α-Stereoselective 3-Deoxy-d-manno-oct-2-ulosonoic Acid (Kdo) O-Glycosylation with a p-Toluenethioglycoside Donor by the (p-Tol)2SO/Tf2O Preactivation Strategy.

A convenient and efficient approach was developed to synthesize α-Kdo O-glycosides based on the Tf2O/(p-Tol)2SO preactivation strategy using peracetylated Kdo thioglycoside as a donor. Under the optimized reaction conditions, several O-glycoside products, including α-(2 → 1)-, α-(2 → 2)-, α-(2 → 3)-, and α-(2 → 6)-Kdo products, were stereoselectively synthesized in high yields. Remarkably, a series of aromatic α-Kdo O-glycosides were first and successfully constructed in high yields. An SN2-like mechanism was revealed by DFT calculations and experimental results.

Chemical constituents isolated from stems of Schisandra chinensis and their antifeedant activity against Tribolium castaneum.

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 chromatography. Based on the results of MS, NMR spectra and comparing with literature data, the six dibenzocyclooctadiene lignans were identified as schizandrin A to C (1-3), schizandrin (4), schisantherin A (5) and gomisin J (6), the two sesquiterpenes were identified as α-iso-cubebenol (7) and α-iso-cubebenol acetate (8), while the two triterpenic acids were identified as ganwuweizic acid (9) and kadsuric acid (10). The antifeedant activity of the 10 compounds against Tribolium castaneum adults was tested. Gomisin J (6) exhibited activity at 1500 ppm concentration with 40.3% antifeeding index percentages. As for the dibenzocyclooctene lignans (compounds 1-3, 6), the number of methylenedioxies and the position of hydroxyl groups were the main factors to affect their antifeedant activities.

Contact toxicity and repellent efficacy of Valerianaceae spp. to three stored-product insects and synergistic interactions between two major compounds camphene and bornyl acetate.

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.

Insecticidal and repellent efficacy against stored-product insects of oxygenated monoterpenes and 2-dodecanone of the essential oil from Zanthoxylum planispinum var. dintanensis.

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.

Seven herbs against the stored product insect: Toxicity evidence and the active sesquiterpenes from Atractylodes lancea.

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 (ß-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 ß-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, N­diethyl­3­methylbenzamide), 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.

Contact Toxicity and Repellency of the Essential Oils of Evodia lenticellata Huang and Evodia rutaecarpa (Juss.) Benth. Leaves against Three Stored Product Insects.

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%), ß-caryophyllene (23.1%), ß-elemene (14.5%), and ß-cubebene (4.7%), while the main components of the E. rutaecarpa EO are α-pinene (39.4%), ß-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.

Toxicity and repellency of essential oil from Evodia lenticellata Huang fruits and its major monoterpenes against three stored-product insects.

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%), ß-pinene (11.5%), 3-carene (9.6%), caryophyllene oxide (8.7%) and ß-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.

Supercritical carbon dioxide extract of Cinnamomum cassia bark: toxicity and repellency against two stored-product beetle species.

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.

Fumigant and repellent activities of essential oil extracted from Artemisia dubia and its main compounds against two stored product pests.

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.

Chemical Constituents of Murraya tetramera Huang and Their Repellent Activity against Tribolium castaneum.

Sixteen compounds were isolated from the leaves and stems of Murrayatetramera 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-1ß,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.

NMR solution structure study of one saturated sulphur-containing amides from Glycosmis lucida.

One sulphur-containing amide (N-[2-(4-Hydroxyphenyl)-ethyl]-3-methanesulfonyl-N-methyl-propionamide) which was isolated from Glycosmis lucida Wall ex Huang had a different NMR profile with this kind of compounds' normal case. Based on the information obtained by nuclear magnetic resonance pectroscopy (NMR) and mass spectrometry (MS), its configurations in solution were investigated. The results indicated that the compound would have two stable configurations in solution as the double bond switched between C-N and C-O in an appropriate rate. This phenomenon was clearly exposed by the one dimension selective NOE (1D-NOE) experiments. This conclusion would play an active role in the structure analysis work of this kind of compounds.

Repellence of the main components from the essential oil of Glycosmis lucida Wall. ex Huang against two stored product insects.

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 ß-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.

Chemical Composition of Essential Oils from Zanthoxylum bungeanum Maxim. and Their Bioactivities against Lasioderma serricorne.

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.

Chemical Constituents and Insecticidal Activities of Ajania fruticulosa Essential Oil.

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.

Essential Oil of Amomum maximum Roxb. and Its Bioactivities against Two Stored-Product Insects.

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 ß-pinene (23.39%), ß-caryophyllene (16.43%), α-pinene (7.55%), sylvestrene (6.61%) and ç-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.

Chemical Constituents and Activity of Murraya microphylla Essential Oil against Lasioderma serricorne.

