Production of renewable polymers from crop plants

Plants produce a range of biopolymers for purposes such as maintenance of structural integrity, carbon storage, and defense against pathogens and desiccation. Several of these natural polymers are used by humans as food and materials, and increasingly as an energy carrier. In this review, we focus on plant biopolymers that are used as materials in bulk applications, such as plastics and elastomers, in the context of depleting resources and climate change, and consider technical and scientific bottlenecks in the production of novel or improved materials in transgenic or alternative crop plants. The biopolymers discussed are natural rubber and several polymers that are not naturally produced in plants, such as polyhydroxyalkanoates, fibrous proteins and poly-amino acids. In addition, monomers or precursors for the chemical synthesis of biopolymers, such as 4-hydroxybenzoate, itaconic acid, fructose and sorbitol, are discussed briefly.     

Lipase-catalysed acylation of starch and determination of the degree of substitution by methanolysis and GC

Background  

Natural polysaccharides such as starch are becoming increasingly interesting as renewable starting materials for the synthesis of biodegradable polymers using chemical or enzymatic methods. Given the complexity of polysaccharides, the analysis of reaction products is challenging.     

Silk: molecular organization and control of assembly

The interface between the science and engineering of biology and materials is an area of growing interest. One of the goals of this field is to utilize biological synthesis and processing of polymers as a route to gain insight into topics such as molecular recognition, self-assembly and the formation of materials with well-defined architectures. The biological processes involved in polymer synthesis and assembly can offer important information on fundamental interactions involved in the formation of complex material architectures, as well as practical knowledge into new and important materials related to biomaterial uses and tissue engineering needs. Classic approaches in biology, including genetic engineering, controlled microbial physiology and enzymatic synthesis, are prototypical methods used to control polymer structure and chemistry, including stereoselectivity and regioselectivity, to degrees unattainable using traditional synthetic chemistry. This type of control can lead to detailed and systematic studies of the formation of the structural hierarchy in materials and the subsequent biological responses to these materials.     

Application of imprinted synthetic polymers in binding assay development

The first part of the review describes a method for the synthesis of molecularly imprinted polymers for use in binding assays. The method considers the many factors involved that affect the recognition properties of the materials and describes an approach to screening and optimization of these factors. The second part describes the development of binding assays using such polymers. This includes the use of different labels, the effect of solvent and buffer, the scale of the assay (amount of solid polymer), and how these influence the quality of the assay in terms of sensitivity, selectivity, and speed of analysis.     

Synthetic polymers functionalized by carbohydrates: a review

Polymers based on carbohydrates have re-emerged as exciting topics of polymer research, due to a worldwide focus on sustainable materials. However, multi-step synthesis of these polymers have made their use as commodity plastics uneconomical, and currently their applications are restricted to biomedical fields. Functionalization of polymers has emerged as another important area of polymer science and technology. Chemically linking sugar moeities onto synthetic polymers is a unique method of functionalization of synthetic polymers, whereby not only is the polymer functionalized, but it can also get other desirable properties such as biodegradability—a property much debated and researched in modern times. This paper reviews several methods of anchoring carbohydrates onto polymers and the advantages and the disadvantages associated with each method, their current and potential applications, and their characterization methods.     

Rational design of new materials using recombinant structural proteins: Current state and future challenges

Sequence-definable polymers are seen as a prerequisite for design of future materials, with many polymer scientists regarding such polymers as the holy grail of polymer science. Recombinant proteins are sequence-defined polymers. Proteins are dictated by DNA templates and therefore the sequence of amino acids in a protein is defined, and molecular biology provides tools that allow redesign of the DNA as required. Despite this advantage, proteins are underrepresented in materials science. In this publication we investigate the advantages and limitations of using proteins as templates for rational design of new materials.     

α-Amino acid containing degradable polymers as functional biomaterials: rational design, synthetic pathway, and biomedical applications

