气相中水介导的甲基乙二醛与其偕二醇之间的平衡。
Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol.
机构信息
Department of Chemistry and Biochemistry, and Cooperative Institute for Research in Environmental Sciences, Campus Box 215, University of Colorado, Boulder, CO 80309, USA.
出版信息
Proc Natl Acad Sci U S A. 2010 Apr 13;107(15):6687-92. doi: 10.1073/pnas.0912121107. Epub 2010 Feb 8.
Abstract
In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, K(P), for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, DeltaG(o), obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry.
摘要
在水溶液中，醛类，在较小程度上还有酮类，会水合形成偕二醇。我们研究了在气相中甲基乙二醛（MG）的水合作用，这一过程以前并未被认为在水受限环境中发生。在这项研究中，我们通过光谱学鉴定了甲基乙二醛二醇（MGD），并获得了 MG 和 MGD 在气相中的分压。这些结果与相对湿度结合使用，得到了气相中水介导的 MG 水合的平衡常数 K(P)。由此得到的这个过程的吉布斯自由能ΔG(o)表明气相中二醇的浓度比预期的要大。这对于理解有机物质在大气化学中的作用可能具有重要意义。
相似文献
1
Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol.气相中水介导的甲基乙二醛与其偕二醇之间的平衡。
Proc Natl Acad Sci U S A. 2010 Apr 13;107(15):6687-92. doi: 10.1073/pnas.0912121107. Epub 2010 Feb 8.
2
Hydration, Orientation, and Conformation of Methylglyoxal at the Air-Water Interface.甲基乙二醛在气-水界面的水合作用、取向和构象
J Phys Chem A. 2015 Jun 18;119(24):6391-403. doi: 10.1021/acs.jpca.5b03555. Epub 2015 Jun 1.
3
Potential trace metal-organic complexation in the atmosphere.大气中潜在的痕量金属-有机络合作用。
ScientificWorldJournal. 2002 Mar 21;2:767-86. doi: 10.1100/tsw.2002.132.
4
Secondary organic aerosol formation by self-reactions of methylglyoxal and glyoxal in evaporating droplets.甲基乙二醛和乙二醛在蒸发液滴中的自反应形成二次有机气溶胶。
Environ Sci Technol. 2009 Nov 1;43(21):8184-90. doi: 10.1021/es902152t.
5
Secondary organic aerosol formation by heterogeneous reactions of aldehydes and ketones: a quantum mechanical study.醛酮类化合物非均相反应生成二次有机气溶胶的量子力学研究
Environ Sci Technol. 2006 Apr 1;40(7):2333-8. doi: 10.1021/es0519785.
6
Energetics of the OH radical H-abstraction reactions from simple aldehydes and their geminal diol forms.简单醛及其偕二醇形式的OH自由基夺氢反应的能量学
J Mol Model. 2024 Jul 6;30(8):253. doi: 10.1007/s00894-024-06058-0.
7
Interfacial Tensions of Aged Organic Aerosol Particle Mimics Using a Biphasic Microfluidic Platform.使用双相微流控平台研究老化有机气溶胶颗粒模拟物的界面张力。
Environ Sci Technol. 2016 Feb 2;50(3):1251-9. doi: 10.1021/acs.est.5b04880. Epub 2016 Jan 19.
8
Gas-phase hydration of glyoxylic acid: Kinetics and atmospheric implications.乙醛酸的气相水合作用：动力学及大气影响
Chemosphere. 2017 Nov;186:430-437. doi: 10.1016/j.chemosphere.2017.08.007. Epub 2017 Aug 6.
9
Synthesis of methanediol [CH(OH)]: The simplest geminal diol.合成甲二醇[CH(OH)]：最简单的偕二醇。
Proc Natl Acad Sci U S A. 2022 Jan 4;119(1). doi: 10.1073/pnas.2111938119.
10
Geminal Diol Formation from the Interaction of a Ketone with Water in the Gas Phase: Structure and Reactivity of Cyclooctanone-(HO) Clusters.气相中酮与水相互作用形成偕二醇：环辛酮-(HO)团簇的结构与反应性
J Phys Chem Lett. 2021 Dec 30;12(51):12419-12425. doi: 10.1021/acs.jpclett.1c03493. Epub 2021 Dec 23.
引用本文的文献
1
Energetics of the OH radical H-abstraction reactions from simple aldehydes and their geminal diol forms.简单醛及其偕二醇形式的OH自由基夺氢反应的能量学
J Mol Model. 2024 Jul 6;30(8):253. doi: 10.1007/s00894-024-06058-0.
2
Theoretical Study of the Gas-Phase Hydrolysis of Formaldehyde to Produce Methanediol and Its Implication to New Particle Formation.甲醛气相水解生成甲二醇的理论研究及其对新粒子形成的启示
ACS Omega. 2023 Apr 21;8(17):15467-15478. doi: 10.1021/acsomega.3c00770. eCollection 2023 May 2.
3
Synthesis of methanediol [CH(OH)]: The simplest geminal diol.合成甲二醇[CH(OH)]：最简单的偕二醇。
Proc Natl Acad Sci U S A. 2022 Jan 4;119(1). doi: 10.1073/pnas.2111938119.
