Nanoparticles,Proteins, and Nucleic Acids: Biotechnology Meets Materials Science

Based on fundamental chemistry, biotechnology and materials science have developed over the past three decades into today's powerful disciplines which allow the engineering of advanced technical devices and the industrial production of active substances for pharmaceutical and biomedical applications. This review is focused on current approaches emerging at the intersection of materials research, nanosciences, and molecular biotechnology. This novel and highly interdisciplinary field of chemistry is closely associated with both the physical and chemical properties of organic and inorganic nanoparticles, as well as to the various aspects of molecular cloning, recombinant DNA and protein technology, and immunology. Evolutionary optimized biomolecules such as nucleic acids, proteins, and supramolecular complexes of these components, are utilized in the production of nanostructured and mesoscopic architectures from organic and inorganic materials. The highly developed instruments and techniques of today's materials research are used for basic and applied studies of fundamental biological processes.     

The longest quinoidal oligothiophene: A Raman story

The main research on the family of aromatic and quinoidal oligothiophenes is described, with a focus on their longest members. We have described how the comprehensive understanding of the vibrational Raman spectra of oligothiophenes in a variety of situations permitted the elucidation of properties of fundamental importance, not only for basic research in molecular physics and in physical chemistry, but also for applications. We have written the Raman story that brought us to the elucidation of the biradicaloid nature of the longest quinoidal oligothiophene. DOI 10.1002/tcr.201000022     

Organic electronic devices and their functional interfaces.

A most appealing feature of the development of (opto)electronic devices based on conjugated organic materials is the highly visible link between fundamental research and technological advances. Improved understanding of organic material properties can often instantly be implemented in novel device architectures, which results in rapid progress in the performance and functionality of devices. An essential ingredient for this success is the strong interdisciplinary nature of the field of organic electronics, which brings together experts in chemistry, physics, and engineering, thus softening or even removing traditional boundaries between the disciplines. Naturally, a thorough comprehension of all properties of organic insulators, semiconductors, and conductors is the goal of current efforts. Furthermore, interfaces between dissimilar materials-organic/organic and organic/inorganic-are inherent in organic electronic devices. It has been recognized that these interfaces are a key for device function and efficiency, and detailed investigations of interface physics and chemistry are at the focus of research. Ultimately, a comprehensive understanding of phenomena at interfaces with organic materials will improve the rational design of highly functional organic electronic devices.     

Progress in Molecular Nanoarchitectonics and Materials Nanoarchitectonics

Although various synthetic methodologies including organic synthesis, polymer chemistry, and materials science are the main contributors to the production of functional materials, the importance of regulation of nanoscale structures for better performance has become clear with recent science and technology developments. Therefore, a new research paradigm to produce functional material systems from nanoscale units has to be created as an advancement of nanoscale science. This task is assigned to an emerging concept, nanoarchitectonics, which aims to produce functional materials and functional structures from nanoscale unit components. This can be done through combining nanotechnology with the other research fields such as organic chemistry, supramolecular chemistry, materials science, and bio-related science. In this review article, the basic-level of nanoarchitectonics is first presented with atom/molecular-level structure formations and conversions from molecular units to functional materials. Then, two typical application-oriented nanoarchitectonics efforts in energy-oriented applications and bio-related applications are discussed. Finally, future directions of the molecular and materials nanoarchitectonics concepts for advancement of functional nanomaterials are briefly discussed.     

Covalent Organic Frameworks: Chemical Approaches to Designer Structures and Built‐In Functions

A new approach has been developed to design organic polymers using topology diagrams. This strategy enables covalent integration of organic units into ordered topologies and creates a new polymer form, that is, covalent organic frameworks. This is a breakthrough in chemistry because it sets a molecular platform for synthesizing polymers with predesignable primary and high‐order structures, which has been a central aim for over a century but unattainable with traditional design principles. This new field has its own features that are distinct from conventional polymers. This Review summarizes the fundamentals as well as major progress by focusing on the chemistry used to design structures, including the principles, synthetic strategies, and control methods. We scrutinize built‐in functions that are specific to the structures by revealing various interplays and mechanisms involved in the expression of function. We propose major fundamental issues to be addressed in chemistry as well as future directions from physics, materials, and application perspectives.     

