Synthesis and Characterization of New Antibacterial Fluoride-Releasing Monomer and Dental Composite.

A new dimethacrylate chelating monomer containing a BisGMA-like backbone structure and a bis(carboxymethyl)-L-lysine chelating group and its ternary zirconium-fluoride complex (antibacterial fluoride-releasing monomer) have been synthesized. The monomer structures were confirmed by (1)H-NMR, (13)C-NMR, and ES-MS analysis. Several experimental fluoride-releasing dental composites containing different quantities of the new antibacterial fluoride-releasing monomer were formulated and tested for fluoride release, fluoride recharge, compressive and flexural strengths, water sorption and solubility. These composites displayed high fluoride release and recharge capabilities, as well as good physical and mechanical properties.

Homocystamides promote free-radical and oxidative damage to proteins.

Elevated levels of homocysteine are associated with several major diseases. However, it is not clear whether homocysteine is a marker or a causative agent. The majority (ca. 80%) of the homocysteine present in humans is protein bound. The study of the posttranslational modification of proteins by homocysteine and its cyclic congener, homocysteine thiolactone, is emerging as an area of great current interest for unraveling the ongoing "mediator/marker controversy" [Jacobsen DW (2009) Clin Chem 55:1-2]. Interestingly, many of the pathologies associated with homocysteine are also linked to oxidative stress. In the current study, chemical evidence for a causal relationship between homocysteine-bound proteins and oxidative damage is presented. For example, a reproducible increase in protein carbonyl functionality occurs as a consequence of the reaction of human serum albumin with homocysteine thiolactone. This occurs at physiological temperature upon exposure to air without any added oxidants or free-radical initiators. Alpha-amino acid carbon-centered radicals, well-known precursors of protein carbonyls, are shown to form via a hydrogen atom transfer process involving thiolactone-derived homocystamides. Model peptides in buffer as well as native proteins in human blood plasma additionally exhibit properties in keeping with the homocystamide-facilitated hydrogen atom transfer and resultant carbon-centered radicals.

Stereochemical and regiochemical trends in the selective detection of saccharides.

Several discreet sugar-boronate complexes exist in solution. This is due to the complex equilibria between isomeric species of even the simplest monosaccharides. In the current investigation, we determine the regio- and stereochemical features of the various equilibrating sugar isomers that induce signal transduction in boronic acid chemosensors such as 1 as well as 2 and 3. We present a unique example of a chemosensor (1) that is selective for ribose, adenosine, nucleotides, nucleosides, and congeners. As a result of this study, we are able to predict and achieve selective fluorescence and colorimetric responses to specific disaccharides as a consequence of their terminal sugar residue linkage patterns and configurations. We also find that the combined use of chemosensors exhibiting complementary reactivities may be used cooperatively to obtain enhanced selectivity for ribose and rare saccharides.