Chemical Reactions Directed Peptide Self-Assembly

Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.     

Self-Assembly of Optical Molecules with Supramolecular Concepts

Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces.     

Multifaceted polymersome platforms: Spanning from self-assembly to drug delivery and protocells

Biologically inspired self-assembly processes of amphiphilic copolymers have received an increasing attention for creating innovative and highly advanced functional materials for various biomedical applications. Polymersomes are versatile nanosystems with tremendous potential due to their increased colloidal stability, tunable membrane properties, chemical versatility, and the ability to accommodate a broad range of drugs and biomolecules. In this review, we present the principles of copolymers self-assembly and associated parameters that control the resulting self-assembled morphologies, and various methodologies developed for fabrication of polymersomes. We attempt to discuss how polymersome platforms can be applied for versatile biomedical research, from simple passive nanocarriers for drug delivery to functionalized polymersomes for active targeting approaches and advanced nanoreactors, and protocells to mimic structure and functions of biological systems.     

Templating of inorganic nanomaterials by biomacromolecules and their assemblies

During the past decade biomacromolecules attracted tremendous attention as versatile materials for self-assembly, nanoconstruction, and templating. An increasing number of reports highlights creative applications of DNA, proteins, and their assemblies for construction of materials, which synthesis by traditional top-down techniques is not possible. This review summarizes various aspects of the application of biomacromolecules and their self-organized structures for building-up inorganic nanomaterials of different complicity by metallization or mineralization of natural templates. The central focus of the review is given to DNA-templated and DNA-directed synthesis of nanostructures, as the progress in the utilization of DNA for nanoconstruction is most considerable.     

溶液自组装法制备卟啉纳米材料研究进展

在溶液中,利用自组装方法制备以卟啉化合物为基础的纳米材料具有优良的光物理和光化学性质,在分子器件和人工模拟光合作用等方面具有巨大的应用前景,是目前的研究热点。本文详细介绍了单卟啉组装方法和多卟啉共组装方法,单卟啉组装包括双溶剂法和表面活性剂辅助法两类方法。简要介绍了卟啉自组装纳米材料在集光天线和光催化方面的应用。目前,自组装方法制备的卟啉化合物纳米材料已经出现了丰富的形态,但仍存在不足,即自组装作用机理有待深入研究,且如何将卟啉纳米材料的制备工艺放大并应用于实际,还有待进一步发展。     

Computational Approaches to Understanding the Self-assembly of Peptide-based Nanostructures

The interest in the self-assembly of peptide-based systems has grown significantly over the past 10–15 years, as more and more applications are shown to benefit from the useful properties of the amino acid based monomers. With the desire to apply the principals of self-assembly to systems within new application areas, there has been an increasing emphasis in understanding the governing forces involved in the self-assembly process, and using this understanding to predict the behaviour of, and design, new materials. To this end, computational approaches have played an increasingly important role over the past decade in helping to decode how small changes in the primary structure can lead to significantly different nanostructures with new function. In this review, a brief survey of the different computational approaches employed in this quest for understanding are provided, along with representative examples of the types of questions that can be answered with each of the different approaches.     

Nanoparticles in Liquid Crystals: Synthesis,Self-Assembly,Defect Formation and Potential Applications

Revolutionary developments in the fabrication of nanosized particles have created enormous expectations in the last few years for the use of such materials in areas such as medical diagnostics and drug-delivery, and in high-tech devices. By its very nature, nanotechnology is of immense academic and industrial interest as it involves the creation and exploitation of materials with structural features in between those of atoms and bulk materials, with at least one dimension limited to between 1 and 100 nm. Most importantly, the properties of materials with nanometric dimensions are, in most instances, significantly different from those of atoms or bulk materials. Research efforts geared towards new synthetic procedures for shape and size-uniform nanoscale building blocks as well as efficient self-assembly protocols for manipulation of these building blocks into functional materials has created enormous excitement in the field of liquid crystal research. Liquid crystals (LCs) by their very nature are suitable candidates for matrix-guided synthesis and self-assembly of nanoscale materials, since the liquid crystalline state combines order and mobility at the molecular (nanoscale) level. Based on selected relevant examples, this review attempts to give a short overview of current research efforts in LC-nanoscience. The areas addressed in this review include the synthesis of nanomaterials using LCs as templates, the design of LC nanomaterials, self-assembly of nanomaterials using LC phases, defect formation in LC-nanoparticle suspensions, and potential applications. Despite the seeming diversity of these research topics, this review will make an effort to establish logical links between these different research areas.     

