Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces

Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.     

All-conjugated block copolymers

All-conjugated block copolymers of the rod-rod type came into the focus of interest because of their unique and attractive combination of nanostructure formation and electronic activity. Potential applications in a next generation of organic polymer materials for photovoltaic devices ("bulk heterojunction"-type solar cells) or (bio)sensors have been proposed. Combining the fascinating self-assembly properties of block copolymers with the active electronic and/or optical function of conjugated polymers in all-conjugated block copolymers is, therefore, a very challenging goal of synthetic polymer chemistry. First examples of such all-conjugated block copolymers from a couple of research groups all over the world demonstrate possible synthetic approaches and the rich application potential in electronic devices. A crucial point in such a development of novel polymer materials is a rational control over their nanostructure formation. All-conjugated di- or triblock copolymers may allow for an organization of the copolymer materials into large-area ordered arrays with a length scale of nanostructure formation of the order of the exciton diffusion length of organic semiconductors (typically ca. 10 nm). Especially for amphiphilic, all-conjugated copolymers the formation of well-defined supramolecular structures (vesicles) has been observed. However, intense further research is necessary toward tailor-made, all-conjugated block copolymers for specific applications. The search for optimized block copolymer materials should consider the electronic as well as the morphological (self-assembly) properties.     

单分散SiO2/Ag/SiO2核壳结构微球制备及自组装光子晶体

应用湿化学方法,在SiO2微球表面先后包覆5 nm银层、20 nm SiO2介质膜,制备了直径约300 nm的单分散SiO2/Ag/SiO2核壳结构微球.用提拉技术实现微球的自组装,获得了长程有序的面心立方结构排列的光子晶体,并研究了其光学性能.结果表明:在可见至近红外波段存在非完全光子带隙;SiO2/Ag/SiO2球体自组装成的光子晶体并非完全密堆排列.     

A facile method of shielding from UV damage by polymer photonic crystals

BACKGROUND: UV radiation is a potent and ubiquitous carcinogen, which is responsible for most of the skin cancer in the human population. General UV protection materials may produce dangerous degradation products under UV irradiation; therefore, safe, nontoxic and simple UV protection approaches are urgent requirements. RESULTS: A series of photonic crystals with stopband covering the range 200–400 nm have been fabricated which can shield radiation from the whole UV range. Both UV‐visible and ¹H NMR results confirm the effective protection from UV light of 254 nm. CONCLUSIONS: A facile method for UV protection has been demonstrated by utilizing the unusual optical properties of photonic crystals that can inhibit light propagation at a given frequency without specific requirement of chemical composition. This approach opens a new way to protect from UV damage using safe materials, which is of great significance for extending the practical applications of photonic crystals. Copyright © 2007 Society of Chemical Industry     

Supramolecular Polymers – we've Come Full Circle

Since the first polymers were discovered, scientists have debated their structures. Before Hermann Staudinger published the brilliant concept of macromolecules, polymer properties were generally believed to be based on the colloidal aggregation of small particles or molecules. From 1920 onwards, polymers and macromolecules are synonymous with each other; i. e. materials made by many covalent bonds connecting monomers in 2 or 3 dimensions. Although supramolecular interactions between macromolecular chains are evidently important, e. g. in nylons, it was unheard of to proposing polymeric materials based on the interaction of small molecules. Breakthroughs in supramolecular chemistry, however, showed that polymer materials can be made by small molecules using strong directional secondary interactions; the field of supramolecular polymers emerged. In a way, we have come full circle. In this essay we give a personal story about the birth of supramolecular polymers, with special emphasis on their structures, way of formation, and the dynamic nature of their bonding. The adaptivity of supramolecular polymers has become a major asset for novel applications, e. g. in the direction for the sustainable use of polymers, but also in biomedicine and electronics as well as self-healing materials. The lessons learned in the past years include aspects that forecast a bright future for the use of supramolecular interactions in polymer materials in general and for supramolecular polymers in particular. In order to give full tribute to Staudinger in the year celebrating 100 years of macromolecules, we will show that many of the concepts of macromolecular polymers apply to supramolecular polymers, with only one important difference with fascinating consequences: the dynamic nature of the bonds that form polymer chains.     

