Acidic and Alkaline pH Controlled Oxygen Reduction Reaction Pathway over Co-N4C Catalyst.

Enhanced oxygen reduction reaction (ORR) kinetics and selectivity are crucial to advance energy technologies like fuel cells and metal-air batteries. Single-atom catalysts (SACs) with M-N4/C structure have been recognized to be highly effective for ORR. However, the lack of a comprehensive understanding of the mechanistic differences in the activity under acidic and alkaline environments is limiting the full potential of the energy devices. Here, a porous SAC is synthesized where a cobalt atom is coordinated with doped nitrogen in a graphene framework (pCo-N4C). The resulting pCo-N4C catalyst demonstrates a direct 4e- ORR process and exhibits kinetics comparable to the state-of-the-art (Pt/C) catalyst. Its higher activity in an acidic electrolyte is attributed to the tuned porosity-induced hydrophobicity. However, the pCo-N4C catalyst displays a difference in ORR activity in 0.1 m HClO4 and 0.1 m KOH, with onset potentials of 0.82 V and 0.91 V versus RHE, respectively. This notable activity difference in acidic and alkaline media is due to the protonation of coordinated nitrogen, restricted proton coupled electron transfer (PCET) at the electrode/electrolyte interface. The effect of pH over the catalytic activity is further verified by Ab-initio molecular dynamics (AIMD) simulations using density functional theory (DFT) calculations.

A substituent-modified new salicylaldehyde-diphenyl-azine based AIEgen: A promising skeleton for copper ion sensor.

In this study, we have reported a novel 4-bromo-salicylaldehyde-diphenyl-azine (B-1), a new member of salicylaldehyde-diphenyl-azine (SDPA) family known for its excellent sensing properties. In contrast to the previously reported AIEgens, we found that the bromo-substitution at the 4th position of the salicylaldehyde moiety blue-shifted the emission by 10 and 15 nm as compared to the unsubstituted (Tong et.al 2017) and Bromo at the 5th position (Jain et.al 2023) respectively. Moreover, B-1 crystallizes instantly as the cooling process starts, which was not observed in the previously reported scaffolds. The sensing investigation again demonstrated the precise and ultrasensitive behavior of B-1 for copper ions. B-1 has a very low LOD value i.e. 29.2 x 10-8 M with a high association constant and binds with copper ion in 2:1 mode. This time we also analyzed the practical applicability in the solid phase using cotton swabs and performed the real-time estimation of copper ions in water and biological samples like urine and blood serum. The excellent percentage recovery and the RSD value suggest the precision of the experiments. Further, we also perform the sensing in living cancer HeLa cells. Altogether, we found that the SDPA skeleton is precise and ultrasensitive for copper ions and versatile which can be used variously to detect copper ions in the real world. This research will surely help in developing new specific skeleton-based AIEgens with desirable emission properties and precise applications in the future.

Indole-based NNN donor Schiff base ligand and its complexes: Sonication-assisted synthesis, characterization, DNA binding, anti-cancer evaluation and in-vitro biological assay.

