Terpene Chemistry Research Articles

Nighttime chemistry of furanoids and terpenes: Temperature dependent kinetics with NO3 radicals and insights into the reaction mechanism

In this study, the gas phase reaction of NO3 radical with three furanoids, furan (F), 2-methylfuran (2-MF) and 2,5-dimethylfuran (2,5-DMF) were investigated using a relative rate method in a temperature regulated atmospheric simulation chamber (THALAMOS). As part of this study, the temperature dependence of two monoterpenes, α-pinene (α-P) and 2-carene (2-C), that were used as reference molecules, is also reported. The kinetic measurements were performed in the range of 263–373 K, atmospheric pressure using zero air as bath gas. The reaction was followed using Selected ion flow tube mass spectrometry (SIFT-MS) to monitor in real time the mixing ratios of the investigated species. The corresponding Arrhenius expressions obtained were:kα−P+NO3(263−378K)=(1.32±0.16)×10−12×e462±70Tcm3molecule‐1s‐1.k2−C+NO3296–433K=8.77±2.71×10−13×e904±96Tcm3molecule‐1s‐1.kF+NO3263−353K=7.55±1.96×10−13×e254±79Tcm3molecule‐1s‐1.k2−MF+NO3263−373K=7.76±2.62×10−13×e922±262Tcm3molecule‐1s‐1.k2,5−DMF+NO3298–353K=2.58±0.77×10−13×e1692±136Tcm3molecule‐1s‐1.Where the estimated uncertainties include the 1σ precision of the fit and the estimated uncertainty in the precision of the Arhenius fit of the reference compound. In the case of furanoids, the negative temperature-dependence of the rate coefficients shows that the reaction mechanism is complex, indicating that the reaction involves the formation of an adduct that could lead either to NO3 addition to the double bond, as well as, in the case of 2-MF and 2,5-DMF, the H-abstraction from the methyl group attached to the ring. In addition to the kinetics measurements, the major products formed from the reaction of furan and 2,5-DMF with NO3 were studied. The two identified products from the reaction of furan with NO3, were 3H-furan-2-one (C4H4O2) and 2-butenedial (C4H4O2), formed by NO3 addition to the double bond of the furan ring. 3-Hexene-2,5-dione (C6H8O2) and 5-methylfurfural (C6H6O2) are the two major products of 2,5-DMF reaction with NO3, linked to the addition and abstraction pathways, respectively. Considering that 5-methylfurfural is the only primary product of the H elimination pathway of 2,5-DMF, the determination of its formation yields as a function of temperature, allowed us to extract the temperature dependence of the rate coefficients of the abstraction and addition pathways.Overall, the NO3 oxidation of the studied furanoids, is expected to be the dominant tropospheric loss process, in the studied temperature range.

Benign synthesis of terpene-based 1,4-p-menthane diamine

Terpenes represent a promising renewable feedstock for the substitution of fossil resources in the synthesis of renewable platform chemicals, like diamines. This work describes the synthesis and full characterization of 1,4-p-menthane diamine (1,4-PMD) obtained from α-terpinene (1). A two-step procedure using dibenzyl azodicarboxylate (DBAD) and H2 as rather benign reagents was employed under comparatively mild conditions. Both C–N bonds were formed simultaneously during a visible-light mediated Diels–Alder reaction, which was investigated in batch or flow, avoiding regioselectivity issues during the amination steps that are otherwise typical for terpene chemistry. Heterogeneously catalyzed quadruple hydrogenation of the cycloadduct (2a) yielded 1,4‑PMD (3). While the intermediate cycloadduct was shown to be distillable, the target diamine can be sublimed, offering sustainable purification methods.

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements.

