The novel pyramidal-shaped ternary molybdenum nickel selenide (MoNiSe4) nanomaterial was successfully synthesized using a solvothermal technique for the first time. The structural, optical and electrochemical properties of the synthesized sample were analyzed through XPS, XRD, UV-visible spectroscopy, Fourier Transform infrared (FTIR), field emission scanning electron microscope (FESEM) and EDX analyses. The XRD pattern revealed a distinct shift of the main diffraction peaks toward lower angle side compared to pure MoSe3, validating the effective incorporation of nickel and the formation of the MoNiSe4phase with an average crystallite size of 44 nm. The optical band gap of the material was estimated as 1.41 eV. FTIR spectra confirmed the presence of relevant metal-selenide bonds and its functional groups. Morphological analysis by FESEM revealed a pyramidal shape with triangular surfaces featuring sharp edges and distinct facets that reflect its high crystallinity. Elemental analysis through energy dispersive x-ray spectroscopy validated the stoichiometric composition of Mo, Ni and Se, whereas XPS analysis confirmed the oxidation states as Mo6+, Ni2+and Se2-, further supporting the formation of the MoNiSe4phase. Electrochemical analysis demonstrated superior supercapacitive characteristics of the MoNiSe4electrode. Cyclic voltammetry exhibited a pseudocapacitive nature with specific capacitances of 304 F g-1and 161 F g-1at the scan rates of 50 and 100 mV s-1respectively. Galvanostatic charge-discharge studies showed remarkable cycling stability with good capacitance retention even after 1500 cycles. The calculated specific capacitance, energy density and power density after 1500 cycles were 5695 × 10-5F g-1, 285 × 10-9Wh kg-1and 24 × 10-3W kg-1respectively. The Nyquist and Bode plots indicated ideal capacitive and pseudocapacitive behavior, confirming the efficient charge storage performance of the electrode. Overall, the MoNiSe4demonstrates strong potential as a highly effective electrode material for advanced supercapacitor applications.
Two Streptomyces spp. were isolated from open ocean waters of the Gulf of Mannar. Of the two isolates, one was identified as Streptomyces coelicolor through conventional and molecular approaches, and it was found to produce a siderophore. Characterization revealed the siderophore to be of trihydroxamate type with hexadentate iron-binding capacity. FTIR analysis indicated the presence of aromatic rings with C-O and C = C stretching, while 1H and 13C NMR together with mass spectrometry confirmed the hydroxamate nature and identified the siderophore as ferrioxamine. A narrow shift in λ max indicate the photoreactive nature of the siderophore on exposure to sunlight. The cell-free supernatant of S. coelicolor and the purified siderophore dose-dependently inhibited the growth of microbial pathogens. Quorum quenching activity was confirmed using the indicator strain Chromobacterium violaceum. Both the cell-free supernatant and siderophore were found to inhibit biofilm formation and induce reactive oxygen species (ROS) generation in pathogens. The siderophore also suppressed the proliferation of the breast cancer cell line (MCF-7) by disturbing iron homeostasis. Optimization of International Streptomyces Project (ISP2) medium constituents using two-level factorial design and response surface methodology (RSM) enabled cost-effective siderophore production. In addition to iron, the siderophore exhibited binding affinity for other heavy metals including zinc, cobalt, cadmium, lead, and magnesium.
This study presents a multi-faceted investigation into the structural, electronic, and therapeutic profiles of the crown and chair conformers of CPRA, 2HPRA, 3HPRA, and 4HPRA macrocycles. A dispersion corrected standard density functional theory (DFT/B3LYP-D3) calculations were utilized for geometric optimization, Mulliken atomic charge analysis, and to evaluate conformational stability based on relative energy values. Frontier Molecular Orbital (FMO) analysis, global reactivity descriptors, and dipole moments reveal that the crown conformers exhibit significantly elevated chemical reactivity compared to their chair counterparts. Thermodynamic assessments further delineate the reaction pathways, confirming the kinetic and thermodynamic stability of the products. These theoretical insights are corroborated by topological mapping include Molecular Electrostatic Potential (MESP), Electron Localization Function (ELF), and Localization of Electron Density (LOL) analyses which map the reactive sites, electron distribution, and intramolecular hydrogen bonding networks. Experimentally, the macrocycles were rapidly synthesized within 30–60 min, and their crown-chair conformations were confirmed via 1H-NMR and 13C-NMR spectroscopy. UV-Visible and fluorescence analyses indicate that phenyl and hydroxyphenyl substitutions on the methine bridges pivotally modulate charge-transfer and proton-transfer transitions, yielding distinct photophysical properties and Stokes shift values. Biologically, blind molecular docking (CB-Dock2) underscores the medicinal potential of these macrocycles, demonstrating high binding affinity and specific interactions with the p53 cellular tumor antigen. Furthermore, phosphomolybdate and Kirby-Bauer assays reveal potent antioxidant and antibacterial activities against both Gram-positive and Gram-negative bacteria. Collectively, these computational and experimental findings position these macrocycles as promising candidates for novel anticancer and antibacterial drug development, as well as high-sensitivity molecular probes for advanced photophysical sensing.
Oxido-decarboxylation mechanism of phenylsulphinylacetic acid (PSAA) by means of eight iron(III)salen complexes in aqueous N,N′-dimethylformamide (DMF) was studied. The active oxidizing species is identified as [FeIII(salen)]+ ion. Complex formation between PSAA and [FeIII(salen)]+ ion was confirmed through Michaelis-Menten kinetics and spectral changes. Introducing diverse electron-withdrawing and releasing groups (except p-OMe) in PSAA slows the reaction rate, with a non-linear Hammett correlation indicating that the influence of substituents shifts in PSAA. Electron-withdrawing groups impede electron transfer (ET) reaction between PSAA and iron-complex, while electron-releasing groups enhance it but also reduce the nucleophilic attack by water. A mechanism involving simultaneous electron transfer and decarboxylation leading to sulfone formation is proposed, with the non-linear Hammett correlation attributed to the development and decay of sulfoxide radical cations influenced by means of substituents.
