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Molecules (Basel, Switzerland) Oct 2022For the first time, monoterpene trifluoromethylated β-hydroxy-benzyl--oximes were synthesized in 81-95% yields by nucleophilic addition of the Ruppert-Prakash reagent...
For the first time, monoterpene trifluoromethylated β-hydroxy-benzyl--oximes were synthesized in 81-95% yields by nucleophilic addition of the Ruppert-Prakash reagent (TMSCF) to the corresponding β-keto-benzyl--oximes based on (+)-nopinone, (-)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed chemo- and stereoselective at the C=O rather than C=N bond. Trifluoromethylated benzyl--oximes were reduced to the corresponding α-trifluoromethyl-β-amino alcohols in 82-88% yields. The structure and configuration of the compounds obtained have been established.
Topics: Amino Alcohols; Molecular Structure; Monoterpenes; Indicators and Reagents; Oximes
PubMed: 36296661
DOI: 10.3390/molecules27207068 -
Nature Sep 2022Monoterpenes (CH) are emitted in large quantities by vegetation to the atmosphere (>100 TgC year), where they readily react with hydroxyl radicals and ozone to form...
Monoterpenes (CH) are emitted in large quantities by vegetation to the atmosphere (>100 TgC year), where they readily react with hydroxyl radicals and ozone to form new particles and, hence, clouds, affecting the Earth's radiative budget and, thereby, climate change. Although most monoterpenes exist in two chiral mirror-image forms termed enantiomers, these (+) and (-) forms are rarely distinguished in measurement or modelling studies. Therefore, the individual formation pathways of monoterpene enantiomers in plants and their ecological functions are poorly understood. Here we present enantiomerically separated atmospheric monoterpene and isoprene data from an enclosed tropical rainforest ecosystem in the absence of ultraviolet light and atmospheric oxidation chemistry, during a four-month controlled drought and rewetting experiment. Surprisingly, the emitted enantiomers showed distinct diel emission peaks, which responded differently to progressive drying. Isotopic labelling established that vegetation emitted mainly de novo-synthesized (-)-α-pinene, whereas (+)-α-pinene was emitted from storage pools. As drought progressed, the source of (-)-α-pinene emissions shifted to storage pools, favouring cloud formation. Pre-drought mixing ratios of both α-pinene enantiomers correlated better with other monoterpenes than with each other, indicating different enzymatic controls. These results show that enantiomeric distribution is key to understanding the underlying processes driving monoterpene emissions from forest ecosystems and predicting atmospheric feedbacks in response to climate change.
Topics: Atmosphere; Climate Change; Droughts; Forests; Monoterpenes; Trees
PubMed: 36071188
DOI: 10.1038/s41586-022-05020-5 -
Biomedicine & Pharmacotherapy =... Oct 2020Increasing pharmacological evidence supports that paeoniflorin, a water-soluble monoterpene glycoside isolated from Paeonia lactiflora Pall. (Shaoyao in Chinese), has a... (Review)
Review
Increasing pharmacological evidence supports that paeoniflorin, a water-soluble monoterpene glycoside isolated from Paeonia lactiflora Pall. (Shaoyao in Chinese), has a wide range of medicinal properties including anti-inflammatory, antioxidant, antithrombotic, anticonvulsive, analgesic, cardioprotective, neuroprotective, hepatoprotective, antidepressant-like, antitumoral, and immune-regulatory activities; as well as enhancing cognition and attenuating learning impairment. In addition to pharmacodynamic studies, information on pharmacokinetics is also significant for the further development and utilization of paeoniflorin. The present review focuses on the absorption, distribution, metabolism, and excretion of paeoniflorin, especially main pharmacological activities of paeoniflorin on inflammation and immune function. According to the findings obtained both in vitro and in vivo, a broad application prospect has been opened for paeoniflorin. However, further studies are needed to clarity the direct molecular mechanisms and key targets underlying the beneficial effects of paeoniflorin on inflammation and immunity.
Topics: Animals; Anti-Inflammatory Agents; Glucosides; Humans; Immunologic Factors; Inflammation; Monoterpenes; Paeonia; Signal Transduction
PubMed: 32682112
DOI: 10.1016/j.biopha.2020.110505 -
Zeitschrift Fur Naturforschung. C,... Jul 2020Isothiocyanates, monoterpenes, and leaf volatiles that are components of essential oils induce the expression of heat shock protein genes in plant systems. Here, the... (Review)
Review
Isothiocyanates, monoterpenes, and leaf volatiles that are components of essential oils induce the expression of heat shock protein genes in plant systems. Here, the modes of heat shock responses induced by the essential oil compounds and their heat-tolerance-enhancing activities are described. Traditionally, green manure produced from essential-oil-containing plants has been used because such manure is thought to have beneficial effects in fertilizing, allelopathic, antibacterial, and animal-repellent activities. In addition to these effects, stress (especially heat stress)-tolerance-enhancing activities can be expected. Biostimulants containing such essential oils may be able to maintain the yield and quality of crops under increasing ambient temperatures. In this review, chemicals that enhance the heat tolerance of plants are designated as heat tolerance enhancers (HTLEs). Some essential oil compounds can be categorized as HTLEs available for biostimulants.
