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• Increasing the potential of Adenostemma lavenia through some types of fertilizer. • Fertilizer application resulted in better growth of A. lavenia compared to control. • The secondary metabolite production is increased when fertilizer is added. • The PCA patterns in A. lavenia extract are clustered based on fertilizer types. • The combination of fertilizers leads to improved growth and chemical compounds. Adenostemma lavenia , a member of the Asteraceae family, possesses numerous medicinal properties, although it is not extensively cultivated. The objective of this research initiative is to determine the optimal fertilizer dosages that result in the optimal productivity of 11α-OH KA, a diterpenoid, phenolic, flavonoid, and terpenoid compounds, as well as growth, in A. lavenia. A one-factor randomized block design was employed with five fertilizer doses: without fertilizer (control), cow manure (20 tons ha−1) (F1), NPK (urea, SP-36, and KCl: 135, 100, 135 kg ha−1, respectively) (F2), the first combination consisting of cow manure (10 tons ha−1) + NPK (urea, SP-36, and KCl: 67.5, 50, 67.5 kg ha−1, respectively) (F3), and the second combination consisting of cow manure (20 tons ha−1) + NPK (urea, SP-36, and KCl: 135, 100, 135 kg ha−1, respectively) (F4). The application of fertilizers stimulates plant development. LC-MS/MS analysis of the methanol extract of A. lavenia revealed the presence of the following compounds: 2 additional compounds, 7 terpenoids, 3 alkaloids, 3 phenolics, 2 fatty acids, 1 flavonoid, and 1 steroid. Combining F2, F3, and F4 makes it possible to produce plants with the highest leaf number, number of branches, and height. The combination of F4 generated the highest phenolic and flavonoid yields (409.88 μmol Gallic Acid Equivalent/plant) and 69.71 μmol Quercetin Equivalent/plant. These yields were not significantly different from those obtained when F2 and F3 were applied. Additionally, F4 produced the highest terpenoids and 11α-OH KA yields (61.48 mmol Nerol Equivalent/plant) and 29.81 mM 11α-OH KA/plant. The medical potential of A. lavenia can be enhanced by applying a mixture consisting of NPK (urea, SP-36, and KCl in a ratio of 135 kg ha−1, respectively) and cow manure (20 tons ha−1). [ABSTRACT FROM AUTHOR]

Adenostemma madurense is one of the Asteraceae with many medical properties but has not been widely cultivated. This study aims to determine the different fertilizer doses that can produce the best growth, phenolic, flavonoid, terpenoid, and the 11α-OH KA (a diterpenoid found in A. madurense productivity), resulting in the high antioxidant capacity of A. madurense. A one-factor randomized block design was employed in five fertilizer doses, control/without fertilizer, 100 % cow manure (20 tons/ha), 100 % NPK (in the form of urea, SP-36, and KCl:135, 100, 135 kg/ha, respectively), a combination of 50 % cow manure + 50 % NPK, and a combination of 100 % cow manure + 100 % NPK. Fertilizers increase plant growth. Applying the combination of 100 % cow manure + 100 % NPK was the best fertilizer composition, which produced the highest plant height, leaf, and branch number. This fertilizer combination produced total phenolic, flavonoid productivity of 739.50 μmol Gallic Acid Equivalent/plant, 97.37 μmol Quercetin Equivalent/plant, not significantly different from applying 100 % NPK and the combination of 50 % cow manure + 50 % NPK, and terpenoid productivity of 77.51 mmol Nerol Equivalent/plant. The 11α-OH KA productivity and antioxidant capacity of this fertilizer is 18.00 mM 11α-OH KA/plant and 601.76 μmol Ascorbic Acid Equivalent/g dry sample, not significantly different from applying 100 % NPK. Applying 100 % cow manure + 100 % NPK may enhance the medicinal plant A. madurense 's efficacy, especially for antioxidants. [ABSTRACT FROM AUTHOR]

Terpenoids are used in various industries, and Saccharomyces cerevisiae is a promising microorganism for terpenoid production. Introducing the mevalonate (MVA) pathway into the mitochondria of a strain with an augmented inherent cytosolic MVA pathway increased terpenoid production but also led to the accumulation of toxic pyrophosphate intermediates that negatively affected terpenoid production. We first engineered the inherent MVA pathway in the cytosol and then introduced the MVA pathway into the mitochondria using several promoter combinations, considering the toxicity of pyrophosphate intermediates. However, the highest titer, 183 mg/L, tends to be only 5% higher than that of the strain that only augmented the inherent MVA pathway (SYCM1; 174 mg/L). Next, we hypothesized that, in addition to the toxicity of pyrophosphate, other compounds in the MVA pathway could affect the squalene titer. Thus, we constructed a combinatorial strain library expressing MVA pathway enzymes in the mitochondria with various promoter combinations. The highest squalene titer (230 mg/L) was 32% higher than that of SYCM1. The promoter set revealed that mitigation of mono- and pyrophosphate compound accumulation was important for mitochondrial usage. This study demonstrated that a combinatorial strain library is useful for discovering the optimal gene expression balance in engineering yeast. [ABSTRACT FROM AUTHOR]

The investigation on the fruits of Pittosporum elevaticostatum Chang et Yan led to the isolation of two undescribed metabolites (1 – 2, named pitelevatin A and B) and twelve known ones (3 – 14), including one phthalide (1), four monoquiterpenoids (2 – 5), two sesquiterpenoids (6 – 7), two diterpenoids (8 – 9), and five phenolic analogues (10 – 14). The structures of 1 and 2 were elucidated based on spectroscopic methods, including high resolution electrospray ionization mass spectroscopy (HR-ESI-MS), one demension (1D) and 2D nuclear magnetic resonance (NMR), ultraviloet (UV), electronic circular dichroism (ECD) spectra and experimental and calculated specific optical rotation (SOR). Compounds 1 – 3 , 7 and 11 showed significant nitric oxide (NO) production inhibitory activity in lipopolysaccharide (LPS)-induced BV-2 microglial cells by inhibiting the expression of nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2), with IC 50 values ranging from 6.35 to 25.75 μ M. Western blot analysis confirmed the results above. [Display omitted] • First report of chemical constituents of P. elevaticostatum Chang et Yan. • Fourteen compounds, including two undescribed ones were isolated and identified from P. elevaticostatum fruits. • Pitelevatin A (1) showed NO production inhibition in BV-2 cells (IC 50 6.35 µM). Western blot analysis revealed the possible anti-inflammatory mechanism. [ABSTRACT FROM AUTHOR]

• In vitro regeneration on nodes of Aphanamixis polystachya tree showed breakage of recalcitrance. • Biomass content was higher on cytokinins 2-ip (N6-(2-Isopentyl) Adenine) supplemented Murashige and Skoog's medium. • HPTLC analysis of showed higher diversity of phytochemicals in the in vitro shoots without any supplementation of elicitors. • Comparison between the in vitro shoots and mature plants shown the presence of majority of phytochemicals in both groups. Aphanamixis polystachya is an evergreen tree belonging to the Meliaceae family used for centuries in traditional medicines. Various metabolites that were isolated from the barks showed high therapeutic value. Isolation of pharmaceutically active compounds imposes pressure on harvesting the plants from the wild, resulting in the endangerment of the tree. The development of an alternate method for the isolation of phytochemicals is the need of the hour. The current study evaluated the phytochemical screening of bioactive compounds from the tree parts and in vitro regenerated shoots of A. polystachya. Due to its recalcitrancy, tissue culture data remains inaccessible, and the present investigation was first attempt on developing a protocol for generating plantlets using in vitro culture. Murashige and Skoog's medium fortified with cytokinins like BAP (6-Benzylaminopurine), Kinetin, 2-ip (N6-(2-Isopentyl) Adenine), and TDZ (Thidiazuron) were used, and maximum biomass was produced from 3 mg/L of 2-ip. Meanwhile, HPTLC fingerprinting analysis on the tree parts (bark and leaves) and in vitro shoots showed similar diversity among metabolites. The secondary metabolites produced in the in vitro plants were the same with mature trees for standards like Rutin, Stigmasterol, β-Sitosterol, Piscidinol A, Bourjotinolone B, and Niloticin. [ABSTRACT FROM AUTHOR]

