Efficient biodegradation of the recalcitrant organochlorine pesticide chlordecone under methanogenic conditions.

Anaerobic digestion (AD) has long been studied as an effective environmental and economic strategy for treating matrices contaminated with recalcitrant pollutants. In the present work, we investigated the bioremediation potential of AD on organic waste contaminated with chlordecone (CLD), an organochlorine pesticide extensively used in the French West Indies and classified among the most persistent organic pollutants. Digestates from animal and plant origins were supplemented with CLD and incubated under methanogenic conditions for over 40 days. The redox potential and pH monitoring showed that methanogenic conditions were preserved during the entire incubation period despite the presence of CLD. In addition, the comparison of the total biogas generated from digestates with and without CLD demonstrated no adverse effects of CLD on biogas production. For the first time, a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method, followed by GC-MS and LC-HRMS analyses, was developed to quantify CLD and its main known transformation products (TPs) in AD experiments. A decrease in CLD concentrations was evident to a greater extent under thermophilic conditions (55 °C) compared to mesophilic conditions (37.5 °C) (CLD removal of 85 % and 42 %, respectively, after 40 days of incubation). CLD degradation was confirmed by the detection and quantification of several TPs: 10-monohydroCLD (A1), two dihydroCLDs different from 2,8-dihydroCLD (A3), pentachloroindene (B1), tetrachloroindenes (B2, B3/B4), tetra- and tri-chloroindenecarboxylic acids (C1/C2, C3/C4). Determining TPs concentrations using the QuEChERS method provided an overview of CLD fate in AD. Overall, these results reveal that AD processes can efficiently degrade CLD into several TPs from A, B, and C families while maintaining satisfactory biogas production. They pave the way to developing a scaled-up AD process capable of treating CLD-contaminated organic wastes produced by farming, thus stopping any further transfer of CLD.

Development of a new dual electrochemical immunosensor for a rapid and sensitive detection of enrofloxacin in meat samples.

A novel dual electrochemical immunosensor was fabricated for the rapid and sensitive detection of enrofloxacin (EF) antibiotic in meat. Anti-quinolone antibody was immobilized onto screen-printed dual carbon electrodes via carbodiimide coupling. A new electrochemical probe was synthesized by conjugating difloxacin and aminoferrocene, whose oxidation was measured at + 0.2 V vs. Ag/AgCl by differential pulse voltammetry. The detection principle was based on the competitive binding of this conjugate and free EF on immobilized antibodies. The proposed immunosensor allowed detection of EF at concentrations ranging from 0.005 µg.mL-1 to 0.01 µg.mL-1 with a detection limit of 0.003 µg.mL-1. The immunosensor was stable for at least 1 month at 4 °C and displayed a good specificity for other fluoroquinolones. The new dual electrode design offered an improved accuracy as one electrode was used as negative control. The efficiency of the sensor and the adequacy of the extraction process were finally validated by detecting EF in different meat samples.

Synthesis and Characterization of Bis-1,2,3-Triazole Ligand and its Corresponding Copper Complex for the Development of Electrochemical Affinity Biosensors.

The bis-triazole ligand and its corresponding copper complexes were synthesized and characterized for the first time and proposed as new labels for the development of electrochemical aptasensors. The bis-triazole ligand was prepared from methyl 1,6-heptadiyne-4-carboxylate and 2-(azidomethyl)phenol using classical CuAAC in presence of different copper salts. The X-ray structure of bis-triazole showed a symmetry center (C1). UV-Vis and X-band EPR spectra showed that the coordination capacity of the bis-triazole ligand was improved in the presence of triethylamine due to deprotonation of the triazole and phenolate moieties. After complexation with copper, the obtained complex was successfully attached to an anti-estradiol aptamer through thiol-maleimide coupling, and the resulting labelled aptamer was immobilized on a carbon screen-printed electrode by carbodiimide coupling. The electrochemical response of the resulting sensor was shown to decrease in the presence of estradiol, demonstrating that the developed complexes can be applied for the development of aptasensors.

Effect of Distortions on the Geometric and Electronic Structures of One-Electron Oxidized Vanadium(IV), Copper(II), and Cobalt(II)/(III) Salen Complexes.