The impact of organometallic chemistry on the terpene field only really blossomed in the 1960s and 1970s with the realisation that carbon-carbon bond formation under mild conditions could be achieved by using nickel or iron carbonyls as synthetic reagents. Concomitantly, the development of palladium derivatives capable of the controlled coupling of isoprene units attracted the attention of numerous highly talented researchers, including future Nobel laureates. We discuss briefly how early work on the syntheses of simple monoterpenes soon progressed to sesquiterpenes and diterpenes of increasing complexity, such as humulene, flexibilene, vitamin A, or pheromones of commercial value, in particular those used in perfumery (muscone, lavandulol), or grandisol and red scale pheromone as replacements for harmful pesticides. As the field progressed, there has been more emphasis on developing organometallic routes to enantiopure rather than racemic products, as well as gaining precise mechanistic data on the transformations, notably the course of metal-promoted molecular rearrangements that have long been a feature of terpene chemistry. We note the impact of the enormously enhanced analytical techniques, high-field NMR spectroscopy and X-ray crystallography, and their use to re-examine the originally proposed structures of terpenes and their organometallic derivatives. Finally, we highlight the very recent ground-breaking use of the crystalline sponge method to acquire structural data on low-melting or volatile terpenes. The literature cited herein covers the period 1959 to 2023.

A terpene synthase supergene locus determines chemotype in Melaleuca alternifolia (tea tree).

Leaf oil terpenes vary categorically in many plant populations, leading to discrete phenotypes of adaptive and economic significance, but for most species, a genetic explanation for the concerted fluctuation in terpene chemistry remains unresolved. To uncover the genetic architecture underlying multi-component terpene chemotypes in Melaleuca alternifolia (tea tree), a genome-wide association study was undertaken for 148 individuals representing all six recognised chemotypes. A number of single nucleotide polymorphisms in a genomic region of c. 400 kb explained large proportions of the variation in key monoterpenes of tea tree oil. The region contained a cluster of 10 monoterpene synthase genes, including four genes predicted to encode synthases for 1,8-cineole, terpinolene, and the terpinen-4-ol precursor, sabinene hydrate. Chemotype-dependent null alleles at some sites suggested structural variants within this gene cluster, providing a possible basis for linkage disequilibrium in this region. Genotyping in a separate domesticated population revealed that all alleles surrounding this gene cluster were fixed after artificial selection for a single chemotype. These observations indicate that a supergene accounts for chemotypes in M. alternifolia. A genetic model with three haplotypes, encompassing the four characterised monoterpene synthase genes, explained the six terpene chemotypes, and was consistent with available biparental cross-segregation data.

The terpene synthase genes of Melaleuca alternifolia (tea tree) and comparative gene family analysis among Myrtaceae essential oil crops

Terpene synthases (TPS) are responsible for the terminal biosynthetic step of terpenoid production. They are encoded by a highly diverse gene family believed to evolve by tandem duplication in response to adaptive pressures. Taxa in the Myrtaceae family are renowned for their diversity of terpenoid-rich essential oils, and among them, the tribe Eucalypteae has the largest TPS gene family found in any plant (> 100 TPS). In this study, comparative analysis of Melaleuca alternifolia (tea tree), from the related tribe Melaleuceae, revealed some Myrtaceae have smaller TPS families, as a total of 58 putatively functional full-length TPS genes, and 21 pseudogenes were identified by manual annotation of a newly released long-read assembly of the genome. The TPS-a and TPS-b2 subfamilies that synthesise secondary compounds often mediating plant-environment interactions were more diminutive than those in eucalypts, probably reflecting key differences in the evolutionary histories of the two lineages. Of the putatively functional TPS-b1, 13 clustered into a region of around 400 kb on one scaffold. The organisation of these TPS suggested that tandem duplication was instrumental in the evolution and diversity of terpene chemistry in Melaleuca. Four TPS-b1 likely to catalyse the synthesis of the three monoterpenoid components that are used to classify tea tree chemotypes were encoded within a single small region of 87 kb in the larger cluster of TPS-b1, raising the possibility that coregulation and linkage may lead to their behaviour as a single locus, providing an explanation for the categorical inheritance of complex multiple-component chemotypes in the taxon.

Bark Beetles Utilize Ophiostomatoid Fungi to Circumvent Host Tree Defenses.

