Synthesis and insect antifeedant activity of precocene derivatives with lactone moiety

Starting from precocenes I and II, four of their derivatives with a lactone moiety were obtained. The compounds have been assessed as antifeedants against several diverse insect species including the storage pests the confused flour beetle (Tribolium confusum Duv., larvae and adults), the granary weevil beetle (Sitophilus granarius L., adults), and the khapra beetle (Trogoderma granarium Ev., larvae) and against the herbivorous pest insects Colorado potato beetle (Leptinotarsa decemlineata Say, adults and larvae) and aphids (Myzus persicae Sulz.). Precocenes, especially precocene II, showed a very strong antifeedant effect against all storage pests and aphids. The introduction of a lactone moiety caused a decrease in antifeedant activity against these species. Both precocenes were moderately active against L. decemlineata adults. The best antifeedants to this species were precocene derivatives, especially iodolactones. The introduction of iodine into a molecule had a great effect on the antifeedant activity of those compounds.     

Citrus limonoids and their semisynthetic derivatives as antifeedant agents against Spodoptera frugiperda larvae. A structure-activity relationship study

The antifeedant activity of Citrus-derived limonoids limonin (1), nomilin (2), and obacunone (3) and their semisynthetic derivatives 4-26 was evaluated against a commercially important pest, Spodoptera frugiperda. Simple chemical conversions were carried out on the natural limonoids obtained from seeds of Citrus limon. These conversions focused on functional groups considered to be important for the biological activity, namely the C-7 carbonyl and the furan ring. In particular, reduction at C-7 afforded the related alcohols, and from these their acetates, oximes, and methoximes were prepared. Hydrogenation of the furan ring was also performed on limonin and obacunone. The known antifeedant properties of the Citrus limonoids are confirmed. Comparison with previously reported data shows that insect species vary in their behavioral responses to these structural modifications. Highly significant antifeedant activity (P < 0.01) for two natural (1 and 3) and three semisynthetic limonoids (4, 8, and 10) was observed against S. frugiperda.     

Insect repellent/antifeedant activity of 2,4-methanoproline and derivatives against a leaf- and seed-feeding pest insect

2,4-methanoproline is a natural product isolated from the seeds of Ateleia herbert smithii Pittier that was formerly suggested to have insect repellent/antifeedant activity; however, this was not tested quantitatively. In this study the insect repellent/antifeedant potency of methanoproline was measured against larvae of the cotton leafworm, Spodoptera littoralis (Boisd.), and adults of the cowpea weevil, Callosobruchus maculatus (F.). In addition, several N-alkyl, amino, and nitrile derivatives of methanoproline with varying stereodemanding substituents were synthesized and also tested. It was shown that in S. littoralis methanoproline itself did not show any significant activity but that derivatives 5, 7, 8, and 10 did show a reasonable repulsive/antifeedant activity that was comparable to the commercial repellent DEET. A significant repellent activity was scored for methanoproline in adults of C. maculatus that was similar to DEET.     

Structure- and species-dependent insecticidal effects of neo-clerodane diterpenes

Several natural neo-clerodane diterpenoids isolated from Linaria saxatilis and some semisynthetic derivatives were tested against several insect species with different feeding adaptations. The antifeedant tests showed that the oliphagous Leptinotarsa decemlineata was the most sensitive insect, followed by the aphid Myzus persicae. The polyphagous Spodoptera littoralis was not deterred by these diterpenoids; however, following oral administration, some of these compounds did have postingestive antifeedant effects on this insect. In general terms, the antifeedant effects of these compounds were species-dependent and more selective than their toxic/postingestive effects. The study of their structure-activity relationships showed that both the decalin moiety and the chain at C-9 determined their bioactivity. Furthermore, the presence of a 4,18-epoxy/diol moiety was an important feature for both the antifeedant and the toxic/postingestive effects.     

Insect antifeedant activity of tetranortriterpenoids from the Rutales. A perusal of structural relations

Structure-related insect antifeedant relationship of 56 limonoids (both natural and modified) from the plants belonging to the order Rutales was attempted considering substitution patterns, oxidation states, and hydrophobicity, as well as distant geometry derived through conformational analysis on molecular modeling. Orientation of the furan and hydroxylation at specific carbon sites have been shown to influence the antifeedancy against the fall armyworm, Spodoptera litura.     

