Search

By implementing NMR, inductively coupled plasma-atomic emission spectrometry (ICP-AES), and the UV–vis spectroscopic techniques, metabolites, mineral elements, and antioxidant activities (DPPH) of Peganum harmala L. samples from Manasi and Fuhai of Xinjiang were studied in this research to investigate the geographical environment impact at the molecular level. First of all, partial least squares discriminant analysis was conducted to explore differential endogenous metabolites. A total of 18 metabolites were identified, and 14 mineral element contents were calculated quantitatively, which displayed diverse changing trends from these two origins. Valine, succinic acid, betaine, sucrose, and vasicine exhibited significant differences between these two groups as well as mineral nutrient profiles (Mg, Cu, N, K, Na, P, Zn, C) and DPPH antioxidant activities (EC50). The obvious different characteristics of chemical components and antioxidant activities in these two groups were further verified by heat map cluster analysis. Pearson correlation analysis also revealed the remarkable relationship of chemical components and antioxidant activities, which are strongly associated with the regional environment. This study showed that the combination of methodologies proposed will be highly useful in evaluating the environmental variation and diversity in terrestrial ecosystems.

The insecticidal and repellent activities of the essential oil (EO) from Atalantia buxifolia leaves were evaluated against three stored product insects, including Tribolium castaneum, Lasioderma se...

Essential oils (EOs) extracted from leaves (EL) and fruit pericarp (EFP) of Zanthoxylum planispinum var. dintanensis were analyzed for their chemical composition by GC-MS technique and evaluated for their fumigant, contact toxicity and repellency against three stored-product insects, namely Tribolium castaneum, Lasioderma serricorne, and Liposcelis bostrychophila adults. Results of GC-MS analysis manifested that EL and EFP of Z. planispinum var. dintanensis were mainly composed of oxygenated monoterpenes. Major components included linalool, sylvestrene and terpinen-4-ol. The obvious variation observed between two oil samples was that EL contained 2-dodecanone (11.52%) in addition to the above mentioned components, while this constituent was not detected in EFP. Bioassays of insecticidal and repellent activities were performed for EL, EFP as well as some of their individual compounds (linalool, terpinen-4-ol and 2-dodecanone). Testing results indicated that EL, EFP, linalool, terpinen-4-ol and 2-dodecanone exhibited potent insecticidal and repellent activities against the three target insects selected. Among the three individual compounds, 2-dodecanone was significantly toxic to T. castaneum (LD50 = 5.21 μg/adult), L. serricorne (LD50 = 2.54 μg/adult) and L. bostrychophila (LD50 = 23.41 μg/cm2) in contact assays and had beneficial repellent effects on L. serricorne at 2 and 4 h post-exposure. The anti-insect efficacy of Z. planispinum var. dintanensis EO suggests it has potential to be used as botanical insecticide or repellent to control pest damage in warehouses and grain stores.

Continuous use of synthetic insecticides increases environmental contamination and resistance in many species. Botanical insecticides, such as essential oil, were considered to be suitable alternatives due to multiple modes of action and low mammalian toxicity. Haplophyllum dauricum is a overlooked plant for the control of stored-product insects. Five essential oils (EOs) from Haplophyllum dauricum collected in October and November, rich in pinene, were extracted and evaluated on anti-insect activity against two stored-product insects, Tribolium castaneum (Coleoptera: Tenebrionidae) and Lasioderma serricorne (Coleoptera: Anobiidae). The lethal doses (LD50 and LD90), lethal concentrations (LC50 and LC90) and percentage repellency (PR) were evaluated. The GC-MS analysis showed that pinene (α-pinene and β-pinene) were major constituent of the EOs (54.61% and 57.33% in fruits, 46.80% in stems + leaves, and 30.57% in leaves), followed by β-phellandrene (14.49% and 21.34% in fruits and leaves), 3-carene (26.84% in leaves) and limonene (15.77%, 11.09%, 12.40%, 7.59%, and 6.24% in five EOs, respectively). Five EOs and selected major compounds provided promising fumigant, contact and repellent activity against T. castaneum and L. serricorne. The EO of stems + leaves collected in October showed the strongest contact toxicity on T. castaneum (LD50 = 20.21μg/adult), as well as fumigant and contact toxicity on L. serricorne (LC50 = 17.17 mg/L air, LD50 = 25.46 μg/adult). All the five EOs exhibited effective repellent activity (PR>80%) against T. castaneum. The results highlight that the EOs from H. dauricum have a promising potential as eco-friendly botanical insecticides.

The aim of this research was to determine the chemical constituents and toxicity of the oil derived from Alpinia katsumadai seeds against Tribolium castaneum, Liposcelis bostrychophila and Lasioder...

In this work, the essential oils (EO) were extracted from seven typical Chinese herbs, and their repellent and contact toxicities against Tribolium castaneum adults (red flour beetles) were evaluated. The experimental results showed that the above EOs presented the various levels of repellent and contact toxicities. The EOs extracted from A. lancea and A argyi of the Compositae (Asteraceae) family presented obvious repellent effects (Repellency Percentage > 90% at 3.15 nL/cm2 after 4 h exposure) and strong contact toxicity with LD50 values of 5.78 and 3.09 μg/adult respectively. Based on literature researches and screening results, the EO from A. lancea was analyzed by GC-MS and chosen for further identification of bioactive components. Altogether 59 chemical components were identified and 17 of them were recognized as sesquiterpene compounds, accounting for 57.8% of the total weight of the EO. From the identified sesquiterpenes, three individual compounds (β-eudesmol, hinesol, valencene) were selected for the laboratory bioassays of the toxicity against red flour beetles. It was found that all the three compounds expressed some repellent effects. Although β-eudesmol (31.2%) and hinesol (5.1%) were identified as main constituents and had been considered to be symbolic characteristics of high medicinal value, valencene (0.3%) showed strong repellent property which could be comparable to that of DEET (N, N‑diethyl‑3‑methylbenzamide), a powerful commercial pesticides, and it had best toxicity with LD50 values of 3.25 (μg/adult) in the contact test. This work may provide toxicity evidence of seven common herbs against red flour beetles, add the information for the development and comprehensive utilization of A. lancea, and will contribute to the application of grain preservation.