Bark beetles maintain symbiotic associations with a diversity of microbial organisms, including ophiostomatoid fungi. Studies have frequently reported the role of ophiostomatoid fungi in bark beetle biology, but how fungal symbionts interact with host chemical defenses over time is needed. We first investigated how inoculations by three fungal symbionts of mountain pine beetle affect the terpene chemistry of live lodgepole pine trees. We then conducted a complimentary laboratory experiment specifically measuring the host metabolite degradation by fungi and collected the fungal organic volatiles following inoculations with the same fungal species on lodgepole pine logs. In both experiments, we analyzed the infected tissues for their terpene chemistry. Additionally, we conducted an olfactometer assay to determine whether adult beetles respond to the volatile organic chemicals emitted from each of the three fungal species. We found that all fungi upregulated terpenes as early as two weeks after inoculations. Similarly, oxygenated monoterpene concentrations also increased by several folds (only in logs). A large majority of beetles tested showed a strong attraction to two fungal species, whereas the other fungus repelled the beetles. Together this study shows that fungal symbionts can alter host defense chemistry, assist beetles in overcoming metabolite toxicity, and provide possible chemical cues for bark beetle attraction.

Genetic architecture of terpene chemistry and growth traits and the impact of inbreeding on these traits in western redcedar (Thuja plicata).

Western redcedar (WRC; Thuja plicata) is a conifer of the Pacific Northwest of North America prized for its durable and rot-resistant wood. WRC has naturally low outcrossing rates and readily self-fertilizes in nature. Challenges faced in WRC breeding and propagation involve selecting trees for accelerated growth while also ensuring enhanced heartwood rot resistance and resistance to ungulate browsing, as well as mitigating potential effects of inbreeding depression. Terpenes, a large and diverse class of specialized metabolites, confer both rot and browse resistance in the wood and foliage of WRC, respectively. Using a Bayesian modelling approach, we isolated single nucleotide polymorphism (SNP) markers estimated to be associated with three different foliar terpene traits and four different heartwood terpene traits, as well as two growth traits. We found that all traits were complex, being associated with between 1700 and 3600 SNPs linked with putatively causal loci, with significant polygenic components. Growth traits tended to have a larger polygenic component while terpene traits had larger major gene components; SNPs with small or polygenic effect were spread across the genome, while larger-effect SNPs tended to be localized to specific linkage groups. To determine whether there was inbreeding depression for terpene chemistry or growth traits, we used mixed linear models for a genomic selection training population to estimate the effect of the inbreeding coefficient F on foliar terpenes, heartwood terpenes and several growth and dendrochronological traits. We did not find significant inbreeding depression for any assessed trait. We further assessed inbreeding depression across four generations of complete selfing and found that not only was inbreeding depression not significant but that selection for height growth was the only significant predictor for growth during selfing, suggesting that inbreeding depression due to selfing during operational breeding can be mitigated by increased selection intensity.

The chemical biogeography of a widespread aromatic plant species shows both spatial and temporal variation.

Plants produce a wide variety of secondary metabolites, but intraspecific variation in space and time can alter the ecological interactions these compounds mediate. The aim of this work was to document the spatial and temporal chemical biogeography of Monarda fistulosa. I collected leaves from 1587 M. fistulosa individuals from 86 populations from Colorado to Manitoba, extracted and analyzed their terpenes with gas chromatography, mapped monoterpene chemotypes, and analyzed chemical variation with principal component analysis. I also measured the amounts of terpenes in different plant tissues to examine intraplant variation and monitored leaf terpene chemistry over a single growing season to examine temporal patterns. Finally, I extracted terpenes from herbarium samples up to 125 years old and compared the chemotypes with recent samples from the same sites. M. fistulosa populations consisted mostly of thymol (T) and carvacrol (C) chemotypes, but geraniol (G) and (R)‐(−)‐linalool (L), a chemotype new to this species, were also present. A principal component analysis showed that most of the chemical variation across populations was due to the amounts of the dominant terpene in plants. Intraplant tissue chemistry revealed that leaves mostly had the greatest amounts of terpenes, followed by floral structures, stems, and roots. Short‐term temporal variation in leaf chemistry of T and C plants over a growing season showed that plants produced the highest levels of biosynthetic precursors early in the season and their dominant monoterpenes peaked in mid‐summer. Plant chemotype was discernable in the oldest herbarium samples, and 15 of 18 historic samples matched the majority chemotype currently at the site, indicating that population chemotype ratios may remain stable over longer time scales. Overall, the results show that plant species' secondary chemistry can vary both spatially and temporally, which may alter the biological interactions that these compounds mediate over space and time.