棒状线圈三嵌段共聚物的液晶超分子结构研究进展

如何获得能形成纳米尺寸的新型超分子材料以及研究这些结构对材料性质的影响成为当今分子设计的热点。由刚性芳香核(棒状Rod:B)及柔性链(线圈状Coil:A或C)组成的棒状线圈三嵌段共聚物能在纳米尺度上自组装出丰富多彩的纳米液晶超分子结构。介绍了不对称ABC(Coil-Rod-Coil)、对称ABA(Coil-Rod-Coil)及BAB(Rod-Coil-Rod)棒状线圈三嵌段共聚物的液晶超分子行为,讨论了疏水性作用力、各嵌段体积大小、分子形状、分子长度等结构因素的改变对这类三嵌段共聚物液晶分子自组装结构的影响,介绍了棒状线圈三嵌段共聚物组装形成的一序列一维层列相、二维柱相及三维的立方、四方相等多种连续的及不连续的复杂纳米液晶超分子结构。     

3-D molecular assembly of function in titania-based composite material systems

Various examples of composite titania-based nanostructured materials exhibiting cooperative functionalities between different active components are presented. The fabrication of these integrated composite materials is based on one-pot supramolecular templating techniques combined with acidic sol-gel chemistry. The defined 3-D nanoscale organization and integration of various functional components results in advanced optoelectronic and photonic applications such as visible light sensitization of mesoporous titania photocatalysts with cadmium sulfide nanocrystals acting as sensitizing integral part of the mesopore wall structure, narrow bandwidth emission from rare earth ion activated nanocrystalline mesoporous titania films, and mirrorless lasing in dye-doped hybrid organic/inorganic mesostructured titania waveguides.     

Densification and properties of bulk nanocrystalline functional ceramics with grain size below 50 nm

The synthesis and functional characterization of dense bulk nanometric oxides are reviewed, with particular emphasis on the modifications that a grain size in the low nanometric range (10–50 nm) introduces in their physical properties. The preparation of ceramics with low porosity and extremely small grain size is particularly challenging and mostly relies on the sintering of extremely fine nanopowder. The most popular methods for the preparation of the starting nanopowders are introduced and briefly discussed as well as the most widely employed densification techniques. The role of nanostructure in controlling phase stability, electrical and thermal transport, optical and magnetic properties of nano-oxides is discussed in details. Several examples are given where bulk materials prepared with grain size equal or below 50 nm show characteristics that are either enhanced or, in some cases, completely different from those possessed by the same materials, but with larger grain sizes.     

Hydrogen Bonding Modules for Use in Supramolecular Polymers

Supramolecular polymer chemistry has emerged as a major research focus within polymer science, because of the potential to improve material properties, through the combination of noncovalent interactions and synthetic polymers. As a supramolecular handle, the most useful noncovalent interaction is hydrogen bonding, which has been used extensively, because of advantages such as synthetic accessibility, directionality, fidelity, and, most importantly, responsiveness to external stimuli. This review introduces recent advances in the development of hydrogen bonding modules that can be useful for creating a variety of supramolecular polymers. Furthermore, we present selected examples of hydrogen bonded supramolecular polymers from the literature, by dividing them into three categories: supramolecular polymers assembled from small molecules, and main-chain and side-chain supramolecular polymers.     

Clay particle engineering: A potential new technology with diverse applications

The ability to disperse different clay materials in aqueous suspensions into fundamental particles 1–10 nm thick and combine them in various combinations and proportions has stimulated research into the more effective use of the unique properties of these materials. These properties include high surface area (up to 800 m²/g). cation exchange capacity (up to 120 meq./100 g) and anion exchange capacity (up to 25 meq./100 g) which can be utilized in a variety of industrial processes and other commerical applications. The products of such combinations are synthetic, randomly interstratified clays whose adsorption/desorption characteristics, micro-porosity, permeability, and interlayer chemistry can be modified to optimize their performance as chemical supports and heterogeneous catalysts. Thin films (10–100 nm) can be formed from these materials with a wide range of compositions and properties with possible applications in the medical treatment of burns and wounds, as release agents and coatings in pharmaceuticals and agricultural products, for the immobilization of bacteria and as enzyme supports in biotechnology. The coatings and films can be fired at temperatures of 1000°C to produce micro-ceramic products which could lead to applications such as electrical insulators and semiconductors and as protective coatings and bonding intermediates in the material sciences. This report outlines the methods of preparation and properties of these clay materials and presents analytical and experimental results demonstrating the promise of this technology.     