The Photophysics and Photochemistry of Melanin- Like Nanomaterials Depend on Morphology and Structure

Melanin-like nanomaterials have found application in a large variety of high economic and social impact fields as medicine, energy conversion and storage, photothermal catalysis and environmental remediation. These materials have been used mostly for their optical and electronic properties, but also for their high biocompatibility and simplicity and versatility of preparation. Beside this, their chemistry is complex and it yields structures with different molecular weight and composition ranging from oligomers, to polymers as well as nanoparticles (NP). The comprehension of the correlation of the different compositions and morphologies to the optical properties of melanin is still incomplete and challenging, even if it is fundamental also from a technological point of view. In this minireview we focus on scientific papers, mostly recent ones, that indeed examine the link between composition and structural feature and photophysical and photochemical properties proposing this approach as a general one for future research.     

A look at molecular nanosized magnets from the aspect of inter-molecular interactions

Nanosized molecular magnetic materials such as single-molecule magnets and single-chain magnets are recent attractive research targets in the fields of materials chemistry and physics, not only because of their fundamental fascination, but also because of their potential applications as ultimate memory devices or in quantum computations. In this paper, we give our personal perspectives on these materials. In particular "magnetic assemblies of single-molecule magnets", in which inter-molecular interaction is an essential factor in determining their properties, will be focused on together with related compounds reported recently.     

Chemistry and Crystal Growth

Single-crystal materials, along with other forms of condensed matter (ceramics, polymers, liquid crystals, etc.) are fundamental to modern technology. The basic research and production of new materials with “tailored” solid-state physical properties therefore necessitate not only chemical synthesis but also the production of single crystals of a particular morphology (either bulk or thin layer crystals) and well-defined crystal defects (doping). In this review, an attempt is made to broaden the traditional synthetic concept of chemistry to the process of single-crystal synthesis. The methods of the resulting approach, which takes into account the specific properties of solid materials, are discussed and illustrated by experimental set-ups for the solution of a range of problems in chemical crystallization. Also included is recent work on the growing of single crystals of high-temperature superconductors, organic non-linear optical compounds, and proteins.     

Interfaces between Molecular and Polymeric “Metals”: Electrically Conductive,Structure-Enforced Assemblies of Metallomacrocycles

The design, synthesis, characterization, and understanding of new molecular and macro-molecular substances with “metal-like” electrical properties represents an active research area at the interface of chemistry, physics, and materials science. An important, long-range goal in this field of “materials by design” is to construct supermolecular assemblies which exhibit preordained collective phenomena by virtue of “engineered” interactions between molecular building blocks. In this review, such a class of designed materials is discussed which, in addition, bridges the gap between molecular and polymeric conductors: assemblies of electrically conductive metallomacrocycles. It is seen that efforts to rationally construct stacked metal-like molecular arrays lead logically to structure-enforced macromolecular assemblies of covalently linked molecular subunits. Typical building blocks are robust, chemically versatile metallophthalocyanines. The electrical optical, and magnetic properties of these metallomacrocyclic assemblies and the fragments thereof, provide fundamental information on the connections between local atomic-scale architecture, electronic structure, and the macroscopic collective properties of the bulk solid.     

Ceramics and Nanostructures from Molecular Precursors

The elaboration of solids from the molecular scale by a kinetically controlled methodology is one of the main challenges of molecular chemistry. In the long term, this should permit the design of solids with desired properties. Here, some examples are given which show a few methods that have been used for the preparation of solids from molecular precursors. The one-pot synthesis of rheologically controlled SiC is described. Access to a new kind of ceramic is obtained by the same methodology using molecular precursors. Mixed ceramics with interpenetrating networks are not accessible by the chemical thermodynamic route. The chemistry of hybrid materials obtained from molecular precursors through inorganic polymerization is presented. This class of materials offers wide perspectives because of 1) the large possibilities opened by the organic unit, 2) the kinetic control, which permits any kind of texture for the solid, and 3) the aptitude of these solids to become nanostructured.     

Uniform polyolefin and polymethacrylate

Preparations and properties of synthetic uniform polyolefins and polymethacrylates are described with emphasizing the necessity of their utilization for understanding the fundamental problems in polymer chemistry. Uniform polymer is a polymer composed of molecules uniform with respect to molecular weight and constitution. While classical organic chemistry provides means of constructing uniform polymers such as poly(methylene)s in stepwise manners, recent advances in separation technology such as supercritical fluid chromatography (SFC) have made it possible to isolate synthetic uniform polymers from its homologous mixture. Combinations of stereospecific polymerizations and the SFC technique have enabled us to prepare uniform polystyrenes and poly(methyl methacrylate)s with high stereoregularities, which are very useful for systematic studies on the nature of polymers. The thermal properties of these uniform polymers are discussed in some detail.     

