Abundant Monoterpenes Research Articles

Nocturnal atmospheric synergistic oxidation reduces the formation of low-volatility organic compounds from biogenic emissions

Abstract. Volatile organic compounds (VOCs) are often subject to synergistic oxidation by different oxidants in the atmosphere. However, the exact synergistic-oxidation mechanism of atmospheric VOCs and its role in particle formation remain poorly understood. In particular, the reaction kinetics of the key reactive intermediates, organic peroxy radicals (RO2), during synergistic oxidation is rarely studied. Here, we conducted a combined experimental and kinetic modeling study of the nocturnal synergistic oxidation of α-pinene (the most abundant monoterpene) by O3 and NO3 radicals as well as its influences on the formation of highly oxygenated organic molecules (HOMs) and particles. We find that in the synergistic O3 + NO3 regime, where OH radicals are abundantly formed via decomposition of ozonolysis-derived Criegee intermediates, the production of CxHyOz HOMs is substantially suppressed compared to that in the O3-only regime, mainly because of the depletion of α-pinene RO2 derived from ozonolysis and OH oxidation by those arising from NO3 oxidation via cross reactions. Measurement–model comparisons further reveal that the cross-reaction rate constants of NO3-derived RO2 with O3-derived RO2 are on average 10–100 times larger than those of NO3-derived RO2 with OH-derived RO2. Despite a strong production of organic nitrates in the synergistic-oxidation regime, the substantial decrease in CxHyOz HOM formation leads to a significant reduction in ultralow- and extremely low-volatility organic compounds, which significantly inhibits the formation of new particles. This work provides valuable mechanistic and quantitative insights into the nocturnal synergistic-oxidation chemistry of biogenic emissions and will help to better understand the formation of low-volatility organic compounds and particles in the atmosphere.

Effects of NOx and NH3 on the secondary organic aerosol formation from α-pinene photooxidation

Understanding the effects of mixed anthropogenic pollutants on the photooxidation of volatile organic compounds (VOCs) is essential for unraveling the formation pathways of secondary organic aerosols (SOA). Yet, it remains a highly challenging experimental target owing to the complexities in the precise measurement of molecular compositions of products and number/mass concentrations of particles as a function of pollutant concentration in the ambient atmosphere. Here, a series of well-defined chamber experiments were performed to explore the effects of NOx and NH3 on the SOA formation from photooxidation of the most abundant monoterpene, α-pinene. The results indicate that the suppression effect of NO and NO2 on the α-pinene photooxidation shows monotonous and parabolic trends, respectively. The presence of NH3 enhances particle number concentrations during the α-pinene + NOx photooxidation by participating in reactions with organic acids. New compounds, including organic peroxides, esters, organic nitrates, and peroxyacyl nitrates, are observed at molecular weight (MW) = 166, 173, 217, 231, 280, 282, 304, and 410 through threshold photoionization making use of a recently constructed vacuum ultraviolet free electron laser in positive ion mode. The molecular structures and formation paths of these species are speculated, which advance the category of VOC oxidation products. Our study provides significant understanding of the influence of NOx and NH3 on the VOC photooxidation, which can be utilized to establish predictive SOA formation networks and to improve atmospheric models.

Biotransformation of monoterpenes using Streptomyces strains from the rhizosphere of Inga edulis Martius from in an Amazonian urban forest fragment

To investigate the biocatalytic potential of Amazonian actinomycetes for monoterpenes biotransformation. To carry out the present study, eleven actinomycetes of the genus Streptomyces isolated from inga-cipó (Inga edulis Mart.) rhizospheres were tested for their ability to bioconvert the substrates R-(+)-limonene, S-(-)-limonene, 1S-(-)-α-pinene, and (-)–β–pinene as sole carbon and energy source. According to gas chromatography-mass spectrometry analysis, three strains, LabMicra B270, LaBMicrA B310, and LaBMicrA B314, were able to biotransform 1S-(-)-α-pinene after 96 h of growth. However, Streptomyces LaBMicrA B270 was the most promising since it converted after only 72 h all the 1S-(-)-α-pinene mainly into cis-verbenol (74.9±1.24%) and verbenone (18.2±1.20%), compounds that have important biological activities and great industrial interest as additives in foods and cosmetics. These findings can stimulate the development of natural aromas using naturally abundant monoterpenes, ratify the potential of microorganisms from almost unexplored niches such as the Amazonian rhizosphere, and reinforce the importance of preserving those niches.

