The discovery of an anti-inflammatory monoterpenoid, neoroseoside from the Zea mays.

A new monoterpenoid, neoroseoside (1), along with two previously reported compounds, 2″-O-α-l-rhamnosyl-6-C-fucosylluteolin (2) and farobin A (3) were isolated from the Zea mays. The structure of compound 1 was determined through the analysis spectroscopic data, including mass spectrometry (MS), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) data. The absolute configurations of 1 were deduced from the comparing the values of optical rotations and from the interpretation of electronic circular dichroism (ECD) spectra. Compounds 2 and 3 displayed moderate antibacterial activity against Streptococcus mutans ATCC 25175 (inhibition rates 24 % and 28 %, respectively) and Streptococcus sobrinus ATCC 33478 (inhibition rate of 26 %), at a concentration of 100 µg/mL, whereas compound 1 did not have any significant antibacterial activities. The compounds 1-3 also showed anti-inflammatory activity on cytokine IL-6 and TNF-α.

Chalcone-Monoterpene Derivatives from the Buds of Cleistocalyx operculatus and Their Potential as Protein Tyrosine Phosphatase 1B Inhibitors.

Four new compounds, racemic chalcone-monoterpene hybrids (1-3) and a chalcone (9), along with nine known compounds (4-8, 10-13), have been isolated from the buds of Cleistocalyx operculatus. The chemical structures of the isolated compounds were identified through NMR data analysis and confirmed by computational methods, including electronic circular dichroism (ECD) calculations, and further synthetic approaches. Compounds 1-5 were synthesized via a Diels-Alder reaction, a process informed by biomimetic condensation studies that combined chalcones and monoterpenes. These synthetic approaches also yielded various unnatural chalcone-monoterpene derivatives (14-23). The inhibitory effects on protein tyrosine phosphatase 1B (PTP1B) of both naturally isolated and synthetically obtained compounds were evaluated. Compounds 4, 9, 13, and 16b exhibited potent PTP1B inhibitory activity, with IC50 values ranging from 0.9 ± 0.2 to 3.9 ± 0.7 µM. The enantiomers (+)-4 and (-)-16b showed enhanced activity compared to their respective enantiomers. Kinetic studies indicate that all active compounds inhibit PTP1B through mixed mechanisms, and molecular docking simulations agree with the experimental assays on PTP1B. Our results suggest that chalcone-meroterpene adducts from the buds of C. operculatus exhibit potential as antidiabetic agents, partly due to their PTP1B enzyme inhibition.

In vitro and in vivo anthelmintic effect of essential oil obtained from Thymus capitatus flowers against Haemonchus contortus and Heligmosomoides polygyrus.

Sheep haemonchosis is a disease that causes serious losses in livestock production, particularly with the increase of cases of anthelmintic resistance around the world. This justifies the urgent need of alternative solutions. The aim of this study was to determine the chemical profile, in vitro, and, in vivo, anthelmintic properties of Thymus capitatus essential oil. To evaluate the, in vitro, anthelmintic activity of the T. capitatus EO on Haemonchus contortus, two tests were used: egg hatch assay (EHA) and adult worm motility (AWM) assay. The nematicidal effect of this oil was evaluated, in vivo, in mice infected artificially with Heligmosomoides polygyrus using faecal egg count reduction (FECR) and total worm count reduction (TWCR). Chromatographic characterization of T.capitatus composition using gas chromatography coupled to mass spectrometry (GC-MS) demonstrated the presence of carvacrol (81.16%), as the major constituents. The IC50 values obtained was 1.9 mg/mL in the EHT. In the AWM assay; T. capitatus essential oil achieved 70.8% inhibition at 1 mg/mL after 8 h incubation. The in vivo, evaluation on H. polygyrus revealed a significant nematicidal effect 7 days post-treatment by inducing 49.5% FECR and 64.5% TWCR, using the highest dose (1600 mg/kg). The results of present study, demonstrate that T.capitatus EO possess a significant anthelmintic properties. Furthermore, it could be an alternative source of anthelmintic agents against gastrointestinal infections caused by H. contortus.