In this work, coacervation in primary amines solutions with hydrophobic natural deep eutectic solvents based on terpenoids and carboxylic acids was demonstrated for the first time. A liquid-phase microextraction approach was developed based on supramolecular solvent formation with primary amine acting as amphiphile and hydrophobic deep eutectic solvent making up mixed vesicles and serving as coacervation agent. Such supramolecular solvents could be used to separate wide range of substances from different aqueous media, such as food products, biological liquids and wastewaters. It is important that both hydrophobic and ionic interactions with supramolecular aggregates take place ensuring synergetic effect and better extraction ability, which is significant in separating relatively polar analytes. Different primary amines and deep eutectic solvents were investigated for liquid-phase microextraction of proof-of-concept amphoteric analyte (enrofloxacin, widely used veterinary fluoroquinolone antibiotic) and its determination by high-performance liquid chromatography with fluorescence detection using Shimadzu LC-20 Prominence chromatograph and RF-20A fluorescence detector. It was found that the supramolecular solvent based on 1-nonylamine, formed after addition of a deep eutectic solvent based on menthol and hexanoic acid (molar ratio of 1:1), provided maximum extraction recovery (85 %) and maximum enrichment factor (34). To characterize the extraction system, the composition of the phases was investigated, and cryo-transmission electron microscopy images were obtained. Vesicular aggregates were observed in the supramolecular solvent. The extraction mechanism was proposed in terms of formation of mixed aggregates to capture the analyte. Limit of detection was found to be 7 μg kg−1, while linear range of 20–250 μg kg−1 was established. Relative standard deviation values were lower than 7 %. Relative bias did not exceed 12 %. [Display omitted] • DESs based on terpenoids and fatty alcohols/fatty acids as coacervation agents. • Microvolume of coacervation agent was needed to induce phase separation. • Structure of primary amine-based SUPRAS was found to be vesicular. • Fast microextraction of enrofloxacin from milk after protein precipitation. [ABSTRACT FROM AUTHOR]

Plant-associated streptomycetes play important roles in plant growth and development. However, knowledge of volatile-mediated crosstalk between Streptomyces spp. and plants remains limited. In this study, we investigated the impact of volatiles from nine endophytic Streptomyces strains on the growth and development of plants. One versatile strain, Streptomyces setonii WY228, was found to significantly promote the growth of Arabidopsis thaliana and tomato seedlings, confer salt tolerance, and induce early flowering and increased fruit yield following volatile treatment. Analysis of plant growth-promoting traits revealed that S. setonii WY228 could produce indole-3-acetic acid, siderophores, ACC deaminase, fix nitrogen, and solubilize inorganic phosphate. These capabilities were further confirmed through genome sequencing and analysis. Volatilome analysis indicated that the volatile organic compounds emitted from ISP-2 medium predominantly comprised sesquiterpenes and 2-ethyl-5-methylpyrazine. Further investigations showed that 2-ethyl-5-methylpyrazine and sesquiterpenoid volatiles were the primary regulators promoting growth, as confirmed by experiments using the terpene synthesis inhibitor phosphomycin, pure compounds, and comparisons of volatile components. Transcriptome analysis, combined with mutant and inhibitor studies, demonstrated that WY228 volatiles promoted root growth by activating Arabidopsis auxin signaling and polar transport, and enhanced root hair development through ethylene signaling activation. Additionally, it was confirmed that volatiles can stimulate plant abscisic acid signaling and activate the MYB75 transcription factor, thereby promoting anthocyanin synthesis and enhancing plant salt stress tolerance. Our findings suggest that aerial signaling-mediated plant growth promotion and abiotic stress tolerance represent potentially overlooked mechanisms of Streptomyces -plant interactions. This study also provides an exciting strategy for the regulation of plant growth and the improvement of horticultural crop yields within sustainable agricultural practices. • VOCs from strain WY228 can significantly promote the growth of Arabidopsis and tomato seedlings. • WY228 could produce IAA, siderophores, ACC deaminase, fix nitrogen, and solubilize phosphate. • 2-Ethyl-5-methylpyrazine and sesquiterpenoid VOCs were the main growth-promoting regulators. • WY228 VOCs triggered Arabidopsis auxin and ethylene signaling to promote plant growth. • VOCs stimulated plant ABA signaling and anthocyanin synthesis to enhance plant salt tolerance. [ABSTRACT FROM AUTHOR]

The plant hormone, methyl jasmonate (MeJA), is an orthodox elicitor of secondary metabolites, including terpenoids. Lavandula angustifolia is an important aromatic plant generating, yet few studies have been performed to evaluate the function of MeJA on the biosynthesis of terpenoids in lavender. Five treatments (with concentrations of 0, 0.4, 4, 8, and 16 mM) were set, and the physiological indicators of each group were determined after 0, 6, 12, 24, 48, and 72 h. The results illustrate that (1) MeJA could affect the diurnal rhythm of the emission of volatiles and MeJA acted in a dose-dependent and time-dependent manner; (2) 8 mM MeJA treatment increased the total content of the volatiles, and the contents of monoterpenoids and sesquiterpenoids were up-regulated 0.46– and 0.74– fold than the control at 24 h and 12 h, respectively; (3) after MeJA treatment, all the genes expression analyzed changed to varying degrees, of which 3-carene synthase (La3CARS) gene changed most significantly (7.66– to 38.02– fold than the control); (4) MeJA application was associated with a rise in glandular trichome density. The positive effects of MeJA indicate that the exogenous application of MeJA could be a beneficial mean for studies on the biosynthesis of terpenoids in lavender. • The establishment of multiple control groups eliminated the influence of time differences. • MeJA changed the synthesis and release of VOCs and acted in a dose-dependent and time-dependent manner. • Volatile terpenoids had different sensitivities to MeJA. • All the gene expressions analyzed changed to varying degrees, of which 3-carene synthase gene changed most significantly. [ABSTRACT FROM AUTHOR]

• This review focuses on terpenoids extracted from essential oils. • Terpenoids have enantiomers with distinct physiological activities. • Predominant extraction methods are HD, SFME, HS-SPME and supercritical fluid. • 2D GC is found to have stronger chiral chromatography resolution ability. • Specific distribution and enantiomer excess results could be used as quality markers. Terpenoids possess significant physiological activities and are rich in essential oils. Some terpenoids have chiral centers and could form enantiomers with distinct physiological activities. Therefore, the extraction and separation of terpenoids enantiomers are very important and have attracted extensive attention in recent years. Meanwhile, the specific distribution and enantiomer excess results (the excess of one enantiomer over the other in a mixture of enantiomers) could be used as quality markers for illegitimate adulteration, origin identification, and exploring component variations and functional interrelations across different plant tissues. In this study, an overview of the progress in the extraction of terpenoids from essential oils and the separation of their enantiomers over the past two decades has been made. Extraction methods were retrieved by the resultant network visualization findings. The results showed that the predominant methods are hydrodistillation, solvent-free microwave extraction, headspace solid-phase microextraction and supercritical fluid extraction methods. GC–MS combined with chiral chromatography columns is commonly used for the separation of enantiomers, while 2D GC is found to have stronger resolution ability. Finally, some prospects for future research directions in the extraction and separation identification of essential oils are proposed. [ABSTRACT FROM AUTHOR]

Plant galls are an important chemical resource, and allow scientists to explore the active substances resulting from continuous interactions between plants and gall-inducing insects. In this study, the gall-inducing insect, Cryptosiphum atriplicivorum (Hemiptera: Aphididae), was identified for the first time from galls on Artemisia sieversiana and A. sylvatica. The chemical components of the galls were analyzed using hydro-distillation, and higher concentrations of essential oils (EOs) were found in galls on A. sylvatica than in those from A. sylvatica. GC-MS analysis revealed that the major chemical components in the EOs from A. sieversiana and A. sylvatica galls were monoterpenoids and sesquiterpenoids, including eucalyptol, (–)-borneol, (+)-camphor, β -caryophyllene, and (E)- β -farnesene. Concentrations of these chemicals were higher in the galls than in uninfected plants. Fumigant toxicity assays demonstrated that A. sylvatica and A. sieversiana gall EOs had strong insecticidal activity against C. chinensis , with LC 50 values of 7.65 ± 1.84 and 46.79 ± 5.21 μL/L, respectively. Moreover, the monoterpenoids eucalyptol, (–)-borneol, and (+)-camphor, which were prominent in the gall tissues, all exhibited significant fumigant activity against Callosobruchus chinensis (Coleoptera: Bruchidae), with LC 50 values of 20.96 ± 4.19 μL/L, 7.37 ± 0.60 μL/L, and 4.89 ± 1.52 μL/L, respectively. Interestingly, fumigation with these EOs at insecticidal concentrations did not affect soybean seed germination or seedling growth. These results illustrate that chemicals from the galls on A. sieversiana and A. sylvatica have the potential to be exploited as insecticides for overcoming storage pests. [Display omitted] • Aphid galls are quite abundant resources with defensive components. • Cryptosiphum atriplicivoru identified for the first time here as a gall-inducing insect from the Artemisia spp. • EOs extracted from these galls contain high concentrations of volatile terpenoids. • Gall EOs showed fumigant toxicity against the storage pest Callosobruchus chinensis. [ABSTRACT FROM AUTHOR]