Recent Advances in Fullerene‐free Polymer Solar Cells: Materials and Devices

What is the most favorite and original chemistry developed in your research group? We focus on developing new organic photovoltaic materials and exploring their applications in photovoltaic devices. Based on the new materials, we can figure out the correlations among chemical strictures, optoelectronic properties, and photovoltaic behaviors. Our group originally demonstrated quite a few build blocks for making conjugated polymers for photovoltaic applications, some of them have been broadly used by the researchers in the field. How do you get into this specific field? Could you please share some experiences with our readers? I got into this field when I was a graduate student in 2002, just because my supervisor gave me a research topic for synthesis of new conjugated polymers. At that moment, as a fresh graduate student, I had no chance to say yes or no, but to do it. The field of organic solar cells is oriented by the new organic photovoltaic materials. In the past decades, the materials have been updated for a few generations, which promoted the device performance to be higher and closer to practical applications. We have to concentrate on the fundamental problems but also need to follow the pace of the filed. How do you supervise your students? In my opinion, the students need more specific projects to get into the field so as to be well trained at the beginning. In the later stage, I prefer to encourage them to find and creatively figure out the real fundamental problems. I used to give them a few questions: Why do you need to do this project? How to make a clear definition for the problem? Can you suggest a new and better approach to solve it? What is the most important personality for scientific research? Passion, perseverance and sense of innovation. What is your favorite journal(s)? The journals publishing the latest and/or systematic research works in chemistry and material science.     

专辑主编寄语

喜逢中国科学院长春应用化学研究所建所70周年华诞之际,真诚感谢安立佳院士作为客座编辑邀请国内化学相关领域著名院士和专家出版这一期纪念刊专辑。《应用化学》创刊于1983年,为中国科学院长春应用化学研究所的发展和国内相关化学领域提供了一个学术交流的平台,始终秉持“应用化学,追求卓越”的办刊理念,面向科研单位、大专院校和化学化工领域的科研及技术人员,着重报道化学及交叉学科有应用前景的创新性基础科学研究和创造性科研技术成果,介绍该领域中的新发现、新理论、新方法、新技术、新产品及相关科技信息,为推动应用化学学科的发展、加强国内国际间的学术交流、人才培养和现代化建设服务。该专辑的出版必将对该领域的发展起到重要的促进作用。     

Oxidation potential of thiophene oligomers: Theoretical and experimental approach

Intrinsic properties of conducting polymers, such as oxidation potential and band gap, are very important for designing new materials with improved properties. Computational chemistry offers suitable tools capable of predicting these quantities. This work presents electrochemical information about accurate oxidation potentials of oligothiophenes and polymer band gap. These are compared to theoretical predictions based on electronic structure calculations at Density Functional Theory levels, coupled with self‐consistent reaction field. All computational protocols gave a qualitative prediction of the experimental trend. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

First‐Principles Investigation of Anisotropic Electron and Hole Mobility in Heterocyclic Oligomer Crystals

Based on quantum chemistry calculations combined with the Marcus–Hush electron transfer theory, we investigated the charge‐transport properties of oligothiophenes (nTs) and oligopyrroles (nPs) (n=6, 7, 8) as potential p‐ or n‐type organic semiconductor materials. The results of our calculations indicate that 1) the nPs show intrinsic hole mobilities as high as or even higher than those of nTs, and 2) the vertical ionization potentials (VIPs) of the nPs are about 0.6–0.7 eV smaller than the corresponding VIPs of the nTs. Based on their charge‐transport ability and hole‐injection efficiency, the nPs have potential as p‐type organic semiconducting materials. Furthermore, it was also found that the maximum values of the electron‐transfer mobility for the nTs are larger by one‐to‐two orders of magnitude than the corresponding maximum values of hole‐transfer mobility, which suggests that the nTs have the potential to be developed as promising n‐type organic semiconducting materials owing to their electron mobility.     

A NEW APPROACH TO ELECTROACTIVE POLYMERS VIA WELL-DEFINED OLIGOMERRS WITH FURTHER POLYMERIZABLE END-GROUPS

Among the inherent drawbacks of conducting polymers are the limited processibility, uneven polydispersity inmolecular weigh and the existence of structure defects, which become the obstacles for many electronic, optical andbiological applications that demand the materials to have well-defined structures and high chemical purity. To solve theseproblems, our research in the last decade or so has focused on the synthesis of electroactive oligomers of well-definedstructures, controllable molecular weighs, narrow or uniform polydispersity. We have developed a general strategy for thesynthesis of such oligomers based on the theory of non-classical or reactivation chain polymerization. The aniline oligomerswith minimum 4 nitrogen atoms and 3 phenylene rings exhibit similar characteristic redox behavior and electroactivity aspolyaniline. Electronic conductivity of the oligomers of 7 or 8 aniline units approaches that of polyaniline. Solubility of theoligomers is much improved over that of conventional polyaniline. Various functional groups can be introduced into theoligomers either by proper selection of starting materials or by post-synthesis modifications via common organic reactions.The functionalized oligomers undergo further polymerizations to afford a variety of new electroactive materials, includingpolyamides, polyimides, polyureas, polyurethanes, polyacrylamides and epoxy polymers. Numerous potential applications,particularly as anticorrosion materials, are discussed for the oligomers and their polymeric derivatives.     