A novel indole based NNN donor Schiff base ligand and its Ni(II), Zn(II) and Cd(II) complexes have been synthesized using sonication-assisted method which is a highly efficient eco-friendly mechanism. The synthesized complexes have been characterized using elemental analysis, UV-Vis spectroscopy, mass spectrometry, FT-IR, and NMR and are optimized using DFT approach, which provided their theoretical framework. The stoichiometry between the ligand and the metal ions was also determined using Job's method. The thermogravimetric (TGA/DSC) analyses confirm the stability for all complexes at room temperature followed by thermal decomposition in different steps. DNA binding activities have been assessed by employing UV-visible and fluorescence spectra using the CT-DNA. The estimated intrinsic binding constant (Kb) for NiL, ZnL, and CdL complexes was 6.00 × 105, 5.58 × 105, and 4.7 × 105, respectively. In accordance with the Kb value, the quenching constant (Ksv) values of NiL, ZnL, and CdL are 5.59 × 105 M-1, 4.3 × 105 M-1, and 4.08 × 105 M-1 respectively. The anticancer properties have been assessed using MTT Assay. It has been found that the Ni(II) complex (NiL) is the most potent among the series with IC50 of 169 µg/mL. An in-vitro antioxidant experiment using DPPH was used to evaluate the synthesizedcomplexes' ability to scavenge free radicals. The findings indicated that the complexes exhibited notable antioxidant properties. The antioxidant property ZnL has been found to be the highest with an IC50 of 2.91 µg/mL and it follows the order is ZnL > NiL > CdL > L. Using the egg albumin denaturation technique, the anti-inflammatory property have been assessed, and the amount of protein denaturation inhibition has been computed. NiL has the highest % inhibition among the series studied. Comparatively, the metal complexes have been reported to exhibit higher biological activities than the prepared Schiff base ligand. The reason for the excellent biological properties observed in the metal complexes could be attributed to the incorporation of the electron-withdrawing CH3COO- during complexation. Molecular docking studies have been performed on the 2GYT protein and it has been found that the complexes have excellent binding affinity, with NiL having the lowest binding energy of -6.93 Kcal mol-1. The values suggested that NiL is more effective against HePG2 cancer cells, which is also in accordance with the MTT Assay results.

The solvent-regulated excited state reaction mechanism of 2-(2'-hydroxyphenyl)benzothiazole aggregates.

The excited state relaxation dynamics of 2-(2'-hydroxyphenyl)benzothiazole (HBT) in the gas phase and the solvents have been explored experimentally and theoretically. However, the fundamental mechanism of its emission in aggregates is still unexplored. In this article, we have presented a detail investigation of solvent-regulated excited state (ES) reactions for HBT aggregates with the aid of several experimental and theoretical research. The careful investigation of solvatochromic and electrochemical behavior elucidates that the emission around 460 nm of HBT in DMSO and DMSO-water fraction correspond to the excited state internal charge transfer (ESICT). The quantum chemical analysis further supports this observation. The concentration-dependent 1H NMR and emission studies of HBT in DMSO revealed the formation of aggregates at higher concentrations that facilitate the charge transfer. The emission pattern of HBT in the AcN-water fraction demonstrates that the sequential internal charge transfer-proton transfer (ESICT-ESIPT) occurs in HBT aggregates. The pH studies show that HBT aggregates are potential ratiometric sensors for near-physiological pH ranges. Moreover, a ground-state zwitterionic conformation of HBT is observed in the basic medium formed by ground-state internal proton transfer (GSIPT). Overall, this study provides a better understanding of solvent-regulated ES reaction mechanism in the case of HBT aggregates and other substituted HBT compound aggregates published previously.

Thioether-based novel transition metal complexes: Synthesis, DNA interaction, in vitro biological assay, DFT calculations, and molecular docking studies.

A novel Schiff base ligand 2-(((2-(benzylthio)phenyl)imino)methyl)-4-chlorophenol and its cobalt, nickel, copper, and zinc metal complexes were prepared. Using B3LYP/6-31++G(d,p) method with LanL2DZ as basis set, the molecular structure of metal complexes has been optimized, and their parameters have been explored. The distorted octahedral geometries have been observed in cobalt, nickel, and copper complexes. In contrast, zinc complex exhibited distorted tetrahedral geometry indicating the coordination of metal ions with ligands through ONS binding sites, which are confirmed by various spectroscopic techniques, magnetic measurements, molar conductivity, elemental analysis, and DFT studies. The intercalative binding mode between CT-DNA and synthesized metal complexes has been determined by absorption and fluorescence spectroscopy. The binding constant values of metal complexes found to be varied from 5.28 × 103 M-1 to 9.18 × 104 M-1. Furthermore, several methods have been used to scrutinize the bioactivities, such as in vitro anti-diabetic, anti-inflammatory, and antioxidant. From the obtained results, it can be concluded that zinc metal complex exhibited excellent anti-inflammatory and anti-diabetic activity compared to others. However, the copper complex has good antioxidant property. Besides deducing the prospective binding energies of inhibitors, molecular docking simulations have also been conducted utilizing the enzyme structures of B-DNA, 6-COX, α-amylase, and α-glucosidase.

