PxRdl2 dsRNA increased the insecticidal activities of GABAR-targeting compounds against Plutella xylostella.

The utilization of RNA interference (RNAi) for pest management has garnered global interest. The bioassay results suggested the knockout of the PxRdl2 gene significantly increased the insecticidal activities of the γ-aminobutyric acid receptor (GABAR)-targeting compounds (fipronil, two pyrazoloquinazolines, and two isoxazolines), thereby presenting a viable target gene for RNAi-mediated pest control. Consequently, we suggest enhancing the insecticidal activities of GABAR-targeting compounds by knockdown the transcript level of PxRdl2. Furthermore, PxRdl2 dsRNA was expressed in HT115 Escherichia coli to reduce costs and protect dsRNA against degradation. In comparison to in vitro synthesized dsRNA, the recombinant bacteria (ds-B) exhibited superior interference efficiency and greater stability when exposed to UV irradiation. Collectively, our results provide a strategy for insecticide spray that combines synergistically with insecticidal activities by suppressing PxRdl2 using ds-B and may be beneficial for reducing the usage of insecticide and slowing pest resistance.

Discovery and Biomimetic Synthesis of a Phloroglucinol-Terpene Adduct Collection from Baeckea frutescens and Its Biogenetic Origin Insight.

A phloroglucinol-terpene adduct (PTA) collection consisting of twenty-four molecules featuring three skeletons was discovered from Baeckea frutescens. Inspired by its biosynthetic hypothesis, we synthesized this PTA collection by reductive activation of stable phloroglucinol precursors into highly reactive ortho-quinone methide (o-QM) intermediates and subsequently Diels-Alder cycloaddition. We also demonstrated, for the first time, the generation process of the active o-QM by performing dynamic NMR and HPLC-MS monitoring experiments. Moreover, the PTA collection showed significant antifeedant effect toward the Plutella xylostella larvae.

Synthesis and antiphytoviral activity of α-aminophosphonates containing 3, 5-diphenyl-2-isoxazoline as potential papaya ringspot virus inhibitors.

α-Aminophosphonates compounds containing 3,5-diphenyl-2-isoxazoline were synthesized and evaluated for their bioactivity. Seventeen of them showed good bioactivity (protection effect > 50%) in vivo against papaya ringspot virus, while two of them (V29 and V45) exhibited excellent antiviral activity (both 77.8%). In the latter case, the antiviral activity was close to that of antiphytovirucides ningnanmycin and dufulin (both 83.3%) at 500 mg/L. The preliminary structure-activity relationships indicated that the bioactivity was strongly influenced by the substituents.

HFIP-Promoted Bischler Indole Synthesis under Microwave Irradiation.

1,1,1,3,3,3-Hexafluoropropan-2-ol (HFIP) was found to be effective for the Bischler indole synthesis under microwave irradiation in the absence of a metal catalyst. Under the catalysis of HFIP, a wide range of α-amino arylacetones were successfully transformed into indole derivatives with moderate to good yields.

Preparation, Characterization and Intracellular Imaging of 2,4-Dichlorophenoxyacetic Acid Conjugated Gold Nanorods.

Visualizing the biodistribution of pesticides inside living cells is great importance for enhancing targeting of pesticides. Here we reported for the first time that gold nanorods (Au NRs) with size of 39.4 nm x 11.3 nm could be used as a fluorescent tracer to examine the distribution of a typical herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), in tobacco bright yellow 2 (BY-2) cells. The nanostructures of hybrid materials were analyzed by using Raman spectra and X-ray photoelectron spectroscopy (XPS), including spectra assignments and electronic property. These data revealed 2,4-D has successfully conjugated MP-Au NRs according to Raman and XPS. The biodistribution of the conjugates inside BY-2 cells was directly examined at 12 and 24 h by the two-photon microscopy. The intensity of two-photon luminescence (TPL) inside cells demonstrated that the conjugates could be localized and excluded by BY-2 cells. Thus, this labeling approach opens up new avenues to the facile and efficient labeling of pesticides.

Flavonoids from Pronephrium megacuspe.

A chemical investigation of the whole plant of Pronephrium megacuspe (Bak.) Holtt. led to the isolation of four flavonoids, pronephrones A-D (1-4), which were firstly reported. The chemical structures of four compounds were established using spectroscopic methods. These isolates were further evaluated for cytotoxicity to ovarian cells of Spodoptera litura Fabricius.

Biosynthesis of Gold Nanoparticles Using Novel Bamboo (Bambusa chungii) Leaf Extracts.

