Sequence‐Mandated,Distinct Assembly of Giant Molecules

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain‐like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence‐dependent phase structures. Not only compositional variation changed the self‐assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank–Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence‐mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self‐assembly.     

Sequence‐Mandated,Distinct Assembly of Giant Molecules

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain‐like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence‐dependent phase structures. Not only compositional variation changed the self‐assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank–Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence‐mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self‐assembly.     

Giant surfactants based on molecular nanoparticles: Precise synthesis and solution self‐assembly

Giant surfactants are polymer‐tethered molecular nanoparticles (MNPs) and can be considered as a subclass of giant molecules. The MNPs serve as functionalized heads with persistent shape and volume, which may vary in size, symmetry, and surface chemistry. The covalent conjugation of MNPs and polymer tails affords giant surfactants with diverse composition and architecture. Synthetic strategies such as “grafting‐from” and “grafting‐onto” have been successfully applied to the precise synthesis of giant surfactants, which is further facilitated by the emergence of “click” chemistry reactions. In many aspects, giant surfactants capture the essential features of small‐molecule surfactants, yet they have much larger sizes. They bridge the gap between small‐molecule surfactants and traditional amphiphilic macromolecules. Their self‐assembly behaviors in solution are summarized in this Review. Micelle formation is affected not only by their primary chemical structures, but also by the experimental conditions. This new class of materials is expected to deliver general implications on the design of novel functional materials based on MNP building blocks in the bottom‐up fabrication of well‐defined nanostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1309–1325     

有机大分子导向无机纳米粒子的分级有序自组装

本文主要综述了基于特定分子设计的有机大分子导向下的无机纳米粒子的分级有序自组装.可以有效导向无机纳米粒子组织的有机大分子主要包括合成大分子和生物大分子,前者如具有氢键识别功能的大分子、聚电解质、嵌段大分子、树枝状大分子;后者如DNA、糖类以及蛋白质.所涉及的无机纳米粒子通常需要通过单层修饰使之与特定的大分子具有识别功能,或者设计表面带有正或负电荷使之与带有负或正电荷的大分子相互识别.该领域的研究在先进功能材料及仿生材料方面具有重要意义.     

Toward rational and modular molecular design in soft matter engineering

This essay discusses some preliminary thoughts on the development of a rational and modular approach for molecular design in soft matter engineering and proposes ideas of structural and functional synthons for advanced functional materials. It echoes the Materials Genome Initiative by practicing a tentative retro-functional analysis(RFA) scheme. The importance of hierarchical structures in transferring and amplifying molecular functions into macroscopic properties is recognized and emphasized. According to the role of molecular segments in final materials, there are two types of building blocks: structural synthon and functional synthon. Guided by a specific structure for a desired function, these synthons can be modularly combined in various ways to construct molecular scaffolds. Detailed molecular structures are then deduced, designed and synthesized precisely and modularly. While the assembled structure and property may deviate from the original design, the study may allow further refinement of the molecular design toward the target function. The strategy has been used in the development of soft fullerene materials and other giant molecules. There are a few aspects that are not yet well addressed:(1) function and structure are not fully decoupled and(2) the assembled hierarchical structures are sensitive to secondary interactions and molecular geometries across different length scales. Nevertheless, the RFA approach provides a starting point and an alternative thinking pathway by provoking creativity with considerations from both chemistry and physics. This is particularly useful for engineering soft matters with supramolecular lattice formation, as in giant molecules, where the synthons are relatively independent of each other.     

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

A modular synthetic approach to degradable metathesis polymers is presented using acetal‐containing enyne monomers. The monomers are prepared in a short and divergent synthetic sequence that features two points of modification to tune polymerization behavior and introduce molecular cargo. Steric and stereochemical elements are critical in the monomer design in order to provide rapid and living polymerizations capable of generating block polymers. The developed polyacetal materials readily undergo pH‐dependent degradation in aqueous mixtures, and the rate of hydrolysis can be tuned through post‐polymerization modification with triazolinedione click chemistry. This presents a new scaffold for responsive metathesis polymers that may find use in applications that requires controllable breakdown and release of small molecules.     

Creation of hierarchical carbon nanotube assemblies through alternative packing of complementary semi-artificial beta-1,3-glucan/carbon nanotube composites

Much attention has been focused on exploiting novel strategies for the creation of hierarchical polymer assemblies by the control of the assembling number or the relative location among neighboring polymers. We here propose a novel strategy toward the creation of "hierarchical" single-walled carbon nanotube (SWNT) architectures by utilizing SWNT composites with cationic or anionic complementary semi-artificial beta-1,3-glucans as "building blocks". These beta-1,3-glucans are known to wrap SWNTs helically, to create one-dimensional superstructural composites. If the cationic composite is neutralized by an anionic composite, a well ordered SWNT-based sheet structure was created. Transmission electron microscopy (TEM) observation revealed that this sheet structure is composed of highly-ordered fibrous assemblies of SWNTs. This suggests that the cationic and anionic composites are tightly packed through electrostatic interactions. Moreover, both of the final assembly structures are readily tunable by adjusting the cation/anion ratio. The self-assembling modulation of functional polymers is associated with the progress in ultimate nanotechnologies, thus enabling us to create numerous functional nanomaterials. We believe, therefore, that the present system will extend the frontier of SWNT research to assembly chemistry including "hierarchical" superstructures.     

