Département de Chimie, Laboratoire des Mécanismes Réactionnels, Ecole Polytechnique, 91120, Palaiseau, France.
Mass Spectrom Rev. 2015 Sep-Oct;34(5):493-534. doi: 10.1002/mas.21416. Epub 2014 Jan 7.
This article constitutes the fourth part of a general review of the gas-phase protonation thermochemistry of polyfunctional molecules (Part 1: Theory and methods, Mass Spectrom Rev 2007, 26:775-835, Part 2: Saturated basic sites, Mass Spectrom Rev 2012, 31:353-390, Part 3: Amino acids, Mass Spectrom Rev 2012, 31:391-435). This fourth part is devoted to carbonyl containing polyfunctional molecules. After a short reminder of the methods of determination of gas-phase basicity and the underlying physicochemical concepts, specific examples are examined under two major chapters. In the first one, aliphatic and unsaturated (conjugated and cyclic) ketones, diketones, ketoalcohols, and ketoethers are considered. A second chapter describes the protonation energetic of gaseous acids and derivatives including diacids, diesters, diamides, anhydrides, imides, ureas, carbamates, amino acid derivatives, and peptides. Experimental data were re-evaluated according to the presently adopted basicity scale. Structural and energetic information given by G3 and G4 quantum chemistry computations on typical systems are presented.
这篇文章是多官能团分子气相质子化热化学综述的第四部分（第一部分：理论和方法，质谱评论 2007，26：775-835；第二部分：饱和碱性位点，质谱评论 2012，31：353-390；第三部分：氨基酸，质谱评论 2012，31：391-435）。第四部分专门讨论含羰基的多官能团分子。在简要回顾确定气相碱性的方法和基础物理化学概念之后，主要分为两章来考察具体实例。在第一章中，考虑了脂肪族和不饱和（共轭和环状）酮、二酮、酮醇和酮醚。第二章描述了包括二酸、二酯、二酰胺、酸酐、酰亚胺、脲、氨基甲酸酯、氨基酸衍生物和肽在内的气态酸及其衍生物的质子化能。根据目前采用的碱性标度重新评估了实验数据。给出了典型体系的 G3 和 G4 量子化学计算的结构和能量信息。