Exploring the Relationship between Trichome and Terpene Chemistry in Chrysanthemum.

Chrysanthemum is a popular ornamental plant with a long history of cultivation. Both the leaf and flowerhead of Chrysanthemum are known to produce diverse secondary metabolites, particularly terpenoids. Here we aimed to determine the relationship between terpene chemistry and the trichome traits in Chrysanthemum. In our examination of three cultivars of C. morifilium and three accessions of C. indicum, all plants contained T-shaped trichomes and biseriate peltate glandular trichomes. The biseriate peltate glandular trichome contained two basal cells, two stalk cells, six secondary cells and a subcuticular space, while the non-glandular T-shaped trichome was only composed of stalk cells and elongated cells. Histochemical staining analysis indicated that the biseriate peltate glandular trichome contained terpenoids and lipid oil droplets but not the T-shaped trichome. Next, experiments were performed to determine the relationship between the accumulation and emission of the volatile terpenoids and the density of trichomes on the leaves and flowerheads in all six Chrysanthemum cultivars\\accessions. A significant correlation was identified between the monoterpenoid and sesquiterpenoid content and the density of glandular trichomes on the leaves, with the correlation coefficients being 0.88, 0.86 and 0.90, respectively. In contrast, there was no significant correlation between the volatile terpenoid content and the density of T-shaped trichomes on the leaves. In flowerheads, a significant correlation was identified between the emission rate of terpenoids and the number of glandular trichomes on the disc florets, with a correlation coefficient of 0.95. Interestingly, the correlation between the density of glandular trichomes and concentrations of terpenoids was insignificant. In summary, the relationship between trichomes and terpenoid chemistry in Chrysanthemum is clearly established. Such knowledge may be helpful for breeding aromatic Chrysanthemum cultivars by modulating the trichome trait.

Variation in Methyl Jasmonate-Induced Defense Among Norway Spruce Clones and Trade-Offs in Resistance Against a Fungal and an Insect Pest.

An essential component of plant defense is the change that occurs from a constitutive to an induced state following damage or infection. Exogenous application of the plant hormone methyl jasmonate (MeJA) has shown great potential to be used as a defense inducer prior to pest exposure, and could be used as a plant protection measure. Here, we examined (1) the importance of MeJA-mediated induction for Norway spruce (Picea abies) resistance against damage by the pine weevil Hylobius abietis, which poses a threat to seedling survival, and infection by the spruce bark beetle-associated blue-stain fungus Endoconidiophora polonica, (2) genotypic variation in MeJA-induced defense (terpene chemistry), and (3) correlations among resistance to each pest. In a semi-field experiment, we exposed rooted-cuttings from nine different Norway spruce clones to insect damage and fungal infection separately. Plants were treated with 0, 25, or 50 mM MeJA, and planted in blocks where only pine weevils were released, or in a separate block in which plants were fungus-inoculated or not (control group). As measures of resistance, stem area debarked and fungal lesion lengths were assessed, and as a measure of defensive capacity, terpene chemistry was examined. We found that MeJA treatment increased resistance to H. abietis and E. polonica, but effects varied with clone. Norway spruce clones that exhibited high constitutive resistance did not show large changes in area debarked or lesion length when MeJA-treated, and vice versa. Moreover, insect damage negatively correlated with fungal infection. Clones receiving little pine weevil damage experienced larger lesion lengths, and vice versa, both in the constitutive and induced states. Changes in absolute terpene concentrations occurred with MeJA treatment (but not on proportional terpene concentrations), however, variation in chemistry was mostly explained by differences between clones. We conclude that MeJA can enhance protection against H. abietis and E. polonica, but the extent of protection will depend on the importance of constitutive and induced resistance for the Norway spruce clone in question. Trade-offs among resistances do not necessarily hinder the use of MeJA, as clones that are constitutively more resistant to either pest, should show greater MeJA-induced resistance against the other.