Crithmum maritimum L.-Study on the Histochemical Localization of Essential Oil.

Crithmum maritimum L. is a perennial halophyte plant that is a medicinal herb known by people from different cultures since ancient times. However, the therapeutic potential of this halophyte has not been completely investigated, and the scientific data on it are limited. The purpose of the present study was to estimate the chemical composition of the essential oil (EO) obtained from the aerial parts of Crithmum maritimum L. growing wild in Bulgaria, as well as the histolocalization of secretory structures for the synthesis and accumulation of volatile oils. The results obtained on the EO composition of Bulgarian Crithmum maritimum L. provide an opportunity to reveal potential future applications in various fields, such as medicine, pharmacy, agriculture, food, and the cosmetic industry. Gas chromatography with mass spectrometry was performed to assess the chemical profile of the isolated EO. The phenylpropanoid dillapiole was identified as the major compound in the EO, accounting for 34.09% of the total EO. Monoterpene hydrocarbons represented 62.07% of the total oil composition. γ-Terpinene, D-limonene, and β-pinene were the most abundant monoterpene hydrocarbons in the composition of the EO. In addition, histochemical localization of EO in the stem and leaves of Crithmum maritimum L. was carried out. The secretory structures were located in the cortical region of the stem and in the mesophyll tissues of the leaves in the form of secretory ducts. The performed histochemical analysis confirmed the lipophilic nature of the secretion from the duct cells. This is the first report related to the histolocalization and chemical composition of the EO from Bulgarian Crithmum maritimum L. Furthermore, our data indicate some potential possibilities for the evaluation of the therapeutic activity of the EO obtained from this plant species and outline its future applications as a therapeutic agent. Also, the EO from the studied halophyte plant has prominent potential to be used as a biopesticide, which is an environmentally friendly option compared to standard pesticides.

Dynamic Physiological Responses of Cinnamomum camphora with Monoterpene Protection under High Temperature Shock

Monoterpenes can protect plants against high temperature, but the early events of protection are still unknown. In this study, the dynamic variations in reactive oxygen species metabolism, photosynthetic capacity, and related gene expression in linalool, eucalyptol, and camphor chemotypes of Cinnamomum camphora with and without monoterpene emission under 6 h high-temperature stress were investigated. With respect to the control (28 °C), 40 °C and Fos + 40 °C (fosmidomycin inhibited monoterpene biosynthesis under 40 °C) treatments increased H2O2 and thiobarbituric acid reactive substance levels in the three chemotypes, but without significant differences between the two treatments after 2 h. Compared with the 40 °C treatment, the Fos + 40 °C treatment further aggravated the increase after 4 h, with increases of 13.8%, 12.3%, and 12.3% in H2O2 levels as well as 16.5%, 17.4%, and 9.1% in thiobarbituric acid reactive substance levels, respectively, in linalool, eucalyptol, and camphor chemotypes. When the three chemotypes were treated with 40 °C and Fos + 40 °C, the ascorbic acid content was gradually decreased during the 2 h treatment. After 4 h, the Fos + 40 °C treatment further aggravated the decrease in ascorbic acid content, with decreases of 10.6%, 9.8%, and 20.1%, respectively, in the eucalyptol, linalool, and camphor chemotypes. This could be caused by the further down-regulation of the key gene GGP in antioxidant biosynthesis. Meanwhile, two genes (VTE3 and 4CL) in other non-enzymatic antioxidant formation were also further down-regulated in Fos + 40 °C treatment for 4 h. These might lead to the further increase in reactive oxygen species levels in Fos + 40 °C treatment lacking non-enzymatic antioxidants. The photosynthetic electron yield and transfer (φPo, Ψo and φEo) in the three chemotypes were significantly (p < 0.05) decreased under the 40 °C and Fos + 40 °C treatments for 0.5 h, and the photosynthetic rate was significantly (p < 0.05) decreased in the two treatments for 1 h. After 4 h, the Fos + 40 °C treatment aggravated the decrease, as the genes encoding the components of photosystem II (psbP and psbW) and ribulose-1,5-bisphosphate carboxylase/oxygenase (rbcS and rbcL) were further down-regulated. These dynamic variations in the early events suggested that monoterpenes should act as signaling molecules to improve plant thermotolerance, as blocking monoterpene biosynthesis did not cause immediate effects on the physiological responses in contrast to the monoterpene-emitting plants during the 2 h high temperature stress, but resulted in serious damages after 4 h for suppressing related gene expression. This not only provides new proof for the isoprenoid thermotolerance mechanism by serving a signaling function, but also promotes the utilization of monoterpenes as anti-high-temperature agents, and the cultivation of high-temperature tolerance varieties with abundant monoterpene emission.