The ligands N,N'-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-ethanediamine and N,N'-bis(3-tert-butyl-5-methoxysalicylidene)-1,3-propanediamine were chelated to V(IV)═O (1, 2), Cu(II) (3, 4), Co(II) (5), and Co(III) (6). The X-ray crystal structures of 1-6 were solved. The vanadium center in 1-2 resides in square pyramidal geometry, with an axially bound oxo ligand, whereas the metal ion displays a tetrahedrally distorted square planar geometry in 3-5. The extent of distortion is correlated to the length of the diamine spacer: The longer the linker, the larger the tetrahedral distortions. Complex 6 is octahedral with a bidentate acetate molecule that completes the coordination sphere. All the complexes were characterized by UV-vis and EPR spectroscopies, as well as DFT calculations and electrochemistry. Complexes 1-6 exhibit a reversible one-electron oxidation wave in the range -0.11-0.26 V vs Fc+/Fc. The cations 1+ and 2+ were structurally characterized, showing an octahedral V(V) ion with one oxo and one water molecule coordinated in axial positions. Their vis-NIR spectra are dominated by a band at 727 and 815 nm, respectively, which is assigned to a phenolate-to-vanadium(V) charge transfer (CT) transition. The crystal structures of 3+ and 4+ are congruent with Cu(II)-radical species, wherein the metal center remains four-coordinated. Both feature a Class II (Robin-Day classification scale) IVCT transition at around 1200 nm (ε > 1 mM cm-1), indicative of partial localization of the radical. The structure of 5+ displays a square pyramidal cobalt ion, where the fifth (axial) coordination is occupied by a water molecule. It displays a NIR feature at 1244 nm and is described as intermediate between high spin Co(III) and Co(II) radical. In the presence of acetate the dimer [(5)2(µ-OAc)]+ forms, which was structurally characterized and shows a blue shift and lowering in intensity of the NIR absorption band in comparison to 5+. Complex 6+ is a genuine Co(III) radical complex, wherein the phenoxyl moiety is localized on one side of the molecule.

Reducing a model of sugar metabolism in peach to catch different patterns among genotypes.

Several studies have been conducted to understand the dynamic of primary metabolisms in fruit by translating them into mathematics models. An ODE kinetic model of sugar metabolism has been developed by Desnoues et al. (2018) to simulate the accumulation of different sugars during peach fruit development. Two major drawbacks of this model are (a) the number of parameters to calibrate and (b) its integration time that can be long due to non-linearity and time-dependent input functions. Together, these issues hamper the use of the model for a large panel of genotypes, for which few data are available. In this paper, we present a model reduction scheme that explicitly addresses the specificity of genetic studies in that: (i) it yields a reduced model that is adapted to the whole expected genetic diversity (ii) it maintains network structure and variable identity, in order to facilitate biological interpretation. The proposed approach is based on the combination and the systematic evaluation of different reduction methods. Thus, we combined multivariate sensitivity analysis, structural simplification and timescale-based approaches to simplify the number and the structure of ordinary differential equations of the model. The original and reduced models were compared based on three criteria, namely the corrected Aikake Information Criterion (AICC), the calibration time and the expected error of the reduced model over a progeny of virtual genotypes. The resulting reduced model not only reproduces the predictions of the original one but presents many advantages including a reduced number of parameters to be estimated and shorter calibration time, opening new promising perspectives for genetic studies and virtual breeding. The validity of the reduced model was further evaluated by calibration on 30 additional genotypes of an inter-specific peach progeny for which few data were available.

Salen/salan metallic complexes as redox labels for electrochemical aptasensors.

This work presents the synthesis and characterization of salen/salan metal complexes for their future application as electrochemical labels in affinity sensors. Due to its stability and electrochemical properties, an oxovanadium salan complex was selected and coupled to an estradiol-specific aptamer. The response of the resulting aptasensor was shown to decrease with increasing estradiol concentration.

Chemiluminescence immunoassays for estradiol and ethinylestradiol based on new biotinylated estrogen derivatives.

New chemiluminescence-based immunoassays for sensitive detection of 17-ß estradiol (E2) and ethinylestradiol (EE2) are described on the basis of the use of biotinylated estrogen derivatives. Estrogen derivatives bearing a carboxylic group (E2-COOH and EE2-COOH) on C-3 position were synthesized, covalently bound to aminated biotin and subsequently immobilized on avidin-coated microtiter plates. The assay principle was based on competition between free and immobilized estrogens for their binding to primary antibodies, with subsequent revelation using horseradish peroxidase (HRP)-labeled secondary antibodies. Under optimized conditions, the chemiluminescence immunoassays showed a highly sensitive response to E2 and EE2, with respective detection limits of 0.5 and 1.2 ng L-1. The LOD achieved using biotinylated E2 was in the same order of magnitude as those obtained using commercially available E2-bovine serum albumin conjugate (E2-BSA). The developed devices were successfully applied to analysis wastewater treatment plants effluents (WWTP) with negligible matrix effect.