Extraction Kinetics of Brazilian Green Propolis and Chemical Characterization of its Volatiles.

Propolis is a natural resinous product produced by Apis mellifera bees from the exudates of various plants. The color of propolis (green) is a consequence of its botanical origin, as bees collect young tissues and leaves of Baccaris dracunculifolia. This study evaluated the chemical composition and extraction kinetics of essential oils obtained from Brazilian green propolis by hydrodistillation. Hydrodistillation was performed for 360 min and analyzed at different times (30, 60, 120, 240, and 360 min), allowing the calculation of the accumulated content (% w/w) and the identification of the essential oil chemical profile. The GC/FID and GC/MS analysis led to the annotation of 60 compounds with estragole (13.30 %), benzyl propanoate (14.59 %), and (E)-nerolidol (13.57 %) as the main compounds. The optimum conditions for extraction of phenylpropanoids (PP), hydrocarbons (HD), monoterpenes (MT), and oxygenated monoterpenes (OMT) are between 30 and 120 min. In comparison, sesquiterpenes (ST) and oxygenated sesquiterpenes (OST) are extracted more efficiently between 240 and 360 min. The optimal extraction speed determination is essential for industrial-scale processing to obtain components such as sesquiterpenes, which have a high economic value in the cosmetic/perfumery and pharmaceutical industries.

Halogenated Cyclic Monoterpenoids with Anti-Biofouling Activity from the Okinawan Red Marine Algae Portieria Hornemannii.

The red algal genus Portieria is a prolific producer of halogenated monoterpenoids. In this study, we isolated and characterised monoterpenoids from the Okinawan red algae Portieria hornemannii. A new polyhalogenated cyclic monoterpenoid, 2(R)-chloro-1,6(S)-dibromo-3(8)(Z)-ochtoden-4(R)-ol (1), along with three known monoterpenoids, (2R,3(8)E,4S,6R)-6-bromo-2-chloro-1,4-oxido-3(8)-ochtodene (2), 1-bromo-2-chloroochtoda-3(8),5-dien-4-one (3), and 2-chloro-1-hydroxyochtoda-3(8),5-dien-4-one (4) were isolated from the methanol extract of three populations of P. hornemannii. These compounds were characterised using a combination of spectroscopic methods and chemical synthesis, and the absolute stereochemistry of compounds 1 and 2 was determined. In addition, all isolated compounds were screened for their anti-biofouling activity against the mussel Mytilus galloprovincialis, and 1 exhibited strong activity. Therefore, halogenated monoterpenoids have the potential to be used as natural anti-biofouling drugs.

Inhibitory Effects of Endemic Thyme's Thymol-Carvacrol Chemotype Essential Oil on Aspergillus Species with Free Radical Scavenging Properties.

There is a burgeoning focus on utilizing the antifungal and antioxidant properties of essential oils derived from various plants as a modern and natural approach to combat the growth of fungi that contaminate food. In this study, we used essential oils extracted from Thymus daenensis Celak. subsp. daenensis to address three mycotoxin-producing species of Aspergillus, specifically A. flavus, A. parasiticus, and A. niger, all of which are recognized contaminants of food and agricultural products. Concurrently, the antioxidant properties of the essential oils were evaluated, revealing their noteworthy role in the antifungal activity. Essential oils were derived from T. daenensis subsp. daenensis was observed to have a significant inhibitory effect on all three species of Aspergillus, as evidenced by the minimum inhibitory concentration (MIC) ranging from 575 to 707 ppm and the half-maximal inhibitory concentration (IC50) ranging from 237 to 280 ppm. These results confirm the strong antifungal activity of the essential oils. Furthermore, the essential oil exhibited free radical scavenging activity, resulting in an EC50 value of 37.1 µg/ml. In summary, T. daenensis subsp. daenensis essential oil demonstrated a competitive advantage over other similar plants and synthetic antibiotics. This indicates the promising potential of this essential oil as a natural antifungal agent to control Aspergillus growth and mycotoxin contamination. It offers an alternative or complementary approach to conventional antifungal agents and could be a valuable addition to the arsenal of natural remedies to address fungal contamination in food and agricultural products.