Echinophora tenuifolia subsp. sibthorpiana—Study of the Histochemical Localization of Essential Oil

Echinophora tenuifolia L. subsp. sibthorpiana is a perennial, aromatic plant used in traditional folk medicine and cuisine of the Mediterranean and the Middle East. However, scholars have not fully studied the pharmacological potential of the herb, and the scientific data on this plant species are limited. This study aimed to evaluate the chemical composition of the essential oil (EO) obtained from the aerial parts of E. tenuifolia subsp. sibthorpiana growing wild in Bulgaria and to perform histochemical analysis. A microscopic histochemical analysis and gas chromatography with mass spectrometry were performed. The histochemical analysis confirmed the presence of terpenes in the stem and leaf of E. tenuifolia subsp. sibthorpiana. The phenylpropanoid methyleugenol was identified as the main compound in the EO, representing 48.13% of the total oil composition. There were also found considerable amounts of monoterpene hydrocarbons, representing 41.68% of the total EO. Alpha-phellandrene, o-cymene, and β-phellandrene were the most abundant monoterpene hydrocarbons. This is the first histochemical analysis performed on E. tenuifolia subsp. sibthorpiana. This is the first report of the EO composition from Bulgarian E. tenuifolia subsp. sibthorpiana, and our results indicate some future possibilities for evaluating of the biological activity of the EO of E. tenuifolia subsp. sibthorpiana and highlight the potential future use of the EO of this plant species. E. tenuifolia L. subsp. sibthorpiana EO possesses a good potential for use as a biopesticide and repellent an environmentally friendly alternative of synthetic pesticides.

The Populus koreana genome provides insights into the biosynthesis of plant aroma

Populus koreana is a tree species that shows unique fragrance traits because of the emission of volatiles from tissues, thus it has great potential for the study of aroma in forest trees. The genome of P. koreana, with a size of 429.47 Mb and N50 contigs of 4.97 Mb, was assembled into 19 chromosomes and 38,075 genes were predicted. P. koreana and Populus trichocarpa diverged from a common ancestor before 6.14 million years ago (Mya). Metabolome results suggested that the main aroma components terpenes and esters are significantly enriched in P. koreana leaves. Compared with that of P. trichocarpa, the P. koreana genome contains many more terpene synthase genes (TPSs), which encode proteins enriched in terpenoid-related metabolic pathways associated with the production of plant volatiles. Among these TPS genes, TPS-a/b might largely contribute to the synthesis of abundant sesquiterpenes and monoterpenes. Our results provide a valuable genomic resource for the further study of the production of aromatic volatiles by forest trees. Gene families related to terpenoid biosynthesis are substantially expanded in P. koreana, mainly resulting from tandem duplications and lineage specific whole-genome duplications. The evidence presented in this study increases our understanding of the evolution and diversity of plant volatile compounds, which could accelerate the selective breeding on traits of interest in Populus. Data availability statementThe datasets of transcriptome and genome were uploaded in NCBI and China national center for bioinformation, respectively. The accession numbers were PRJCA012303, CRA012924, and PRJNA886606 (NCBI).