Gold nanoparticles (Au NPs) have drawn significant interest because of their antisotropic physical properties in biomedical applications. In this paper, we reported the application of bamboo (Bambusa chung) leaf extracts, previously not exploited, in the synthesis of Au NPs at ambient temperature. The average dimension of quasi-spherical Au NPs was 28.8±4.5 nm by transmission electron microscopy (TEM). The UV-vis spectroscopy gave an optimal reaction time of 180 min in the process of bioreduction. The organic shell of Au NPs was characterized by Fourier transform infrared (FTIR) spectra and thermogravimetric analysis (TGA), suggesting that the main compositions of the organic shell were hydroxyflavones. The X-ray diffraction (XRD) studies indicated the Au NPs were (111) oriented. This eco-friendly method for the synthesis of Au NPs was simple, amenable for large scale commercial production and biological applications to future in vivo imaging and cancer therapy.

Design and synthesis of N-alkyl-N'-substituted 2,4-dioxo-3,4-dihydropyrimidin-1-diacylhydrazine derivatives as ecdysone receptor agonist.

Based on the discovery of thymine as an ecdysteroid agonist, a series of 1,4-disubstituted diacylhydrazine derivatives with a thymine moiety were designed and synthesized. The activities of these compounds against Spodoptera litura (Fabricius) were evaluated by the insect immersion method. Results showed that compound 2h with an N-cyclohexylmethyl substituent exhibits the most potent agonist activity with a median lethal concentration of 23.21 µg/mL. This compound also caused malformation of molting larvae and adults. Compound 2 h was further demonstrated as an ecdysteroid agonist by reporter gene assay on the Spodoptera frugiperda cell line (Sf9 cells). A molecular docking study indicated that hydrophobic interactions and the formation of hydrogen bonds between the compounds and the ecdysone receptor play critical roles in promoting the binding affinity of the compound. The structure of compound 2h may serve as a favorable template for the development of new ecdysteroid agonists with a pyrimidinedione moiety.

A new antifungal and cytotoxic C-methylated flavone glycoside from Picea neoveitchii.

A new C-methylated flavone glycoside, 5,7-dihydroxy-3-methoxy-6-C-methylflavone 8,4'-di-O-ß-D-glucopyranoside (1), was isolated from the twigs and leaves of Picea neoveitchii Mast, together with eight known compounds, 5,7,8,4'-tetrahydroxy-3-methoxy-6-methylflavone 8-O-ß-D-glucopyranoside (2) kaempferol 3,4'-di-O-ß-D-glucopyranoside (3), apigenin 7-O-ß-D-glucopyranoside (4), tiliroside (5), massonianoside B (6), umbeliferone 7-O-ß-D-glucopyranoside (7), dihydroconiferin (8) and gleditschiaside A (9). Their structures were elucidated on the basis of analyses of spectroscopic data. Compound 1 showed moderate antifungal activity against tested plant pathogens (Pyricularia grisea (Cooke) Sacc., Sclerotium rocfsii Sacc. and Alternaria mali Roberts), however, compounds 2 and 5 had obvious inhibitory effect against S. rocfsii and A. mali, respectively. Compounds 1, 2, 3 and 9 also exhibited potent cytotoxicity against Spodoptera litura Fabricius cells.

High quality gold nanorods and nanospheres for surface-enhanced Raman scattering detection of 2,4-dichlorophenoxyacetic acid.

Nearly monodisperse Au nanorods (NRs) with different aspect ratios were separated from home-synthesized polydisperse samples using a gradient centrifugation method. The morphology, size and its distribution, and photo-absorption property were analyzed by transmission electron microscopy, atomic force microscopy and UV-visible spectroscopy. Subsequently, using colloidal Au NRs (36.2 nm ×10.7 nm) with 97.4% yield after centrifugation and Au nanospheres (NSs) (22.9 ± 1.0 nm in diameter) with 97.6% yield as Au substrates, surface-enhanced Raman scattering (SERS) spectra of 2,4-dichlorophenoxyacetic acid (2,4-D) were recorded using laser excitation at 632.8 nm. Results show that surface enhancement factors (EF) for Au NRs and NSs are 6.2 × 10(5) and 5.7 × 10(4) using 1.0 × 10(-6) M 2,4-D, respectively, illustrating that EF value is a factor of ~10 greater for Au NRs substrates than for Au NSs substrates. As a result, large EF are a mainly result of chemical enhancement mechanisms. Thus, it is expected that Au NPs can find a comprehensive SERS application in the trace detection of pesticide residues.

Anthriscifolcine A, a C18-diterpenoid alkaloid.

The title compound, C(26)H(39)NO(7), which was isolated from Delphinium anthriscifolium var. majus, has a lycoctonine carbon skeleton containing four six-membered rings (A, B, D and E) and three five-membered rings (C, F and G). Rings A, B and E adopt chair conformation, while ring D adopts a boat conformation. Rings C and F adopt envelope conformations.

