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sparser
"Several regions along the palm and thumb domains of the protein also become solvent protected in the presence of USP30-I-1 ."

sparser
"USP30-I-1 has a cyanopyrrolidine warhead for the covalent reaction with Cys77 of USP30."

sparser
"USP30 inhibitor USP30-I-1 synthesis and characterization was reported previously (patent WO2020212350A1; Mission Therapeutics). xref , xref , xref The inhibitor was confirmed to bind to recombinant USP30 by RapidFire MS analysis ()."

sparser
"Our results highlight advantages in developing covalent inhibitors, such as USP30-I-1 , for targeting USP30 as treatment of disorders with impaired mitophagy."

sparser
"We now extend our study to structurally profile USP30s interaction with a small, covalent, cyanopyrrolidine scaffold-containing inhibitor, USP30-I-1 (patent WO2020212350A1; Mission Therapeutics). xref , xref Covalent inhibitors possess significant advantages over their noncovalent counterparts, including a more prolonged duration of action and the formation of more specific and irreversible bonds with their substrates, enhancing the overall drug efficacy. xref Newer-generation USP30 inhibitors are therefore likely to harness covalent bond formation between the compound and protein."

sparser
"Using a biophysical and structural proteomics approach similar to our previous work, xref we show that USP30-I-1 is highly selective and potent against endogenous USP30 when compared to the >40 other endogenous DUBs identified in the neuroblastoma-derived SH-SY5Y cell line."

sparser
"Covalent USP30-I-1 binds to USP30 with a similar affinity to the previously characterized noncovalent USP30 inh , with binding primarily restricted to a small region covering the USP30 active site cysteine residue."

sparser
"For in-solution HDX-MS, a working sample of USP30 and USP30-I-1 (i.e., the holo-USP30) was prepared by a volume-to-volume mixture at a molar ratio of 1:2 (USP30: USP30-I-1 ) and diluted to a nominal concentration of 11 μM for the USP30 and 22 μM for USP30-I-1 ."

sparser
"Approximately, 3.5 μL of the USP30 with USP30-I-1 complex mixture was diluted with the labeling buffer (1:20 ratio, achieving an excess D 2 O concentration of 95%) and incubated in D 2 O buffer at 20 °C for 30, 60, 600, and 3600 s in triplicate."

sparser
"The highest resolution human USP30 catalytic domain inhibitor complex structure (corresponding to PDB code:) in which the Fab fragment antibody and covalent inhibitor, 552, had been removed, was used as the target receptor for docking studies with USP30-I-1 ."

sparser
"The in silico binding pose of USP30-I-1 with the best docking score is shown in xref ."

sparser
"USP30-I-1 Targets Endogenous USP30 in a Highly Potent and Selective Manner."

sparser
"We performed ABPP-MS in SH-SY5Y neuroblastoma cell lysates to determine the potency and selectivity of USP30-I-1 , a substituted cyanopyrrolidine derivative ( xref A)."

sparser
"Endogenous USP30 inhibition was confirmed via the prevention of HA-Ub-PA-USP30 binding by USP30-I-1 in a concentration-dependent fashion ( xref B)."

sparser
"USP30-I-1 was observed to be a potent inhibitor of USP30, with an IC 50 of 94 nM ( xref C)."

sparser
"Our quantitative MS analysis showcased the high selectivity of USP30-I-1 for USP30, with no significant activity against any of the other 40 endogenous DUBs detected in SH-SY5Y extracts at the lowest inhibitor concentrations ( xref D,E)."

sparser
"At higher concentrations of 10 μM, however, we observed that USP30-I-1 reduces the HA-Ub-PA labeling of a number of other DUBs ()."

sparser
"However, as USP10 is not strongly labeled by HA-Ub-PA, the inhibitory profile of USP10 by USP30-I-1 could not be validated by the Western blot ()."

sparser
"Moreover, USP30-I-1 is far more potent for USP30 than it is for USP10 ()."

sparser
"In conclusion, ABPP-MS demonstrated that USP30-I-1 is a selective and potent inhibitor of USP30 at concentrations ≤1 μM."

sparser
"We then undertook in vitro biochemical assays to determine the full enzyme kinetics of USP30-I-1 ."

sparser
"USP30-I-1 inhibited USP30 in a dose-dependent manner, with an IC 50 of ∼4 nΜ when USP30 was preincubated with inhibitors for 30 min ( xref A)."

sparser
"The lower IC 50 value observed for USP30-I-1 in the in vitro work was likely a result of reduced nonspecific inhibitor occlusion as compared to the cellular matrix, and a similar phenomenon was observed in our USP30 inh work. xref Rates of inhibition determined from the Ub-rhodamine cleavage progress curves ( xref B) without USP30 preincubation were plotted against [ USP30-I-1 ] ( xref B Inset) to determine k inact / K I (traditional method)."

