Voltammetric studies of damages in DNA by mutagenic and carcinogenic alkylating chemicals

Voltammetry provides new insights into the effects exerted in vitro by methylation of native DNA. Applying single sweep voltammetry at a stationary mercury electrode the successive steps of the destabilization of alkylated DNA are investigated. The methylation of the nucleic acids is manifested by a specific electrochemical response, due to the 7‐methylguanine, a major product of the methylation of DNA. Short time effects of the methylation include the labilization of 4 to 5 base pairs per methylated guanine base. Furthermore, uncommon protonation properties of the base 7‐methylguanine‐cytosine have been detected. Long term effects of the methylation are ultimately spontaneous hydrolytic strand breaks induced by the prior depurination connected with the release of the 7‐methylguanine from the methylated DNA. A half time t_1/2 of 102 h for the depurination at 37°C has been determined. The depurination and the subsequent strand breaks alter the hydrodynamic properties of the damaged DNA, an effect which can be sensitively followed with voltammetry via the resulting changes in the diffusion coefficient of the damaged biopolymer.     

Polarographic investigations on the complexation of cadmium and zinc by thiol peptides

Complex formation of Cd²⁺ and Zn²⁺ with thiol derivatives has been investigated by differential pulse polarography. The binding of Cd²⁺ and Zn²⁺ with cysteine (CySH), glutathione (GSH) and the model peptide N‐acetyl‐cysteine‐methylamide (ASH) reveals different stoichiometry. Thus, Cd²⁺ forms 1:1 and 1:2 complexes with CySH while 1:2 and 1:4 complexes have been observed with GSH and ASH, respectively. Overall formation constants of Cd²⁺ with CySH (Iogβ ₂ 15.3) and with GSH (Iogβ5₂ 14.4) have been estimated using competitive complexation with nitrilotriacetic acid (NTA). Investigation of competition between Zn²⁺ and Cd²⁺ for the thiol complexation has underlined the role played by the amino group in CySH for the stabilization of Zn complexes in contrary to Cd complexes.     

Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

Sublethal concentrations of azinphos-methyl induce biochemical and morphological alterations in Rhinella arenarum embryos

Considering that amphibians are good sentinels of environmental conditions, Rhinella arenarum embryos were used to investigate the effects of sublethal concentrations of the organophosphorus insecticide azinphos-methyl, focusing on its anticholinesterasic or pro-oxidant actions and its possible connection with the appearance of morphological alterations. Early amphibian embryos exposed to azinphos-methyl displayed a protective response through glutathione S-transferase induction, along with superoxide dismutase inhibition. At intermediate embryonic stages, embryos exposed to azinphos-methyl displayed superoxide dismutase inhibition and morphological alterations, although cholinesterase activity was not altered, suggesting that molecular targets other than cholinesterase were involved in the development of morphological alterations. At the end of embryonic development, decreases in reduced glutathione and cholinesterase inhibition were observed, along with a significant increase in the number of malformed embryos. The connection between biochemical alterations and the appearance of malformations was not evident in R. arenarum embryos. However, increased glutathione S-transferase and decreased superoxide dismutase activities could be considered as early markers of exposure to azinphos-methyl. The results obtained demonstrate that sublethal concentrations of azinphos-methyl are a serious threat to toad embryos in their natural habitats because biochemical and morphological alterations could impair their ability to deal with environmental stresses.     

Temporal variation of the concentration and biochemical composition of seston within the Humboldt Current System off northern Chile (21°S)

Seasonal differences in the concentration and biochemical composition of seston have been assessed for the first time in the Humboldt Current System off northern Chile (21°S). The study comprised four seasonal surveys in the Bay of Chipana, including the summer and winter of 2006 and 2007, when El Niño 2006 and La Niña 2007 developed. Protein, lipid, carbohydrate and biogenic silica contents were measured in samples collected at four selected depths. The highest protein, lipid and carbohydrate concentrations were found at the fluorescence maximum (between 10 and 15 m depth), whereas the highest biogenic silica concentration was found 1 m above the seabed. When El Niño started developing, every variable showed low values throughout the water column; however, the lowest values were found when La Niña conditions dominated, together with low oxygen concentrations. Samples collected within the oxygen minimum zone (65 m depth) showed the lowest values for the water column and the lowest seasonal variations. After the evident decline coincident with El Niño 2006, the abundance and biochemical quality (high protein and lipid contents) of seston recovered earlier in the surface layer (upper 15 m) than at other depths.     