Emerging Synthetic Methods and Applications of MOF-Based Gels in Supercapacitors,Water Treatment,Catalysis, Adsorption,and Energy Storage

Metal–organic frameworks (MOFs), which are synthesized through the self-assembly of organic ligands and inorganic metals, have drawn considerable research interest owing to their unique properties and attractive structures. Many studies on various MOF derivatives, such as MOFs and cellulose aerogels, hydrogel composite materials, and bimetallic-centered MOF materials, have provided the potential for wide application of MOFs. However, MOFs mostly exist in the form of powder particles, which are difficult to form. In addition, MOFs have problems with structural instability. MOF-based gels can overcome this problem. MOF-based gels also have significant advantages in secondary processing. In this review, synthetic methods for MOF-based gels, particularly the synergistic effect with other materials, are introduced. The applications of MOF-based hydrogels and aerogels in supercapacitors, water treatment, catalysis, adsorption, and energy storage are also discussed.     

Recent Progress on Cyclic Peptides’ Assembly and Biomedical Applications

Cyclic peptides are important building blocks for forming functional structures and have been applied in various fields. Considering the significant structural and functional roles of cyclic peptides in materials science and the attributed biophysical advantages, we provide an overview of cyclic peptide types that can self-assemble to form nanotubes, recent progress in stimuli-triggered cyclic peptide assembly, and methods to construct peptide and polymer conjugates based on cyclic peptides with alternative chirality. Specifically, we highlight the roles that stimuli-triggered cyclic peptides and their conjugates play in biomedical applications. Recent progress in other cyclic peptides acting as gelators in drug delivery and biomedicine are also summarized. These cyclic peptides with self-assembly properties are expected to act as adaptive systems for drug delivery and selective disease targeting.     

Recent developments in plant oil based functional materials

The increasing interest of academic and industrial sectors in the use of bio‐based materials mirrors the overwhelming need for replacing, as much as possible, petroleum derived chemicals, reducing the negative environmental impact derived from their usage. Vegetable oils fulfill this goal extremely well, because of their worldwide availability, large volume production at comparatively low prices and versatility of the modifications and reactions in which they can participate to produce a large variety of different monomers and polymer precursors. Further reactions of these chemicals can lead to very different types of final materials with varied applications. It is because of this remarkable versatility that many review articles have appeared during the last few years; many of them have dealt with the various routes for vegetable oil modification and options for polymer synthesis, whilst others were dedicated to the analysis of the properties of the derived materials, generally focusing on structural properties. In this review, we focus on the capabilities of vegetable oils to be modified and/or reacted to obtain materials with functional properties suitable for use in coatings, conductive or insulating materials, biomedical, shape memory, self‐healing and thermoreversible materials as well as other special functional applications. © 2015 Society of Chemical Industry     

Covalently Assembled Dipeptide Nanoparticles with Adjustable Fluorescence Emission for Multicolor Bioimaging

Peptide self-assembly, inspired by the naturally occurring fabrication principle, remains the most attractive in constructing fluorescent nanoagents towards bioimaging. However, the noncovalent interactions that drive peptide self-assembly are usually susceptible to the complex physiological environment; thus leading to disassembly and dysfunction of fluorescent nanoagents. Herein, a covalently crosslinked assembly strategy for fabrication of stable peptide-based nanoparticles with adjustable emission is introduced. In the process of cationic diphenylalanine peptide (H-Phe-Phe-NH₂ ⋅ HCl) self-assembly, glutaraldehyde is used as a crosslinker and the resulting product of the Schiff base reaction can be fluorescent. More importantly, the emission wavelength can be readily tuned by controlling the covalent reaction time. It has been demonstrated that the nanoparticles are stable, even after intracellular uptake, and can be used for sustainable multicolor fluorescent imaging. The strategy with integrating peptide self-assembly and covalent crosslinking could be promising for the design and engineering of functional fluorescent nanoparticles with robust physiological stability and adjustable emission towards improved bioimaging applications.     

