Rapidly self-deoxygenating controlled radical polymerization in water via in situ disproportionation of Cu(i)

Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(I)/Me6Tren in water towards Cu(II) and highly reactive Cu(0) leads to O2-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O2-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail

Dual-functional materials via CCTP and selective orthogonal thiol-Michael addition/epoxide ring opening reactions

Poly(glycidyl methacrylate) (PGMA) has been synthesised by cobalt catalysed chain transfer polymerisation (CCTP) yielding, in one step, polymers with two points for post polymerisation functionalisation; the activated terminal vinyl bond and in chain epoxide groups. Epoxide ring-opening and a combination of thiol-Michael addition and epoxide ring-opening has been used for the post-functionalisation with amines and thiols to prepare a range of functional materials

A detailed study on understanding glycopolymer library and Con A interactions

Synthetic glycopolymers are important natural oligosaccharides mimics for many biological applications. To develop glycopolymeric drugs and therapeutic agents, factors that control the receptor-ligand interaction need to be investigated. A library of well-defined glycopolymers has been prepared by the combination of copper mediated living radical polymerization and CuAAC click reaction via post-functionalization of alkyne-containing precursor polymers with different sugar azides. Employing Concanavalin A as the model receptor, we explored the influence of the nature and densities of different sugars residues (mannose, galactose, and glucose) on the stoichiometry of the cluster, the rate of the cluster formation, the inhibitory potency of the glycopolymers, and the stability of the turbidity through quantitative precipitation assays, turbidimetry assays, inhibitory potency assays, and reversal aggregation assays. The diversities of binding properties contributed by different clustering parameters will make it possible to define the structures of the multivalent ligands and densities of binding epitopes tailor-made for specific functions in the lectin-ligand interaction. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2588–259

α-aldehyde terminally functional methacrylic polymers from living radical polymerization : application in protein conjugation “pegylation”

Application of proteins and peptides as human therapeutics is expanding rapidly as drug discovery becomes more prevalent. Conjugation of polymers to proteins can circumvent many problems and pegylation of proteins is now emerging as acceptable practice. This paper describes the synthesis of α-aldehyde-terminated poly(methoxyPEG)methacrylates from Cu(I) mediated living radical polymerization (Mn = 11 000, 22 000 and 32 000; PDi < 1.15), and their efficient conjugation to lysozyme, as a model protein. This offers an attractive and flexible alternative to linear poly(ethylene glycol) opening up the possibility of using the full power of living radical polymerization

Defect-related luminescent nanostructured hydroxyapatite promotes mineralization through both intracellular and extracellular pathways

Hydroxyapatite (HAP) is a widely used biomaterial for bone tissue substitution due to its chemical similarity with the natural bone. Defect-related luminescent HAP materials have the same chemical composition as normal HAP and excellent biocompatibility. However, only few works have focused on the defect-related luminescent HAP materials on bone regeneration. In this work, we systematically investigated the bone regeneration pathway induced by nanostructured particles using defect-related luminescent hydroxyapatite (S2) materials. We monitored the subcellular distribution and location of S2 during osteoblast differentiation with the property of defect-related luminescence. Nano-scale S2 could be internalized by osteoblasts (OBs) via caveolae-mediated endocytosis and macropinocytosis. S2 incorporated into the lysosomes dissolved and released calcium ions for the formation of mineralized nodules. Extracellular S2 also promoted bone regeneration as a nucleation site. Taken together, the physical properties of hydroxyapatite control the bone regeneration pathway in osteoblasts

Aqueous copper(II) photoinduced polymerization of acrylates : low copper concentration and the importance of sodium halide salts

Photoinduced metal mediated radical polymerization is a rapidly developing technique which allows for the synthesis of macromolecules with defined molecular weight and narrow molecular weight distributions, although typically exhibiting significant limitations in aqueous media. Herein we demonstrate that the presence of alkali metal halide salts in conjunction with low copper concentration and UV irradiation, allows for the controlled polymerization of water soluble acrylates in aqueous media, yielding narrow molecular weight distributions and high conversions. Despite the aqueous environment which typically compromises polymer end group fidelity, chain extensions have also been successfully performed and different degrees of polymerization were targeted. Importantly, no conversion was observed in the absence of UV light and the polymerization could be switched “on” and “off” upon demand as demonstrated by intermittent light and dark periods and thus allowing access to spatiotemporal control

