials might contribute to the development of new peptide-based biomaterials.     

Self-assembly of surfactant-like peptides and their applications

Numerous peptides derived from naturally occurring proteins or de novo designed have been found to self-assemble into various nanostructures.These well-defined nanostructures have shown great potential for a variety of biomedical and biotechnological applications.In particular,surfactant-like peptides(SLPs)have distinctive advantages in their length,aggregating ability,and water solubility.In this article,we report recent advances in the mechanistic understanding of the self-assembly principles of SLPs and in their applications,most of which have been made in our laboratory.Hydrogen bonding between peptide backbones,hydrophobic interaction between hydrophobic side chains,and electrostatic repulsion between charged head groups all have roles in mediating the self-assembly of SLPs;the final self-assembled nanostructures are therefore dependent on their interplay.SLPs have shown diverse applications ranging from membrane protein stabilization and antimicrobial/anticancer agents to nanofabrication and biomineralization.Future advances in the self-assembly of SLPs will hinge on their large-scale production,the design of new functional SLPs with targeted properties,and the exploitation of new or improved applications.     

Functional supramolecular assemblies derived from dendritic building blocks

Control of the structure and function of self-assembled materials has been a significant issue in many areas of nanoscience. Among many different types of building blocks, dendritic ones have shown interesting self-assembly behaviour and functional performances due to their unique shape and multiple functionalities. Dendritic building blocks exhibit unique self-assembly behaviour in diverse environments such as aqueous and organic solutions, solid-liquid interfaces, and thermotropic solid conditions. Tuning the balance between hydrophilic and hydrophobic parts, as well as the external conditions for self-assembly, provides unique opportunities for control of supramolecular architectures. Furthermore, the introduction of suitable functional moieties into dendrons enables us to control self-assembly characteristics, allowing nanostructures to exhibit smart performances for electronic or biological applications. The self-assembly characteristics of amphiphilic dendrons under various conditions were investigated to elucidate how dendrons can assemble into nanoscopic structures and how these nanoassemblies exhibit unique properties. Well-defined nanostructures derived from self-assembly of dendrons provide an efficient approach for exhibition of unique functions at the nanoscale. This feature article describes the unique self-assembly characteristics of various types of dendritic building blocks and their potential applications as advanced materials.     

Recent Progress in Azobenzene-Based Supramolecular Materials and Applications

Azobenzene-containing small molecules and polymers are functional photoswitchable molecules to form supramolecular nanomaterials for various applications. Recently, supramolecular nanomaterials have received enormous attention in material science because of their simple bottom-up synthesis approach, understandable mechanisms and structural features, and batch-to-batch reproducibility. Azobenzene is a light-responsive functional moiety in the molecular design of small molecules and polymers and is used to switch the photophysical properties of supramolecular nanomaterials. Herein, we review the latest literature on supramolecular nano- and micro-materials formed from azobenzene-containing small molecules and polymers through the combinatorial effect of weak molecular interactions. Different classes including complex coacervates, host-guest systems, co-assembled, and self-assembled supramolecular materials, where azobenzene is an essential moiety in small molecules, and photophysical properties are discussed. Afterward, azobenzene-containing polymers-based supramolecular photoresponsive materials formed through the host-guest approach, polymerization-induced self-assembly, and post-polymerization assembly techniques are highlighted. In addition to this, the applications of photoswitchable supramolecular materials in pH sensing, and CO₂ capture are presented. In the end, the conclusion and future perspective of azobenzene-based supramolecular materials for molecular assembly design, and applications are given.     

Self-assembly of beta-sheets into nanostructures by poly(alanine) segments incorporated in multiblock copolymers inspired by spider silk.