Selective insect antifeedant and toxic action of ryanoid diterpenes.

In this work, we have studied the antifeedant and insecticidal effects of several natural ryanoid diterpenes. These compounds can be classified in two groups according to their chemical structures: ryanodol/isoryanodol-type (nonalkaloidal type) and ryanodine-type (alkaloidal type) ryanoids. The nonalkaloidal ryanoids were isolated from Persea indica (Lauraceae) while the alkaloidal ryanoids (ryanodines and spiganthines) were isolated from Spigelia anthelmia (Loganiaceae). The effects of these compounds on the feeding behavior and performance (with and without piperonyl butoxide pretreatment) of Spodoptera littoralis larvae and Leptinotarsa decemlineata adults indicate that some strongly deterred these insects, L. decemlineata being less sensitive than S. littoralis. Their antifeedant effects did not parallel their toxic action. Additionally, more than 60% of the nonalkaloidal ryanoids were antifeedants and/or toxic in contrast to 30% of active alkaloidal ones, supporting the hypothesis of a ryanodol-specific mode of action in insects.     

Insect antifeedant activity of flavones and chromones against Spodoptera litura

The antifeedant polymethylated flavones 5-hydroxy-3,6,7,8,4'-heptamethoxyflavone, 5-hydroxy-3,6,7,8-tetramethoxyflavone, and 5,6-dihydroxy-3,7-dimethoxyflavone have been isolated from the cudweed, Gnaphalium affine D. Don (Compositae). These flavonoids and authentic analogues showed insect antifeedant activity against the common cutworm (Spodoptera litura F.). In a previous paper, it was suggested that there was no substituent on the B-ring of the flavonoid for the beneficial antifeedant activity against the common cutworm. These flavonoids having a phenyl group as the B-ring and the chromone as elimination of the B-ring from the flavonoids were used to test the hypothesis of the previously described B-ring effect. The known fact is that Sculletaria baicarensis (Rutaceae) produced the 2-phenyl flavone. Test compounds and their methylated derivatives were prepared from this material for the structure-activity relationship (SAR) study of insect antifeedant activity. In spite of the 2-phenyl flavonoids, some tested compounds did not show any insect antifeedant activity against the common cutworm, although these inactive flavonoids were deficient in the 6-substituent group on the A-ring of the flavonoid. This 6-position-substituted derivative almost showed strong insect antifeedant activity against common cutworm. Moreover, the tested flavonoids having a hydroxyl group as a substituent on any of the positions tended to increase the activity. These results suggested the importance of the 6-position substitution on the flavonoid; however, hydrophilic substituents decreased the activity. Baicalein (5,6,7-trihydroxyflavone) derivatives did not show any activity despite having the 6-substituent derivative. Although the activity of some chromones increased the activity of the flavone, the bulky B-ring was a disadvantage for the antifeedant activity. It was suggested that the charge on C(3) and C(5) of the flavonoid was important for the biological activity. Additionally, an adequate hydrogen bonding property, which is different from lipophilicity, was an advantage for the activity on the basis of a QSAR analysis.     

Synthesis and insect antifeedant activity of aurones against Spodoptera litura larvae

A series of aurones were prepared from various phenols via phenoxy acetic acids and coumaranones and evaluated for insect antifeedant activity against the common cutworm (Spodoptera litura). The naturally occurring aurone was most active at an ED50 of 0.12 micromol/cm2. The synthetic precursor, coumaranones, showed that the introduction of methoxyl and methyl groups to the benzene ring increased insect antifeedant activity. Similarly, the tested aurones showed that the introduction of methoxyl group to the A and/or B rings increased the insect antifeedant activity, but 4,5,6- and 3',4',5'-trisubstituted compounds did not show this activity in this test. The hydroxylation of aurones in the B ring should be disadvantageous for insect antifeedant activity against S. litura. Although the melting points did not correlate well with the insect antifeedant activity, compounds that were nearly inactive had high melting points. A significant correlation was noted between biological activity (pED50) and a hydrogen-bonding parameter calculated from the Rf value obtained from SiOH thin-layer chromatography and a lipophilicity parameter (log k) calculated from the retention time in ODS high-performance liquid chromatography. The respective correlation coefficients (r) were -0.83 and -0.70. The introduction of alkoxy and alkyl groups along with adequate hydrogen bonding seems to contribute to the antifeedant activity of the compounds tested.     

