Α-pinene Oxide Research Articles

Four- and Five-Carbon Dicarboxylic Acids Present in Secondary Organic Aerosol Produced from Anthropogenic and Biogenic Volatile Organic Compounds

To better understand precursors of dicarboxylic acids in ambient secondary organic aerosol (SOA), we studied C4–C9 dicarboxylic acids present in SOA formed from the oxidation of toluene, naphthalene, α-pinene, and isoprene. C4–C9 dicarboxylic acids present in SOA were analyzed by offline derivatization gas chromatography–mass spectrometry. We revealed that C4 dicarboxylic acids including succinic acid, maleic acid, fumaric acid, malic acid, DL-tartaric acid, and meso-tartaric acid are produced by the photooxidation of toluene. Since meso-tartaric acid barely occurs in nature, it is a potential aerosol tracer of photochemical reaction products. In SOA particles from toluene, we also detected a compound and its isomer with similar mass spectra to methyltartaric acid standard; the compound and the isomer are tentatively identified as 2,3-dihydroxypentanedioic acid isomers. The ratio of detected C4–C5 dicarboxylic acids to total toluene SOA mass had no significant dependence on the initial VOC/NOx condition. Trace levels of maleic acid and fumaric acid were detected during the photooxidation of naphthalene. Malic acid was produced from the oxidation of α-pinene and isoprene. A trace amount of succinic acid was detected in the SOA produced from the oxidation of isoprene.

The Studies on α-Pinene Oxidation over the TS-1. The Influence of the Temperature, Reaction Time, Titanium and Catalyst Content

The work presents the results of studies on α-pinene oxidation over the TS-1 catalysts with different Ti content (in wt%): TS-1_1 (9.92), TS-1_2 (5.42), TS-1_3 (3.39) and TS-1_4 (3.08). No solvent was used in the oxidation studies, and molecular oxygen was used as the oxidizing agent. The effect of titanium content in the TS-1 catalyst, temperature, reaction time and amount of the catalyst in the reaction mixture on the conversion of α-pinene and the selectivities of appropriate products was investigated. It was found that it is most advantageous to carry out the process of α-pinene oxidation in the presence of the TS-1 catalyst with the titanium content of 5.42 wt% (TS-1_2), at the temperature of 85 °C, for 6 h and with the catalyst TS-1 content in the reaction mixture of 1 wt%. Under these conditions the conversion of α-pinene amounted to 34 mol%, and the selectivities of main products of α-pinene oxidation process were: α-pinene oxide (29 mol%), verbenol (15 mol%) and verbenone (12 mol%). In smaller quantities also campholenic aldehyde, trans-pinocarveol, myrtenal, myrtenol, L-carveol, carvone and 1,2-pinanediol were also formed. These products are of great practical importance in food, cosmetics, perfumery and medicine industries. Kinetic studies were also performed for the studied process.

Computational Investigation of the Formation of Peroxide (ROOR) Accretion Products in the OH- and NO3-Initiated Oxidation of α-Pinene.

The formation of accretion products (“dimers”) from recombination reactions of peroxyl radicals (RO2) is a key step in the gas-phase generation of low-volatility vapors, leading to atmospheric aerosol particles. We have recently demonstrated that this recombination reaction very likely proceeds via an intermediate complex of two alkoxy radicals (RO···OR′) and that the accretion product pathway involves an intersystem crossing (ISC) of this complex from the triplet to the singlet surface. However, ISC rates have hitherto not been computed for large and chemically complex RO···OR′ systems actually relevant to atmospheric aerosol formation. Here, we carry out systematic conformational sampling and ISC rate calculations on 3(RO···OR′) clusters formed in the recombination reactions of different diastereomers of the first-generation peroxyl radicals originating in both OH- and NO3-initiated reactions of α-pinene, a key biogenic hydrocarbon for atmospheric aerosol formation. While we find large differences between the ISC rates of different diastereomer pairs, all systems have ISC rates of at least 106 s–1, and many have rates exceeding 1010 s–1. Especially the latter value demonstrates that accretion product formation via the suggested pathway is a competitive process also for α-pinene-derived RO2 and likely explains the experimentally observed gas-phase formation of C20 compounds in α-pinene oxidation.

