Maleimides are remarkably versatile functional groups, capable of participating in homo- and copolymerizations, Diels-Alder and (photo)cycloadditions, Michael additions, and other reactions. Their reactivity has afforded materials ranging from polyimides with high upper service temperatures to hydrogels for regenerative medicine applications. Moreover, maleimides have proven to be an enabling chemistry for pharmaceutical development and bioconjugation via straightforward modification of cysteine residues. To exert spatiotemporal control over reactions with maleimides, multiple approaches have been developed to photocage nucleophiles, dienes, and dipoles. Additionally, further substitution of the maleimide alkene (e.g., mono- and di-halo-, thio-, amino-, and methyl-maleimides, among other substituents) confers tunable reactivity and dynamicity, as well as responsive mechanical and optical properties. In this mini-review, we highlight the diverse functionality of maleimides, underscoring their notable impact in polymer science. This moiety and related heterocycles will play an important role in future innovations in chemistry, biomedical, and materials research.

Poly(N-isopropylacrylamide) PNIPAAm was polymerized with co-monomers containing a biphenyl moiety to create a unique thermoresponsive physically crosslinked system due to the presence of pi-pi interactions between the biphenyl moieties. The biphenyl monomers used were 2-phenylphenol monoacrylate (2PPMA) and 4-phenylphenol monoacrylate (4PPMA). These monomers were utilized to synthesize a set of polymers with biphenyl monomer (2PPMA/4PPMA) content from 2.5 to 7.5 mole percent and with initiator concentrations from 0.1 and 1.0 weight percent. The resulting polymers were characterized by various techniques, such as gel permeation chromatography (GPC), swelling studies and mechanical testing. The decrease in the average molecular weight of the polymers due to the increase in the concentration of initiator was confirmed by GPC results. Swelling studies confirmed the expected temperature dependent swelling properties and explored the impact of the biphenyl comonomers. These studies indicated that with the increase in biphenyl comonomers, the physical crosslinking increases which leads to decrease in the swelling ratio. The results from the mechanical tests also depict the effect of the concentration of biphenyl comonomers. These physically crosslinked polymeric systems with their unique properties have potential applications spanning environmental remediation/sensing, biomedicine, etc.

Owing to the high water content, porous structure, biocompatibility and tissue-like viscoelasticity, hydrogels have become attractive and promising biomaterials for use in drug delivery, 3D cell culture and tissue engineering applications. Various chemical approaches have been developed for hydrogel synthesis using monomers or polymers carrying reactive functional groups. For tissue repair and cell culture purposes, it is desirable that the crosslinking reactions occur under mild conditions, do not interfere with biological processes and proceed at high yield with exceptional selectivity. Additionally, the cross-linking reaction should allow straightforward incorporation of bioactive motifs or signaling molecules, at the same time, providing tunability of the hydrogel microstructure, mechanical properties, and degradation rates. In this review, we discuss various chemical approaches applied to the synthesis of complex hydrogel networks, highlighting recent developments from our group. The discovery of new chemistries and novel materials fabrication methods will lead to the development of the next generation biomimetic hydrogels with complex structures and diverse functionalities. These materials will likely facilitate the construction of engineered tissue models that may bridge the gap between 2D experiments and animal studies, providing preliminary insight prior to assessments.

Blends of poliglecaprone (PGC) and polycaprolactone (PCL) of varying compositions were electrospun into tubular conduits and their mechanical, morphological, thermal and degradation properties were evaluated under simulated physiological conditions. Generally, mechanical strength, modulus and hydrophilic nature were enhanced by the addition of PGC to PCL. An degradation study in phosphate-buffered saline (pH 7.3) was carried out for up to 1 month to understand the hydrolytic degradation effect on the mechanical properties in both the longitudinal and circumferential directions. Pure PCL and 4:1 PCL/PGC blend scaffolds exhibited considerable elastic stiffening after a 1 month degradation. Fourier transform infrared spectroscopic and DSC techniques were used to understand the degradation behavior and the changes in structure and crystallinity of the polymeric blends. A 3:1 PCL/PGC blend was concluded to be a judicious blend composition for tubular grafts based on overall results on the mechanical properties and performance after a 1 month degradation study.

Due to the increasing demand to generate thick and vascularized tissue engineered constructs, novel strategies are currently being developed. An emerging example is the generation of oxygen-releasing biomaterials to tackle mass transport and diffusion limitations within engineered tissue-like constructs. Biomaterials containing oxygen releasing molecules can be fabricated in various forms such as, hybrid thin films, microparticles, or three dimensional (3D) scaffolds. In this perspective, we will summarize various oxygen-releasing reagents and their potential applications in regenerative engineering. Moreover, we will review the main approaches to fabricate oxygen-releasing biomaterials for a range of tissue engineering applications.

