University of Sargodha

The properties of rare-earth spinel chalcogenides depend strongly on how exchange-correlation and relativistic effects are treated. Here, the stability and the mechanical, electronic, magnetic, optical, thermoelectric and thermodynamic properties of the cubic (Fd-3m) spinels BaGd2X4 (X = S, Se) are investigated using the FP-LAPW method. The electronic and transport responses are compared under five schemes: GGA, GGA + mBJ, GGA + SOC, GGA + U and GGA + SOC + U. Negative formation energies (-2.43 and -2.13 eV/atom), a ferromagnetic ground state below two antiferromagnetic configurations, and elastic constants satisfying the Born criteria confirm stability. Pugh (4.60, 4.67) and Poisson (0.39, 0.40) ratios indicate ductility. Both compounds remain spin-polarised semiconductors under every scheme. The Hubbard term (U_eff = 6.6 eV on Gd-4f) widens the gaps to 1.60 eV (BaGd2S4) and 1.40 eV (BaGd2Se4), whereas SOC narrows them to 1.04 and 0.71 eV, with the Se compound more sensitive to relativistic corrections. The total moment of 28 mu B per cell is carried mainly by Gd3+ (approximate to 6.9 mu B) and is unchanged by SOC and U, consistent with the half-filled 4f7 shell. The optical spectra (0-8 eV) show an absorption onset near 1 eV, a static refractive index of 2.3-3.7 depending on the scheme, and strongest absorption at 6-7.5 eV. Boltzmann transport gives positive Seebeck coefficients of about 250 mu V/K at 300 K, indicating p-type conduction. Slack's model yields lattice thermal conductivities of approximate to 0.07 and approximate to 0.26 W m-1 K-1 at 300 K. Quasi-harmonic analysis (0-8 GPa, 200-800 K) shows the Debye temperature rising with pressure. These findings identify BaGd2X4 as candidate p-type thermoelectric and ultraviolet optoelectronic materials.

Hypopharyngeal cancer contributes 3% of the overall head and neck cancers. The identification of major biochemical disease symptoms can be effective for diagnosing early stage of hypopharyngeal cancer. In the current work, gold nanoparticles (Au-NPs) were used as substrate for enhancement of Raman signal for the analysis of blood serum of different stages of hypopharyngeal cancer by surface-enhanced Raman spectroscopy (SERS). Major SERS spectral differentiating peaks were observed at 326, 446, 574, 622, 637, 680, 821, 876, 940, 964, 1081, 1133, 1284, 1325, 1432, 1451, 1574 and 1587 cm-1 corresponding to biochemical changes of metabolites in blood serum of hypopharyngeal cancer patients. Moreover, chemometric tools like principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA) and support vector machine (SVM) were applied for the effective differentiation and identification of biological changes along with sensitivity, specificity, precision, and accuracy of SERS for the classification of spectral groups of healthy and cancer samples.

This study investigates the effects of fluoride exposure on tissue accumulation, behavior, oxidative stress, neurotoxicity, metabolomic, and molecular alterations in Cyprinus carpio. The effects were evaluated at four different concentrations (Control: 0.8 mg/L, Group 1: 1.52 mg/L, Group 2: 3.0 mg/L, Group 3: 4.2 mg/L) over a 30-day period. Behavioral analysis revealed progressive neurobehavioral impairments including erratic swimming, lethargy, and respiratory distress. Fluoride accumulation followed the order: bone > gill > skin > muscle, indicating both systemic absorption and organ-specific retention. Enzymatic assays showed significant elevation of antioxidant enzymes (SOD, CAT, GPx) coupled with acetylcholinesterase inhibition, signifying oxidative stress and neurotoxicity. Metabolomic profiling demonstrated marked depletion of glutathione and ATP, with elevated lactate, AMP, and succinate levels, reflecting mitochondrial dysfunction and energy crisis. Concurrently, upregulation of IL-17, TNF-α, RORγ, and FoxO3a, alongside downregulation of IL-10 and Foxp3, indicated transcriptional signatures consistent with Th17-associated pro-inflammatory signaling and reduced Treg-related gene expression. Apoptotic gene activation (JNK, Bax, PUMA, Apaf-1, Caspase-9/3) and Bcl-2 suppression confirmed intrinsic mitochondrial apoptosis. Collectively, fluoride toxicity appears to progress through an integrated oxidative stress–mitochondrial dysfunction–immune imbalance–apoptotic cascade, which suggests that oxidative stress may function as an upstream trigger. These findings demonstrate that fluoride induces behavioral impairments, tissue accumulation, oxidative stress, metabolic disruption, immune imbalance, and apoptosis in C. carpio, with effects showing a strong dose-dependent (graded) response pattern, and identify key metabolites and molecular markers as early indicators of fluoride toxicity in aquatic environments.

Polymorphism is the exciting feature of compounds existing in different crystalline forms. The present research is focused on the two polymorphic forms, 3A and 3B, of (E)-1-(3-hydroxyphenyl)-3-(naphthalen-1-yl)prop-2-en-1-one obtained by the Claisen-Schmidt condensation reaction of 1-(3-hydroxyphenyl)ethan-1-one and 1-naphthaldehyde. Both polymorphic forms were characterized by single-crystal X-ray diffraction (SC-XRD) analysis. The supramolecular assemblies of these polymorphic forms were found to be stabilized by various intermolecular interactions as revealed by the Hirshfeld surface analysis. The interaction energy calculations were carried out at the B3LYP/6-31G(d, p) level to further investigate the supramolecular assembly of these polymorphs. Moreover, antifungal, antibacterial, and antioxidant activities of these polymorphs were investigated, showing reasonable and slightly different potential of both polymorphs in these areas. Also, density functional theory (DFT) study of both polymorphs was performed, using the B3LYP-GD3/6-311 + + G(d, p) approach, with the analysis of Natural Bond Orbital (NBO) charges and donor-acceptor interactions, frontier molecular orbitals (FMOs), molecular electrostatic potentials (MEP), non-covalent interactions (NCI), Laplacian bond orders, localized orbital locator (LOL), and global reactivity parameters (GRPs). The obtained results provided support for the SC-XRD and Hirshfeld surface analysis results. Next, the quantum theory of atoms in molecules (QTAIM) and NCI analyses of the 3A and 3B crystal structures fragments provided strong support for the existence of off-set π ⋯ π stacking interactions and C-H⋯π interactions and hydrogen bonds in the 3A and 3B crystal structures.

Research on sustainable energy storage and conversion techniques is advancing due to rising energy use. Supercapacitors, high-power-density capacitors, are in high demand due to their quick energy release and absorption capabilities. In this study, NiO/Co3O4/BaO/Al2O3 (NCBA) and NiO/Co3O4/BaO/Al2O3@g-C3N4 (NCBACN) nanocomposites were synthesized, characterized, and their electrochemical performance was checked as a supercapacitor and for photodegradation of dyes. The NCBA and NCBACN nanocomposites were prepared using co-precipitation and ultra-sonication methods. The NCBACN electrode had a higher specific capacitance (2190 F/g) than the NCBA electrode (476 F/g). NCBACN demonstrated superior efficiency in reducing Rhodamine-B and Congo red dyes, with 97