Doping the Backbone of π‐Conjugated Polymers with Tricoordinate Boron: Synthetic Strategies and Emerging Applications

The doping of π‐conjugated organic compounds with trivalent boron atoms produces materials with intriguing properties and functions that result from the interaction of the π‐electron system with the vacant p orbital on boron. This offers unique opportunities in various applications such as organic (opto)electronics, biomedical imaging, and sensors for physiologically relevant anions or amines, as demonstrated by numerous examples on the molecular scale. Recently, the B‐doping strategy has been expanded to polymer chemistry with a view to benefit from the best of both worlds. Herein, recent advances in the synthesis of π‐conjugated polymers doped with tricoordinate boron in the backbone are reviewed. Selected applications are described where these functional materials have already been successfully implemented.     

Supramolecular coordination chemistry of aromatic polyoxalamide ligands: A metallosupramolecular approach toward functional magnetic materials

The impressive potential of the metallosupramolecular approach in designing new functional magnetic materials constitutes a great scientific challenge for the chemical research community that requires an interdisciplinary collaboration. New fundamental concepts and future applications in nanoscience and nanotechnology will emerge from the study of magnetism as a supramolecular function in metallosupramolecular chemistry. Our recent work on the rich supramolecular coordination chemistry of a novel family of aromatic polyoxalamide (APOXA) ligands with first-row transition metal ions has allowed us to move one step further in the rational design of metallosupramolecular assemblies of increasing structural and magnetic complexity. Thus, we have taken advantage of the new developments of metallosupramolecular chemistry and, in particular, the molecular-programmed self-assembly methods that exploit the coordination preferences of paramagnetic metal ions and suitable designed polytopic ligands. The resulting self-assembled di- and trinuclear metallacyclic complexes with APOXA ligands, either metallacyclophanes or metallacryptands, are indeed ideal model systems for the study of the electron exchange mechanism between paramagnetic metal centers through extended π-conjugated aromatic bridges. So, the influence of different factors such as the topology and conformation of the bridging ligand or the electronic configuration and magnetic anisotropy of the metal ion have been investigated in a systematic way. These oligonuclear metallacyclic complexes can be important in the development of a new class of molecular magnetic devices, such as molecular magnetic wires (MMWs) and switches (MMSs), which are major goals in the field of molecular electronics and spintronics. On the other hand, because of their metal binding capacity through the outer carbonyl-oxygen atoms of the oxamato groups, they can further be used as ligands, referred to as metal–organic ligands (MOLs), toward either coordinatively unsaturated metal complexes or fully solvated metal ions. This well-known “complex-as-ligand” approach affords a wide variety of high-nuclearity metal–organic clusters (MOCs) and high-dimensionality metal–organic polymers (MOPs). The judicious choice of the oligonuclear MOL, ranging from mono- to di- and trinuclear species, has allowed us to control the overall structure and magnetic properties of the final oxamato-bridged multidimensional (nD, n = 0–3) MOCs and MOPs. The intercrossing between short- (nanoscopic) and long-range (macroscopic) magnetic behavior has been investigated in this unique family of oxamato-bridged metallosupramolecular magnetic materials expanding the examples of low-dimensional, single-molecule (SMMs) and single-chain (SCMs) magnets and high-dimensional, open-framework magnets (OFMs), which are brand-new targets in the field of molecular magnetism and materials science.     

无机材料的仿生合成

生物矿化重要的特征之一是细胞分泌的有机基质调制无机矿物的成核和生长, 形成具有特殊组装方式和多级结构特点的生物矿化材料(如骨、牙和贝壳)。仿生合成就是将生物矿化的机理引入无机材料合成, 以有机物的组装体为模板, 去控制无机物的形成,制备具有独特显微结构特点的无机材料, 使材料具有优异的物理和化学性能。仿生合成已成为无机材料化学的研究前沿。本文综述了无机材料仿生合成的发展现状。