Kinetics, products, and mechanisms of secondary organic aerosol formation

Secondary organic aerosol (SOA) is formed in the atmosphere when volatile organic compounds (VOCs) emitted from anthropogenic and biogenic sources are oxidized by reactions with OH radicals, O(3), NO(3) radicals, or Cl atoms to form less volatile products that subsequently partition into aerosol particles. Once in particles, these organic compounds can undergo heterogenous/multiphase reactions to form more highly oxidized or oligomeric products. SOA comprises a large fraction of atmospheric aerosol mass and can have significant effects on atmospheric chemistry, visibility, human health, and climate. Previous articles have reviewed the kinetics, products, and mechanisms of atmospheric VOC reactions and the general chemistry and physics involved in SOA formation. In this article we present a detailed review of VOC and heterogeneous/multiphase chemistry as they apply to SOA formation, with a focus on the effects of VOC molecular structure on the kinetics of initial reactions with the major atmospheric oxidants, the subsequent reactions of alkyl, alkyl peroxy, and alkoxy radical intermediates, and the composition of the resulting products. Structural features of reactants and products discussed include compound carbon number; linear, branched, and cyclic configurations; the presence of C[double bond, length as m-dash]C bonds and aromatic rings; and functional groups such as carbonyl, hydroxyl, ester, hydroxperoxy, carboxyl, peroxycarboxyl, nitrate, and peroxynitrate. The intention of this review is to provide atmospheric chemists with sufficient information to understand the dominant pathways by which the major classes of atmospheric VOCs react to form SOA products, and the further reactions of these products in particles. This will allow reasonable predictions to be made, based on molecular structure, about the kinetics, products, and mechanisms of VOC and heterogeneous/multiphase reactions, including the effects of important variables such as VOC, oxidant, and NO(x) concentrations as well as temperature, humidity, and particle acidity. Such knowledge should be useful for interpreting the results of laboratory and field studies and for developing atmospheric chemistry models. A number of recommendations for future research are also presented.     

Mechanism and Kinetics of the Reaction of Nitrosamines with OH Radical: A Theoretical Study

The reaction of nitrosodimethylamine, nitrosoazetidine, nitrosopyrrolidine, and nitrosopiperidine with the hydroxyl radical has been studied using electronic structure calculations in gas and aqueous phases. The rate constant was calculated using variational transition state theory. The reactions are initiated by H‐atom abstraction from the αC─H group of nitrosamines and leads to the formation of alkyl radical intermediate. In the subsequent reactions, the initially formed alkyl radical intermediate reacts with O₂ forming a peroxy radical. The reaction of peroxy radical with other atmospheric oxidants, such as HO₂ and NO radicals, is studied. The structures of the reactive species were optimized by using the density functional theory methods, such as M06‐2X, MPW1K, and BHandHLYP, and hybrid methods G3B3. The single‐point energy calculations were also performed at CCSD(T)/6‐311+G(d,p)// M062X/6‐311+G(d,p) level. The calculated thermodynamical parameters show that the reactions corresponding to the formation of intermediates and products are highly exothermic. We have calculated the rate constant for the initial H‐atom abstraction and subsequent favorable secondary reactions using canonical variational transition state theory over the temperature range of 150–400 K. The calculated rate constant for initial H‐atom abstraction reaction is ∼3 × 10⁻¹² cm³ molecule⁻¹ s⁻¹ and is in agreement with the previous experimental results. The calculated thermochemical data and rate constants show that the reaction profile and kinetics of the reactions are less dependent on the number of methyl groups present in the nitrosoamines. Furthermore, it has been found that the atmospheric lifetime of nitrosamines is around 5 days in the normal atmospheric OH concentration.     

Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx

A detailed photochemical mechanism for the atmospheric reactions of isoprene and its major oxidation products in the presence of NO_x, which incorporates the most recent laboratory results and our current understanding of the system, is described. It is evaluated by comparing its predictions against results of NO_x-air irradiations of isoprene and its two major products, methacrolein, and methyl vinyl ketone (MVK), in five different types of environmental chambers at two different laboratories. In most cases it simulated experimental results within the uncertainty of the data and the chamber and run characterization model. However, the photodecomposition quantum yields of methacrolein and MVK and the organic nitrate yield from the OH + isoprene reaction had to be adjusted to obtain satisfactory simulations of the data. The major discrepancy observed was that the model tended to underpredict PAN by ca. 40% in the isoprene experiments, despite the fact that the model predicted PAN from methacrolein and MVK reasonably well. The uncertainties and additional data needed to completely characterize the isoprene atmospheric photooxidation system are discussed. © 1996 John Wiley & Sons, Inc.     