Graphiumisides A-D, Monoterpene Glycosides from an Animal-Derived Endophytic Fungus Graphium sp. GD-11.

Four new monoterpene rhamnosides, graphiumisides A-D (1-4), along with four known steroid compounds (5-8) were isolated from the fermentation extract of animal-derived endophytic fungus, Graphium sp. GD-11. The chemical structures of all compounds were elucidated using 1D and 2D NMR, HRESIMS spectroscopic analyses, and other spectroscopic methods. Compounds 1-4 exhibit a distinctive structure connected by one p-menthane type monoterpene and one L-rhamnose. This is the first report of monoterpene glycosides from Graphium sp. All compounds (1-8) were tested for cytotoxic activities against four cancer cell lines (HepG2, SMMC7721, SW480, and A549), and only compound 1 showed weak anti-tumor activity against SMMC7721 cells.

Chemical Composition of Artemisia Scoparia and Their Bioactivities.

Three undescribed sesquiterpenes (1-3), two enantiomeric pairs of monoterpenes (4a/4b-5a/5b), one alkyne (6), two known alkynes (7-8) and eight known coumarins (9-16) were isolated from the aerial parts extracts of Artemisia scoparia. The structures of these compounds were fully elucidated by their 1D and 2D NMR, HRESIMS spectral data analyses, and comparison with literature. The absolute configurations of compounds were determined by single-crystal X-ray crystallography (1), a comparison of experimental and calculated electronic circular dichroism (ECD) data (2-6). 15 showed moderate inhibitory activity with the NO release in LPS-induced RAW264.7 cells. 9-16 showed varying degrees of promoting melanogenesis and tyrosinase activity in B16 cells.

Comparative Analysis of Hydrosol Volatile Components of Citrus × Aurantium 'Daidai' and Citrus × Aurantium L. Dried Buds with Different Extraction Processes Using Headspace-Solid-Phase Microextraction with Gas Chromatography-Mass Spectrometry.

This work used headspace solid-phase microextraction with gas chromatography-mass spectrometry (HS-SPME-GC-MS) to analyze the volatile components of hydrosols of Citrus × aurantium 'Daidai' and Citrus × aurantium L. dried buds (CAVAs and CADBs) by immersion and ultrasound-microwave synergistic-assisted steam distillation. The results show that a total of 106 volatiles were detected in hydrosols, mainly alcohols, alkenes, and esters, and the high content components of hydrosols were linalool, α-terpineol, and trans-geraniol. In terms of variety, the total and unique components of CAVA hydrosols were much higher than those of CADB hydrosols; the relative contents of 13 components of CAVA hydrosols were greater than those of CADB hydrosols, with geranyl acetate up to 15-fold; all hydrosols had a citrus, floral, and woody aroma. From the pretreatment, more volatile components were retained in the immersion; the relative contents of linalool and α-terpineol were increased by the ultrasound-microwave procedure; and the ultrasound-microwave procedure was favorable for the stimulation of the aroma of CAVA hydrosols, but it diminished the aroma of the CADB hydrosols. This study provides theoretical support for in-depth exploration based on the medicine food homology properties of CAVA and for improving the utilization rate of waste resources.

New Monoterpenoid Glycosides from the Fruits of Hypericum patulum Thunb.

