Both urea and urease were subjects of early scientific investigations. Urea was the first organic molecule to be synthesized and jack bean urease was the first enzyme ever to be crystallized. About 50 years later it was shown to be the first nickel metalloenzyme. Since then, nickel-dependent ureases have been isolated from many bacteria, fungi and higher plants. They have similar structures and...

Department of Chemistry, The Johns Hopkins University, Charles and 34th Streets, Baltimore, Maryland 21218, Kluyver Laboratory for Biotechnology, Delft University of Technology, 2628 BC Delft, The Netherlands, Department of Biochemistry and Molecular Biology, OGI School of Science and Engineering at OHSU, Beaverton, Oregon 97006, and Department of Microbiology and Molecular Genetics, University...

The mouse brown locus encodes a putative membrane-bound metalloenzyme, tyrosinase-related protein-1 (TRP-1). We have examined the effect on mRNA expression of the locus of a number of mutant alleles. The common null mutant allele, brown, produces wild-type levels of TRP-1 mRNA, which is nonfunctional. Another recessive allele, cordovan-Harwell, has an intermediate, dark-brown phenotype and prod...

Bacterial acetone carboxylase catalyzes the ATP-dependent carboxylation of acetone to acetoacetate with the concomitant production of AMP and two inorganic phosphates. The importance of manganese in Rhodobacter capsulatus acetone carboxylase has been established through a combination of physiological, biochemical, and spectroscopic studies. Depletion of manganese from the R. capsulatus growth m...

Artificial metalloenzymes (ArMs) formed by incorporating synthetic metal catalysts into protein scaffolds have the potential to impart to chemical reactions selectivity that would be difficult to achieve using metal catalysts alone. In this work, we covalently link an alkyne-substituted dirhodium catalyst to a prolyl oligopeptidase containing a genetically encoded L-4-azidophenylalanine residue...

The nucleophilicity of transition metal thiolates is well-documented. Biologically relevant electrophilic substrates include oxygen or oxygen-transfer agents (such as H2O2) and alkylation agents (such as CH3I). Nature makes use of the latter with Zn-containing de-alkylation proteins such as the Ada repair mechanism and the former in the case of the post-translationally modified active form of N...

Gas-processing metalloenzymes are of interest to future bio- and bioinspired technologies. Of particular importance hydrogenases nitrogenases, which both produce molecular hydrogen (H2) from proton (H+) reduction. Herein, we report on the use rotating ring–disk electrochemistry (RRDE) mass spectrometry (MS) follow production H2 isotopes produced deuteron (D+) reduction (HD D2) using [FeFe]-hydr...

Based on the supramolecular interaction between vancomycin (Van), an antibiotic glycopeptide, and D-Ala-D-Ala (DADA) dipeptides, a novel class of artificial metalloenzymes was synthesized characterized. The presence iridium(III) ligand at N-terminus DADA allowed use metalloenzyme as catalyst in asymmetric transfer hydrogenation cyclic imines. In particular, type link metal-chelating moiety foun...