One new sesquiterpene (α-iso-cubebenol acetate, 8), together with 9 known compounds (1-7, 9, 10) were isolated from the stems of Schisandra chinensis (Turcz.) Baill. by repeated silica gel column c...

The extract from Cinnamomum cassia Presl bark was obtained with supercritical CO2 fluid extraction (SFE). Chemical components of the SFE extract were characterized by GC-MS spectrometry. The repellency and contact toxicity of the SFE extract were evaluated against the adults of Tribolium castaneum and Lasioderma serricorne along with those of its two main compounds. The results of GC-MS analysis indicated that 33 volatile constituents were identified from the extract. The main components included trans-cinnamaldehyde (32.1%), 3,3-dimethylhexane (10.6%) and 2,4-di-tert-butylphenol (7.9%). Testing results showed that the SFE extract had potent contact toxicity against T. castaneum and L. serricorne with LD50 values of 3.96 and 23.89 μg/adult, respectively. LD50 values of trans-cinnamaldehyde against T. castaneum and L. serricorne were 5.78 and 3.24 μg/adult, respectively. Additionally, percentage repellency values of the SFE extract and trans-cinnamaldehyde against T. castaneum and L. serricorne were rather high (PR = 100% and PR > 90%, respectively) at 78.63 and 15.73 nL/cm2 at 2 h post-exposure. 2,4-Di-tert-butylphenol showed some repellency against both beetle species. Considering its insecticidal and repellent effects, the SFE extract from C. cassia bark might be used in integrated pest management programs for T. castaneum and L. serricorne.

The essential oils (EOs) extracted from Evodia lenticellata Huang and Evodia rutaecarpa (Juss.) Benth. leaves are screened to evaluate their contact toxicity and repellency towards Tribolium castaneum (Coleoptera: Tenebrionidae), Lasioderma serricorne (Coleoptera: Anobiidae) and Liposcelis bostrychophila (Psocoptera: Liposcelididae) adults. The EOs are obtained by hydrodistillation and analyzed by gas chromatography-mass spectrometry (GC-MS). The principal components in the E. lenticellata EO are identified to be caryophyllene oxide (28.5%), β-caryophyllene (23.1%), β-elemene (14.5%), and β-cubebene (4.7%), while the main components of the E. rutaecarpa EO are α-pinene (39.4%), β-elemene (13.5%), α-ocimene (7.6%), and α-selinene (4.0%). These two kinds of EOs and their individual compounds all showed different levels of contact toxicity and repellent activity against three stored-product insects.

The Amomum villosum essential oil was obtained from hydrodistillation and was investigated by GC-MS. The main constituents were bornyl acetate (51.6%), camphor (19.8%), camphene (8.9%) and limonene (6.2%). Insecticidal toxicity of the essential oil was evaluated in this study. It showed that the essential oil possessed contact toxicity against Tribolium castaneum and Lasioderma serricorne (LD50 = 32.4 and 20.4 μg/adult). Three monoterpenoids camphor, camphene and limonene showed strong fumigant toxicity against T. castaneum (LC50 ＜ 2.3, LC50 ＝ 6.2 and 6.2 mg/L air). In addition, repellency of the essential oil was also evaluated. Data showed that the essential oil and all four compounds had repellent activity against T. castaneum and L. serricorne at high concentration (78.63 nL/cm2). But with the decrease of concentration, they showed a different degree of attractant properties.

Five polyacetylenes (1-5) were isolated from Artemisia ordosica, one of the main arido-active shrubs growing in the arid areas in China. Their molecular structures were identified with NMR spectroscopy. The compounds were confirmed as capillene, capillin, capillinol, cis-dehydromatricaria ester and trans-dehydromatricaria ester. It was found that three compounds (1-3) had similiar structural skeleton of 2,4-hexadiyn-1-ylbenzene. The repellent and fumigant activities against Tribolium castaneum adults were investigated for compounds isolated and the essential oil. Bioassays showed that the essential oil extracted from the aerial parts of A. ordosica possessed fumigant toxicity of LC50 = 18.65 mg/L air, and compounds (1-4) had stronger activities from LC50 = 4.06 mg/L air to 6.16 mg/L air against T. castaneum adults. At the tested concentrations (62.91 and 12.58 nL/cm2), the crude essential oil and compounds (1, 2 and 4) showed the same repellent activity (p > 0.05) with DEET against T. castaneum adults at both 2 h and 4 h after exposure. Compound 2 showed strong repellence (PR = 100%) at tested concentrations of 62.91, 12.58 and 2.52 nL/cm2 at 2 h after exposure. Moreover, at tested concentration (62.91, 12.58, 2.52 and 0.5 nL/cm2), the PR value of compound 4 was all higher than 90% at both 2 h and 4 h after exposure. The results showed that the crude essential oil and the isolated polyacetylenes possessed fair repellent and fumigant activities. Furthermore, potential relationships between structure and bioactivity were also discussed. It might be found that the existence of acetylenic bonds was the principal factor of fumigant activity, and with the increase of acetylenic bonds, the fumigant activity would enhance. In addition, it was believed that oxygenous groups connected to the acetylenic bonds might contribute to fumigant toxicity against T. castaneum adults.

Murraya alata Drake is a shrub that is distributed in the underwood of sandy areas near sea level in China and Vietnam. Twenty-two compounds were isolated from the leaves and stems of M. alata, including six new coumarins (6, 8–10, 17, 19) named muralatins L–Q. The structures were identified on the base of NMR and MS spectral analysis. Furthermore, the repellent activity against Tribolium castaneum was tested for fourteen isolated compounds. A statistic model-grey relational analysis was introduced to evaluate repellent activity directly based on relative correlation degree. This statistical analysis was suitable for complex problems of multiple indexes. The testing compounds exhibited various repellent activities against T. castaneum. Among them, compounds 1 (meranzin), 2 (phebalosin) and 16 (muralatin K) showed significant repellent activity against T. castaneum with ri values of 0.7047, 0.6990 and 0.6884, respectively, comparable to that of the positive control, N, N-diethyl-3-methylbenzamide (DEET, ri = 0.7013). The optimal compounds might be considered as potential leading compounds for the development of natural repellents.

