Synthetic biodegradable functional polymers for tissue engineering: a brief review

Scaffolds play a crucial role in tissue engineering. Biodegradable polymers with great processing flexibility are the predominant scaffolding materials. Synthetic biodegradable polymers with well-defined structure and without immunological concerns associated with naturally derived polymers are widely used in tissue engineering. The synthetic biodegradable polymers that are widely used in tissue engineering, including polyesters, polyanhydrides, polyphosphazenes, polyurethane, and poly (glycerol sebacate) are summarized in this article. New developments in conducting polymers, photoresponsive polymers, amino-acid-based polymers, enzymatically degradable polymers, and peptide-activated polymers are also discussed. In addition to chemical functionalization, the scaffold designs that mimic the nano and micro features of the extracellular matrix (ECM) are presented as well, and composite and nanocomposite scaffolds are also reviewed.     

Horizons in the development of polymer engineering materials

Some problems related to conservation of existing organic large-scale polymers (polyolefins, PS, PVC, polyesters, PA, etc.) and their replacement with recycled polymers and inorganic polyoxides are revisited: recycling of polymer materials; recyclable sources, such as cellulose, chitin, starch, etc.; enrichment of composites with an inorganic component; inorganic polymers; nanomaterials; and gradient materials.     

Side-chain engineering of high-efficiency conjugated polymer photovoltaic materials

In recent years,conjugated polymers have attracted great attention in the application as photovoltaic donor materials in polymer solar cells(PSCs).Broad absorption,lower-energy bandgap,higher hole mobility,relatively lower HOMO energy levels,and higher solubility are important for the conjugated polymer donor materials to achieve high photovoltaic performance.Side-chain engineering plays a very important role in optimizing the physicochemical properties of the conjugated polymers.In this article,we review recent progress on the side-chain engineering of conjugated polymer donor materials,including the optimization of flexible side-chains for balancing solubility and intermolecular packing(aggregation),electron-withdrawing substituents for lowering HOMO energy levels,and two-dimension(2D)-conjugated polymers with conjugated side-chains for broadening absorption and enhancing hole mobility.After the molecular structural optimization by side-chain engineering,the2D-conjugated polymers based on benzodithiophene units demonstrated the best photovoltaic performance,with powerconversion efficiency higher than 9%.     

New engineering polymers for blow-moulding

The combination of using high performance flexible engineering polymers and their processing by blow moulding technology allows traditional rubber and rubber-metal composite parts to be replaced to obtain improved performance, lower cost and greater design freedom. Two examples of automobile applications are detailed to support this concept - constant velocity joint boots and engine air ducting.     

Biodegradable polymer matrix nanocomposites for tissue engineering: A review

Nanocomposites have emerged in the last two decades as an efficient strategy to upgrade the structural and functional properties of synthetic polymers. Aliphatic polyesters as polylactide (PLA), poly(glycolides) (PGA), poly(?-caprolactone) (PCL) have attracted wide attention for their biodegradability and biocompatibility in the human body. A logic consequence has been the introduction of organic and inorganic nanofillers into biodegradable polymers to produce nanocomposites based on hydroxyapatite, metal nanoparticles or carbon nanotructures, in order to prepare new biomaterials with enhanced properties. Consequently, the improvement of interfacial adhesion between the polymer and the nanostructures has become the key technique in the nanocomposite process. In this review, different results on the fabrication of nanocomposites based on biodegradable polymers for specific field of tissue engineering are presented. The combination of bioresorbable polymers and nanostructures open new perspectives in the self-assembly of nanomaterials for biomedical applications with tuneable mechanical, thermal and electrical properties.     