Hydrogen‐bonded supramolecular polyurethanes

As a class of materials, supramolecular polymers represent an exciting area of advanced materials research. The combination of unique properties, easy synthesis and response to the environment or external and temporal stimuli makes them important as a focus for the next generation of materials. Understanding and manipulating the non‐covalent interactions leading to polymer assembly allows control over properties by selecting specific building blocks with well‐understood non‐covalent chemistry from an established toolkit. This allows assembly of defined and easily manipulated architectures, where physical characteristics similar to conventional high‐molecular‐weight polymers can be realized. Herein, we describe recent studies of the self‐assembly of polyurethane‐based supramolecular materials. © 2014 Society of Chemical Industry     

陶瓷基光子晶体的研究进展

采用以陶瓷材料为母体制备光子晶体是光子晶体制备的一个重要研究发展方向.本文介绍了陶瓷基光子晶体的几种主要的制备方法以及光子晶体在微波和红外、可见光频段中的应用.基于功能陶瓷所具有丰富的光/电功能可以制备陶瓷基光子晶体,文中介绍了可调带隙光子晶体和光子晶体中自发辐射方面的一些研究成果.陶瓷基光子晶体由于具有折射率高,功能广泛,制备手段多样等特点,因而具有广泛的应用前景,如用作电场调节的光开关和在显示领域中基于光子晶体各向异性发光特点的具有定向光发射性能的光源.     

Hydrogen bond‐mediated self‐assembly and supramolecular structures of diblock copolymer mixtures

This review summarizes recent advances in the preparation of hydrogen bonding block copolymer mixtures and the supramolecular structures they form through multiple hydrogen bonding interactions. Hydrogen bonding in block copolymer mixtures that form nanostructures and have unusual electronic, photonic and magnetic properties is a topic of great interest in polymer science. Combining the self‐assembly of block copolymers with supramolecular structures offers unique possibilities to create new materials with tunable and responsive properties. The self‐assembly of structures from diblock copolymer mixtures in the bulk state is readily controlled by varying the weight fraction of the block copolymer mixture and the copolymer composition; in solution, the morphologies are dependent on the copolymer composition, the copolymer concentration, the nature of the common solvent, the amount of the selective solvent and, most importantly, the hydrogen bonding strength. Copyright © 2008 Society of Chemical Industry     

Side‐chain functionalized supramolecular polymers

Over the past two decades, the field of supramolecular polymer chemistry has developed from a curiosity to a mature area of polymer science. Among the most promising subjects in this large field are noncovalently functionalized side‐chain polymers that have been investigated extensively as a result of their modular character and ease of synthesis. Side‐chain functionalized polymers have the potential for a profound impact on complex materials. For example, for side‐chain functionalized polymers based on a single noncovalent interaction, materials for a variety of applications ranging from liquid crystalline and electro‐optical materials to drug delivery systems have been reported. Furthermore, materials based on this novel methodology may overcome several shortcomings of current covalent multifunctionalization strategies such as highly complex materials that are extremely difficult or impossible to fabricate with current methods. In this review, basic design requirements, advantages and potential applications are presented. Copyright © 2006 Society of Chemical Industry     

Structure,properties and corrosion resistivity of polymeric nanocomposite coatings based on layered silicates

This paper reviews the recent research and development of polymeric nanocomposite coatings based on layered silicates. In the past few decades, extensive research activities have been conducted on clay minerals due to their unique layered structure, rich intercalation chemistry and availability at low cost, environmental stability, and good processability. One of the most important categories of layered silicates is nanoclays. The nanoclay is considered as reinforcement for polymers in the manufacture of low-cost, lightweight and high performance nanocomposite coatings. In this paper, we try to introduce the structure, properties, and surface modification of clay minerals. Different properties of polymer clay nanocomposite coatings consisting of different polymers are also reviewed. These coatings may consist of conductive and nonconductive polymers. The corrosion resistance of each type is discussed separately. Some novel properties can be observed from the interaction of two dissimilar chemical components at the molecular level that posses enhancements in corrosion inhibition on metallic substrates. Finally, the prospective problems of industrial usage of these materials are mentioned.     

Complex macromolecular architecture design via cyclodextrin host/guest complexes

The design of complex macromolecular architectures has driven macromolecular engineering over the past decades. The introduction of supramolecular chemistry into polymer chemistry provides novel opportunities for the generation of macromolecular architecture with specific functions. Cyclodextrins are attractive design elements as they form supramolecular inclusion complexes with hydrophobic guest molecules in aqueous solution affording the possibility to combine a large variety of building blocks to form novel macromolecular architectures. In the present critical review, the design of a broad range of macromolecular architectures driven by cyclodextrin host/guest chemistry is discussed, including supramolecular block copolymers, polymer brushes, star and branched polymers.     