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Abstract. Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

Peroxy Radical Processes and Product Formation in the OH Radical-Initiated Oxidation of α-Pinene for Near-Atmospheric Conditions.

α-Pinene, C10H16, represents one of the most important biogenic emissions into the atmosphere. The formation of RO2 radicals HO-C10H16Ox, x = 2-6, and their closed-shell products from the OH + α-pinene reaction has been measured for close to atmospheric reaction conditions in the presence of NO with concentrations of (1.7-490) × 109 molecules cm-3. Main closed-shell products are substances with the composition C10H16O2 and C10H16O4, most likely carbonyls, obtained with molar yields in the range 0.42-0.45 and 0.17-0.19, respectively, for NO concentrations >5 × 1010 molecules cm-3. The corresponding total product yields amount to 0.75-0.81, indicating efficient product detection by the mass spectrometric method applied. All stated molar yields represent lower limit values affected with an uncertainty of [Formula: see text]. Kinetic and product analysis consistently revealed the suppression of the formation of highly oxygenated organic molecules (HOMs) by a factor of 2-2.2 for the highest NO concentration used. The findings of this study provide insights into the RO2 radical processes of the OH + α-pinene reaction for atmospheric conditions and give an overview about the first-generation products.

Molecular Chirality and Cloud Activation Potentials of Dimeric α-Pinene Oxidation Products.

The surface activity of ten atmospherically relevant α-pinene-derived dimers having varying terminal functional groups and backbone stereochemistry is reported. We find ∼10% differences in surface activity between diastereomers of the same dimer, demonstrating that surface activity depends upon backbone stereochemistry. Octanol-water (KOW) and octanol-ammonium sulfate partitioning coefficient (KOAS) measurements of our standards align well with the surface activity measurements, with the more surface-active dimers exhibiting increased hydrophobicity. Our findings establish a link between molecular chirality and cloud activation potential of secondary organic aerosol particles. Given the diurnal variations in enantiomeric excess of biogenic emissions, possible contributions of such a link to biosphere:atmosphere feedbacks as well as aerosol particle viscosity and phase separation are discussed.

Plants growing in Colombia as sources of active ingredients for sunscreens

Introduction Plants can be sources of photoprotective/antigenotoxic compounds that prevent cellular mutations involved in skin cancer and aging by regulating UV-induced mutability. Purpose The study was aimed at investigating the sunscreen properties of plants growing in Colombia. Materials and Methods Ultraviolet (UV) radiation-absorption capability of different plant extracts was examined. In vitro photoprotection efficacies were evaluated using in vitro indices such as sun protection factor (SPFin vitro) and critical wavelength (λc). Pearson correlation analysis was used to examine the relationship between SPFin vitro and complementary UVB- antigenotoxicity estimates (%GI) based on SOS Chromotest database. The cytotoxicity in human fibroblasts was studied using the trypan blue exclusion assay. Major compounds of promising plant extracts were determined by gas chromatography coupled to mass spectrometry (GC/MS). Results We showed that plant extracts have sunscreen properties against UVB, whereas broad-spectrum radiation protection efficacy was poor. SPFin vitro and %GI were correlated (R = 0.71, p < 0.0001) for the plant extracts under study. Three extracts obtained from Achyrocline satureioides, Chromolaena pellia, and Lippia origanoides species resulted to possess high protection efficacy and relatively low cytotoxicity in human fibroblasts. These plant extracts contained major compounds such as α-pinene, trans-β-caryophyllene, γ-muurolene, γ-cadinene and caryophyllene oxide in A. Satureioides extract, trans-β-caryophyllene, caryophyllene oxide, squalene and α-amyrin in C. pellia extract, and p-cymene, carvacrol, trans-β-caryophyllene and pinocembrin in L. origanoides extract. Conclusions Plants growing in Colombia contain compounds which ca be useful for potential sunscreens. SPFin vitro and %GI estimates were correlated, but %GI estimates were more sensitive detecting activity at lower plant extract concentrations. Our results supported the need to use DNA damage detection assays as a complement to photoprotection efficacy measurement.

