Experimental and Theoretical Studies of the Environmental Sensitivity of the Absorption Spectra and Photochemistry of Nitenpyram and Analogs

Neonicotinoid (NN) pesticides have widespread use, largely replacing other pesticides such as the carbamates. Hence, there is a need to understand their environmental fates at a molecular level in various media, especially water. We report here the studies of a nitroenamine NN, nitenpyram (NPM), in aqueous solution where the absorption cross sections in the actinic region above 290 nm are observed to dramatically decrease compared to those in nonaqueous solvents. Quantum chemical calculations show that addition of a proton to the tertiary amine nitrogen in NPM breaks the conjugation in the chromophore, shifting the absorption to shorter wavelengths, consistent with experiment. However, surprisingly, adding a proton to the secondary amine nitrogen leads to its immediate transfer to the NO2 group, preserving the conjugation. This explains why the UV absorption of ranitidine (RAN), which has a similar chromophore but only secondary amine nitrogens, does not show a similar large blue shift in water. Photolysis quantum yields in aqueous NPM solutions were measured to be φ = 0.18 ± 0.07 at 254 nm, (9.4 ± 1.6) × 10-2 with broadband radiation centered at 313 nm and (5.2 ± 1.1) × 10-2 for broadband radiation centered at 350 nm (errors are 2σ). The major products in aqueous solutions are an imine that was also formed in the photolysis of the solid and a carboxylic acid derivative that is unique to the photolysis in water. Combining the larger quantum yields in water with the reduced absorption cross sections results in a calculated lifetime of NPM of only 5 min at a solar zenith angle of 35°, typical of 40°N latitude on April 1. The products do not absorb in the actinic region and hence will be long-lived with respect to photolysis

A Meta-analysis of Attachment to Parents and Delinquency

To investigate the link between attachment to parents and delinquency, and the potential moderating effects of age and sex, 74 published and unpublished manuscripts (N = 55,537 participants) were subjected to a multilevel meta-analysis. A mean small to moderate effect size was found (r = 0.18). Poor attachment to parents was significantly linked to delinquency in boys and girls. Stronger effect sizes were found for attachment to mothers than attachment to fathers. In addition, stronger effect sizes were found if the child and the parent had the same sex compared to cross-sex pairs of children and parents. Age of the participants moderated the link between attachment and delinquency: larger effect sizes were found in younger than in older participants. It can be concluded that attachment is associated with juvenile delinquency. Attachment could therefore be a target for intervention to reduce or prevent future delinquent behavior in juveniles

Experimental and Theoretical Studies of the Environmental Sensitivity of the Absorption Spectra and Photochemistry of Nitenpyram and Analogs

Neonicotinoid (NN) pesticides have widespread use, largely replacing other pesticides such as the carbamates. Hence, there is a need to understand their environmental fates at a molecular level in various media, especially water. We report here the studies of a nitroenamine NN, nitenpyram (NPM), in aqueous solution where the absorption cross sections in the actinic region above 290 nm are observed to dramatically decrease compared to those in nonaqueous solvents. Quantum chemical calculations show that addition of a proton to the tertiary amine nitrogen in NPM breaks the conjugation in the chromophore, shifting the absorption to shorter wavelengths, consistent with experiment. However, surprisingly, adding a proton to the secondary amine nitrogen leads to its immediate transfer to the NO2 group, preserving the conjugation. This explains why the UV absorption of ranitidine (RAN), which has a similar chromophore but only secondary amine nitrogens, does not show a similar large blue shift in water. Photolysis quantum yields in aqueous NPM solutions were measured to be φ = 0.18 ± 0.07 at 254 nm, (9.4 ± 1.6) × 10-2 with broadband radiation centered at 313 nm and (5.2 ± 1.1) × 10-2 for broadband radiation centered at 350 nm (errors are 2σ). The major products in aqueous solutions are an imine that was also formed in the photolysis of the solid and a carboxylic acid derivative that is unique to the photolysis in water. Combining the larger quantum yields in water with the reduced absorption cross sections results in a calculated lifetime of NPM of only 5 min at a solar zenith angle of 35°, typical of 40°N latitude on April 1. The products do not absorb in the actinic region and hence will be long-lived with respect to photolysis

Oxidation of solid thin films of neonicotinoid pesticides by gas phase hydroxyl radicals

Neonicotinoids (NNs) are commonly found throughout the environment on surfaces such as seeds, soil, vegetation, and blowing dust particles. However, there is a paucity of data on the kinetics and oxidation products formed on contact with the atmosphere which limits understanding of their potentially far-reaching impacts. In this study, in situ attenuated total reflectance (ATR) FTIR spectroscopy was used to investigate the OH oxidation of thin films of three solid NNs, imidacloprid (IMD), dinotefuran (DNF) and clothianidin (CLD) at 295 ± 3 K. The experimentally measured reaction probabilities based on initial rates of NN loss are (1.6 ± 0.8) × 10-2 for IMD, (1.5 ± 0.6) × 10-2 for DNF and (0.9 ± 0.2) × 10-2 for CLD (±1s), suggesting initial NN lifetimes with respect to OH of 10-17 days. The kinetics were interpreted using a multiphase kinetics model, KM-SUB, which showed that the OH uptake and reaction occurred primarily in the surface layer. Products identified by mass spectrometry included carbonyl-, alcohol- and olefin-containing species formed via hydrogen abstraction from aliphatic C-H groups. Additionally, carbonyl-containing desnitro and urea derivative products were observed from secondary reactions of the initially formed photodegradation products. Reaction with OH will contribute to NN loss both during the day as well as at night when there are non-photolytic sources of this radical. Thus, OH reactions with both the parent neonicotinoid and its photodegradation products should be considered in assessing their environmental impacts