Conjugated-polymer grafting on inorganic and organic substrates: A new trend in organic electronic materials

This review highlights recent developments in the grafting of conjugated polymers onto various substrates for organic electronic devices. The rapid development of multi-layer architectures demands the preparation of well-defined interfaces between both compatible and incompatible materials. It is promising therefore that interface-engineering is now known to help passivate charge trap states, control energy level alignments, enhance charge extraction, guide active-layer morphologies, and improve material compatibility, adhesion and device stability. In organic electronic devices, conjugated polymers are in contact with a wide range of constituents, such as metals, metal oxides, organic materials, and inorganic particles. Covalent bonds between these materials and macromolecules are desired to yield intimate contacts and well-defined interfaces. Following an overview of the various synthetic methodologies of conjugated polymers, the chemistry of tethering macromolecular chains onto nanoparticles and flat surfaces is described. The creation of functional hybrid materials offers the potential to deliver efficient and low-cost devices.     

Telechelic polymers by living and controlled/living polymerization methods

Telechelic polymers, defined as macromolecules that contain two reactive end groups, are used as cross-linkers, chain extenders, and important building blocks for various macromolecular structures, including block and graft copolymers, star, hyperbranched or dendritic polymers. This review article describes the general techniques for the preparation of telechelic polymers by living and controlled/living polymerization methods; namely atom transfer radical polymerization, nitroxide mediated radical polymerization, reversible addition-fragmentation chain transfer polymerization, iniferters, iodine transfer polymerization, cobalt mediated radical polymerization, organotellurium-, organostibine-, organobismuthine-mediated living radical polymerization, living anionic polymerization, living cationic polymerization, and ring opening metathesis polymerization. The efficient click reactions for the synthesis of telechelic polymers are also presented.     

Synthesis and functionalization of nanoengineered materials using click chemistry

The synthesis of nanoengineered materials with precise control over material composition, architecture and functionality is integral to advances in diverse fields, including biomedicine. Over the last 10 years, click chemistry has emerged as a prominent and versatile approach to engineer materials with specific properties. Herein, we highlight the application of click chemistry for the synthesis of nanoengineered materials, ranging from ultrathin films to delivery systems such as polymersomes, dendrimers and capsules. In addition, we discuss the use of click chemistry for functionalizing such materials, focusing on modifications aimed at biomedical applications.     

Zwitterion effect in polyelectrolyte gels based on lithium methacrylate-N,N-dimethyl acrylamide copolymer

Zwitterionic compounds such as those based on 1-butylimidazolium-3-(n-butanesulfonate) have previously been shown to have positive effects on the transport properties of polyelectrolytes. The addition of the zwitterion has been found to, in some cases, increase the dissociation of the lithium ion and enhance the conductivity by almost an order of magnitude. In this work, we report the effects of adding the above-mentioned zwitterion into the polyelectrolyte gel system poly(lithium methacrylate-co-N,N-dimethyl acrylamide); the anionic group being a stronger base leads to different behaviour for this copolymer compared to previous work. Polyelectrolyte gels based on dimethyl sulfoxide and polyether solvents were investigated to determine the breadth of applicability of the zwitterion in improving lithium ion transport. Impedance spectroscopy and pulse field gradient-NMR diffusion indicate an increase in the number of available charge carriers with zwitterion addition in some gel systems, however, the effect is not universal.     

Electroactive phases of poly(vinylidene fluoride): Determination,processing and applications

Poly(vinylidene fluoride), PVDF, and its copolymers are the family of polymers with the highest dielectric constant and electroactive response, including piezoelectric, pyroelectric and ferroelectric effects. The electroactive properties are increasingly important in a wide range of applications such as in biomedicine, energy generation and storage, monitoring and control, and include the development of sensors and actuators, separator and filtration membranes and smart scaffolds, among others. For many of these applications the polymer should be in one of its electroactive phases. This review presents the developments and summarizes the main characteristics of the electroactive phases of PVDF and copolymers, indicates the different processing strategies as well as the way in which the phase content is identified and quantified. Additionally, recent advances in the development of electroactive composites allowing novel effects, such as magnetoelectric responses, and opening new applications areas are presented. Finally, some of the more interesting potential applications and processing challenges are discussed.     