• Volatile metabolome and transcriptome assays for single- and double-petal jasmines. • Sixteen volatiles were identified as their key odorants. • Identified genes on terpenoid and phenylpropane pathways that may shape the characteristic aroma of those two jasmines. • Four transcription factors may contribute to the regulation of aroma volatiles in those two jasmines. Jasminum sambac (L.) Aiton exists in single-petal (SP), double-petal (DP), and multi-petal (MP) phenotypes, which have a sweet floral scent and release aroma when the flowers open. A total of 103 volatiles were discovered from SP and DP jasmines. 16 volatiles were identified as their key odorants. Caryophyllene, geraniol, linalool, α -farnesene, β -ocimene, methyl anthranilate, methyl salicylate, benzeneacetaldehyde and hexanal may form the overall aroma of those two jasmines during flowering. High-resolution transcriptional profiles of those two jasmines at four flowering stages were generated from our recently reported chromosome-level genome assembly, from which we identified 35 differentially expressed genes (DEGs) involved in terpenoid metabolic pathways and 10 DEGs involved in the phenylpropane/benzene metabolic pathway, which may shape the characteristic aroma of those two jasmines at the molecular level. Through co-expression network analysis of key odorants, we found that bZIP8, bHLH6, MYB4 , and AP2/ERF3 may contribute to the regulation of aroma volatiles in those two jasmines. These results offer an important theoretical foundation for studying the regulation of aroma formation for SP and DP jasmines. [ABSTRACT FROM AUTHOR]

For the first time, terpene-functionalized pillar[5]arenes containing geranyl, perillyl or farnesyl fragments were synthesized. The obtained compounds did not have a pronounced cytotoxic effect on A549 cells in the studied concentration range (0.025–1 mg/mL). The ability of the obtained compounds to self-assemble in aqueous solutions was evaluated by DLS method. It was shown that the synthesized compounds are formed monodisperse nanosized aggregates with a diameter of 87–180 nm (PDI 0.18–0.33). The morphology of the formed aggregates was studied by transmission electron microscopy. The incorporation of the obtained amphiphilic macrocycles into the lipid bilayer of model lipid biomembranes was definitely confirmed by turbidimetry. Synthesized pillar [5]arenes form a complex with the aza dye methyl orange in a 1:2 ratio (logK 11 = 2.12, logK 12 = 8.63) This complex retains stability both in neutral (pH 7.4) and in an acidic environment (pH 2.7). [Display omitted] [ABSTRACT FROM AUTHOR]

Aster tataricus L.f. is highly valued for its rich reserves of bioactive compounds. Our research focused on the identification of previously unreported compounds found within the ethanol extract of A. tataricus. Through meticulous spectroscopic analyses and computational methods like NMR calculations and ECD, we successfully elucidated the structures of five novel compounds termed tatarisides A-E (1–5), alongside two known compounds (6, 7). The anti-inflammatory assays conducted yielded noteworthy results, particularly in relation to compounds 1 and 5. These compounds exhibited significant potential in inhibiting the release of NO in LPS-induced RAW 264.7 cells, as evidenced by their respective IC 50 values of 17.81 ± 1.25 μM and 13.32 ± 0.84 μM. The discovery of these new compounds adds to the existing knowledge of A. tataricus 's chemical composition and potential applications. [Display omitted] [ABSTRACT FROM AUTHOR]

Satureja hortensis L. (SH) is a medicinal and aromatic herb utilized markedly in the food, pharmaceutical, and cosmetic industries because of its specific secondary metabolites (SMs), especially monoterpenoids. However, the impact of elicitors on the expression of monoterpene synthase genes in SH remains unexplored. Therefore, the supreme objective of this research was to elucidate the phyto-biochemical and targeted genes expression responses of SH to the exogenous application of methyl jasmonate (MeJA). Accordingly, having chosen four concentrations of MeJA, they sprayed at the five-leaf stage for two weeks, and then leaves were harvested at two exposure times of 24 and 48 hrs for further analysis, using spectrophotometric, real time-quantitative polymerase chain reaction (RT-qPCR), and gas chromatography−mass spectrometric (GC–MS) methods. The results highlight that not only were the highest contents of phenolic, flavonoids, peroxidase, superoxide dismutase, proline, and malondialdehyde in the elicited SHs but also the highest expression of β-farnesene synthase (BFS) and 1-deoxy-D-xylulose 5-phosphate reductase (DXR) genes together with the highest amount of carvacrol were up-regulated in them compared to their respective control. In conclusion, these findings demonstrate the great industrial potential of MeJA in improving the production of phytochemicals in medicinal plants, particularly in SH. [ABSTRACT FROM AUTHOR]

• Three new terpenoids (2 – 4) were obtained from Trichoderma asperellum A-YMD-9-2. • Isolate 2 may be an intermediate in the biosynthesis of harziandione from harzianone. • Isolates 3 and 4 represent the second occurrence of cadinanes in Trichoderma. In addition to the known harziandione (1), one new diterpenoid, 3 S -hydroxyharzianone (2), and two new sesquiterpenoids, 4-cadinen-11,12-diol (3) and 4-cadinen-11,13-diol (4), were isolated from the culture of Trichoderma asperellum A-YMD-9-2, an endophytic fungal strain from the marine red alga Gracilaria verrucosa. The structures and relative configurations of new isolates were established by analysis of spectroscopic techniques, including 1D/2D NMR, IR, and MS, and their absolute configurations, except for those at C-11 of 3 and 4 , were assigned by comparison of the ECD curve or specific optical rotation data with those of analogues. Compound 2 may be an intermediate in the biosynthesis of harziandione from harzianone, while 3 and 4 represent the second occurrence of cadinane sesquiterpenoids in Trichoderma. Compounds 2 − 4 exhibited potent inhibition of several marine phytoplankton species. [ABSTRACT FROM AUTHOR]

Terpenoids represent 60% of known natural products, including many drugs and drug candidates, and their biosynthesis is attracting great interest. However, the unknown cytochrome P450s (CYPs) in terpenoid biosynthetic pathways make the heterologous production of related terpenoids impossible, while the slow kinetics of some known CYPs greatly limit the efficiency of terpenoid biosynthesis. Thus, there is a compelling need to discover and engineer CYPs for terpenoid biosynthesis to fully realize their great potential for industrial application. This review article summarizes the current state of CYP discovery and engineering in terpenoid biosynthesis, focusing on recent synthetic biology approaches toward prototyping CYPs in heterologous hosts. We also propose several strategies for further accelerating CYP discovery and engineering. CYP discovery and engineering are crucial for terpenoid biosynthesis, which has recently attracted great academic and industrial interest. Major obstacles to traditional CYP discovery methods are the inaccessibility of genetic tools in native hosts and the low activity of CYPs. Synthetic biology approaches based on multi-omics studies, heterologous CYP expression, and metabolic engineering of chassis cells have revolutionized CYP discovery platforms and significantly accelerated their discovery rate. Harnessing the great potential of genome engineering and robotic automation will further increase the likelihood of discovering or engineering CYP with desired activity as well as enhance the production of terpenoids with commercial value. [ABSTRACT FROM AUTHOR]

S -(+)-linalool is a phytochemical with proven sedative and anesthetic effects in silver catfish (Rhamdia quelen); however, the pharmacokinetic profile of this compound in fish remains unknown. Therefore, this study describes the pharmacokinetics of S -(+)-linalool in silver catfish anesthetized by immersion bath. Fish were exposed to 153 mg/L S -(+)-linalool for a maximum of 30 min. Blood and brain samples were collected at several time-points up to 4.0 h (0.5 h of anesthesia and 3.5 h of recovery) after the onset of exposure. Before each tissue/blood sampling, the anesthesia stage of each animal was recorded. Following S -(+)-linalool quantification in plasma and brain tissue by gas chromatography with flame ionization, concentration curves were constructed for determination of the pharmacokinetic parameters. S -(+)-linalool in the plasma and brain was detected within the first 2 min (0.03 h) of exposure, with maximum times (T max) of 0.50 and 0.33 h and maximum concentrations (C max) of 129.33 μg/mL and 113.92 μg/g, respectively. Other parameters estimated for the plasma and brain were terminal half-lives (T 1/2β) of 1.36 and 57.27 h, elimination constants (K el) of 0.50 and 0.01/h, areas under the curve from zero to 4.0 h (AUC 0–t) of 120.98 μg/mL/h and 250.57 μg/g/h, and AUCs from zero to infinity (ASC 0–∞) of 132.15 μg/mL/h and 4946.13 μg/g/h, respectively. After 10 min (equivalent to a collection time of 0.66 h) in a drug-free bath, all animals recovered from anesthesia. These results suggest that S -(+)-linalool is promptly absorbed into the bloodstream and widely distributed to the brain. Elimination is efficient in plasma but slower in the brain, yet this factor does not impair the recovery of animals, which occurs quickly. Therefore, S -(+)-linalool holds a pharmacokinetic profile suitable for its application as an anesthetic in aquaculture. • This study describes for the first time the pharmacokinetics of S -(+)-linalool in a fish species. • S -(+)-linalool is rapidly absorbed, distributed to the brain and eliminated in silver catfish. • The elimination kinetics of S -(+)-linalool in the brain is slower than in the plasma. [ABSTRACT FROM AUTHOR]