Atomistic band gap engineering in donor-acceptor polymers

We have synthesized a series of cyclopentadithiophene-benzochalcogenodiazole donor-acceptor (D-A) copolymers, wherein a single atom in the benzochalcogenodiazole unit is varied from sulfur to selenium to tellurium, which allows us to explicitly study sulfur to selenium to tellurium substitution in D-A copolymers for the first time. The synthesis of S- and Se-containing polymers is straightforward; however, Te-containing polymers must be prepared by postpolymerization single atom substitution. All of the polymers have the representative dual-band optical absorption profile, consisting of both a low- and high-energy optical transition. Optical spectroscopy reveals that heavy atom substitution leads to a red-shift in the low-energy transition, while the high-energy band remains relatively constant in energy. The red-shift in the low-energy transition leads to optical band gap values of 1.59, 1.46, and 1.06 eV for the S-, Se-, and Te-containing polymers, respectively. Additionally, the strength of the low-energy band decreases, while the high-energy band remains constant. These trends cannot be explained by the present D and A theory where optical properties are governed exclusively by the strength of D and A units. A series of optical spectroscopy experiments, solvatochromism studies, density functional theory (DFT) calculations, and time-dependent DFT calculations are used to understand these trends. The red-shift in low-energy absorption is likely due to both a decrease in ionization potential and an increase in bond length and decrease in acceptor aromaticity. The loss of intensity of the low-energy band is likely the result of a loss of electronegativity and the acceptor unit's ability to separate charge. Overall, in addition to the established theory that difference in electron density of the D and A units controls the band gap, single atom substitution at key positions can be used to control the band gap of D-A copolymers.     

Dendritic analogues of engineering plastics - a general one-step synthesis of dendritic polyaryl ethers

The first general single-step route to dendritic or cascade polyaryl ethers analogous to common linear polyaryl ethers is described. The sodium salts of four AB₂ monomers each containing a single phenolic hydroxyl group and two aryl fluorides activated toward nucleophilic substitution by carbonyl, sulphonyl, or tetrafluorophenyl moieties are shown to polymerize in hot N, N-dimethylacetamide. The products are high molecular weight polymers (7000 < M_n < 36000), have narrow polydispersities (1.50 < M_w/M_n < 4.50), and are highly soluble in organic solvents. The molecular weights of two of the polymers increase with monomer concentration. The polymers are thermally stable (500 °C under N₂) and have glass transition temperatures ranging from 135 to 231 °C.     

Recent advances in macromolecular engineering via ionic methods

Selected recent developments in the field of macromolecular engineering via ionic methods are presented: ω-functional polymers and macromonomers, ampholytic block copolymers and novel thermoplastic block copolymers, star shaped macromolecules of several kinds. Attention is called upon the absolute necessity of adequately characterizing the samples obtained, in order to check wether their structure meets with expectation.     

Crystal engineering of binary metal imidazolate and triazolate frameworks

This article summarizes the recent advances in the crystal growth, structural control strategies and diverse structures of the binary metal imidazolate and triazolate frameworks, which are the simplest systems for crystal engineering of two-, three- and four-connected coordination polymers.     

Developments in inorganic crystal engineering

The design and synthesis of crystalline materials through the self-assembly of molecular building blocks and the pursuit of functional materials based upon this approach are usually classified under the banner Crystal Engineering. The field is interdisciplinary in nature involving synthetic, materials, structural and theoretical chemists. There are strong ties to modern crystallography which can offer rapid and accurate structure determination and, in particular, insight into molecular and intermolecular geometries. Illustrative examples that chart the development field and provide an assessment of the current state of the art will be reviewed with an emphasis on inorganic chemistry. Broadly speaking, two classes of compounds will be discussed: those based upon molecules or ions linked into networks via noncovalent interactions and those (coordination polymers) in which metal centres are linked using coordination bonds through bridging ligands into extended networks.     