Predicting gas–particle partitioning coefficients of atmospheric molecules with machine learning

Abstract. The formation, properties, and lifetime of secondary organic aerosols in the atmosphere are largely determined by gas–particle partitioning coefficients of the participating organic vapours. Since these coefficients are often difficult to measure and to compute, we developed a machine learning model to predict them given molecular structure as input. Our data-driven approach is based on the dataset by Wang et al. (2017), who computed the partitioning coefficients and saturation vapour pressures of 3414 atmospheric oxidation products from the Master Chemical Mechanism using the COSMOtherm programme. We trained a kernel ridge regression (KRR) machine learning model on the saturation vapour pressure (Psat) and on two equilibrium partitioning coefficients: between a water-insoluble organic matter phase and the gas phase (KWIOM/G) and between an infinitely dilute solution with pure water and the gas phase (KW/G). For the input representation of the atomic structure of each organic molecule to the machine, we tested different descriptors. We find that the many-body tensor representation (MBTR) works best for our application, but the topological fingerprint (TopFP) approach is almost as good and computationally cheaper to evaluate. Our best machine learning model (KRR with a Gaussian kernel + MBTR) predicts Psat and KWIOM/G to within 0.3 logarithmic units and KW/G to within 0.4 logarithmic units of the original COSMOtherm calculations. This is equal to or better than the typical accuracy of COSMOtherm predictions compared to experimental data (where available). We then applied our machine learning model to a dataset of 35 383 molecules that we generated based on a carbon-10 backbone functionalized with zero to six carboxyl, carbonyl, or hydroxyl groups to evaluate its performance for polyfunctional compounds with potentially low Psat. The resulting saturation vapour pressure and partitioning coefficient distributions were physico-chemically reasonable, for example, in terms of the average effects of the addition of single functional groups. The volatility predictions for the most highly oxidized compounds were in qualitative agreement with experimentally inferred volatilities of, for example, α-pinene oxidation products with as yet unknown structures but similar elemental compositions.

Chlorine-Initiated Oxidation of α-Pinene: Formation of Secondary Organic Aerosol and Highly Oxygenated Organic Molecules

Chlorine-Initiated Oxidation of α-Pinene: Formation of Secondary Organic Aerosol and Highly Oxygenated Organic Molecules

Using GECKO-A to derive mechanistic understanding of secondary organic aerosol formation from the ubiquitous but understudied camphene

