Synthesis, characterisation and magnetic properties of cobalt (II) complexes with 3-hydroxypicolinic acid (HpicOH): [Co(picOH)2(H2O)(2)] and mer-[N(CH3)(4)][Co(picOH)(3)] . H2O

Two complexes with Co2+ and 3-hydroxypicolinic acid, [Co(picOH)2(H2O)2] (I) and mer-[N(CH3)4][Co(picOH)3] Æ H2O (II), have been synthesised and characterised using single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, and thermoanalytical measurements. The 3-hydroxypicolinate ligands are coordinated to the Co2+ centres via its typical N,O-chelating coordination fashion. While in I the presence of two coordinated water molecules leads to the formation of a neutral [Co(picOH)2(H2O)2] complex which is strongly hydrogen bonded to another four neighbouring complexes, in II the inclusion of a third picOH ligand leads to an anionic octahedral complex, [Co(picOH)3] , in which all the N- and O-atoms are occupying mer positions. The properties of these two compounds were further investigated by measuring their magnetic behaviour

Synthesis, characterisation and magnetic properties of copper(II) complexes with 3-hydroxypicolinic acid (HpicOH): the crystal structure of [Cu(picOH)(2)(BPE)](2) . [Cu(picOH)(2)(BPE)(2)] . 8H(2)O

A novel 1D coordination polymer, [Cu(picOH)2(BPE)] (IIa), and neutral [Cu(picOH)2(BPE)2] (IIb) complexes, can be simultaneously isolated (structure II) when neutral [Cu(picOH)2] (I) species are axially bridged by 1,2-bis(4-pyridyl)ethane (BPE) molecules. The compound has been characterised structurally using single-crystal X-ray diffraction, elemental analysis, infrared and Raman spectroscopies and thermoanalytical measurements. In both structures the 3-hydroxypicolinate ligands are coordinated to the Cu2C centres through their typical N,O-chelating coordination, with the increase of coordination number in II leading to a typical Jahn–Teller distorted octahedral coordination geometry. Although the structure of I has already been reported, we have re-determined its single-crystal structure at the low temperature of 180(2) K for comparative purposes. The magnetic properties of both compounds have also been investigated

Lipid peroxidation and its control in Anguilla anguilla hepatocytes under silica-coated iron oxide nanoparticles (with or without mercury) exposure

Having multidisciplinary applications, iron oxide nanoparticles can inevitably enter aquatic system and impact inhabitants such as fish. However, the studies in this context have ignored the significance of obvious interaction of iron oxide nanoparticles with other persistent co-contaminants such as mercury (Hg) in the modulation of the toxicity and underlying mechanisms of iron oxide nanoparticles and Hg alone, and concomitant exposures. This study aimed to evaluate lipid peroxidation (LPO) and its control with glutathione (GSH) and associated enzymes (such as glutathione reductase, GR; glutathione peroxidase, GPX; glutathione sulfo-transferase, GST) in European eel (Anguilla anguilla L.) hepatocytes exposed to stressors with following schemes: (i) no silica-coated iron oxide nanoparticles functionalized with dithiocarbamate (Fe3O4@SiO2/Si DTC, hereafter called 'FeNPs'; size range 82 +/- 21 to 100 +/- 30 nm) or Hg, (ii) FeNPs (2.5 mu g L-1) alone, (iii) Hg (50 mu g L-1) alone and (iv) FeNPs + Hg concomitant condition during 0 to 72 h. The exhibition of a differential coordination between GSH regeneration (determined as GR activity) and GSH metabolism (determined as the activity of GPX and GST) was perceptible in A. anguilla hepatocytes in order to control FeNPs, Hg and FeNPs + Hg exposure condition-mediated LPO. This study revealed the significance of a fine tuning among GR, GPX and GST in keeping LPO level under control during FeNPs or Hg alone exposure, and a direct role of total GSH (TGSH) in the control of LPO level and impaired GSH metabolism under the concomitant (FeNPs + Hg) exposure. An interpretation of the fish risk to FeNPs in a multi-pollution state should equally consider the potential outcome of the interaction of FeNPs with other contaminants

An integrated approach for trace detection of pollutants in water using polyelectrolyte functionalized magneto-plasmonic nanosorbents