Silica nanoparticles self-assembly process in polymer composites: Towards advanced materials

The incorporation of silica nanoparticles (Si-NPs) into the polymer matrix is a growing area of interest research to produce high-performance polymer nanocomposites (NCs) across a wide range of nanotechnology applications. This improvement is due to the Si-NPs capability to self-assembly giving rise to specific well-organized structures with both short- and long-range order across a hierarchy of spatial scales, determined by both NP-NP and NP-matrix interactions, involving a careful balance among attractive driving forces, repulsive forces, and directional forces.Respect to this, the aim of the present paper is to systematically review the use of Si-NPs in polymer NCs and on the role of NPs self-assembly in determining the final material properties.Firstly, we explored the synthesis and modification of both isotropic and anisotropic Si-NPs in relation with use in NC materials, focusing on NPs dispersion and distribution, as well as on the functionalization strategies of Si-NPs. Besides Si-NPs functionalization with conventional small organic molecules, a large section is devoted to an emerging class of functionalized Si-NPs with macromolecules, namely silica hairy NPs (Si-HNPs), able to give rise a rich variety of complex assemblies and materials with new structures and functionalities. Successively, NCs materials containing Si-NPs and Si-HNPs have been explored in terms of synthetic preparation and properties. The self-organization of Si-NPs and Si-HNPs in polymer matrices has been reported and its effect on the functional materials properties have been evaluated with a critical point of view on the results, limits, and future perspectives.Our review can be considered a tutorial work, aiming at providing useful insights to researchers in the field of nanotechnology and nanoscience, taking into consideration the fundamental role of NPs self-assembly processes in determining the functional material properties.     

Chemical Reactions Trigger Peptide Self-Assembly in vivo for Tumor Therapy

Self-assembly peptide materials have promoted the development of science research including life science, optics, medicine, and catalysis over the past two decades. Especially in tumor treatment, peptide self-assembly strategies have exhibited promising potential by their high degree of biocompatibility, construction modularization, and diversity in structure controllability. Driven by physical and chemical triggers, peptides can self-assemble in vivo to form fibers, spheres, hydrogels, or ribbons to achieve predeterminate biological functions. Peptide self-assembly triggered by chemical reactions provides superior specificity and intelligent responsiveness to produce assembly-induced biological effects in target regions. Herein, from the perspective of triggers of peptide assembly, we briefly review the applications of in vivo peptide self-assembly strategies for tumor treatment, including tumor-pathology-factor-induced chemical reactions and bio-orthogonal reactions     

Preparation and Applications of Chiral Polymeric Particles

Chiral polymeric particles (CPPs) have been gathering increasing interest as typical functional polymeric particles in recent decades. This article presents a review on the preparation and applications of CPPs. The methods for preparing CPPs are classified into two major groups: The first one is the direct polymerization of monomers and the other is the post-treatment of preformed polymers. CPPs have been explored as a unique type of chiral materials in various fields like asymmetric catalysis, enantioselective release, enantioselective crystallization, and enantioseparation. This review article is expected to accelerate the progress of scientific research dealing with CPPs and their applications in chirality-related fields.     

金属有机框架材料的绿色合成

金属有机框架化合物（Metal-organic frameworks,简称MOFs）是由金属离子（或簇）与有机配体配位并经由自组装而形成的一类多孔材料^[1]。MOFs具有极其发达的孔道结构,比表面积和孔容远超其他多孔材料。有机/无机杂化这一特点也赋予了MOFs其他材料（例如沸石、活性炭等）所不具备的无限结构功能可调性^[2]。此外,MOFs具有移除客体分子而主体框架完好保持的持久孔道或孔穴,这使得MOFs具有超乎寻常的化学及物理稳定性。正是基于以上这些特点,MOFs在许多领域有着丰富的应用^[3-4],例如催化^[5]、H₂储存^[6]、CO₂捕集^[7]、药物运输^[8]、污染物吸附^[9]、生物医学成像^[10]等方面。MOFs的商业化探索成为了目前的热点。MOFs的很多应用都与可持续发展及“绿色材料”有关,但MOFs本身的合成过程也需要考虑可持续性和环境影响。金属有机化学所面临的环境挑战是独特的,因为它将金属离子、有机配体的危害联系在一起,且合成过程大多需要大量能耗。主要介绍了金属有机框架材料的绿色可持续合成,主要分为4个方面：1）使用更安全或生物相容性的配体;2）使用更绿色、低成本的金属源;3）绿色溶剂的开发;4）无溶剂合成法。     

Innovative Diagnostic Peptide-Based Technologies for Cancer Diagnosis: Focus on EGFR-Targeting Peptides

Active targeting using biological ligands has emerged as a novel strategy for the targeted delivery of diagnostic agents to tumor cells. Conjugating functional targeting moieties with diagnostic probes can increase their accumulation in tumor cells and tissues, enhancing signal detection and, thus, the sensitivity of diagnosis. Due to their small size, ease of chemical synthesis and site-specific modification, high tissue penetration, low immunogenicity, rapid blood clearance, low cost, and biosafety, peptides offer several advantages over antibodies and proteins in diagnostic applications. Epidermal growth factor receptor (EGFR) is one of the most promising cancer biomarkers for actively targeting diagnostic and therapeutic agents to tumor cells due to its active involvement and overexpression in various cancers. Several peptides for EGFR-targeting have been identified in the last decades, which have been obtained by multiple means including derivation from natural proteins, phage display screening, positional scanning synthetic combinatorial library, and in silico screening. Many studies have used these peptides as a targeting moiety for diagnosing different cancers in vitro, in vivo, and in clinical trials. This review summarizes the progress of EGFR-targeting peptide-based assays in the molecular diagnosis of cancer.     