Synthesis and antifeedant activity of new oxadiazolyl 3(2H)-pyridazinones

A total of 20 new compounds containing the oxadiazolyl 3(2H)-pyridazinone moiety were synthesized. The structures of all the compounds were confirmed by (1)H NMR, IR, MS, and elemental analysis. Their insect antifeedant activities against Asiatic corn borer Ostrinia furnacalis (Guenee) were examined and compared with commercial azadirachtin. The compounds exhibited significant levels of activity. The feeding deterrency values of IIIa,j were 57% and 51% at 500 mg/kg concentration, respectively.     

Chemical basis for the antifeedant activity of natural hydroxamic acids and related compounds

Natural hydroxamic acids and related compounds derived from the 1,4-benzoxazin-3-one structure show antifeedant activity against the aphid Rhopalosiphum padi. This antifeeding activity is based on the electrophilic character of the hydroxamic acid function, the opening of the hemiacetal function and the lipophilic character of the molecule. In addition, the antifeedant activity of the aqueous extracts of different tissues of Acanthus mollis (Acanthaceae) was determined. The activity observed is attributed to the presence of 2,4-dihydroxy-1,4-benzoxazin-3-one in the extracts.     

Phenolic derivatives from soy flour ethanol extract are potent in vitro quinone reductase (QR) inducing agents

The fractionation of soy flour directed by a cellular bioassay for induction of phase 2 detoxification enzymes was used to identify quinone reductase (QR) inducing agents. A phospholipid-depleted, 80% methanol-partitioned isolate from a crude ethanol extract of soy flour was resolved using normal phase medium-pressure liquid chromatography (MPLC). Early eluting fractions were found to be the most potent QR inducing agents among the separated fractions. Fraction 2 was the most potent, doubling QR at <2 mug/mL. Further fractionation of this isolate led to the identification of several constituents. Fatty acids and sn-1 and sn-2 monoacylglycerols were identified, but were not highly potent QR inducers. Benzofuran-3-carbaldehyde, 4-hydroxybenzaldeyde, 4-ethoxybenzoic acid, 4-ethoxycinnamic acid, benzofuran-2-carboxylic ethyl ester, and ferulic acid ethyl ester (FAEE) were also identified as QR inducing constituents of this fraction. FAEE was the most potent of the identified constituents, doubling QR specific activity at 3.2 muM in the cellular bioassay.     

A specific and potent inhibitor of brassinosteroid biosynthesis possessing a dioxolane ring

Screening for brassinosteroid biosynthesis inhibitors was performed to find azole derivatives that induced dwarfism, to resemble brassinosteroid-deficient mutants in Arabidopsis, and which could be rescued by brassinosteroid. Through this screening experiment, propiconazole fungicide was selected as a likely inhibitor of brassinosteroid biosynthesis and, thus, propiconazole derivatives with optimized activity and selectivity were synthesized. The biological activity of these compounds was evaluated by examining cress stem elongation. Among the compounds tested, 2RS,4RS-1-[2-(4-trifluoromethylphenyl)-4-n-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole (12) showed the most potent capability to retard cress stem elongation in the light. The compound-induced hypocotyl dwarfism was restored by the coapplication of 10 nM brassinolide but not by 1 microM gibberellin. These results suggest that 12 should affect brassinosteroid biosynthesis. The potency and specificity of 12 were greater than those of brassinazole, a previously reported brassinosteroid biosynthesis inhibitor.     