Topics: Gene Expression Regulation, Plant; Heat-Shock Response; Isothiocyanates; Monoterpenes; Oils, Volatile; Plant Physiological Phenomena; Thermotolerance
PubMed: 32755102
DOI: 10.1515/znc-2019-0233 -
Frontiers in Immunology 2022Epidemiological studies have shown that the incidence, prevalence and mortality of atherosclerotic cardiovascular disease (ASCVD) are increasing globally.... (Review)
Review
Epidemiological studies have shown that the incidence, prevalence and mortality of atherosclerotic cardiovascular disease (ASCVD) are increasing globally. Atherosclerosis is characterized as a chronic inflammatory disease which involves inflammation and immune dysfunction. Pall. is a plant origin traditional medicine that has been widely used for the treatment of various diseases for more than a millennium in China, Japan and Korean. Paeoniflorin is a bioactive monomer extracted from Pall. with anti-atherosclerosis effects. In this article, we comprehensively reviewed the potential therapeutic effects and molecular mechanism whereby paeoniflorin protects against atherosclerosis from the unique angle of inflammation and immune-related pathway dysfunction in vascular endothelial cells, smooth muscle cells, monocytes, macrophages, platelets and mast cells. Paeoniflorin, with multiple protective effects in atherosclerosis, has the potential to be used as a promising therapeutic agent for the treatment of atherosclerosis and its complications. We conclude with a detailed discussion of the challenges and future perspective of paeoniflorin in translational cardiovascular medicine.
Topics: Humans; Endothelial Cells; Glucosides; Inflammation; Monoterpenes
PubMed: 36618414
DOI: 10.3389/fimmu.2022.1072007 -
Molecules (Basel, Switzerland) Oct 2022Monoterpene pyridine alkaloids (MTPAs) are alkaloids derived from iridoid glycosides (IGs). The common molecular structure of MTPAs is the pyridine ring, while some of... (Review)
Review
Monoterpene pyridine alkaloids (MTPAs) are alkaloids derived from iridoid glycosides (IGs). The common molecular structure of MTPAs is the pyridine ring, while some of them have a cyclopenta[c]pyridine skeleton. Some compounds containing this structure are potentially bioactive medicinal agents. In this paper, seven drug candidates (-), ninety natural source products (-), thirty-seven synthesized compounds (-), as well as twenty-six key intermediates (-) were summarized. We categorized five types of MTPAs and one type of cyclopenta[c]pyridine alkaloids in all. Additionally, their possible genetic pathways were proposed. Then, the chemical transformation, biotransformation, chemical synthesis, as well as the bioactivity of MTPAs and cyclopenta[c]pyridine derivatives were analyzed and summarized. Cyclopenta[c]pyridine derivatives can be concisely and chirally synthesized, and they have shown potentials with antibacterial, insecticidal, antiviral, anti-inflammatory, and neuropharmacological activities.
Topics: Monoterpenes; Alkaloids; Molecular Structure; Pyridines; Biological Products
PubMed: 36364013
DOI: 10.3390/molecules27217187 -
Current Opinion in Chemical Biology Oct 2016Synthetic biology is opening up new opportunities for the sustainable and efficient production of valuable chemicals in engineered microbial factories. Here we review... (Review)
Review
Synthetic biology is opening up new opportunities for the sustainable and efficient production of valuable chemicals in engineered microbial factories. Here we review the application of synthetic biology approaches to the engineering of monoterpene/monoterpenoid production, highlighting the discovery of novel catalytic building blocks, their accelerated assembly into functional pathways, general strategies for product diversification, and new methods for the optimization of productivity to economically viable levels. Together, these emerging tools allow the rapid creation of microbial production systems for a wide range of monoterpenes and their derivatives for a diversity of industrial applications.
Topics: Monoterpenes; Synthetic Biology
PubMed: 27315341
DOI: 10.1016/j.cbpa.2016.06.002 -
The Plant Journal : For Cell and... Apr 2023Terrestrial plants emit volatiles into the atmosphere to attract both pollinators and the enemies of herbivores, for defense. Phalaenopsis bellina is a scented orchid...