The objective of this study was to analyze six essential oils fromZanthoxylumgenus (family Rutaceae) in China and evaluate their repellent activities againstTribolium castaneumandLasioderma serricorneadults. Six essential oils fromZanthoxylumgenus, includingZ. armatum,Z. dimorphophyllum,Z. dimorphophyllumvar.spinifolium,Z. piasezkii,Z. stenophyllum,andZ. dissitum,were obtained by hydrodistillation and their yields were ranging from 0.02% to 0.53%. Totally, there were 39 chemical components revealed by GC-MS. Among them, some components with high relative content existed in more than threeZanthoxylumspecies. For instance, bothδ-cadinene (1.21%–17.15%) and spathulenol (0.36%–10.19%) appeared in essential oils ofZ. dimorphophyllum,Z. piasezkii,Z. stenophyllum,andZ. dissitumwhich were found to have higher content of sesquiterpenoids. The repellent activities of six essential oil samples againstT. castaneumandL. serricorneadults were investigated for the first time. Data demonstrated that sixZanthoxylumspecies had much stronger repellent activities againstT. castaneumthanL. serricorneadults, especially in 2 hours after exposure. The results indicate that these six essential oils fromZanthoxylumhave significant potential to be developed into natural repellents to control insects in grains, food, and traditional Chinese medicinal materials.

In this work, the essential oil (EO) and supercritical CO2 fluid extract (SF extract) of four Valerianaceae plants (Valeriana officinalis L., Valeriana officinalis L. var. latifolia Miq., Valeriana jatamansi Jones and Nardostachys chinensis Bat.) were chemically characterized. GC-MS analysis identified 74 compounds, representing 35.2%–82.4% of the total EOs and SF extracts. The EO was dominated by low-molecular-weight components while the SF extract was rich in fatty acids. Bornyl acetate and camphene were the characteristic compounds in EO and SF extracts. The efficacy of six extracts against three stored-product insects was investigated. In contact assays, V. officinalis exhibited strongest toxicity to red flour beetle (LD50 = 10.0 μg/adult), and V. jatamansi EO was the most active one against the cigarette beetle (LD50 = 17.6 μg/adult), while V. officinalis var. latifolia EO showed outstanding efficacy against the booklouse (LD50 = 40.2 μg/cm2). Binary mixtures of two major compounds (camphene and bornyl acetate) were assessed for the contact toxicity to the red flour beetle. Additive effect existed in the natural proportion of V. officinalis, and synergism was observed in that of V. officinalis var. latifolia. This work confirmed the insecticidal efficacy of the species of the Valerianaceae family, and it would offer some information for the development of botanical insecticide.

A screening of Chinese medicinal herbs and wild plants for agrochemicals was carried out; the essential oil of Glycosmis lucida leaves was found to possess significant repellent activity against Tribolium castaneum and Liposcelis bostrychophila. It was found that the main components included elixene (19.81%), spathulenol (10.68%), anethole (12.05%), verbenone (10.32%) followed by β-caryophyllene (6.87%). The essential oil, anethole and verbenone were strongly repellent against T. castaneum (96, 86 and 94%, respectively, at 15.73 nL cm−2) and L. bostrychophila (100, 68 and 72%, respectively, at 31.58 nL cm−2) after a 2h treatment. The results indicate that anethole and verbenone had the potential to be developed as natural repellents for control of stored product insects.

The insecticidal activity and chemical constituents of the essential oil from Ajania fruticulosa were investigated. Twelve constituents representing 91.0% of the essential oil were identified, and the main constituents were 1,8-cineole (41.40%), (+)-camphor (32.10%), and myrtenol (8.15%). The essential oil exhibited contact toxicity against Tribolium castaneum and Liposcelis bostrychophila adults with LD50 values of 105.67 μg/adult and 89.85 μg/cm(2) , respectively. The essential oil also showed fumigant toxicity against two species of insect with LC50 values of 11.52 and 0.65 mg/l, respectively. 1,8-Cineole exhibited excellent fumigant toxicity (LC50 = 5.47 mg/l) against T. castaneum. (+)-Camphor showed obvious fumigant toxicity (LC50 = 0.43 mg/l) against L. bostrychophila. Myrtenol showed contact toxicity (LD50 = 29.40 μg/cm(2) ) and fumigant toxicity (LC50 = 0.50 mg/l) against L. bostrychophila. 1,8-Cineole and (+)-camphor showed strong insecticidal activity to some important insects, and they are main constituents of A. fruticulosa essential oil. The two compounds may be related to insecticidal activity of A. fruticulosa essential oil against T. castaneum and L. bostrychophila.

Two essential oil samples were obtained from the pericarp of Zanthoxylum bungeanum with the methods of hydrodistillation (HD) and supercritical fluid CO2 extraction (SFE), their chemical components were identified, and their bioactivities against Lasioderma serricorne adults were evaluated. In the process of testing, the two samples showed significant bioactivities against Lasioderma serricorne adults. For an example, the SFE-sample expressed relatively stronger fumigant toxicity on Lasioderma serricorne adults (LC50 = 3.99 μg/mL air) than that of the HD-sample (LC50 = 12.54 μg/mL air). According to GC-MS analysis, the chemical components between two samples were different. The major chemical components for HD included linalool (25.99%), limonene (19.34%), linalyl anthranilate (12.22%), 4-terpinenol (10.49%), eucalyptol (6.53%) and α-terpineol (5.02%), while for SFE included nonanoic acid (21.43%), γ-terpinene (14.51%), eucalyptol (13.45%), α-terpineol (5.83%) and caryophyllene oxide (5.48%). The results showed that different chemical components result in different bioactivities. This work provides theoretical basis for traditional Chinese concept of antagonistic storage, and it also provides important information for the development and comprehensive utilization of Zanthoxylum bungeanum.