Antifeedant and growth inhibitory effects of some neo-clerodane diterpenoids isolated from Clerodendron species (Verbenaceae) on Earias vitella and Spodoptera litura

Antifeedant and growth inhibitory effects of various neo-clerodane diterpenoids having a furofuran moiety, isolated from Clerodendron spp., were studied using Earias vitella and Spodoptera litura. The compounds clerodendrin B, 3-epicaryoptin, 15-hydroxyepicaryoptin, and clerodin were effective antifeedants at 10 microg/cm(3) (30 microg/g) of diet against E. vitella and at 10 microg/cm(2) of leaf against S. litura. All of the tested compounds, namely, clerodendrin B, 3-epicaryoptin, clerodendrin C, 15-hydroxyepicaryoptin, clerodendrin B acetate, and clerodin, showed good insect growth inhibitory activity even at lower concentrations.     

利用极浅型潜流人工湿地修复沙漠化土地的可行性研究

[目的]探讨以城市污水作为植物生长的水源和肥源,以期同步实现沙漠化土地的快速修复和污水净化的可行性。[方法]利用极浅型潜流人工湿地,湿地填料为细沙,栽培植物为高羊茅、黑麦草、狗牙根、芦苇和香蒲进行试验设置。[结果]试验仅4个月,细沙容重减小了20%~23%,有机质至少增加了3.9倍,有效磷、pH值、电导率和孔隙率分别增加了16%~103%,3%~5%,1.7~2.6倍和16%~25%,与原细沙差异性显著(p0.05),而碱解氮、全磷和各湿地细沙理化性质无显著性差异(p0.05)。[结论]极浅型潜流人工湿地能够迅速增加细沙养分含量,改善细沙理化性质,以极浅型潜流人工湿地修复沙漠化土地可行。高羊茅和黑麦草可作为修复沙漠化土地的优选植物。     

极浅型潜流人工湿地用于污水处理和风沙土改良的中试研究

[目的]就利用极浅型潜流人工湿地同步处理污水和改良风沙土的可行性进行中试,为后续相关工程的设计、建设和运行提供科学依据。[方法]以污水处理厂初沉池出水为原水,以取自毛乌素沙漠的风沙土为湿地填料,以高羊茅、黑麦草和狗牙根为湿地栽培植物,研究并分析湿地对水中污染物的去除效果和在风沙土的富集特征。[结果]经过15个月的运行,各湿地对污水中COD,TN以及TP的平均去除率分别高于原土68.75%,70.09%和62.74%。运行完毕后,各湿地风沙土较原土有机质、全氮含量显著增加(p0.05),全磷含量虽呈增加趋势但增幅不显著(p0.05),其中风沙土有机质、全氮及全磷含量分别较原土增加了10.64~18.77,8.74~13.98,0.34~0.55倍。[结论]利用极浅型潜流人工湿地同步处理污水和改良风沙土可行。它既能高效净化污水,又可快速提升风沙土的生产力。     

Syntheses, antifeedant activity, and QSAR analysis of new oxa(thia)diazolyl 3(2H)-pyridazinones

Twenty-eight new oxa(thia)diazolyl 3(2H)-pyridazinone derivatives were synthesized. Some compounds showed good chronic growth activities against the armyworm, Pseudaletia separata (Walker). Their EC50 values were determined in vivo. Nineteen 2-tert-butyl-4-chloro-5-[5'-aryl-2'-(1',3',4'-oxadiazolyl)methoxy]-3(2H)-pyridazinones were quantitatively analyzed using the QSAR procedure. The partial least squares method was applied to find relationships between activity and the physicochemical data. The results showed that dipole moment, molar refractivity, and log P are identified as critical parameters for chronic growth effects.     

Nitrogen Dynamic in Soils Amended with Legislated and Extremely High Doses of Pig Slurry

The application of pig slurry as soil amendment is a common agronomic practice, but to avoid environmental hazards the doses are regulated. This article evaluates the N dynamic in two calcareous soils amended with legislated (170 kg N, D1) and high doses (1700 kg N, D2) of pig slurry and incubated for 300 days. Nitrification increased at the end of incubation (39–45 and 154–285 mg kg^?1 in control, D1, and D2). Net N mineralization was similar in all soils (24–36 mg kg–1), but negative in D2 in soil 1 (–72 mg N kg^?1). Soil type was an important factor for nitrification processes, with greater rates in the soil with high calcium carbonate content and with no effects on ammonification. Thus, legislated doses compared to control could be considered a wise practice. Conversely, overdoses displayed potential N processes influenced by the carbonate content and the salinity of the amended soil.     