Currently, biomedical engineering is rapidly expanding, especially in the areas of drug delivery, gene transfer, tissue engineering, and regenerative medicine. A prerequisite for further development is the design and synthesis of novel multifunctional biomaterials that are biocompatible and biologically active, are biodegradable with a controlled degradation rate, and have tunable mechanical properties. In the past decades, different types of α-amino acid-containing degradable polymers have been actively developed with the aim to obtain biomimicking functional biomaterials. The use of α-amino acids as building units for degradable polymers may offer several advantages: (i) imparting chemical functionality, such as hydroxyl, amine, carboxyl, and thiol groups, which not only results in improved hydrophilicity and possible interactions with proteins and genes, but also facilitates further modification with bioactive molecules (e.g., drugs or biological cues); (ii) possibly improving materials biological properties, including cell-materials interactions (e.g., cell adhesion, migration) and degradability; (iii) enhancing thermal and mechanical properties; and (iv) providing metabolizable building units/blocks. In this paper, recent developments in the field of α-amino acid-containing degradable polymers are reviewed. First, synthetic approaches to prepare α-amino acid-containing degradable polymers will be discussed. Subsequently, the biomedical applications of these polymers in areas such as drug delivery, gene delivery and tissue engineering will be reviewed. Finally, the future perspectives of α-amino acid-containing degradable polymers will be evaluated.     

Recent Development of Quinoxaline Based Polymers/Small Molecules for Organic Photovoltaics

Among the various molecular designs developed for the synthesis of conjugated polymers and small molecules for optoelectronic applications, the donor: acceptor (D–A) approach is the most widely explored method over the past decades. Through the covalent linkage of electron‐rich and electron‐deficient units, a plethora of medium‐low band gap materials has been developed and tested in organic photovoltaic devices. In particular, the quinoxaline aromatic structure and its derivatives are among the most studied electron deficient aromatic units used in D–A structures. Quinoxaline based materials are endowed with characteristics that are useful for large scale production in real world applications, such as easy synthetic procedures and excellent stability in air. Moreover, the use of quinoxaline based polymers/small molecules in bulk heterojunction (BHJ) devices led to power conversion efficiencies over 9%. Considering the potential of quinoxaline based materials, this review gathers together quinoxaline based polymers and small molecules reported in the literature during the last 5 years, summarizing and discussing the structure‐properties relationships for this class of organic semiconductors, aiming to serve as a background and to promote efforts for the further development of new quinoxaline derivatives with improved and advanced properties for future applications.     

组织工程支架材料

用于组织工程支架构建的生物材料,分为胶原、多糖、无机及生物衍生物等天然材料和聚酯、聚氨基酸、聚乙二醇等人工合成可生物降解材料两大类,此文分别对它们的研究进行了综述。     

Design of imidazole-containing endosomolytic biopolymers for gene delivery

The development of safe and effective gene delivery agents poses a great challenge in the quest to make human gene therapy a reality. Cationic polymers represent one important class of materials for gene delivery, but to date they have shown only moderate efficiency. Improving the efficiency will require the design of new polymers incorporating optimized gene delivery properties. For example, inefficient release of the DNA/polymer complex from endocytic vesicles into the cytoplasm is one of the primary causes of poor gene delivery. Here we report the synthesis of a biocompatible, imidazole-containing polymer designed to overcome this obstacle. DNA/polymer polyplexes incorporating this polymer were shown to have desirable physico-chemical properties for gene delivery and are essentially nontoxic. Using this system, mammalian cells in vitro were transfected in the absence of any exogenous endosomolytic agent such as chloroquine.     

The XNA world: progress towards replication and evolution of synthetic genetic polymers

Life's diversity is built on the wide range of properties and functions that can be encoded in natural biopolymers such as polypeptides and nucleic acids. However, despite their versatility, the range of chemical functionalities is limited, particularly in the case of nucleic acids. Chemical modification of nucleic acids can greatly increase their functional diversity but access to the full phenotypic potential of such polymers requires a system of replication. Here we review progress in the chemical and enzymatic synthesis, replication and evolution of unnatural nucleic acid polymers, which promises to enable the exploration of a vast sequence space not accessible to nature and deliver ligands, catalysts and materials based on this new class of biopolymers.     

Solution‐Processable Conjugated Polymers as Anode Interfacial Layer Materials for Organic Solar Cells

In recent years, solution‐processed conjugated polymers have been extensively used as anode interfacial layer (AIL) materials in organic solar cells (OSCs) due to their excellent film‐forming property and low‐temperature processing advantages. In this review, the authors focus on the recent advances in conjugated polymers as AIL materials in OSCs. Several of the main classes of solution‐processable conjugated polymers, including poly(3,4‐ethylenedioxythiophene):(styrenesulfonate), polyaniline, polythiophene, conjugated polyelectrolytes, sulfonated poly(diphenylamine), and crosslinked polymers as AIL materials are discussed in depth, and the mechanisms of these AIL materials in enhancing OSC performances are also elucidated. The structure–property relationships of various conjugated polymer AIL materials are analyzed, and some important design rules for such materials toward high efficiencies and stable OSCs are presented. In addition, some chemical and physical approaches to optimize the photoelectronic and physic properties of conjugated polymer AIL materials, which improve their performance in modifying OSCs, are also highlighted. Considering the significance of tandem OSCs, the relevant applications of conjugated polymer AIL materials in constructing interconnection layers for tandem OSCs are also mentioned. Finally, a brief summary is presented and some perspectives to help researchers understand the current challenges and opportunities in this area are proposed.     