Physicochemical properties of non-living water hyacinth (Eichhornia crassipes) and lesser duckweed (Lemna minor) and their influence on the As(V) adsorption processes

Eichhornia crassipes (Ec) and Lemna minor (Lm) are aquatic plants. They are considered as weeds of the water and approach being a scourge in many parts of the world, choking waterways and hindering transport upon them. At the same time they are known to readily remove heavy metal ions from water. This paper considers the use of non-living plants as novel and inexpensive biosorbent for the removal of As(V) from watersheds. In the first place they were conditioned and characterised to determine their physicochemical and surface properties and in the second place their adsorption properties for As(V) from aqueous solution were evaluated considering the toxicity of this metalloid in the environment. It describes the methodology to prepare the non-living biomasses; the physicochemical characterisation by SEM, XRD, FTIR, TGA analyses and surface characterisation of Ec and Lm by specific surface, hydration kinetic, point of zero charge determination by mass titration, active site density and XPS analysis are described. Both studied biomasses were found to be potential bio-sorbents for arsenic ions from aqueous solution. According to their efficiency to remove arsenic, they can be used in a very low cost metalloid ions removal system.     

How age and sex drive the foraging behaviour in the king penguin

As predicted by life history theory, once recruited into the breeding population and with increasing age, long-lived animals should be able to manage more efficiently the conflict between self-maintenance and reproduction. Consequently, breeding performances should improve with age before stabilizing at a certain level. Using temperature–depth recorders and isotopic analysis, we tested how age affects the foraging behaviour of king penguin Aptenodytes patagonicus during one trip in the chick-rearing phase. Depending on sex and age, king penguins expressed two different foraging strategies. Older birds gained more daily mass per unit body mass than younger ones. Older females conducted shorter trips, dived deeper and performed more prey pursuits. They also had higher blood levels of δ¹⁵N than younger individuals and males indicating sex- and age-specific dietary regimes. However, we found no differences in carbon isotopic signature, suggesting that individuals exploited the same foraging areas independently of sex and age. Our results suggest that king penguins are able to increase the quantity of energy extracted with increasing age and that such a strategy is sex-related. Our study is the first to reveal of an interaction between age and sex in determining foraging efficiency in king penguins.     

Regional extinction of a conspicuous dorid nudibranch (Mollusca: Gastropoda) in California

Felimare californiensis (=Hypselodoris californiensis) was once common throughout the Southern California Bight (SCB) and California Channel Islands. This well-known shallow-water nudibranch, which specializes on dysideid sponges, has persisted for decades in Mexico, but in California disappeared from its entire range by 1984. Since reappearing in 2003, it has been found only at Santa Catalina Island, plus sightings of single individuals in 2011 at Santa Cruz Island and San Diego. The decline of F. californiensis in California was documented using published historical records, museum collections, unpublished field accounts, and images posted online. The loss of this emblematic species is unique among Californian nudibranchs, including (1) its congener Felimare porterae (=Mexichromis porterae), with which it appears to overlap in diet, and (2) opisthobranch species with similar historical geographic ranges and mode of development. The decline in F. californiensis is not predicted by warming trends and climate variation over the past 40 years, including the strong El Niño events of 1983 and 1998. Coastal pollution from the large human population in southern California may have impacted Dysidea amblia, the primary reported prey of F. californiensis. Historical overcollecting of the nudibranch and habitat loss through the development of major ports likely also contributed to its decline. Sightings since 2003 are consistent with a nascent recovery, as elements of water quality have improved in the SCB in recent decades.