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Chitosan, the N-deacetylated derivative of chitin, is a potential biopolysaccharide owing to its specific structure and properties. In this paper, we report on the synthesis of 24 new chitosan derivatives, N-alkyl chitosans (NAC) and N-benzyl chitosans (NBC), that are soluble in dilute aqueous acetic acid. The different derivatives were synthesized by reductive amination and analyzed by 1H NMR spectroscopy. A high degree of substitution (DS) was obtained with N-(butyl)chitosan (DS 0.36) at a 1:1 mole ratio for NAC derivatives and N-(2,4-dichlorobenzyl)chitosan (DS 0.52) for NBC derivatives. Their insecticidal and fungicidal activities were tested against larvae of the cotton leafworm Spodoptera littoralis (Boisduval) (Lepidoptera: Noctuidae), the grey mould Botrytis cinerea Pers (Leotiales: Sclerotiniaceae) and the rice leaf blast Pyricularia grisea Cavara (Teleomorph: Magnaporthe grisea (Hebert) Barr). The oral feeding bioassay indicated that all the derivatives had significant insecticidal activity at 5 g kg(-1) in artificial diet. The most active was N-(2-chloro-6-fluorobenzyl)chitosan, which caused 100% mortality at 0.625 g kg(-1), with an estimated LC50 of 0.32 g kg(-1). Treated larvae ceased feeding after 2-3 days; the mechanism of action remains unknown. In a radial hyphal growth bioassay with both plant pathogens, all derivatives showed a higher fungicidal action than chitosan. N-Dodecylchitosan, N-(p-isopropylbenzyl)chitosan and N-(2,6-dichlorobenzyl)chitosan were the most active against B cinerea, with EC50 values of 0.57, 0.57 and 0.52 g litre(-1), respectively. Against P grisea, N-(m-nitrobenzyl)chitosan was the most active, with 77% inhibition at 5 g litre(-1). The effect of different substitutions is discussed in relation to insecticidal and fungicidal activity.  相似文献   
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BACKGROUND: The moulting accelerating compounds (MACs) or ecdysteroid agonists represent a selective group of insecticides acting upon binding to the ecdysteroid receptor (EcR) and leading to lethal premature moulting in larval stages and aborted reproduction in adults. Psyttalia concolor Szèpl. is a useful parasitic wasp attacking important tephritid pests such as the medfly and olive fruit fly. RESULTS: Contact and oral exposure in the laboratory of female parasitic wasps to the dibenzoylhydrazine‐based methoxyfenozide, tebufenozide and RH‐5849 did not provoke negative effects. No mortality and no reduction in beneficial capacity were observed. The ligand‐binding domain (LBD) of the EcR of P. concolor was sequenced, and a homology protein model was constructed which confirmed a cavity structure with 12 α‐helices, harbouring the natural insect moulting hormone 20‐hydroxyecdysone. However, a steric clash occurred for the MAC insecticides owing to a restricted extent of the ligand‐binding cavity of the PcLBD‐EcR, while they did dock well in that of susceptible insects. CONCLUSIONS: The insect toxicity assays demonstrated that MACs are selective for P. concolor. The modelling/docking experiments are indications that these insecticides do not bind with the LBD‐EcR of P. concolor and support the theory that they show no biological effects in the parasitic wasp. These data may help in explaining the compatible use of MACs together with parasitic wasps in IPM programmes. Copyright © 2012 Society of Chemical Industry  相似文献   
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BACKGROUND: Saponins are a class of secondary plant metabolites consisting of a sugar moiety glycosidically linked to a hydrophobic aglycone (sapogenin) that often possess insecticidal activities. Four saponins were selected: two triterpene saponins, Q. saponaria saponins and aescin, and two steroidal saponins, digitonin and diosgenin. Their effects were investigated on an important pest species and a model piercing‐sucking insect, the pea aphid Acyrthosiphon pisum. The triterpene Q. saponaria saponins bark saponin received special attention because of its high activity. Aphids were challenged by oral and contact exposure to demonstrate aphicidal activities, and in choice experiments to support use as a natural deterrent. RESULTS: When aphids were exposed to supplemented artificial diet for 3 days, a strong aphicidal activity was recorded for three of the four saponins, with an LC50 