Biodegradable poly(ester amide)s – A remarkable opportunity for the biomedical area: Review on the synthesis,characterization and applications

Poly(ester amide)s have emerged in the last years as an important family of biodegradable synthetic polymers. These polymers present both ester and amide linkages in their structure and they gather in the same entity the good degradability of polyesters with the good thermo-mechanical properties of polyamides. Particularly, poly(ester amide)s containing α-amino acids have risen as important materials in the biomedical field. The presence of the α-amino acid contributes to better cell–polymer interactions, allows the introduction of pendant reactive groups, and enhances the overall biodegradability of the polymers.     

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.     

The chemistry of tissue adhesive materials

Each year millions of people sustain traumatic or surgical wounds, which require proper closure. Conventional closure techniques, including suturing and stapling, have many disadvantages. They inflict additional damage on the tissue, elicit inflammatory responses and have a relatively long application time. Especially for the more demanding wounds, where fluids or gasses are to be sealed off, these techniques are often insufficient. Therefore, a large variety of tissue adhesives, sealants and hemostatic agents have been developed. This review provides an overview of such tissue adhesive materials from a polymer chemistry perspective. The materials are divided into synthetic polymer, polysaccharide and protein based adhesives. Their specific properties and behavior are discussed and related to their clinical application. Though each type has its specific advantages, yet few have become standard in clinical practice. Biomimetic based adhesives and other novel products have shown promising results but also face specific problems. For now, the search for better adhering, stronger, easier applicable and cheaper adhesives continues and this review is intended as starting point and inspiration for these future research efforts to develop the next generation tissue adhesives.     

Lithium salts based on oligoether sulfate esters

Salts based on oligoether sulfate have been synthesized. Two families of lithium salt were synthesized, mono and disulfate. The results, in term of ionic conductivities, thermal behaviour, viscosity, transference number and electrochemical stability are reported. These salts have sufficient thermal and electrochemical stabilities and, in addition, they have a cationic transference number close to unity. The influence of alkaline cation was evaluated on conductivity and thermal stability measurements.     

Complex polymer architectures via RAFT polymerization: From fundamental process to extending the scope using click chemistry and nature's building blocks

Reversible addition fragmentation chain transfer (RAFT) polymerization has made a huge impact in macromolecular design. The first block copolymers were described early on, followed by star polymers and then graft polymers. In the last five years, the types of architectures available have become more and more complex. Star and graft polymers now have block structures within their branches, or a range of different branches can be found growing from one core or backbone. Even the synthesis of hyperbranched polymers can be positively influenced by RAFT polymerization, allowing end group control or control over the branching density. The creative combination of RAFT polymerization with other polymerization techniques, such as ATRP or ring-opening polymerization, has extended the array of available architectures. In addition, dendrimers were incorporated either as star core or endfunctionalities. A range of synthetic chemistry pathways have been utilized and combined with polymer chemistry, pathways such as ‘click chemistry’. These combinations have allowed the creation of novel structures. RAFT processes have been combined with natural polymers and other naturally occurring building blocks, including carbohydrates, polysaccharides, cyclodextrins, proteins and peptides. The result from the intertwining of natural and synthetic materials has resulted in the formation of hybrid biopolymers. Following these developments over the last few years, it is remarkable to see that RAFT polymerization has grown from a lab curiosity to a polymerization tool that is now been used with confidence in material design. Most of the described synthetic procedures in the literature in recent years, which incorporate RAFT polymerization, have been undertaken in order to design advanced materials.     

Segmented copolymers with monodisperse crystallizable hard segments: Novel semi-crystalline materials

Segmented block copolymers with short monodisperse crystallizable hard segments have interesting structures and properties. In the melt, such short monodisperse segments are miscible with the matrix segments. Moreover, upon cooling, they crystallize fast, demonstrating a very high crystallinity, and only a small crystallization window is needed. The melting temperature of the short segments is high, provided that they can H-bond and/or contain aromatic groups. The melting temperature was found to decrease with increasing matrix segment concentration, due to the solvent effect of the matrix segments. At concentrations of crystallizable segment of 4-35 wt%, good dimensional and solvent stabilities were obtained.The monodisperse segments crystallized into nano-ribbons with uniform thickness and high aspect ratio, and these dispersed nano-ribbon crystallites constituted physical crosslinks, while acting also as reinforcing fillers. At concentrations of the monodisperse segments below 20 wt% no spherulitic ordering took place, and the semi-crystalline polymers were transparent. The monodisperse crystallizable segments can be used in combination with matrix segments of either low or high glass transition temperature, and may even contain (bio)functional units.     

