The traditional infrared spectroscopic methods for assessing the degree of polymerization of dental monomers are often hampered by the difficulties of sample preparation and, in the case of composites, by interference from the filler component. These difficulties may be circumvented by the use of another technique, differential scanning calorimetry (DSC). In this preliminary investigation, DSC was used to ascertain the degree of vinyl polymerization of an experimental monomer system consisting of seven parts BIS-GMA and three parts TEGDMA (triethylene glycol dimethacrylate). Thermally-activated polymerizations of this monomer system were studied using benzoyl peroxide (BP) as the initiator. Both the heating rate and the concentration of BP affected the percent of reacted vinyl groups. For a BP concentration of 0.39% and heating rates of 10 degrees/min and 2.5 degrees/min, conversions were 73 and 38%, respectively. Chemically-activated polymerizations using BP and fast-acting amine accelerators (e.g., p-t-butyl-N,N-dimethylaniline) gave approximately the same results (e.g., 50% conversion) as those obtained with slower-acting promoters (e.g., ascorbyl palmitate). Experimental difficulties are encountered in observing an exotherm with the very reactive accelerators unless the other parameters (e.g., BP or inhibitor content) involved in the reaction are adjusted accordingly. As a method for evaluating the performance of various dental monomers, initiator systems, and inhibitors, DSC has great potential utility.
Dental composite restorations have been examined using a silver staining method to elucidate in vivo wear mechanisms. Emphasis was placed on examination of material immediately beneath the wearing surfaces. Several in vitro tests were also investigated for their ability to generate in vivo-like surface defects. For all the clinically worn composite restorations, a porous layer has been observed beneath those surfaces exposed to the oral environment. A laboratory test using certain substances to simulate the oral environmental effects can reproduce this porous layer. These results suggest that the in vivo wear process of dental composites is one accelerated by environmental softening of the composites.
The toxicity of and resistance to platinum complexes as cisplatin, oxaliplatin or carboplatin calls for the replacement of these therapeutic agents in clinical settings. We have previously identified a set of half sandwich-type osmium, ruthenium and iridium complexes with bidentate glycosyl heterocyclic ligands exerting specific cytostatic activity on cancer cells but not on non-transformed primary cells. The apolar nature of the complexes, conferred by large, apolar benzoyl protective groups on the hydroxyl groups of the carbohydrate moiety, was the main molecular feature to induce cytostasis. We exchanged the benzoyl protective groups to straight chain alkanoyl groups with varying length (3 to 7 carbon units) that increased the IC50 value as compared to the benzoyl-protected complexes and rendered the complexes toxic. These results suggest a need for aromatic groups in the molecule. The pyridine moiety of the bidentate ligand was exchanged for a quinoline group to enlarge the apolar surface of the molecule. This modification decreased the IC50 value of the complexes. The complexes containing [(η6-p-cymene)Ru(II)], [(η6-p-cymene)Os(II)] or [(η5-Cp*)Ir(III)] were biologically active unlike the complex containing [(η5-Cp*)Rh(III)]. The complexes with cytostatic activity were active on ovarian cancer (A2780, ID8), pancreatic adenocarcinoma (Capan2), sarcoma (Saos) and lymphoma cell lines (L428), but not on primary dermal fibroblasts and their activity was dependent on reactive oxygen species production. Importantly, these complexes were cytostatic on cisplatin-resistant A2780 ovarian cancer cells with similar IC50 values as on cisplatin-sensitive A2780 cells. In addition, the quinoline-containing Ru and Os complexes and the short chain alkanoyl-modified complexes (C3 and C4) proved to be bacteriostatic in multiresistant Gram-positive Enterococcus and Staphylococcus aureus isolates. Hereby, we identified a set of complexes with submicromolar to low micromolar inhibitory constants against a wide range of cancer cells, including platinum resistant cells and against multiresistant Gram-positive bacteria.
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