Seasonal and Diurnal Variability of Monoterpenes in the Eastern Mediterranean Atmosphere

Monoterpenes significantly affect air quality and climate as they participate in tropospheric ozone formation, new particle formation (NPF), and growth through their oxidation products. Vegetation is responsible for most biogenic volatile organic compound (BVOC) emissions released into the atmosphere, yet the contribution of shrub and regional transport to the ambient monoterpene mixing ratios is not sufficiently documented. In this study, we present one-year systematic observations of monoterpenes in the Eastern Mediterranean at a remote coastal site, affected mainly by the typical phrygana vegetation found on the Island of Crete in Greece. A total of 345 air samples were collected in absorption tubes and analyzed by a GC-FID system during three intensive campaigns (in spring 2014, summer 2014, and spring 2015) in addition to the systematic collection of one diurnal cycle per week from October 2014 to April 2015. Limonene, α-pinene and 1,8-cineol have been detected. The mixing ratios of α-pinene during spring and summer show a cycle that is typical for biogenic compounds, with high levels during the night and early morning, followed by an abrupt decrease around midday, which results from the strong photochemical depletion of this compound. Limonene was the most abundant monoterpene, with average mixing ratios of 36.3 ± 66 ppt. The highest mixing ratios were observed during autumn and spring, with a maximum mixing ratio in the early afternoon. The spring and autumn maxima could be attributed to the seasonal behavior of vegetation growth at Finokalia. The green period starts in late autumn when phrygana vegetation grows because of the rainfall; the temperature is still high at this time, as Finokalia is located in the southeast part of Europe. Statistical analyses of the observations showed that limonene and α-pinene have different sources, and none of the studied monoterpenes is correlated with the anthropogenic sources. Finally, the seasonality of the new particle formation (NPF) events and monoterpene mixing ratios show similarities, with a maximum occurring in spring, indicating that monoterpenes may contribute to the production of new particles.

Peroxy Radical Autoxidation and Sequential Oxidation in Organic Nitrate Formation during Limonene Nighttime Oxidation.

Limonene is an abundant monoterpene released into the atmosphere via biogenic emissions and biomass burning. However, the atmospheric oxidation and secondary organic aerosol (SOA) formation mechanisms of limonene, especially during nighttime, remain largely understudied. In this work, limonene was oxidized synergistically by ozone (O3) and nitrate radicals (NO3) in a flow tube reactor and a continuous flow stirred tank reactor. Upon oxidation, many highly oxidized organic nitrates and nitrooxy peroxy radicals (RO2) were observed in the gas phase within 1 min. Combining quantum chemical calculations with kinetic simulations, we found that the primary nitrooxy RO2 (C10H16NO5) through NO3 addition at the more substituted endocyclic double bond and at the exocyclic double bond (previously considered as minor pathways) can undergo autoxidation with rate constants of around 0.02 and 20 s-1 at 298 K, respectively. These pathways could explain a major portion of the observed highly oxidized organic nitrates. In the SOA, highly oxidized mono- and dinitrates (e.g., C10H17NO7-8 and C10H16,18N2O8-10) make up a significant contribution, highlighting nitrooxy RO2 autoxidation and sequential NO3 oxidation of limonene. The same organic nitrates are also observed in ambient aerosol during biomass burning and nighttime in the southeastern United States. Therefore, the present work provides new insights into the nighttime oxidation of limonene and SOA formation in the atmosphere.

Unexpected significance of a minor reaction pathway in daytime formation of biogenic highly oxygenated organic compounds.