Five TPSs are responsible for volatile terpenoid biosynthesis in Albizia julibrissin

Silk tree, Albizia julibrissin Duraz, is an old ornamental plant and extensively cultivated in Asia. Previous works have discovered that the terpenoids were the dominating compounds in the floral VOC of A. julibrissin, however the biosynthesis of these terpenoids was poorly understood so far. Here, 11 terpene synthase genes (TPSs) were identified by transcriptome sequencing that fell into TPS-a, TPS-b and TPS-g subfamilies. The enzymatic activity tests showed that five genes were functional: AjTPS2 was a sesquiterpene synthase and produced α-farnesene and (Z, E)-β-farnesene; AjTPS5 was able to catalyze the formation of five monoterpenes and nine sesquiterpenes; AjTPS7, AjTPS9 and AjTPS10 were dedicated monoterpene synthases, as AjTPS7 and AjTPS10 formed the single product β-ocimene and linalool, respectively, and AjTPS9 produced γ-terpinene with other three monoterpenes. More importantly, the main catalytic products of the characterized AjTPSs were consistent with the terpenoids observed in A. julibrissin volatiles. Combining terpene chemistry, TPSs biochemical activities and gene expression analysis, we demonstrate that AjTPS2, AjTPS5, AjTPS7, AjTPS9 and AjTPS10 are responsible for the volatile terpenoids biosynthesis in A. julibrissin.

Taxane Meets Propellane: First Chemical Synthesis of Highly Complex Diterpene Canataxpropellane.

The features of two iconic chemical classes are united in the structure of the highly complex diterpene canataxpropellane and set a daunting challenge that has been met by the Gaich group. Their daring strategy and its benefit to the field of terpene chemistry is presented and discussed in this Highlight.

Comprehensive isoprene and terpene gas-phase chemistry improves simulated surface ozone in the southeastern US

Abstract. Ozone is a greenhouse gas and air pollutant that is harmful to human health and plants. During the summer in the southeastern US, many regional and global models are biased high for surface ozone compared to observations. Past studies have suggested different solutions including the need for updates to model representation of clouds, chemistry, ozone deposition, and emissions of nitrogen oxides (NOx) or biogenic hydrocarbons. Here, due to the high biogenic emissions in the southeastern US, more comprehensive and updated isoprene and terpene chemistry is added into CESM/CAM-chem (Community Earth System Model/Community Atmosphere Model with full chemistry) to evaluate the impact of chemistry on simulated ozone. Comparisons of the model results with data collected during the Studies of Emissions Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) field campaign and from the US EPA (Environmental Protection Agency) CASTNET (Clean Air Status and Trends Network) monitoring stations confirm the updated chemistry improves simulated surface ozone, ozone precursors, and NOx reservoir compounds. The isoprene and terpene chemistry updates reduce the bias in the daily maximum 8 h average (MDA8) surface ozone by up to 7 ppb. In the past, terpene oxidation in particular has been ignored or heavily reduced in chemical schemes used in many regional and global models, and this study demonstrates that comprehensive isoprene and terpene chemistry is needed to reduce surface ozone model biases. Sensitivity tests were performed in order to evaluate the impact of lingering uncertainties in isoprene and terpene oxidation on ozone. Results suggest that even though isoprene emissions are higher than terpene emissions in the southeastern US, remaining uncertainties in isoprene and terpene oxidation have similar impacts on ozone due to lower uncertainties in isoprene oxidation. Additionally, this study identifies the need for further constraints on the aerosol uptake of organic nitrates derived from isoprene and terpenes in order to reduce uncertainty in simulated ozone. Although the updates to isoprene and terpene chemistry greatly reduce the ozone bias in CAM-chem, a large bias remains. Evaluation against SEAC4RS field campaign results suggests future improvements to horizontal resolution and cloud parameterizations in CAM-chem may be particularly important for further reducing this bias.

Does the ubiquitous use of essential oil-based products promote indoor air quality? A critical literature review.