Overview of bacterial cellulose composites: A multipurpose advanced material

Bacterial cellulose (BC) has received substantial interest owing to its unique structural features and impressive physico-mechanical properties. BC has a variety of applications in biomedical fields, including use as biomaterial for artificial skin, artificial blood vessels, vascular grafts, scaffolds for tissue engineering, and wound dressing. However, pristine BC lacks certain properties, which limits its applications in various fields; therefore, synthesis of BC composites has been conducted to address these limitations. A variety of BC composite synthetic strategies have been developed based on the nature and relevant applications of the combined materials. BC composites are primarily synthesized through in situ addition of reinforcement materials to BC synthetic media or the ex situ penetration of such materials into BC microfibrils. Polymer blending and solution mixing are less frequently used synthetic approaches. BC composites have been synthesized using numerous materials ranging from organic polymers to inorganic nanoparticles. In medical fields, these composites are used for tissue regeneration, healing of deep wounds, enzyme immobilization, and synthesis of medical devices that could replace cardiovascular and other connective tissues. Various electrical products, including biosensors, biocatalysts, E-papers, display devices, electrical instruments, and optoelectronic devices, are prepared from BC composites with conductive materials. In this review, we compiled various synthetic approaches for BC composite synthesis, classes of BC composites, and applications of BC composites. This study will increase interest in BC composites and the development of new ideas in this field.     

Acoustic levitation: recent developments and emerging opportunities in biomaterials research

Containerless sample environments (levitation) are useful for study of nucleation, supercooling, and vitrification and for synthesis of new materials, often with non-equilibrium structures. Elimination of extrinsic nucleation by container walls extends access to supercooled and supersaturated liquids under high-purity conditions. Acoustic levitation is well suited to the study of liquids including aqueous solutions, organics, soft materials, polymers, and pharmaceuticals at around room temperature. This article briefly reviews recent developments and applications of acoustic levitation in materials R&D. Examples of experiments yielding amorphous pharmaceutical materials are presented. The implementation and results of experiments on supercooled and supersaturated liquids using an acoustic levitator at a high-energy X-ray beamline are described.     

Hybrid solar cells

Historically, conventional solar cells were built from inorganic materials such as silicon. Although the efficiency of such conventional solar cells is high, very expensive materials and energy intensive processing techniques are required.Hybrid and photoelectrochemical (dye sensitized) solar cells have been the cheap alternatives for conventional silicon solar cells. A hybrid solar cell consists of a combination of both organic and inorganic materials therefore, combines the unique properties of inorganic semiconductors with the film forming properties of the conjugated polymers. Organic materials are inexpensive, easily processable and their functionality can be tailored by molecular design and chemical synthesis. On the other hand, inorganic semiconductors can be manufactured as nanoparticles and inorganic semiconductor nanoparticles offer the advantage of having high absorption coefficients and size tunability. By varying the size of the nanoparticles the bandgap can be tuned therefore the absorption range can be tailored.In this short review, we will focus on the concepts of organic/inorganic “hybrid” solar cells.     

Confined Synthesis of 2D Nanostructured Materials toward Electrocatalysis

2D nanostructured materials have shown great application prospects in energy conversion, owing to their unique structural features and fascinating physicochemical properties. Developing efficient approaches for the synthesis of well‐defined 2D nanostructured materials with controllable composition and morphology is critical. The emerging concept, confined synthesis, has been regarded as a promising strategy to design and synthesize novel 2D nanostructured materials. This review mainly summarizes the recent advances in confined synthesis of 2D nanostructured materials by using layered materials as host matrices (also denoted as “nanoreactors”). By virtue of the space‐ and surface‐confinement effects of these layered hosts, various well‐organized 2D nanostructured materials, including 2D metals, 2D metal compounds, 2D carbon materials, 2D polymers, 2D metal‐organic frameworks (MOFs) and covalent‐organic frameworks (COFs), as well as 2D carbon nitrides are successfully synthesized. The wide employment of these 2D materials in electrocatalytic applications (e.g., electrochemical oxygen/hydrogen evolution reactions, small molecule oxidation, and oxygen reduction reaction) is presented and discussed. In the final section, challenges and prospects in 2D confined synthesis from the viewpoint of designing new materials and exploring practical applications are commented, which would push this fast‐evolving field a step further toward greater success in both fundamental studies and ultimate industrialization.     

