Mechanisms and Energetics for Acid Catalyzed β-D-Glucose Conversion to 5-Hydroxymethylfurfurl

被引：55

作者：

Qian, Xianghong ^{[1
]}

机构：

[1] Univ Arkansas, Dept Chem Engn, Fayetteville, AR 72701 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 42期

基金：

美国国家科学基金会;

关键词：

MOLECULAR-DYNAMICS SIMULATIONS; D-FRUCTOSE; D-XYLOSE; CONDENSATION-REACTIONS; HIGH-TEMPERATURE; LIQUID ALKANES; WATER; DEHYDRATION; 5-HYDROXYMETHYL-2-FURALDEHYDE; DENSITY;

D O I：

10.1021/jp2041982

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Car-Parrinello based ab initio molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations were carried out to investigate the mechanism and energetics for acid-catalyzed beta-D-glucose conversion to 5-hydroxymethylfurfurl (HMF) in water. HMF is a critical intermediate for biomass conversion to biofuels. It was found that protonation of the C2-OH on glucose, the breakage of the C2-O2 bond, and the formation of the C2-O5 bond is the critical rate-limiting step for the direct glucose conversion to HMF without converting to fructose first, contrary to the wide-spread assumption in literature that fructose is the main intermediate for glucose conversion to HMF. The calculated reaction barrier of 30-35 kcal/mol appears to be solvent-induced and is in excellent agreement with experimental observations.

引用

页码：11740 / 11748

页数：9

共 57 条

[1] MOLECULAR-DYNAMICS SIMULATIONS AT CONSTANT PRESSURE AND-OR TEMPERATURE [J].

ANDERSEN, HC .

JOURNAL OF CHEMICAL PHYSICS, 1980, 72 (04) :2384-2393

[2] A tribute to Michele Parrinello: From physics via chemistry to biology [J].

Andreoni, W ;

Marx, D ;

Sprik, M .

CHEMPHYSCHEM, 2005, 6 (09) :1671-1676

[3] New advances in chemistry and materials science with CPMD and parallel computing [J].

Andreoni, W ;

Curioni, A .

PARALLEL COMPUTING, 2000, 26 (7-8) :819-842

[4] THE COMPOSITION OF REDUCING SUGARS IN SOLUTION [J].

ANGYAL, SJ .

ADVANCES IN CARBOHYDRATE CHEMISTRY AND BIOCHEMISTRY, 1984, 42 :15-68

[5]

[Anonymous], REP PROG PHYS

[6]

[Anonymous], 1921, ANN PHYS-NEW YORK, DOI DOI 10.1002/ANDP.19213690304

[7] KINETIC-STUDIES OF THE REACTIONS OF KETOSES AND ALDOSES IN WATER AT HIGH-TEMPERATURE .1. MECHANISM OF FORMATION OF 5-(HYDROXYMETHYL)-2-FURALDEHYDE FROM D-FRUCTOSE AND SUCROSE [J].

ANTAL, MJ ;

MOK, WSL ;

RICHARDS, GN .

CARBOHYDRATE RESEARCH, 1990, 199 (01) :91-109

[8] KINETIC-STUDIES OF THE REACTIONS OF KETOSES AND ALDOSES IN WATER AT HIGH-TEMPERATURE .3. MECHANISM OF FORMATION OF 2-FURALDEHYDE FROM D-XYLOSE [J].

ANTAL, MJ ;

LEESOMBOON, T ;

MOK, WS ;

RICHARDS, GN .

CARBOHYDRATE RESEARCH, 1991, 217 :71-85

[9] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[10] Substrate distortion in the michaelis complex of Bacillus 1,3-1,4-β-glucanase -: Insight from first principles molecular dynamics simulations [J].

Biarnés, X ;

Nieto, J ;

Planas, A ;

Rovira, C .

JOURNAL OF BIOLOGICAL CHEMISTRY, 2006, 281 (03) :1432-1441

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