Abstract. Camphene, a dominant monoterpene emitted from both biogenic and pyrogenic sources, has been significantly understudied, particularly in regard to secondary organic aerosol (SOA) formation. When camphene represents a significant fraction of emissions, the lack of model parameterizations for camphene can result in inadequate representation of gas-phase chemistry and underprediction of SOA formation. In this work, the first mechanistic study of SOA formation from camphene was performed using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). GECKO-A was used to generate gas-phase chemical mechanisms for camphene and two well-studied monoterpenes, α-pinene and limonene, as well as to predict SOA mass formation and composition based on gas/particle partitioning theory. The model simulations represented observed trends in published gas-phase reaction pathways and SOA yields well under chamber-relevant photooxidation and dark ozonolysis conditions. For photooxidation conditions, 70 % of the simulated α-pinene oxidation products remained in the gas phase compared to 50 % for limonene, supporting model predictions and observations of limonene having higher SOA yields than α-pinene under equivalent conditions. The top 10 simulated particle-phase products in the α-pinene and limonene simulations represented 37 %–50 % of the SOA mass formed and 6 %–27 % of the hydrocarbon mass reacted. To facilitate comparison of camphene with α-pinene and limonene, model simulations were run under idealized atmospheric conditions, wherein the gas-phase oxidant levels were controlled, and peroxy radicals reacted equally with HO2 and NO. Metrics for comparison included gas-phase reactivity profiles, time-evolution of SOA mass and yields, and physicochemical property distributions of gas- and particle-phase products. The controlled-reactivity simulations demonstrated that (1) in the early stages of oxidation, camphene is predicted to form very low-volatility products, lower than α-pinene and limonene, which condense at low mass loadings; and (2) the final simulated SOA yield for camphene (46 %) was relatively high, in between α-pinene (25 %) and limonene (74 %). A 50 % α-pinene + 50 % limonene mixture was then used as a surrogate to represent SOA formation from camphene; while simulated SOA mass and yield were well represented, the volatility distribution of the particle-phase products was not. To demonstrate the potential importance of including a parameterized representation of SOA formation by camphene in air quality models, SOA mass and yield were predicted for three wildland fire fuels based on measured monoterpene distributions and published SOA parameterizations for α-pinene and limonene. Using the 50/50 surrogate mixture to represent camphene increased predicted SOA mass by 43 %–50 % for black spruce and by 56 %–108 % for Douglas fir. This first detailed modeling study of the gas-phase oxidation of camphene and subsequent SOA formation highlights opportunities for future measurement–model comparisons and lays a foundation for developing chemical mechanisms and SOA parameterizations for camphene that are suitable for air quality modeling.

Идентификация кристаллического продукта жидкофазного окисления α-пинена кислородом воздуха в присутствии стеарата кобальта (II)

One of the possible directions of liquid-phase oxidation of α-pinene by atmospheric oxygen leads to the formation of a mixture of terpene oxygen-containing compounds (epoxides, alcohols, ketones, etc.). The problem of this direction is the formation of a large amount of 2,3-epoxypinane which over time turns into trans-sobrerol, campholene aldehyde, trans-pinocarveol, trans-carveol, and trans-3-pinen-2-ol as a result of hydrolysis. One of the abovementioned substances with a solid crystalline structure is trans-sobrerol. Sobrerol is widely used in perfumery for synthesis of synthetically fragrant substances and pharmaceutical industry, in particular, it is a part of medicines with mucolytic action, as well as in the treatment of headaches and diseases such as rhinorrhea and chronic bronchitis. The aim of this work is to identify a crystalline product produced by liquid-phase oxidation of α-pinene with atmospheric oxygen in the presence of cobalt (II) stearate. The process of liquid-phase oxidation was carried out in the following conditions: temperature – 70 °С, air consumption – 16.67 cm3/s, duration – 5 h, amount of catalyst – 0.2–0.5 wt.%. Then the mixture was exposed to steam distillation in order to separate monomers (they contain terpene oxygen-containing compounds and hydrocarbons) from polymers. As a result of settling and storage of the mixture, crystals were found and isolated from the mother liquor solution. Their identification was carried out using IR and 13C NMR spectroscopy as well as scanning electron microscopy. It was found that the spatial organization of the isolated crystals and the standard sample (Sigma Aldrich) is represented by multilayer rectangular plates. Analysis of the IR spectra of the crystals showed that the absorption band at a wave number of 3318 cm–1 corresponds to intramolecular and intermolecular hydrogen bonds in hydroxyl groups, at wave numbers of 2887, 2935, 2975 cm–1 it corresponds to methyl groups. The results obtained are comparable with the results of the IR-spectrum of the standard sample. Given the results of previous studies of 1H NMR spectrum [15] and 13C NMR spectrum, it was determined that the resulting crystalline product of liquid-phase oxidation of α-pinene is trans-sobrerol.

