Biomimetic self-templating supramolecular structures

In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials. During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures. A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres, distinctively coloured skin tissues from cholesteric phase fibre bundles, and mineralized tissues from hierarchically organized fibres. Nature's self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods. However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.     

Inkjet printing for flexible electronics: Materials,processes and equipments

Inkjet printing, known as digital writing technique, can directly deposit functional materials to form pattern onto substrate. This paper provides an overview of inkjet printing technologies for flexible electronics. Firstly, we highlight materials challenges in implementing flexible devices into practical application, especially for inkjet printing process. Then the micro/nano-patterning technologies of inkjet printing are discussed, including conventional inkjet printing techniques and electrohydrodynamic printing techniques. Thirdly, the related equipments on inkjet printing are shown. Finally, challenges for its future development are also discussed. The main purpose of the work is to condense the basic knowledge and highlight the challenges associated with the burgeoning and exciting field of inkjet printing for flexible electronics.     

Microperiodic structures: direct writing of three-dimensional webs

Applications are emerging that require the creation of fine-scale structures in three dimensions--examples include scaffolds for tissue engineering, micro-fluidic devices and photonic materials that control light propagation over a range of frequencies. But writing methods such as dip-pen nanolithography and ink-jet printing are either confined to two dimensions or beset by wetting and spreading problems. Here we use concentrated polyelectrolyte inks to write three-dimensional microperiodic structures directly without using masks. Our technique enables us to write arbitrary three-dimensional patterns whose features are nearly two orders of magnitude smaller than those attained with other multilayer printing techniques.     

Organoplatinum crystals for gas-triggered switches

Considerable effort is being devoted to the fabrication of nanoscale devices. Molecular machines, motors and switches have been made, generally operating in solution, but for most device applications (such as electronics and opto-electronics), a maximal degree of order and regularity is required. Crystalline materials would be excellent systems for these purposes, as crystals comprise a vast number of self-assembled molecules, with a perfectly ordered three-dimensional structure. In non-porous crystals, however, the molecules are densely packed and any change in them (due, for example, to a reaction) is likely to destroy the crystal and its properties. Here we report the controlled and fully reversible crystalline-state reaction of gaseous SO2 with non-porous crystalline materials consisting of organoplatinum molecules. This process, including repetitive expansion-reduction sequences (on gas uptake and release) of the crystal lattice, modifies the structures of these molecules without affecting their crystallinity. The process is based on the incorporation of SO2 into the colourless crystals and its subsequent liberation from the orange adducts by reversible bond formation and cleavage. We therefore expect that these crystalline materials will find applications for gas storage devices and as opto-electronic switches.     

Self-directed self-assembly of nanoparticle/copolymer mixtures

The organization of inorganic nanostructures within self-assembled organic or biological templates is receiving the attention of scientists interested in developing functional hybrid materials. Previous efforts have concentrated on using such scaffolds to spatially arrange nanoscopic elements as a strategy for tailoring the electrical, magnetic or photonic properties of the material. Recent theoretical arguments have suggested that synergistic interactions between self-organizing particles and a self-assembling matrix material can lead to hierarchically ordered structures. Here we show that mixtures of diblock copolymers and either cadmium selenide- or ferritin-based nanoparticles exhibit cooperative, coupled self-assembly on the nanoscale. In thin films, the copolymers assemble into cylindrical domains, which dictate the spatial distribution of the nanoparticles; segregation of the particles to the interfaces mediates interfacial interactions and orients the copolymer domains normal to the surface, even when one of the blocks is strongly attracted to the substrate. Organization of both the polymeric and particulate entities is thus achieved without the use of external fields, opening a simple and general route for fabrication of nanostructured materials with hierarchical order.     

导数空间的新型D'Alembert原理及任意阶非完整系统的Gibbs-Appell方程

在导数空间中,将非完整系统变成为形式上的完整系统,建立了导数空间中新型的Ｄ’Ａｌｅｍｂｅｒｔ原理,得到了任意阶非完整系统通常形式和新型形式的ＧｉｂｂｓＡｐｐｅｌｌ 方程,并给出方程的算例。     

Optical gain in silicon nanocrystals

Adding optical functionality to a silicon microelectronic chip is one of the most challenging problems of materials research. Silicon is an indirect-bandgap semiconductor and so is an inefficient emitter of light. For this reason, integration of optically functional elements with silicon microelectronic circuitry has largely been achieved through the use of direct-bandgap compound semiconductors. For optoelectronic applications, the key device is the light source--a laser. Compound semiconductor lasers exploit low-dimensional electronic systems, such as quantum wells and quantum dots, as the active optical amplifying medium. Here we demonstrate that light amplification is possible using silicon itself, in the form of quantum dots dispersed in a silicon dioxide matrix. Net optical gain is seen in both waveguide and transmission configurations, with the material gain being of the same order as that of direct-bandgap quantum dots. We explain the observations using a model based on population inversion of radiative states associated with the Si/SiO2 interface. These findings open a route to the fabrication of a silicon laser.     