Distinct roles of two RDL GABA receptors in fipronil action in the diamondback moth (Plutella xylostella).

The phenylpyrazole insecticide fipronil blocks resistance to dieldrin (RDL) γ-aminobutyric acid (GABA) receptors in insects, thereby impairing inhibitory neurotransmission. Some insect species, such as the diamondback moth (Plutella xylostella), possess more than one Rdl gene. The involvement of multiple Rdls in fipronil toxicity and resistance remains largely unknown. In this study, we investigated the roles of two Rdl genes, PxRdl1 and PxRdl2, in P. xylostella fipronil action. In Xenopus oocytes, PxRDL2 receptors were 40 times less sensitive to fipronil than PxRDL1. PxRDL2 receptors were also less sensitive to GABA compared with PxRDL1. Knockout of the fipronil-sensitive PxRdl1 reduced the fipronil potency 10-fold, whereas knockout of the fipronil-resistant PxRdl2 enhanced the fipronil potency 4.4-fold. Furthermore, in two fipronil-resistant diamondback moth field populations, PxRdl2 expression was elevated 3.7- and 4.1-fold compared with a susceptible strain, whereas PxRdl1 expression was comparable among the resistant and susceptible strains. Collectively, our results indicate antagonistic effects of PxRDL1 and PxRDL2 on fipronil action in vivo and suggest that enhanced expression of fipronil-resistant PxRdl2 is potentially a new mechanism of fipronil resistance in insects.

1-[2,6-Dichloro-4-(trifluoro-meth-yl)phen-yl]-5-iodo-4-trifluoro-methyl-sulfinyl-1H-pyrazole-3-carbonitrile.

In the title compound, C(12)H(2)Cl(2)F(6)IN(3)OS, the dihedral angle between the planes of the benzene and pyrazole rings is 77.8 (2)°. In the crystal, a short I⋯N contact of 2.897 (5) Šoccurs.

DMSO-mediated palladium-catalyzed cyclization of two isothiocyanates via C-H sulfurization: a new route to 2-aminobenzothiazoles.

DMSO was found to activate arylisothiocyanates for self-nucleophilic addition. A subsequent intramolecular C-H sulfurization catalyzed by PdBr2 enables access to a wide range of 2-aminobenzothiazole derivatives in moderate to good yields. This is the first example of a DMSO-mediated Pd-catalyzed synthesis of 2-aminobenzothiazoles through cyclization/C-H sulfurization of two isothiocyanates.

AtLHT1 Transporter Can Facilitate the Uptake and Translocation of a Glycinergic-Chlorantraniliprole Conjugate in Arabidopsis thaliana.

Understanding of the transporters involved in the uptake and translocation of agrochemicals in plants could provide an opportunity to guide pesticide to the site of insect feeding. The product of Arabidopsis thaliana gene AtLHT1 makes a major contribution to the uptake into the roots of free amino acids and some of their derivatives. Here, a chlorantraniliprole-glycine conjugate (CAP-Gly-1) was tested for its affinity to AtLHT1 both in planta and in vitro. Seedlings deficient in AtLHT1 exhibited a reduction with respect to both the uptake and root-to-shoot transfer of CAP-Gly-1; plants in which AtLHT1 was constitutively expressed were more effective than wild type in term of their root uptake of CAP-Gly-1. Protoplast patch clamping showed that the presence in the external medium of CAP-Gly-1 was able to induce AtLHT1 genotype-dependent inward currents. An electrophysiology-based experiment carried out in Xenopus laevis oocytes expressing AtLHT1 showed that AtLHT1 had a high in vitro affinity for CAP-Gly-1. The observations supported the possibility of exploiting AtLHT1 as a critical component of a novel delivery system for amino acid-based pesticide conjugates.

The synthesis and photolarvicidal activity of 2,5-diarylethynylthiophenes.

The photoactivatable insecticides have photoactive features and broad applications. The derivatives of the alpha-terthienyl analogues were synthesized for evaluating their photolarvicidal activities and 13 2,5-diarylethynylthiophenes were investigated to determine their effect on the second-instar larvae of Plutella xylostella L. Based on their photolarvicidal activities, the 2,5-Dithienylethynylthiophene, 2,5-Diphenylethynylthiophene, 2,5-Di-4-Methoxylphenylethynylthiophene and 2,5-Di-3,4-Methylenedioxyphenylethynylthiophene were found to be the most potent compounds, and their LC(50) values were 34.1 mg l(-1), 48.4 mg l(-1), 60.8 mg l(-1) and 42.7 mg l(-1), respectively. The relationship analysis between structure and activity showed that the middle thiophene ring played an important role on the activities. The electron donor substituents increased the photolarvicidal activities and the length of the alkyl chain had negative influence on the activities.