Quantification of hydroxycarbonyls from OH-isoprene reactions

Hydroxycarbonyls arising from OH-initiated reactions of isoprene have been quantified by the technique of a flow reactor coupled to proton-transfer reaction mass spectrometry (PTR-MS) detection. The yields of C5- and C4-hydroxycarbonyls are (19.3 +/- 6.1)% and (3.3 +/- 1.6)%, respectively, measured at a flow tube pressure of about 100 Torr and at a temperature of 298 +/- 2 K. A yield of (8.4 +/- 2.4)% is obtained for the unsaturated carbonyl C5H8O, confirming that internal OH addition represents the minor channel in the initial OH-isoprene reaction. The results show that those carbonyl compounds account for the most previously unquantified carbon, enabling the isoprene carbon closure. The study also reveals novel aspects of the delta-hydroxyalkoxy radical degradation mechanism, which is essential for modeling tropospheric O3 formation. In addition, this work demonstrates the application of PTR-MS for quantification of products of hydrocarbon reactions, which should have profound impacts on elucidation of the chemistry of atmospheric anthropogenic and biogenic hydrocarbons.     

Formation of 3-Methylfuran from the gas-phase reaction of OH radicals with isoprene and the rate constant for its reaction with the OH radical

3-Methylfuran has been identified as a product of the gas-phase reaction of the OH radical with isoprene, and under simulated atmospheric conditions a formation yield of 0.044 ± 0.006 was determined. In an analogous manner, the OH radical reaction with 1,3-butadiene formed furan with a yield of 0.039 ± 0.011. Using a relative rate method, a rate constant for the reaction of the OH radical with 3-methylfuran of 9.35 × 10^?11 cm³ molecule^?1 s^?1 (with an estimated overall uncertainty of ±20%) at 296 ± 2 K was also determined. These data show that 3-methylfuran is a reactive compound which will be present in the troposphere at concentrations ?5% of those of its isoprene precursor.     

Highly Oxygenated Molecules from Atmospheric Autoxidation of Hydrocarbons: A Prominent Challenge for Chemical Kinetics Studies

Recent advances in chemical ionization mass spectrometry have allowed the detection of a new group of compounds termed highly oxygenated molecules (HOM). These are atmospheric oxidation products of volatile organic compounds (VOC) retaining most of their carbon backbone, and with O/C ratios around unity. Owing to their surprisingly high yields and low vapor pressures, the importance of HOM for aerosol formation has been easy to verify. However, the opposite can be said concerning the exact formation pathways of HOM from major aerosol precursor VOC. While the role of peroxy radical autoxidation, i.e., consecutive intramolecular H‐shifts followed by O₂ addition, has been recognized, the detailed formation mechanisms remain highly uncertain. A primary reason is that the autoxidation process occurs on sub‐second timescales and is extremely sensitive to environmental conditions like gas composition, temperature, and pressure. This, in turn, poses a great challenge for chemical kinetics studies to be able to mimic the relevant atmospheric reaction pathways, while simultaneously using conditions suitable for studying the short‐lived radical intermediates. In this perspective, we define six specific challenges for this community to directly observe the initial steps of atmospherically relevant autoxidation reactions and thereby facilitate vital improvements in the understanding of VOC degradation and organic aerosol formation.     

Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

The propagation kinetics of isoprene radical polymerizations in bulk and in solution are investigated via pulsed laser initiated polymerizations and subsequent polymer analyses via size‐exclusion chromatography, the PLP‐SEC method. Because of low polymerization rate and high volatility of isoprene, the polymerizations are carried out at elevated pressure ranging from 134 to 1320 bar. The temperatures are varied between 55 and 105 °C. PLP‐SEC yields activation parameters of k_p (Arrhenius parameters and activation volume) over a wide temperature and pressure range that allow for the calculation of k_p at technically relevant ambient pressure conditions. The k_p values determined are very low, e.g., 99 L mol^?1 s^?1 at 50 °C, which is even lower than the corresponding value for styrene polymerizations. The presence of a polar solvent results in a slight increase of k_p compared to the bulk system. The k_p values reported are important for determining rate coefficients of other elemental reactions from coupled parameters as well as for modeling isoprene free‐radical polymerizations and reversible deactivation radical polymerization with respect to tailored polymer properties and optimizing the polymerization processes.     

Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues

Radical S‐adenosyl‐l ‐methionine (SAM) enzymes utilize a [4Fe‐4S] cluster to bind SAM and reductively cleave its carbon–sulfur bond to produce a highly reactive 5′‐deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical‐based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical‐based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside‐containing compounds by using radical SAM‐dependent reactions.     

