Ab-initio and experimental study of pentose sugar dehydration mechanism in the gas phase

被引：13

作者：

Antonini, L. ^{[1
,2
,4
]}

Garzoli, S. ^{[1
]}

Ricci, A. ^{[3
]}

Troiani, A. ^{[1
]}

Salvitti, C. ^{[1
]}

Giacomello, P. ^{[1
]}

Ragno, R. ^{[1
,2
,4
]}

Patsilinakos, A. ^{[1
,2
,4
]}

Di Rienzo, B. ^{[3
]}

Pepi, F. ^{[1
]}

机构：

[1] Sapienza Univ Rome, Dept Chem & Drug Technol, Ple A Moro 5, I-00185 Rome, Italy

[2] Sapienza Univ Rome, Rome Ctr Mol Design, Ple A Moro 5, I-00185 Rome, Italy

[3] Yet Second Univ Naples, L Vanvitelli Univ Campania, Dept Math & Phys, Viale Lincoln 5, I-81100 Caserta, Italy

[4] Alchem Dynam Srl, I-00125 Rome, Italy

来源：

CARBOHYDRATE RESEARCH | 2018年 / 458卷

关键词：

Biomass; Xylose; Ribose; Arabinose; Gas phase dehydration; Mass spectrometry; D-XYLOSE; ACID; 2-FURALDEHYDE; CHEMICALS; BIOFUELS; GLUCOSE; HYBRID; WATER;

D O I：

10.1016/j.carres.2018.01.007

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

In this work pentose sugar (D-xylose, D-ribose and D-arabinose) gas phase dehydration reaction was investigated by means of mass spectrometric techniques and theoretical calculations. The ionic species derived from the dehydration reaction of protonated D-ribose and D-arabinose were structurally characterized by their fragmentation patterns and the relative dehydration energies measured by energy resolved CAD mass spectra. The results were compared with those recently obtained for D-xylose in the same mass spectrometric experimental conditions. Dehydration of C1-OH protonated sugars was theoretically investigated at the CCSD(T)/cc-pVTZ//M11/6-311thornthornG(2d, 2p) level of theory. Protonated pentoses are not stable and promptly lose a water molecule giving rise to the dehydrated ions at m/z 133. D-xylose, D-ribose and D-arabinose dehydration follows a common reaction pathway with ionic intermediates and transition states characterized by similar structures. Slightly different dehydration energies were experimentally measured and the relative trend was theoretically confirmed. The overall dehydration activation energy follows the order arabinose < ribose < xylose. Gas-phase pentose sugar dehydration leads to the formation of protonated 2-furaldehyde as final product. Based on the experimental and theoretical evidence a new mechanistic hypothesis starting from C1-OH protonation was proposed. (c) 2018 Elsevier Ltd. All rights reserved.

引用

页码：19 / 28

页数：10

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