No abstract

ABSTRACT:Previous studies have shown that the interaction of carboxylic acid groups with the amine functionalities of aryl amines, especially secondary and tertiary aryl amines, can lead to the free-radical polymerization of acrylic monomers such as methyl methacrylate. In this study, the Michael addition reaction of primary and secondary aryl amines with acrylic monomers such as acrylic acid (AA) was investigated. Equivalent amounts of either p-toluidine (PT) or N-phenylglycine (NPG) and AA were combined in polar solvents such as ethanol. The reactions were conducted at ambient (23ЊC) or near-ambient (37-60ЊC) temperatures. Samples (about 3-5 mg) of these products were then trimethylsilylated with a solution consisting of 0.4 mL of bis(trimethylsilyl)-trifluoroacetamide (BSTFA) and 0.4 mL of acetonitrile by heating for 30 min at 140ЊC under N 2 . These derivatives were characterized by gas chromatography-mass spectrometry (GC-MS). The GC-MS analyses suggest that 1 mol of the primary amine PT had reacted with 2 mol of AA to yield the expected N-p-tolyliminodipropionic acid. Similarly, the secondary amine NPG added to 1 mol of AA yielded the corresponding mixed iminodiacid, N-phenyliminoacetic-propionic acid. It would appear that the Michael reaction of primary and secondary amines with acrylic monomers may offer a general, facile synthetic route to a variety of tertiary amines. Aryl amino acids of the type synthesized in this study may find use in a number of dental applications, e.g., as surface-active adhesive agents and as polymerization initiators or activators.

Reactions of radiation-generated OH radicals with tyrosine and its homopeptides, i.e. L-Tyr-L-Tyr and L-Tyr-L-Tyr-L-Tyr, in N2O saturated solutions were shown to give crosslinks between the peptide chains with high yields. High-performance liquid chromatography, capillary gas chromatography and mass spectrometry were used for isolation and identification of the monomeric and dimeric products. Evidence is presented for the crosslinking to occur through C-C and C-O-C bonds. To the best of our knowledge, the formation of the ether type of crosslink is demonstrated for the first time. Mechanisms of product formation are also discussed, which involve radicals that were described in previous pulse radiolysis studies.

Mechanisms of formation of o-tyrosine (o-Tyr) and thymine glycol (TG), the two possible markers of OH radical generation in biosystems and in vivo are described. The o-Tyr measurements require invasive approaches, while TG detection may be accomplished by noninvasive analysis in the urine.

Energy deposition and cellular radiation effects arising from the interaction of single 218Po and 214Po alpha particles with basal and secretory cell nuclei were simulated for different target cell depths in the bronchial epithelium of human airway generations 2, 4, 6, and 10. To relate the random chord lengths of alpha particle tracks through spherical cell nuclei to the resulting biological endpoints, probabilities per unit track length for different cellular radiation effects as functions of LET were derived from in vitro experiments. The radiobiological data employed in the present study were inactivation and mutation (mutant frequency at the HPRT gene) in V79 Chinese hamster cells and inactivation and transformation in C3H 10T1/2 cells. Based on computed LET spectra and relative frequencies of target cells, probabilities for transformation, mutation, and cell killing in basal and secretory cells were computed for a lifetime exposure of 20 WLM. While predicted transformation probabilities were about two orders of magnitude higher than mutation probabilities, they were still about two orders of magnitude lower than inactivation probabilities. Furthermore transformation probabilities for basal cells are generally higher than those for secretory cells, and 214Po alpha particles are primarily responsible for transformations in bronchial target cells.