Synthesis and applications of stimuli-responsive hyperbranched polymers

Benefiting from their responsiveness and adaptability, the stimuli-responsive polymers have been widely investigated and exploited in the various fields, such as environmental monitoring, electronics, photonics, controlled drug delivery, medical imaging and diagnostics. These potential applications have greatly promoted the development of advanced functional materials, and meanwhile set higher requirements for the smart materials in the aspects of the spatial structures, diverse linkages and variable functions. However, the linear functional polymers can not satisfy all the requirements of the multi-dimensional molecular design and acute sensitiveness due to the architectural limitation. Accordingly, stimuli-responsive hyperbranched polymers (HBPs) have been drawing more and more attention in recent years owing to their unique globular void-containing topological structure featured with a large number of terminal functional groups and branches, lower solution or melt viscosity, and better solubility. Therefore, design and synthesis of stimuli-responsive HBPs provide a robust tool for controlling the structure transition and creating the hierarchical sensitivity driven by different triggers. In this review, the developments and recent advances of preparation procedures, performance control and promising applications of various stimuli-responsive HBPs have been comprehensively summarized. Besides, the developing trend of stimuli-responsive HBPs is also discussed. It can be found that stimuli-responsive HBPs with different synthetic strategies and diverse performances have manifested more and more versatile applications.     

微流控模板法制备功能化非球形微颗粒研究新进展

功能化非球形微颗粒在生物医药、吸附、传感与检测等方面具有非常广泛的应用。相对于其他非球形微颗粒制备方法,近年来兴起的微流控技术,由于对微尺度流体具有超灵敏的操控特性,在制备和精确调控微米级功能材料方面具有很大的优势。通过精确控制流体在微尺度通道内的流动和剪切,微流控技术可以实现多种形态和结构的微尺度流体、乳液和纤维的可控构建,为非球形微颗粒的可控制造提供了优良的模板。同时,通过在制备过程中引入功能性材料,这些非球形微颗粒将具备更多的功能,从而极大地拓展和丰富了其应用范围。本文综述了近年来采用微流控技术制备功能化非球形微颗粒的研究新进展,重点介绍了以微流控技术构建得到的微流体、多相乳液及微纤维为模板可控制备功能化非球形微颗粒的研究现状。     

热致变色功能薄膜的制备及应用研究进展

热致变色功能薄膜作为一类很有潜力的功能材料,在生产、生活等许多领域发挥着非常重要的作用.本论文系统介绍了真空蒸镀法、反应溅射法、化学气相沉积法、溶胶-凝胶法、组合遥控体系"M-ist Combi"法、L-B膜法以及分子自组装法等热致变色功能薄膜的制备方法,综述了其最新应用进展,并对其发展趋势进行了展望.     

3D Conformal Surface Engineering of Continuous Fibers with Porous Microstructures for 1D Advanced Functional Materials

One-dimensional (1D) continuous advanced functional materials and devices with inherent flexibility for complex deformations facilitate a broad range of applications in wearable technology. This communication presents a new electrostatic self-assembly strategy for controllable assembly of nanomaterials to fabricate 1D continuous materials with customizable functions based on a kind of continuous fiber fully surface-engineered with 3D conformal porous microstructures (F@3CPMs) by a unique self-assembly approach of breath figure using water microdroplet arrays. Through gently rubbing the modified fibers with suitable triboelectric materials, either positively or negatively charged F@3CPMs can be rationally prepared with adjustable triboelectric charge intensity. Besides showing superiority in incorporating desired components, such kind of F@3CPMs are demonstrated to have general applicability and enhanced performance in controllable self-assembly of polymeric, metal, and carbon nanomaterials for customizable functionalizations. Moreover, taking advantages of continuous fibers that can deform largely, functional F@3CPMs are further applied for development of 1D flexible motion sensing devices by twisting directly, which can be either used as 1D freestanding devices for straightforward integration with conventional fabrics or woven as a fabric structure integrity for a kind of self-powered interactive textiles without additional battery as power resources to detect and monitor the body motions of human beings.