Carbon nanomaterial functionalization with pesticide-detoxifying carboxylesterase.

Four carbon materials, spent coffee-ground biochar, carbon black, short CNTs, and nitrogen-doped few-layer graphene (N-graphene) were tested for their functionalization with a commercial carboxylesterase. Their robustness to variations in time and key physicochemical parameters (temperature and pH) was analysed. In general, carbon nanomaterials showed better performance than biochar, both in terms of binding capacity and resilience in harsh conditions, at statistically significant levels. Among the tested materials, functionalized N-graphene also showed the highest level of inhibition of carboxylesterase by pesticide exposure. Therefore, N-graphene was selected for biotechnological application of pesticide scavenging toxicity in T. thermophila, a ciliate bioindicator of water quality. While immobilization of the enzyme was not effective in the case of carbaryl, a methyl carbamate, in the case of the organophosphorus dichlorvos, a 1- or 30-min contact time with a water solution containing 5 times the LC100 - 0.5 mM - allowed 50% and 100% rescue of ciliate survival, respectively. These results suggest that functionalization with carboxylesterase may be of additional benefit compared to bare carbon in water clean-up procedures, especially for highly hydrophilic pesticides such as dichlorvos.

Triple Oxygen Isotope Measurements (Δ'17O) of Body Water Reflect Water Intake, Metabolism, and δ18O of Ingested Water in Passerines.

Understanding physiological traits and ecological conditions that influence a species reliance on metabolic water is critical to creating accurate physiological models that can assess their ability to adapt to environmental perturbations (e.g., drought) that impact water availability. However, relatively few studies have examined variation in the sources of water animals use to maintain water balance, and even fewer have focused on the role of metabolic water. A key reason is methodological limitations. Here, we applied a new method that measures the triple oxygen isotopic composition of a single blood sample to estimate the contribution of metabolic water to the body water pool of three passerine species. This approach relies on Δ'17O, defined as the residual from the tight linear correlation that naturally exists between δ17O and δ18O values. Importantly, Δ'17O is relatively insensitive to key fractionation processes, such as Rayleigh distillation in the water cycle that have hindered previous isotope-based assessments of animal water balance. We evaluated the effects of changes in metabolic rate and water intake on Δ'17O values of captive rufous-collared sparrows (Zonotrichia capensis) and two invertivorous passerine species in the genus Cinclodes from the field. As predicted, colder acclimation temperatures induced increases in metabolic rate, decreases in water intake, and increases in the contribution of metabolic water to the body water pool of Z. capensis, causing a consistent change in Δ'17O. Measurement of Δ'17O also provides an estimate of the δ18O composition of ingested pre-formed (drinking/food) water. Estimated δ18O values of drinking/food water for captive Z. capensis were ~ -11‰, which is consistent with that of tap water in Santiago, Chile. In contrast, δ18O values of drinking/food water ingested by wild-caught Cinclodes were similar to that of seawater, which is consistent with their reliance on marine resources. Our results confirm the utility of this method for quantifying the relative contribution of metabolic versus pre-formed drinking/food water to the body water pool in birds.

The interplay between ambient temperature and salt intake affects oxidative status and immune responses in a ubiquitous Neotropical passerine, the rufous-collared sparrow.

Physiological traits associated with maintenance, growth, and reproduction demand a large amount of energy and thus directly influence an animal's energy budget, which is also regulated by environmental conditions. In this study, we evaluated the interplay between ambient temperature and salinity of drinking water on energy budgets and physiological responses in adult Rufous-collared sparrow (Zonotrichia capensis), an omnivorous passerine that is ubiquitous in Chile and inhabits a wide range of environments. We acclimated birds to 30 days at two ambient temperatures (27 °C and 17 °C) and drinking water salinity (200 mM NaCl and fresh water) conditions. We evaluated: 1) the aerobic scope and the activities of mitochondrial metabolic enzymes, 2) osmoregulatory parameters, 3) the skin-swelling immune response to an antigen, 4) oxidative status, and 5) the length of telomeres of red blood cells. Our results confirm that Z. capensis tolerates the chronic consumption of moderate levels of salt, maintaining body mass but increasing their basal metabolic rates consistent with expected osmoregulatory costs. Additionally, the factorial aerobic scope was higher in birds acclimated to fresh (tap) water at both 17° and 27 °C. Drinking water salinity and low ambient temperatures negatively impacted inflammatory response, and we observed an increase in lipid peroxidation and high levels of circulating antioxidants at low temperatures. Finally, telomere length was not affected by osmo- and thermoregulatory stress. Our results did not support the existence of an interplay between environmental temperature and drinking water salinity on most physiological and biochemical traits in Z. capensis, but the negative effect of these two factors on the inflammatory immune response suggests the existence of an energetic trade-off between biological functions that act in parallel to control immune function.

Plasma esterases in the tegu lizard Tupinambis merianae (Reptilia, Teiidae): impact of developmental stage, sex, and organophosphorus in vitro exposure.

PURPOSE: In this study, we determined normal serum butyrylcholinesterase (BChE) and carboxylesterase (CbE) activities in Tupinambis merianae in order to obtain reference values for organophosphorus pesticide monitoring. METHODS: Forty-two T. merianae individuals were grouped by sex and size to identify potential differences in their enzyme levels to allow for proper representation of normal values for females, males, juveniles, and hatchlings. Mean CbE was determined using two model substrates: alpha-naphtylacetate (α-NA) and p-nitrophenyl valerate (4-NPV). BChE and CbE sensitivity to malaoxon (Mx) was also evaluated as well as the possibility of BChE reactivation with pyridine-2-aldoxime methochloride (2-PAM). RESULTS: Mean adult females' BChE was significantly higher than adult males, juveniles, and hatchlings. No significant differences were found between groups regarding CbE. CbE (4-NPV) activity showed slightly negative correlation with lizard snout-vent length, while BChE and CbE (α-NA) showed no correlation with body size. Apparent IC(50) values for BChE and CbE (α-NA) suggested different sensitivities among groups. CbE (4-NPV) could not be inhibited. All Mx-inhibited groups treated with 2-PAM in a final concentration of 2.8 mM showed clear signs of reactivation. CONCLUSIONS: In conclusion, the results demonstrate that (1) plasma esterase activity did not vary with age and sex, except for BChE activity, and (2) because biological and environmental variables could be confounding factors in the response of plasma cholinesterases, complementary biomarkers like CbE inhibition and oxime-induced reactivation of esterases are strongly recommended.