Controlled accommodation of metal nanostructures within the matrices of polymer architectures through solution-based synthetic strategies

Controlled accommodation of metal nanostructures (MNSs) into the matrix of a well-defined polymer architecture offers an effective approach to achieve hierarchically structured nanocomposites with tunable synergistic properties to broaden application potentials in the emerging fields of energy, environmental science, and medicine. This review focuses on the recently developed zero-dimensional and one-dimensional MNSs@polymer hybrid nanostructures obtained by solution-based synthetic strategies. Progress in the controlled synthesis of those hybrid nanostructures in terms of the number (e.g., monomer, dimer and trimer), organization manner (e.g., linear alignment or confined assembly in certain domains), and spatial arrangement (e.g., in the core and shell) of the MNSs within the distinct polymer matrices are detailed. The synergistic properties and potential applications of those MNSs@polymer hybrids associated with their compositions and morphologies are also reviewed.     

Polymer vectors via controlled/living radical polymerization for gene delivery

The design of efficient gene delivery vectors is a challenging task in gene therapy. Recent progress in living/controlled radical polymerizations (LRPs), in particular atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization providing a means for the design and synthesis of new polymeric gene vectors with well-defined compositions, architectures and functionalities is reviewed here. Polymeric gene vectors with different architectures, including homopolymers, block copolymers, graft copolymers, and star-shaped polymers, are conveniently prepared via ATRP and RAFT polymerization. The corresponding synthesis strategies are described in detail. The recent research activities indicate that ATRP and RAFT polymerization have become essential tools for the design and synthesis of advanced, noble and novel gene carriers.     

ATRP in the design of functional materials for biomedical applications

Atom Transfer Radical Polymerization (ATRP) is an effective technique for the design and preparation of multifunctional, nanostructured materials for a variety of applications in biology and medicine. ATRP enables precise control over macromolecular structure, order, and functionality, which are important considerations for emerging biomedical designs. This article reviews recent advances in the preparation of polymer-based nanomaterials using ATRP, including polymer bioconjugates, block copolymer-based drug delivery systems, cross-linked microgels/nanogels, diagnostic and imaging platforms, tissue engineering hydrogels, and degradable polymers. It is envisioned that precise engineering at the molecular level will translate to tailored macroscopic physical properties, thus enabling control of the key elements for realized biomedical applications.     

Chitin and chitosan in selected biomedical applications

Chitin (CT), the well-known natural biopolymer and chitosan (CS) (bio-based or “artificial polymer”) are non-toxic, biodegradable and biocompatible in nature. The advantages of these biomaterials are such that, they can be easily processed into different forms such as membranes, sponges, gels, scaffolds, microparticles, nanoparticles and nanofibers for a variety of biomedical applications such as drug delivery, gene therapy, tissue engineering and wound healing. Present review focuses on the diverse applications of CT and CS membranes and scaffolds for drug delivery, tissue engineering and targeted regenerative medicine. The chitinous scaffolds of marine sponges’ origin are discussed here for the first time. These CT based scaffolds obtained from Porifera possess remarkable and unique properties such as hydration, interconnected channels and diverse structural architecture. This review will provide a brief overview of CT and CS membranes and scaffolds toward different kinds of delivery applications such as anticancer drug delivery, osteogenic drug delivery, and growth factor delivery, because of their inimitable release behavior, degradation profile, mucoadhesive nature, etc. The review also provides an overview of the key features of CT and CS membranes and scaffolds such as their biodegradability, cytocompatibility and mechanical properties toward applications in tissue engineering and wound healing.     

Interpolymer radical coupling: A toolbox complementary to controlled radical polymerization

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.     