In this work, we investigated the chemical constituents of the essential oil extracted from the leaves of Rhododendron thymifolium and their insecticidal and repellent activities against Liposcelis bostrychophila and Tribolium castaneum. 14 chemical components were identified from the essential oil and included germacrone (20.83%), γ-elemene (11.10%), selina-3,7(11)-diene (6.18%), α-oxobisabolene (5.39%), β-sesquiphellandrene (2.44%), β-elemenone (35.17%), Z,Z,Z-1,5,9,9-tetramethyl-1,4,7,-cycloundecatriene (3.64%) and 1-(4-ethylphenyl)-3-methyl-pyrazol-(4H)-one (2.91%). Among them, the first five components were isolated and identified. The results showed that the essential oil and five pure compounds possessed the obvious repellent activity and various levels of contact activities against the two species of stored insects. The essential oil possessed the contact toxicity (LD50 = 19.63 μg/cm2) which was quite close to the toxicity of positive control pyrethrins (LD50 = 18.72 μg/cm2) against L. bostrychophila. The five pure compounds might individually or together effect the contact toxicity of the essential oil against L. bostrychophila. The essential oil possessed the contact toxicity (LD50 = 29.82 μg/adult) against T. castaneum, but only germacrone revealed strong contact toxicity (LD50 = 0.97 μg/adult), which was comparable with the toxicity of pyrethrins (LD50 = 0.24 μg/adult) among five compounds against T. castaneum. The existence of germacrone might be one of the key elements which affected the contact toxicity of R. thymifolium essential oil against T. castaneum. The insecticidal and repellent activities of essential oil and five compounds were evaluated, the results provide a basis of the development and utilization in the future for control of insects.

Murraya genus (family Rutaceae) has been widely used as local traditional medicines in East Asia. The chemical composition of essential oils extracted from six Murraya species and their repellent activity against Tribolium castaneum was investigated. From the samples of Murraya tetramera , Murraya euchrestifolia , Murraya koenigii , Murraya kwangsiensis , Murraya exotica , and Murraya alata , essential oils were obtained by hydrodistillation and their yields were various from 0.03 to 0.23%. All together 36 components were identified by GC–MS from the essential oils samples. The constituents with relatively higher contents included α-cedrene (4.22–21.82%), β-caryophyllene (8.15–27.73%), γ-elemene (4.38–12.65%), γ-selinene (3.80–21.09%), α-selinene (2.60–10.68%), α-zingiberene (2.08–12.68%), spathulenol (3.08–11.80%), caryophyllene oxide (1.58–10.59%), β-eudesmol (1.33–25.32%), etc. Moreover, eight compounds, which were recognized as significant components in the essential oils of M. tetramera , and M. kwangsiensis , were isolated and they were identified as α-terpinene, β-caryophyllene, α-caryophyllene, alloaromadendrene, spathulenol, β-eudesmol, camphene and caryophyllene oxide. The repellent activity against T. castaneum was tested for all the six samples of essential oils and eight isolated compounds. The testing samples exhibited a variety of repellent activity against T. castaneum . Among them, the essential oils of two species ( M. tetramera and M. kwangsiensis ) and three isolated compounds (alloaromadendrene, spathulenol and caryophyllene oxide) showed the fair repellent activity with relatively higher yields of contents. They might be considered as potential materials for the development of natural repellents for control of insects in stored products. Meanwhile, cluster analysis was performed using the collectives of data which were obtained in the process of the experiments. It was found that the characteristics of the repellent activity against T. castaneum could be related to the chemical composition of the essential oils. There were some interesting senses brought out as well. Such as, the repellent activity of the essential oils would not be depend on the contents of individual bioactive compound, and the existence of some compounds might affect the repellent activity of the essential oils.

Zanthoxylum species and volatile oils have shown to have insect resistance. The present work was conducted to find alternative botanical source with significant activity on storage pests control. Chemical examination of Zanthoxylum dimorphophyllum Hemsl. var. spinifolium Rehder et E. H. Wilson stem bark has led to fifteen coumarins, which including two were novel compounds named 6-(2′,3′-dihydroxy-3′-methylbutyl)-7-hydroxyl-8-(3″-methyl-2″-butenyl)-2H-1-benzopyran-2-one (7) and 6-(2′-hydroxyl-3′-methyl-3′-butenyl)-7-methoxyl-8-(3″-methyl-2″-butenyl)-2H-1-benzopyran-2-one (8). All the chemical structures were elucidated on the basis of nuclear magnetic resonance spectroscopy and high resolution electrospray ionization mass spectrometry analysis. Additionally, dose-dependent feeding deterrent activities of fifteen coumarins against Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae) were evaluated scientifically. Among them, compound 12 (phellopterin) exhibited stronger feeding deterrent activity (EC50 = 64.00 ppm) than the positive control, toosendanin. While, compound 11 (imperatorin) displayed the same level of feeding deterrent activity as the positive control with median effect concentration of 73.10 ppm. The relationship between chemical structure and effectiveness showed that compounds with epoxy structure or isopentenyl group exhibited higher feeding deterrent activities and might have potential to be developed into novel feeding deterrent reagents or potential lead compounds on storage insect prevention and control.

The essential oils (EOs) extracted from Evodia lenticellata Huang and Evodia rutaecarpa (Juss.) Benth. leaves are screened to evaluate their contact toxicity and repellency towards Tribolium castaneum (Coleoptera: Tenebrionidae), Lasioderma serricorne (Coleoptera: Anobiidae) and Liposcelis bostrychophila (Psocoptera: Liposcelididae) adults. The EOs are obtained by hydrodistillation and analyzed by gas chromatography-mass spectrometry (GC-MS). The principal components in the E. lenticellata EO are identified to be caryophyllene oxide (28.5%), β-caryophyllene (23.1%), β-elemene (14.5%), and β-cubebene (4.7%), while the main components of the E. rutaecarpa EO are α-pinene (39.4%), β-elemene (13.5%), α-ocimene (7.6%), and α-selinene (4.0%). These two kinds of EOs and their individual compounds all showed different levels of contact toxicity and repellent activity against three stored-product insects.

