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Harding, C. J.

Publications and source records attributed to Harding, C. J..

4 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↗

A C-terminal Processing Protease Implicated in Flagellin Turnover and Developmental Progression in a Bacterial Predator

Carboxy-terminal processing proteases (CTPs) are widely conserved bacterial proteases implicated in protein maturation, quality control, and stress responses, yet many family members functions remain unclear. Here, we characterise Bd0967, a previously unstudied CTP from the predatory bacterium Bdellovibrio bacteriovorus, and its role in flagellar function during predatory development. Crystal structures reveal a self-compartmentalised protease in which a PDZ domain forms a lid over a large internal cavity accessed through a proteolytic tunnel. Co-purifying peptides occupied two distinct substrate-binding sites, suggesting a coordinated recognition mechanism. Affinity pulldowns coupled with mass spectrometry identified several Bdellovibrio flagellins as candidate substrates, which were subsequently validated by biochemical assays and shown to be selectively degraded through recognition of a conserved C-terminal motif. A Bd0967-mCherry translational fusion localised to periplasmic foci during the intracellular predatory growth, consistent with flagellar resorption and flagellin turnover following prey invasion. Deletion of bd0967 caused developmental defects, including aberrant Bdellovibrio cell morphology and reduced predation efficiency. Together, these findings establish Bd0967 as a specialised CTP that couples flagellin degradation and developmental progression in a predatory bacterium.

biochemistry↗

Improved nucleoside (2'-deoxy)ribosyltransferases maximize enzyme promiscuity while maintaining catalytic efficiency

Nucleoside analogues have been extensively used to treat viral and bacterial infections and cancer for the past 60 years. However, their chemical synthesis is complex and often requires multiple steps and a dedicated synthetic route for every new nucleoside to be produced. Wild type nucleoside 2'-deoxyribosyltransferase enzymes are promising for biocatalysis. Guided by the structure of the enzyme from the thermophilic organism Chroococcidiopsis thermalis PCC 7203 (CtNDT) bound to the ribonucleoside analogue Immucillin-H, we designed mutants of CtNDT and the psychrotolerant Bacillus psychrosaccharolyticus (BpNDT) to improve catalytic efficiency with 3'-deoxynucleosides and ribonucleosides, while maintaining nucleobase promiscuity to generate over 100 distinct nucleoside products. Enhanced catalytic efficiency towards ribonucleosides and 3'-deoxyribonucleosides occurred via gains in turnover rate, rather than improved substrate binding. We determined crystal structures of two engineered variants as well as kinetic parameters with different substrates, unveiling molecular details underlying their expanded substrate scope. Our rational approach generated robust enzymes and a roadmap for reaction conditions applicable to a wide variety of substrates. Insert Table of Contents artwork here O_FIG O_LINKSMALLFIG WIDTH=200 HEIGHT=98 SRC="FIGDIR/small/641663v2_ufig1.gif" ALT="Figure 1"> View larger version (29K): org.highwire.dtl.DTLVardef@3ef466org.highwire.dtl.DTLVardef@11f55b0org.highwire.dtl.DTLVardef@32d0dcorg.highwire.dtl.DTLVardef@2e22cc_HPS_FORMAT_FIGEXP M_FIG C_FIG

biochemistry↗

Broad substrate scope C-C oxidation in cyclodipeptides catalysed by a flavin-dependent filament

Cyclic dipeptides are produced by organisms in all domains of life. Many possess biological activities as anticancer and antimicrobial compounds. Oxidations are frequently present in these biologically active peptides. C-C bond oxidation is catalysed by tailoring enzymes, including cyclodipeptide oxidases. These flavin-dependent enzymes are underexplored due to their complex three-dimensional arrangement involving multiple copies of two distinct small subunits and unclear mechanistic features underlying substrate selection and catalysis. Here, we determined the structure and mechanism of the cyclodipeptide oxidase from the halophile Nocardiopsis dassonvillei (NdasCDO), part of the biosynthetic pathway for nocazine natural products. We show NdasCDO forms filaments in solution with a covalently bound FMN cofactor in the interface between three distinct subunits. The enzyme is promiscuous, using many cyclic dipeptides as substrates in a distributive manner. The reaction is optimal at high pH, involving the formation of a radical intermediate. Pre-steady state kinetics, a sizeable solvent kinetic isotope effect and lack of viscosity effects support that a step coupled to FMN regeneration determines the rate of the reaction. Our work dissects the complex mechanistic and structural features of this dehydrogenation reaction. This sets the stage to utilizing NdasCDO as a biocatalyst and expands the FMN-dependent oxidase family to include enzyme filaments.

biochemistry↗