Self-replication of information-bearing nanoscale patterns

DNA molecules provide what is probably the most iconic example of self-replication--the ability of a system to replicate, or make copies of, itself. In living cells the process is mediated by enzymes and occurs autonomously, with the number of replicas increasing exponentially over time without the need for external manipulation. Self-replication has also been implemented with synthetic systems, including RNA enzymes designed to undergo self-sustained exponential amplification. An exciting next step would be to use self-replication in materials fabrication, which requires robust and general systems capable of copying and amplifying functional materials or structures. Here we report a first development in this direction, using DNA tile motifs that can recognize and bind complementary tiles in a pre-programmed fashion. We first design tile motifs so they form a seven-tile seed sequence; then use the seeds to instruct the formation of a first generation of complementary seven-tile daughter sequences; and finally use the daughters to instruct the formation of seven-tile granddaughter sequences that are identical to the initial seed sequences. Considering that DNA is a functional material that can organize itself and other molecules into useful structures, our findings raise the tantalizing prospect that we may one day be able to realize self-replicating materials with various patterns or useful functions.     

Inkjet printing of single-crystal films

The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science. Whether based on inorganic or organic materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. 'Printed electronics' is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials. However, because of the strong self-organizing tendency of the deposited materials, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid-air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C(8)-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4?cm(2)?V(-1)?s(-1). This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.     

Functionalizing hydrogen-bonded surface networks with self-assembled monolayers

One of the central challenges in nanotechnology is the development of flexible and efficient methods for creating ordered structures with nanometre precision over an extended length scale. Supramolecular self-assembly on surfaces offers attractive features in this regard: it is a 'bottom-up' approach and thus allows the simple and rapid creation of surface assemblies, which are readily tuned through the choice of molecular building blocks used and stabilized by hydrogen bonding, van der Waals interactions, pi-pi bonding or metal coordination between the blocks. Assemblies in the form of two-dimensional open networks are of particular interest for possible applications because well-defined pores can be used for the precise localization and confinement of guest entities such as molecules or clusters, which can add functionality to the supramolecular network. Another widely used method for producing surface structures involves self-assembled monolayers (SAMs), which have introduced unprecedented flexibility in our ability to tailor interfaces and generate patterned surfaces. But SAMs are part of a top-down technology that is limited in terms of the spatial resolution that can be achieved. We therefore rationalized that a particularly powerful fabrication platform might be realized by combining non-covalent self-assembly of porous networks and SAMs, with the former providing nanometre-scale precision and the latter allowing versatile functionalization. Here we show that the two strategies can indeed be combined to create integrated network-SAM hybrid systems that are sufficiently robust for further processing. We show that the supramolecular network and the SAM can both be deposited from solution, which should enable the widespread and flexible use of this combined fabrication method.     

适应性安全的多主密钥KP-ABE方案

功能加密能很好地满足多对多的网络环境下的机密性需求,功能性函数提供了比传统公钥更灵活的密文存取能力.已有的功能加密系统均只支持单主密钥功能性函数,本文提出了功能加密子类KP-ABE(key-policy attribute-based encryption)上的多主密钥适应性安全模型,该模型具有更强的表达能力及更广义的特性.利用线性多秘密共享方案,设计了该安全模型下的一个加密方案,并采用对偶法在标准模型下证明方案是IND-CPA(indistinguishability against chosen-ciphertext attacks)安全的.该方案加密数据的存取策略更为灵活,用户可根据权限存取多种类型的密文;提出的构造方法可应用于功能加密的其他子类,且计算量与单主密钥方案相比不存在线性扩张,具有较高的效率.     

Patterning of polymer-supported metal films by microcutting

The ability to micropattern materials is of great importance for manufacturing advanced electronic, optical and mechanical devices ranging from displays to biosensors. For this purpose a variety of methods have been developed, including X-ray, electron-beam and photo-lithography, microcontact printing, embossing, micromouldings and cold welding. But these techniques are often of restricted applicability, involve a multitude of elaborate and cumbersome processing steps, or require aggressive chemistry. Here we describe a simple and versatile way to create well resolved metallic structures on polymer substrates, which is based on solid-state embossing of metal-coated polymer films. Ductility of both the metal layer and the polymer substrate permits the metal to be cut into surprisingly regular, micrometre-size structures. We illustrate the method by preparing patterned electrically conducting structures, highly efficient infrared polarizers and polarization-dependent colour filters.     

