三维宏观网络状囊泡薄膜的分级自组装研究

分别合成以疏水性超支化聚醚(HBPO)为核,以亲水性聚环氧乙烷(EO)和聚甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)为臂的两亲性超支化多臂共聚物HBPO-star-PEO和HBPO-star-PDMAEMA.通过两者在水溶液中的复合自组装制备得到具有pH响应性的巨型聚合物囊泡(1~10μm),并用zeta电位仪,激光共聚焦显微镜及光学显微镜对囊泡的自组装行为进行了研究.结果表明,在等电点以前,复合囊泡始终以单个囊泡形式存在;随着溶液pH的升高,囊泡逐步线型缔合成串珠结构;在更高的pH下,囊泡进一步二次聚集形成具有宏观尺度的三维蜘蛛网状超分子结构,这是一类新的自组装体.     

Self-assembly of Amphiphilic Alternating Copolymers

Polymer self-assembly has been a hot research topic for several decades. Different types of polymers with various architectures, like block copolymers, brush polymers, hyperbranched polymers and dendrimers, etc., are currently being investigated. Alternating copolymers (ACPs) are regular copolymers with an alternating monomeric unit structure in the polymer backbones. However, despite the great progress in the synthesis of ACPs, their self-assembly is still in an infant stage. Very recently, our group reported a new type of amphiphilic ACPs through click copolymerization and obtained spheres, vesicles, nanotubes, and even hierarchical sea urchin-like aggregates through the self-assembly process. In addition, we have found some intriguing features in the self-assembly of amphiphilic ACPs when compared with other copolymers, including their facile syntheses, readily functionalization, novel self-assembly structures, new folding-chain mechanisms, and uniform but ultrathin feature length. In this Concept article, we present the self-assembly of amphiphilic ACPs together with their unique features by reviewing our latest results and related studies. Moreover, the future perspective on the self-assembly of amphiphilic ACPs is also proposed. Our aim is to capture the attention and interest of chemists in this new area of polymerization.     

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.     

Phase diagrams,mechanisms and unique characteristics of alternating-structured polymer self-assembly via simulations

Alternating-structured polymers(ASPs), like alternating copolymers, regular multiblock copolymers and polycondensates, are very important polymer structures with broad applications in photoelectric materials. However, their self-assembly behaviors,especially the self-assembly of alternating copolymers, have not been clearly studied up to now. Meanwhile, the unique characteristics therein have not been systematically disclosed yet by both experiments and theories. Herein, we have performed a systematic simulation study on the self-assembly of ASPs with two coil alternating segments in solution through dissipative particle dynamics(DPD) simulations. Several morphological phase diagrams were constructed as functions of different impact parameters. Diverse self-assemblies were observed, including spherical micelles, micelle networks, worm-like micelles, disklike micelles, multimicelle aggregates, bicontinuous micelles, vesicles, nanotubes and channelized micelles. Furthermore, a morphological evolutionary roadmap for all these self-assemblies was constructed, along with which the detailed molecular packing models and self-assembly mechanisms for each aggregate were disclosed. The ASPs were found to adopt a folded-chain mechanism in the self-assemblies. Finally, the unique characteristics for the self-assembly of alternating copolymers were revealed especially, including(1) ultra-fine and uniform feature sizes of the aggregates;(2) independence of self-assembled structures from molecular weight and molecular weight distribution;(3) ultra-small unimolecular aggregates. We believe the current work is beneficial for understanding the self-assembly of alternating structured polymers in solution and can serve as a guide for the further experiments.     

Inorganic Self-assembly: Going Bio

The use of self-assembly for building complex functional structures is a current topic of interest in supramolecular chemistry. In this context, the use of biomolecule-based building blocks has paved the way for the development of intracellular assemblies. Currently, the potential functionality of such assemblies in biomedical applications is being disclosed. On the other hand, the use of inorganic (metal-based) building blocks is still in its infancy. The construction of inorganic self-assemblies in-bio is particularly challenging and demands great efforts to reach applications. However, the plethora of thinkable advantages related to the use of inorganic self-assembly in living cells must fuel new discoveries in this area. This Concept reviews the current advances, perspectives, and challenges in inorganic self-assembly in living systems.     

