Local Site Selectivity and Conformational Structures in the Glycosidic Bond Scission of Cellobiose
Car–Parrinello molecular dynamics combined with metadynamics simulations were used to study the acid-catalyzed hydrolysis of cellobiose (CB) in aqueous solution. The hydrolysis was studied in two steps. Step 1 involves the proton transfer from solvent to CB and dissociation of the glycosidic bond to...
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| Veröffentlicht in: | The journal of physical chemistry. B 2011-09, Vol.115 (36), p.10682-10691 |
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| container_issue | 36 |
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| container_title | The journal of physical chemistry. B |
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| creator | Liang, Xiao Montoya, Alejandro Haynes, Brian S. |
| description | Car–Parrinello molecular dynamics combined with metadynamics simulations were used to study the acid-catalyzed hydrolysis of cellobiose (CB) in aqueous solution. The hydrolysis was studied in two steps. Step 1 involves the proton transfer from solvent to CB and dissociation of the glycosidic bond to β-glucose and oxacarbenium ion species. Step 2 involves the formation of α-glucose from oxacarbenium and regeneration of the acid proton species. Step 1 is endothermic, while Step 2 is exothermic. The overall activation free energy of CB hydrolysis is 32.5 kcal mol–1, and the overall reaction free energy is −5.9 kcal mol–l, consistent with available experimental data. We observe that a stepwise mechanism generally described in the literature for Step 1 is not significantly favored relative to a concerted β-1,4′ linkage dissociation process. |
| doi_str_mv | 10.1021/jp204199h |
| format | Article |
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The hydrolysis was studied in two steps. Step 1 involves the proton transfer from solvent to CB and dissociation of the glycosidic bond to β-glucose and oxacarbenium ion species. Step 2 involves the formation of α-glucose from oxacarbenium and regeneration of the acid proton species. Step 1 is endothermic, while Step 2 is exothermic. The overall activation free energy of CB hydrolysis is 32.5 kcal mol–1, and the overall reaction free energy is −5.9 kcal mol–l, consistent with available experimental data. We observe that a stepwise mechanism generally described in the literature for Step 1 is not significantly favored relative to a concerted β-1,4′ linkage dissociation process.</description><identifier>ISSN: 1520-6106</identifier><identifier>EISSN: 1520-5207</identifier><identifier>DOI: 10.1021/jp204199h</identifier><identifier>PMID: 21800820</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>B: Statistical Mechanics, Thermodynamics, Medium Effects ; Bonding ; Catalysis ; Cellobiose - chemistry ; Endothermic reactions ; Entropy ; Exothermic reactions ; Free energy ; Glucose - chemistry ; Glycosides - chemistry ; Hydrolysis ; Molecular Conformation ; Molecular Dynamics Simulation ; Scission ; Simulation ; Solvents</subject><ispartof>The journal of physical chemistry. 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We observe that a stepwise mechanism generally described in the literature for Step 1 is not significantly favored relative to a concerted β-1,4′ linkage dissociation process.</description><subject>B: Statistical Mechanics, Thermodynamics, Medium Effects</subject><subject>Bonding</subject><subject>Catalysis</subject><subject>Cellobiose - chemistry</subject><subject>Endothermic reactions</subject><subject>Entropy</subject><subject>Exothermic reactions</subject><subject>Free energy</subject><subject>Glucose - chemistry</subject><subject>Glycosides - chemistry</subject><subject>Hydrolysis</subject><subject>Molecular Conformation</subject><subject>Molecular Dynamics Simulation</subject><subject>Scission</subject><subject>Simulation</subject><subject>Solvents</subject><issn>1520-6106</issn><issn>1520-5207</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp90MtKAzEUBuAgipfqwheQbERdVHOZSTNLLVqFgovqesjlDE2ZTmqSEfr2prR2JS7CyeI7P4cfoUtK7ilh9GGxYqSgVTU_QKe0ZGSY3-hw9xeUiBN0FuOCEFYyKY7RCaOSEMnIKdJTb1SLZy4BnkELJrlvl9ZYdRaPfdf4sFTJ-W5jUuhN6gNE7Dqc5oAn7dr46Kwz-MnnhZlxMWaMfYPH0LZeOx_hHB01qo1wsZsD9Pny_DF-HU7fJ2_jx-lQFZSnoW4AjJZG07Kk3DaqqSy3glsjWKVFqXhBOAg2KiUYVnFNK2kLKIQWUGlr-ADdbHNXwX_1EFO9dNHkM1QHvo-1lDJHSEGzvP1X0lHJSzoigmd6t6Um-BgDNPUquKUK65qSelN-vS8_26tdbK-XYPfyt-0MrrdAmVgvfB9yrfGPoB_k_YwH</recordid><startdate>20110915</startdate><enddate>20110915</enddate><creator>Liang, Xiao</creator><creator>Montoya, Alejandro</creator><creator>Haynes, Brian S.</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope></search><sort><creationdate>20110915</creationdate><title>Local Site Selectivity and Conformational Structures in the Glycosidic Bond Scission of Cellobiose</title><author>Liang, Xiao ; Montoya, Alejandro ; Haynes, Brian S.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a413t-bfeecb8cb15513dfaf9d3d63dc629b65a3403e62758ec293b198d4e46b6e9bdc3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>B: Statistical Mechanics, Thermodynamics, Medium Effects</topic><topic>Bonding</topic><topic>Catalysis</topic><topic>Cellobiose - chemistry</topic><topic>Endothermic reactions</topic><topic>Entropy</topic><topic>Exothermic reactions</topic><topic>Free energy</topic><topic>Glucose - chemistry</topic><topic>Glycosides - chemistry</topic><topic>Hydrolysis</topic><topic>Molecular Conformation</topic><topic>Molecular Dynamics Simulation</topic><topic>Scission</topic><topic>Simulation</topic><topic>Solvents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liang, Xiao</creatorcontrib><creatorcontrib>Montoya, Alejandro</creatorcontrib><creatorcontrib>Haynes, Brian S.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. 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| ispartof | The journal of physical chemistry. B, 2011-09, Vol.115 (36), p.10682-10691 |
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| subjects | B: Statistical Mechanics, Thermodynamics, Medium Effects Bonding Catalysis Cellobiose - chemistry Endothermic reactions Entropy Exothermic reactions Free energy Glucose - chemistry Glycosides - chemistry Hydrolysis Molecular Conformation Molecular Dynamics Simulation Scission Simulation Solvents |
| title | Local Site Selectivity and Conformational Structures in the Glycosidic Bond Scission of Cellobiose |
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