Redox-active ligands in artificial photosynthesis: a review

Environmental Chemistry Letters - Given the rising socioeconomic issues of fossil fuels, efficient artificial photosynthesis would be an important milestone toward a sustainable world. A key step...     

Biological evaluation of SZI‐121, a new miticide

Abstract

A large number of tetrazine analogues were synthetised and tested as miticides. A comprehensive screening system was applied to recognise some effects important in terms of field performance. A promising new substance, coded as SZI‐121 was choosen for further development. It proved to be about four‐times more active as an ovicide (LC₅₀=0.05 ppm) than the reference clofentezine, when administered to the eggs directly (LC₅₀=0.23 ppm). In contrast to clofentezine which has solely a contact mode of action, SZI‐121 has excelent translaminar activity acting on already laid eggs (LC₅₀= 18.66 ppm) or those in females feeding on the opposite, non‐treated side of the leaf (LC₅₀=5.11 ppm). High toxicity of SZI‐121 to the chrysalis form (LC₅₀=0.39 ppm) was also observed. The field rate of SZI‐121 is 60–100 g a.i./ha against a wide range of phytophagous mites including European red mite (Panonychus ulmi), two spotted spider mite (Tetranychus urticae), grape leaf rust mite (Calepitrimerus vitis), vine leaf blister mite (Colomerus vitis), apple leaf rust mite (Aculus schlechtendali), stone fruit leaf rust mite (Vasates fockeui). Because it stops the development of mites in egg and chrysalis forms simultaneously, SZI‐121 can be used independently from actual development stages of mites during the whole season as the field trials demonstrated. These characteristics permit SZI‐121 to be easily fitted into integrated pest management.     

A SPE-HPLC-MS/MS method for the simultaneous determination of prioritised pharmaceuticals and EDCs with high environmental risk potential in freshwater

This work describes the development, optimisation and validation of an analytical method for the rapid determination of 17 priority pharmaceutical compounds and endocrine disrupting chemicals (EDCs). Rather than studying compounds from the same therapeutic class, the analyses aimed to determine target compounds with the highest risk potential (with particular regard to Scotland), providing a tool for further monitoring in different water matrices. Prioritisation was based on a systematic environmental risk assessment approach, using consumption data; wastewater treatment removal efficiency; environmental occurrence; toxicological effects; and pre-existing regulatory indicators. This process highlighted 17 compounds across various therapeutic classes, which were then quantified, at environmentally relevant concentrations, by a single analytical methodology. Analytical determination was achieved using a single-step solid phase extraction (SPE) procedure followed by high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The fully optimised method performed well for the majority of target compounds, with recoveries >71% for 15 of 17 analytes. The limits of quantification for most target analytes (14 of 17) ranged from 0.07 ng/L to 1.88 ng/L in river waters. The utility of this method was then demonstrated using real water samples associated with a rural hospital/setting. Eight compounds were targeted and detected, with the highest levels found for the analgesic, paracetamol (at up to 105,910 ng/L in the hospital discharge). This method offers a robust tool to monitor high priority pharmaceutical and EDC levels in various aqueous sample matrices.     

The synthetic pyrethroid isomers II. Biological activity

Abstract

Pure optical isomers of phenothrin, permethin and cypermethrin were synthesised and tested on a wide spectrum of insects (Blattella germanica, Leptinotarsa decemlineata, Tribolium confusum, Oncopeltus fasciatus, Musca domestica, Aedes aegypti). Our results suggest that in the structurally related series phenothrin, permethrin and cypermethrin the chemical modifications had only a small influence on intrinsic activity of the compounds at the target site. The activity of piperonylbutoxide synergised 1Rtrans phenothrin and 1Rcis permethrin (LD₅₀=1.2 ng/fly in both cases) is in a similar range to the most active 1RcisS cypermethrin isomer alone or with PB (LD₅₀=0.9 and 0.4 ng/fly, respectively). Some cypermethrin isomers considered previously to be totally inactive show significant activity depending on the tested insect species. The 1ReisR and 1RtransR isomers proved to be as active as the most potent isomers on mosquito. A similarly unexpected result was that in the case of mosquito all four trans isomers were significantly more active than the corresponding eis isomers.