The Over-Riding Role of Autocatalysis in Allylic Oxidation

In this paper we aim to highlight the need to consider the possible role of autocatalysis in oxidation reactions when using molecular oxygen as the terminal oxidant. Oxygen in its ground state is a diradical, and depending on the reaction conditions, it can initiate oxidation through radical pathways through mechanisms which do not require the presence of a catalyst. Consequently, we contrast the oxidation of benzyl alcohol with oxidation of α-pinene. For benzyl alcohol oxidation the initial reaction is the oxidative dehydrogenation to form benzaldehyde, a non-radical process; but the subsequent over-oxidation to benzoic acid is a radical process. In this case the role of the autocatalysed reaction can be minimised. With α-pinene, the oxidation reaction is via radical pathways and now the autocatalysed reaction can be dominant and, indeed, can be the preferred pathway for the formation of high yields of the desired verbenone product.Graphic

Improved efficiency of lipase-mediated epoxidation of α-pinene using H2O2 in single-phase systems

Taking advantage of the intersolubility of alcohol and water, we developed an efficient single-phase system for chemoenzymatic epoxidation of (-)-α-pinene. Different from traditional methods, it included all substrates, such as (-)-α-pinene, acyl donors and oxidants, into one phase. Isopropanol was eventually selected as the epoxidation medium to optimize three controllable parameters. Under the optimal conditions of 3.35 mol/L ethyl acetate and 1.1 mol/L H2O2, the conversion and selectivity reached 92.3% and 86.6% in 90 min, respectively, and the initial reaction rate was 13.58×10−4 mmol·min−1·mg−1 with Novozym435 as a catalyst. Trisodium citrate was screened as an acid-trapping reagent to eliminate the negative impact of acetic acid on (-)-α-pinene oxide. The enzyme reusability was at least 6 cycles with a relative activity of 57.5% at the sixth cycle.

Essential Oils of New Lippia alba Genotypes Analyzed by Flow-Modulated Comprehensive Two-Dimensional Gas Chromatography (GC×GC) and Chemometric Analysis.

Lippia alba (Mill.) N. E. Br. (Verbenaceae) is an aromatic shrub whose essential oils have stood out as a promising source for application in several industrial fields. In this study, the essential oils chemical characterization of eight new L. alba genotypes was performed. The selected materials were collected from the Active Germplasm Bank of the Agronomic Institute and the essential oils were extracted by hydrodistillation. Flow-modulated comprehensive two-dimensional gas chromatography coupled to mass spectrometry (GC×GC-MS) was employed for chemical characterization and evaluation of possible co-eluted compounds. In addition, the chemical analyses were submitted to multivariate statistical analyses. From this investigation, 73 metabolites were identified in the essential oils of the genotypes, from which α-pinene, β-myrcene, 1,8-cineole, linalool, neral, geranial, and caryophyllene oxide were the most abundant compounds among the accessions. This is the first report disclosing α-pinene in higher amounts in L. alba (19.69%). In addition, sabinene, trans-verbenol, myrtenol, (E)-caryophyllene, α-guaiene, germacrene D, and α-bulnesene were also found in relevant quantities in some of the genotypes, and myrtenal and myrtenol could be well separated through the second dimension. Such results contributed to the understanding of the chemical composition of those new genotypes, being important to drive a future industrial applicability and studies in genetic breeding.

Toxicokinetic evaluation of the common indoor air pollutant, α-pinene, and its potential reactive metabolite, α-pinene oxide, following inhalation exposure in rodents