sparser
"To conclude, USP30-I-1 binds to USP30 in a tight manner and displays kinetic properties consistent with covalent attachment."

sparser
"USP30-I-1 Binds to the Catalytic Cysteine of USP30, Inducing Conformational Changes in the Active Site."

sparser
"We used HDX-MS to determine the conformational dynamics associated with the interaction between USP30-I-1 and USP30, in addition to pinpointing its precise location for small-molecule binding."

sparser
"When directly comparing apo-USP30 to holo-USP30, the majority of the USP30 protein sequence had no significant differential deuterium uptake in the presence of USP30-I-1 , confirming that, as one may expect upon interaction of a small-molecule with a much larger protein, binding was restricted to only a small portion of USP30 itself ( xref A and)."

sparser
"Nevertheless, these observations provide an additional layer of confidence that catalytic Cys77 is indeed the primary binding site of USP30-I-1 on the protein."

sparser
"Our mapping further highlighted the strong interaction of USP30-I-1 with the region encompassing the catalytic Cys77 (highlighted in magenta in xref B) but also supported the identification of other regions of human USP30 catalytic domain (highlighted in red) that become solvent protected, albeit to a much lesser extent."

sparser
"In conclusion, our differential HDX-MS allowed us to pinpoint regions of USP30 that are involved in USP30-I-1 binding."

sparser
"As illustrated in the pose displayed in xref B,C, USP30-I-1 is predicted to bind in the thumb-palm cleft that guides the ubiquitin C-terminus into the active site."

sparser
"USP30-I-1 forms a thioimidate with the catalytic cysteine Cys77, with the imine moiety accepting a hydrogen bond from the side chain of Asn72 and acting as a hydrogen bond donor to the main chain carbonyl of Gly74."

sparser
"In addition, the amide moiety of USP30-I-1 hydrogen bonds to the main chain carbonyl of Gln160 ( xref C)."

sparser
"The docking pose for USP30-I-1 correlates perfectly with our HDX-MS results with both suggesting that the USP30 catalytic Cys77 is the primary binding site of USP30-I-1 ."

sparser
"In addition, the docking pose of USP30-I-1 correlates well with the X-ray structures of human USP30 catalytic domain in complex with the covalent inhibitors, 552 (PDB code:; unpublished) and 829 (PDB code:; unpublished) ( xref A,B,C)."

sparser
"Hence, the predicted binding site of USP30-I-1 based on our modeling studies would sterically clash with the C-terminal tail of ubiquitin ( xref D,E)."

sparser
"For example, the noncovalent USP7 inhibitor, FT671 (PDB code:), and covalent USP7 inhibitor, FT827 (PDB code:), specifically target the catalytically incompetent apo-form state in which the switching loop adopts an “in” conformation. xref A comparison of USP30-I-1 with FT827 reveals that the binding site is broadly similar but that there are conformational differences in the region accommodating the catalytic cysteine, the switching loop, and blocking loops 1 and 2 ( xref A,B)."

sparser
"These conformational differences result in FT827 extending closer toward the finger subdomain than the modeled position of USP30-I-1 ."

sparser
"There are 26 residues with an atom residing within 5 Å of the predicted USP30-I-1 binding site ( xref B)."

sparser
"Inhibitor selectivity is likely to be conferred by sequence substitutions in these residues compared with other USP family members coupled with conformational differences in the regions flanking the proposed USP30-I-1 binding site, including the switching and blocking loops."

sparser
"In summary, our molecular docking analysis identified residues implicated in USP30-I-1 binding, which is in perfect agreement with those identified through differential HDX-MS."

sparser
"Comparison of USP30 Inhibition by Covalent Cyanopyrrolidine USP30-I-1 and Noncovalent Benzosulfonamide USP30 inh Compound."

sparser
"USP30-I-1 shows both a high initial binding affinity ( K I ∼ 350 nM) and a fast rate of specific inactivation ( k inact ∼ 0.15 s –1 )."

sparser
"Both USP30-I-1 and noncovalent USP30 inh show time-dependent inhibition, with USP30 inh showing two-step, slow, and tight binding kinetic behavior consistent with a covalent inhibitor."

sparser
"The second step of inhibition by USP30 inh is essentially irreversible ( k 6 = 0.00033 s –1 ) allowing us to compare k 5 / K iapp for USP30 inh with k inact / K I for USP30-I-1 as a measure of potency."