Novel thin layer flow-cell screen-printed graphene electrode for enzymatic sensors.

A new Screen-printed electrodes (SPE) integrated in one channel flow-cell was developed. The one channel flow-cell is attached and directly changeable with electrode. In the new flow-cell the injection is done through an "in-line luer injection port" which can be less aggressive than wall-jet flow cell for a biological recognition element immobilized on the surface of the electrode. The sample volume can be easily controlled by the operator through a syringe. In this novel thin layer flow-cell screen-printed electrodes, the working electrode was modified with graphene materials, and an enhancement of electroactive area to 388% over a standard electrode was found. This new configuration was applied to study the entrapped cellobiose dehydrogenase from the ascomycete Corynascus thermophilus (CtCDH) in a photocrosslinkable PVA-based polymer. The calibration curve of lactose using optimized parameters shows a wide linear measurement ranges between 0.25 and 5mM. A good operational stability of the CtCDH-PVA-modified graphene electrode is obtained, which keeps the same initial activity during 8h and exhibits a good storage stability with a decrease of only 9% in analytical response after 3 months storage at 4◦C.

Immunosensors for estradiol and ethinylestradiol based on new synthetic estrogen derivatives: application to wastewater analysis.

Novel electrochemical immunosensors for sensitive detection of 17-ß estradiol (E2) and ethinylestradiol (EE2) are described on the basis of the use of magnetic beads (MBs) as solid support and screen-printed electrodes as sensing platforms. Four synthetic estrogen derivatives containing either a carboxylic group or an amine group at the C-3 position were synthesized and covalently bound to MBs functionalized with amine or carboxyl groups, respectively. The assay was based on competition between the free and immobilized estrogen for the binding sites of the primary antibody, with subsequent revelation using alkaline phosphatase-labeled secondary antibody. Preliminary colorimetric tests were performed in order to validate the applicability of the synthetic estrogens to immuno-recognition and to optimize different experimental parameters. In a second step, electrochemical detection was carried out by square wave voltammetry (SWV). Under the optimized working conditions, the electrochemical immunosensors showed a highly sensitive response to E2 and EE2, with respective detection limits of 1 and 10 ng/L. Cross-reactivity evaluated against other hormones demonstrated an excellent selectivity. The developed devices were successfully applied to analysis of spiked and natural water samples. These new immunosensors offer the advantages of being highly sensitive, easy, and rapid to prepare, with a short assay time.

Ligand contributions to the electronic structures of the oxidized cobalt(II) salen complexes.

Square planar cobalt(II) complexes of salen ligands N,N'-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexanediamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized into cations [1-H(2)O](+) and [2-H(2)O](+) in CH(2)Cl(2). The chemically generated [1-H(2)O](SbF(6))·0.68 H(2)O·0.82CH(2)Cl(2) and [2-H(2)O](SbF(6))·0.3H(2)O·0.85CH(2)Cl(2) were characterized by X-ray diffraction and NIR spectroscopy. Both complexes are paramagnetic species containing a square pyramidal cobalt ion coordinated at the apical position by an exogenous water molecule. They exhibit remarkable NIR bands at 1220 (7370 M(-1) cm(-1)) and 1060 nm (5560 M(-1) cm(-1)), respectively, assigned to a CT transition. DFT calculations and magnetic measurements confirm the paramagnetic (S = 1) ground spin state of the cations. They show that more than 70% of the total spin density in [1-H(2)O](+) and [2-H(2)O](+) is localized on the metal, the remaining spin density being distributed over the aromatic rings (30% phenoxyl character). In the presence of N-methylimidazole 1 and 2 are irreversibly oxidized by air into the genuine octahedral cobalt(III) bis(phenolate) complexes [1-im(2)](+) and [2-im(2)](+), the former being structurally characterized. Neither [1-im(2)](+) nor [2-im(2)](+) exhibits a NIR feature in its electronic spectrum. 1 and 2 were electrochemically two-electron oxidized into [1](2+) and [2](2+). The cations were identified as Co(III)-phenoxyl species by their characteristic absorption band at ca. 400 nm in the UV-vis spectrum. Coordination of the phenoxyl radical to the cobalt(III) metal ion is evidenced by the EPR signal centered at g = 2.00.