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

A mild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. A variety of sulfur containing motifs including alkanethiols, thiophenols and thioacids undergo an atmospheric oxygen-mediated radical hydrothiolation reaction with a plethora of alkenes in good yield with excellent functional group compatibility, typically with short reaction times to furnish a range of functionalized products. Biomolecules proved tolerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds through radical intermediates in a thiol-ene reaction manifold. The methodology offers an efficient “green” approach for thiol-ene mediated “click” ligation and a milder alternative to thermally initiated hydrothiolation processes.     

Product formation from the reaction of the NO3 radical with isoprene and rate constants for the reactions of methacrolein and methyl vinyl ketone with the NO3 radical

Using a relative rate method, rate constants for the gas-phase reactions of the NO₃ radical with methacrolein and methyl vinyl ketone were determined to be (4.4 ± 1.7) × 10⁻¹⁵ cm³ molecule⁻¹ s⁻¹ and <6 × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹, respectively, at 296 ± 2 K. The molar formation yields of methacrolein and methyl vinyl ketone from the gas-phase reaction of the NO₃ radical with isoprene at 296 ± 2 K and atmospheric pressure of air were measured to be 0.035 ± 0.014 each. The tropospheric implications of these kinetic and product data are discussed, and it is concluded that the nighttime NO₃ radical reactions with methacrolein and methyl vinyl ketone are not important. However, during nighttime the formation of methacrolein and methyl vinyl ketone from the reaction of isoprene with the NO₃ radical may dominate over their formation from the O₃ reaction with isoprene. Atmospheric pressure ionization tandem mass spectrometry (API-MS/MS) was used to investigate the products of the reactions of the NO₃ radical with isoprene and isoprene-d₈, and C₅-nitrooxycarbonyl(s) (e.g., O₂NOCH₂C(CH₃) (DOUBLEBOND) CHCHO), C₅-hydroxynitrate(s) (e.g., O₂NOCH₂C(CH₃)(DOUBLEBOND) CHCH₂OH), C₅-nitrooxyhydroperoxide(s) (e.g., O₂NOCH₂C(CH₃)(DOUBLEBOND) CHCH₂OOH), and C₅-hydroxycarbonyl(s) (e.g., HOCH₂CH(DOUBLEBOND) C(CH₃)CHO) and their deuterated analogs were observed from these reactions. © 1996 John Wiley & Sons, Inc.     

Kinetics Investigation of OH reaction with isoprene at 240-340 K and 1-3 torr using the relative rate/discharge flow/mass spectrometry technique

The kinetics of the reaction of OH radical with isoprene has been investigated at a total pressure of 1-3 Torr over a temperature range of 240-340 K using the relative rate/discharge flow/mass spectrometry (RR/DF/MS) technique. The reaction of isoprene with OH was found to be independent of pressure over the pressure range of 1-3 Torr at 298 K, and the reaction had reached its high-pressure limit at 1 Torr. However, the rate constant of this reaction is found to positively depend on pressure at 1-3 Torr and 340 K. At 298 K, the rate constant of this reaction was determined to be k1 = (10.4 +/- 1.9) x 10(-11) cm3 molecule(-1) s(-1), which is in good agreement with literature values. The Arrhenius expression for this reaction was determined to be k1 = (2.33 +/- 0.09) x 10(-11) exp[(444 +/- 27)/T] cm3 molecule(-1) s(-1) at 240-340 K. The atmospheric lifetime of isoprene was estimated to be 2.9 h based on the rate constant of isoprene + OH determined at 277 K in the present work.     

Detection of transient radical cations in electron transfer-initiated Diels-Alder reactions by electrospray ionization mass spectrometry

The coupling of a simple microreactor to an atmospheric pressure ion source, such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), allows the investigation of reactions in solution by mass spectrometry. The tris(p-bromophenyl)aminium hexachloroantimonate (1(*)(+)SbCl(6)(-))-initiated reactions of phenylvinylsulfide (2) and cyclopentadiene (3) and of trans-anethole (5) and isoprene (6) and the dimerization of 1,3-cyclohexadiene (8) to give the respective Diels-Alder products were studied. These preparatively interesting reactions proceed as radical cation chain reactions via the transient radical cations of the respective dienophiles and of the respective Diels-Alder addition products. These radical cations could be detected directly and characterized unambiguously in the reacting solution by ESI-MS-MS. The identity was confirmed by comparison with MS-MS spectra of the authentic radical cations obtained by APCI-MS and by CID experiments of the corresponding molecular ions generated by EI-MS. In addition, substrates and products could be monitored easily in the reacting solution by APCI-MS.     

Catalysis of Radical Reactions: A Radical Chemistry Perspective

The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in “catalytic amounts” is a catalyst, an initiator, or something else? Herein we critically address both catalyst‐free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non‐chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.     