The speciation of a methanolic extract of Zanthoxylum armatum stem bark has enabled the isolation and characterization of 11 known lignans. Among them, five compounds (6, 8–11) are reported in this plant for the first time. All of the chemical structures were elucidated on the basis of NMR spectral analysis. Additionally, their antifeedant activities against Tribolium castaneum were evaluated scientifically. Among them, asarinin (1), with an EC50 of 25.64 ppm, exhibited a much stronger antifeedant activity than the positive control, toosendanin (EC50 = 71.69 ppm). Moreover, fargesin (2), horsfieldin (3), and magnolone (10), with EC50 values of 63.24, 68.39, and 78.37 ppm, showed almost the same antifeedant activity as the positive control. From the perspective of structure-effectiveness relationship, compounds with the chemical group of methylenedioxy exhibited higher antifeedant activities and have potential to be developed into novel antifeedants or potential lead compounds to protect food and crops in storage.

A nuclear magnetic resonance- (NMR-) based metabolomics method was used to identify differential metabolites of methanol extracts obtained from six parts of Peganum harmala L. (P. harmala), namely, the root, stem, leaf, flower, testa, and seed. Two multivariate statistical analysis methods, principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA), were combined to clearly distinguish among the P. harmala samples from the six different parts. Eleven differential components were screened by the PLS-DA loading plot, and the relative contents were calculated by univariate analysis of variance. Chemometric results showed significant differences in the metabolites of the different parts of P. harmala. The seeds contained large amounts of harmaline, harmine, and vasicine compared to other organs. The acetic acid, proline, lysine, and sucrose contents of the roots were significantly higher than those of the other parts. In the testa, the vasicine, asparagine, choline, and 4-hydroxyisoleucine contents were clearly dominant. The obtained data revealed the distribution characteristics of the metabolomes of the different P. harmala parts and provided fundamental knowledge for the rational development of its medicinal parts.

To develop natural product resources from the Clausena genus (Rutaceae), the essential oils (EOs) from four Clausena plants (Clausena excavata, C. lansium, C. emarginata, and C. dunniana) were analyzed by GC-MS. Their lethal (contact toxicity) and sublethal effects (repellency) against Liposcelis bostrychophila (LB) adults were also evaluated. Santalene sesquiterpene was the precursor substance of santalol, a valuable perfumery. It was found that plenty of α-santalol (31.7%) and α-santalane (19.5%) contained in C. lansium from Guangxi Province and α-santalene (1.5%) existed in C. emarginata. Contact toxicity of the four EOs was observed, especially C. dunniana (LD50 = 37.26 µg/cm2). Santalol (LD50 = 30.26 µg/cm2) and estragole (LD50 = 30.22 µg/cm2) were the two most toxic compounds. In repellency assays, C. excavate, C. lansium, and C. emarginata exhibited repellent effect at the dose of 63.17 nL/cm2 2 h after exposure (percentage repellencies were 100%, 98%, and 96%, respectively). Four Clausena EOs and santalol had an excellent potential for application in the management of LB. Clausena plants could be further developed to find more resources of natural products.

In this work, the essential oil (EO) was extracted from the fruits of Evodia lenticellata, and the fumigant toxicity, contact toxicity and repellency against three stored-product insect species were evaluated for the obtained EO and several of its chemical components. The target insects were the adults of Tribolium castaneum (Coleoptera: Tenebrionidae), Lasioderma serricorne (Coleoptera: Anobiidae) and Liposcelis bostrychophila (Psocoptera: Liposcelididae). The EO was obtained with hydrodistillation and its chemical components were analyzed with the gas chromatography-mass spectrometry (GC-MS). Twenty-seven compounds, accounting for 83.1% of the total amount of the oil, were identified from the EO sample. The main compounds included linalool (12.0%), β-pinene (11.5%), 3-carene (9.6%), caryophyllene oxide (8.7%) and β-caryophyllene (7.9%). Among them, the amounts of monoterpenes and sesquiterpenes were as high as 52.7% and 22.7% to the total amount of EO respectively. The results of bioactivity test showed that the EO and its testing compounds had interspecific toxicity and repellent activity. So that, it might be expected that the EO extracted from the fruits of E. lenticellata could be developed to a new type of eco-friendly natural insecticide or repellent for the control of stored-product insects.

Antifeedant activities of the methanol extracts from Zanthoxylum bungeanum , Zanthoxylum schinifolium , Zanthoxylum armatum and Zanthoxylum dissitum were assessed on Tribolium castaneum adults. It was found that the methanol extract of stem bark of Z. schinifolium had the highest antifeedant activity at 41.12% (antifeedant index). Based on bioactivity-guided fractionation, six benzophenanthridines norchelerythrine ( 1 ), decarine ( 2 ), 8-hydroxy-9-methoxy-2,3-(methylenedioxy) benzophenanthridine ( 3 ), 6-hydroxydihydrochelerythrine ( 4 ), 6-methoxy-7-hydroxydihydrochelerythrine ( 5 ) and oxychelerythrine ( 6 ) were isolated from the stem barks of Z. schinifolium . And their antifeeding activities were also evaluated against T. castaneum . All of them exhibited strong antifeeding activity in a concentration-dependant manner with EC 50 of 62.67, 66.97, 151.39, 96.72, 141.61 and 192.32 ppm, respectively. The six bioactive compounds from the stem bark of Z. schinifolium might be used as antifeedants against T. castaneum .