The whole Hypericum patulum Thunb. plant is utilized in traditional medicine for its properties of clearing heat, detoxifying, soothing meridians, relaxing the liver, and stopping bleeding. In folk medicine, it is frequently used to treat hepatitis, colds, tonsillitis, and bruises. Phytochemical investigation of a 30% ethanol extract of the fresh ripe fruits of H. patulum has resulted in the isolation of two new pinane-type monoterpenoid glycosides 1-2, named patulumside E-F, and three new chain-shaped monoterpenoid glycosides 3-5, named patulumside G-H, J. Their structures were determined using extensive spectroscopic techniques, such as HR-ESI-MS, 1D and 2D NMR spectroscopy, and electronic circular dichroism (ECD) calculation. The anti-inflammatory activities of these compounds were evaluated in the LPS-induced RAW264.7 cells. This research represents the inaugural comprehensive phytochemical study of H. patulum, paving the way for further exploration of monoterpenoid glycosides.

Gelstriamine A, a Triamino Monoterpene Indole Alkaloid with a Caged 6/5/7/6/6/5 Scaffold and Analgesic Alkaloids from Gelsemium elegans Stems.

A novel triamino monoterpene indole alkaloid with an unprecedented skeleton, gelstriamine A (1), four new monoterpene indole alkaloids (2-5), and 12 known analogues (6-17) were isolated from Gelsemium elegans. The structures of 1-5 were established using extensive spectroscopic techniques, NMR calculations with iJ/dJ-DP4 and 2D C-H COSY ANNs analysis, ECD calculations, chemical methods, and single crystal X-ray diffraction analysis. Gelstriamine A (1) possesses an unprecedented 6/5/7/6/6/5 heterohexacyclic scaffold bearing a unique hexahydrooxazolo[4,5-b]pyridin-2(3H)-one motif, and a plausible biosynthetic pathway was proposed. All the isolated alkaloids 1-17 showed discernible analgesic activities in an acetic acid-induced writhing test in mice, and N-desmethoxyhumantenine N4-oxide (3) exhibited more potent analgesic activities than those of morphine at doses of 0.04 and 0.2 mg/kg.

(±)-Caryopterisines A and B, dimeric monoterpene alkaloids with unprecedented 6/5/5/5/6 pentacyclic rings scaffold from Caryopteris glutinosa.

(±)-Caryopterisines A (1) and B (2) featuring an unprecedented 6/5/5/5/6 pentacyclic rings system were isolated from Caryopteris glutinosa. The structures were determined by spectroscopic and X-ray crystallographic data analyses as well as theoretical calculations. Chiral HPLC resolution of both racemic 1 and 2 afforded their corresponding enantiotropic enantiomers. A plausible biogenesis for 1 and 2 may be originated from Diels-Alder reaction between pyridine-containing oxerine derivatives. The enantiotropic conversion mechanism of the enantiomers was demonstrated by H-D exchange and 18O incorporation studies. Compounds 1 and 2 showed moderate inhibition of estrogen E2 biosynthesis in human ovarian granulosa-like KGN cells. These two alkaloids reduced kynurenine biosynthesis at moderate level via inhibition of indoleamine 2,3-dioxygenase. Alkaloid 2 exhibited moderate inhibition of the release of interleukin-1ß.

Bioactive monoterpene phenol dimers from the fruits of Psoralea corylifolia L.

Nine undescribed monoterpene phenol dimers, bisbakuchiols D-L (1-9), were isolated from the fruits of Psoralea corylifolia L. Their structures were elucidated based on extensive spectral analysis. The absolute configurations of 1-9 were specified by experimental and quantum chemical calculations of ECD spectra, and that of 1 was further established by X-ray diffraction analysis using Cu Kα radiation. Bisbakuchiols (1-4) were composed of two bakuchiols, one of which was cyclized via a C-7'/ C-12' single bond to form a six-member ring, and connect to each other by C-4-O-C-13' bonds. Bisbakuchiols (7-9) had a pyran ring by linkage of C-8-O-C-12. In the enzyme assay, compounds 5 and 9 exhibited significant PTP1B inhibitory activities with IC50 values of 0.69 and 0.73 µM, and compounds 1 and 3 showed moderate PTP1B inhibitory activities. Furthermore, a molecular docking simulation of PTP1B and active compounds 5 and 9 showed that these active compounds possess low binding affinities ranging from -6.9 to -7.1 kcal/mol.