sparser
"Using these values, the compounds have a similar potency (0.18 and 0.20 μM –1 s –1 for USP30-I-1 and USP30 inh , respectively), in the case of USP30 inh , the potency is driven by the rate at which the irreversible complex forms with the initial affinity being lower than that of USP30-I-1 (1.27 μM and 350 nM for USP30-I-1 and USP30 inh , respectively)."

sparser
"Our previous study also employed HDX-MS and computational docking to elucidate the molecular architecture and geometry of USP30 complex formation with the noncovalent inhibitor, USP30 inh . xref Both compounds interact with the catalytic Cys77, but USP30-I-1 induces a higher degree of solvent protection than does USP30 inh ."

sparser
"However, compared with USP30-I-1 , which forms a covalent adduct with the catalytic Cys77, the modeled position of USP30 inh resides approximately 7.9 Å away at its closest point from the thiol side chain of this cysteine ( xref C,D)."

sparser
"The X-ray structure of human USP30 catalytic domain in complex with UbPA (PDB code:; Gersch et al., 2017 xref ) was used as the target receptor for USP30 inh because there were no inhibitor-bound structures available at that time, which results in differences in conformation in the switching and blocking loop regions compared with the structure of USP30 in complex with the covalent inhibitor, 552 (PDB code:), that was used for USP30-I-1 docking studies."

sparser
"We subsequently expanded on the study by comparing our results to those obtained on a covalent USP30 inhibitor, USP30-I-1 ( xref )."

sparser
"Hence, while both studies indicate that USP30 inh and USP30-I-1 are likely to reside within the thumb-palm cleft, differences in their HDX-MS profiles suggest that there are differences in their binding modes, which places USP30 inh closer toward the fingers subdomain compared with the predicted binding site for USP30-I-1 ( xref E)."

sparser
"In the current study, the inhibitor, USP30-I-1 , forms a covalent adduct with the catalytic cysteine, Cys77, and is predicted to reside in the thumb-palm cleft that guides the ubiquitin C-terminus into the active site."

sparser
"We are confident in the predicted binding mode of USP30-I-1 since it correlates well with the HDX-MS data presented in this paper."

sparser
"In addition, the docking pose of USP30-I-1 agrees with the experimental structures of USP30 in complex with the covalent inhibitors, 552 (PDB code:; unpublished) and 829 (PDB code:; unpublished), in which the switching loop adopts an “in” conformation, suggesting that it is unlikely USP30-I-1 will occupy a cryptic pocket."

sparser
"However, an experimental structure of USP30 in complex with USP30-I-1 would be required to validate the docking results."

sparser
"USP30-I-1 represents a covalent small-molecule cyanopyrrolidine inhibitor that exhibits high potency and selectivity for the mitochondrial DUB, USP30."

sparser
"Covalent inhibitors, such as USP30-I-1, which contain a cyanopyrrolidine reactive group, form strong bonds with regions around the catalytic cysteine and create a binding pocket within the thumb and palm domains of the protein ( xref )."

sparser
"HDXMS studies reveal that covalent attachment of USP30-I-1 to Cys77 results in significant solvent protection in the region that flanks the catalytic cysteine, whereas less noticeable structural and conformational changes are seen in other regions."

sparser
"We integrated structural and quantitative proteomics with biochemical assays to decipher the mode of action of covalent USP30 inhibition by a small-molecule containing a cyanopyrrolidine reactive group, USP30-I-1 ."

sparser
"HA-Ub-PA was synthesized as outlined previously. xref , xref Methodology for HA-Ub-PA activity-based probe profiling was described in our previous study on a USP30 noncovalent inhibitor. xref Briefly, SH-SY5Y lysates were incubated for 1 h at 37 °C with either USP30-I-1 or dimethyl sulfoxide (DMSO) at the indicated concentrations in duplicate."

sparser
"The IC 50 was extracted from fitting USP30-I-1 inhibition quantitation with the equation: Y = 100/(1 + 10 × ( X – Log IC 50 )) in Prism (version 10.1.1)."

sparser
"All activity assays were performed in black 384-well plates in assay buffer (20 mM Tris–HCl, pH 8.0, 150 mM Potassium Glutamate, 0.1 mM TCEP and 0.03% Bovine Gamma Globulin) with a final assay volume of 20 μL. A concentration of 0.2 nM USP30 [residues 64-502Δ179-216 and 288-305, Viva Biotech (Shanghai) Ltd.] was added and preincubated with USP30-I-1 for 30 min."

sparser
"K inact / K I was also determined using the traditional method of fitting the progress curves to xref and plotting k obs vs [ USP30-I-1 ] and fitting with xref (supplemental)."

sparser
"Initial stock concentrations of USP30 and compound USP30-I-1 in DMSO were 66 μM and 10 mM, respectively."