高分子囊泡和空心球的制备和几个研究亮点

聚合物囊泡和空心球是具有重要理论研究价值和在很多领域特别是在生物医药方面具有潜在应用的大分子组装体本文综述了高分子囊泡及空心球的制备方法及某些新发展其传统的制备方法主要包括嵌段共聚物自组装法和聚合物胶束去核法以及模板上合成着重讨论了近年来新发展起来的非共价键合自组装法(NCCM)以及通过化学反应一步从单体获得聚合物空心...     

Polymeric amphiphile branching leads to rare nanodisc shaped planar self-assemblies

Self-assembly is fundamental to the biological function of cells and the fabrication of nanomaterials. However, the origin of the shape of various self-assemblies, such as the shape of cells, is not altogether clear. Polymeric, oligomeric, or low molecular weight amphiphiles are a rich source of nanomaterials, and controlling their self-assembly is the route to tailored nanosystems with specific functionalities. Here, we provide direct evidence that a particular molecular architecture, polymeric branching, leads to a rare form of self-assembly, the planar nanodisc. Cholesterol containing self-assemblies formed from amphiphilic linear or branched cetyl poly(ethylenimine) (Mn approximately 1000 Da) or amphiphilic cetyl poly(propylenimine) dendrimer derivatives (Mn approximately 2000 Da) show that branching, by reducing the hydrophilic headgroup area, alters the shape of the self-assemblies transforming closed 60 nm spherical bilayer vesicles to rare 50 nm x 10 nm planar bilayer discs. Increasing the hydrophilic headgroup area, by the inclusion of methoxy poly(ethylene glycol) moieties into the amphiphilic headgroup, transforms the planar discs to 100 nm spherical bilayer vesicles. This study provides insight into the key role played by molecular shape on molecular self-organization into rare nanodiscs.     

Controlled Self-assembly of Thermo-responsive Amphiphilic H-shaped Polymer for Adjustable Drug Release

Despite the fact that some progress has been made in the self-assembly of H-shaped polymers,the corresponding self-assemblies that respond to external stimulus and are further utilized to adjust the release of drugs are still deficient.The stimuli-responsive segments with amphiphilic H-shaped structure are generally expected to enhance the controllability of self-assembly process.The synthesis and self-assembly behavior of thermo-responsive amphiphilic H-shaped polymers with poly(ethylene glycol) (PEG),polytetrahydrofuran (PTHF) and poly(N-isopropyl acrylamide) (PNIPAM) as building blocks are reported in this paper.The inner architecture structure and size of complex micelles formed by H-shaped self-assemblies were effectively adjusted when the solution temperature was increased above the lower critical solution temperature of PNIPAM segments.Furthermore,it was found that the architecture of self-assemblies underwent a transition from the complex micelles based on primary micelles with hybrid PEG/PNIPAM shells to large complex micelles based on primary micelles with hybrid PTHF/PNIPAM cores and PEG shells during the thermal-induced self-assembly process.The adjustable release rate of doxorubicin (DOX) from the DOX-loaded complex micelles and basic cell experiments further proved the feasibility of these self-assemblies as the thermal-responsive drug delivery system.     

仿病毒衣壳自组装体及其生物医学应用

仿病毒衣壳结构自组装体具有重要的基础研究和应用价值,是化学、材料、生物医学等多学科前沿交叉领域.本文从天然病毒衣壳的基本结构和特征出发,立足于从结构仿生到功能仿生的角度,综述了以天然病毒衣壳蛋白质和人工合成材料为组装基元构建仿病毒衣壳自组装体的策略,及其形态结构的调控和功能优化等.重点论述了近年来合成肽类分子在仿病毒衣壳自组装体结构和功能方面的进展.同时,就仿病毒衣壳自组装体在药物控释、基因传递等生物医学领域的应用也做了论述.     

