Abstract Flash pyrolysis in air of the complete set of 13C1 isotopologs of D-glucose, monitored by GC/MS using an efficient column for separating the light gases, allowed us to determine the sources within D-glucose for a range of light hydrocarbons and carbon oxides. These include carbon monoxide (CO), carbon dioxide (CO2), ethyne, ethene, ethane, propadiene, propene, propane, various isomers of butene, 1,3-butadiene, 1,3-cyclopentadiene and benzene. Inasmuch as the pyrolysis product was swept into the chromatographic column as formed, changes in isotopic incorporation with temperature rise could be qualitatively observed as changes of isotopic content across the chromatographic peak. There was significant divergence in labeled origin of CO and CO2, suggesting substantial mutual independence of formation. For both, however, composition was dominated by the first four carbons of D-glucose. The high-temperature range of formation of these may reflect the composition of the underlying char undergoing combustion. Similarities in isotopic content of ethene and ethane, or of allene, propylene and propane or of the various C4 species suggest that the least saturated versions are formed initially, and then undergo free-radical chain induced hydrogenation. Concerted electrocyclic fragmentations were invoked to explain the dominant formation of ethene, ethyne, propadiene and 1,3-butadiene. CO formation was postulated to arise in part from the fragmentation of glyoxal. CO and CO2 showed strong evidence of preferential ionization of the 13C isotopologs relative to the 12C ipsologs under our conditions, due to the magnetic isotope effect. Overlaid on this was a partial chromatographic enrichment of 13CO2 in the leading edge of the chromatographic peak. The data were normalized to adjust for both effects.

中文翻译：

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来自同位素标记的碳水化合物热解机制。第 5 部分。 D-葡萄糖的热解：来自 D-葡萄糖分子的轻气体的来源

摘要 在空气中快速热解 D-葡萄糖的全套 13C1 同位素，通过 GC/MS 监测，使用有效的色谱柱分离轻质气体，使我们能够确定 D-葡萄糖中一系列轻烃和碳的来源氧化物。这些包括一氧化碳 (CO)、二氧化碳 (CO2)、乙炔、乙烯、乙烷、丙二烯、丙烯、丙烷、丁烯的各种异构体、1,3-丁二烯、1,3-环戊二烯和苯。由于热解产物在形成时被扫入色谱柱，因此可以定性地观察到同位素掺入随温度升高的变化，作为跨色谱峰的同位素含量的变化。CO 和 CO2 的标记来源存在显着差异，表明形成的基本相互独立性。然而，对于两者来说，组成以 D-葡萄糖的前四个碳为主。这些形成的高温范围可能反映了下面正在燃烧的炭的组成。乙烯和乙烷或丙二烯、丙烯和丙烷或各种 C4 物种的同位素含量的相似性表明，最初形成饱和度最低的版本，然后进行自由基链诱导的氢化。调用协同电环碎裂来解释乙烯、乙炔、丙二烯和 1,3-丁二烯的主要形成。推测 CO 的形成部分来自乙二醛的碎裂。由于磁同位素效应，在我们的条件下，CO 和 CO2 显示出 13C 同位素相对于 12C 同位素优先电离的有力证据。叠加在色谱峰前沿的 13CO2 部分色谱富集。将数据标准化以针对两种效应进行调整。