Physicochemical property guidelines for modern agrochemicals

The relentless need for the discovery and development of new agrochemicals continues as a result of driving forces such as loss of existing products through the development of resistance, the necessity for products with more favorable environmental and toxicological profiles, shifting pest spectra, and the changing agricultural needs and practices of the farming community. These new challenges underscore the demand for novel, high‐quality starting points to accelerate the discovery of new agrochemicals that address market challenges. This article discusses the efforts to identify the optimum ranges of physicochemical properties of agrochemicals through analysis of modern commercial products. Specifically, we reviewed literature studies examining physicochemical property effects and analyzed the properties typical of successful fungicides, herbicides, and insecticides (chewing and sap‐feeding pests). From the analysis, a new set of physicochemical property guidelines for each discipline, as well as building block class, are proposed. These new guidelines should significantly aid in the discovery of next‐generation agrochemicals. © 2018 Society of Chemical Industry     

Physicochemical factors affecting the uptake by roots and translocation to shoots of amine bases in barley

The uptake by barley roots from nutrient solution and subsequent transport to shoots of two series of amine bases were measured over 6 to 72 h. The compounds were chosen to span systematically ranges of lipophilicity (assessed using 1-octanol/water partition coefficients, K_ow) and pKa that would include commercial pesticide amines. In a series of six substituted phenethyl amines, strong bases with pKa∽9·5, all the compounds were strongly taken up by roots from solutions of pH 8·0; uptake declined substantially as the pH was lowered to 5·0, especially for the compounds of intermediate lipophilicity (log K_ow 2 to 3). This uptake could be ascribed to three processes: (i) accumulation of the cation inside the root cells due to the negative charge on the plasmalemma, as given by the Nernst equation and important only for the polar compounds which have low permeation rates through membranes; (ii) accumulation into the vacuole by ion-trapping, which was the dominant process at high pH for all compounds and at all pH values for the compounds of intermediate lipophilicity; (iii) partitioning on to the root solids, substantial only for the most lipophilic compounds. Translocation to shoots was proportional to uptake by roots, this ratio being independent of external pH for each compound and being optimal for the compounds of intermediate lipophilicity. Such proportionality was also observed in a series of three weaker bases of intermediate lipophilicity, in which compounds of pKa 7·4 to 8·0 were also well taken up and translocated whereas the very weak base 4-ethylaniline (pKa 5·03) was much less so. Tests with quaternised pyridines confirmed that organic cations move only slowly through membranes. The observed behaviour of the amines could be modelled reasonably well assuming that transport within the plant was dominated by movement across membranes of the non-ionised species, and this appeared to be true even for the most lipophilic phenethylamine (log K_ow 4·67) studied, though its long-distance movement would be as the protonated species. © 1998 Society of Chemical Industry     

4种表面活性剂对水中土霉素光解的影响

为研究表面活性剂对抗生素光解的影响,采用模拟日光（氙灯,λ>290 nm）光解实验考察了土霉素在CTAB、SDS、SDBS和Tween80 4种表面活性剂溶液中的光解。在模拟日光下,土霉素在pH=7.5的纯水和4种表面活性剂溶液中的光解遵循一级反应动力学,4种表面活性剂均促进了土霉素的光解,其中CTAB的促进作用最明显。CTAB的作用受pH值和浓度影响,pH=5.5时抑制土霉素的光解;pH=7.5和pH=9.0时促进土霉素的光解,促进作用与CTAB浓度呈正相关。CTAB可以降低土霉素的pKa,增大其阴离子形态比例,这可能是CTAB促进土霉素光解的重要原因。在自然光照下,纯水和地表水中CTAB的存在分别使土霉素的光解加快了1.62和4.96倍。     

Uptake by roots and translocation to shoots of two morpholine fungicides in barley

Despite being lipophilic, morpholine fungicides are systemic in plants. Such transport may be explicable by their protonation (pKa∽7·5) at the pH of plant compartments to yield the more polar cation. This behaviour might be a useful attribute to be incorporated into other classes of lipophilic pesticides. To understand quantitatively the behaviour of the morpholine fungicides, the uptake by roots and transport to shoots in barley of two such ¹⁴C-labelled compounds, dodemorph and tridemorph, were investigated using bathing solutions of differing pH. At pH 5, uptake and transport were small, but increased by approximately two orders of magnitude at pH 8. Tridemorph, the more lipophilic of the two compounds, was highly accumulated by roots at pH 8 and moderately translocated to shoots. In contrast, dodemorph was translocated to shoots at pH 8 with remarkable efficiency, moving into the xylem across the endodermis at 23 times the efficiency of water, though accumulation in roots was less than that of tridemorph. Behaviour at 24 h was largely similar to that at 48 h for both compounds, indicating that uptake and translocation are equilibrium processes maintained over time. Transport to shoots for each compound was directly proportional to the concentrations accumulated in the roots, except at low pH where partitioning into root solids became proportionately more important with such material not being directly available for transport to the xylem across the endodermis. Uptake and transport of these basic fungicides are explained in terms of their partitioning and of their accumulation in acidic plant compartments by ion trapping as the protonated form; this behaviour is discussed in relation to the pKa and lipophilicity of these compounds. © 1998 Society of Chemical Industry