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A methodology for resolving TpRe(CO)(1-methylimidazole)(eta(2)-benzene) has been developed utilizing (R)-alpha-pinene. Each enantiomer of the [TpRe(CO)(MeIm)] system can be obtained with the enantiomer ratio (er) = 97:3 by taking advantage of differing rates of pinene substitution for the two diastereomers of TpRe(CO)(MeIm)(eta(2)-(R)-alpha-pinene).
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PURPOSE: To design glucose-responsive gels based on the complexation between polymers having phenylboronic acid groups and poly (vinyl alcohol). Specifically, high-glucose sensitivity at physiological pH was achieved through the interaction of phenylborate with amino groups. METHOD: Terpolymers of m-acrylamidophenylboronic acid, N,N-dimethylaminopropylacrylamide (DMAPAA), and N,N-dimethylacrylamide were prepared. DMAPAA was introduced in the terpolymer to stabilize phenylborate-polyol complex at physiological pH. The effect of amino groups on complex stabilization was estimated from viscosity as well as UV spectrum measurements. RESULTS: A good correlation was observed between complexation rate and fraction of phenylborate as well as DMAPAA in the terpolymers. In line with this increased complexation rate, UV difference spectra measurement revealed that ionization of phenylboronic acid was facilitated in the terpolymer due to the interaction with DMAPAA. Further, sensitive change in the complexation rate was demonstrated with a variation in glucose concentration, which is in sharp contrast with the poor glucose-sensitivity of the polymer without DMAPAA. CONCLUSIONS: The introduction of an amino group into phenylborate polymers was quite effective for increasing the complexation ability and the glucose responsivity at physiological pH. These results suggest the feasibility of this complex-gel system in designing a self-regulated insulin-releasing device.
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A series of potassium organotrifluoroborates were synthesized. Their stability to hydrolysis was determined in D2O, TRIS and phosphate buffer. It was found that in both D2O and TRIS buffers, these compounds are quite stable, whereas in phosphate buffer rapid hydrolysis occurs. Based on these results, a study was undertaken to determine whether potassium organotrifluoroborates can serve as protease inhibitors. It was found that potassium organotrifluoroborates increased inhibition by at least an order of magnitude over the corresponding boronates. Dixon plots showed that these compounds are reversible competitive inhibitors of alpha-chymotrypsin and trypsin. Based on 19F NMR, we speculate that they inactivate the enzymes as a result of the formation of hydrogen-bonds between fluorine atoms of the inhibitors and the serine protease.
Ethylene polymerisation productivities of tris(pyrazolyl)methane-supported catalysts [Ti(NR){HC(Me2pz)3}Cl2] show a dramatically different dependence on the imido R-group compared to those of their TACN analogues, attributed to differences in fac-N3 donor topology; when treated with AliBu3, the zwitterionic tris(pyrazolyl)methide compound [Ti(N-2-C6H4tBu){C(Me2pz)3}Cl(THF)] also acts as a highly active, single site catalyst (TACN = 1,4,7-trimethyltriazacyclononane).
Serologic procedures were performed in parallel using hydrophilized polystyrene cuvettes and conventional glass test tubes. Consistent and comparable results were obtained with both containers. No significant differences in antibody titer, specificity, neutralization, or elution were observed. The effect of a proteolytic enzyme on red blood cell antigen was not altered by the hydrophilized plastic tubes. There was no difference in the stability of immune sera stored in glass or plastic at 4 degrees C and--30 degrees C. However, hemolysis of stored red blood cells was significantly slower in the hydrophilized plastic cuvettes.
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