Comparison of the adsorption of carbofuran at the silica–liquid and liquid–vapour interfaces

The adsorption processes of carbofuran from an aqueous solution have been determined at the solid–liquid interface, onto silica and at liquid–vapour interfaces. At the solid–liquid interface, the adsorption isotherms and their evolution with temperature reveal that adsorption is generally weak but increases with temperature. Adsorption also significantly increases with concentration when the solubility limit is approached. The study at the liquid–vapour interface reveals that adsorption at this interface is 70 times larger than at the solid–liquid interface. Again, adsorption values at the liquid–vapour interface increase with temperature (below 30°C) and near the solubility limit. Consequences of the observations on the behaviour of carbofuran in the environment are discussed. © 1998 SCI     

Synthetic pyrethroids containing a C–C triple bond

The three commercial synthetic pyrethroids containing a carbon–carbon triple bond, α-ethynyl-2-methylpent-2-enyl (1R)-trans-chrysanthemate, (S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-trans,cis-chrysanthemate and [2,5-dioxo-3-(2-propynyl)-1-imidazolidinyl]methyl (1R)-trans-chrysanthemate are reviewed with emphasis on their inventive histories. Their chemistry and efficacy are described briefly. The relationship between stereochemistry and the biological activity is also discussed. © 1998 SCI.     

The push–pull strategy for citrus psyllid control

The Asian citrus psyllid (ACP), Diaphorina citri Kuwayama (Hemiptera: Psyllidae), is the only natural vector of Candidatus Liberibacter asiaticus that causes citrus huanglongbing (HLB), a most destructive disease of citrus. Currently, no remedial therapy exists for the disease, and so effective control of ACP is very important in curbing the transmission of the disease. The push–pull strategy should be thoroughly explored as an approach to ACP management. This mini‐review summarises the current progress towards more effective repellent and attractant chemicals through investigating known repellent and attractive plants. Interactions between ACP and its host plants are also addressed, with emphasis on the possible involvement of the host biochemicals in attracting the insect. Potential ways to increase the effectiveness of the pull–push strategy are briefly discussed. It is expected that the pull–push strategy will be gradually developed following more extensive research. © 2014 Society of Chemical Industry     

Structure–Activity Relationships of Herbicidal Aryltriazolinones

A series of substituted aryltriazolinones, known to inhibit protoporphyrinogen oxidase, were prepared and their structure–activity requirements at positions 4 and 5 of the aromatic ring investigated. A QSAR equation obtained for substituents at the 5 position identified the hydrophobicity term π and the Sterimol minimum width B₁ as the two parameters affecting in-vitro biological activity. Greenhouse pre-emergence activity correlated with in-vitro activity and the hydrophobicity term π of the substituent at that position. It was found that the phenoxy-4-oxyacetate group at aromatic position 5 was an outlier and had to be considered separately. SAR analysis of substituents at aromatic position 4 revealed that two different models were required to explain all observed substituent effects. In the first model, where the 5 position was occupied by hydrogen, the 4-chlorobenzyloxy group at aromatic position 4 gave the best compound. The second model, where the 5 position of the aromatic ring was occupied by a group other than hydrogen, resulted in a QSAR equation, previously derived, which links substituent effects at position 4 with π and with the electronic para inductive term F_p. In this model the chloro group provides optimum biological activity. The need to separate the aryltriazolinone herbicides into several different classes in order to explain their substituent effects at aromatic positions 4 and 5 could be rationalized if more than one binding conformation, within the same binding site, is possible. © 1997 SCI     

Biology and management of the fast‐emerging threat of broomrape in rapeseed–mustard