Organic-inorganic nanocomposite polymer electrolyte membranes for fuel cell applications

Organic-inorganic nanocomposite polymer electrolyte membrane (PEM) contains nano-sized inorganic building blocks in organic polymer by molecular level of hybridization. This architecture has opened the possibility to combine in a single solid both the attractive properties of a mechanically and thermally stable inorganic backbone and the specific chemical reactivity, dielectric, ductility, flexibility, and processability of the organic polymer. The state-of-the-art of polymer electrolyte membrane fuel cell technology is based on perfluoro sulfonic acid membranes, which have some key issues and shortcomings such as: water management, CO poisoning, hydrogen reformate and fuel crossover. Organic-inorganic nanocomposite PEM show excellent potential for solving these problems and have attracted a lot of attention during the last ten years. Disparate characteristics (e.g., solubility and thermal stability) of the two components, provide potential barriers towards convenient membrane preparation strategies, but recent research demonstrates relatively simple processes for developing highly efficient nanocomposite PEMs. Objectives for the development of organic-inorganic nanocomposite PEM reported in the literature include several modifications: (1) improving the self-humidification of the membrane; (2) reducing the electro-osmotic drag and fuel crossover; (3) improving the mechanical and thermal strengths without deteriorating proton conductivity; (4) enhancing the proton conductivity by introducing solid inorganic proton conductors; and (5) achieving slow drying PEMs with high water retention capability. Research carried out during the last decade on this topic can be divided into four categories: (i) doping inorganic proton conductors in PEMs; (ii) nanocomposites by sol-gel method; (iii) covalently bonded inorganic segments with organic polymer chains; and (iv) acid-base PEM nanocomposites. The purpose here is to summarize the state-of-the-art in the development of organic-inorganic nanocomposite PEMs for fuel cell applications.     

Stimuli-triggered structural engineering of synthetic and biological polymeric assemblies

Response to external stimuli is a fundamental and intrinsic behavior of living systems. There has been increasing interest for designing and constructing responsive polymeric superstructures by self-assembly. Stimuli-induced self-assembly and post-assembly triggering strategies provide an alternative approach for the manipulation of self-assembled architectures of either biological or synthetic polymeric materials. Stimuli-induced structural transformations may produce ensembles with new topologies or materials with exceptionally complex features inaccessible via conventional self-assembly processes. This is in contrast to materials that simply undergo stimuli-induced degradation, or disassembly processes. Since a variety of cellular processes depend on responses to environmental stimuli that lead to more complexity and increased function, and are related to structural transitions over the nano- to microscale, insights into stimuli-triggered morphogenesis can further deepen our understanding of cellular behaviors. Indeed, an understanding of these processes will likely inspire scientists to develop materials with advanced and tailored architectures for biosensing, diagnosis and therapy as well as other biomedical applications. Herein, we highlight state-of-the-art achievements in the stimuli-triggered structural manipulation of polymer assemblies. Furthermore, future developments in this nascent and growing field are briefly discussed.     

Preparation of nanoscale carbon black dispersion using hyper-branched poly(styrene-alt-maleic anhydride)

Hyper-branched poly(styrene-alt-maleic anhydride) (BPSMA) was used as a dispersant to disperse carbon black (CB) in aqueous media. The dispersing ability of BPSMA for CB was estimated by measuring the particle size, zeta potential, stability to temperature and centrifugal stability of BPSMA-dispersed CB dispersions. The experimental results showed that BPSMA prepared with a molar ratio of 4-vinylphenyl methanethiol (VPMT), St and MA at 6:47:47 and a mass ratio of BPO and (VPMT + St + MA) at 1:50 exhibited optimal dispersing ability when the CB dispersion was at pH 8, and a mass ratio of BPSMA and CB was about 1:5. Compared to linear poly(styrene-alt-maleic anhydride) (LPSMA), BPSMA prepared CB pigment dispersion with a smaller particle size, a more narrow particle size distribution and higher stabilities.     

When emulsification meets self-assembly: The role of emulsification in directing block copolymer assembly

Emulsification is used to generate spherical particles or droplets of immiscible liquids, while block copolymer self-assembly yields a wide variety of nanostructures. The combination of these two methodologies can yield a variety of structures that would not be otherwise observed. The emulsification/solvent evaporation process provides a powerful means to direct block copolymer assembly. Various factors arising from the emulsification can direct the block copolymer assembly, such as confinement effects, interfacial tension, as well as other conditions. In this review, various emulsification techniques are discussed, such as oil-in-water emulsions, double emulsions, as well as the use of microfluidic devices. While emulsification-induced self-assembly may be used to control internal morphologies as well as overall shapes of particles, it also lends a convenient method for controlling surface structures. Examples of exotic structures that may be obtained through the use of these techniques will be described. Also, ways in which morphologies may be controlled using these methods will be discussed.