Family of Ricinus communis Monosaccharide Transporters and RcSTP1 in Promoting the Uptake of a Glucose-Fipronil Conjugate.

Enhancing the systemic distribution of a bioactive compound by exploiting the vascular transport system of a plant presents a means of reducing both the volume and frequency of pesticide/fungicide application. The foliar uptake of the glucose-fipronil conjugate N-[3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazol-5-yl]-1-(ß-d-glucopyranosyl)-1H-1,2,3-triazole-4-methanamine (GTF) achieved in castor bean (Ricinus communis) and its transport via the phloem are known to be mediated by monosaccharide transporter(s) [MST(s)], although neither the identity of the key MST(s) involved nor the mechanistic basis of its movement have yet to be described. On the basis of homology with Arabidopsis thaliana sugar transporters, the castor bean genome was concluded to harbor 53 genes encoding a sugar transporter, falling into the eight previously defined subfamilies INT, PMT, VGT, STP, ERD6, pGlucT, TMT, and SUT. Transcriptional profiling identified the product of RcSTP1 as a candidate for mediating GTF uptake, because this gene was induced by exposure of the plant to GTF. When RcSTP1 was transiently expressed in onion epidermis cells, the site of RcSTP1 deposition was shown to be the plasma membrane. A functional analysis based on RcSTP1 expression in Xenopus laevis oocytes demonstrated that its product has a high affinity for GTF. The long-distance root-to-shoot transport of GTF was enhanced in a transgenic soybean chimera constitutively expressing RcSTP1.

Glycinergic-Fipronil Uptake Is Mediated by an Amino Acid Carrier System and Induces the Expression of Amino Acid Transporter Genes in Ricinus communis Seedlings.

Phloem-mobile insecticides are efficient for piercing and sucking insect control. Introduction of sugar or amino acid groups to the parent compound can improve the phloem mobility of insecticides, so a glycinergic-fipronil conjugate (GlyF), 2-(3-(3-cyano-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-5-yl)ureido) acetic acid, was designed and synthesized. Although the "Kleier model" predicted that this conjugate is not phloem mobile, GlyF can be continually detected during a 5 h collection of Ricinus communis phloem sap. Furthermore, an R. communis seedling cotyledon disk uptake experiment demonstrates that the uptake of GlyF is sensitive to pH, carbonyl cyanide m-chlorophenylhydrazone (CCCP), temperature, and p-chloromercuribenzenesulfonic acid (pCMBS) and is likely mediated by amino acid carrier system. To explore the roles of amino acid transporters (AATs) in GlyF uptake, a total of 62 AAT genes were identified from the R. communis genome in silico. Phylogenetic analysis revealed that AATs in R. communis were organized into the ATF (amino acid transporter) and APC (amino acid, polyaminem and choline transporter) superfamilies, with five subfamilies in ATF and two in APC. Furthermore, the expression profiles of 20 abundantly expressed AATs (cycle threshold (Ct) values <27) were analyzed at 1, 3, and 6 h after GlyF treatment by RT-qPCR. The results demonstrated that expression levels of four AAT genes, RcLHT6, RcANT15, RcProT2, and RcCAT2, were induced by the GlyF treatment in R. communis seedlings. On the basis of the observation that the expression profile of the four candidate genes is similar to the time course observation for GlyF foliar disk uptake, it is suggested that those four genes are possible candidates involved in the uptake of GlyF. These results contribute to a better understanding of the mechanism of GlyF uptake as well as phloem loading from a molecular biology perspective and facilitate functional characterization of candidate AAT genes in future studies.

Synthesis of spiroketal enol ethers related to tonghaosu and their insecticidal activities.

This paper describes the syntheses and biological activities of a number of spiroketal enol ethers which are analogues of the plant extract tonghaosu. The insecticidal potential of this spiroketal system is assessed.

Synthesis and antifeeding activities of Tonghaosu analogues.

Tonghaosu (1), a lead for a botanical antifeedant, and its 22 analogues were synthesized according to a previously reported concise and straightforward procedure. The structures of all new compounds were confirmed by NMR, IR, MS, and HREIMS or elemental analysis. Their insect antifeedant activities against the large white butterfly (Pieris brassicae L.) were examined, and six analogues (Z- and E-6h and Z-isomers of 6i-l), which contain 1,3-diyn or 3,4-methylenedioxyphenyl acetylene group, showed considerable antifeedant activity. Interestingly, Z-isomers of 6i-k are much more active than their corresponding E-isomers.