Terrestrial plants emit volatiles into the atmosphere to attract both pollinators and the enemies of herbivores, for defense. Phalaenopsis bellina is a scented orchid species in which the main scent components are monoterpenes, including linalool and geraniol, and their derivatives. Here, we investigated whether ABC transporters are involved in floral scent emission. We carried out whole-genome identification of ABC transporter-related genes using four floral transcriptomics libraries of P. bellina. We identified 86 ABC subfamily G genes related to terpenoid transport. After comparing the gene expression patterns of P. bellina with that of Phalaenopsis aphrodite subsp. formosana, a scentless species, followed by gene-to-gene correlation analysis, PbABCG1 and PbABCG2 were selected. The temporal expression of both PbABCG1 and PbABCG2 was highly correlated with that of the key enzyme PbGDPS and the major transcription factor PbbHLH4 in monoterpene biosynthesis, with optimal expression on day 5 post-anthesis. Spatial gene expression analysis showed that PbABCG1 was highly expressed in sepals, whereas PbABCG2 was expressed in the lip. Subcellular localization with a GFP fusion protein revealed that both PbABCG1 and PbABCG2 are cytoplasmic membrane proteins. Co-downregulation of PbABCG1 and PbABCG2 using both double-strand RNA interference and tobacco rattle virus-based gene silencing led to a significant decrease in monoterpene emission, accompanied by an increase in the internal monoterpene pools. Furthermore, ectopic expression of PbABCG1 and PbABCG2 in an ABC16 mutant yeast strain rescued its tolerance to geraniol. Altogether, our results indicate that PbABCG1 and PbABCG2 play substantial roles in monoterpene transport/emission in P. bellina floral scent.
Topics: Monoterpenes; Plant Proteins; Flowers; Orchidaceae
PubMed: 36738107
DOI: 10.1111/tpj.16133 -
The Journal of Physical Chemistry. A Aug 2022Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly...
Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly emitted hydrocarbons improves the understanding of aerosol properties and their influence on the climate. In this study, we measure the electrical mobility and mass-to-charge ratio of α-pinene oxidation products using a secondary electrospray-differential mobility analyzer-mass spectrometer (SESI-DMA-MS). The mass-mobility spectrum of the oxidation products is measured with seven different reagent ions generated by the electrospray. We analyzed the mobility-mass spectra of the oxidation products CHO. Our results show that acetate and chloride yield the highest charging efficiencies. Analysis of the mobility spectra suggests that the clusters have 1-5 isomeric structures (i.e., ion-molecule cluster structures with distinct mobilities), and the number is affected by the reagent ion. Most of the isomers are likely cluster isomers originating from binding of the reagent ion to different sites of the molecule. By comparing the number of observed isomers and measured mobilities and collision cross sections between standard pinanediol and pinonic acid to the values observed for CHO and CHO produced from oxidation of α-pinene, we confirm that pinanediol and pinonic acid are the only isomers for these elemental compositions in our experimental conditions. Our study shows that the SESI-DMA-MS produces new information from the first steps of oxidation of α-pinene.
Topics: Aerosols; Air Pollutants; Bicyclic Monoterpenes; Ions; Monoterpenes; Ozone
PubMed: 35862553
DOI: 10.1021/acs.jpca.2c03366 -
Molecules (Basel, Switzerland) Apr 2022Carvone is a monoterpene compound that has been widely used as a pesticide for more than 10 years. However, little is known regarding the fate of carvone, or its...
Carvone is a monoterpene compound that has been widely used as a pesticide for more than 10 years. However, little is known regarding the fate of carvone, or its degradation products, in the environment. We used GC-MS (gas chromatography-mass spectrometry) to study the fate of carvone and its degradation and photolysis products under different soil and light conditions. We identified and quantified three degradation products of carvone in soil and water samples: dihydrocarvone, dihydrocarveol, and carvone camphor. In soil, dihydrocarveol was produced at very low levels (≤0.067 mg/kg), while dihydrocarvone was produced at much higher levels (≤2.07 mg/kg). In water exposed to differing light conditions, carvone was degraded to carvone camphor. The photolysis rate of carvone camphor under a mercury lamp was faster, but its persistence was lower than under a xenon lamp. The results of this study provide fundamental data to better understand the fate and degradation of carvone and its metabolites in the environment.
Topics: Camphor; Cyclohexane Monoterpenes; Photolysis; Soil; Water; Water Pollutants, Chemical
PubMed: 35458614
DOI: 10.3390/molecules27082415