Selective replacement of the amorphous peptide domain of a spider silk with poly(ethylene glycol) gave N. clavipes silk-inspired polymers having similar solid-state structures and very good mechanical properties. The tendency of poly(alanine) having appropriate chain length to form beta-sheets and the facility with which the beta-sheets self-assemble have been retained in the polymers. Solid-state (13)C NMR, solid-state FTIR, X-ray diffraction, and AFM studies showed that the polymers formed predominantly antiparallel beta-sheets that self-assembled into discrete nanostructures. The longer the peptide segment was, the greater was the tendency to self-assemble into antiparallel beta-sheet aggregates. AFM revealed that the morphology of the polymers was a microphase-separated architecture that contained irregularly shaped 100-200 nm poly(alanine) nanodomains interspersed within the PEG phase. The results suggest that the poly(alanine) domain influences the solid-state properties of spider silk through beta-sheet self-assembly into temporary cross-links. The results further demonstrate that by selectively replacing certain segments of a naturally occurring biopolymer with a judiciously selected nonnative segment while, at the same time, retaining other segments known to be critical for the essential properties of the native biopolymer, a synthetic polymer with similar properties and function can be obtained.     

Synthesis, self-assembly, and characterization of supramolecular polymers from electroactive dendron rodcoil molecules

We report here the synthesis and self-assembly of a series of three molecules with dendron rodcoil architecture that contain conjugated segments of oligo(thiophene), oligo(phenylene-vinylene), and oligo(phenylene). Despite their structural differences, all three molecules yield similar self-assembled structures. Electron and atomic force microscopy reveals the self-assembly of the molecules into high aspect ratio ribbon-like nanostructures which at low concentrations induce gelation in nonpolar solvent. Self-assembly results in a blue-shifted absorption spectrum and a red-shifted, quenched fluorescence spectrum, indicating aggregation of the conjugated segments within the ribbon-like structures. The assembly of these molecules into one-dimensional nanostructures is a route to pi-pi stacked supramolecular polymers for organic electronic functions. In the oligo(thiophene) derivative, self-assembly leads to a 3 orders of magnitude increase in the conductivity of iodine-doped films due to self-assembly. We also found that electric field alignment of these supramolecular assemblies can be used to create arrays of self-assembled nanowires on a device substrate.     

Nanoscale characterization of zein self-assembly

Zein, a major protein of corn, is rich in α-helical structure. It has an amphiphilic character and is capable of self-assembly. Zein can self-assemble into various mesostructures that may find applications in food, agricultural, and biomedical engineering. Understanding the mechanism of zein self-assembly at the nanoscale is important for further development of zein structures. In this work, high-resolution transmission electron microscopy (TEM) images revealed nanosize zein stripes, rings, and discs containing a 0.35 nm periodicity, which is characteristic of β-sheet. TEM images were interpreted in terms of the transformation of original α-helices into β-sheet conformation after evaporation-induced self-assembly (EISA). The presence of β-sheet was also detected by circular dichroism (CD) spectroscopy. Zein β-sheets self-assembled into stripes, which curled into rings. Rings formed discs and eventually spheres. The formation of zein nanostructures was believed to be the result of β-sheet orientation, alignment, and packing.     

[60]富勒烯的超分子自组装研究进展

超分子自组装是发展超分子电子学的重要途径。随着纳米科学和技术的迅速发展,自组装技术已成功地应用于纳米尺度物质的维数、形貌和功能等的调控。作为构筑分子水平上一维、二维、三维有序功能结构和高有序分子聚集态结构的关键技术,超分子自组装技术有力地推动了具有优良光、电、磁性能的分子材料和纳米功能材料更深层次的研究。本文综述了超分子自组装在富勒烯科学领域的基础研究和应用,特别是对有利于自组织和自组装功能的富勒烯基衍生物的设计与合成、超分子作用力引导的具有特定结构的分子体系的可控自组装、以及富勒烯分子聚集态结构材料的光物理过程、超分子中电子转移和能量转移现象进行了描述;并对卟啉、四硫富瓦烯、碗烯和杯芳烃等一系列富π电子化合物和大环主体分子等包含[60]富勒烯的主体化合物的超分子作用和超分自组装体以及通过氢键、π-π作用、静电力和范德华力和金属配位作用形成的[60]富勒烯超分子自组装体进行了总结,对未来发展进行了展望。     

Ordered patterns and structures via interfacial self-assembly: superlattices, honeycomb structures and coffee rings

Self-assembly is now being intensively studied in chemistry, physics, biology, and materials engineering and has become an important "bottom-up" approach to create intriguing structures for different applications. Self-assembly is not only a practical approach for creating a variety of nanostructures, but also shows great superiority in building hierarchical structures with orders on different length scales. The early work in self-assembly focused on molecular self-assembly in bulk solution, including the resultant dye aggregates, liposomes, vesicles, liquid crystals, gels and so on. Interfacial self-assembly has been a great concern over the last two decades, largely because of the unique and ingenious roles of this method for constructing materials at interfaces, such as self-assembled monolayers, Langmuir-Blodgett films, and capsules. Nanocrystal superlattices, honeycomb films and coffee rings are intriguing structural materials with more complex features and can be prepared by interfacial self-assembly on different length scales. In this critical review, we outline the recent development in the preparation and application of colloidal nanocrystal superlattices, honeycomb-patterned macroporous structures by the breath figure method, and coffee-ring-like patterns (247 references).     

Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro-organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self-assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro-organic chemistry from synthetic concepts to materials properties, with a focus on self-assembly and molecular recognition. Finally, an outlook for future research directions is provided.     

Inverting structures: from micelles via emulsions to internally self-assembled water and oil continuous nanocarriers

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.     

Electrochemical recognition of tryptophan enantiomers using self-assembled diphenylalanine structures induced by graphene quantum dots,chitosan and CTAB

Molecular self-assembly offers a promising route to the preparation of advanced materials for the construction of novel chiral sensing devices, and the inspiration for the development of such systems is often derived from simple biological models. Diphenylalanine (FF), an extensively studied short peptide, can self-assemble into highly ordered nano-/micro-structures. Here we report the electrochemical recognition of tryptophan enantiomers using three FF self-assembled structures produced in the presence of graphene quantum dots (GQDs), chitosan (CS) and cetyltrimethylammonium bromide (CTAB). Although the difference in the peak potentials of the enantiomers is very small, enantiomeric differences can be detected by the magnitude of the DPV current signals. The recognition efficiencies of the three self-assembled materials are different, due to the different structures formed during the self-assembly process.     

Role of alkylated residues in the tetrapeptide self-assembly—A molecular dynamics study

Designing peptide sequences that self-assemble into well-defined nanostructures can open a new venue for the development of novel drug carriers and molecular contrast agents. Current approaches are often based on a linear block-design of amphiphilic peptides where a hydrophilic peptide chain is terminated by a hydrophobic tail. Here, a new template for a self-assembling tetrapeptide (YXKX, Y = tyrosine, X = alkylated tyrosine, K = lysine) is proposed with two distinct sides relative to the peptide's backbone: alkylated hydrophobic residues on one side and hydrophilic residues on the other side. Using all-atom molecular dynamics simulations, the self-assembly pathway of the tetrapeptide is analyzed for two different concentrations. At both concentrations, tetrapeptides self-assembled into a nanosphere structure. The alkylated tyrosines initialize the self-assembly process via a strong hydrophobic effect and to reduce exposure to the aqueous solvent, they formed a hydrophobic core. The hydrophilic residues occupied the surface of the self-assembled nanosphere. Ordered arrangement of tetrapeptides within the nanosphere with the backbone hydrogen bonding led to a beta sheet formation. Alkyl chain length constrained the size and shape of the nanosphere. This study provides foundation for further exploration of self-assembling structures that are based on peptides with hydrophobic and hydrophilic moieties located on the opposite sides of a peptide backbone.     

Emerging advances in plasmonic nanoassemblies for biosensing and cell imaging

Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties, which are not available for single nanoparticles. Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects. Thus, plasmonic assemblies enable better performance in plasmon-based applications,such as enhanced fluorescence and Raman effects. This makes them hold great potential...     

The review on properties of solid catanionic surfactants: Main applications and perspectives of new catanionic surfactants and compounds with catanionic assisted synthesis

Mixtures of anionic and cationic surfactants display varied aggregate structures. Solid catanionic systems and metaloamphiphilic complexes, amphiphilic host–guest systems, as well as amphiphilic hydrogen bond pairs are a kind of hybrid amphiphiles, all of which self-organize into supramolecular membranes. Amphiphilicity of the supermolecules drives their hierarchical self-assembly. This review mainly discusses the current applications of well-ordered catanionic materials that show a variety of functionalities in material and life science. Widely studied rational molecular design can create self-assembled structures through various noncovalent interactions combined with numerous modification strategies. Possible applications are at early stage to access the entire potential, but may provide new and interesting interdisciplinary directions for further studies.