Wang Jia, Marks Joshua H, Fortenberry Ryan C, Kaiser Ralf I
W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, HI 96822, USA.
Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, USA.
Sci Adv. 2024 Mar 15;10(11):eadl3236. doi: 10.1126/sciadv.adl3236. Epub 2024 Mar 13.
Glyceric acid [HOCHCH(OH)COOH]-the simplest sugar acid-represents a key molecule in biochemical processes vital for metabolism in living organisms such as glycolysis. Although critically linked to the origins of life and identified in carbonaceous meteorites with abundances comparable to amino acids, the underlying mechanisms of its formation have remained elusive. Here, we report the very first abiotic synthesis of racemic glyceric acid via the barrierless radical-radical reaction of the hydroxycarbonyl radical (HOĊO) with 1,2-dihydroxyethyl (HOĊHCHOH) radical in low-temperature carbon dioxide (CO) and ethylene glycol (HOCHCHOH) ices. Using isomer-selective vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry, glyceric acid was identified in the gas phase based on the adiabatic ionization energies and isotopic substitution studies. This work reveals the key reaction pathways for glyceric acid synthesis through nonequilibrium reactions from ubiquitous precursor molecules, advancing our fundamental knowledge of the formation pathways of key biorelevant organics-sugar acids-in deep space.
甘油酸[HOCHCH(OH)COOH]——最简单的糖酸——是生物体内糖酵解等新陈代谢至关重要的生化过程中的关键分子。尽管它与生命起源密切相关,且在碳质陨石中被发现,其丰度与氨基酸相当,但其形成的潜在机制仍不清楚。在此,我们报告了通过羟基羰基自由基(HOĊO)与1,2 -二羟乙基(HOĊHCHOH)自由基在低温二氧化碳(CO)和乙二醇(HOCHCHOH)冰中的无障碍自由基-自由基反应首次非生物合成外消旋甘油酸。使用异构体选择性真空紫外光电离反射式飞行时间质谱,基于绝热电离能和同位素取代研究在气相中鉴定出了甘油酸。这项工作揭示了通过普遍存在的前体分子的非平衡反应合成甘油酸的关键反应途径,推进了我们对深空中关键生物相关有机物——糖酸——形成途径的基础知识。