Broomrapes (Phelipanche and Orobanche spp.) are obligate root parasites of the family Orobanchaceae. The natural variation in Orobanchaceae exists in plants involving Triphysaria versicolor (facultative hemiparasite), Striga hermonthica (obligate hemiparasite) and Phelipanche aegyptiaca, formerly Orobanche aegyptiaca (holoparasite). The family Orobanchaceae has 90 genera. The four major parasitic species of broomrape are Phelipanche ramosa in the Brassicas, especially in rapeseed, Phelipanche cernua in tobacco and sunflower, P. aegyptiaca in solanacious crops and in Brassica juncea and Phelipanche crenata in leguminous crops. They are prevalent, infesting nearly 1.2% of the world's arable land. In India, P. ramosa and P. aegyptiaca cause severe infestations of Brassica and have threatened its cultivation in major growing areas. In addition, a single broomrape plant can release >100 000 seeds that remain viable for decades in the soil. This provides the parasite with a great genetic adaptability to environmental changes, including host resistance, agronomical practices and herbicide treatments. Different control measures, such as manual weeding, herbicide applications, solarization, crop rotation and integrated broomrape management practices, have been proposed in order to reduce the broomrape menace and improve yields in farmers' fields. Breeding for broomrape resistance also could be an economic, feasible and environmental friendly control method. The present article reviews the current status of research on broomrape in India and abroad, as well as suggests strategies for its effective management.     

Bis-pyrimidylpyrazolinones – a new class of acetohydroxy-acid synthase (AHAS) inhibitor

Hydroxypyrazolinones which bear two pyrimidine rings (on N-1 and C-4) were found to be potent inhibitors of acetohydroxy-acid synthase which displayed good herbicidal activity in vivo. Structure–activity relationship studies suggested the presence of a second binding niche on the enzyme for a 4,6-dimethoxypyrimidine ring.     

‘Universal’ spray droplet adhesion model – accounting for hairy leaves

The adhesion of a spray droplet upon initial contact with a leaf surface is extremely important to spray efficacy and is dependent on dynamic interactions between droplets (formulation, size, velocity) and leaf (micro‐topography, surface chemistry, veininess, hairiness and orientation). A ‘universal’ spray droplet adhesion model has previously been developed, using 50% aqueous acetone contact angles as a measure of leaf surface properties; this model satisfactorily predicts initial adhesion over a range of formulation surface tensions, droplet sizes and velocities. However, it failed to fit data from hairier leaves. This study investigates initial spray droplet adhesion on hairy leaves. Two categories of hairy leaves were identified by how the droplets penetrate the leaf hairs, Wenzel (hairy) and Cassie–Baxter (super hairy). For the Wenzel‐type, a simple constant accounted for the increased droplet shatter caused by the hairs. For the Cassie–Baxter‐type, a cushioning factor was introduced to account for the absorption of kinetic energy at impact by the hair mat. The cushioning factor was estimated by measuring the relative height of the hair mat. By including these two parameters, the new model successfully predicted the mean adhesion of non‐hairy, hairy and super‐hairy plants (R² = 0.96). This model and the underlying principles determining hairy leaf adhesion developed in this article will help develop spray formulations effective at targeting hairy‐leaved weed and crop species.     

Synthesis and Structure–Activity Relationships of Miticidal 4,5-Dihydropyrazole-5-thiones

A series of novel 4,5-dihydropyrazole-5-thiones (DHPs) was synthesised by treating the corresponding dihydropyrazolones with ‘Lawesson’s reagent and evaluated for miticidal activity against two-spotted spider mites (Tetranychus urticae Koch). Of these, 3-(4-chlorophenyl)-4,4-dimethyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-4-ethyl-4-methyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-1-phenyl-4,5-dihydropyrazole-5-thione-4-spirocyclopentane and 4,4-dimethyl-1-phenyl-3-(4-trifluoromethyl-phenyl)-4,5-dihydropyrazole-5-thione were highly active (pEC₅₀>4·0) and were more effective than the miticide dicofol (pEC₅₀=3·879), which has traditionally been used for the control of phytophagous mites. Structure–activity relationship (SAR) studies were performed on each position of the pyrazole ring of DHPs. The results indicated that the unsubstituted phenyl, 4-substituted phenyl and thioxo groups on the 1-, 3- and 5-positions of DHPs respectively were required for activity. Quantitative SAR studies using physicochemical parameters of substituents and the capacity factor k′ as a hydrophobicity index suggested that: (a) the activities of all types of DHPs examined were mainly dominated by hydrophobicity, (b) the bulkiness of 4-substituents of the 3-phenyl ring favoured the activity and (c) the log k′ optimum for all DHPs was 1·675, equivalent to a log P_ow value of c. 5·0.