Five new sulphur-containing amides (2, 5–8) and three known analogue compounds (1, 3–4) were isolated from the leaves of Glycosmis lucida which were collected in Yunnan province, China. Their structures were elucidated with NMR spectroscopy and mass spectrometry. The compounds were identified as N-(p-hydroxyphenethyl)-3-(methylsulfonyl)-propenamide (1), N-[2-(4- hydroxyphenyl)-ethyl]-3-methanesulfonyl-N-methyl-propionamide (2), methylgerambullin (3), methylisogerambullone (4), methylgerambullindiol (5), N-{2-[4-(6,7-hydroxy-3,7-dimethyl-oct- 2-enyloxy)-phenyl]-ethyl}-3-methanesulfonyl-N-methyl-acrylamide (6), N-{2-[4-(6,7-dihydroxy- 3,7-dimethyl-oct-2-enyloxy)-phenyl]-ethyl}-3-methanesulfonyl-N-methyl-propionamide (7), (E)-N-{2-[4-(6-hydroxy-7-dimethyl-oct-2-enyloxy)-phenyl]-ethyl}-3-methanesulfinyl-N-methyl- acrylamide (8). Feeding deterrent activities of these surphur-containing derivatives against Tribolium castaneum were assayed for the first time. Compound 2, 3, 6 possessed significant feeding deterrent activities against T. castaneum adults (EC50 = 311.6, 244.9 and 108.3 ppm, respectively). These results demonstrated that some sulphur-containing amides are promising candidates as insect antifeedant agents.

Rapeseeds (Brassica napus L.) are major source of edible oil-consumed in daily life. However, the high erucic acid content in some rapeseeds is harmful to the human health. So it is essential to explore a convenient and rapid method to identify which content of erucic acid is less than 5 %. Since the derivation procedure of traditional identification method (gas chromatography) is cumbersome, it consumes much time in analysis. In this work, a rapid method based on nuclear magnetic resonance (NMR) technology is developed. Firstly, 1H NMR spectra of rapeseeds extract were collected, and then 1H NMR data were analyzed by hierarchical cluster analysis and t test. The results indicated that statistically significant differences (p

The chemical composition of the essential oil obtained by hydrodistillation from the aerial parts of Mentha haplocalyx was investigated by GC-FID and GC/MS analyses. In sum, 23 components, representing 92.88% of the total oil composition, were identified, and the main compounds were found to be menthol (59.71%), menthyl acetate (7.83%), limonene (6.98%), and menthone (4.44%). By bioassay-guided fractionation (contact toxicity), three compounds were obtained from the essential oil and identified as menthol, menthyl acetate, and limonene. The essential oil and the three isolated compounds exhibited potent contact toxicity against Lasioderma serricorne adults, with LD50 values of 16.5, 7.91, 5.96, and 13.7 μg/adult, respectively. Moreover, the oil and its isolated compounds also exhibited strong repellency against L. serricorne adults. At the lower concentrations tested and at 2 h after exposure, menthol showed even significantly stronger repellency than the positive control DEET. The study revealed that the bioactivity properties of the essential oil can be attributed to the synergistic effects of its diverse major and minor components, which indicates that the M. haplocalyx oil and its isolated compounds have potential for the development as natural insecticides and/or repellents to control insects in stored grains and traditional Chinese medicinal materials.

During a screening program for new agrochemicals from Chinese medicinal herbs and local wild plants, the petroleum ether (PE) extract of Atractylodes lancea (Thunb.) rhizomes was found to possess repellent and contact activities against Tribolium castaneum adults. Bioactivity-directed chromatographic separation of PE extract on repeated silica-gel columns led to the isolation of two polyacetylenes, atractylodin and atractylodinol (1 and 2, resp.), and two lactones, atractylenolides II and III (3 and 4, resp.). The structures of the compounds were elucidated based on NMR spectra. The four isolated compounds were evaluated for their insecticidal and repellent activities against T. castaneum. Atractylodin exhibited strong contact activity against T. castaneum adults with a LD50 value of 1.83 μg/adult. Atractylodin and atractylenolide II also possessed strong repellenct activities against T. castaneum adults. After 4-h exposure,90% repellency was achieved with atractylodin at a low concentration of 0.63 μg/cm(2) . The results indicated that atractylodin (1) and atractylenolide II (3) have a good potential as a source for natural repellents, and 1 has the potential to be developed as natural insecticide.

The insecticidal and repellent activities of the essential oil extracted from Zingiber purpureum Roscoe rhizomes were evaluated against Tribolium castaneum (Herbst) and Lasioderma serricorne (L.) adults. During our screening program for agrochemicals from Chinese medicinal herbs and wild plants, the essential oil of Z. purpureum rhizomes was found to possess strong contact toxicity against T. castaneum and L. serricorne adults, with LD50 values of 39.0 and 16.3 µg per adult, respectively, and also showed strong fumigant toxicity against the two grain storage insects with LC50 values of 13.6 and 9.3 mg/liter of air, respectively. The essential oil obtained by hydrodistillation was investigated by gas chromatography-mass spectrometry. The main components of the essential oil were identified to be sabinene (48.1%), terpinen-4-ol (25.1%), and γ-terpinene (6.7%), followed by α-terpinene (4.3%), β-thujene (3.4%), and α-phellandrene (2.7%). Sabinene, terpinen-4-ol, and γ-terpinene were separated and purified by silica gel column chromatography and preparative thin-layer chromatography. Terpinen-4-ol showed the strongest contact toxicity against T. castaneum and L. serricorne (LD50=19.7 and 5.4 µg per adult, respectively) and also the strongest fumigant toxicity against T. castaneum and L. serricorne (LC50=3.7 and 1.3 mg/liter of air, respectively). Otherwise, sabinene and terpinen-4-ol were strongly repellent against T. castaneum as well as the essential oil, while γ-terpinene exhibited weaker repellency against T. castaneum compared with the positive control, DEET (N, N-diethyl-3-methylbenzamide). Moreover, only the essential oil exhibited strong repellency against L. serricorne, the three compounds exhibited weaker repellency against L. serricorne relative to DEET.

The toxic and repellent activities of the essential oil extracted from the leaves of Atalantia guillauminii Swingle were evaluated against three stored product insects, red flour beetles (Tribolium castaneum), cigarette beetles (Lasioderma serricorne) and booklice (Liposcelis bostrychophila). The essential oil obtained by hydrodistillation was investigated by GC-MS. The main constituents of the essential oil were β-thujene (27.18%), elemicin (15.03%), eudesma-3, 7(11)-diene (9.64%), followed by (-)-4-terpeniol (6.70%) and spathulenol (5.25%). The crude oil showed remarkable contact toxicity against T. castaneum, L. serricorne adults and L. bostrychophila with LD50 values of 17.11, 24.07 µg/adult and 55.83 µg/cm(2) respectively and it also displayed strong fumigant toxicity against T. castaneum, L. serricorne adults with LC50 values of 17.60 and 12.06 mg/L respectively, while weak fumigant toxicity against L. bostrychophila with a LC50 value of 16.75 mg/L. Moreover, the essential oil also exhibited the same level repellency against the three stored product insects, relative to the positive control, DEET. At the same concentrations, the essential oil was more repellent to T. castaneum than to L. serricorne. Thus, the essential oil of A. guillauminii may be potential to be developed as a new natural fumigant/repellent in the control of stored product insects.