Essential oils are frequently used as natural fragrances in housecleaning products and air fresheners marketed as green and healthy. However, these substances are volatile and reactive chemical species. This review focuses on the impact of essential oil-based household products on indoor air quality. First, housecleaning products containing essential oils are explored in terms of composition and existing regulations. Specific insight is provided regarding terpenes in fragranced housecleaning products, air fresheners, and pure essential oils. Second, experimental methodologies for terpene monitoring, from sampling to experimental chambers and analytical methods, are addressed, emphasizing the experimental issues in monitoring terpenes in indoor air. Third, the temporal dynamics of terpene emissions reported in the literature are discussed. Despite experimental discrepancies, essential oil-based products are significant sources of terpenes in indoor air, inducing a high exposure of occupants to terpenes. Finally, the fate of terpenes is explored from sorptive and reactive points of view. In addition to terpene deposition on surfaces, indoor oxidants may induce homogeneous and heterogeneous reactions, resulting in secondary pollutants, such as formaldehyde and secondary organic aerosols. Overall, essential oil-based products can negatively impact indoor air quality; therefore, standard protocols and real-scale approaches are needed to explore the indoor physics and chemistry of terpenes, from emissions to reactivity.

Terpenes and their oxidation products in the French Landes forest: insights from Vocus PTR-TOF measurements

Abstract. The capabilities of the recently developed Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF) are reported for the first time based on ambient measurements. With the deployment of the Vocus PTR-TOF, we present an overview of the observed gas-phase (oxygenated) molecules in the French Landes forest during summertime 2018 and gain insights into the atmospheric oxidation of terpenes, which are emitted in large quantities in the atmosphere and play important roles in secondary organic aerosol production. Due to the greatly improved detection efficiency compared to conventional PTR instruments, the Vocus PTR-TOF identifies a large number of gas-phase signals with elemental composition categories including CH, CHO, CHN, CHS, CHON, CHOS, and others. Multiple hydrocarbons are detected, with carbon numbers up to 20. Particularly, we report the first direct observations of low-volatility diterpenes in the ambient air. The diurnal cycle of diterpenes is similar to that of monoterpenes and sesquiterpenes but contrary to that of isoprene. Various types of terpene reaction products and intermediates are also characterized. Generally, the more oxidized products from terpene oxidations show a broad peak in the day due to the strong photochemical effects, while the less oxygenated products peak in the early morning and/or in the evening. To evaluate the importance of different formation pathways in terpene chemistry, the reaction rates of terpenes with main oxidants (i.e., hydroxyl radical, OH; ozone, O3; and nitrate radical, NO3) are calculated. For the less oxidized non-nitrate monoterpene oxidation products, their morning and evening peaks have contributions from both O3- and OH-initiated monoterpene oxidation. For the monoterpene-derived organic nitrates, oxidations by O3, OH, and NO3 radicals all contribute to their formation, with their relative roles varying considerably over the course of the day. Through a detailed analysis of terpene chemistry, this study demonstrates the capability of the Vocus PTR-TOF in the detection of a wide range of oxidized reaction products in ambient and remote conditions, which highlights its importance in investigating atmospheric oxidation processes.

Terpene synthases in disguise: enzymology, structure, and opportunities of non-canonical terpene synthases.

Covering: up to July 2019 Terpene synthases (TSs) are responsible for generating much of the structural diversity found in the superfamily of terpenoid natural products. These elegant enzymes mediate complex carbocation-based cyclization and rearrangement cascades with a variety of electron-rich linear and cyclic substrates. For decades, two main classes of TSs, divided by how they generate the reaction-triggering initial carbocation, have dominated the field of terpene enzymology. Recently, several novel and unconventional TSs that perform TS-like reactions but do not resemble canonical TSs in sequence or structure have been discovered. In this review, we identify 12 families of non-canonical TSs and examine their sequences, structures, functions, and proposed mechanisms. Nature provides a wide diversity of enzymes, including prenyltransferases, methyltransferases, P450s, and NAD+-dependent dehydrogenases, as well as completely new enzymes, that utilize distinctive reaction mechanisms for TS chemistry. These unique non-canonical TSs provide immense opportunities to understand how nature evolved different tools for terpene biosynthesis by structural and mechanistic characterization while affording new probes for the discovery of novel terpenoid natural products and gene clusters via genome mining. With every new discovery, the dualistic paradigm of TSs is contradicted and the field of terpene chemistry and enzymology continues to expand.