Resistance of pathogenic micro-organisms to conventional antibiotics is an essential issue for public health. The presence of such pharmaceuticals in aquatic ecosystems has been of major concern for which remediation and ultra-sensitive monitoring methods have been proposed. A less explored strategy involves the application of multifunctional nanosorbents for the uptake and subsequent detection of vestigial contaminants. In this study, colloidal nanoparticles (NPs) of iron oxide and gold were encapsulated in multi-layers of a charged polyelectrolyte (PEI: polyethyleneimine), envisaging the effective capture of tetracycline (TC) and its subsequent detection by Surface Enhanced Raman Scattering (SERS). Adsorption studies were performed by varying operational parameters, such as the solution pH and contact time, in order to evaluate the performance of the nanosorbents for the uptake of TC from water. While the magnetic nanosorbents with an external PEI layer (Fe3O4@PEI and Fe3O4@PEI-Au@PEI particles) have shown better uptake efficiency for TC, these materials showed less SERS sensitivity than the Fe3O4@PEI- Au nanosorbents, whose SERS sensitivity for TC in water has reached the limit of detection of 10 nM. Thus, this study highlights the potential of such magneto-plasmonic nanosorbents as multi-functional platforms for targeting specific contaminants in water, by taking into consideration both functionalities investigated: the removal by adsorption and the SERS detection across the nanosorbents' surfaces.publishe

Phagocytic cell responses to silica-coated dithiocarbamate-functionalized iron oxide nanoparticles and mercury co-exposures in Anguilla anguilla L.

Immune system responses in fish are considered as suitable and sensitive biomarkers for monitoring aquatic pollution. However, a clear knowledge gap persists in the literture on the immunotoxic potential of engineered nanoparticles toward aquatic organisms such as fish. Employing major enzymatic- (glutathione reductase, GR; glutathione peroxidase, GPX; glutathione sulfo-transferase, GST; catalase, CAT) and thiol- (non-protein thiols, NP-SH; total glutathione, TGSH)-based defense biomarkers, this study assessed the response of phagocytes isolated from peritoneum (P-phagocytes), gill (G-phagocytes), head kidney (HK-phagocytes), and spleen (S-phagocytes) of European eel (Anguilla anguilla L.) to silica-coated magnetite particles (Fe3O4@SiO2/SiDTC, hereafter called IONP; size range: 82 +/- 21 to 100 +/- 30 nm; 2.5 mg L-1) alone and IONP and mercury (Hg; 50 mu g L-1) concomitant exposures. Responses of previous biomarkers were studied in P-phagocytes, G-phagocytes, HK-phagocytes, and S-phagocytes collected during 0, 2, 4, 8, 16, 24, 48, and 72 h of exposures. Contingent to hour of exposure to IONP, Hg, and IONP + Hg GST, GPX, CAT, NP-SH, and TGSH exhibited their differential responses in all the phagocytic cells considered. In particular, under IONP exposure, the potential occurrence of the GSH-independent antioxidant defense was indicated by the observed herein inhibition in the enzymatic- and thiol-based defense in A. anguilla phagocytes. In contrast, the response of P-, G-, HK-, and S-phagocytes to the increasing Hg exposure period reflected an increased detoxification activity. Notably, the occurrence of an antagonism between IONP and Hg was depicted during late hours (72 h) under IONP + Hg concomitant exposure, where elevations in the defense biomarkers were depicted. Overall, the P-, G-, HK-, and S-phagocytic cells exhibited a differential induction in the studied enzymes and thiols to counteract impacts of IONP, Hg, and IONP + Hg concomitant exposures. Future studies on the fish immunotoxicity responses to IONP exposure in multi-pollution conditions can be benefited with the major outcomes of the present study

Brain glutathione redox system significance for the control of silica-coated magnetite nanoparticles with or without mercury co-exposures mediated oxidative stress in European eel (Anguilla anguilla L.)

This in vitro study investigates the impact of silicacoated magnetite particles (Fe3O4@SiO2/SiDTC, hereafter called IONP; 2.5 mg L-1) and its interference with coexposure to persistent contaminant (mercury, Hg; 50 mu g L-1) during 0, 2, 4, 8, 16, 24, 48, and 72 h on European eel (Anguilla anguilla) brain and evaluates the significance of the glutathione (GSH) redox system in this context. The extent of damage (membrane lipid peroxidation, measured as thiobarbituric acid reactive substances, TBARS; protein oxidation, measured as reactive carbonyls, RCs) decreased with increasing period of exposure to IONP or IONP + Hg which was accompanied with differential responses of glutathione redox system major components (glutathione reductase, GR; glutathione peroxidase, GPX; total GSH, TGSH). The occurrence of antagonism between IONP and Hg impacts was evident at late hour (72 h), where significantly decreased TBARS and RC levels and GR and glutathione sulfotransferase (GST) activity imply the positive effect of IONP + Hg concomitant exposure against Hg-accrued negative impacts [vs. early (2 h) hour of exposure]. A period of exposuredependent IONP alone and IONP + Hg joint exposureaccrued impact was perceptible. Additionally, increased susceptibility of the GSH redox system to increased period of exposure to Hg was depicted, where insufficiency of elevated GR for the maintenance of TGSH required for membrane lipid and cellular protein protection was displayed. Overall, a finetuning among brain glutathione redox system components was revealed controlling IONP + Hg interactive impacts successfully