التفاصيل البيبلوغرافية
| العنوان: |
Cooperative Activation of Cellulose with Natural Calcium |
| المؤلفون: |
Gregory G. Facas (10178967), Vineet Maliekkal (5017910), Cheng Zhu (138742), Matthew Neurock (1396330), Paul J. Dauenhauer (1303581) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Cell Biology, Molecular Biology, Inorganic Chemistry, Hematology, Infectious Diseases, Computational Biology, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, role, pulse-heated analysis, glycosidic ether scission, binding configurations, transglycosylation kinetics, millisecond kinetics, Natural Calcium, PHASR, activation barrier, First-principles density, calcium cooperativity, transition states, Cooperative Activation, DFT, rate dependence, mol, intermonomer β- glycosidic bonds, surface reactions, calcium-catalyzed cycle, calcium-catalyzed reactions |
| الوصف: |
Naturally occurring metals, such as calcium, catalytically activate the intermonomer β-glycosidic bonds in long chains of cellulose, initiating reactions with volatile oxygenates for renewable applications. In this work, the millisecond kinetics of calcium-catalyzed reactions were measured via the method of the pulse-heated analysis of solid and surface reactions (PHASR) at high temperatures (370–430 °C) to reveal accelerated glycosidic ether scission with a second-order rate dependence on the Ca 2+ ions. First-principles density functional theory (DFT) calculations were used to identify stable binding configurations for two Ca 2+ ions that demonstrated accelerated transglycosylation kinetics, with an apparent activation barrier of 50 kcal mol –1 for a cooperative calcium-catalyzed cycle. The agreement of the mechanism with calcium cooperativity to the experimental barrier (48.7 ± 2.8 kcal mol –1 ) suggests that calcium enhances the reactivity through a primary role of stabilizing charged transition states and a secondary role of disrupting native H-bonding. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Cooperative_Activation_of_Cellulose_with_Natural_Calcium/14079453 |
| DOI: |
10.1021/jacsau.0c00092.s001 |
| الاتاحة: |
https://doi.org/10.1021/jacsau.0c00092.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.740038EC |
| قاعدة البيانات: |
BASE |