Surface modification of iron oxide nanoparticles by biocompatible polymers for tissue imaging and targeting

Superparamagnetic iron oxide nanoparticles (SPIONs) are excellent MR contrast agents when coated with biocompatible polymers such as hydrophilic synthetic polymers, proteins, polysaccharides, and lipids, which improve their stability and biocompatibility and reduce their aggregation. Various biocompatible materials, coated or conjugated with targeting moieties such as galactose, mannose, folic acid, antibodies and RGD, have been applied to SPION surfaces to provide tissue specificity to hepatocytes, macrophages, and tumor regions in order to reduce non-specific uptake and improve biocompatibility. This review discusses the recent progress in the development of biocompatible and hydrophilic polymers for improving stability of SPIONs and describes the carbohydrates based biocompatible materials that are providing SPIONs with cell/tissue specificity as ligands.     

Green synthesis of conductive polyaniline by Trametes versicolor laccase using a DNA template

The green synthesis of highly conductive polyaniline by using two biological macromolecules, i.e laccase as biocatalyst, and DNA as template/dopant, was achieved in this work. Trametes versicolor laccase B (TvB) was found effective in oxidizing both aniline and its less toxic/mutagenic dimer N‐phenyl‐p‐phenylenediamine (DANI) to conductive polyaniline. Reaction conditions for synthesis of conductive polyanilines were set‐up, and structural and electrochemical properties of the two polymers were extensively investigated. When the less toxic aniline dimer was used as substrate, the polymerization reaction was faster and gave less‐branched polymer. DNA was proven to work as hard template for both enzymatically synthesized polymers, conferring them a semi‐ordered morphology. Moreover, DNA also acts as dopant leading to polymers with extraordinary conductive properties (～6 S/cm). It can be envisaged that polymer properties are magnified by the concomitant action of DNA as template and dopant. Herein, the developed combination of laccase and DNA represents a breakthrough in the green synthesis of conductive materials.     

Designing dendrimers for biological applications

Dendrimers are branched, synthetic polymers with layered architectures that show promise in several biomedical applications. By regulating dendrimer synthesis, it is possible to precisely manipulate both their molecular weight and chemical composition, thereby allowing predictable tuning of their biocompatibility and pharmacokinetics. Advances in our understanding of the role of molecular weight and architecture on the in vivo behavior of dendrimers, together with recent progress in the design of biodegradable chemistries, has enabled the application of these branched polymers as anti-viral drugs, tissue repair scaffolds, targeted carriers of chemotherapeutics and optical oxygen sensors. Before such products can reach the market, however, the field must not only address the cost of manufacture and quality control of pharmaceutical-grade materials, but also assess the long-term human and environmental health consequences of dendrimer exposure in vivo.     

Polyhydroxyalkanoates: Current applications in the medical field

Polyhydroxyalkanoates (PHAs) are a class of biopolyesters that are synthesized intracellularly by microorganisms, mainly by different genera of eubacteria. These biopolymers have diverse physical and chemical properties that also classify them as biodegradable in nature and make them compatible to living systems. In the last two decades or so, PHAs have emerged as potential useful materials in the medical field for different applications owing to their unique properties. The lower acidity and bioactivity of PHAs confer them with minimal risk compared to other biopolymers such as poly-lactic acid (PLA) and poly-glycolic acid (PGA). Therefore, the versatility of PHAs in terms of their non-toxic degradation products, biocompatibility, desired surface modifications, wide range of physical and chemical properties, cellular growth support, and attachment without carcinogenic effects have enabled their use as in vivo implants such as sutures, adhesion barriers, and valves to guide tissue repair and in regeneration devices such as cardiovascular patches, articular cartilage repair scaffolds, bone graft substitutes, and nerve guides. Here, we briefly describe some of the most recent innovative research involving the use of PHAs in medical applications. Microbial production of PHAs also provides the opportunity to develop PHAs with more unique monomer compositions economically through metabolic engineering approaches. At present, it is generally established that the PHA monomer composition and surface modifications influence cell responses.PHA synthesis by bacteria does not require the use of a catalyst (used in the synthesis of other polymers), which further promotes the biocompatibility of PHA-derived polymers.