of 0.55 mg mL?1 for Q. saponaria saponins, 0.62 mg mL?1 for aescin and 0.45 mg mL?1 for digitonin. The LT50 values ranged between 1 and 4 days, depending on the dose. For diosgenin, only low toxicity (14%) was scored for concentrations up to 5 mg mL?1. In choice experiments with treated diet, a deterrence index of 0.97 was scored for Q. saponaria saponins at 1 mg mL?1. In contrast, direct contact showed no repellent effect. Spraying of faba bean plants with Q. saponaria saponins resulted in an LC50 of 8.2 mg mL?1. Finally, histological analysis in aphids fed with Q. saponaria saponins demonstrated strong aberrations of the aphid gut epithelium, and exposure of midgut CF‐203 cell lines to Q. saponaria saponins in vitro confirmed the cytotoxic effect. CONCLUSIONS: The present insect experiments provide strong evidence that saponins, as tested here with triterpene Q. saponaria saponins, can be useful as natural aphicides and deterrents. Furthermore, the insect midgut epithelium is suggested to be a primary target of saponin activity.Copyright © 2011 Society of Chemical Industry  相似文献   
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BACKGROUND: Bacillus thuringiensis (Bt) and its protein crystals are used worldwide, either as a spray or when expressed in transgenic crops, for the control of pest insects. However, owing to their intensive use, there exists a debate regarding the involvement of this microbial insecticide in bee colony losses. In this study, in a tiered approach using laboratory microcolonies, an evaluation was made of the potential lethal and sublethal hazards on colony reproduction and foraging behaviour of workers of the bumblebee Bombus terrestris (L.) of two commercial Bt strains: kurstaki (Dipel®) and aizawai (Xentari®). Bumblebees, like honey bees, are intensively used in modern agriculture for pollination and fulfil a crucial role in the natural ecosystem. RESULTS: Exposure of bumblebees dermally or via treated pollen to either of the two Bt formulations at their field recommended rates (0.1%) caused no reduction in survival. However, when applied in the feeding sugar water, aizawai killed all workers at a concentration of 0.1%, but this lethal effect was lost at 0.01%. With respect to reproductive effects, kurstaki was harmless, while aizawai at 0.1% delivered in the feeding sugar water and pollen reduced reproduction by 100 and 31% respectively. Lower doses of 0.01% aizawai in the sugar water showed no more effect. In addition, kurstaki at 0.1% and aizawai at 0.01% in the feeding sugar water did not impair the foraging behaviour, resulting in normal nest colony performance. CONCLUSION: The results with kurstaki and aizawai demonstrated that, in general, the Bt strains are safe to B. terrestris bumblebees, although in some cases there were detrimental effects that depended on strain and route of exposure. In addition, the authors believe that to draw firm conclusions regarding the hazards of Bt to bumblebees would require more information on relevant concentrations of Bt products in the environment. Hence, routine testing for lethal and sublethal effects is recommended to ascertain combined use of Bt products and bumblebees in modern agriculture. Copyright © 2009 Society of Chemical Industry  相似文献   
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In this project we report on the angiotensin I-converting enzyme (ACE)-inhibitory activity of a bovine gelatin hydrolysate (Bh2) that was submitted to further hydrolysis by different enzymes. The thermolysin hydrolysate (Bh2t) showed the highest in vitro ACE inhibitory activity, and interestingly a marked in vivo blood pressure-lowering effect was demonstrated in spontaneously hypertensive rats (SHR). In contrast, Bh2 showed no effect in SHR, confirming the need for the extra thermolysin hydrolysis. Hence, an angiotensin I-evoked contractile response in isolated rat aortic rings was inhibited by Bh2t, but not by Bh2, suggesting ACE inhibition as the underlying antihypertensive mechanism for Bh2t. Using mass spectrometry, seven small peptides, AG, AGP, VGP, PY, QY, DY and IY or LY or HO-PY were identified in Bh2t. As these peptides showed ACE inhibitory activity and were more prominent in Bh2t than in Bh2, the current data provide evidence that these contribute to the antihypertensive effect of Bh2t.  相似文献   
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