In the course of our search for natural bioactive chemicals and investigations on their insecticidal activities from some medicinal plants growing in China, the essential oil derived from the twigs of Zanthoxylum armatum (Rutaceae) was found to possess strong insecticidal activities against two stored-product insects, Lasioderma serricorne and Tribolium castaneum. A total of 32 constituents of the essential oil were identified by GC and GC-MS analysis, and it revealed (E)-anethole (20.5%), 1,8-cineole (14.0%), 2-tridecanone (12.5%), limonene (9.0%) and piperitone (8.0%) as major components, followed by β-phellandrene (6.3%), β-pinene (5.1%) and 4-terpineol (4.4%). From the essential oil, five compounds were isolated and identified as (E)-anethole, 1,8-cineole, 2-tridecanone, limonene and piperitone. The results of insecticidal bioassays showed that the essential oil of Z. armatum exhibited strong fumigant toxicity towards L. serricorne and T. castaneum with LC50 values of 13.83 and 4.28 mg/L air, respectively, and also possessed contact toxicity against two insect species with LD50 values of 18.74 and 32.16 μg/adult, respectively. Among the active compounds, piperitone performed the strongest fumigant toxicity against L. serricorne (LC50 = 1.21 mg/L air) and contact toxicity against T. castaneum (LD50 = 3.16 μg/adult). 1,8-Cineole, limonene and piperitone showed similar fumigant toxicity against T. castaneum with LC50 values of 5.47, 6.21 and 7.12 mg/L air, respectively. Meanwhile, L. serricorne was the most sensitive to 2-tridecanone (LD50 = 5.74 μg/adult) in the progress of contact toxicity assay.

Dendranthema indicum (L.) Des Moul. is a perennial herb commonly used as a traditional Chinese medicine for a long time. In this work, we took Dendranthema indicum as a target plant and two stored insects which include Tribolium castaneum and Stegobium paniceum adults as target insects. Essential oil obtained from Dendranthema indicum was analyzed by gas chromatography-mass spectrometry (GC-MS). A total of 31 components representing 92.44% of the oil were identified and the main compounds were found to be chamazulene (15.93%), β-caryophyllene (13.78%), germacrene D (9.11%), and b-cis-farnesene (6.59%). With a further isolation, three constituents were obtained from the essential oil and identified as chamazulene, β-caryophyllene and eucalyptol. Significantly, in the progress of assay, it showed that the essential oil and chamazulene exhibited stronger insecticidal and repellent activities against Stegobium paniceum than Tribolium castaneum. The results indicate that additional to its traditional use as Chinese medicinal herb, the essential oil of Dendranthema indicum aerial parts and isolated compounds have potential to be developed into natural insecticides or repellents for control of insects in stored grains.

Amomum maximum Roxb. is a perennial herb distributed in South China and Southeast Asia. The objective of this work was to analyze the chemical constituents and assess insecticidal and repellent activities of the essential oil from Amomum maximum fruits against Tribolium castaneum (Herbst) and Liposcelis bostrychophila (Badonnel). The essential oil was obtained by hydrodistillation and analyzed by gas chromatography-flame ionization detector and gas chromatography-mass spectrometry. The main components of the essential oil were identified to be β-pinene (23.39%), β-caryophyllene (16.43%), α-pinene (7.55%), sylvestrene (6.61%) and c-cadinene (4.19%). It was found that the essential oil of A. maximum fruits possessed contact and fumigant toxicities against T. castaneum adults (LD50 = 29.57 μg/adult and LC(50) = 23.09 mg/L air, respectively) and showed contact toxicity against L. bostrychophila (LD(50) = 67.46 μg/cm(2)). Repellency of the crude oil was also evaluated. After 2 h treatment, the essential oil possessed 100% repellency at 78.63 nL/cm(2) against T. castaneum and 84% repellency at 63.17 nL/cm(2) against L. bostrychophila. The results indicated that the essential oil of A. maximum fruits had the potential to be developed as a natural insecticide and repellent for control of T. castaneum and L. bostrychophila.

Monitoring physical training is important for the health and performance of athletes, and real-time assessment of fatigue is crucial to improve training efficiency. The relationship between key biomarkers and exercise has been reported. The aim of this study was to determine the effects of different levels of training exercises on the urine metabolome.1H NMR-based metabolomics analysis was performed on urine samples from half-pipe snowboarders, and spectral profiles were subjected to PCA and PLS-DA. Our results show that metabolic profiles varied during different stages of exercises. Lactate, alanine, trimethylamine, malonate, taurine, and glycine levels decreased while TMAO and phenylalanine levels increased in the stage with higher amount and intensity of exercise. Although the amount of exercise was reduced in subsequent stage, no significant variations of metabolic profile were found. Metabolic changes induced by training level were analyzed with related metabolic pathway. Studying metabolome changes can provide a better understanding of the physiology of athletes and could aid in adjusting training.