纳米Fe3O4/氟碳树脂磁场诱导自组装抗反射薄膜的制备及表征

为了获得高度取向的阵列材料,以水热合成的纳米Fe₃O₄磁性颗粒为功能物质,氟碳树脂为薄膜基体,在磁场作用下定向生长成具有磁性针状阵列结构的自组装抗反射薄膜,并考察不同Fe₃O₄含量对磁性阵列结构的影响;利用体视显微镜和扫描电镜（SEM）对薄膜表面结构进行了表征;采用紫外可见近红外分光光度计（UV/Vis/NIR）来表征自组装薄膜的反射率。结果表明:随着Fe₃O₄含量的增加,阵列高度逐渐增高;当粉体质量分数为10%时,阵列的间距为300～600μm,阵列中单个针状结构中间的直径约为100μm;薄膜表面的阵列结构对于反射率的降低有明显效果     

溶液与界面的协同与融合——自组装聚集结构

自聚集作用使体相溶液和界面协同与融合。溶液和界面聚集结构研究是表面活性剂科学研究中最重要的研究内容之一,也是近年来软物质科学研究中的主要内容。本文基于近年来山东大学胶体与界面化学教育部重点实验室在溶液聚集体构筑、聚集体结构(特别是囊泡相)和性能以及界面自组装结构薄膜研究等方面的研究成果,阐述了胶体与界面(表面活性剂)科学研究中的新观点——自组装聚集结构使溶液和界面协同与融合。     

基于FDM技术的多料口粒料3D打印 供料及挤料系统设计

FDM 3D打印机多采用由颗粒状热塑性材料加工而成的丝状热塑性材料,材料成本较高,且由于材料本身丝状的几何形状难以实现均匀混合,使得FDM彩色混色3D打印技术具有一定的局限性,难以实现多色混色打印。针对以上问题,根据传统挤出技术并结合熔融沉积(FDM)技术特点,研制了粒料式FDM 3D打印设备供料及挤出系统,原材料直接选用颗粒状塑料,并设计了多个进料口、储料仓和排气螺杆,进料采用穴播轮控制方式。设计结果可以实现不同颜色、不同塑料进料量的合理配比,使颗粒塑料实现充分熔化、加压、均化、排气、再均化、挤出过程,实现均质材质的粒料3D打印过程及多色混色打印过程。所提出的设计可以使用粒料直接进行3D打印,既降低了制料成本、缩短了制料周期,又实现了废料的有效利用,可为3D打印技术的发展提供参考。     

石墨烯基墨水的制备及其在印刷电子中的应用

 石墨烯材料具有优异的导电性、柔性、化学稳定性等特征,在印刷电子领域中具有广阔的应用前景。概述了石墨烯材料的宏量制备方法,结合喷墨打印、丝网印刷和3D打印等方法介绍了石墨烯墨水制备的技术特点和要求,展示了石墨烯在印刷电子功能器件中的应用,主要类型包括透明导电薄膜、柔性电路、超级电容器和可穿戴传感器等。总结了该领域当前研究进展中存在的问题和挑战,从材料设计、加工制备和器件应用方面进行了展望。在未来发展中可通过丰富石墨烯打印线路的结构形式,并注重利用组装的策略增强结构有序性,实现多功能、高性能的器件制备和应用。     

Modular and predictable assembly of porous organic molecular crystals

Nanoporous molecular frameworks are important in applications such as separation, storage and catalysis. Empirical rules exist for their assembly but it is still challenging to place and segregate functionality in three-dimensional porous solids in a predictable way. Indeed, recent studies of mixed crystalline frameworks suggest a preference for the statistical distribution of functionalities throughout the pores rather than, for example, the functional group localization found in the reactive sites of enzymes. This is a potential limitation for 'one-pot' chemical syntheses of porous frameworks from simple starting materials. An alternative strategy is to prepare porous solids from synthetically preorganized molecular pores. In principle, functional organic pore modules could be covalently prefabricated and then assembled to produce materials with specific properties. However, this vision of mix-and-match assembly is far from being realized, not least because of the challenge in reliably predicting three-dimensional structures for molecular crystals, which lack the strong directional bonding found in networks. Here we show that highly porous crystalline solids can be produced by mixing different organic cage modules that self-assemble by means of chiral recognition. The structures of the resulting materials can be predicted computationally, allowing in silico materials design strategies. The constituent pore modules are synthesized in high yields on gram scales in a one-step reaction. Assembly of the porous co-crystals is as simple as combining the modules in solution and removing the solvent. In some cases, the chiral recognition between modules can be exploited to produce porous organic nanoparticles. We show that the method is valid for four different cage modules and can in principle be generalized in a computationally predictable manner based on a lock-and-key assembly between modules.     

Reconfigurable self-assembly through chiral control of interfacial tension

From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil-water interfaces. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex topologies.     

基于α-氰基二苯乙烯纳米组装的研究进展

π-共轭分子的自组装体系因具备优异的光电性质而成为开发新型有机功能材料诱人的平台.文章主要综述了基于α-氰基二苯乙烯及其衍生物的自组装纳米聚集体和凝胶以及它们用于构建有机超分子功能和智能材料的最新研究进展.对α-氰基二苯乙烯的一般结构特点,α-氰基二苯乙烯超分子纳米结构的强发光、手性光学性质和可控纳米组装,以及其凝胶系统的多重刺激响应性进行了综述.此外,还特别介绍了α-氰基二苯乙烯的光反应及其应用于自组装系统的特色工作.最后介绍了作者课题组在这一领域的相关工作.