Secondary organic aerosol (SOA), formed by oxidation of volatile organic compounds, substantially influence air quality and climate. Highly oxygenated organic molecules (HOMs), particularly those formed from biogenic monoterpenes, contribute a large fraction of SOA. During daytime, hydroxyl radicals initiate monoterpene oxidation, mainly by hydroxyl addition to monoterpene double bonds. Naturally, related HOM formation mechanisms should be induced by that reaction route, too. However, for α-pinene, the most abundant atmospheric monoterpene, we find a previously unidentified competitive pathway under atmospherically relevant conditions: HOM formation is predominately induced via hydrogen abstraction by hydroxyl radicals, a generally minor reaction pathway. We show by observations and theoretical calculations that hydrogen abstraction followed by formation and rearrangement of alkoxy radicals is a prerequisite for fast daytime HOM formation. Our analysis provides an accurate mechanism and yield, demonstrating that minor reaction pathways can become major, here for SOA formation and growth and related impacts on air quality and climate.

Artemisia annua L. plants lacking Bornyl diPhosphate Synthase reallocate carbon from monoterpenes to sesquiterpenes except artemisinin.

The monoterpene camphor is produced in glandular secretory trichomes of the medicinal plant Artemisia annua, which also produces the antimalarial drug artemisinin. We have found that, depending on growth conditions, camphor can accumulate at levels ranging from 1- 10% leaf dry weight (LDW) in the Artemis F1 hybrid, which has been developed for commercial production of artemisinin at up to 1% LDW. We discovered that a camphor null (camphor-0) phenotype segregates in the progeny of self-pollinated Artemis material. Camphor-0 plants also show reduced levels of other less abundant monoterpenes and increased levels of the sesquiterpene precursor farnesyl pyrophosphate plus sesquiterpenes, including enzymatically derived artemisinin pathway intermediates but not artemisinin. One possible explanation for this is that high camphor concentrations in the glandular secretory trichomes play an important role in generating the hydrophobic conditions required for the non-enzymatic conversion of dihydroartemisinic acid tertiary hydroperoxide to artemisinin. We established that the camphor-0 phenotype associates with a genomic deletion that results in loss of a Bornyl diPhosphate Synthase (AaBPS) gene candidate. Functional characterization of the corresponding enzyme in vitro confirmed it can catalyze the first committed step in not only camphor biosynthesis but also in a number of other monoterpenes, accounting for over 60% of total volatiles in A. annua leaves. This in vitro analysis is consistent with loss of monoterpenes in camphor-0 plants. The AaBPS promoter drives high reporter gene expression in A. annua glandular secretory trichomes of juvenile leaves with expression shifting to non-glandular trichomes in mature leaves, which is consistent with AaBPS transcript abundance.

Effectiveness of Helichrysum italicum Essential Oil on Wound Healing

Helichrysum italicum essential oils (EOs) has long been known as a medicinal agent, especially in wound healing. This is inseparable from the chemical compounds contained in it, such as abundant monoterpenes and sesquiterpenes. The purpose of this systematic review is to examine various studies on the effectiveness of H. italicum EOs on wound healing. Research data searches were conducted through Google Scholar, Proquest, Science Direct, SpringerLink, Wiley Online Library, Taylor & Francis Online and PubMed over the last 10 years by following inclusion and exclusion criteria. Obtained as many as 11 studies that match the criteria. Based on the review of these studies, it was found that H. italicum EOs has good wound healing abilities when viewed from various aspects such as its chemical components, biological activity and its effect on injured body tissues. These chemical components vary in type and amount because they are influenced by various aspects. Biological activities such as antioxidant, antimicrobial, and anti-inflammatory effects have also been shown to be contained in this oil because it affects various phases of wound healing, namely hemostasis, inflammation, proliferation and remodeling phases. This is also inseparable from the accuracy of the type of vehicle used.

Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products.