The superiority of the (S)‐α configuration over (R)‐α was found. It does not result from a higher intrinsic activity at the target site, but rather from the enhanced metabolic resistance of (S)‐α‐esters to ester cleavage as confirmed by Synergist studies. The activity of the two most potent stereoisomers, 1ReisS and 1RtransS, could not be elevated by quinalphos, while the inactive 1ScisR and 1StransR isomers showed significant activity with the esterase inhibitor quinalphos administered sublethally.

In contrast with the antagonism between (S)‐ and (R)‐α‐epimers of cypermethrin reported earlier a considerable synergism was observed between 1RtransS and 1StransR enantiomer pair on flour beetle and housefly in tarsal contact tests.

The results with stereoisomers and their mixtures were utilised in the development of two new products, Chinmix (beta‐cypermetrhin) and Transmix (theta‐cypermetrhin).     

Preen gland removal increases plumage bacterial load but not that of feather-degrading bacteria

The preen gland is a holocrine sebaceous gland of the avian integument which produces an oily secretion that is spread on the plumage during preening. It has been suggested that birds may defend themselves against feather-degrading bacteria (FDB) and other potential pathogens using preen gland secretions. However, besides some in vitro studies, the in vivo bacterial inhibitory effects of the preen oil on the abundance of feather-associated bacterial species has not yet been studied in passerines. Here we tested the effect of gland removal on the abundance of FDB and other-cultivable bacterial loads (OCB) of male house sparrows (Passer domesticus). Our results did not support earlier results on in vitro antibacterial activity of preen oil against FDB since the absence of the preen gland did not significantly affect their loads related to the control birds. In contrast, we found that preen gland removal led to higher loads of OCB. This result suggests that the antimicrobial spectrum of the preen oil is broader than previously thought and that, by reducing the overall feather bacterial loads, the preen gland could help birds to protect themselves against a variety of potentially harmful bacteria.     

Chemical evaluation of SZI‐121, a tetrazine type miticide

Abstract

SZI‐121, a tetrazine type acaricide, has been improved by Chinoin. The compound is very active against phytophagous mites and has good toxicological and environmental properties. The chemical structure was designed to get improvements in mode of action and efficacy simultaneously. SZI‐121 acts not only as a contact ovicide but due to very good translaminar activity it can enter mites via ingestion. SZI‐121 possesses transovarian activity and it also able to stop the development of mites at chrysalis stages.     

The synthetic pyrethroid isomers I. Preparation

Abstract

Enantiomers and racemic mixtures of selected benzilic esters using resolved and raceme permethrinic or chrysanthemic acids of high purity were synthesised via improved methods based on conventional steps. Nine basic structures of selected derivatives having hydrogen, bromo or phenoxy group at meta position were prepared including the well known insecticides of phenothrin, permethrin and cypermethrin. The optical purity of these compounds were determined via an NMR method applying chiral shift reagents. The configuration of the isomers of new a‐cyano‐benzyl esters were assigned via a rule realized by comparing the characteristic 1H NMR shifts of the dimethyl groups attached to the cyclopropane ring.     

Sexual dimorphism in immune function changes during the annual cycle in house sparrows

Difference between sexes in parasitism is a common phenomenon among birds, which may be related to differences between males and females in their investment into immune functions or as a consequence of differential exposure to parasites. Because life-history strategies change sex specifically during the annual cycle, immunological responses of the host aiming to reduce the impact of parasites may be sexually dimorphic. Despite the great complexity of the immune system, studies on immunoecology generally characterise the immune status through a few variables, often overlooking potentially important seasonal and gender effects. However, because of the differences in physiological and defence mechanisms among different arms of the immune system, we expect divergent responses of immune components to environmental seasonality. In male and female house sparrows (Passer domesticus), we measured the major components of the immune system (innate, acquired, cellular and humoral) during four important life-history stages across the year: (1) mating, (2) breeding, (3) moulting and (4) during the winter capture and also following introduction to captivity in aviary. Different individuals were sampled from the same population during the four life cycle stages. We found that three out of eight immune variables showed a significant life cycle stage × sex interaction. The difference in immune response between the sexes was significant in five immune variables during the mating stage, when females had consistently stronger immune function than males, while variables varied generally non-significantly with sex during the remaining three life cycle stages. Our results show that the immune system is highly variable between life cycle stages and sexes, highlighting the potential fine tuning of the immune system to specific physiological states and environmental conditions.