Wang Jia, Turner Andrew M, 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.
Chemphyschem. 2024 Nov 18;25(22):e202400837. doi: 10.1002/cphc.202400837. Epub 2024 Nov 8.
Acetaldehyde (CHCHO) plays a crucial role in the synthesis of prebiotic molecules such as amino acids, sugars, and sugar-related compounds, and in the progress of chain reaction polymerization in deep space. Here, we report the first formation of the cyclic acetaldehyde trimer - paraldehyde (CHO) - in low-temperature interstellar analog ices exposed to energetic irradiation as proxies of galactic cosmic rays (GCRs). Utilizing vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and isotopic substitution experiments, paraldehyde was identified in the gas phase during the temperature-programmed desorption of the irradiated acetaldehyde ices based on the calculated adiabatic ionization energies and isomer-specific dissociative fragmentation patterns upon photoionization. As acetaldehyde is ubiquitous throughout the interstellar medium and has been tentatively identified in interstellar ices, paraldehyde could have formed in acetaldehyde-containing ices in a cold molecular cloud and is an excellent candidate for gas-phase observation in star-forming regions via radio telescopes. The identification of paraldehyde in the gas phase from the processed acetaldehyde ices advances our understanding of how complex organic molecules can be synthesized through polymerization reactions in extraterrestrial ices exposed to GCRs.
乙醛(CHCHO)在诸如氨基酸、糖类及糖相关化合物等益生元分子的合成过程中,以及在深空中的链式反应聚合进程中发挥着关键作用。在此,我们报告了在模拟银河宇宙射线(GCRs)高能辐照的低温星际冰中首次形成环状乙醛三聚体——仲醛(CHO)。利用真空紫外光电离反射式飞行时间质谱和同位素取代实验,基于计算出的绝热电离能以及光电离时异构体特异性的解离碎片模式,在辐照乙醛冰的程序升温脱附过程中,在气相中鉴定出了仲醛。由于乙醛在整个星际介质中普遍存在,并且已在星际冰中初步鉴定出来,仲醛可能在冷分子云中含乙醛的冰中形成,并且是通过射电望远镜在恒星形成区域进行气相观测的极佳候选物。从经过处理的乙醛冰中气相鉴定出仲醛,推进了我们对于在外星冰中暴露于GCRs时如何通过聚合反应合成复杂有机分子的理解。