揭示手性在单萜烯氧化中的作用。

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Linyu Gao, Sébastien Perrier, Siddharth Iyer, Laurent Vanoye, Fabienne Fache, Megan S. Claflin, Theo Kurten and Matthieu Riva*, 
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引用次数: 0

摘要

单萜烯氧化是大气中二次有机气溶胶(SOA)形成和生长的主要因素。尽管大多数单萜天然以两种对映体形式存在,但它们的分子手性对SOA形成的影响一直被忽视,部分原因是假设前体的手性不会影响气态氧化过程,当考虑非手性氧化剂(例如,O3, OH自由基)时。在这项研究中,我们系统地研究了两种常见的单萜烯(±)-α-蒎烯和(±)-柠檬烯在大气相关浓度下的气相氧化。与(-)对映体相比,(+)-α-蒎烯和(+)-柠檬烯的氧化有机分子(OOMs)的形成率分别为15±0.3%和19±0.2%。我们认为这些观察结果是由于氧化过程中与RO2寿命和双分子反应相关的关键中间步骤的差异。例如,(+)-柠檬烯的氧化促进烷氧基自由基的形成,烷氧基自由基主要经过异构化和随后的自由基增殖,导致OOM的产生增加。相反,(-)-柠檬烯氧化有利于碳骨架的断裂,产生更多的挥发性产物。所观察到的对映体种群之间产品产量的差异预计会对SOA的形成产生大气影响,因为植被胁迫事件(如气候变化引起的干旱)和挥发性化学产品的使用改变了对映体的组成。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Unveiling the Role of Chirality in the Oxidation of Monoterpenes

Unveiling the Role of Chirality in the Oxidation of Monoterpenes

Monoterpene oxidation is a major contributor to the formation and growth of a secondary organic aerosol (SOA) in the atmosphere. Although most monoterpenes naturally exist in two enantiomeric forms, the impact of their molecular chirality on SOA formation has been neglected, in part due to the hypothesis that a precursor’s chirality will not impact gaseous oxidation processes when considering achiral oxidants (e.g., O3, OH radicals). Within this study, we systematically investigated the gas-phase oxidation of the enantiomers of two common monoterpenes, (±)-α-pinene and (±)-limonene, at atmospherically relevant concentrations. We demonstrate greater formation (15 ± 0.3% and 19 ± 0.2%) of oxidized organic molecules (OOMs) for (+)-α-pinene and (+)-limonene, respectively, compared to their (−) enantiomers. We propose these observations are due to differences in key intermediate steps within the oxidation process that correlate with RO2 lifetime and bimolecular reactions. For example, oxidation of (+)-limonene promotes the formation of alkoxy radicals, which predominately undergo isomerization and subsequent radical propagation, leading to enhanced OOM production. In contrast, (−)-limonene oxidation favors the scission of the carbon skeleton, producing more volatile products. The observed differences in product yields between the enantiomer populations are expected to have atmospheric repercussions on SOA formation due to shifting enantiomer compositions from vegetation stress events (e.g., drought due to climate change) and the use of volatile chemical products.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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