Anticancer evaluation of a manganese complex on HeLa and MCF-7 cancer cells: design, deterministic solvothermal synthesis approach, Hirshfeld analysis, DNA binding, intracellular reactive oxygen species production, electrochemical characterization and density functional theory.

Herein, a deterministic solvothermal strategy was employed to synthesize an efficient anticancer agent 'cis-dichlorobis(1,10-phenanthroline)manganese(II)' (Mn(phen)2Cl2). A single-crystal X-ray diffraction analysis revealed that Mn(phen)2Cl2 crystallizes in a triclinic system with the space group P-1. Cyclic voltammetric studies of Mn(phen)2Cl2 indicated that the electrode process occurs only due to complex formation and has a diffusion-controlled mechanism. Density functional theory estimations showed that the Mn(phen)2Cl2 is quite stable and exists in sextet spin state (five unpaired electrons) as the most stable form and hence, Mn(phen)2Cl2 is a high spin complex. Mn(phen)2Cl2 demonstrated significant anticancer potential against HeLa and MCF-7 cancer cells and less toxic behaviour towards normal BHK-21 cells. Fluorescence imaging confirmed that the production of reactive oxygen species (ROS) in HeLa cells by Mn(phen)2Cl2 induces oxidized fluorescence of dichlorofluorescein which emitted fluorescence at 530 nm after excitation at 488 nm. The microscopic investigation of apoptotic effect of Mn(phen)2Cl2 using propidium iodide and 4',6-diamidino-2-phenylindole staining indicated that nuclear condensation, cell detachment and shrinkage occur after treatment with IC50 values of Mn(phen)2Cl2. Furthermore, an assessment of caspase-9 and caspase-3 activity after exposure to Mn(phen)2Cl2 in HeLa cells indicated that at IC50 values of Mn(phen)2Cl2, 1.5 fold and 4.8 fold increase in caspase-9 and caspase-3 activity, respectively, occurs. The measurement of mitochondrial membrane potential of a cationic dye (JC-1) showed a decrease in mitochondrial membrane potential in both HeLa and MCF-7 cells depicting that compound might have adopted intrinsic pathway of apoptosis. Ability of Mn(phen)2Cl2 to interact with HS-DNA demonstrates hyperchromicity with slight blue shift from 269 nm to 265 nm showing a non-covalent interaction with Gibbs free energy of ΔG = -14.62 kJ/mol. Communicated by Ramaswamy H. Sarma.

Water Oxidation Electrocatalysis with a Cobalt-Borate-Based Hybrid System under Neutral Conditions.

The development of new water oxidation electrocatalysts that are both stable and efficient, particularly in neutral conditions, holds great promise for overall water splitting. In this study, the electrocatalytic water oxidation performance of a new cobalt-based catalyst, Co3 (BO3 )2 , with a Kotoite-type crystal structure is investigated under neutral conditions. The catalyst is also hybridized with CNTs to enhance its electrocatalytic properties. A remarkable increase in catalytic current along with a significant shift in the onset overpotential is observed in Co3 (BO3 )2 @CNT. Additionally, CNT addition also greatly influences the surface concentration of the catalyst: 12.7 nmol cm-2 for Co3 (BO3 )2 @CNT compared with 3.9 nmol cm-2 for Co3 (BO3 )2 . Co3 (BO3 )2 @CNT demands overpotentials of 303 and 487 mV to attain current densities of 1 and 10 mA cm-2 , respectively, at pH 7. Electrochemical and characterization studies performed over varying pH conditions reveal that the catalyst retains its stability over a pH range of 3-14. Multi-reference quantum chemical calculations are performed to study the nature of the active cobalt sites and the effect of boron atoms on the activity of the cobalt ions.

Tuning the Electronic Properties of Prussian Blue Analogues for Efficient Water Oxidation Electrocatalysis: Experimental and Computational Studies.

Although several Prussian Blue analogues (PBAs) have been investigated as water oxidation catalysts, the field lacks a comprehensive study that focuses on the design of the ideal PBA for this purpose. Here, members of a series of PBAs with different cyanide precursors have been investigated to study the effect of hexacyanometal groups on their electrocatalytic water oxidation activities. Cyclic voltammetric, chronoamperometric, and chronopotentiometric measurements have revealed a close relationship between the electron density of electroactive cobalt sites and electrocatalytic activity, which has also been confirmed by infrared and XPS studies. Furthermore, pH-dependent cyclic voltammetry and computational studies have been performed to gain insight into the catalytic mechanism and electronic structure of cyanide-based systems to identify possible intermediates and to assign the rate-determining step of the target process.

Electrode Prepared with Combination of Different Conductive Polymers for Hydroquinone Determination in River Water.

Modified electrode based on combination of different conductive polymers (Polyaniline - Poly(3-methylthiophene) - Poly(3,3' diaminobenzidine) (PANI - P3MT - PDAB)) was previously synthesized in dichloromethane containing HClO(4) and tetrabutylammoniumperchlorate (TBAP) supporting electrolyte. In this study, determination of hydroquinone (HQ) with amperometric I-t method over this modified and its homopolymers coated electrode was successfully carried out in river water as real sample and in solution consisting of NaHSO(4)/Na(2)SO(4) (pH 2.0). For this method, potentials between 0.45 V and 0.65 V were applied and the best analytical response was obtained at 0.55 V using this modified electrode when compared its homopolymer. The limit of detection (LOD), limit of quantification (LOQ) , the linear dynamic range and regression coefficient (R(2)) were found as 1.31 x 10(-4) mM, 4.37 x 10(-4) mM, 4.37 x 10(-4)- 95.0 mM and 0.998, respectively. These results were compared to homopolymers coated and uncoated Pt electrodes. For checking on the accuracy of the developed method and the matrices interference, determination of HQ was performed in artificially contaminated river water samples with HQ concentration 5.0 mM and 10.0 mM using this modified electrode and recovery values were calculated as % 100.6 and % 100.1, respectively.