Organonitrates (ON) are important components of secondary organic aerosols (SOAs). α-Pinene (C10H16), the most abundant monoterpene in the troposphere, is a precursor for the formation of several of these compounds. ON from α-pinene can be produced in the gas phase via photochemical processes and/or following reactions with oxidizers including hydroxyl radical and ozone. Gas-phase nitrogen oxides (NO2, NO3) are N sources for ON formation. Although gas-phase reactions of α-pinene that yield ON are fairly well understood, little is known about their formation through heterogeneous and multiphase pathways. In the current study, surface reactions of α-pinene with nitrogen oxides on hematite (α-Fe2O3) and kaolinite (SiO2Al2O3(OH)4) surfaces, common components of mineral dust, have been investigated. α-Pinene oxidizes upon adsorption on kaolinite, forming pinonaldehyde, which then dimerizes on the surface. Furthermore, α-pinene is shown to react with adsorbed nitrate species on these mineral surfaces producing multiple ON and other oxidation products. Additionally, gas-phase oxidation products of α-pinene on mineral surfaces are shown to more strongly adsorb on the surface compared to α-pinene. Overall, this study reveals the complexity of reactions of prevalent organic compounds such as α-pinene with adsorbed nitrate and nitrogen dioxide, revealing new heterogeneous reaction pathways for SOA formation that is mineralogy specific.

Isomer-Resolved Reactivity of Organic Peroxides in Monoterpene-Derived Secondary Organic Aerosol.

Organic peroxides play a vital role in the formation, evolution, and health impacts of atmospheric aerosols, yet their molecular composition and fate in the particle phase remain poorly understood. Here, we identified, using iodometry-assisted liquid chromatography mass spectrometry, a large suite of isomer-resolved peroxide monomers (C8-10H12-18O5-8) and dimers (C15-20H22-34O5-14) in secondary organic aerosol formed from ozonolysis of the most abundant monoterpene (α-pinene). Combining aerosol isothermal evaporation experiments and multilayer kinetic modeling, bulk peroxides were found to undergo rapid particle-phase chemical transformation with an average lifetime of several hours under humid conditions, while the individual peroxides decompose on timescales of half an hour to a few days. Meanwhile, the majority of isomeric peroxides exhibit distinct particle-phase behaviors, highlighting the importance of the characterization of isomer-resolved peroxide reactivity. Furthermore, the reactivity of most peroxides increases with aerosol water content faster in a low relative humidity (RH) range than in a high RH range. Such non-uniform water effects imply a more important role of water as a plasticizer than as a reactant in influencing the peroxide reactivity. The high particle-phase reactivity of organic peroxides and its striking dependence on RH should be considered in atmospheric modeling of their fate and impacts on aerosol chemistry and health effects.

Vacuum ultraviolet free-electron laser photoionization mass spectrometry of alpha-pinene ozonolysis

α-pinene is the most abundant monoterpene that represents an important family of volatile organic compounds. Molecular identification of key transient compounds during the α-pinene ozonolysis has been proven to be a challenging experimental target because of a large number of intermediates and products involved. Here we exploit the recently developed hybrid instruments that integrate aerosol mass spectrometry with a vacuum ultraviolet free-electron laser to study the α-pinene ozonolysis. The experiments of α-pinene ozonolysis are performed in an indoor smog chamber, with reactor having a volume of 2 m3 which is made of fluorinated ethylene propylene film. Distinct mass spectral peaks provide direct experimental signatures of previously unseen compounds produced from the reaction of α-pinene with O3. With the aid of quantum chemical calculations, plausible mechanisms for the formation of these new compounds are proposed. These findings provide crucial information on fundamental understanding of the initial steps of α-pinene oxidation and the subsequent processes of new particle formation.

Thermal Degradation Products of <i>α</i>-Pinene in a Tubular Furnace in the Temperature Range from 300°C to 900°C: Contribution to Wildfire Flashovers