Highlights • Analyzed diterpenoids in 43 conifer species and Gingko biloba from California. • Phylogenetic signal present in the proportion of abietanes and tetracyclics. • Closely related species do not always have similar diterpenoid compositions. • Phylogenetic signal present in terpenoid carbon isotope fractionation. • Chemotaxonomic assignment might be possible for some families in past. Abstract Plant-derived diterpenoids are commonly used as conifer-specific biomarkers and for chemotaxonomic assignment or confirmation. Numerous studies have reported on the utility of diterpenoids as chemotaxonomic indicators, but few have quantitatively analyzed diterpenoid concentrations, especially with respect to conifer phylogeny. In addition, the carbon isotope values (δ13C) of diterpenoids provide a means to track conifer-specific δ13C values, which is useful for tracking water availability and the carbon cycle. To expand on previous work, we measured diterpenoid concentrations and carbon isotopes of 43 conifer species, and Ginkgo biloba , collected at the University of California Botanical Garden at Berkeley. In this collection, all extant conifer families and almost two-thirds of extant genera are present, including many subtropical and Southern Hemisphere groups that were once common and widespread components of fossil assemblages. Overall, we found diterpenoid concentrations were highly variable among species and families. Despite this variability, there is coarse family-level phylogenetic structuring with the lowest concentrations in Pinaceae. When diterpenoid concentrations are fitted to a model of trait evolution (Brownian motion), we however find that there is no phylogenetic signal. In contrast, when terpenoids are analyzed by the proportion of diterpenoid compound structure classes (abietanes, labdanes, pimaranes, tetracyclics, and totarols/sempervirol), there was significant phylogenic signal for the abietane and tetracyclic structures. Diterpenoid biosynthetic carbon isotope fractionation, as expressed between diterpenoids and leaf tissue (ε diterpenoid), also contained a phylogenetic signal, as well as the broad phylogenetic structuring observed in total diterpenoid concentrations. Overall, these results indicate that the Pinaceae is unique among conifer clades with respect to terpenoid structure classes, concentrations and ε diterpenoid. When diterpenoids are applied to taxonomic assignment of fossils, it would be useful to combine several traits (concentration, proportion, and ε diterpenoid). In this context, it should be possible to broadly distinguish three major conifer groups: Cupressaceae, Podocarpaceae and Pinaceae. However, based on these results, we recommend against assuming that closely related species have similar diterpenoid compositions. [ABSTRACT FROM AUTHOR]

Abstract This study demonstrated the selective production of a single acyclic monoterpene, β-myrcene, by photosynthetic, clonal microplantlet suspension cultures of the macrophytic red alga Ochtodes secundiramea (Cryptonemiales, Rhizophyllidaceae). Microplantlets were cultivated within an airlift photobioreactor under continuous medium perfusion with enhanced nutrients (nitrate, phosphate) and 3500 ppm CO 2 in the aeration gas to provide nutrient-replete conditions. The removal of bromide (Br-) and vanadate (VO 4 3−) from the medium shut down bromoperoxidase-catalyzed halogenation, so that only the common precursor to halogenated monoterpenes, β-myrcene, accumulated within the biomass. Nutrient-replete cultivation enabled near-exponential biomass production to density of 6 g DW/L, with specific growth rate of 4.4 ± 0.1% per day over the 36 day cultivation period at near-saturation light intensity. Myrcene was produced during biomass production, and the specific rate of β-myrcene production within the biomass exceeded the specific rate of biomass production, so that β-myrcene accumulated within the biomass. Increasing the mean light intensity from approximately 60 to 95% of light saturation linearly increased the growth rate, but did not increase the specific rate of β-myrcene production. At near saturation light intensity, the specific rate of β-myrcene production was 6.8 ± 0.7% per day (1.0 S.E.) with yield of 40 μmol/g DW after 36 days. Although the yields of β-myrcene were low (0.6 wt% in biomass), the potential for high biomass density, ease of microplantlet separation, and high selectivity of hydrocarbon biosynthesis suggest that microplantlets of terpenoid-producing red macroalgae have promise as a new platform for advanced hydrocarbon biofuel production from CO 2 , provided new strategies can be developed to enhance monoterpene yield. Highlights • Clonal microplantlets of the red macroalga Ochtodes secundiramea selectively produced the monoterpene β-myrcene. • Perfusion cultivation in bromide-free medium shut down bio-halogenation processes. • Myrcene production rate exceeded growth rate and accumulated within biomass. • Growth rate was dependent on light intensity but myrcene production was not. • Yield of myrcene, a C 10 hydrocarbon biofuel precursor, was 40 μmol/g DW. [ABSTRACT FROM AUTHOR]

The objective of this study is to find out the role of terpenoid compounds as potential inhibitors against certain protein targets of dengue virus. The 2-dimensional structures of terpenoid compounds were retrieved from the PubChem database. They were analysed for their interactions with target proteins of dengue virus such as envelope (1OKE), NS5 (1R6A-RPV & SHA) and NS2B/NS3 (4M9K) by docking studies followed by molecular dynamics (MD) simulations using Schrödinger software, version 10.7. Out of 513 terpenoid compounds studied, malacitanolide showed the highest interaction energy values of −7.072 kcal/mol (hydrogen bond (HB) interactions with Thr280, Gln200, Gln271, Gln49 and Ala50), −5.295 kcal/mol (HB interactions with Ser150, Lys29, Ser214) and −4.030 kcal/mol (HB interactions with Glu1169 and Asn1119) against 1OKE, 1R6A-RPV and 4M9K targets, respectively. Paclitaxel had shown the interaction energy value of −9.334 kcal/mol (HB with Lys61, Asp146, Trp87, Gly148, and Arg84) with 1R6A-SAH. MD simulation studies revealed that the best interacting compound malacitanolide maintained a stable complex with 1OKE of dengue virus. Malacitanolide, reissantin E, and paclitaxel exhibited very good interactions with all three-protein targets of dengue virus and had also shown significant stability. In the present study, it is concluded that the terpenoid compounds malacitanolide, reissantin E, and paclitaxel could act as potential inhibitors against all three target proteins of dengue virus. [ABSTRACT FROM AUTHOR]

[Display omitted] • New terpenoid-based HDES were developed and characterised. • Physiochemical properties of density and polarity were investigated. • Extraction of carnosic acid and carnosol from rosemary. • Geraniol-Dodecanol based DES had the highest yields. • Developed DES had higher extraction yields than organic solvents. With the increasing demand for sustainability and green practices in industrial operations, deep eutectic solvents (DES) emerge as promising alternatives to organic solvents for the extraction of bioactive compounds. However, the inclusion of DES in industrial processes is severely limited by their hig density and viscosity as it hinders mass transfer. Additionally, low selectivity towards medium and amphiphilic bioactive compounds leads to unfavourable efficiency. This study aimed to develop, characterise, and evaluate low-density novel terpenoid-based DESs, containing fatty acid and alcohol, as effective hydrophobic extractants. The formation and stability of the newly developed DES were confirmed by validating the hydrogen bonds. The density as a function of temperature was investigated, revealing that all the developed hydrophobic DES had densities lower than water. The polarity of the solvents was assessed as it plays a vital role in the "solvation" of the bioactive compounds through Nile red assay. Although the hydrophobic DES had lower polarity than organic solvents, the screened DES showed a higher extraction yield of amphiphilic compounds of carnosic acid and carnosol, demonstrating their effectiveness. This is due to the high van der Waals interactions between the amphiphilic compounds and the alkyl chain of fatty acids and alcohols in the DES. Overall, the low density and high selectivity of the new hydrophobic DES developed in this study were found to be viable extractants for the sustainable extraction of bioactive compounds, particularly amphiphilic compounds. [ABSTRACT FROM AUTHOR]

