A recyclable bifunctional acid-base organocatalyst with ionic liquid character. The role of site separation and spatial configuration on different condensation reactions.

A series of bifunctional organic catalysts containing acid and basic sites with ionic liquid characteristics have been prepared and their catalytic activity and reaction coordinate for aldol and Knoevenagel condensations have been compared. While the only factor controlling catalyst activity for the Knoevenagel condensation was the distance between the acid and base sites, the spatial orientation of the organocatalyst is also key to achieve high activity and selectivity in the Claisen-Schmidt condensation. Mechanistic studies based on theoretical DFT calculations show that the acid-base bifunctional organocatalyst follows a mechanism inspired in natural aldolases for the synthesis of trans-chalcones, being able to produce a large variety of these compounds of industrial interest. The combination of the acid-base pairs within the proper geometry and the ionic liquid nature makes this catalyst active, selective and recyclable.

Legacy and current-use pesticides (CUPs) in the atmosphere of a rural area in central Chile, using passive air samplers.

Polyurethane foam (PUF) disks in passive air samplers (PAS) and passive dry deposition (Pas-DD) collectors were used to assess the presence of persistent organic pollutants (POPs) and current-use pesticides (CUPs) in a rural area of central Chile (Peumo, VI Region). The samplers were exposed from September 2015 (spring) to March 2016 (summer), with the PUFs collected at intervals of 30, 60, and 90 days. Both samplers (PUF-PAS and Pas-DD) captured more than one pesticide per sampling period. Chlorpyrifos-ethyl and pyrimethanil presented the highest air concentration with PUF-PAS (3470.2 ng m-3 for chlorpyrifos-ethyl and 52.8 ng m-3 for pyrimethanil). The deposited amount of chlorpyrifos-ethyl, pyrimethanil, penconazole, diazinon and malathion in some Pas-DD, was superior to amount of pesticides captured by PUF-PAS. Differences between the amount deposited and captured by each sampler should be studied in greater detail, because wind speed, atmospheric particulate matter size and sampler design are some fundamental variables in this process. These results provide preliminary information on the presence of current-use pesticides in the atmosphere of Peumo, VI Region, serving as a foundation for future environmental monitoring programs.

Residues of pesticides and some metabolites in dissolved and particulate phase in surface stream water of Cachapoal River basin, central Chile.

In the last twenty years, pesticide use in Chile has increased more than 160%, generating a greater risk of water resources pollution. The objective of this study was to assess the presence of 22 pesticides and 12 degradation products in surface water samples from the Cachapoal River basin, Central Chile, an area characterized by intense agricultural activity. Pesticide concentrations in the dissolved phase (DP) and particulate phase (PP) in samples collected in the dry season and after precipitation events was assessed. The solid-phase extraction technique was used to preconcentrate the samples and GC/MS and LC/MS were used to detect pesticides. The results present spatio-temporal variations in the proportion and concentration of pesticides and their degradation products in both the DP and PP for each site and sampling period. The most ubiquitous compounds in the dissolved phase were atrazine, atrazine-2-hydroxy (HA), cyprodinil, pyrimethanil, and tebuconazole, while in the particulate phase HA, imidacloprid, diazinon and pyrimidinol were detected. The results presented in this study make up the first record of pesticides in the dissolved and particulate phases in surface water in Chile. They show that the problem of pesticide contamination undoubtedly affects the quality of bodies of water in agricultural areas in Chile and support the need for a proper assessment of the water quality of the Cachapoal River in the future.

Historical anthropogenic mercury in two lakes of Central Chile: comparison between an urban and rural lake.

Mercury concentrations in the environment tend to decrease in recent years due to environmental restrictions. Lakes store mercury in their sediments, making them potential secondary contamination sources. In South America, the occurrence of mercury in lake systems has been associated mainly with volcanic emissions and only few records anthropogenic contamination in the pre-Hispanic period. The objective of this research was to study historical anthropogenic mercury concentration in two lakes in Central Chile (La Señoraza and Pillo), in order to establish background mercury levels and their variations from preindustrial to modern periods. Different background levels and mercury concentrations were found in each lake, with significantly higher concentrations in Lake La Señoraza during the last 150 years. Mining-related activities during the nineteenth century could have a negligible influence on mercury concentrations. Later on, the use of coal railroads and subsequent employment of mercury in the cellulose industry were associated with three- and fourfold increases in mercury concentration over the nineteenth century background levels, which decrease once these activities ceased. However, in the case of Lake Pillo, an important increase in mercury concentration can be observed between 1990 and the early twenty-first century, which could be related to a higher watershed/lake area ratio, extensive agriculture, and volcanic emission, being the latter that could have contributed with mercury to both systems. Nevertheless, sedimentological characteristics in Lake Pillo can be favorable to retain mercury in this aquatic system up to the present day.

Model studies on a carprofen derivative as dual photosensitizer for thymine dimerization and (6-4) photoproduct repair.

Cyclobutane pyrimidine dimers (CPD) and (6-4) photoproducts are among the main UV-induced DNA lesions. Both types of damage are mostly repaired in prokaryotes by photolyase enzymes. The repair mechanism of (6-4) photolyases has still not been fully elucidated, but it is assumed that back rearrangement to the oxetane occurs prior to repair. In this work, a non-steroidal anti-inflammatory drug derivative corresponding to the dechlorinated methyl ester of carprofen (namely methyl 2-(carbazol-2-yl)propanoate, PPMe) has been used to achieve the photosensitized cycloreversion of model oxetanes (formally resulting from photocycloaddition between benzophenone and 1,3-dimethylthymine or 2'-deoxyuridine), by employing fluorescence spectroscopy, laser flash photolysis, HPLC and NMR. Although PPMe is able to photoinduce the cycloreversion of both oxetanes, the fluorescence quenching of PPMe is faster for the 2'-deoxyribose-containing oxetane; this underlines the importance of the structure in such studies. Moreover, PPMe was shown to photoinduce the formation of thymidine cyclobutane dimers through a triplet-triplet energy transfer from a vibrationally excited state, as suggested by the enhanced PPMe triplet quenching by thymidine with increasing temperature. These results reveal a dual role of PPMe in DNA photosensitization, in that it photoinduces either damage or repair.