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.     

Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis,Assembly, and Applications

Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high‐temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono‐functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS‐based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS‐based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.     

Arborescent polymers and other dendrigraft polymers: A journey into structural diversity

Arborescent polymers are characterized by a dendritic, multilevel branched architecture derived from successive grafting reactions. In spite of their much larger size, these materials display properties analogous to dendrimers and hyperbranched polymers, the two other dendritic polymer families. The distinguishing features of arborescent polymers are their assembly from polymeric building blocks of uniform size and their very high molecular weights attained in few synthetic steps. This article offers an overview of the historical aspects of the development of dendrigraft polymers, starting from our initial efforts on the synthesis of arborescent polystyrenes. Major subsequent developments in the synthetic techniques from our and other research groups allowing the synthesis of dendrigraft copolymers, tailoring of the structural characteristics of the molecules, and further simplifications to their synthesis are also reviewed, with emphasis over the broad range of architectures attainable in these systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3803–3810, 2007     

Enzyme-responsive polymeric assemblies, nanoparticles and hydrogels

Being responsive and adaptive to external stimuli is an intrinsic feature characteristic of all living organisms and soft matter. Specifically, responsive polymers can exhibit reversible or irreversible changes in chemical structures and/or physical properties in response to a specific signal input such as pH, temperature, ionic strength, light irradiation, mechanical force, electric and magnetic fields, and analyte of interest (e.g., ions, bioactive molecules, etc.) or an integration of them. The past decade has evidenced tremendous growth in the fundamental research of responsive polymers, and accordingly, diverse applications in fields ranging from drug or gene nanocarriers, imaging, diagnostics, smart actuators, adaptive coatings, to self-healing materials have been explored and suggested. Among a variety of external stimuli that have been utilized for the design of novel responsive polymers, enzymes have recently emerged to be a promising triggering motif. Enzyme-catalyzed reactions are highly selective and efficient toward specific substrates under mild conditions. They are involved in all biological and metabolic processes, serving as the prime protagonists in the chemistry of living organisms at a molecular level. The integration of enzyme-catalyzed reactions with responsive polymers can further broaden the design flexibility and scope of applications by endowing the latter with enhanced triggering specificity and selectivity. In this tutorial review, we describe recent developments concerning enzyme-responsive polymeric assemblies, nanoparticles, and hydrogels by highlighting this research area with selected literature reports. Three different types of systems, namely, enzyme-triggered self-assembly and aggregation of synthetic polymers, enzyme-driven disintegration and structural reorganization of polymeric assemblies and nanoparticles, and enzyme-triggered sol-to-gel and gel-to-sol transitions, are described. Their promising applications in drug controlled release, biocatalysis, imaging, sensing, and diagnostics are also discussed.     

Synthetic Uniform Polymers and Their Use for Understanding Fundamental Problems in Polymer Chemistry

Summary: A uniform polymer is a polymer composed of molecules that are uniform with respect to molecular weight and constitution. Besides natural uniform polymers such as nucleic acids and polypeptide, synthetic uniform polymers have been obtained by a variety of approaches. In particular, a combination of living polymerization and supercritical fluid chromatography (SFC) separation is one of the promising ways for the preparation of uniform polymers. End‐functionalized uniform polymers enabled us to prepare uniform polymer architectures such as block, graft, comb, and star polymers. Their use for understanding the fundamental problems in polymer chemistry is discussed; topics include crystallization of polymers, chain conformation in solution, and association of stereoregular polymers in solution.

SFC traces of isotactic PMMA containing an authentic sample of the 45‐mer (a) and of the isolated uniform PMMA of 100‐mer (b).     

Synthetic Bilayer Membranes: Molecular Design,Self-Organization,and Application

Lipid bilayers are a most central building block of the biological molecular organization. Their two-dimensional self-assembly is essential to the generation of biological shapes and sizes on the molecular level. The observation that a totally synthetic amphiphile in water is spontaneously assembled to a bilayer structure suggested that bilayer formation is a general physicochemical phenomenon that is not restricted to particular structures of biolipid molecules. Bilayer formation is now observed for a large variety of synthetic amphiphiles which contain one, two, three, or four alkyl tails. The flexible alkyl tail may be replaced by perfluoroalkyl chains. The supramolecular structures obtained therefrom can be related to the component's molecular structure in many cases. The structural variety and the ease of molecular design make the synthetic bilayer an attractive vehicle for organizing covalently bound functional units and guest molecules. In addition, stable monolayers on water, planar lipid membranes (BLM), and free-standing cast films are obtainable because of the self-assembling property of bilayer-forming compounds. These molecular organizations display common supramolecular features. The use of the cast film as a molecular template provides exciting potential for the production of novel two-dimensional materials.     

