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Hamill, C.

Publications and source records attributed to Hamill, C..

2 recordsLinked to original sources

Structural basis for autoinhibition and self-activation in the Pseudomonas aeruginosa virulence factor protease IV (PIV)

Secreted proteases enable Pseudomonas aeruginosa to damage host tissues and evade host immune defences, but the molecular basis by which protease IV (PIV) is maintained as an inactive precursor remains unclear. Here we determined a 2.17 A crystal structure of catalytically inactive PIVS409A. The precursor comprises an N-terminal Cap region, a CUB domain and a C-terminal trypsin-like protease domain. The Cap region forms an extended clamp across the precursor, and residues at the Cap-CUB junction lie above the catalytic cleft. Structural comparison with a modelled peptide substrate indicates that the Cap does not engage the substrate-recognition pockets as a pseudosubstrate; instead, it sterically prevents access to the S1 pocket, oxyanion hole and catalytic triad. Wild-type PIV undergoes progressive processing to a 27.6-kDa mature species, whereas the S409A variant remains resistant to activation by exogenous mature enzyme, supporting an intramolecular initiating step. Mature PIV is weakly inhibited by an ornithine-containing peptide mimicking the Cap domain, is not inhibited by phenylmethylsulfonyl fluoride and is slowly irreversibly inhibited by TLCK, demonstrating unique characteristics in comparison to other proteases from the same family. Finally, mature PIV increases the activity of aminopeptidase PaAP, likely through maturation of this enzyme, as part of a protease activation cascade. These findings define the architecture of the PIV precursor and provide a structural framework for understanding its activation and selective autoinhibition.

biochemistry↗

Dimerization and Threonine-Dependent Stabilization Govern Human YRDC Catalysis

Addition of N6-threonylcarbamoyladenosine occurs at position 37 (tA37) of five mitochondrial tRNA species, influencing translation fidelity and efficiency. Mutations in YRDC, the enzyme catalyzing the first step in tA37 synthesis, cause severe neurological and renal diseases in humans, including in Galloway-Mowatt disease (GAMOS). YRDC generates threonylcarbamoyl-AMP (TC-AMP) using ATP, threonine and bicarbonate as substrates, yet their binding order, residues involved in amino-acid selectivity, and precisely how mutations contribute to disease remain unclear. Here, we combine protein biophysics, mass spectrometry, NMR, mutagenesis and kinetics to define how the human enzyme operates. Differential scanning fluorimetry and circular dichroism identify L-threonine as the gatekeeper ligand. It binds with millimolar affinity, stabilizing YRDC and enhancing ATP binding nearly fortyfold, enabling bicarbonate association. Several amino acids can form aminoacylcarbamoyl-AMP adducts in vitro, but threonine yields superior protein stabilization and product formation. Native mass spectrometry and single-molecule mass photometry corroborate YRDCs dimeric state. GAMOS-linked mutations destabilize folding, disrupting dimerization and uncoupling substrate binding from catalysis, explaining functional losses. Supported by kinetic data and NMR, we propose a chemical mechanism for the reaction and identify dimerization and conformational stability as control points for activity. This work provides a foundation for designing selective YRDC inhibitors or enhancers.

biochemistry↗