Synthetic terpenoids in the world of fragrances: Iso E Super® is the showcase.

The history of fragrances is closely associated with the chemistry of terpenes and terpenoids. For thousands of years mankind mainly used plant extracts to collect ingredients for the creation of perfumes. Many of these extracts contain complex mixtures of terpenes, that show distinct olfactoric properties as pure compounds. When organic synthesis appeared on the scene, the portfolio of new scents increased either in order to substitute natural fragrances without change of olfactoric properties or to broaden the scope of scents. This short review describes the story of the most successful synthetic fragrance ever which is called Iso E Super® as it is an ingredient in a large number of perfumes with varying percentages and is the first example being used as a pure fragrance. Structurally, it is related to natural terpenes like many other synthetic fragrances. And indeed, the story began with a classic in the field of fragrances, the natural product ionone.

Sexual and genotypic variation in terpene quantitative and qualitative profiles in the dioecious shrub Baccharis salicifolia

Terpenoids are secondary metabolites produced in most plant tissues and are often considered toxic or repellent to plant enemies. Previous work has typically reported on intra-specific variation in terpene profiles, but the effects of plant sex, an important axis of genetic variation, have been less studied for chemical defences in general, and terpenes in particular. In a prior study, we found strong genetic variation (but not sexual dimorphism) in terpene amounts in leaves of the dioecious shrub Baccharis salicifolia. Here we build on these findings and provide a more in-depth analysis of terpene chemistry on these same plants from an experiment consisting of a common garden with male (N = 19) and female (N = 20) genotypes sourced from a single population. Our goal in the present study was to investigate quantitative and qualitative differences in terpene profiles associated with plant sex and genotypic variation. For this, we quantified leaf mono- and sesquiterpene amount, richness, and diversity (quantitative profile), as well as the composition of compounds (qualitative profile). We found no evidence of sexual dimorphism in monoterpene or sesquiterpene profiles. We did, however, find significant genotypic variation in amount, diversity, and composition of monoterpenes, but no effects on sesquiterpenes. These findings indicated that genotypic variation in terpene profiles largely surpassed variation due to sexual dimorphism for the studied population of this species.

Secondary Organic Aerosol Formation from Healthy and Aphid-Stressed Scots Pine Emissions.

One barrier to predicting biogenic secondary organic aerosol (SOA) formation in a changing climate can be attributed to the complex nature of plant volatile emissions. Plant volatile emissions are dynamic over space and time, and change in response to environmental stressors. This study investigated SOA production from emissions of healthy and aphid-stressed Scots pine saplings via dark ozonolysis and photooxidation chemistry. Laboratory experiments using a batch reaction chamber were used to investigate SOA production from different plant volatile mixtures. The volatile mixture from healthy plants included monoterpenes, aromatics, and a small amount of sesquiterpenes. The biggest change in the volatile mixture for aphid-stressed plants was a large increase (from 1.4 to 7.9 ppb) in sesquiterpenes—particularly acyclic sesquiterpenes, such as the farnesene isomers. Acyclic sesquiterpenes had different effects on SOA production depending on the chemical mechanism. Farnesenes suppressed SOA formation from ozonolysis with a 9.7–14.6% SOA mass yield from healthy plant emissions and a 6.9–10.4% SOA mass yield from aphid-stressed plant emissions. Ozonolysis of volatile mixtures containing more farnesenes promoted fragmentation reactions, which produced higher volatility oxidation products. In contrast, plant volatile mixtures containing more farnesenes did not appreciably change SOA production from photooxidation. SOA mass yields ranged from 10.8 to 23.2% from healthy plant emissions and 17.8–26.8% for aphid-stressed plant emissions. This study highlights the potential importance of acyclic terpene chemistry in a future climate regime with an increased presence of plant stress volatiles.

Special Issue: Symposium on the Chemistry of Terpenes, Essential Oils and Aromatics (TEAC)

Special Issue: Symposium on the Chemistry of Terpenes, Essential Oils and Aromatics (TEAC)