Rapidly SO2-responsive vesicles with intrinsic fluorescent indicators for membrane structure evolution

Stimuli-responsive vesicles (SRVs) have been widely exploited as smart nanocarriers for biomedical applications. Herein, high-performance SO₂-responsive nanovesicles were reported to exemplify a new mode of SRVs. Structurally, the sensory vesicles were based on amphiphilic hydrogen-bonded (HB) polymers which can be facilely fabricated via modular self-assembly. The HB polymers are designed to consist of a melamine-barbituric acid HB skeleton with pendant anthracene fluorophores and amphiphilic side chains. Upon stimulation with increasing amount of SO₂, the vesicles in aqueous solution undergo an unusual morphology evolution including rapid fission into small ones, swelling and final collapse of the offspring vesicles. During this process, the intrinsic fluorescence response of the vesicles allows intuitive tracking of the hierarchical structural evolution of the self-assembled membranes and straightforward quantitation of the stimuli. This work exemplifies a rational design of auto-recording stimuli-responsive nanovesicles.     

Self-assembled Supramolecular Artificial Transmembrane Ion Channels: Recent Progress and Application

Natural protein channels have evolved with fantastic spatial structures, which play pivotal physiological functions in all living systems. Learning from nature, chemical scientists have developed a myriad of artificial transmembrane ion channels by using various chemical strategies, among which the non-covalent supramolecular ion channels exhibit remarkable advantages over other forms(e.g., single-molecule ion channel), which exhibited facile preparation methods, easier structural modification and functionalization. In this review, we have systematically summarized the recent progress of supramolecular self-assembled artificial transmembrane ion channels, which were classified by different self-assembly mechanisms, such as hydrogen bonds, π-π interactions, etc. Detailed preparation process and self-assembly strategies of the supramolecular ion channels have been described. Moreover, potential biomedical applications of the supramolecular ion channels have also been carefully discussed in this review. Finally, future opportunities and challenges facing this field were also elaborately discussed. It is anticipated that this review could provide a panoramic sketch and future directions towards the construction of novel artificial ion channels with novel functions and biomedical applications.     

无机半导体纳米晶光学性质的设计、调控及其生物医学应用

半导体纳米晶由于其丰富的能带结构和光学性质,在光电器件和生物医学应用等领域展现出了广阔的应用前景,且在过去的几十年中得到了广泛关注.因此,对其光学性质进行理性设计和精确调控具有重要的研究意义.本文简要综述了本研究组近年来在不同能带隙的无机半导体纳米晶的可控制备技术以及利用DNA纳米技术和蛋白质自组装手段构建具有特异光学性质的纳米结构等方面的相关研究工作,最后对这些纳米晶和纳米结构的独特光学性质及其在生物医学领域的应用研究进行了总结.     

Temperature-responsive phase transition of polymer vesicles: real-time morphology observation and molecular mechanism

Novel thermosensitive polymer vesicles with controlled temperature-responsive phase transition at the lower critical solution temperature (LCST) varying from 8 to 81 degrees C were prepared via self-assembly of amphiphilic hyperbranched star copolymers having a hydrophobic hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO) core and many hydrophilic polyethylene oxide (PEO) arms. Real-time optical microscopic observation revealed that the polymer vesicles have undergone sequential morphology changes including enrichment, aggregation, fusion, and vesicle-to-membrane transformation near the LCST. Molecular-level investigation indicates that the LCST transition results from the decreasing water solubility of the polymer vesicles with increasing temperature based on the partial dehydration of the PEO vesicle corona. On the basis of these results, a LCST transition mechanism, in view of the molecular configuration, balance of hydrophilic and hydrophobic moieties, and the vesicle morphology transformations, was proposed. As far as we know, the work presented here is the first demonstration of thermosensitive vesicles based on PEO, and the finding may be useful to design the thermosensitive core-shell structures by introducing the PEO segments.     

Synthesis of hyperbranched polymers from vegetable oil based monomers via ozonolysis pathway

In this work, a variety of hyperbranched polymers (HBPs), such as hyperbranched polycarbonates, polyesters, polyurethanes and polyacetals, was successfully synthesized from castor oil and soybean oil based monomers via a A₂ + B₃ polycondensation. First, B₃ monomer triols (TriOL), trialdehydes (TriAD), and tricarboxylic acids (TriAC) were obtained by ozonolysis of castor oil and soybean oil with following reductive or oxidative treatment. Their structures were characterized by ¹H NMR and ATR‐FTIR spectroscopy as well as electrospray ionization‐Time of Flight‐mass spectrometry. These trifunctional B₃ monomers were applied in the preparation of HBPs. The resulting HBPs had number averaged molar mass (M_n) up to 9400 g/mol and weight averaged molar mass (M_w) up to 40,000 g/mol. Through adjusting the initial molar ratio of A₂ to B₃ monomers, hydroxyl terminated (from TriOL monomers) or carboxylic acid (from TriAC monomers) terminated HBPs could be obtained. All the HBPs were characterized by ¹H NMR, size exclusion chromatography, and DSC. These HBPs are potential candidates for the synthesis of cross‐linked polymeric materials or in biomedical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2104–2114     