Methylene blue removal using raw and modified biomass Plumeria alba (white frangipani) in batch mode: isotherm, kinetics, and thermodynamic studies.

Hazardous dyes used in textile industries are considered high-risk pollutants to the environment. The raw as well as acid-treated Plumeria alba (white frangipani) leaf powder (WFLP and SWFLP) were used for the adsorption of methylene blue (MB) that is available in industrial wastewaters following the batch adsorption technique. The characterizations of adsorbents were done by FTIR, SEM, EDX, TGA, and zeta potential parameters. The adsorption was considered for the effects of temperature, initial dye concentration, solution pH, adsorbent dosage, and contact time. The experimental results obtained in the adsorption of MB were examined by nonlinear error functions like chi-square (χ2), ARE, and MPSD for three isotherm models: Langmuir, Freundlich, and Temkin. The maximum monolayer adsorption capacity, qmax (mg/g), was 45.45 mg/g for raw WFLP and 250 mg/g for SWFLP. The adsorbents fitted to the pseudo-second-order kinetic model (R2 = 0.99) using the experimental data of batch adsorption. The thermodynamic studies explained the spontaneity and nature of adsorption for raw and acid-treated adsorbents. The batch experimental results and characterizations of the adsorbents revealed that the selected adsorbents would be the best adsorbents for the removal of MB from the wastewater solution.

Synthesis, characterization, and DNA binding study of ruthenium(II/III) complexes containing ONS donor Schiff base.

A chelating ligand of thioether with ONS donor Schiff base HL [(E)-2-(((2-(benzylthio)phenyl)imino)methyl)napthalen-1-ol] and its metal complexes (RuL1 and RuL2) have been synthesized. They have been characterized by UV-Vis, FTIR, 1H NMR, 13C NMR, mass spectrometry methods. The formulas of the synthesized compounds have been confirmed by elemental analysis and magnetic susceptibility measurements. The binding ability studies of the ligand (HL) and its Ru complexes (RuL1 and RuL2), with calf-thymus DNA have been explored by the absorption titration method. The binding interaction study reveals that the ligand (HL) and the complex RuL1 interact with CT-DNA through an intercalative mode of binding whereas the complex RuL2 does not show any interaction with CT-DNA due to steric effect.

Recent Advances in Schiff Base Ruthenium Metal Complexes: Synthesis and Applications.

This review concentrates on recent developments in ruthenium Schiff bases, whose steric and electronic characteristics can be manipulated easily by selecting suitable condensing aldehydes or ketones and primary amines, and their metal complexes. Ruthenium metal-based complexes and Schiff base ligands are rapidly becoming conventionally considered for biological applications (antioxidant, anticancer, antimicrobial), in catalysis, in functional materials, in sensors, and as pigments for dyes. Ruthenium complexes exhibit a broad variety of activities concerning simple Schiff base ligands. This may be due to the octahedral bonding of both Ru(II) and Ru(III) complexes, which acquire an extended reservoir of a three-dimensional framework, providing the potential for an elevated degree of site selectivity for binding to their biological targets. This review provides an overview of this field, and intends to highlight both ligand design and synthetic methodology development, as well as significant applications of these metal complexes. In this review, we summarize our work on the development of ruthenium complexes, which was performed over the last few years.

Iron-polyphenol complex nanoparticles for removal of greenhouse gas emission from bitumen and formation of paraffins.

