Correction to "Upgraded Valorization of Biowaste: Laser-Assisted Synthesis of Pd/Calcium Lignosulfonate Nanocomposite for Hydrogen Storage and Environmental Remediation".

[This corrects the article DOI: 10.1021/acsomega.9b04149.].

Electrochemical study of 2-amino-5-mercapto-1,3,4-thiadiazole in the absence and presence of p-benzoquinone: an efficient strategy for the electrosynthesis of new 1,3,4-thiadiazole derivatives.

In this study, first, the electrochemical behavior of 2-amino-5-mercapto-1,3,4-thiadiazole (AMT) was fully investigated in the absence and presence of electrochemically generated p-benzoquinone (p-BQ, which is the oxidized form of hydroquinone), as an electrophile, via cyclic voltammetry (CV) at a glassy carbon electrode (GCE) and in an acetic acid buffer (0.2 M)/ethanol solution mixture. Then, an E-pH diagram was proposed for different structures of AMT at various pH values. The obtained voltammograms also exhibited an "electron transfer + chemical reaction" (EC) mechanism. Besides the voltammetric exploration, electrosynthesis of new 1,3,4-thiadiazole derivatives was conducted by constant current electrolysis (CCE) as a facile and cost-effective method for the formation of S-S and S-C bonds. Finally, the biological activity of products was also analyzed via an in silico method.

Green electrochemical method for the synthesis of nitro and azo derivatives based on mefenamic acid.

Electrochemical study of mefenamic acid (MFA) was carried out with details in water/ethanol mixture by the various voltammetric techniques. The results showed that the oxidation of MFA is highly dependent on pH and follows the Eir mechanism. The EpA1-pH diagram plotted based on the differential pulse voltammograms shows two linear segments, 66 and 26 mV/pH slope. Also, the diffusion coefficient and the surface excess, Ó¶* of MFA in aqueous buffered solution, determined by using the single potential-step chronoamperometry and chronocoulometry methods. Electrochemical nitration of MFA in an aqueous solution and the presence of nitrite ion (1) were both investigated by the cyclic voltammetry and controlled-potential coulometry techniques. Our results indicate that the oxidized form of MFA participates in a Michael-type addition reaction with nitrite ion (1) to form the corresponding Nitromefenamic acids (MFA-4-NO2 and MFA-5-NO2). Also, in another part, a computational study based on the density functional theory (DFT/B3LYP) was performed for the prediction of the best possible pathway in the nucleophilic addition of nitrite ion (1). The electrochemical reduction of produced nitromefenamic acids was investigated using cyclic voltammetry and controlled-potential coulometry techniques. Eventually, two new azo derivatives have been generated via electroreduction of produced nitromefenamic acids and conduction of diazotization reaction, respectively. Both nitro and azo products are approved as paints.

Deep eutectic solvent based ultrasound assisted emulsification microextraction for preconcentration and voltammetric determination of aflatoxin B1 in cereal samples.

A new and simple deep eutectic solvent based ultrasound-assisted emulsification microextraction (DES-UAEME) procedure has been developed for preconcentration and voltammetric determination of aflatoxin B1 (AFB1) in cereal products. The method is based on the acetonitrile-based extraction of AFB1 from homogenized cereal samples followed by a DES-UAEME procedure for subsequent differential pulse voltammetry (DPV) determination in a microcell. A DES composed of choline chloride and urea (ChCl-Ur) was used as the extraction solvent and electrolyte for DPV detection. Various parameters affecting the extraction efficiency of AFB1 were evaluated and optimized. Under optimum conditions the calibration graph was linear in the range of 0.2-80.0 µg L-1 (R2 = 0.9966) and the limit of detection (3Sb) was estimated to be 0.05 µg L-1. The intra-day and inter-day precision (RSD%) for determination of 5.0 µg L-1 AFB1 were 3.4% and 3.9%, respectively. The proposed method was also successfully applied for preconcentration and determination of AFB1 in different cereal samples and good relative recoveries were obtained over a range of 94 to 104%.