The chemical composition, contact and repellent activities of the essential oil from Murraya microphylla branches and leaves against Lasioderma serricorne adults were determined and six compounds from the essential oil were isolated as well. The essential oil of M microphylla obtained by hydrodistillation was analyzed by gas chromatography-mass spectrometric (GC-MS) analysis; 22 compounds were identified. The main constituents of the essential oil included ß-caryophyllene (18.0%), α-pinene (13.8%), spathulenol (9.5%), α-humulene (6.0%), γ-elemene (5.1%) and zingiberene (4.6%), followed by α-cadinol (3.9%) and caryophyllene oxide (3.8%). Six of these compounds were isolated and fully identified as α-pinene, ß-caryophyllene, α-humulene, caryophyllene oxide, spathulenol and α-cadinol. L. serricorne adults had different sensitivities to the crude essential oil and isolated compounds. α-Humulene exhibited the strongest contact activity against L. serricorne, showing an LD50 value of 13.1 µg adult(-1). However, spathulenol, the crude essential oil and α-cadinol showed stronger contact activity against L. serricorne than caryophyllene oxide and ß-caryophyllene. The essential oil, α-humulene and spathulenol showed comparable repellency against L. serricorne adults at 2 h after exposure, relative to the positive control, DEET. The results demonstrate that the essential oil and isolated compounds exhibited important contact and repellent activities against L. serricorne. Thus, they could become potential natural insecticides or repellents for control of insects in stored products.

Repellent activity of Glycosmis plant extracts against two stored product insects / Actividad repelente de extractos de plantas Glycosmis contra dos insectos de productos almacenados

In the present study, the repellent activities of the leaf and/or stem crude extracts of Glycosmis lucida Wall. ex Huang, G. craibii var. glabra, G. craibii Tanaka, G. oligantha Huang, G. pentaphylla (Retz) Correa. and G. esquirolii (Levl.) Tanaka were analyzed by using assays on petri dishes against Tribolium castaneum and Liposcelis bostrychophila. The leaf and stem extracts of G. lucida, G. craibii var. glabra, G. craibii Tanaka, G. oligantha and G. esquirolii possessed significant repellent activities against T. castaneum, the same level repellent with the positive control, DEET. However, the extracts of G. pentaphylla, no repellency but some insect attractant was observed. Moreover, they also showed repellent activities against L. bostrychophila. These results indicate that extracts from G. lucida and G. oligantha leaf could be a source of novel repellent against insects.

En el presente estudio, las actividades repelentes de la hoja y/o tronco de los extractos crudos de Glycosmis lucida Wall. ex Huang, G. craibii var. glabra, G. craibii Tanaka, G. oligantha Huang, G. pentaphylla (Retz) Correa y G. esquirolii (Levl.) Tanaka se analizaron mediante el uso de ensayos en placas de Petri contra Tribolium castaneum y Liposcelis bostrychophila. Los extractos de las hojas y tallo de G. lucida, G. craibii var. glabra, G. craibii Tanaka, G. oligantha y G. esquirolii poseían actividades repelentes significativas contra T. castaneum, el mismo nivel repelente del control positivo, el DEET. Sin embargo, los extractos de G. pentaphylla, no se observó la repelencia pero sí actividad atrayente de insectos. Por otra parte, también se mostraron las actividades repelentes contra L. bostrychophila. Estos resultados indican que los extractos de hojas de G. lucida y G. oligantha podrían ser una fuente de repelente contra los insectos.

Chemical Composition and Bioactivity of Essential Oil of Atalantia guillauminii against Three Species Stored Product Insects.

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 ß-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.

Chemical Composition and Bioactivities of the Essential Oil from Etlingera yunnanensis against Two Stored Product Insects.

The chemical composition of the essential oil of Etlingera yunnanensis rhizomes and its contact and repellent activities against Tribolium castaneum (Herbst) and Liposcelis bostrychophila (Badonnel) were investigated. The essential oil obtained from E. yunnanensis rhizomes with hydrodistillation was performed by gas chromatography-flame ionization detection and gas chromatography-mass spectrometry. The main components of the essential oil were identified to be estragole (65.2%), ß-caryophyllene (6.4%), 1,8-cineole (6.4%), limonene (5.2%), and α-pinene (2.4%). It was found that the essential oil of E. yunnanensis rhizomes possessed contact toxicity against T. castaneum and L. bostrychophila (LD50 = 23.33 µg/adult and LD50 = 47.38 µg/cm², respectively). Estragole, 1,8-cineole, and limonene exhibited stronger contact toxicity (LD50 values of 20.41, 18.86, and 13.40 µg/adult, respectively) than ß-caryophyllene (LD50 = 41.72 µg/adult) against T. castaneum adults. Estragole possessed stronger contact toxicity (LD50 = 30.22 µg/cm²) than ß-caryophyllene, 1,8-cineole, and limonene (LD50 values of 74.11, 321.20, and 239.62 µg/adult, respectively) against L. bostrychophila adults. Repellency of the crude oil was also evaluated. The essential oil and constituents possessed strong repellent activity against T. castaneum adults. The four individual constituents showed weaker repellent activity than the essential oil against L. bostrychophila adults. The results indicated that the essential oil of E. yunnanensis rhizomes and the individual constituents had the potential to be developed as a natural insecticide and repellent for the control of T. castaneum and L. bostrychophila.