Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases.

Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H(2) have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P(2)(Ph)N(2)(Ph))(2)(CH(3)CN)](BF(4))(2), 3a (where P(2)(Ph)N(2)(Ph) is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane), permits a limiting value of the H(2) production rate to be determined. The turnover frequency of 350 s(-1) establishes that the rate of H(2) production for the mononuclear nickel catalyst 3a is comparable to those observed for Ni-Fe hydrogenase enzymes. In the electrochemical oxidation of hydrogen catalyzed by [Ni(P(2)(Cy)N(2)(Bz))(2)](BF(4))(2), 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (K(eq) = 190 atm(-1) at 25 degrees C). The hydrogen addition product exists as three nearly isoenergetic isomers 4A-4C, which have been identified by a combination of one- and two-dimensional (1)H, (31)P, and (15)N NMR spectroscopies as Ni(0) complexes with a protonated amine in each cyclic ligand. The nature of the isomers, together with calculations, suggests a mode of hydrogen activation that involves a symmetrical interaction of a nickel dihydrogen ligand with two amine bases in the diphosphine ligands. Single deprotonation of 4 by an external base results in a rearrangement to [HNi(P(2)(Cy)N(2)(Bz))(2)](BF(4)), 5, and this reaction is reversed by the addition of a proton to the nickel hydride complex. The small energy differences associated with significantly different distributions in electron density and protons within these molecules may contribute to their high catalytic activity.

Alveolar bone height and postcranial bone mineral density: negative effects of cigarette smoking and parity.

BACKGROUND: Our objective was to test the association between cemento-enamel junction, alveolar-crest distance (CEJ-AC, as measured on digitized vertical bite-wing radiographs) and postcranial bone mineral density (BMD) relative to clinical, dietary, and demographic variables. METHODS: Data were collected in a cross-sectional study of 134 postmenopausal women. CEJ-AC distances were determined from digitized vertical bite-wing radiographs. Lumbar spine and proximal femur BMDs were determined from dual-energy x-ray absorptiometric scans. Correlation analysis and Student t tests were used to identify those variables most associated with CEJ-AC distance. The selected variables were modeled with a backward stepwise regression analysis, with CEJ-AC distance as the dependent variable. RESULTS: Parity (number of pregnancies to term), cigarette smoking, and the interaction of lateral spine BMD with cigarette smoking were independent predictors of CEJ-AC distance (P < or =0.05). Statistical models containing these variables accounted for 19% of the variation in CEJ-AC distances. CONCLUSIONS: CEJ-AC distance in postmenopausal women is the result of a complicated interaction of many effects, including but not limited to, parity, cigarette smoking, and skeletal BMD.

Attachment loss with postmenopausal age and smoking.

To determine whether postmenopausal bone loss and factors associated with osteoporosis affect tooth retention, we examined vertebral and proximal femoral (postcranial) bone mineral density in relation to tooth loss and attachment loss in a cross-sectional study of 135 postmenopausal women (age range 41-70 yr). Women had at least 10 teeth and no evidence of moderate or severe periodontal disease. Full-mouth attachment loss measurements were made using a pressure-sensitive probe, and bone density was determined by dual-energy X-ray absorptiometry. Attachment loss was correlated with tooth loss (number of remaining teeth, radiologically determined), but not with vertebral or proximal femur bone density. Multivariate analysis showed current smoking (p = 0.01), years since menopause (p = 0.02) and the interaction of age and current smoking (p < 0.01), to be statistically significant predictors of attachment loss in our study population.