The toxicokinetic behavior of α-pinene and its potential reactive metabolite, α-pinene oxide, was investigated following whole body inhalation exposure to 50 and 100 ppm α-pinene in rats and mice for 6 h per day for 7d. In both species and sexes, the maximum blood concentration (Cmax) increased more than proportionally while the increase in area under the concentration time curve (AUC) was proportional to the exposure concentration. When normalized to the calculated dose (D), both Cmax/D (male rats, 12.2–54.5; female rats, 17.4–74.1; male mice, 7.41–14.2; female mice, 6.59–13.0 (ng/mL)/(mg/kg)) and AUC/D (male rats, 28.9–31.1; female rats, 55.8–56.8; male mice, 18.1–19.4; female mice, 19.2–22.5 (h*ng/mL)/(mg/kg)) in rats were higher than in mice and in female rats were higher than in male rats; no sex difference was observed in mice. α-Pinene was eliminated from blood with half-lives between 12.2 and 17.4 h in rats and 6.18–19.4 h in mice. At the low dose, the ratio of α-pinene oxide to α-pinene, based on Cmax and AUC, respectively, was 0.200–0.237 and 0.279–0.615 in rats and 0.060–0.086 and 0.036–0.011 in mice demonstrating lower formation of the oxide in mice than in rats. At the high dose, the ratio decreased considerably in both species pointing to saturation of pathways leading to the formation of α-pinene oxide. α-Pinene and the oxide were quantified in the mammary glands of rats and mice with tissue to blood ratios of ≥23 demonstrating retention of these analytes in mammary glands. The findings of epoxide formation and species- and sex-differences in systemic exposure may be important in providing context and relating animal findings to human exposures.

Identification of Diurnal Variation of Essential Oil Components of Hypericum perfoliatumL.(Hypericaceae)

In this study, the diurnal variability of essential oil components of the species Hypericum perfoliatum was investigated. To determine diurnal variation, during the flowering period collection was carried out at three different times of the day (9a.m., 12a.m., 4p.m.). As a result of this research, it was aimed to determine the most appropriate harvest time during the day. The essential oil components were analyzed using GC-MS device after the production of essential oil was determined by hydrodystylation method. The main components of essential oils were found to contain mainly α-pinene (41.2%), β-pinene (6.2%), n-nonane (5.6%), ϒ-muurolene (4.7%), α-calacorene (4.2%), δ-cadinene (3.7%), n-undecane (3.2%) and caryophyllene oxide (3.1%).

Cascade Biocatalysis Designed for the Allylic Oxidation of α-Pinene

A biocatalytic cascade system using a cocktail of oxidoreductase enzymes (2-1B peroxidase and M120 laccase) was designed for the allylic oxidation of (+)-α-pinene into value-added products (e.g., verbenol and verbenone). The oxidative transformation involved a two-step process as follows: (+)-α-pinene was (i) oxidized on the allylic position with H2O2 mainly assisted by 2-1B peroxidase leading to verbenol as the principal reaction product, and (ii) directed to verbenone in the presence of M120 laccase responsible for further oxidation of verbenol to verbenone. The reaction environment was ensured by the acetate buffer (0.1 M, pH = 5). Optimum values for the experimental parameters (e.g., concentration of 2-1B peroxidase, M120 laccase, and H2O2) were set up. The biocatalytic cascade process was monitored for 24 h in order to evaluate the process pathway. Maximum performance under optimum conditions was reached after 5 h incubation time (e.g., 80% (+)-α-pinene conversion and 70% yield in verbenol). Therefore, the developed biocatalytic cascade system offered promising perspectives for (+)-α-pinene valorization.

Development of rapid and selective epoxidation of α-pinene using single-step addition of H2O2 in an organic solvent-free process.

This study reports substantial improvement in the process for oxidising α-pinene, using environmentally friendly H2O2 at high atom economy (∼93%) and selectivity to α-pinene oxide (100%). The epoxidation of α-pinene with H2O2 was catalysed by tungsten-based polyoxometalates without any solvent. The variables in the screening parameters were temperatures (30–70 °C), oxidant amount (100–200 mol%), acid concentrations (0.02–0.09 M) and solvent types (i.e., 1,2-dichloroethane, toluene, p-cymene and acetonitrile). Screening the process parameters revealed that almost 100% selective epoxidation of α-pinene to α-pinene oxide was possible with negligible side product formation within a short reaction time (∼20 min), using process conditions of a 50 °C temperature in the absence of solvent and α-pinene/H2O2/catalyst molar ratio of 5 : 1 : 0.01. A kinetic investigation showed that the reaction was first-order for α-pinene and catalyst concentration, and a fractional order (∼0.5) for H2O2 concentration. The activation energy (Ea) for the epoxidation of α-pinene was ∼35 kJ mol−1. The advantages of the epoxidation reported here are that the reaction could be performed isothermally in an organic solvent-free environment to enhance the reaction rate, achieving nearly 100% selectivity to α-pinene oxide.

