Photodegradation Kinetics and Solvent Effect of New Brominated Flame Retardants (NBFRS) in Liquid Medium.

The photolysis of four typical NBFRs, hexabromobenzene (HBB), pentabromotoluene (PBT), pentabromobenzyl acrylateare (PBBA) and pentabromoethylbenzene (PBEB), were explored under different irradiation light wavelengths, initial concentrations and organic solvents. Density functional theory was used for chemical calculation to explore the internal mechanism of solvent effect. All degradation kinetics conformed to the first-order kinetic model. Under different irradiation light wavelengths, the degradation rates were in the following order: 180~400 nm (0.1702~0.3008 min-1) > 334~365 nm (0.0265~0.0433 min-1) > 400~700 nm (0.0058~0.0099 min-1). When the initial concentration varied from 0.25 mg/L to 1 mg/L, the degradation rate decreased from 0.0379~0.0784 min-1 to 0.0265~0.0433 min-1 under 334~365 nm irradiation, which might be attributed to the reduction in light energy received per unit area and competition from intermediate metabolites. In different organic solvents, the degradation rates were in the order of acetone (0.1702~0.3008 min-1) > toluene (0.0408~0.0534 min-1) > n-hexane (0.0124~0.0299 min-1). Quantum chemical calculation and analysis showed that the energy change in electron transfer between solvent and NBFRs was the key factor to solvent effect in the degradation of NBFRs. The active sites and degradation pathways of NBFRs were also speculated, the nucleophilic reaction of the Br atom on a benzene ring was the main process of photodegradation and it was preferential to remove the bromine and then the ethyl group on the benzene ring. Our research will be helpful in predicting and evaluating their photochemical behavior in different environment conditions.

Amelogenin "nanorods" formation during proteolysis by Mmp-20.

Amelogenin is cleaved by enamelysin (Mmp-20) soon after its secretion, and the cleavage products accumulate in specific locations during enamel formation, suggesting that parent amelogenin proteolysis is necessary for activating its functions. To investigate the precise roles of Mmp-20 and its influence on the assembly of amelogenin, an in vitro enzymatic digestion process mimicking the initial stages of amelogenin proteolysis was investigated at near-physiological conditions using recombinant porcine amelogenin (rP172) and enamelysin. Hierarchically organized nanorod structures formed during different digestion stages were detected by TEM. At the earliest stage, uniformly dispersed parent amelogenin spherical particles, mixed with some darker stained smaller spheres, and accompanying elongated chain-like nanostructures were observed. Cylindrical nanorods, which appeared to be the result of tight assembly of thin subunit cylindrical discs with thicknesses ranging from ∼2.5 to ∼6.0nm, were formed after an hour of proteolysis. These subunit building blocks stacked to form nanorods with maximum length of ∼100nm. With the production of more cleavage products, additional morphologies spontaneously evolved from the cylindrical nanorods. Larger ball-like aggregates ultimately formed at the end of proteolysis. The uniform spherical particles, nanorods, morphological patterns evolved from nanorods, and globular aggregated microstructures were successively formed by means of co-assembly of amelogenin and its cleavage products during a comparatively slow proteolysis process. We propose that, following the C-terminal cleavage of amelogenin, co-assembly with its fragments leads to formation of nanorod structures whose properties eventually dictate the super-structural organization of enamel matrix, controlling the elongated growth of enamel apatite crystals.