The removal of greenhouse gas (GHG) emission from bitumen used in the construction of flexible pavement by iron-polyphenol complex nanoparticles (Fe-PNPs) has been examined in the study. Laboratory studies indicated the removal of carbon dioxide (CO2) with Fe-PNPs is a function of the amount of additive (Fe-PNPs). From the experimental data, it was found that the reduction of CO2 increases with increasing amount of additive up to a dosage of 4% (by weight of bitumen) without severely changing the basic engineering properties of the bitumen. The reduction of GHG is due to the conversion of the CO2 to a mixture of hydrocarbon in the presence of Fe-PNPs. The characterization of the additive by SEM, FTIR, UV, and XRD indicated the formation of the Fe-PNPs. The analysis of the basic engineering properties of bitumen such as penetration value, softening point of the bitumen, flash point, fire point, and ductility in the presence of additive as well as without the additive were studied and reflected a noticeable effect in the reduction of the CO2. The reduction of GHG by Fe-PNPs minimizes the environmental impact and saving energy by increasing the yield of hydrocarbons.

Synthesis of a new series of Ni(ii), Cu(ii), Co(ii) and Pd(ii) complexes with an ONS donor Schiff base: crystal structure, DFT study and catalytic investigation of palladium and nickel complexes towards deacylative sulfenylation of active methylenes and regioselective 3-sulfenylation of indoles via thiouronium salt formation.

A series of Ni(ii), Cu(ii), Co(ii), and Pd(ii) complexes have been synthesized with a chelating Schiff base ligand coordinated to a metal center with ONS donor atoms. The ligand and complexes are characterized by elemental analysis and spectroscopic techniques like FT-IR, 1H-NMR, and UV-Visible spectroscopy. The single crystal structure of the Pd(ii) complex is obtained by X-ray diffraction analysis and exhibits slightly distorted square planar geometry. The structure is optimized by DFT, TD-DFT calculation to elaborate the electronic structure and NBO for the charge distribution analysis of the Pd(ii) complex. The synthesized Pd(ii) and Ni(ii) complexes as catalysts have been investigated in the C-S cross-coupling of indoles and active methylenes. The metal propelled regioselective transformation afforded 3-sulfenylated indoles while ß-diketones favored deacylated monosulfenyl ketones in an excellent yield via thiouronium salt formation. The Pd(ii) complex displays slightly better reactivity whereas the Ni(ii) complex is cost-efficient. The method is fast, easy to handle and cost effective in terms of high reactivity of catalysts, use of non-toxic solvents, and cheaper aryl halides and thiourea replace conventional sulfur sources, providing a practical access to organic transformations.

Role of TBATB in nano indium oxide catalyzed C-S bond formation.

Nano sized indium oxide is found to be an efficient catalyst for the conversion of thiols to sulfides using Na2CO3 as base and TBATB as reagent in DMSO at 110 °C. Here in situ generation of bromo intermediate by TBATB takes place through indium surface. A variety of aryl sulfides can be synthesized in excellent yields from less reactive chlorides, boronic acids and thiols.

1-Benzoyl-3-[(2-benzylsulfanyl)phenyl]thiourea.

In the title compound, C(21)H(18)N(2)OS(2), a strong intramolecular N-H...O hydrogen bond [N...O = 2.642 (3) Å] between the amide N atom and the benzoyl O atom forms an almost planar six-membered ring in the central part of the molecule. In the crystal, molecules are packed through weak N-H...S interactions. Intra- and intermolecular hydrogen bonds and van der Waals interactions are the stabilizing forces for the crystal structure.

1-Benzyl-sulfanyl-2-[(2-chloro-phen-yl)diazen-yl]benzene.

The title compound, C(19)H(15)ClN(2)S, a divalent organosulfur compound belonging to the class of ortho-mercaptoazo compounds, is non-ionic in nature. The azo group in the mol-ecule is moved away from the S atom to attain the stable trans-azo configuration. Here the S atom is not electron deficient, so no intra-molecular N⋯S inter-action exists. Due to steric reasons, the mol-ecule is non-planar: the chlorophenyl and benzyl rings are oriented at dihedral angles of 3.21 (8) and 78.18 (5)°, respectively, with respect to the thiophenyl ring. There are no hydrogen bonds and the crystal structure is stabilized by van der Waals inter-actions.