Monoterpene-flavonoid conjugates from Sarcandra glabra and their autophagy modulating activities.

Fourteen new monoterpene-flavonoid conjugates including four monoterpene-conjugated chalcones (glabratins A-D, 1-4), seven monoterpene-conjugated dihydrochalcones (glabratins E-K, 5-11), and three monoterpene-conjugated flavanones (glabratins L-N, 12-14), together with four known analogues (15-18) were isolated from the aerial parts of Sarcandra glabra. The structures and the absolute configurations of these compounds were elucidated by the spectroscopic data, single-crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 1, 4-6, 9-14, and 18 showed obvious cell autophagy-inducing activities at 25 µM in HEK293 cells. Furthermore, the bioassay results also showed that 18 induced cell autophagy in a dose dependent manner. Our findings revealed a rare class of monoterpene-flavonoid conjugates in nature and firstly reported their autophagy-inducing activities.

Mosquitocidal effect of monoterpene ester and its acetyl derivative from Blumea mollis (D. Don) Merr against Culex quinquefasciatus (Diptera: Culicidae) and their insilico studies.

The present study was conducted to assess the mosquitocidal efficiency of compound isolated from Blumea mollis (D. Don) Merr against Culex quinquefasciatus. Eggs and larvae of Cx. uinquefasciatus were exposed to different concentrations 0.5, 1.0, 1.5 and 2.0 ppm of compounds prepared using DMSO. Compound 1 was identified as (4R, 5S)-4-hydroxy-7-tigloyloxy carvotanacetone, from which new derivative was synthesized and confirmed as (4R, 5S)-4-acetoxy-7-tigloyloxy carvotanacetone. Both the compounds presented larvicidal and ovicidal activities. Compounds 1 and 2 at 2-ppm concentration showed 64% and 78% larval mortality in 24 h, respectively. The LC50and LC90values of compounds 1 and 2 on Cx. quinquefasciatus larvae were 1.73, 1.27 and 4.59, 3.33 ppm, respectively. The eluted compound 1 and synthesized compound 2 presented 68% and 77% of ovicidal activity, respectively, against eggs of Cx. quinquefasciatus at 120 h post-treatment. Histopathological studies of the compound-treated larvae revealed serious damage on the larval midgut cells. Furthermore, compounds 1 and 2 was tested for toxicity study and the results showed both the compounds were found to be harmless to non-target organism Poecilia reticulata. Computational analysis of compound 2 showed strong binding interaction with the AChE1 of Cx. quinquefasciatus. These results clearly suggest that compounds from Blumea mollis could act as good mosquitocidal agents against Cx.quinquefasciatus and compound 2 was first time reported.

A New Monoterpene from the Rhizomes of Alpinia galanga and Its Anti-Vpr Activity.

A new menthane-type monoterpene, alpigalanol (1), together with four known terpenes (2-5) were isolated from the ethyl acetate soluble fraction of the 70 % ethanol extract of the Alpinia galanga rhizomes. The structure of 1 was determined by spectroscopic analyses, including 1D- and 2D-NMR. The extract of the A. galanga rhizomes and all isolated compounds (1-5) possessed Vpr inhibitory activities against the TREx-HeLa-Vpr cells at a concentration of 1.25 µM without showing any cytotoxicity.

Chemical Constituents from Staminate Flowers of Eucommia ulmoides Oliver and Their Anti-Inflammation Activity in Vitro.

Three new monoterpenoids, named eucomylides A-C (1-3), along with six known compounds (4-9) were isolated from the staminate flowers of Eucommia ulmoides Oliver. The structures were elucidated by extensive analyses of spectroscopic methods, and their absolute configurations were established by time-dependent density functional theory electronic circular dichroism (TDDFT ECD) calculation. All the compounds along with previously isolated components (10-14) were tested for their anti-inflammatory effects. Two iridoid glycosides (11 and 12) and a flavonoid glycoside (14) showed potent suppressive effects on nitric oxide (NO) production in RAW 264.7 cells, with IC50 values ranging from 17.11 to 22.26 µM.