A genetic algorithm for the automated generation of molecules within constraints

Summary A genetic algorithm has been designed which generates molecular structures within constraints. The constraints may be any useful function, for example an enzyme active site, a pharmacophore or molecular properties from pattern recognition or rule-induction analyses. The starting point may be random or may utilise known molecules. These are modified to grow into families of structures which, using the evolutionary operators of selection, crossover and mutation evolve to better fit the constraints. The basis of the algorithm is described together with some applications in lead generation, 3D database construction and drug design. Genetic algorithms of this type may have wider applications in chemistry, for example in the design and optimisation of new polymers, materials (e.g. superconducting materials) or synthetic enzymes.     

Developments in inorganic crystal engineering

The design and synthesis of crystalline materials through the self-assembly of molecular building blocks and the pursuit of functional materials based upon this approach are usually classified under the banner Crystal Engineering. The field is interdisciplinary in nature involving synthetic, materials, structural and theoretical chemists. There are strong ties to modern crystallography which can offer rapid and accurate structure determination and, in particular, insight into molecular and intermolecular geometries. Illustrative examples that chart the development field and provide an assessment of the current state of the art will be reviewed with an emphasis on inorganic chemistry. Broadly speaking, two classes of compounds will be discussed: those based upon molecules or ions linked into networks via noncovalent interactions and those (coordination polymers) in which metal centres are linked using coordination bonds through bridging ligands into extended networks.     

A general concept for the preparation of hierarchically structured pi-conjugated polymers

Typical biopolymers exhibit structures and order on different length scales. By contrast, the number of synthetic polymers with a similar degree of hierarchical structure formation is still limited. Starting from recent investigations on the structures of amyloid proteins as well as research activities toward nanoscopic scaffolds from synthetic oligopeptides and their polymer conjugates, a general strategy toward hierarchically structured pi-conjugated polymers can be developed. The approach relies on the supramolecular self-assembly of diacetylene macromonomers based on beta-sheet forming oligopeptides equipped with hydrophobic polymer segments. Polymerization of these macromonomers proceeds under retention of the previously assembled hierarchical structure and yields pi-conjugated polymers with multi-stranded, multiple-helical quaternary structures.     

Mirror image nanostructures

Chiral molecules that self-assemble to form chiral supramolecular structures exhibit interesting structural features reminiscent of tertiary and quaternary structures of proteins and have applications in catalysis and nonlinear optics. Often, these structures are hierarchical, with their chiral structure difficult to interpret on the molecular scale. In this communication, we observe chiral assembling molecules that form well-defined helices with a pitch of 28 nm. We observe the behavior in both R- and S-enantiomers of the molecule, forming mirror image nanostructures. The molecular chirality is determined by the dimethyloctyl alkyl coil of the molecule and is located more than 4 nm from the hydrogen-bonding segment. The nanostructures observed are not hierarchical, which could be a result of the significant separation between the stereocenter and hydrogen-bonding dendron. The subtle structural modification at the periphery of the molecule biases the supramolecular assembly, which is driven primarily by strong hydrogen-bonding and pi-pi stacking interactions.     

Synthetic and biological polymers--merging the interface

The increasing control that synthetic chemists are able to exert over molecular architecture is allowing the design and preparation of macromolecular and polymeric systems of unprecedented sophistication. In form and function, synthetic polymers are able to mimic many biological polymers, in effect ‘blurring the boundaries’ between the worlds of artificial and natural materials. In this review, some key examples from the merging interface between synthetic and natural polymers are considered, and illustrations of both ‘bio-inspired’ synthetic macromolecular chemistry and new directions in polymer materials are given.     

分子识别指导下的有机分子设计、合成和组装——世纪交替时代的有机化学

在21世纪即将来临之际,有机化学将面临生命科学、环境科学和材料科学越来越多的挑战。本文回顾了在分子识别指导下的有机分子的设计、合成和组装这个新领域的诞生和发展,认为这个领域将成为新世纪有机化学发展的一个重要方向。它的发展和应用不仅使得有机化学可能较好地面对新挑战,同时能推动有机合成化学自身的发展。     

Self-assembled free-floating nanomaterials from sequence-defined polymers

Sequence-defined polymers can be programmed to self-assemble into precise nanostructures for applications in biosensing, drug delivery, optics, and molecular computation. Inspired by the natural self-assembly processes present in biological protein and DNA systems, sets of molecular design rules have emerged across materials classes as instructions to build a variety of tunable structures. This review highlights recent advances in self-assembled sequence-defined and sequence-specific polymers across peptides, peptoids, DNA, and non-biological synthetic materials, with a focus on synthesis, assembly processes and overall structure. Specifically, these self-assembled structures are free-floating, as such constructs can potentially serve as a platform for the aforementioned applications. Emphasis is placed on the molecular design of polymers that self-assemble into zero-dimensional, one-dimensional, two-dimensional, or three-dimensional nanostructures. With the development of automated syntheses and increasing control over self-assembly, future work may focus on emerging classes of compatible hybrid materials with exciting directions toward new architectures and applications.