Black rice is famed because of its high antioxidants content. The cooperation and contribution of endophytes towards growth and antioxidant properties of black rice has been experimented. The efficient endophytes were isolated from black rice, and Enterobacter sp. , Kluyvera sp. and Bacillus subtilis were selected. The whole genome of these endophytes contained genes required for IAA production (trpAB.Z), phosphate solubilization (pqqAB), siderophore production (entABCD), colonization (fliAB.Z ; cheAB.Z) and antioxidant activity (bglAB), which were further validated through biochemical and physiological analysis. The inoculation of these three effective endophytes resulted in enhancement of growth by 33.33%, 30.23% and 33.33% and antioxidant properties by 31.57%, 35.33% and 27.87% in Enterobacter , Kluyvera and B. subtilis treated plants respectively. The transcriptome of black rice plant, when colonized by these endophytes, resulted in 506 up-regulated and 332 down-regulated genes. Transcripts upregulated in response to endophytic colonization were mainly involved in plant growth, antioxidant properties, interactions, and synthesis of aroma compounds (terpenoid synthase). The overall patterns of functions encoded on the genome of endophytes and expressed in black rice plants were highly correlated. The strain specific augmentation through endophytism was used to achieve the desired properties in black rice. [Display omitted] Effective endophytic isolates were enriched with plant supportive genes in their genomes. Colonization of effective endophytes was checked by confocal microscopy of the GFP tagged variants. The inoculation of effective endophytes resulted in improved plant growth and antioxidant activity. Transcriptome study suggested upregulation of genes for plant growth, antioxidant, and aroma, in response to endophyte. [ABSTRACT FROM AUTHOR]

Highlights • The methylated naphthalene compositions are controlled by source and clay mineral. • 1,5-, 1,6-DMNs and 1,2,5-TMN can be useful indicators of terrestrial oils. • 1,3- and 1,7-DMNs were dominant methylated naphthalenes in marine oils. • The ratio of TMNs to MNs in oils may be an indicator of source rock lithology. • Naphthalene indices are proposed to evaluate the source rock type of degraded oils. Abstract Methylated naphthalenes in oils/condensates are relatively resistant to bio- and thermal degradation and can be useful compounds for evaluating the source organic matter and source rock lithology. Assuming that cadinene, abietic acid, and cholesterol are major precursors of methylated naphthalenes in oils and condensates, laboratory hydrous pyrolysis experiments for these possible precursors were performed to understand the precursor/products relationship. The major dimethylnaphthalenes (DMNs) and trimethylnaphthalenes (TMNs) in pyrolyzates of cadinene and abietic acid were 1,2,5-TMN and 1,6- and 1,5-DMNs, whereas those in pyrolyzates of cholesterol were 2,3,6-TMN and 1,3- and 1,7-DMNs. The experimental results suggested that the dimethylnaphthalene ratio (DMR) of [1,5- + 1,6-DMNs]/[1,3- + 1,7-DMNs], and the trimethylnaphthalene ratio (TMR) of 1,2,5-TMN/2,3,6-TMN, can be potential indicators of source organic matter. The relative abundance of TMNs in the pyrolyzates was controlled largely by the maturity level and presence or absence of montmorillonite catalyst. The relative abundance of total TMNs to total MNs (ΣTMNs/ΣMNs ratio) can be a novel indicator for evaluating the clay-catalytic effect in source rocks. A lower ΣTMNs/ΣMNs ratio is related to clay-poor source rocks, such as coal, carbonates, and siliceous rocks, whereas a higher ΣTMNs/ΣMNs ratio suggests shaly (clay-rich) source rocks. The DMR, TMR, and ΣTMNs/ΣMNs ratios of various oils and condensates are very consistent with their source organic matter and source rock lithology, indicating that these indicators are practically useful. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Three new 7-oxoabietane-type diterpenoids were isolated from the bark of Cryptomeria japonica. • Structures of these isolates were elucidated by spectroscopic methods. • Two 7-oxoabietane-type diterpenoids exhibited xanthine oxidase inhibitory activity. Abstract Three new 7-oxoabietane-type diterpenoids, 3-oxosugiol methyl ether (1), 18-hydroxysugiol (2), and 1β-hydroxysugiol (3), as well as two known 7-oxoabietane-type diterpenoids, 6α-hydroxysugiol (4) and 6α-acetoxysugiol (5), were isolated from the bark of Cryptomeria japonica D. Don. Their structures were elucidated mainly by NMR and HREIMS, as well as on comparison with the data of known analogues. At the concentration of 75 μM, compounds 2 and 5 exhibited 11.9 and 21.7% xanthine oxidase inhibitory activity, respectively. [ABSTRACT FROM AUTHOR]

Highlights • β-Eudesmol decreases efferent adrenal sympathetic nerve activity (ASNA). • Stomach may be critical organ for the β-eudesmol effect on ASNA. • TRPA1 channel is involved in β-eudesmol effect on ASNA. Abstract The autonomic nervous system innervates various peripheral tissue functions. Various external stimuli affect autonomic nerve activity, however, there is little information about the involvement of sensory receptors in the responses. The TRPA1 is a calcium-permeable non-selective cation channel which plays a crucial role in the susceptibility to various stimuli. β-Eudesmol, an oxygenated sesquiterpene found in hop essential oil and beer, activates the TRPA1. Intragastric administration of β-eudesmol decreased efferent adrenal sympathetic nerve activity (ASNA) in rats, whereas subcutaneous administration did not. ASNA suppression by β-eudesmol was not observed in TRPA1 knockout rats. The β-eudesmol derived ASNA suppression was partially, but significantly, eliminated by subdiaphragmatic vagotomy in rats, suggesting the afferent vagal nerve from the gastrointestinal tract to the brain is involved in the effect of β-eudesmol on ASNA. Our results indicate that β-eudesmol suppresses ASNA, partly through TRPA1 and the afferent vagus nerve. These findings introduce the physiological significance of the TRPA1 in the control of ASNA. [ABSTRACT FROM AUTHOR]

As a bioactive triterpenoid, squalene is widely used in the food industry, cosmetics, and pharmacology. Squalene’s major commercial sources are the liver oil of deep-sea sharks and plant oils. In this study, we focused on the enhancement of squalene biosynthesis in Yarrowia lipolytica , with particular attention to the engineering of acetyl-CoA metabolism based on genome-scale metabolic reaction network analysis. Although the overexpression of the rate-limiting endogenous ylHMG1 (3-hydroxy-3-methylglutaryl-CoA reductase gene) could improve squalene synthesis by 3.2-fold over that by the control strain, the availability of the key intracellular precursor, acetyl-CoA, was found to play a more significant role in elevating squalene production. Analysis of metabolic networks with the newly constructed genome-scale metabolic model of Y. lipolytica iYL_2.0 showed that the acetyl-CoA pool size could be increased by redirecting carbon flux of pyruvate dehydrogenation towards the ligation of acetate and CoA or the cleavage of citrate to form oxaloacetate and acetyl-CoA. The overexpression of either acetyl-CoA synthetase gene from Salmonella enterica ( acs* ) or the endogenous ATP citrate lyase gene ( ylACL1 ) resulted in a more than 50% increase in the cytosolic acetyl-CoA level. Moreover, iterative chromosomal integration of the ylHMG1 , asc* , and ylACL1 genes resulted in a significant improvement in squalene production (16.4-fold increase in squalene content over that in the control strain). We also found that supplementation with 10 mM citrate in a flask culture further enhanced squalene production to 10 mg/g DCW. The information obtained in this study demonstrates that rationally engineering acetyl-CoA metabolism to ensure the supply of this key metabolic precursor is an efficient strategy for the enhancement of squalene biosynthesis. [ABSTRACT FROM AUTHOR]

Highlights • Several alternatives to chemically synthesised food preservatives are reviewed. • Terpenoids from plant essential oils have interesting antibacterial properties. • Flavonoids can act as strong antimicrobials at micromolar concentrations. ABSTRACT Synthetic food additives generate a negative perception in consumers. Therefore, food manufacturers search for safer natural alternatives such as those involving phytochemicals and plant essential oils. These bioactive compounds have antimicrobial activities widely proven in in vitro tests. Foodborne diseases cause thousands of deaths and millions of infections every year, mainly due to pathogenic bacteria such as Salmonella spp., Campylobacter spp., Escherichia coli, Bacillus cereus, Listeria monocytogenes and Staphylococcus aureus. This review summarises industrially interesting antimicrobial bioactivities as well as their mechanisms of action for three main types of plant nutraceuticals, namely terpenoids (e.g. carnosic acid), polyphenols (e.g. quercetin) and thiols (e.g. allicin), which are important constituents of plant essential oils with a broad range of antimicrobial effects. These phytochemicals are widely distributed in fruits and vegetables and are especially useful in food preservation as microbial growth inhibitors. [ABSTRACT FROM AUTHOR]

