Glyphosate-Exonuclease Interactions: Reduced Enzymatic Activity as a Route to Glyphosate Biosensing.

N-phosphonomethyle-glycine (glyphosate) is the most widely used pesticide worldwide due to its effectiveness in killing weeds at a moderate cost, bringing significant economic benefits. However, owing to its massive use, glyphosate and its residues contaminate surface waters. On site, fast monitoring of contamination is therefore urgently needed to alert local authorities and raise population awareness. Here the hindrance of the activity of two enzymes, the exonuclease I (Exo I) and the T5 exonuclease (T5 Exo) by glyphosate, is reported. These two enzymes digest oligonucleotides into shorter sequences, down to single nucleotides. The presence of glyphosate in the reaction medium hampers the activity of both enzymes, slowing down enzymatic digestion. It is shown by fluorescence spectroscopy that the inhibition of ExoI enzymatic activity is specific to glyphosate, paving the way for the development of a biosensor to detect this pollutant in drinking water at suitable detection limits, i.e., 0.6 nm.

ISIDORE, a Probe for In Situ Trace Metal Speciation Based on the Donnan Membrane Technique and Electrochemical Detection Part 2: Cd and Pb Measurements during the Accumulation Time of the Donnan Membrane Technique.

The Donnan membrane technique (DMT), in which a synthetic or natural solution (the "donor") is separated from a ligand-free solution (the "acceptor") by a cation-exchange membrane, is a recognized technique for measuring the concentration of a free metal ion in situ, with coupling to electrochemical detection allowing for the quantification of the free metal ion directly on site. However, the use of the DMT requires waiting for the free metal ion equilibrium between the donor and the acceptor solution. In this paper, we investigated the possibility of using the kinetic information and showed that non-equilibrium experimental calibrations of Cd and Pb with the ISIDORE probe could be used to measure free metal concentrations under conditions of membrane-controlled diffusion transport. The application of this dynamic approach made it possible to successfully determine the concentration of free Cd in synthetic and natural river samples. Furthermore, it was found that the determination of free Cd from the slope was not affected by the Ca concentration ratio between the acceptor and donor solution, as opposed to the traditional approach based on Donnan equilibrium. This ISIDORE probe appears to be a promising tool for determining free metal ions in natural samples.

Direct analysis of trace elements in crude oils by high-repetition-rate femtosecond laser ablation coupled to ICPMS detection.

IR-femtosecond pulses were used at high repetition rates (up to 10 kHz) to ablate viscous crude oils for the determination of trace elements by ICPMS. A special internal glass cap was fitted into the ablation cell to minimise oil splashes and remove big particles that would be otherwise spread into the cell. Laser ablation in static and dynamic conditions (i.e. the laser beam being moved rapidly at the surface of the sample) was studied together with some fundamental parameters like repetition rate and fluence. Signal sensitivity and stability were found to be strongly affected by repetition rate and fluence, though not in linear manner, and in some circumstances by the laser beam velocity. Sample transport efficiency was found to decrease with increasing repetition rate, probably due to stronger particle agglomeration when increasing the density of primary particles. ICPMS plasma atomisation/ionisation efficiency was also found to be affected to some extent at the highest repetition rates. Moderate repetition rate (1 kHz), high fluence (24 J cm(-2)) and fast scanning velocity (100 mm s(-1)) were preferred taking into account signal intensity and stability. Sample transport elemental fractionation was also evidenced, particularly as regards to carbon due to volatilisation of volatile organic species. Matrix effect occurring when comparing the ablation of transparent (base oil) and opaque (crude oil) samples could not be completely suppressed by the use of IR femtosecond pulses, requiring a matrix matching or a standard addition calibration approach. This approach provided good accuracy and very low detection limits in the crude oil, in the range of ng g(-1).