Natural supramolecular building blocks: from virus coat proteins to viral nanoparticles

Viruses belong to a fascinating class of natural supramolecular structures, composed of multiple copies of coat proteins (CPs) that assemble into different shapes with a variety of sizes from tens to hundreds of nanometres. Because of their advantages including simple/economic production, well-defined structural features, unique shapes and sizes, genetic programmability and robust chemistries, recently viruses and virus-like nanoparticles (VLPs) have been used widely in biomedical applications and materials synthesis. In this critical review, we highlight recent advances in the use of virus coat proteins (VCPs) and viral nanoparticles (VNPs) as building blocks in self-assembly studies and materials development. We first discuss the self-assembly of VCPs into VLPs, which can efficiently incorporate a variety of different materials as cores inside the viral protein shells. Then, the self-assembly of VNPs at surfaces or interfaces is summarized. Finally, we discuss the co-assembly of VNPs with different functional materials (178 references).     

Recent development of pillar[n]arene-based amphiphiles

Pillar[n]arene-based amphiphiles,mainly including amphiphilic pillar[n]arenes and supra-amphiphilic pillar[n]arenes,have obtained considerable interests in recent years due to their fascinating chemical structures,various self-assembly behaviors,and widely applications.Thanks to the pillar-like frameworks and the rich host-guest recognitions of the cavities,these amphiphiles can be easily controlled to form dimensional and morphologic assemblies for multiple applications.Compared with traditional linear covalent amphiphiles,the introduction of host-guest recognitions facilitated the preparation and controllability of these supramolecular amphiphilic systems.Moreover,the host-guest recognitions endow the assemblies from pillar[n]arene-based amphiphiles with stimuli-responsive functions.In this mini-review,we summarized the chemical structures,self-assembly features,and the applications of pillar[n]arene-based amphiphiles.However,several research topics of pillar[n]arenebased amphiphiles can be further developed in the future,such as larger cavity amphiphilic pillar[n]arenes,co-assembly with 2 D materials and utilization of the host-guest interactions.     

Structure of polypeptide-based diblock copolymers in solution: stimuli-responsive vesicles and micelles

Polypeptide-based diblock copolymers forming either well-defined self-assembled micelles or vesicles after direct dissolution in water or in dichloromethane have been studied combining light and neutron scattering with electron microscopy experiments. The size of these structures could be reversibly manipulated as a function of environmental changes such as pH and ionic strength in water. Compared to other pH-responsive self-assembled systems based on "classical" polyelectrolytes, these polypeptide-based nanostructures present the ability to give a response in highly salted media as the chain conformational ordering can be controlled. This makes these micelles and vesicles suitable for biological applications: they provide significant advantages in the control of the structure and function of supramolecular self-assemblies.     

Fluorescent assemblies: Synergistic of amphiphilic molecules and fluorescent elements

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.     

Influence of branching architecture on polymer properties

Hyperbranched polymers (HBPs), invented at the end of 1980s, are one important subclass of the fourth generation macromolecular architectures following the linear, branched, and crosslinking polymers. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. HBPs are composed of linear units, dendritic units, and terminal units. The degree of branching (DB), a term to describe the composition of these three structure units and thus the branching architecture of polymers, is one of the most important intrinsic parameters for HBPs. This review has summarized the effect of the DB on the physical and chemical properties of HBPs, including the rheological property, crystallization and melting behaviors, glass transition, thermal and hydrolytic degradations, phase characteristics, lower critical solution temperature phase transition, optoelectronic properties, encapsulation capability, self‐assembly behavior, biomedical applications, and so on. Such a structure and property relationship will build a bridge between the syntheses and applications of HBPs, especially in the application areas of functional materials, biomedical materials, and nanotechnology. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1277–1286, 2011     

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.