Artemisia stolonifera, a perennial herb, is widely distrbuted in China. The aim of this study was to analyze the essential oil from the aerial parts of Artemisia stolonifera, as well as to evaluate the bioactivity of the oil and its main constituents. The essential oil was analyzed by gas chromatography-flame ionization detector and gas chromatography-mass spectrometry that allowed characterizing 22 compounds. The main components were eucalyptol (32.93%), β-pinene (8.18%), camphor (6.12%) and terpinen-4-ol (6.11%), and obtained from the essential oil after a further isolation. During the contact toxicity tests, the essential oil (LD50 = 8.60 μg/adult) exhibited stronger toxicity against Tribolium castaneum adults than those isolated constituents, however, camphor and terpinen-4-ol showed 1 and 2 times toxicity against Lasioderma serricorne adults than the essential oil (LD50 = 12.68 μg/adult) with LD50 values of 11.30 and 5.42 μg/adult, respectively. In the fumigant toxicity tests, especially on Tribolium castaneum, the essential oil (LC50 = 1.86 mg/L air) showed almost the same level toxicity as positive control, methyl bromide (LC50 = 1.75 mg/L air). Moreover, the essential oil and its four isolated constituents also exhibited strong repellency against two stored-product insects.

A new myrsinol-type diterpene (1), three myrsinol-type diterpenes (2–4), three ent-abietane-type diterpenes (5–7), one tigliane-type diterpene (8), two cycloartane-type triterpenes (9–10), and two tirucallane-type triterpenes (11–12) were isolated from the roots of Euphorbia nematocypha Hand.-Mazz. Their structures were identified by spectroscopic analyses and by comparison of their spectral data with those reported in the literature. Compound 12 was isolated and reported from plants for the first time. All compounds were isolated from E. nematocypha for the first time.

Sixteen compounds were isolated from the leaves and stems of Murraya tetramera Huang. Based on the NMR and MS spectral results, the structures were determined. It was confirmed that the isolated compounds included three new compounds (9, 10 and 13) and one new natural product (8), which were identified asmurratetra A (9), murratetra B (10), murratetra C (13) and [2-(7-methoxy-2-oxochromen-8-yl)-3-methylbut-2-enyl]3-methylbut-2-enoate (8), respectively. Meanwhile, the repellent activity against Tribolium castaneum was investigated for 13 of these isolated compounds. The results showed that the tested compounds had various levels of repellent activity against T. castaneum. Among them, compounds 1 (4(15)-eudesmene-1β,6α-diol), 11 (isoferulic acid) and 16 (2,3-dihydroxypropyl hexadecanoate) showed fair repellent activity against T. castaneum. They might be considered as potential leading compounds for the development of natural repellents.

The major chemical constituents of the essential oil extracted from Artemisia dubia wall. ex Bess. (Family: Asteraceae) were found as terpinolene (19.02%), limonene (17.40%), 2,5-etheno[4.2.2]propella-3,7,9-triene (11.29%), isoelemicin (11.05%) and p-cymene-8-ol (5.93%). Terpinolene and limonene were separated as main components from the essential oil. The essential oil showed fumigant toxicity against Tribolium castaneum and Liposcelis bostrychophila with LC50 values of 49.54 and 0.74 mg/L, respectively. The essential oil and isolated compounds of A. dubia showed repellency activities against both insects. Terpinolene and limonene showed the fumigant toxicity against T. castaneum. Terpinolene showed obvious fumigant toxicity against L. bostrychophila. The results indicated that the essential oil of A. dubia had potential to be developed into natural insecticides for controlling stored product pests.

Purple Perilla (Perilla frutescens (L.) Britt.) is an annual herb commonly used as a traditional Chinese medicine for more than 1000 years. This work investigated the chemical composition, insecticidal and repellent activities of the essential oil of Purple Perilla aerial parts against Lasioderma serricorne (Fabricius). Moreover, we also isolated active constituents from the essential oil. The experiment was investigated in 2013 in Beijing. The essential oil of Purple Perilla was obtained by hydrodistillation and a total of 47 components in the essential oil were identified with GC–MS. It was found that the main compounds included carvone (32.55%), perilla aldehyde (20.52%), caryophyllene (9.85%), 2-furyl methyl ketone (7.53%), 2,6-dimethyl-6-(4-methyl-3-pentenyl)-2-norpinene (5.17%), and β-terpinyl acetate (3.41%). With a further isolation, four active constituents were obtained from the essential oil and identified as R-(+)-carvone, perilla aldehyde, 2-furyl methyl ketone, and β-caryophyllene. In the progress of assay, it showed that the essential oil, R-(+)-carvone, perilla aldehyde, and 2-furyl methyl ketone exhibited stronger insecticidal and repellent activities against L. serricorne than β-caryophyllene. The results indicate that the essential oil of Purple Perilla aerial parts and isolated compounds have potential for development into natural insecticides or repellents for control of insects in stored products.

During our screening program for agrochemicals from Chinese medicinal herbs and wild plants, the essential oil of Litsea cubeba fruits was found to possess strong contact toxicity against the cigarette beetle Lasioderma serricorne adults and the booklouse Liposcelis bostrychophila , with LD 50 values of 27.33 μg/adult and 71.56 μg/cm 2 , respectively, and also showed strong fumigant toxicity against the two stored product insects with LC 50 values of 22.97 and 0.73 mg/L, respectively. The essential oil obtained by hydrodistillation was investigated by GC MS. The main components of the essential oil were identified to be E-citral (geranial) (27.49%), Z-citral (neral) (23.57%) and d -limonene (18.82%) followed by β-thujene (3.34%), β-pinene (2.85%), α-pinene (2.57%), 6-methyl-5-hepten-2-one (2.40%) and linalool (2.36%). Citral (Z/E-citral), d -limonene, β-pinene, α-pinene and linalool were separated and purified by silica gel column chromatography and preparative thin layer chromatography, and further identified by means of physicochemical and spectrometric analysis. Citral and linalool showed strong contact toxicity against L. serricorne and L. bostrychophila (LD 50 = 11.76, 12.74 μg/adult and 20.15, 99.97 μg/cm 2 , respectively) and fumigant toxicity against L. serricorne and L. bostrychophila (16.54, 18.04 mg/L air and 0.14, 0.71 mg/L air, respectively). Otherwise, citral, d -limonene and linalool were strongly repellent against the cigarette beetle L. serricorne as the essential oil whereas β-pinene and α-pinene exhibited weaker repellency against the cigarette beetle compared with the positive control, DEET. Moreover, except α-pinene and linalool, the other three compounds as well as the essential oil exhibited comparable repellency against the booklouse relative to DEET.