Red‐Light‐Induced Decomposition of an Organic Peroxy Radical: A New Source of the HO2 Radical

The gas‐phase decomposition of the α‐hydroxy methylperoxy radical has been theoretically examined, and the results provide insight into a new source of the hydroperoxy radical (HO₂) in the troposphere. Bimolecular peroxy decomposition is promoted by the red‐light or near‐IR radiation excitation. The calculations suggest for the first time, an important chemical role for the H₂O?HO₂ radical complex that exist in significant abundance in the troposphere. In particular, the reaction of organic peroxy radicals with the HO₂ radical and the H₂O?HO₂ radical complex represent an autocatalytic source of atmospheric HO₂. This reaction is a new example of red‐light‐initiated atmospheric chemistry that may help in understanding the discrepancy between the observed and measured levels of the HO_x at sunrise.     

Anodic Cyclizations,Seven‐Membered Rings,and the Choice of Radical Cation vs. Radical Pathways

While many steps in an oxidative cyclization reaction can be important, it is the cyclization step itself that plays the central role. If this step does not proceed well, then optimization of the rest of the sequence is futile. We report here that the key to the cyclization is channeling the reaction down the correct pathway. Some reactions require the use of a radical pathway and some require the use of a radical cation pathway. An example of each is provided along with a strategy for accessing both pathways using a common intermediate.     

Dearomatization of Biaryls through Polarity Mismatched Radical Spirocyclization

Dearomatization reactions involving radical cyclizations can facilitate the synthesis of complex polycyclic systems that find applications in medicinal chemistry and natural product synthesis. Here we employ redox-neutral photocatalysis to affect a radical spirocyclization that transforms biaryls into spirocyclic cyclohexadienones under mild reaction conditions. In a departure from previously reported methods, our work demonstrates the polarity mismatched addition of a nucleophilic radical to an electron rich arene, and allows the regioselective synthesis of 2,4- or 2,5-cyclohexadienones with broad functional group tolerance. By transforming biaryls into spirocycles, our methodology accesses underexplored three-dimensional chemical space, and provides an efficient means of creating quaternary spirocenters that we apply to the first synthesis of the cytotoxic plant metabolite denobilone A.     

A product study of the gas-phase reaction of Isoprene with the OH radical in the presence of NOx

The gas-phase reaction of isoprene with the OH radical, in the resence of NO_x, was investigated at 298 ± 2 K and atmospheric pressure of air by long path length FT-IR spectroscopy. The primary products identified and their formation yields were: methacrolein, 0.21 ± 0.05; methyl vinyl ketone, 0.29 ± 0.07; and HCHO, with the observed yield being consistent with the sum of the methacrolein and methyl vinyl ketone yields. Combined with the previously reported yield of 0.044 ± 0.006 for 3-methylfuran, these products accounted for 55 ± 9% of the isoprene which reacted. Under conditions where the dark reaction of isoprene with NO₂is not significant, the balance of the isoprene consumed could possibly be accounted for by the “organic nitrates” and “other carbonyl compounds” formed in estimated overall yields of ca. 12% and ca. 25%, respectively.     

C2H与HO2双自由基反应的密度泛函理论研究

应用量子化学从头算和密度泛函理论(DFT)对C₂H与HO₂双自由基的单重态反应进行了研究.在UB3LYP/6-311G水平上优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型.在CCSD(T)/6-311G^{**水平上计算了各物种的单点能,并对总能量进行了零点能校正.研究结果表明,反应物中自由基C₂H的边端C进攻自由基HO₂的边端O是主要的进攻方式.首先形成了中间体1(HCCOOH),由此经过不同的反应通道可以得到主要产物P1,次要产物P2,P3和P5.生成P1的反应热为-814.40kJ/mol.自由基C₂H的中间C进攻自由基HO₂的边端O是次要的进攻方式,可以得到产物P4和P6.根据势能面分析,所有反应均是放热反应.}     

自由基三氟甲基化反应进展

近年来,三氟甲基化反应得到了快速的发展和广泛的关注,由于三氟甲基本身的一些特殊化学和物理性质,使得其在医药、农药和材料等领域发挥着越来越重要的作用。 随着有机氟化学的发展,对于自由基三氟甲基化反应也有了新的认识。 本文通过对不同的三氟甲基试剂作为三氟甲基自由基的前体,综述了近年来自由基三氟甲基化反应的研究进展,并予以展望。     

分子间自由基正离子反应研究进展

自由基正离子含有一个正电荷和一对未成对电子,是很多有机化学反应的重要的活性中间体。文章综述了近几年自由基正离子反应研究进展,主要包括化学氧化剂诱导的自由基正离子反应、可见光诱导的自由基正离子反应、电诱导的自由基正离子反应等方面的研究。