Helminthosporol, a natural growth regulator isolated from a fungus, stimulates hypocotyl growth and seed germination, similar to gibberellin (GA). We recently reported that helminthosporic acid (H-acid), a synthetic analog of helminthosporol, acts as an agonist of GA receptor. In this study, we showed that a H-acid analog, in which the hydroxymethyl group at the C-8 position of H-acid was converted to a keto group, acts as a selective GA receptor agonist. 1) This analog shows higher hypocotyl elongation activity in Arabidopsis than H-acid does, and induces the degradation of DELLA protein and 2) leads to the formation of the GID1-DELLA complex and 3) regulates the expression of GA-related genes. In addition, 4) its hypocotyl elongation activity was not observed in a atgid1a single mutant, and 5) this analog could promote only the interaction between specific GA receptors and DELLA proteins in vitro . Taken together, our results strongly suggest that the selectivity of the reported H-acid analog depends on the specificity of its GA receptor binding activity. [ABSTRACT FROM AUTHOR]

Acid-catalyzed conversion of caryolan-1-ol to isoclovene involves a multi-step carbocation rearrangement. Electronic structure calculations show that the pathway proceeds through an initial 3° carbocation, as well as a series of three other 3° carbocations. The key stage in which the ring structure is rearranged occurs not as might initially be imagined, in two separate steps with the intermediacy of a 2° carbocation, but rather in a single, concerted but highly asynchronous dyotropic rearrangement. The transition structure for this dyotropic rearrangement strongly resembles the 2° carbocation that would be involved in a stepwise mechanism. However, the dyotropic rearrangement is stereochemically unusual. While one of the bond migrations is suprafacial, as expected, the other is effectively antarafacial. This unusual stereochemical outcome is enforced by the geometric constraints of the polycyclic structure. [ABSTRACT FROM AUTHOR]

The plant metabolite salvinorin A potently and selectively agonizes the human kappa -opioid receptor, an emerging target for next-generation analgesics. Here we review analogs of the salvinorin chemotype and their effects on selectivity, affinity and potency. Extensive peripheral modifications using isolated salvinorin A have delivered a trove of SAR information. More deep-seated changes are now possible by advances in chemical synthesis. [ABSTRACT FROM AUTHOR]

Oleocellosis is a serious physiological disorder in citrus fruit that mainly results in appearance and quality deterioration. It has been well established that the occurrence of oleocellosis is highly correlated with the release of peel oil from citrus fruit, while there is little information on the dynamic changes in the content of the volatile constituents and the expression of genes involved in terpenoid metabolism during oleocellosis development. In the present research, large changes in the volatile profiles and gene expression in terpenoid metabolism were observed in oleocellosis peels compared to healthy ones. Among volatiles, the decreased contents of α-pinene, d -limonene, β-myrcene, linalool, β-caryophyllene, α-terpineol, nonanal, neryl acetate and (−)-carvone played a major role in these changes. For gene expressions in terpenoid metabolism, the up-regulated genes aldehyde dehydrogenase (NAD+) ( ALDH ) and the down-regulated genes β-caryophyllene synthase 1 ( BCS1 ), α-terpineol synthase 2 ( TES2 ) and myrcene synthase ( MS ) were the main differences in oleocellosis peels. [ABSTRACT FROM AUTHOR]

Fungi are known to produce hundreds of different polyketide, terpene, and terpenoid compounds and based on their chemical structures, 33 of these were selected for further assessment to identify compounds with potential for liquid transportation fuels. Eight of the 33 compounds were identified as having potential as gasoline blend components. Based on predicted boiling points and octane numbers, 2-ethyl-5,5-dimethyl-1,3-cyclopentadiene, sabinene, isobutyric acid,1,8-cineole and linalool met the boiling point and octane number requirements used for the assessment, while 2-ethyl-5,5-dimethyl-1,3-cyclopentadiene and isobutyric acid would require some upgrading. Limonene, isoamyl acetate, and 2,2,5,5-tetramethyl-3-hexanone also have gasoline blend potential without upgrading. For diesel fuel, only 3,3,5-trimethyldecane met the boiling point, cetane number, and flashpoint requirements used for the assessment; however, with upgrading, 18 of the 33 compounds evaluated could potentially serve as blend components of diesel fuel. None of the 33 compounds without upgrading met the four ASTM D1655 specifications for Jet A and Jet A-1 fuel, but 3,3,5-trimethyldecane and limonene were very close. With chemical upgrading, 22 of the 33 compounds could have potential as jet fuel blend components. The monoterpene limonene and six sesquiterpenes were identified as fungal-derived compounds that with upgrading potentially could serve as components of high-energy jet, missile, or diesel fuels. The increasing availability of fungal genomes and transcriptomes enables the identification of important metabolic pathways for hydrocarbon production. The number of fungal-based compounds having potential for use in hydrocarbon fuels and products is increasing as new compound and pathway discoveries are made and advances in metabolic engineering and synthetic biology enable the production of these compounds. Several challenges remain including increasing carbon flux toward hydrocarbon fuel precursors in primary metabolism, increasing the low titers of hydrocarbons produced, and establishing robust host strains. Also, more fuel property testing of fungal-derived compounds individually or in fuel blendstocks is needed to determine the true potential of these compounds in liquid transportation fuels. [ABSTRACT FROM AUTHOR]

Nepetalactones are iridoid monoterpenes with a broad range of biological activities produced by plants in the Nepeta genus. However, none of the genes for nepetalactone biosynthesis have been discovered. Here we report the transcriptomes of two Nepeta species, each with distinctive profiles of nepetalactone stereoisomers. As a starting point for investigation of nepetalactone biosynthesis in Nepeta , these transcriptomes were used to identify candidate genes for iridoid synthase homologs, an enzyme that has been shown to form the core iridoid skeleton in several iridoid producing plant species. Iridoid synthase homologs identified from the transcriptomes were cloned, heterologously expressed, and then assayed with the 8-oxogeranial substrate. These experiments revealed that catalytically active iridoid synthase enzymes are present in Nepeta, though there are unusual mutations in key active site residues. Nevertheless, these enzymes exhibit similar catalytic activity and product profile compared to previously reported iridoid synthases from other plants. Notably, four nepetalactone stereoisomers with differing stereochemistry at the 4α and 7α positions – which are generated during the iridoid synthase reaction – are observed at different ratios in various Nepeta species. This work strongly suggests that the variable stereochemistry at these 4α and 7α positions of nepetalactone diastereomers is established further downstream in the iridoid pathway in Nepeta . Overall, this work provides a gateway into the biosynthesis of nepetalactones in Nepeta . [ABSTRACT FROM AUTHOR]

CYP106A2 from Bacillus megaterium ATCC13368, was identified in the 1970s as one of the first bacterial steroid hydroxylases responsible for the conversion of progesterone to 15β-hydroxyprogesterone. Later on it has been proven to be a potent hydroxylase of numerous 3-oxo-Δ 4 as well as 3-hydroxy-Δ 5 -steroids and has recently also been characterized as a regioselective allylic bacterial diterpene hydroxylase. The main hydroxylation position of CYP106A2 is thought to be influenced by the functional groups at C3 position in the steroid core leading to a favored 15β-hydroxylation of 3-oxo-Δ 4 -steroids and 7β-hydroxylation of 3-hydroxy-Δ 5 -steroids. However, in some cases the hydroxylation is not strictly selective, resulting in the formation of undesired side-products. To overcome the unspecific hydroxylations or, on the contrary, to gain more of these products in case they are of industrial interest, rational protein design and directed evolution have been successfully performed to shift the stereoselectivity of hydroxylation by CYP106A2. The subsequently obtained hydroxylated steroid and terpene derivatives are especially useful as drug metabolites and drug precursors for the pharmaceutical industry, due to their diverse biological properties and hardship of their chemical synthesis. As a soluble prokaryotic P450 with broad substrate spectrum and hydroxylating capacity, CYP106A2 is an outstanding candidate to establish bioconversion processes. It has been expressed with respectable yields in Escherichia coli and Bacillus megaterium and was applied for the preparative hydroxylation of several steroids and terpenes. Recently, the application of the enzyme was assessed under process conditions as well, depicting a successfully optimized process development and getting us closer to industrial scale process requirements and a future large scale application. This article is part of a Special Issue entitled: Cytochrome P450 biodiversity and biotechnology, edited by Erika Plettner, Gianfranco Gilardi, Luet Wong, Vlada Urlacher, Jared Goldstone. [ABSTRACT FROM AUTHOR]

Two new sesquarterpenoids, i.e. ferrugicadinol A ( 1 ) and ferrugicryptomeridiol ( 3 ), and one known sesquarterpenoid, ferrugicadinol ( 2 ) were isolated from the bark of Cryptomeria japonica D. Don. Their structures were identified by extensive spectral analysis and comparison with the data of known analogues. [ABSTRACT FROM AUTHOR]

