46 research outputs found

    Dip and pull ambient pressure photoelectron spectroscopy as a spectroelectrochemistry tool for probing molecular redox processes

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    Ambient pressure x ray photoelectron spectroscopy APXPS can provide a compelling platform for studying an analyte s oxidation and reduction reactions in solutions. This paper presents proof of principle operando measurements of a model organometallic complex, iron hexacyanide, in an aqueous solution using the dip and pull technique. The data demonstrates that the electrochemically active liquid meniscuses on the working electrodes can undergo controlled redox reactions which were observed using APXPS. A detailed discussion of several critical experimental considerations is included as guidance for anyone undertaking comparable experiment

    Biophysical and electrochemical studies of protein-nucleic acid interactions

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    This review is devoted to biophysical and electrochemical methods used for studying protein-nucleic acid (NA) interactions. The importance of NA structure and protein-NA recognition for essential cellular processes, such as replication or transcription, is discussed to provide background for description of a range of biophysical chemistry methods that are applied to study a wide scope of protein-DNA and protein-RNA complexes. These techniques employ different detection principles with specific advantages and limitations and are often combined as mutually complementary approaches to provide a complete description of the interactions. Electrochemical methods have proven to be of great utility in such studies because they provide sensitive measurements and can be combined with other approaches that facilitate the protein-NA interactions. Recent applications of electrochemical methods in studies of protein-NA interactions are discussed in detail

    Green synthesis of CuO nanoparticles using Hibiscus sabdariffa L. extract to treat wastewater in Soba Sewage Treatment Plant, Sudan

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    Looking for a cost-effective and ecofriendly method for wastewater treatment is a global challenge. Therefore, this study investigated the removal of wastewater pollutants using copper oxide nanoparticles (CuONPs). CuONPs synthesized by a green solution combustion synthesis (SCS) and characterized by ultraviolet–visible spectroscopy (UV–Vis), Fourier transform infrared (FT-IR), powder X-ray diffraction analysis (PXRD), and scanning electron microscopy (SEM) techniques. PXRD showed nanoparticle sizes ranging from 10 to 20 polycrystalline patterns indexed with two peaks corresponding to (111) and (113) reflections of the face-centered cubic CuO crystal. The energy-dispersive spectroscopy analysis obtained in conjunction with SEM analysis proved the presence of Cu and O atoms at 86.3 and 13.6%, respectively, confirming the reduction and capping of Cu with Hibiscus sabdariffa extract's phytochemicals. The CuONPs proved to be a promising decontaminant for wastewater found to reduce biochemical oxygen demand (BOD) and chemical oxygen demand (COD) by 56%, and very efficient in reducing both the total dissolved matter (TDS) and conductivity (σ) by 99%. The CuONPs removed simultaneously chromium, copper, and chloride with respective percentages of 26, 78.8, and 78.2%. Green synthesis of nanoparticles is a simple, rapid, cost-effective, and ecofriendly method that successfully removed contaminants from wastewater. HIGHLIGHTS The green synthetic approaches for CuONPs use Hibiscus sabdariffa leaf extract as an alternative source to the conventional chemical method.; Green copper nanoparticles synthesized from Roselle leaf extract.; The efficiency and feasibility of green copper particles on wastewater decontamination of heavy metals.

    Development and characterization of a clay-HDTMABr composite for the removal of Cr(VI) from aqueous solutions with special emphasis on the electrochemical interface

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    This research aims to study the removal of chromium in its toxic form, Cr (VI), from wastewater, using clay and modified clay with Hexadecyltrimethyl ammonium bromide (HDTMABr)as adsorbents. The modified clay is obtained by impregnating a known quantity of HDTMABr into the clay. The two materials were characterized by different techniques, such as X-ray diffraction, which is used to determine the inorganic composition and the phyllite structures it contains. Thermal analysis TGA isused to understand the thermal behavior as function of the sintering temperature. Nitrogen adsorption/desorption is used to get the pores' size and surface area, using the Brunauer-Emmett-Teller (BET) theory. Scanning electron microscopy (SEM) coupled with Energy Dispersive X-ray Spectroscopy (SEM/EDAX) is used to study the surface morphology of the bare clay and the HDTMABr/clay. The operating conditions, such as contact times, pH, and adsorption temperatures, were studied, and optimized to improve the efficiency of the adsorption process. The adsorption is favored in acidic medium and room temperature, giving adsorption capacities for Cr(VI) of 12 mg/g and 250 mg/g for the clay and clay/HDTMABr, respectively. The reaction kinetics were studied and found to fit a pseudo-second-order model. The standard entropy (ΔS°), enthalpy (ΔH°), and Gibbs free energy (ΔG°) changes indicate that the chromium (VI) adsorption process is a physical, spontaneous, endothermic process. Cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS) are used for the electrochemical characterization of the raw clay and clay/HDTMABr in [Fe(CN)6]3-/4-/ 0.1 M KCl solution. The linear scan anodic stripping voltammetry (LSASV) is used for the reduction the Cr(VI) to Cr(III), indicating that Cr(VI) accumulates better at the surface of clay/HDTMABr compared to the bare graphite and the raw clay