Induced BVOC emissions from pyrolyzed plants that may accumulate in confined topographies have been a controversy for their role in wildfire eruptions or flashovers. α-pinene (C10H16) is one of the most abundant monoterpenes emitted from pyrolyzed Mediterranean vegetation in wildfires. Its thermal degradation under fire thermal stresses produces a range of highly flammable gases. In order to identify these products, thermal degradation experiments were performed on α-pinene in a tubular furnace in an inert atmosphere and a high-temperature range (300°C - 900°C). The pyrolysis products were identified using gas chromatography (GC) linked to a tubular furnace outlet by which their retention times were compared with those of reference standards. The degradation products were mainly terpenoids, aliphatic hydrocarbons (methane, ethane, ethene, propane, propene, 1,3-butadiene, isoprene), and aromatics (benzene, toluene) in addition to hydrogen. The radical mechanisms of the chemical reactions associated with the formation of the products at different experimental temperatures were addressed and compared with the literature. Monoterpenes, butadiene, isoprene, aliphatic hydrocarbons, and aromatics formations from α-pinene were consistent with the literature. However, even if benzene has been identified in our experiments, we cannot support with certainty the mechanisms of its formation described in the literature since acetylene was not observed.

Combined Effect of Altitude, Season and Light on the Accumulation of Extractable Terpenes in Norway Spruce Needles

Plants produce specific terpenes, secondary metabolites conferring tolerance to biotic and abiotic stresses. Our study aims to investigate the effects of altitude, light intensity and season on contents of mono- and sesquiterpenes in needles of coniferous Norway spruce (Picea abies). Needles of current shoots representing upper and lower canopy were collected from adult trees growing along an altitudinal gradient (400–1100 m a.s.l.) in summer and autumn. After the extraction in cold heptane, the content of extractable terpenes was determined by gas chromatography coupled with mass spectrometry. Our results show that the total content of terpenes decreases with increasing altitude regardless of canopy position and season. Needles of the upper canopy have a higher total content of terpenes than lower canopy needles, but this difference decreases with increasing altitude in summer. Total content of extractable terpenes increases in autumn when compared to summer particularly in upper canopy needles of trees from high altitudes. Limonene, camphene, α-pinene and myrcene are the most abundant monoterpenes in spruce needles forming up to 85% of total monoterpenes, while germacrene D-4-ol is the most abundant sesquiterpene. Altitude, canopy position and season have a significant interactive effect on most monoterpenes, but not on sesquiterpenes. Terpenoid biosynthesis is thus tightly linked to growth conditions and likely plays a crucial role in the constitution of stress tolerance in evergreen conifers.

Anti-Hyperalgesic Properties of Menthol and Pulegone.

Context: Menthol, the main monoterpene found in Mentha piperita L. (M. piperita) is known to modulate nociceptive threshold and is present in different curative preparations that reduce sensory hypersensitivities in pain conditions. While for pulegone, a menthol-like monoterpene, only a limited number of studies focus on its putative analgesic effects, pulegone is the most abundant monoterpene present in Calamintha nepeta (L.) Savi (C. nepeta), a plant of the Lamiaceae family used in traditional medicine to alleviate rheumatic disorders, which counts amongst chronic inflammatory diseases. Objectives: Here, we analyzed the monoterpenes composition of C. nepeta and M. piperita. We then compared the putative anti-hyperalgesic effects of the main monoterpenes found, menthol and pulegone, in acute inflammatory pain conditions. Methods: C. nepeta and M. piperita extracts were obtained through pressurized liquid extraction and analyzed by gas chromatography-mass spectrometry. The in vitro anti-inflammatory activity of menthol or pulegone was evaluated by measuring the secretion of the tumour necrosis factor alpha (TNF α) from LPS-stimulated THP-1 cells. The in vivo anti-hyperalgesic effects of menthol and pulegone were tested on a rat inflammatory pain model. Results: Pulegone and menthol are the most abundant monoterpene found in C. nepeta (49.41%) and M. piperita (42.85%) extracts, respectively. In vitro, both pulegone and menthol act as strong anti-inflammatory molecules, with EC50 values of 1.2 ± 0.2 and 1.5 ± 0.1 mM, respectively, and exert cytotoxicity with EC50 values of 6.6 ± 0.3 and 3.5 ± 0.2 mM, respectively. In vivo, 100 mg/kg pulegone exerts a transient anti-hyperalgesic effect on both mechanical (pulegone: 274.25 ± 68.89 g, n = 8; vehicle: 160.88 ± 35.17 g, n = 8, p < 0.0001), thermal heat (pulegone: 4.09 ± 0.62 s, n = 8; vehicle: 2.25 ± 0.34 s, n = 8, p < 0.0001), and cold (pulegone: 2.25 ± 1.28 score, n = 8; vehicle: 4.75 ± 1.04 score, n = 8, p = 0.0003). In a similar way, 100 mg/kg menthol exerts a transient anti-hyperalgesic effect on both mechanical (mechanical: menthol: 281.63 ± 45.52 g, n = 8; vehicle: 166.25 ± 35.4 g, n = 8, p < 0.0001) and thermal heat (menthol: 3.65 ± 0.88 s, n = 8; vehicle: 2.19 ± 0.26 s, n = 8, <0.0001). Conclusion: Here, we show that both pulegone and menthol are anti-inflammatory and anti-hyperalgesic monoterpenes. These results might open the path towards new compound mixes to alleviate the pain sensation.

