Rationally Designed Ag@polymer@2-D LDH Nanoflakes for Bifunctional Efficient Electrochemical Sensing of 4-Nitrophenol and Water Oxidation Reaction.

The rational design and demonstration of a facile sequential template-mediated strategy to construct noble-metal-free efficient bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and electrocatalytic detection of hazardous environmental 4-nitrophenol (4-NP) have continued as a major challenging task. Herein, we construct a novel Ag@polymer/NiAl LDH (designated as APL) nanohybrid as an efficient bifunctional electrocatalyst by a simple hydrolysis method. The well-fabricated APL/GCE exhibited an extensive linear range from 0.1 to 100 µM in optimized conditions. It showed a detection limit (LOD) of 0.0096 µM (9.6 nM) (S/N = 3) for 4-NP in pH 6 by differential pulse voltammetry (DPV). Meanwhile, the newly fabricated APL exhibited outstanding OER activity with a very low overpotential of 259 mV to deliver 10 mA cm-2 current density (J) at a scan rate of 5 mV/s. The Tafel plot value of APL is low (97 mV/dec) compared to that of the benchmark RuO2 due to a fast kinetic reaction. Besides, the durability of the electrocatalyst was assessed by a chronoamperometry test (CA) for 36 h at 1.55 mV vs RHE, and the long-term cycling stability was analyzed by using cyclic voltammetry (CV); after 5000 cycles, the electrocatalyst was highly stable. These demonstrated results could lead to an alternative electrocatalyst construction for the bifunctionally efficient electrochemical sensing of 4-nitrophenol and oxygen evolution reaction.

Nanomolar determination of 4-nitrophenol based on a poly(methylene blue)-modified glassy carbon electrode.

A poly(methylene blue)-modified glassy carbon electrode (PMB/GCE) was fabricated by electropolymerisation of methylene blue on a GCE and further utilized to investigate the electrochemical determination of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), differential pulse voltammetry and chronocoulometry. The morphology of the PMB on GCE was examined using a scanning electron microscope (SEM). An oxidation peak of 4-NP at the PMB modified electrode was observed at 0.28 V, and in the case of bare GCE, no oxidation peak was observed, which indicates that PMB/GCE exhibits a remarkable effect on the electrochemical determination of 4-NP. Due to this remarkable effect of PMB/GCE, a sensitive and simple electrochemical method was proposed for the determination of 4-NP. The effect of the scan rate and pH was investigated to determine the optimum conditions at which the PMB/GCE exhibits a higher sensitivity with a lower detection limit. Moreover, kinetic parameters such as the electron transfer number, proton transfer number and standard heterogeneous rate constant were calculated. Under optimum conditions, the oxidation current of 4-NP is proportional to its concentration in the range of 15-250 nM with a correlation coefficient of 0.9963. The detection limit was found to be 90 nM (S/N = 3). The proposed method based on PMB/GCE is simple, easy and cost effective. To further confirm its possible application, the proposed method was successfully used for the determination of 4-NP in real water samples with recoveries ranging from 97% to 101.6%. The interference due to sodium, potassium, calcium, magnesium, copper, zinc, iron, sulphate, carbonate, chloride, nitrate and phosphate was found to be almost negligible.

New 'side-off' coordination asymmetric homobinuclear Ni(II) and heterobinuclear Ni(II)Zn(II) complexes as models for hydrolysis of p-nitrophenylphosphate: synthesis, characterization and electrochemical studies.

A series of new phenol based coordination asymmetric side-off homobinuclear Ni(II) and heterobinuclear Ni(II)Zn(II) complexes have been synthesized and characterized by elemental analysis and spectral analysis. The electronic spectra of all the complexes show "Red shift" in LMCT band, for the ligand H(2)L(2) having electron donating C(2)H(5) groups as N-substituents in the free side arms compared to ligand H(2)L(1) having relatively lower electron donating CH(3) groups. Electrochemical studies of the complexes reveal that all the binuclear complexes show two irreversible one-electron transfer reduction waves in the cathodic region. There is an "anodic shift" in the first reduction potential of the complexes of the ligand H(2)L(1) when compared to that of the complexes of the ligand H(2)L(2) due to the presence of higher electron donating C(2)H(5) N-substituents in the later case than the relatively lower electron donating N-substituents in the former case. Hydrolysis of p-nitrophenylphosphate using homobinuclear Ni(II) and heterobinuclear Ni(II)-Zn(II) complexes as catalysts showed that the homobinuclear complexes have higher rate constant values than that of the corresponding heterobinuclear complexes. A comparison of the spectral, electrochemical and catalytic behavior of the complexes of the ligands is discussed on the basis of the electron donating nature of the N-substituents at the free side arms.

Protective effect of macrocyclic binuclear oxovanadium complex on oxidative stress in pancreas of streptozotocin induced diabetic rats.

Chronic hyperglycemia in diabetes is a major causative factor of free radical generation which further leads to many secondary diabetic complications via the damage to cellular proteins, membrane lipids, nucleic acids and eventually to cell death. Recently we have reported on the hypoglycemic efficacy of a new macrocyclic binuclear oxovanadium complex and its non-toxic nature. This study focuses on the effect of the above complex in ameliorating oxidative stress in the pancreas of diabetic rats. Streptozotocin induced diabetic rats were treated orally with the vanadium complex (5 mg/kg/body weight) for 30 days and the level of pancreatic antioxidants and lipid peroxides were determined. Treatment with the macrocyclic binuclear oxovanadium complex decreased the lipid peroxides and the antioxidant enzymes such as superoxide dismutase, catalase and glutathione peroxidase to near control levels. Histological examinations also revealed the protective effect of the complex on pancreatic beta cells. The results demonstrate the protective effect of the macrocyclic binuclear oxovanadium complex on the pancreatic antioxidant status.

Effect of macrocyclic binuclear oxovanadium complex on tissue defense system in streptozotocin-induced diabetic rats.

BACKGROUND: Oxidative stress plays an important role in chronic complications of diabetes mellitus and hence the regulation of free radicals is essential in the treatment of diabetes. The protective effect of a new macrocyclic binuclear oxovanadium complex on antioxidant defense systems of liver and kidney was examined in streptozotocin-induced experimental diabetes in rats. METHODS: The levels of lipid peroxides, glutathione and the activities of superoxide dismutase, catalase, glutathione peroxidase and glutathione-S-transferase were assayed according to standard procedures in the liver and kidney of control and experimental groups of rats. RESULTS: A significant decrease (p < 0.05) was observed in both the glutathione content and in the activities of antioxidant enzymes such as superoxide dismutase, catalase, glutathione peroxidase and a concomitant increase in the level of lipid peroxides in diabetic rats. The observed alterations in the antioxidant status of tissues reverted back to near normal levels after the oral administration of macrocyclic vanadium complex at a dose of 5 mg/kg body weight/rat/day for a period of 30 days. CONCLUSION: The normoglycemic efficacy of the vanadium complex alleviates oxidative stress in streptozotocin-induced diabetes in rats.