A phytochemical investigation from methanol extract of Achillea millefolium , (Asteraceae) resulted in the isolation of one new lignan, (+)-lyoniresinol 4- O -α- l −arabinofuranoside ( 1 ) and one new terpenoid, achiterpenoside A ( 2 ), together with four other known compounds, named as Achillinin A ( 3 ), (+)-lyoniresinol ( 4 ), luteolin ( 5 ), camazulene ( 6 ). The structures of 1 and 2 were elucidated based on various spectroscopic data, including IR, HR-EI-MS, 1 H NMR, 13 C NMR, DEPT, COSY, HMBC and HSQC, and compared with previous literature. [ABSTRACT FROM AUTHOR]

Terpenoids are a large class of plant-derived compounds, that constitute the main components of essential oils and are widely used as natural flavors and fragrances. The biosynthesis approach presents a promising alternative route in terpenoid production compared to plant extraction or chemical synthesis. In the past decade, the production of terpenoids using biotechnology has attracted broad attention from both academia and the industry. With the growing market of flavor and fragrance, the production of terpenoids directed by synthetic biology shows great potential in promoting future market prospects. Here, we reviewed the latest advances in terpenoid biosynthesis. The engineering strategies for biosynthetic terpenoids were systematically summarized from the enzyme, metabolic, and cellular dimensions. Additionally, we analyzed the key challenges from laboratory production to scalable production, such as key enzyme improvement, terpenoid toxicity, and volatility loss. To provide comprehensive technical guidance, we collected milestone examples of biosynthetic mono- and sesquiterpenoids, compared the current application status of chemical synthesis and biosynthesis in terpenoid production, and discussed the cost drivers based on the data of techno-economic assessment. It is expected to provide critical insights into developing translational research of terpenoid biomanufacturing. • Reviewed existing strategies in the engineering of terpenoid biosynthesis. • Summarized milestone examples of biosynthetic mono- and sesquiterpenoids. • Analyzed the key challenges from laboratory production to scalable production. • Compared the current status of chemical synthesis and biosynthesis routes. • Listed terpenoid scents for intuitive comprehension of flavors and fragrances. [ABSTRACT FROM AUTHOR]

Five undescribed terpenoids including a polyketide-terpenoid hybrid paraphaone, and four eremophilane sesquiterpenoids, paraphaterpenes A-D, as well as two known compounds were isolated from the endophytic fungus Paraphaeosphaeria sp. cultured by extract of host Ginkgo biloba L. The structures were established by spectroscopic analyses, and the single-crystal X-ray diffraction. The antifungal activity of Paraphaeosphaeria sp. cultured by extract of G. biloba against the plant pathogen Alternaria alternata was significant and higher than that of PDB medium. Tested compounds indicated antifeedant activities against silkworms with feeding deterrence index at 10–70%. Paraphaone, paraphaterpenes A, C, D and alternariol methyl ether showed significant antifungal activities against the phytopathogens A. alternata , Aspergillus fumigatus , and entomopathogen Beauveria bassiana with MICs ≤4 μg/mL. And the preliminary structure-activity relationship of eremophilane sesquiterpenoids was exhibited. The culture of Paraphaeosphaeria sp. by host G. biloba medium afforded agricultural antibiotics. [Display omitted] • Five undescribed terpenoids were found from Paraphaeosphaeria sp. • The meroterpenoid, sesquiterpenoids, and alternariol derivative showed significant antibiosis. • The interaction of Paraphaeosphaeria sp. and host G. biloba induced the antifungal activity. • The structure-activity relationships of eremophilane sesquiterpenoids were indicated. [ABSTRACT FROM AUTHOR]

In this work, a portable-Raman device (excitation wavelength 1064 nm) was employed for the first time for continuously monitoring the complex molecular dynamics of terpenoid resins (dammar, mastic, colophony, sandarac and shellac), which occur during their ageing under artificial light exposure. The instrumentation was equipped with a pyroelectric sensor allowing for temperature control of the sample's irradiated surface while the acquisition of spectra occurs by setting fixed maximum temperature and total radiant exposure. Resins were dropped into special pits over a dedicated rotating wheel moved by a USB motor. The rotation allowed samples sliding between the positions designated for the acquisition of the Raman spectra and that for artificial ageing. Samples were exposed to artificial light for 45-days and almost 400 spectra for each resin sample were collected. The exposure to artificial light led to significant changes allowing the characterization of the alteration process. The automated acquisition of a large number of spectra overtime during light-exposure has given the possibility to distinguish fast dynamics, mainly associated to solvent evaporation, from those slower due to resins photo-degradation processes. [ABSTRACT FROM AUTHOR]

Capped palladium (Pd) nano-particle column chromatography was first used to separate a novel series of high molecular weight terpenoid sulfoxides (HMTSs) from petroleum condensate oil within the heterocyclic polyaromatic sulfur compound (S-PAH) fraction. The separation technique was based on complex formation between nano-sized heavy charged Pd 2 + ions and sulfoxide ligands. HMTSs were identified by interpretation of GC–MS fragmentation patterns. The infrared spectra of the pre-isolated S-PAH fraction confirmed the presence of sulfoxide groups with an absorption band at 1264 cm − 1 . The novel HMTS series included three members with the general formula C 20 H 34 OSR (main compound C 25 H 44 OS). The mass spectra of these three compounds were characterized by a major fragment ion at m / z 322. We identified a relationship between oil emergence and HTMS structure, indicating a base cross-linked macromolecular structure for the tested petroleum condensates and volatile oils. Atomic emission detection (AED) was unable to detect HMTS in spite of its sulfur atoms, most likely due to the high carbon to sulfur atom ratio producing quenching. [ABSTRACT FROM AUTHOR]

Benzodioxinols, compounds with 6-membered heterocycles containing two oxygen atoms, exhibit promising analgesic activity. In the current study, synthesis of dioxinol via two-step approach including Prins cyclization of isopulegol with benzaldehyde to tetrahydropyran and its ring-rearrangement to dioxinol was investigated. Different acidic and basic catalysts were studied in the second step and the highest selectivity toward dioxinol was achieved using mesoporous Ce-composite material. [ABSTRACT FROM AUTHOR]

Four steroids (1 – 4) were isolated from the Antarctic lichen, Ramalina terebrata (Ramalinaceae), along with a lupane type triterpenoid (5) and an anthraquinone derivative (6). The structures of the isolated compounds were characterized by comprehensive spectroscopic analyses and LC-MS analysis. The isolated compounds were identified as brassicasterol (1), (22 E ,24 R)-24-methylcholesta-5,22-diene-3 β ,7 α -diol (2), ergosterol peroxide (3), 9,11-dehydroergosterol peroxide (4), lupeol (5) and parietin (6). It is the first report of the identification of steroids and a triterpenoid from R. terebrata. The chemotaxonomical significance of the isolated compounds is also discussed. • Six compounds (1 – 6) were isolated from the Antarctic lichen Ramalina terebrata. • Steroids and a triterpene were identified from R. terebrata for the first time. • The chemotaxonomic significance of the obtained compounds was discussed. [ABSTRACT FROM AUTHOR]

• Secretion of lipophilic substances is revealed for the first time in the typical peltate trichome of bromeliads. • The exudates comprise complex mixtures with lipophilic and hydrophilic phases. • Secretory products are likely related with protection against biotic/abiotic stressors. Trichomes are a key feature of bromeliads. These structures absorb water and minerals, potentially constituting an important element in plant-environment interactions. Recent studies have shown a glandular function associated with mucilage-secreting scales in inflorescences of bromeliads. During a prospective study of secretions in bromeliad inflorescences, we observed the presence of an oily exudate in three species of Vriesea sect. Xiphion. To verify whether scales in bromeliads can produce lipophilic secretions, we investigated the secretory activity in these species to identify the source and chemical nature of the secretions which spread over the inflorescences. We used standard methods of histochemistry, light, and electron microscopy applied to samples of floral bracts in two distinct phases of development. The secretions comprised hydrophilic and lipophilic substances secreted by trichomes on the adaxial side of bracts. The exudate was heterogeneous in V. aff. bituminosa and V. fenestrali s, with a lipophilic phase composed of terpenoids and lipids. Vriesea aff. bituminosa also presented alkaloids. In V. platynema var. rosea, the lipophilic content was lipids. The secretory activity was restricted to the early stages of organ development and might be characterized by a temporal disjunction between the secretion of hydrophilic and lipophilic contents. The functions of the exudate seem to include protection against herbivores but might also relate to protection against pathogens, water loss and high irradiance. The secretion of lipophilic substances by the typical peltate trichome of bromeliads was reported here for the first time. [ABSTRACT FROM AUTHOR]

