Catalytic asymmetric Michael addition of α,β-unsaturated aldehydes to Ni(II) complexes of the Schiff base of glycine.

The conjugate addition of Ni(II) complexes of glycine Schiff base to α,β-unsaturated aldehydes catalyzed by (S)-2-(diphenyl(trimethylsilyloxy)methyl)pyrrolidine afforded adducts in excellent yields with up to 49:1 dr and 95% ee. This method enables the construction of two adjacent chiral centers in one step, and offers an alternative route to chiral α-amino acid derivatives.

Improved fatigue life of acrylic bone cements reinforced with zirconia fibers.

Poly(methyl methacrylate) (PMMA) bone cements have a long and successful history of use for implant fixation, but suffer from a relatively low fracture and fatigue resistance which can result in failure of the cement and the implant. Fiber or particulate reinforcement has been used to improve mechanical properties, but typically at the expense of the pre-cured cement viscosity, which is critical for successful integration with peri-implant bone tissue. Therefore, the objective of this study was to investigate the effects of zirconia fiber reinforcement on the fatigue life of acrylic bone cements while maintaining a relatively low pre-cured cement viscosity.

Specimen-specific multi-scale model for the anisotropic elastic constants of human cortical bone.

The anisotropic elastic constants of human cortical bone were predicted using a specimen-specific micromechanical model that accounted for structural parameters across multiple length scales. At the nano-scale, the elastic constants of the mineralized collagen fibril were estimated from measured volume fractions of the constituent phases, namely apatite crystals and Type I collagen. The elastic constants of the extracellular matrix (ECM) were predicted using the measured orientation distribution function (ODF) for the apatite crystals to average the contribution of misoriented mineralized collagen fibrils.

Static and fatigue mechanical characterizations of variable diameter fibers reinforced bone cement.

Fibers can be used to improve the mechanical properties of bone cement for the long-term stability of hip prostheses. However, debonding of the fibers from the matrix due to the poor fiber/matrix interface is a major failure mechanism for such fiber reinforced bone cements. In this study, a novel fiber (variable diameter fibers or VDFs) technology for reinforced bone cement was studied to overcome the interface problem of short-fiber composites.

8-Methyl-5-methyl-ene-2-oxotricyclo[5.3.1.1]dodecan-endo-8-ol.

The title compound, C(14)H(20)O(2), crystallizes with homochiral chains of mol-ecules hydrogen bonded together along the b axis. Adjacent chains in the ab plane contain mol-ecules of the same chirality, leading to a chiral segregation of the mol-ecules into layers.

Processing and tensile properties of hydroxyapatite-whisker-reinforced polyetheretherketone.

Polyetheretherketone (PEEK) was reinforced with 0-50 vol% hydroxyapatite (HA) whiskers using a novel powder processing and compression molding technique which enabled uniform mixing at high whisker content. Texture analysis showed that viscous flow during compression molding produced a preferred orientation of whiskers along the specimen tensile axis. Consequently, the elastic modulus or ultimate tensile strength of HA-whisker-reinforced PEEK was able to be tailored to mimic human cortical bone.

Site-specific arylation of rat glutathione s-transferase A1 and A2 by bromobenzene metabolites in vivo.

The hepatotoxicity of bromobenzene (BB) derives from its reactive metabolites (epoxides and quinones), which arylate cellular proteins. Application of proteomic methods to liver proteins from rats treated with a hepatotoxic dose of [14C]-BB has identified more than 40 target proteins, but no adducted peptides have yet been observed. Because such proteins are known to contain bromophenyl- and bromodihydroxyphenyl derivatives of cysteine, histidine, and lysine, the failure to observe modified peptides has been attributed to the low level of total covalent binding and to the "dilution" effect of multiple metabolites reacting at multiple sites on multiple proteins.

Use of isotopic signatures for mass spectral detection of protein adduction by chemically reactive metabolites of bromobenzene: studies with model proteins.

The cytotoxicity of many small organic compounds often apparently derives from their metabolic activation and covalent binding to cellular proteins. It is therefore of considerable interest to be able to determine, for a given protoxin, which metabolites modify which proteins at which sites. Our laboratory has identified more than 45 target proteins for bromobenzene metabolites in liver by peptide mass mapping after two-dimensional electrophoresis.

Enantioselective synthesis of furo[2,3-b]furans, a spongiane diterpenoid substructure.

[structure: see text] A short and enantioselective synthesis of cis-fused 5-oxofuro[2,3-b]furans, being found in many spongiane diterpenoid natural products, is reported starting from inexpensive methyl 2-furoate. Moreover, the acid-catalyzed rearrangement of the furo[2,3-b]furan framework A to B is observed for some derivatives, suggesting a simple connection between natural products differing in the absolute configuration of the 3a,6a ring junction.

Synthesis of N tau-arylhistidine derivatives via direct N-arylation.

N(tau)-Aryl-histidine derivatives were synthesized using a modified one-step Cu-catalyzed coupling of aryl halides and N-acetylhistidine methyl ester. The latter is much less reactive than imidazole toward aryl halides. p-Chloroiodobenzene coupled with iodine displacement only, whereas m- and p-bromoiodobenzene both gave mixtures of bromo- and iodophenyl products.

Synthesis and activity of analogues of the isoleucyl tRNA synthetase inhibitor SB-203207.

Twenty two analogues of SB-203207 have been prepared by total synthesis, and evaluated as inhibitors of a range of tRNA synthetases. Changes to the bicyclic core, removing either the terminal amino substituent or the sulfonyl group from the side chain, and altering either the carbon skeleton or stereochemistry of the isoleucine residue, decreases the potency of inhibition of isoleucyl tRNA synthetase. Substituting the isoleucine residue with other amino acids produces inhibitors of the corresponding synthetases.