Molecular engineering of photoactive liquid crystalline polyester epoxies containing benzylidene moiety

A series of photoactive liquid crystalline polyester epoxies incorporating bisbenzylidene segments as photoactive mesogenic cores were synthesized by polyaddition of diepoxy monomers and terephthalic acid/trimesic acid. To investigate the influence of structural parameters such as, molecular architecture, structural rigidity of mesogenic unit and substituents on thermal, mesogenic, and photoactive properties, the bisbenzylidene segment was incorporated into one acyclic and two cycloalkanone units with two and four substituents, respectively in both linear and hyperbranched architectures. Degree of branching of hyperbranched polymers was found to be in the range of 0.49–0.62. All polymers exhibited nematic mesophase (nematic droplets). Photo induced (2π + 2π) cycloaddition reaction, upon exposure to light at 365 nm, was examined. Inter molecular photocycloaddition was confirmed by photoviscosity measurement of UV irradiated polymer solutions. Faster photo induced reactivity of polymers in hyperbranched architecture was observed when compared to linear structure. Acyclic units facilitated photocycloaddition, and five‐membered ring showed higher photoactivity compared to six‐membered ring. The steric hindrance caused by substituents decreased the photoactivity of polymers. Refractive index change was found to be in the range of 0.015–0.024. Substantial variation of refractive index indicates that these polymers could be used for optical recording. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7637–7655, 2008     

Polypeptoids: A perfect match for molecular definition and macromolecular engineering?

Precision synthesis of polymers has been a hot topic in recent years. While this is notoriously difficult to address for polymers with a C? C backbone, Merrifield has discovered a way many decades ago for polypeptides. Using a similar approach, N‐substituted polypeptides, so‐called polypeptoids have been synthesized and studied for about 20 years. In contrast, the living ring‐opening polymerization (ROP) of N‐substituted N‐carboxyanhydrides was among the first living polymerizations to be discovered. More recently, a surge in new synthetic approaches led to the efficient synthesis of cyclic or linear multiblock copolypeptoids. Thus, polypeptoids can be synthesized either by solid phase synthesis to yield complex and exactly defined oligo‐ and small polymers or by ROP of appropriately N‐substituted N‐carboxyanhydrides (NNCA) to give linear, cyclic, or star‐like polymers. Together with an excellent biocompatibility, this polymer family may have a bright future ahead as biomaterials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2731–2752     

Band‐gap engineering of polythiophenes via dithienophosphole doping

A series of polythiophenes doped with dithieno[3,2‐b:2′,3′‐d]phosphole units at varying levels (0–17%) were synthesized and characterized. Polymer work up provided two series of polymers from chloroform (C) and hexanes (H) for each doping level, respectively. Systematic structure–property studies revealed that the C‐series polymers generally had higher molecular weights than the H‐series, but also slightly higher relative dithienophosphole concentrations, both having a significant impact on the photophysical and electrochemical properties of the polymers. Furthermore, the presence of the dithienophosphole units also stabilizes the LUMO levels, whereas the HOMO levels remain dominated by the thiophene units, resulting in desirable electronics for an interaction with acceptor materials, such as 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl[6,6]C₆₁. Importantly, increasing amount of dithienophosphole doping results in increased conductivities for the polymers in their oxidized state, while concurrently significantly stabilizing the neutral polythiophenes toward oxidation under environmental conditions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Macromolecular engineering by controlled/living ionic and radical polymerizations

Various methods for the synthesis of well‐defined (co)polymers with controlled dimension, polydispersity, topology, composition and functionality are discussed. They include controlled/living vinyl polymerization using anionic, cationic and radical intermediates being in equilibria with dormant species. Special emphasis is placed on the radical polymerization and on the needs for the comprehensive structure property correlation.     

Macromonomers as well-defined building blocks in macromolecular engineering

The present work compares the efficiency of different polymerization methods to design well-defined comb-shaped structures based on macro monomers. Anionic polymerization remains the method of choice and allows the control of polymerization degree of the main chain and the length of the grafts. The presence of an active chain end on the backbone enabled the synthesis of a new type of hyperbranched polymers by reaction with appropriate low molar multifunctional compounds. Free radical polymerization is less efficient for the controlled homopolymerization of macromonomers but less sensitive to the presence of impurities. It requires in most cases long fractionation procedures to access well defined comb-shaped fractions characterized by high molar masses. The controlled free radical polymerization constitutes an interesting alternative. The homopolymerization of macromonomers with late transition metal catalysts was also examined and comb-shaped polymers characterized by a syndiotactic backbone and atactic grafts could be obtained.     