Characterizing the Volatile and Sensory Profiles, and Sugar Content of Beeswax, Beebread, Bee Pollen, and Honey.

Bee products are a well-known remedy against numerous diseases. However, from the consumers' perspective, it is essential to define factors that can affect their sensory acceptance. This investigation aimed to evaluate the volatile and sensory profiles, and sugar composition of beeswax, beebread, pollen, and honey. According to the HS-SPME/GC-MS results, 20 volatiles were identified in beeswax and honey, then 32 in beebread, and 33 in pollen. Alkanes were found to dominate in beeswax, beebread, and pollen, while aldehydes and monoterpenes in honey. In the case of sugars, a higher content of fructose was determined in beebread, bee pollen, and honey, whereas the highest content of glucose was assayed in beeswax. In the QDA, the highest aroma intensity characterized as honey-like and sweet was found in honey, while the acid aroma was typical of beebread. Other odor descriptors, including waxy, pungent, and plant-based aromas were noted only in beeswax, honey, and pollen, respectively.

Optimization of SPME-Arrow-GC/MS Method for Determination of Free and Bound Volatile Organic Compounds from Grape Skins.

(1) Background: Solid phase microextraction (SPME)-Arrow is a new extraction technology recently employed in the analysis of volatiles in food materials. Grape volatile organic compounds (VOC) have a crucial role in the winemaking industry due to their sensory characteristics of wine.; (2) Methods: Box-Behnken experimental design and response surface methodology were used to optimise SPME-Arrow conditions (extraction temperature, incubation time, exposure time, desorption time). Analyzed VOCs were free VOCs directly from grape skins and bound VOCs released from grape skins by acid hydrolysis.; (3) Results: The most significant factors were extraction temperature and exposure time for both free and bound VOCs. For both factors, an increase in their values positively affected the extraction efficiency for almost all classes of VOCs. For free VOCs, the optimum extraction conditions are: extraction temperature 60 °C, incubation time 20 min, exposure time 49 min, and desorption time 7 min, while for the bound VOCs are: extraction temperature 60 °C, incubation time 20 min, exposure time 60 min, desorption time 7 min.; (4) Conclusions: Application of the optimized method provides a powerful tool in the analysis of major classes of volatile organic compounds from grape skins, which can be applied to a large number of samples.

Essential Oils from Bolivia. XV. Herzogole, an Original Monoterpene Benzodioxole from an Essential Oil from Pentacalia herzogii (Cabrera) Cuatrec.

Over 15 years, with the support of a Canadian funding agency, the Universidad Mayor de San Simón, in Bolivia, undertook a large survey of aromatic plants of the South American country. More than a hundred species were studied under various aspects, including the production and characterization of essential oils. As part of this survey, the chemical composition of an essential oil sample obtained from Pentacalia herzogii (Asteraceae) growing wild in the High Valley region of the department of Cochabamba was determined by a combination of GC and GC-MS measurements. α-Pinene was the main constituent of this essential oil (34%), accompanied by limonene (22%) and germacrene D (7.5%) as well as an important fraction of methoxylated monoterpenoids. They were mainly isomers of thymol methyl ether, accounting for 13% of the chromatogram. A new quantitatively important compound (9%) was identified through NMR and chemical synthesis as 4-isopropyl-6-methylbenzo[d][1,3]dioxole, and designated herzogole, alongside the minor related compound 1-isopropyl-2,3-dimethoxy-5-methylbenzene. The monoterpene benzodioxole featured a distinctive green-phenolic aroma which could raise interest for fragrance use. Since these compounds were not known naturally, a biosynthetic mechanism of their formation was proposed and put in perspective to illustrate the metabolic originality of P. herzogii.