    NMR and kinetic studies of the interactions of [Au(<i>cis</i>-DACH)Cl<sub>2</sub>]Cl and [Au(<i>cis</i>-DACH)<sub>2</sub>]Cl<sub>3</sub> with potassium cyanide in aqueous solution

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    <div><p>The interactions of [Au(<i>cis</i>-DACH)Cl<sub>2</sub>]Cl and [Au(<i>cis</i>-DACH)<sub>2</sub>]Cl<sub>3</sub> [where <i>cis</i>-DACH is <i>cis</i>-1,2-diaminocyclohexane] with enriched KCN were carried out in CD<sub>3</sub>OD and D<sub>2</sub>O, respectively. The reaction pathways of these complexes were studied by <sup>1</sup>H, <sup>13</sup>C, <sup>15</sup>N NMR, UV spectrophotometry, and electrochemistry. The kinetic data for the reaction of cyanide with [Au(<i>cis</i>-DACH)<sub>2</sub>]Cl<sub>3</sub> are <i>k</i> = 18 M<sup>−1</sup>s<sup>−1</sup>, ∆<i>H</i><sup>≠</sup> = 11 kJ M<sup>−1</sup>, ∆<i>S</i><sup>≠</sup> = −185 JK<sup>−1</sup> M<sup>−1</sup>, and <i>E</i><sub>a</sub> = 13 kJ M<sup>−1</sup> with square wave voltammetric (SWV) peak +1.35 V, whereas the kinetic data for the reaction of cyanide ion with [Au(<i>cis</i>-DACH)Cl<sub>2</sub>]Cl are <i>k</i> = 148 M<sup>−1</sup>s<sup>−1</sup>, ∆<i>H</i><sup>≠</sup> = 39 kJM<sup>−1</sup>, ∆<i>S</i><sup>≠</sup> = −80 JK<sup>-1</sup> M<sup>−1</sup>, and <i>E</i><sub>a</sub> = 42 kJM<sup>−1</sup> along with SWV peak +0.82 V, indicating much higher reactivity of [Au(<i>cis</i>-DACH)Cl<sub>2</sub>]Cl toward cyanide than [Au(<i>cis</i>-DACH)<sub>2</sub>]Cl<sub>3</sub>. The interaction of these complexes with potassium cyanide resulted in an unstable [Au(<sup>13</sup>CN)<sub>4</sub>]<sup>−</sup> species which readily underwent reductive elimination reaction to generate [Au(<sup>13</sup>CN)<sub>2</sub>]<sup>−</sup> and cyanogen.</p></div

    Potent In Vitro and In Vivo Anticancer Activity of New Bipyridine and Bipyrimidine Gold (III) Dithiocarbamate Derivatives

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    We synthesized eight new bipyridine and bipyrimidine gold (III) dithiocarbamate-containing complexes (C1&#8211;C8) and tested them in a panel of human cancer cell lines. We used osteosarcoma (MG-63), lung (A549), prostate (PC3 and DU145), breast (MCF-7), ovarian (A2780 and A2780cis, cisplatin- and doxorubicin-resistant), and cervical (ME-180 and R-ME-180, cisplatin resistant) cancer cell lines. We found that C2, C3, C6, and C7 were more cytotoxic than cisplatin in all cell lines tested and overcame cisplatin and doxorubicin resistance in A2780cis and R-ME-180 cells. In the PC3 prostate cancer cell line, the gold (III) complex C6 ([Au2(BPM)(DMDTC)2]Cl4) induced apoptosis and double-stranded DNA breaks, modified cell cycle phases, increased Reactive Oxigen Species (ROS) generation, and reduced thioredoxin reductase and proteasome activities. It inhibited PC3 cell migration and was more cytotoxic against PC3 cells than normal human adipose-derived stromal cells. In mice bearing PC3 tumor xenografts, C6 reduced tumor growth by more than 70% without causing weight loss. Altogether, our results demonstrate the anticancer activity of these new gold (III) complexes and support the potential of C6 as a new agent for prostate cancer treatment

    New bipyridine gold(III) dithiocarbamate-containing complexes exerted a potent anticancer activity against cisplatin-resistant cancer cells independent of p53 status

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    We synthesized, characterized and tested in a panel of cancer cell lines, nine new bipyridine gold(III) dithiocarbamate-containing complexes. In vitro studies demonstrated that compounds 1, 2, 4, 5, 7 and 8 were the most cytotoxic in prostate, breast, ovarian cancer cell lines and in Hodgkin lymphoma cells with IC50 values lower than the reference drug cisplatin. The most active compound 1 was more active than cisplatin in ovarian (A2780cis and 2780CP-16) and breast cancer cisplatin-resistant cells. Compound 1 determined an alteration of the cellular redox homeostasis leading to increased ROS levels, a decrease in the mitochondrial membrane potential, cytochrome-c release from the mitochondria and activation of caspases 9 and 3. The ROS scavenger NAC suppressed ROS generation and rescued cells from damage. Compound 1 resulted more active in tumor cells than in normal human Mesenchymal stromal cells. Gold compounds were active independent of p53 status: exerted cytotoxic effects on a panel of non-small cell lung cancer cell lines with different p53 status and in the ovarian A2780 model where the p53 was knocked out. In conclusion, these promising results strongly indicate the need for further preclinical evaluation to test the clinical potential of these new gold(III) complexes
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