Crystal engineering of coordination polymers using 4,4'-bipyridine as a bond between transition metal atoms

Coordination polymers have attracted an enormous interest among chemists due to their novel physical and chemical properties. This review describes the role of 4,4'-bipyridine in discovering various coordination polymers with novel topologies that range from one-dimensional to three dimensional. The geometries of coordination polymers of bipy include linear, zigzag, four-fold helices, molecular antenna, ladder, railroad, double, triple and quadruple chains, bilayer, square and rectangular grid, honeycomb layers, Lincoln Logs, 3D frames, diamondoid, 4(2) x 8(2) and cubic networks.     

Pore surface engineering of microporous coordination polymers

Pore surface control of microporous coordination polymers is of great interest due to the potentially exciting functionalities it presents, such as highly selective separation, chemisorption, and novel catalysts and sensors. A discussion of our unique strategy aimed at surface engineering using metalloligands, i.e., introduction of coordinatively unsaturated metal centers, is presented.     

Noncovalent cell surface engineering: incorporation of bioactive synthetic glycopolymers into cellular membranes

The controlled addition of structurally defined components to live cell membranes can facilitate the molecular level analysis of cell surface phenomena. Here we demonstrate that cell surfaces can be engineered to display synthetic bioactive polymers at defined densities by exogenous membrane insertion. The polymers were designed to mimic native cell-surface mucin glycoproteins, which are defined by their dense glycosylation patterns and rod-like structures. End-functionalization with a hydrophobic anchor permitted incorporation into the membranes of live cultured cells. We probed the dynamic behavior of cell-bound glycopolymers bearing various hydrophobic anchors and glycan structures using fluorescence correlation spectroscopy (FCS). Their diffusion properties mirrored those of many natural membrane-associated biomolecules. Furthermore, the membrane-bound glycopolymers were internalized into early endosomes similarly to endogenous membrane components and were capable of specific interactions with protein receptors. This system provides a platform to study cell-surface phenomena with a degree of chemical control that cannot be achieved using conventional biological tools.     

Novel photopolymerizable biodegradable triblock polymers for tissue engineering scaffolds: synthesis and characterization

For use in micro-patterned scaffolds in tissue engineering, novel diacrylated triblock macromers (PLA-b-PCL-b-PLA, PGA-b-PCL-b-PGA and PCL-b-PEO-b-PCL) were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). All diacrylated polymers were designed as triblock copolymers and involved biodegradable blocks of relatively non-polar epsilon-caprolactone (CL) and polar monomers such as glycolide (GA), lactide (LA) or ethylene oxide (EO). All triblock polymers were prepared in molecular weights of a few kilo daltons via the anionic ring-opening polymerization (ROP) of the corresponding lactide, glycolide or caprolactone using stannous octoate [Sn(Oct)(2)] as catalyst. The polymers had low polydispersity indices, ranging from 1.23 to 1.56. Biodegradable polymeric networks were prepared with conversions of 72-84% via photopolymerization of the triblock diacrylated polymers with 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator. PLA-b-PCL-b-PLA copolymers crumbled easily and were not suitable for micro-patterning. PGA-b-PCL-b-PGA copolymers had higher water contact angles than PCL-b-PEO-b-PCL and were also cytocompatible with Fibroblasts 3T3.     

Quality assurance of recycled engineering plastics using blend technology

The automotive, electrical and electronic sectors account for over 12% of all plastics consumed. A large fraction of these polymers are engineering plastics representing a value considerably higher than that of commodity thermoplastics; hence, mechanical recycling including upgrading efforts appears economically attractive. This paper shows some methods of upgrading the property profile of ABS from dismantled automobiles using polymer blend technology. The results for blends of ABS with PC or PA are reported. The aim of blending of the waste materials is twofold: to reduce the number of plastic materials to be recycled in car dismantling plants, and to improve properties of the ABS scrap, which is the main engineering plastic in the waste stream from automobiles.