4
A family of structural and functional models for the active site of a unique dioxygenase: Acireductone dioxygenase (ARD).一种独特的双氧酶（ARD）活性位点的结构和功能模型的家族。
J Inorg Biochem. 2020 Nov;212:111253. doi: 10.1016/j.jinorgbio.2020.111253. Epub 2020 Sep 14.
5
Hydrolysis of Formyl Fluoride Catalyzed by Sulfuric Acid and Formic Acid in the Atmosphere.大气中硫酸和甲酸催化甲酰氟的水解作用。
ACS Omega. 2019 Nov 7;4(21):18996-19004. doi: 10.1021/acsomega.9b01864. eCollection 2019 Nov 19.
6
Regioselective thioacetylation of chitosan end-groups for nanoparticle gene delivery systems.用于纳米颗粒基因递送系统的壳聚糖端基的区域选择性硫代乙酰化
Chem Sci. 2015 Aug 1;6(8):4650-4664. doi: 10.1039/c5sc00038f. Epub 2015 May 7.
7
Photochemical Synthesis of Oligomeric Amphiphiles from Alkyl Oxoacids in Aqueous Environments.在水相环境中从烷基亚氧羧酸合成低聚两亲物的光化学方法。
J Am Chem Soc. 2017 May 24;139(20):6946-6959. doi: 10.1021/jacs.7b01707. Epub 2017 May 16.
8
DFT study of the mechanism of the reaction of aminoguanidine with methylglyoxal.氨基胍与甲基乙二醛反应机理的密度泛函理论研究
J Mol Model. 2014 Apr;20(4):2202. doi: 10.1007/s00894-014-2202-z. Epub 2014 Apr 5.
9
Photochemistry of aqueous pyruvic acid.水合丙酮酸的光化学。
Proc Natl Acad Sci U S A. 2013 Jul 16;110(29):11714-9. doi: 10.1073/pnas.1303206110. Epub 2013 Jul 2.
10
Methylglyoxal activates nociceptors through transient receptor potential channel A1 (TRPA1): a possible mechanism of metabolic neuropathies.甲基乙二醛通过瞬时受体电位通道 A1（TRPA1）激活伤害感受器：代谢性神经病变的一种可能机制。
J Biol Chem. 2012 Aug 17;287(34):28291-306. doi: 10.1074/jbc.M111.328674. Epub 2012 Jun 27.
本文引用的文献
1
.alpha.-Dicarbonyl yields from the NOx-air photooxidations of a series of aromatic hydrocarbons in air.
Environ Sci Technol. 1986 Apr 1;20(4):383-7. doi: 10.1021/es00146a010.
2
Organic aerosols in the Earth's atmosphere.地球大气中的有机气溶胶。
Environ Sci Technol. 2009 Oct 15;43(20):7614-8. doi: 10.1021/es9006004.
3
Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols.大气中表面的反应：实验与理论的整合是预测气溶胶物理化学性质的必要条件（但不一定充分）。
Phys Chem Chem Phys. 2009 Sep 28;11(36):7760-79. doi: 10.1039/b906540g. Epub 2009 Jul 27.
4
Optical absorptivity versus molecular composition of model organic aerosol matter.光学吸收率与模型有机气溶胶物质的分子组成。
J Phys Chem A. 2009 Oct 1;113(39):10512-20. doi: 10.1021/jp904644n.
5
Thermodynamics and kinetics of methylglyoxal dimer formation: a computational study.甲基乙二醛二聚体形成的热力学与动力学：一项计算研究。
J Phys Chem A. 2009 Jun 25;113(25):6994-7001. doi: 10.1021/jp903213k.
6
Fundamental and overtone vibrational spectra of gas-phase pyruvic acid.气相丙酮酸的基频和泛频振动光谱。
J Phys Chem A. 2009 Jul 2;113(26):7294-303. doi: 10.1021/jp810687t.
7
Spectroscopy of photoreactive systems: implications for atmospheric chemistry.光反应体系的光谱学：对大气化学的影响。
J Phys Chem A. 2009 Jan 8;113(1):5-18. doi: 10.1021/jp806365r.
8
Atmospheric chemistry of acetylacetone.乙酰丙酮的大气化学
Environ Sci Technol. 2008 Nov 1;42(21):7905-10. doi: 10.1021/es8010282.
9
Experimental and theoretical study of the OH vibrational spectra and overtone chemistry of gas-phase vinylacetic acid.气相乙烯基乙酸的OH振动光谱及泛音化学的实验与理论研究
J Phys Chem A. 2008 Oct 16;112(41):10226-35. doi: 10.1021/jp805746t. Epub 2008 Sep 18.
10
Dynamics of vibrational overtone excited pyruvic acid in the gas phase: line broadening through hydrogen-atom chattering.气相中振动泛音激发丙酮酸的动力学：通过氢原子颤动实现谱线展宽
J Phys Chem A. 2008 Aug 14;112(32):7321-31. doi: 10.1021/jp803225c. Epub 2008 Jul 19.
Zotero 插件