| Mechanochemistry: one bond at a time. | |
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MedLine Citation:
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PMID: 19572737 Owner: NLM Status: PubMed-not-MEDLINE |
Abstract/OtherAbstract:
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Single-molecule force-clamp spectroscopy offers a novel platform for mechanically denaturing proteins by applying a constant force to a polyprotein. A powerful emerging application of the technique is that, by introducing a disulfide bond in each protein module, the chemical kinetics of disulfide bond cleavage under different stretching forces can be probed at the single-bond level. Even at forces much lower than that which can rupture the chemical bond, the breaking of the S-S bond at the presence of various chemical reducing agents is significantly accelerated. Our previous work demonstrated that the rate of thiol/disulfide exchange reaction is force-dependent and well-described by an Arrhenius term of the form r = A(exp((FΔx(r) - E(a))/k(B)T)[nucleophile]). From Arrhenius fits to the force dependency of the reduction rate, we measured the bond elongation parameter, Δx(r), along the reaction coordinate to the transition state of the S(N)2 reaction cleaved by different nucleophiles and enzymes, never before observed by any other technique. For S-S cleavage by various reducing agents, obtaining the Δx(r) value can help depicting the energy landscapes and elucidating the mechanisms of the reactions at the single-molecule level. Small nucleophiles, such as 1,4-dl-dithiothreitol (DTT), tris(2-carboxyethyl)phosphine (TCEP), and l-cysteine, react with the S-S bond with monotonically increasing rates under the applied force, while thioredoxin enzymes exhibit both stretching-favored and -resistant reaction-rate regimes. These measurements demonstrate the power of the single-molecule force-clamp spectroscopy approach in providing unprecedented access to chemical reactions. |
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Authors:
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Jian Liang; Julio M Fernández |
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Publication Detail:
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Type: Journal Article Date: 2009-07-02 |
Journal Detail:
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Title: ACS nano Volume: 3 ISSN: 1936-086X ISO Abbreviation: ACS Nano Publication Date: 2009 Jul |
Date Detail:
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Created Date: 2011-04-01 Completed Date: 2012-10-12 Revised Date: 2013-02-11 |
Medline Journal Info:
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Nlm Unique ID: 101313589 Medline TA: ACS Nano Country: United States |
Other Details:
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Languages: eng Pagination: 1628-45 Citation Subset: - |
Affiliation:
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Department of Biological Sciences, Columbia University, New York, New York 10027. |
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Descriptor/Qualifier:
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| Grant Support | |
ID/Acronym/Agency:
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R01 HL061228-12/HL/NHLBI NIH HHS; R01 HL066030-10/HL/NHLBI NIH HHS |
| Comments/Corrections | |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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