Apiospora and Arthrinium have undergone a period of upheaval with disparate phylogenic affiliation during the past ten years. Recently, they were divided into two separate clades with the majority being Apiospora and several species changing genus from Arthrinum to Apiospora. The first genome annotation became available in 2020, and the potential for novel secondary metabolite production appears very high in these yet unexplored genera compared to other more famous filamentous fungi. In this review, we present the current state of knowledge of 269 secondary metabolites isolated from the two fungal genera combined and highlight some of the compounds with known biological or toxic effects. [ABSTRACT FROM AUTHOR]

Hyperjapones F–I ( 1 – 4 ), novel terpenoid polymethylated acylphloroglucinols (TPAPs) with three unusual carbon skeletons, were characterized from Hypericum japonicum . Their structures were determined on the basis of comprehensive MS and NMR spectroscopic data. Compounds 1 and 2 could be formed by hybridization of a trimethylated acylphloroglucinol core with a sabinene-type monoterpenoid unit, while compounds 3 and 4 contained a pinene-type monoterpenoid unit in their molecules. Biosynthetically, a key hetero-Diels–Alder mechanism was proposed for the generation of compounds 1 – 4 . [ABSTRACT FROM AUTHOR]

We report the synthesis of a series of diaminated terpenoids containing, as side-chain of the diamine core, the “head-to-tail” prenyl derivatives, with amino amino spacers of variable length. In vitro biological activity of these compounds was evaluated against Mycobacterium tuberculosis and Leishmania amazonensis , and the structure-activity relationships are discussed. Different biological results were observed depending on the terpenic side-chain length. The best results were obtained for trans,trans -farnesol derivatives. Moreover, these results demonstrated that the stereochemistry of the double bond could play an important role in determining antitubercular and antileishmanial activities of these compounds. [ABSTRACT FROM AUTHOR]

Antiosteoclastogenic-guided screening was conducted with 120 extracts of the medicinal plants collected in Egypt that led to the selection of Artemisia judaica L. (Asteraceae). Three undescribed davanone-related terpenoids, arteperoxides A–C, were isolated from the extract with two known derivatives, hydroxydavanone and davana acid. Structural analysis revealed that arteperoxides A–C were tris -normonoterpene–sesquiterpene conjugates with peroxide bridges. Although davanone derivatives with peroxides, such as a hydroperoxyl and peroxyhemiketal groups, have been isolated from Artemisia species, arteperoxides A–C are the first variations observed to contain peroxide bridges between two terpene-derived units. The absolute configurations of arteperoxides A and B were studied based on their spectroscopic data compared with those of the semisynthetic analogs that have ether linkages. The natural and synthetic compounds were tested for the antiosteoclastogenic activity, and arteperoxide C and hydroxydavanone were more potent than other compounds at 20 μM. [Display omitted] • Antiosteoclastogenic-bioguided screening of 120 medicinal plant extracts. • Artemisia judaica L. (Asteraceae) demonstrated the most potent activity. • Three undescribed davanone-related terpenoids, arteperoxides A–C, were isolated. • Peroxide-bridged containing structures. [ABSTRACT FROM AUTHOR]

The Cinnamomum longepaniculatum (Gamble) N. Chao ex H. W. Li is a traditional aromatic plant, but the differences in leaf antioxidant activity and secondary metabolism between different C. longepaniculatum varieties have not been studied. In this study, two varieties (CLH, CLL) of C. longepaniculatum were used to consider the effect of variety on the essential oils (EOs) content, secondary metabolites and antioxidant activities. The EOs content and composition of different varieties are significantly different. The EOs content of CLH and CLL leaves was 1.85 % and 1.35 %, respectively. The content of 1,8-cineole in CLH and CLL EOs was 57.45 %, and 62.23 %, respectively. The total soluble sugars of CLL and CLH was 955.01 mg g−1, and 916.01 mg g−1, respectively. The lignin of CLL and CLH was 151.54 mg g−1, and 129.22 mg g−1, respectively. The total phenolic of CLL was lower than that of CLH (557.01 mg g−1 vs 553.78 mg g−1). The flavonoid content of CLL and CLH was 32.76 mg g−1, and 28.60 mg g−1, respectively. The T-AOC content of CLL and CLH was 172.56 μmol mL−1, and 172.84 μmol mL−1, respectively. The T-AOC was highly correlated with leaf flavonoid content of leaf (r 2 = 0.6364), but low correlated with total phenol content (r 2 = 0.1382). The chlorophyll content in the leaves of CLL was prominently decreased compared with that in leaves of CLH (25.57 vs 27.90, respectively). These 196 metabolites were identified in the leaves of C. longepaniculatum by metabonomics, and 49 (26 down-regulated and 23 up-regulated) metabolites differed between the two varieties. Based on the detection and verification of terpenoid and phenylpropanoid biosynthesis pathway genes, the results showed that the CLL produces more metabolites through the MEP pathway, which also causes an increase of 1,8-cineole cineole content, the CLH generates more metabolites through the MVA pathway and then generates other terpenoids. The relative expression levels of C4H and ANR were related to the increase in total phenolic content, while PAL , 4CL and DFR were related to the change of flavonoid content. This study analyzed the chemical composition differences of metabolites in leaves of different varieties of C. longepaniculatum , screened the key genes affecting the content and composition of EOs, and provided a theoretical basis for screening and improving new varieties. • The content and composition of essential oils between two varieties were different. • The secondary metabolites of the two varieties were different. • Different varieties affect related genes expression cause metabolites differences. [ABSTRACT FROM AUTHOR]

In this study, we evaluated the efficacy of combinations of the terpenes carvacrol, thymol, and menthol on Dermanyssus gallinae under in vitro (direct contact and vapour efficacy assays) and in-use conditions. Combinations investigated in vitro included carvacrol-menthol, thymol-menthol, carvacrol-thymol, and carvacrol-thymol-menthol. Results from contact efficacy studies showed that carvacrol-thymol-menthol was the most efficacious compared to the other combinations (P < 0.05), killing 100 % of the mites when at a concentration of 0.5 μg/mL. Thymol-menthol showed the weakest acaricidal activity with an approximate 80 % mortality rate at a concentration of 2 μg/mL. Based on the results of the vapour efficacy assay, all tested combinations appear to exert their acaricidal efficacy not only through direct contact, but also by fumigant action. A subsequent in-field efficacy investigation in a cage system laying farm was carried out to confirm the miticidal activity of the carvacrol-thymol-menthol combination. A formulation based on the triple combination of carvacrol-thymol-menthol diluted 1:40 in water was sprayed, with 1-week interval, in an 8000-laying hen farm, in presence of hens. The number of mites were counted by monitoring traps for 21 days through the study. The number of mites in the treated group decreased until day 5 after the first spray, but increased on days 5 and 7. However, after the second spray on day 7, the number of mites showed a significant decrease on day 10. This terpene-based combination which showed promising in vitro and in field miticidal activity can be a step forward in greening the future of pest management, also producing residue-free eggs. • In contact toxicity, carvacrol-thymol-menthol was the most effective combination. • Tested combinations exert their action through direct contact and fumigation. • Field investigation showed promising miticidal activity of combination of terpenes. [ABSTRACT FROM AUTHOR]

The balanced and optimal expression of genes in an engineered pathway is a prerequisite for the overproduction of a natural compound in a customized strain. Hence, 13 new constitutive promoters were characterized and optimized for overexpressing genes in the squalene biosynthetic pathway (SB) and squalene overproduction in Saccharomyces cerevisiae . Subsequently, these newly characterized promoters were employed for overexpressing genes in the mevalonate pathway; as a result, 29.41-fold (100 mg/L) more squalene was produced in the engineered strain (FOH-0) than in the wild-type strain (WS). Afterward, the entire squalene biosynthetic pathway was upregulated with the newly characterized promoters to engineer the FOH-2 strain, and it resulted in the production of 304.16 mg/L of squalene after inhibition of squalene monooxygenase with terbinafine. The FOH-2 strain also overproduced 154.94 mg/L oleic acid, and this was perhaps because of an indirect upregulation of the oleic acid biosynthetic pathway by an unknown regulatory mechanism. The production of ergosterol and biomass in the FOH-2 strain was also increased by up to 34 mg/L and 13.5 g DW/L, respectively, compared to the WS strain. Consequently, the overexpression of genes in the SB pathway increased the production of squalene, oleic acid, ergosterol and biomass by 89.46-, 4.66-, 3.37- and 2.25-fold, respectively, in the FOH-2 strain compared to the WS strain. The growth rate of the FOH-2 strain was also 1.3-fold higher than the WS strain. Finally, our study reports the enhanced coproduction of squalene, ergosterol, oleic acid and biomass in yeast due to the overexpression of genes in the SB pathway by newly characterized constitutive promoters. It also shows that ergosterol overproduction indirectly upregulates its complementary pathway. [ABSTRACT FROM AUTHOR]