Synthesis of biological based hennotannic acid-based salts over porous bismuth coordination polymer with phosphorous acid tags.

In this paper, a novel porous polymer capable of coordinating to bismuth (PCPs-Bi) was synthesized. The Bi-PCPs was then reacted with phosphorous acid to produce a novel polymer PCPs(Bi)N(CH2PO3H2)2 which is shown to act as an efficient and recyclable catalyst. The mentioned catalyst was applied for the efficient synthesis of new mono and bis naphthoquinone-based salts of piperidine and/or piperazine via the reaction of hennotannic acid with various aldehydes, piperidine and/or piperazine, respectively. The structure of the resulting mono and bis substituted piperazine or piperidine-based naphthoquinone salts was thoroughly characterized spectroscopically. The electrochemical behavior of the products was also investigated. The presented protocol has the advantages of excellent yields (82-95%), short reaction times (4-30 min) and simple work-up.

Probing the Strength and Mechanism of Binding Between Amifampridine and Calf Thymus DNA.

In this work, we have investigated the strength and mechanism of amifampridine (3,4-Diaminopyridine/3,4-DAP) interaction with calf thymus DNA (ct-DNA). The existence and the strength of interaction are evaluated using circular dichroism (CD), UV-vis absorption, and differential pulse voltammogram studies. Results from UV-vis absorption technique indicate that amifampridine can significantly interact with DNA through a binding constant of Kb = 1.66 × 105 M-1 at 298 K. The mechanism of the interaction between amifampridine and DNA is also studied using ionic effect investigations, competitive fluorescence experiments, viscosity measurements, and molecular docking studies. The viscosity results indicate that amifampridine can bind to DNA via intercalation binding mode. Competitive fluorescence experiments using Acridine Orange (AO) and Hoechst 33258 (HO) probes also reveal that amifampridine binds to DNA via an intercalation mode of binding. Finally, the molecular docking studies also suggest that amifampridine tends to bind with the G-C rich region of DNA.

Facile synthesis of graphitic carbon nitride/chitosan/Au nanocomposite: A catalyst for electrochemical hydrogen evolution.

This paper reports a novel nanocomposite catalyst comprised of graphitic carbon nitride (g-C3N4), chitosan and gold (Au) nanoparticles, which has been prepared through a facile, clean and low cost method. Graphitic carbon nitride has been fabricated by pyrolysis of urea. Laser ablation in liquid (LAL) was employed in the green synthesis of Au NPs. The g-C3N4/chitosan/Au nanocomposite (denoted as CN/CS/Au) were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analyses. Chitosan biopolymer and a small amount of Au NPs were added to g-C3N4 to modify and improve the catalytic activity of g-C3N4. The activity of the hydrogen evolution reaction (HER) has been investigated using CN/CS/Au nanocomposite coated on a stainless steel mesh by electrochemical method. The amounts of hydrogen stored were calculated from cyclic voltammetry (CV) results. The results confirmed that chitosan and Au NPs were effective on the HER behavior of g-C3N4 and the nanocomposite had a good HER activity and stability.

Upgraded Valorization of Biowaste: Laser-Assisted Synthesis of Pd/Calcium Lignosulfonate Nanocomposite for Hydrogen Storage and Environmental Remediation.

Laser ablation in liquid (LAL), one of the promising pathways to produce nanoparticles, is used herein for the modification of the abundant biowaste, calcium lignosulfonate (CLS), adorning it with palladium nanoparticles (Pd NPs). The ensuing Pd/CLS nanocomposite, fabricated via a simple stirring method, is deployed for hydrogen storage and environmental cleanup studies; a hydrogen storage capacity of about 5.8 C g-1 confirmed that Pd NPs serve as active sites for the adsorption of hydrogen. Additionally, the novel, sustainable, and reusable nanocomposite also exhibits superior catalytic activity toward the reduction of hexavalent chromium [Cr(VI)], 4-nitrophenol (4-NP), and methylene blue (MB) in an aqueous solution in a short time; the synthesized nanocatalyst could be reused for at least eight successive runs.