Gas- and Particle-Phase Products and Their Mechanisms of Formation from the Reaction of Δ-3-Carene with NO3 Radicals.

Monoterpenes are a major component of the large quantities of biogenic volatile organic compounds that are emitted to the atmosphere each year. They have a variety of structures, which influences their subsequent reactions with OH radicals, O3, or NO3 radicals and the tendency for these reactions to form secondary organic aerosol (SOA). Here we report the results of an environmental chamber study of the reaction of Δ-3-carene, an abundant unsaturated C10 bicyclic monoterpene, with NO3 radicals, a major nighttime oxidant. Gas- and particle-phase reaction products were analyzed in real time and offline by using mass spectrometry, gas and liquid chromatography, infrared spectroscopy, and derivatization-spectrophotometric methods. The results were used to identify and quantify functional groups and molecular products and to develop gas- and particle-phase reaction mechanisms to explain their formation. Identified gas-phase products were all first-generation ring-retaining and ring-opened compounds (ten C10 and one C9 monomers) with 2-4 functional groups and one C20 dinitrooxydialkyl peroxide dimer. Upon partitioning to the particle phase, the monomers reacted further to form oligomers consisting almost entirely of C20 acetal and hemiacetal dimers, with those formed from a hydroxynitrate and hydroxycarbonyl nitrate comprising more than 50% of the SOA mass. The SOA contained an average of 0.94, 0.71, 0.15, 0.11, 0.16, 0.13, and 7.80 nitrate, carbonyl, hydroxyl, carboxyl, ester, peroxide, and methylene groups per C10 monomer and was formed with a mass yield of 56%. These results have important similarities and differences to those obtained from a previous similar study of the reaction of β-pinene and yield new insights into the effects of monoterpene structure on gas- and particle-phase reactions that can lead to the formation of a large variety of multifunctional products and significant amounts of SOA.

Effects of Berry Thinning on the Physicochemical, Aromatic, and Sensory Properties of Shine Muscat Grapes

The effects of the level of berry thinning (30% and 50% berry removal) on the quality and sensory properties of Shine Muscat grapes were investigated. As berry thinning increased, the total soluble solids content increased and titratable acidity decreased. Berry thinning increased berry size and cluster weight but caused no change in individual berry weight. Phenolic concentrations as measured by total phenolic, proanthocyanidin, and polymeric tannin concentrations tended to increase with an increase in berry thinning. Gas chromatographic analysis indicated that C6-compounds were the significant constituents of volatile alcohols and aldehydes; linalool was the most abundant monoterpene. Odor activity analysis indicated that (E)-2-hexen-1-ol, (E)-2-hexenal, 1-hexanal, (Z)-3-hexenal, (E)-β-damascenone, linalool, and (E)-linalool oxide were active odorants. Berry thinning increased the accumulation of linalool contributing to high sensory flavor scores in thinned berries. Furthermore, its oxidized derivative-linalool oxide-contributed to enhancing the Muscat flavor. In conclusion, berry thinning induced compositional changes in Shine Muscat grape berries by accelerating the ripening rate, contribution to improved sensory properties.