极端干旱区土壤呼吸对储水灌溉和冻融循环的响应

[目的] 揭示中国极端干旱区甘肃省石羊河流域储水灌溉与季节性冻融叠加作用下对土壤呼吸的影响,为进一步提高极端干旱区灌溉水资源利用效率和节约灌溉水源提供理论基础和技术支撑。[方法] 按照1 199.4 m³/hm²低灌溉定额分为灌水和非灌水处理,将冻融循环分为冻结期、冻融期和解冻期3个时间段,采用LI-8100土壤碳通量全自动测量系统对各处理地块的土壤呼吸速率进行观测与分析。[结果] 极端干旱区储水灌溉在季节性冻融作用下农田生态系统土壤呼吸速率增强,土壤碳排放量增加,农田生态系统碳循环被改变,有利于作物的生长和提高粮食产量。不同土地利用方式下土壤呼吸速率对水分和温度的响应程度不同。整个冻融过程中土壤呼吸速率呈现出：解冻期>冻结期>冻融期的规律。冻结期、冻融期和解冻期3个时期的土壤CO₂都表现为源,但在夜间极低温度时土壤CO₂由源转化为汇。[结论] 储水灌溉调控了整个冻融期土壤呼吸的过程,改变了极端干旱区农田生态系统的碳循环。在水分与季节性冻融叠加作用下,储水灌溉地块土壤呼吸速率相对未储水地块随温度的波动更为剧烈,但与温度的变化趋势一致,水分加剧了其随温度的波动。     

Stimulation of seed germination of Orobanche species by ophiobolin A and fusicoccin derivatives

Various Orobanche species (broomrapes) are serious weed problems and cause severe reduction on yields in many important crops. Seeds of these parasitic weeds may remain dormant in the soil for many years until germination is stimulated by the release of a chemical signal by roots of a host plant. Some fungal metabolites, such as ophiobolin A and fusicoccin derivatives, were assayed to determine their capacity to stimulate the seed germination of several Orobanche species. The results obtained showed that the stimulation of seed germination is species-dependent and also affected by the concentration of the stimulant. Among ophiobolin A, fusicoccin, and its seven derivatives, tested in the concentration range of 10 (-4)-10 (-7) M, the highest stimulatory effect was observed for ophiobolin A and the hexacetyl and pentacetyl isomers of 16- O-demethyl-de- tert-pentenylfusicoccin prepared by chemical modification of the fusicoccin, while the other fusicoccin derivatives appeared to be practically inactive. The most sensitive species appeared to be O. aegyptica, O. cumana, O. minor, and to a lesser extent, O. ramosa.     

Depolymerized products of lambda-carrageenan as a potent angiogenesis inhibitor

Since angiogenesis is involved in initiating and promoting several diseases such as cancer and cardiovascular events, this study was designed to evaluate the anti-angiogenesis of low-molecular-weight (LMW), highly sulfated lambda-carrageenan oligosaccharides (lambda-CO) obtained by carrageenan depolymerization, by CAM (chick chorioallantoic membrane) model and human umbilical vein endothelial cells (HUVECs). Significant inhibition of vessel growth was observed at 200 microg/pellet. A histochemistry assay also revealed a decrease of capillary plexus and connective tissue in lambda-CO treated samples. lambda-CO inhibited the viability of cells at the high concentration of 1 mg/mL, whereas it affected the cell survival slightly (>95%) at a low concentration (<250 microg/mL), and HUVEC is the most sensitive to lambda-CO among three kinds of cells. Furthermore, the inhibitory action of lambda-CO was also observed in the endothelial cell invasion and migration at relatively low concentration (150-300 microg/mL), through down-regulation of intracellular matrix metalloproteinases (MMP-2) expression on endothelial cells. Taken together, these findings demonstrate that lambda-CO is a potential angiogenesis inhibitor with combined effects of inhibiting invasion, migration, and proliferation.