α-Pinene, Limonene, and Cyclohexene Secondary Organic Aerosol Hygroscopicity and Oxidation Level as a Function of Volatility

ABSTRACT The hygroscopicity and oxidation level of secondary organic aerosol (SOA) produced in an atmospheric simulation chamber were measured as a function of volatility. The experimental setup combines thermodenuding, isothermal dilution, aerosol mass spectroscopy, and size-resolved cloud condensation nuclei measurements to separate the SOA by volatility and then measure its physical (hygroscopicity via the hygroscopicity parameter, κ) and chemical (oxidation level via the oxygen-to-carbon ratio, O:C) properties. The technique was applied to SOA from the ozonolysis of α-pinene, limonene, and cyclohexene. The O:C and κ of the α-pinene ozonolysis SOA decreased as volatility decreased. The semi-volatile and the low volatility organic compounds produced during limonene ozonolysis have similar O:C and κ values, but the corresponding extremely low volatility organic compounds have significantly lower oxygen content and hygroscopicity. The average O:C of the cyclohexene ozonolysis SOA increased, but the average κ decreased as volatility decreased. These results suggest that some organic aerosol (OA) systems have a more complex relationship between hygroscopicity, oxidation level, and volatility than originally thought. The two-dimensional volatility basis set framework can help in integrating these results and providing explanations of the measured hygroscopicity. Use of this technique with different OA systems, both laboratory and ambient, can supply parameters that can be incorporated in atmospheric chemical transport models.

Online monitoring of volatile organic compounds emitted from human bronchial epithelial cells as markers for oxidative stress

Particulate air pollution is associated with adverse respiratory effects and is a major factor for premature deaths. In-vitro assays are commonly used for investigating the direct cytotoxicity and inflammatory impacts due to particulate matter (PM) exposure. However, biological tests are often labor-intensive, destructive and limited to endpoints measured offline at single time points, making it impossible to observe the progression of cell response upon exposure. Here we explored the potential of a high-resolution proton transfer reaction mass spectrometer (PTR-MS) to detect the volatile organic compounds (VOCs) emitted by human bronchial epithelial cells (BEAS-2B) upon exposure to PM. Cells were exposed to single components (1,4-naphthoquinone and Cu(II)) known to induce oxidative stress. We also tested filter extracts of aerosols generated in a smog chamber, including fresh and aged wood burning emissions, as well as α-pinene secondary organic aerosol (SOA). We found that 1,4-naphthoquinone was rapidly internalized by the cells. Exposing cells to each of these samples induced the emission of VOCs, which we tentatively assigned to acetonitrile, benzaldehyde and dimethylbenzaldehyde, respectively. Emission rates upon exposure to fresh and aged OA from α-pinene oxidation and from biomass burning significantly exceeded those observed after exposure to similar doses of Cu(II), a proxy for transition metals with high oxidative potential. Emission rates of biomarkers from cell exposure to α-pinene SOA exhibited a statistically significant, but weak dose dependence. The emission rates of benzaldehyde scaled with cell death, estimated by measuring the apical release of cytosolic lactate dehydrogenase. Particle mass doses delivered to the BEAS-2B cells match those deposited in the human tracheobronchial tract after several hours of inhalation at elevated ambient air pollution. The results presented here show that our method has the potential to determine biomarkers of PM induced pulmonary damage in toxicological and epidemiological research on air pollution.