Following Sharpless' visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol-ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol-ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.

Thiol–Ene Click Chemistry

There have been a number of review papers on layered silicate and carbon nanotube reinforced polymer nanocomposites, in which the fillers have high aspect ratios. Particulate–polymer nanocomposites containing fillers with small aspect ratios are also an important class of polymer composites. However, they have been apparently overlooked. Thus, in this paper, detailed discussions on the effects of particle size, particle/matrix interface adhesion and particle loading on the stiffness, strength and toughness of such particulate–polymer composites are reviewed. To develop high performance particulate composites, it is necessary to have some basic understanding of the stiffening, strengthening and toughening mechanisms of these composites. A critical evaluation of published experimental results in comparison with theoretical models is given.

/pdf/effects-of-particle-size-particle-matrix-interface-adhesion-yv055zq7xi.pdf

Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites

This paper reviews the past, present, and future of the hydroxyapatite (HAp)-based biomaterials from the point of view of preparation of hard tissue replacement implants. Properties of the hard tissues are also described. The mechanical reliability of the pure HAp ceramics is low, therefore it cannot be used as artificial teeth or bones. For these reasons, various HAp-based composites have been fabricated, but only the HAp-coated titanium alloys have found wide application. Among the others, the microstructurally controlled HAp ceramics such as fibers/whiskers-reinforced HAp, fibrous HAp-reinforced polymers, or biomimetically fabricated HAp/collagen composites seem to be the most suitable ceramic materials for the future hard tissue replacement implants.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400042527

Processing and properties of hydroxyapatite-based biomaterials for use as hard tissue replacement implants

Background— The US Food and Drug Administration recently issued a warning of subacute thrombosis and hypersensitivity reactions to sirolimus-eluting stents (Cypher). The cause and incidence of these events have not been determined. Methods and Results— We present findings of a 58-year-old man who died of late stent thrombosis 18 months after receiving 2 Cypher stents for unstable angina. Although angiographic and intravascular ultrasound results at 8 months demonstrated the absence of neointimal formation, vessel enlargement was present. An autopsy showed aneurysmal dilation of the stented arterial segments with a severe localized hypersensitivity reaction consisting predominantly of T lymphocytes and eosinophils. Conclusions— The known pharmacokinetic elution profile of Cypher stents and the presence of polymer fragments surrounded by giant cells and eosinophils suggest that a reaction to the polymer may have caused late stent thrombosis. Careful long-term follow-up of patients with vessel enlargement af...

Localized Hypersensitivity and Late Coronary Thrombosis Secondary to a Sirolimus-Eluting Stent: Should We Be Cautious?

Biomedical applications of polymer-composite materials: a review

Polymerization shrinkage of methacrylate esters.

Water absorption characteristics of dental composites incorporating hydroxyapatite filler

Novel hydroxyapatite-based dental composites

The uptake of water by composite filling materials seems to be a diffusion-controlled process; the magnitudes of the diffusion coefficients obtained are consistent with the uptake base through the resin matrix. The diffusion coefficients measured show the diffusion coefficient to decrease with increasing water concentration, which accounts for the protracted nature of the attainment of equilibrium uptake. Diffusion coefficients are generally lower in these composites based on difunctional methacrylates, compared with methyl methacrylate, presumably because of the highly cross-linked nature of the former.

Michael Braden

Papers

Polymerization shrinkage of methacrylate esters.

Water absorption characteristics of dental composites incorporating hydroxyapatite filler

Novel hydroxyapatite-based dental composites

Diffusion of Water in Composite Filling Materials

Water absorption characteristics of dental microfine composite filling materials. I. Proprietary materials.