To investigate the delivery of hydrophobic therapeutic agents, a new class of polymer carriers was synthesized. These carriers are composed of two components: (i) a pH-responsive hydrogel composed of methacrylic acid grafted with poly(ethylene glycol) tethers, P(MAA-g-EG), and (ii) hydrophobic poly(methyl methacrylate) (PMMA) nanoparticles. Before the P(MAA-g-EG) hydrogel was crosslinked, PMMA nanoparticles were added to the solution and upon exposure to UV light they were photoencapsulated throughout the P(MAA-g-EG) hydrogel structure. The pH-responsive behavior of P(MAA-g-EG) is capable of triggered release of a loaded therapeutic agent, such as a low molecular weight drug or protein, when it passes from the stomach (low pH) to upper small intestine (neutral pH). The introduction of PMMA nanoparticles into the hydrogel structure affected the swelling behavior, therapeutic agent loading efficiency, and solute release profiles. In equilibrium swelling conditions the swelling ratio of nanoparticle-containing hydrogels decreased with increasing nanoparticle content. Loading efficiencies of the model therapeutic agent fluorescein ranged from 38 - 51 % and increased with increasing hydrophobic content. Release studies from neat P(MAA-g-EG) and the ensuing P(MAA-g-EG) hydrogels containing nanoparticles indicated that the transition from low pH (2.0) to neutral pH (7.0) triggered fluorescein release. Maximum fluorescein release depended on the structure and hydrophobicity of the carriers used in these studies.

The synthesis of polyaniline (PANI) nanospheres by a simple template-free method has been described. The polymerization of aniline in aqueous medium was accomplished using ammonium persulfate without any protonic acid. The UV-vis spectrum of PANI nanospheres displayed the characteristic absorption peak of π-π* transition of the benzenoid ring at 355 nm. The oxidation state of PANI nanospheres was identified with FT-IR spectroscopy by comparing the two bands at 1582 (ring stretching in quinoid unit) and 1498 cm(-1) (ring stretching in bezenoid unit). The X-ray diffraction patterns demonstrated the low crystalline nature of PANI nanospheres. The morphology of PANI nanospheres was spherical and the mean diameter of nanospheres was found in the range of 3-12 nm. The thermal behavior of PANI nanospheres was studied by thermogravimetric analysis. The effect of doping of HCl and H(2)SO(4) on PANI nanospheres was studied by measuring the current as a function of time of exposure. The high electrical conductivity of 6×10(-2) S cm(-1) was obtained for PANI nanospheres at their optimum doping state by 100 ppm HCl.

Organic electronic devices have demonstrated tremendous versatility in a wide range of applications including consumer electronics, photovoltaics, and biotechnology. The traditional interface of organic electronics with biology, biotechnology, and medicine occurs in the general field of sensing biological phenomena. For example, the fabrication of hybrid electronic structures using both organic semiconductors and bioactive molecules has led to enhancements in sensitivity and specificity within biosensing platforms, which in turn has a potentially wide range of clinical applications. However, the interface of biomolecules and organic semiconductors has also recently explored the potential use of natural and synthetic biomaterials as structural components of electronic devices. The fabrication of electronically active systems using biomaterials-based components has the potential to realize a large set of unique devices including environmentally biodegradable systems and bioresorbable temporary medical devices. This article reviews recent advances in the implementation of biomaterials as structural components in organic electronic devices with a focus on potential applications in biotechnology and medicine.

This mini review highlights issues associated with the use of dendrimers as drug delivery vehicles. The review introduces dendrimers and summarizes findings on their use in vivo and in vitro. Specifically, this review is limited to examples wherein the drug is non-covalently associated with the dendrimer. Examples wherein the drug is covalently attached to the dendrimer are not discussed.

The objective of this study was to elucidate the effect of chemical structure and composition of the polymer matrix on the degree of vinyl conversion (DC) of copolymers (unfilled resins) and their amorphous calcium phosphate (ACP) composites attained upon photo-polymerization. The DC can also be an indicator of the relative potential of these polymeric materials to leach out into the oral environment un-reacted monomers that could adversely affect their biocompatibility. The following resins were examined: 1) 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (1:1 mass ratio; BT resin) combined with hydroxyethyl methacrylate (HEMA; BTH resin) and with HEMA and zirconyl dimethacrylate (BTHZ resin), 2) urethane dimethacrylate (UDMA)/HEMA resins, and 3) pyromellitic glycerol dimethacrylate (PMGDMA)/TEGDMA (PT resin). To make composite specimens, resins were mixed with a mass fraction of 40 % zirconia-hybridized ACP. Copolymers and their composites were evaluated by near infra-red spectroscopy for DC after 1 d and 28 d post-cure at 23 °C. Inclusion of HEMA into the BT and UDMA resins yielded copolymers and composites with the highest DCs. The significantly lower DCs of PT copolymers and their composites are attributed to the rigid aromatic core structure, tetra-vinyl functionality and limited methacrylate side-chain flexibility of the surface-active PMGDMA monomer. There was, however, an increase in the 28 d DC for the PT materials as there was for the BTHZ system. Surprisingly, the usual decrease observed in DC in going from unfilled polymer to composite was reversed for the PT system.