No abstract

The methanolyses of two neutral phosphorus triesters, paraoxon (1) and fenitrothion (3), were investigated as a function of added Zn(OTf)(2) or Zn(ClO(4))(2) in methanol at 25 degrees C either alone or in the presence of equimolar concentrations of the ligands phenanthroline (4), 2,9-dimethylphenanthroline (5), and 1,5,9-triazacyclododecane (6). The catalysis requires the presence of methoxide, and when studied as a function of added NaOCH(3), the rate constants (k(obs)) for methanolysis of Zn(2+) alone or in the presence of equimolar 4 or 5 maximize at different [(-)OCH(3)]/[Zn(2+)](total) ratios of 0.3, 0.5, and 1.0, respectively. Plots of k(obs) vs [Zn(2+)](total) either alone or in the presence of equimolar ligands 4 and 5 at the [(-)OCH(3)]/[Zn(2+)](total) ratios corresponding to the rate maxima are curved and show a nonlinear dependence on [Zn(2+)](total). In the cases of 4 and 5, this is explained as resulting from formation of a nonactive dimer, formulated as a bis-mu-methoxide-bridged form (L:Zn(2+)((-)OCH(3))(2)Zn(2+):L) in equilibrium with an active monomeric form (L:Zn(2+)((-)OCH(3))). In the case of the Zn(2+):6 system, no dimeric forms are present as can be judged by the strict linearity of the plots of k(obs) vs [Zn(2+)](total) in the presence of equimolar 6 and (-)OCH(3). Analysis of the potentiometric titration curves for Zn(2+) alone and in the presence of the ligands allows calculation of the speciation of the various Zn(2+) forms and shows that the binding to ligands 4 and 6 is very strong, while the binding to ligand 5 is weaker. Overall the best catalytic system is provided by equimolar Zn(2+), 5, and (-)OCH(3), which exhibits excellent turnover of the methanolysis of paraoxon when the substrate is in excess. At a concentration of 2 mM in each of these components, which sets the pH of the solution at 9.5, the acceleration of the methanolysis of paraoxon and fenitrothion relative to the methoxide reaction is 1.8 x 10(6)-fold and 13 x 10(6)-fold, respectively. A mechanism for the catalyzed reactions is proposed which involves a dual role for the metal ion as a Lewis acid and source of nucleophilic Zn(2+)-bound (-)OCH(3).

The results suggest that the EDC splitting approach provides more reliable visualization of the anterior half of the radial head while minimizing soft-tissue dissection and reducing the risk of iatrogenic injury to the lateral ulnar collateral ligament.

Objective: To examine the stability of plate (locking and non–) versus screw constructs in the fixation of these fractures. Methods: An anteromedial coronoid facet fracture (OTA/AO type 21–B1, O'Driscoll type 2, subtype 3) was simulated in 24 synthetic ulna bones that were then assigned to 3 fracture fixation groups: non–locking plate, locking plate (LP), or screw fixation. Each construct was first cycled in tension (through a simulated medial collateral ligament) and then in compression. They were then loaded to failure (displacement >2 mm). Fracture fragment displacement was recorded with an optical tracking system. Results: During tension testing, a mean maximum fragment displacement of 12 ± 13 and 14 ± 9 μm was seen in the locking and non–locking constructs, respectively. There was no difference in fragment motion between the plated constructs. All screw-only fixed constructs failed during the tension protocol. During compression testing, the mean maximum fragment displacement for the screw-only construct (64 ± 79 μm) was significantly greater than locking (9 ± 5 μm) and non–locking constructs (10 ± 9 μm). During load to failure testing, the maximum load to failure in the screw-only group (316 ± 83 N) was significantly lower than locking (650.4 ± 107 N) and non–locking constructs (550 ± 76 N). There was no difference in load to failure between the plated groups. Conclusion: Fixation of anteromedial coronoid fractures (type 2, subtype 3) is best achieved with a plating technique. Although LPs had greater stiffness, they did not offer any advantage over conventional non-LPs with respect to fracture fragment displacement in this study. Clinical Relevance: Isolated screw fixation showed inferior stability when compared with plate constructs for these fractures. This could result in loss of fracture reduction leading to instability and posttraumatic arthrosis.