Combining uretdione and disulfide reversibly degradable polyurethanes : route to alternating block copolymers

Uretdione (temperature and catalyst controlled) and disulphide (REDOX controlled) functionalised polyurethanes have been described and the reversibility of these bonds tested. The polymers have been synthesised with reversible covalent groups present throughout their backbone, developing routes to reversibly degradable polyurethanes. These materials degrade and reheal in response to different external stimuli, which supplies a proof of concept for controlling the molecular weight, and therefore, the physical properties of a polyurethane. Further, a unique route to an alternating block copolymer is also discussed that utilises a mixture of disulphide and uretdione functionalised polymers as the reagents to form a thiourethane. The dramatically reduced safety hazards of dealing with the functionalised polymers, in comparison to the free isocyanate and thiols, could be of great interest to industrial application for current drives towards safer routes to polyurethanes

Transdermal delivery of ibuprofen utilizing a novel solvent free pressure sensitive adhesive (PSA) : TEPI® technology

Purpose The main objective of this present study was the investigation of potential novel transdermal patch technology (TEPI®) delivering ibuprofen as the active pharmaceutical ingredient (API) using a novel poly(ether-urethane)-silicone crosslinked pressure-sensitive adhesive (PSA) as the drug reservoir in a solvent-free manufacturing process. Methods The patch was synthesized utilizing the hot-melt crosslinking technique without the addition of solvents at 80 °C in 100% relative humidity. Dissolution and permeation studies performed utilizing diffusion cells and subsequently HPLC validated methods were employed to determine the API content in the acceptor solution. Accelerated stability studies were also performed at 40 °C and 70% relative humidity. The adhesive performance of the fabricated patch was evaluated utilizing loop tack adhesion tests. Results In vitro permeation experiments across both Strat-M® and human skin demonstrated that ibuprofen can easily be released from the adhesive matrix and penetrate through the studied membrane. A comparison on the permeation rates of the API across the two membranes indicated that there is not a strong correlation between the obtained data. The presence of chemical enhancers facilitated an increased flux of the API higher than observed in the basic formulation. Initial stability studies of the optimized formulation showed no degradation with respect to the drug content. Adhesion studies were also performed indicating higher values when compared with commercially available products. Conclusions The present study demonstrated the fabrication of an ibuprofen patch utilizing a versatile, solvent-free drug delivery platform. Upon optimization of the final system, the resulting patch offers many advantages compared to commercially available formulations including high drug loading (up to 25 wt%), good adhesion, and painless removal leaving no residues on the skin. This PSA offers many advantages over existing adhesive technology

Functionalization of BaTiO3 nanoparticles with electron insulating and conducting organophosphazene-based hybrid materials

Novel core–shell structured organophosphazene (OPZ) coated BaTiO3 nanoparticles (OPZ@BaTiO3) were produced via a facile and rapid one-step nucleophilic substitution reaction in ambient conditions. The morphology, structure and textural properties of the core–shell nanoparticles were analysed via electron microscopy, spectroscopy, thermogravimetry and porosimetry, and the dielectric properties were evaluated by impedance spectroscopy. The thickness of the cross-linked OPZ shell was readily tailored by varying the weight ratio of the OPZ monomers to BaTiO3, which in turn affected the relative permittivity and the frequency dependence of the OPZ/BaTiO3 particles. A subsequent carbonisation treatment of the OPZ@BaTiO3 at 700 °C transformed the polymeric OPZ shell to a microporous carbonaceous shell, which dramatically increased the electrical conductivity of the particles. Organophosphazene chemistry offers a facile route to functionalise BaTiO3 nanoparticles without any pre-treatment, and generate a range of core–shell BaTiO3 nanoparticles with tailored dielectric and electrically conductive properties that can be used as active fillers for polymer based nanocomposites and energy storage applications. The effectiveness and advantages of OPZ chemistry over other reported methods in forming core–shell particles are demonstrated