In vitro cytotoxicity and DNA/HSA interaction study of triamterene using molecular modelling and multi-spectroscopic methods.

The anticancer activity of triamterene on HCT116 and CT26 colon cancer cells lines was investigated. Furthermore, the mechanism of interaction between triamterene and calf thymus DNA (ct-DNA) and also human serum albumin (HSA) was conducted using spectroscopic and molecular docking techniques. In vitro cytotoxicity of triamterene against HCT116 and CT26 cells showed promising anticancer effects with IC50 values of 31.30 and 24.45 µM, respectively. Competitive studies of the triamterene with NR (neutral red) and MB (methylene blue) as intercalator probes showed that triamterene can be replaced by these probes. The viscosity data also confirmed that triamterene binds to calf-thymus DNA through intercalation binding mode. Binding properties of triamterene with HSA in the presence of warfarin and ibuprofen showed that triamterene competes with warfarin for the site I of human serum albumin (HSA). In addition, the binding modes of triamterene with DNA and HSA were verified by molecular docking technique. Abbreviations ct-DNA calf thymus DNA CV cyclic voltammetry DNA deoxyribonucleic acid DPV differential pulse voltammetry FBS fetal bovine serum HSA human serum albumin NR neutral red MB methylene blue MTT 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazoliumbromide Communicated by Ramaswamy H. Sarma.

Binding Studies of Isoxsuprine Hydrochloride to Calf Thymus DNA Using Multispectroscopic and Molecular Docking Techniques.

In the present work, the interaction of Isoxsuprine (ISX) with Calf thymus DNA (ct-DNA) under physiological conditions (Tris-HCl buffer of pH 7.4) was investigated by using electronic absorption, circular dichroism, viscosity, electrochemical studies, fluorescence techniques, salt effect studies and computational studies. Competitive fluorimetric studies with Hoechst 33258 have shown that ISX exhibit the ability to displace the DNA-bound Hoechst 33258, indicating that it binds to ct-DNA in strong competition with Hoechst 33258 for the minor groove binding. Furthermore, the resulting data showed that ISX cannot displace methylene blue or acridine orange, which are the common intercalator molecules. The viscosity of ct-DNA solution was almost unchanged on addition of ISX and circular dichroism (CD) spectra of ct-DNA showed small changes in the presence of ISX which is in agreement with groove binding mode of interaction. Thus all above studies showed that the ISX drug binds to ct-DNA in a groove binding mode.The salt-effect studies showed the non-electrostatic nature of binding of ISX to ct-DNA. Moreover, molecular docking results support the above experimental data and suggest that ISX prefers to bind on the minor groove of ct-DNA.

A green strategy for the synthesis of sulfone derivatives of p-methylaminophenol: Kinetic evaluation and antibacterial susceptibility.

This is one of the few examples in which the diverse products have been synthesized just by changing the applied potential. The synthesis of sulfonyl derivatives of p-methylaminophenol were carried out by reaction of the electrogenerated p-methylquinoneimine with sulfinic acids. Various types of mono (MSP), bis (BSP) and tris (TSP) sulfonyl p-methyl aminophenols were obtained by changing the electrode potential, in one pot under green conditions. The mono sulfonyl-p-(methylamino)phenol derivatives (MSP) were assessed for their in vitro antibacterial activity against the gram positive (Staphylococcus aureus) and gram negative (Escherichia coli) strains. It was found that the tested compounds were more active against Staphylococcus aureus than Escherichia coli. We also found that the antimicrobial activity of MSP derivatives to vary in the order MSP4 (R = CH3) > MSP1 (R = p-tolyl) ≈ MSP2 (R = phenyl) > MSP3 (R = p-ClC6H4). Moreover, the observed homogeneous rate constants (k obs) of the reaction of p-methyl quinoneimine with sulfinic acids were estimated in various pH values, based on the EC and ECEC mechanisms, by comparing the simulated cyclic voltammograms with the experimental ones.