Oxide materials for high temperature thermoelectric energy conversion

Thermoelectric energy conversion can be used to capture electric power from waste heat in a variety of applications. The materials that have been shown to have the best thermoelectric properties are compounds containing elements such as tellurium and antimony. These compounds can be oxidized if exposed to the high temperature air that may be present in heat recovery applications. Oxide materials have better stability in oxidizing environments, so their use enables the fabrication of more durable devices. Thus, although the thermoelectric properties of oxides are inferior to those of the compounds mentioned above, their superior stability may expand potential the high temperature application of thermoelectric energy conversion.In this paper, the thermoelectric properties of promising oxide materials are reviewed. The different types of oxides used for thermoelectric applications are compared and approaches for improving performance through doping are discussed.     

Supramolecular control of reactivity in the solid state: from templates to ladderanes to metal-organic frameworks

We describe how reactivity can be controlled in the solid state using molecules and self-assembled metal-organic complexes as templates. Being able to control reactivity in the solid state bears relevance to synthetic chemistry and materials science. The former offers a promise to synthesize molecules that may be impossible to realize from the liquid phase while also taking advantage of the benefits of conducting highly stereocontrolled reactions in a solvent-free environment (i.e., green chemistry). The latter provides an opportunity to modify bulk physical properties of solids (e.g., optical properties) through changes to molecular structure that result from a solid-state reaction. Reactions in the solid state have been difficult to control owing to frustrating effects of molecular close packing. The high degree of order provided by the solid state also means that the templates can be developed to determine how principles of supramolecular chemistry can be generally employed to form covalent bonds. The paradigm of synthetic chemistry employed by Nature is based on integrating noncovalent and covalent bonds. The templates assemble olefins via either hydrogen bond or coordination-driven self-assembly for intermolecular [2 + 2] photodimerizations. The olefins are assembled within discrete, or finite, self-assembled complexes, which effectively decouples chemical reactivity from effects of crystal packing. The control of the solid-state assembly process affords the supramolecular construction of targets in the form of cyclophanes and ladderanes. The targets form stereospecifically, in quantitative yield, and in gram amounts. Both [3]- and [5]-ladderanes have been synthesized. The ladderanes are comparable to natural ladderane lipids, which are a new and exciting class of natural products recently discovered in anaerobic marine bacteria. The organic templates function as either hydrogen bond donors or hydrogen bond acceptors. The donors and acceptors generate cyclobutanes lined with pyridyl and carboxylic acid groups, respectively. The metal-organic templates are based on Zn(II) and Ag(I) ions. The reactivity involving Zn(II) ions is shown to affect optical properties in the form of solid-state fluorescence. The solids based on both the organic and metal-organic templates undergo rare single-crystal-to-single-crystal reactions. We also demonstrate how the cyclobutanes obtained from this method can be applied as novel polytopic ligands of metallosupramolecular assemblies (e.g., self-assembled capsules) and materials (e.g., metal-organic frameworks). Sonochemistry is also used to generate nanostructured single crystals of the multicomponent solids or cocrystals based on the organic templates. Collectively, our observations suggest that the organic solid state can be integrated into more mainstream settings of synthetic organic chemistry and be developed to construct functional crystalline solids.     

热致变色聚合物研究进展

热致变色聚合物具有成本低、易制备、易加工、易修饰、稳定性好等优势,已被应用到温度传感、智能窗、变色涂料、显示器、智能纺织品、防伪等多个领域.根据热致变色机理,总结了共轭聚合物、超分子聚合物、凝胶、光子晶体和液晶聚合物的最新研究进展,并对其变色机理及应用进行了概述及分类归纳.最后,提出了目前热致变色聚合物在应用中还存在的问题,并对未来该领域的研究方向作了展望.     

Multivalency and cooperativity in supramolecular chemistry

Multivalent interactions, which rely upon noncovalent bonds, are essential ingredients in the mediation of biological processes, as well as in the construction of complex (super)structures for materials applications. A fundamental understanding of multivalency in supramolecular chemistry is necessary not only to construct motors and devices on the nanoscale but also to synthesize model systems to provide insight into how biological processes work. This Account focuses on the application of multivalency to supramolecular chemistry in particular and the nanosciences in general.