Matches in SemOpenAlex for { <https://semopenalex.org/work/W2002484920> ?p ?o ?g. }
- W2002484920 endingPage "1352" @default.
- W2002484920 startingPage "1344" @default.
- W2002484920 abstract "Efficient chemical conversion of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level conversion of glucose to useful chemicals, such as furfural, hydroxymethylfurfural, and levulinic acid, is a major step in the biomass conversion but is difficult because of the formation of undesired products and side reactions. To understand the molecular level reaction mechanisms involved in the decomposition of glucose and fructose, we have carried out high-level quantum chemical calculations [Gaussian-4 (G4) theory]. Selective 1,2-dehydration, keto–enol tautomerization, isomerization, retro-aldol condensation, and hydride shifts of glucose and fructose molecules were investigated. Detailed kinetic and thermodynamic analyses indicate that, for acyclic glucose and fructose molecules, the dehydration and isomerization require larger activation barriers compared to the retro-aldol reaction at 298 K in neutral medium. The retro-aldol reaction results in the formation of C2 and C4 species from glucose and C3 species from fructose. The formation of the most stable C3 species, dihydroxyacetone from fructose, is thermodynamically downhill. The 1,3-hydride shift leads to the cleavage of the C–C bond in the acyclic species; however, the enthalpy of activation is significantly higher (50–55 kcal/mol) than that of the retro-aldol reaction (38 kcal/mol) mainly because of the sterically hindered distorted four-membered transition state compared to the hexa-membered transition state in the retro-aldol reaction. Both tautomerization and dehydration are catalyzed by a water molecule in aqueous medium; however, water has little effect on the retro-aldol reaction. Isomerization of glucose to fructose and glyceraldehyde to dihydroxyacetone proceeds through hydride shifts that require an activation enthalpy of about 40 kcal/mol at 298 K in water medium. This investigation maps out accurate energetics of the decomposition of glucose and fructose molecules that is needed to help find more efficient catalyts for the conversion of hexose to useful chemicals." @default.
- W2002484920 created "2016-06-24" @default.
- W2002484920 creator A5058864798 @default.
- W2002484920 creator A5089808892 @default.
- W2002484920 date "2012-01-17" @default.
- W2002484920 modified "2023-09-25" @default.
- W2002484920 title "Comparison of Sugar Molecule Decomposition through Glucose and Fructose: A High-Level Quantum Chemical Study" @default.
- W2002484920 cites W1970800994 @default.
- W2002484920 cites W1973632156 @default.
- W2002484920 cites W1975173430 @default.
- W2002484920 cites W1982516235 @default.
- W2002484920 cites W1983566725 @default.
- W2002484920 cites W1991967257 @default.
- W2002484920 cites W1995541505 @default.
- W2002484920 cites W1999159184 @default.
- W2002484920 cites W1999948593 @default.
- W2002484920 cites W2017447614 @default.
- W2002484920 cites W2021222373 @default.
- W2002484920 cites W2026347204 @default.
- W2002484920 cites W2027502414 @default.
- W2002484920 cites W2039827935 @default.
- W2002484920 cites W2039877599 @default.
- W2002484920 cites W2045063489 @default.
- W2002484920 cites W2048704620 @default.
- W2002484920 cites W2049383638 @default.
- W2002484920 cites W2056047688 @default.
- W2002484920 cites W2058024159 @default.
- W2002484920 cites W2060746784 @default.
- W2002484920 cites W2061627141 @default.
- W2002484920 cites W2061808215 @default.
- W2002484920 cites W2067296924 @default.
- W2002484920 cites W2068654934 @default.
- W2002484920 cites W2069121950 @default.
- W2002484920 cites W2069434657 @default.
- W2002484920 cites W2075711588 @default.
- W2002484920 cites W2079061428 @default.
- W2002484920 cites W2084726128 @default.
- W2002484920 cites W2089772278 @default.
- W2002484920 cites W2096605011 @default.
- W2002484920 cites W2103099844 @default.
- W2002484920 cites W2109816957 @default.
- W2002484920 cites W2120446525 @default.
- W2002484920 cites W2124869374 @default.
- W2002484920 cites W2150962987 @default.
- W2002484920 cites W2152065044 @default.
- W2002484920 cites W2152123339 @default.
- W2002484920 cites W2320360017 @default.
- W2002484920 cites W2326005538 @default.
- W2002484920 cites W2328984905 @default.
- W2002484920 doi "https://doi.org/10.1021/ef201654s" @default.
- W2002484920 hasPublicationYear "2012" @default.
- W2002484920 type Work @default.
- W2002484920 sameAs 2002484920 @default.
- W2002484920 citedByCount "91" @default.
- W2002484920 countsByYear W20024849202012 @default.
- W2002484920 countsByYear W20024849202013 @default.
- W2002484920 countsByYear W20024849202014 @default.
- W2002484920 countsByYear W20024849202015 @default.
- W2002484920 countsByYear W20024849202016 @default.
- W2002484920 countsByYear W20024849202017 @default.
- W2002484920 countsByYear W20024849202018 @default.
- W2002484920 countsByYear W20024849202019 @default.
- W2002484920 countsByYear W20024849202020 @default.
- W2002484920 countsByYear W20024849202021 @default.
- W2002484920 countsByYear W20024849202022 @default.
- W2002484920 countsByYear W20024849202023 @default.
- W2002484920 crossrefType "journal-article" @default.
- W2002484920 hasAuthorship W2002484920A5058864798 @default.
- W2002484920 hasAuthorship W2002484920A5089808892 @default.
- W2002484920 hasConcept C111233374 @default.
- W2002484920 hasConcept C126661725 @default.
- W2002484920 hasConcept C161790260 @default.
- W2002484920 hasConcept C178790620 @default.
- W2002484920 hasConcept C185592680 @default.
- W2002484920 hasConcept C18616679 @default.
- W2002484920 hasConcept C2776339268 @default.
- W2002484920 hasConcept C2776970464 @default.
- W2002484920 hasConcept C2780604391 @default.
- W2002484920 hasConcept C61156836 @default.
- W2002484920 hasConcept C75473681 @default.
- W2002484920 hasConcept C89031862 @default.
- W2002484920 hasConceptScore W2002484920C111233374 @default.
- W2002484920 hasConceptScore W2002484920C126661725 @default.
- W2002484920 hasConceptScore W2002484920C161790260 @default.
- W2002484920 hasConceptScore W2002484920C178790620 @default.
- W2002484920 hasConceptScore W2002484920C185592680 @default.
- W2002484920 hasConceptScore W2002484920C18616679 @default.
- W2002484920 hasConceptScore W2002484920C2776339268 @default.
- W2002484920 hasConceptScore W2002484920C2776970464 @default.
- W2002484920 hasConceptScore W2002484920C2780604391 @default.
- W2002484920 hasConceptScore W2002484920C61156836 @default.
- W2002484920 hasConceptScore W2002484920C75473681 @default.
- W2002484920 hasConceptScore W2002484920C89031862 @default.
- W2002484920 hasIssue "2" @default.
- W2002484920 hasLocation W20024849201 @default.
- W2002484920 hasOpenAccess W2002484920 @default.
- W2002484920 hasPrimaryLocation W20024849201 @default.
- W2002484920 hasRelatedWork W1557655644 @default.