Case fatality rates associated with osteosarcoma increase sharply in patients with metastatic disease involving multiple sites. The tendency of osteosarcoma to metastasise has been linked to the presence of osteosarcoma stem cells (OSCs). Here, we report a gallium(III) complex (1) containing two 3,4,7,8-tetramethyl-1,10-phenanthroline ligands and chrysin, and investigate its in vitro anti-OSC activity. Complex 1 effectively eliminates OSCs grown in both two- and three-dimensional cultures at sub-micromolar to micromolar concentrations and is up to 130-fold more potent (based on half-maximal inhibitory concentration values) than the frontline anti-osteosarcoma metallodrug, cisplatin. Intracellular reactive oxygen species (ROS) studies suggest that the cytotoxic activity of 1 towards both bulk osteosarcoma cells and OSCs is mediated, at least in part, by intracellular ROS level elevation. Overall, this study highlights the promising anti-OSC potential of gallium(III)-based coordination complexes and represents the first report of an anti-OSC metal-flavonoid complex.
We extend the Coulomb Snapshot model from one-dimensional conjugated chains to two-dimensional polycyclic aromatic hydrocarbons (PAHs). The original 1D formulation, which quantifies π-electron delocalization through electron–nuclear Coulombic interactions, showed strong logarithmic correlations ( R 2 = 0.98) with experimental absorption wavelengths and combustion enthalpies in linear oligoenes and oligoynes. The 2D extension introduces geometry-specific interaction factors for rectangular, linear, and hexagonal (regular and irregular) PAH topologies. Statistical validation on 20 structurally diverse PAHs (C 12 –C 54 ) yields R 2 = 0.656 for ionization energy (IE) (mean absolute error (MAE) = 0.221 eV) and R 2 = 0.672 for the fundamental gap (MAE = 0.441 eV) across the complete dataset; after z-score outlier removal (| z| > 1.5σ), these improve to mean relative errors of 2.25% for IE (MAE = 0.154 eV, R 2 = 0.857) and 5.29% for the fundamental gap (MAE = 0.298 eV, R 2 = 0.843). Three outliers (acenaphthylene, fluoranthene, dibenzo[bc, kl]coronene) show systematic deviations attributable to five-membered-ring fusion and extended irregular hexagonal geometries not fully captured by the simplified geometric factors. Error analysis—normally distributed residuals, a narrow 95% prediction band (±0.38 eV for IE, ±0.75 eV for the fundamental gap), and consistent performance across molecular sizes—supports predictive reliability while maintaining physical interpretability and minimal computational cost. Although developed and evaluated on a relatively small dataset, the 2D-Snapshot model thus offers a fast, physically interpretable estimate of the electronic properties of benzenoid PAHs and represents a promising framework for rapid screening in organic materials design that warrants validation on larger, more structurally diverse sets.
We report the synthesis and testing of a new reagent for selective 2′-hydroxyl acylation analyzed by primer extension (SHAPE). We report the synthesis and testing of a nitrone acyl imidazole that is capable of labelling RNA (DMImO-AI) for applications including in vivo click SHAPE (icSHAPE). The new reagent has a reasonable lifetime for in vivo applications and can undergo strain-promoted alkyne-nitrone cycloaddition reactions that more rapidly conjugates labelled RNA than 2-(azidomethyl)nicotinic acid imidazolide (NAI-N 3 ). We show that DMImO-AI is a useful reagent for SHAPE mapping experiments of RNA from A549 cells with a faster reacting nitrone moiety for bioorthogonal conjugation.
The synthesis and solid-state characterization of the dissymmetric aminopyrazole ester ligand methyl-6-(5-amino-1-(pyridine-2-yl)-1 H-pyrazol-3-yl)picolinate, L1-CH 3 , and three Ni(II) and Co(II) complexes are reported. Under protic solvent conditions in the presence of transition-metal salts, L1-CH 3 undergoes apparent in situ ester hydrolysis to generate the monoanionic carboxylate ligand L1, which supports the formation of [(L1) 2 Ni]·MeOH·H 2 O (1), [(L1) 3 Ni 2 ]Cl (2), and [(L1) 5 Co 3 ](NO 3 ) (3). Single-crystal X-ray diffraction reveals that 1 is a mononuclear Ni(II) complex with a distorted octahedral N 4 O 2 coordination environment, while 2 is a dinuclear Ni(II) complex in which three L1 ligands bridge the two metal centres and generate two distinct N/O donor environments. Compound 3 is a trinuclear Co(II) complex containing an approximately linear Co 3 arrangement, with terminal distorted octahedral Co(II) centres and a central distorted square-pyramidal Co(II) centre. Hirshfeld surface analysis shows that metal complexation reduces the contribution from C···C contacts relative to L1-CH 3 , consistent with loss of ligand planarity and diminished π-stacking. These results demonstrate that ester/carboxylate functionalization can alter both ligand reactivity and coordination outcomes in aminopyrazole systems, enabling access to mono-, di-, and trinuclear architectures and providing a basis for future mixed-donor and heterometallic ligand design.
Our group has previously studied the atypical electron-deficient cluster [(iPr3P)Ni]5H6 for the activation of inert bonds and as a catalyst for nearly barrierless alkene dimerization and stereoselective [2+2] cycloadditions. This study examines alternative phosphines to the iPr3P supporting ligand in [iPr3P)Ni]5H6 for their ability to stabilize related pentanuclear clusters. The reaction of [(iPr3P)2Ni]2(μ-N2) (3⸱iPr3P) with H2 was found to feature two spectroscopically identified intermediates, trans-(iPr3P)2NiH2 (4⸱iPr3P) and [(iPr3P)2Ni]2(µ-H)2 (5⸱iPr3P) prior to cluster formation. Attempts at analogous chemistry supported by Cy3P (Cy = cyclohexyl) led to the spectroscopically identified trans-(Cy3P)2NiH2, which underwent P−C bond cleavage to give the dinuclear Ni(II) product [(Cy3P)NiH]2(µ-PCy2)(µ-H). Similar P−C bond cleavage chemistry was observed with Cyp3P (Cyp = cyclopentyl). The tBu2MeP supported complex [(tBu2MeP)2Ni]2(μ-N2) reacted under H2 to give [(tBu2MeP)Ni]5H6 (1H6⸱tBu2MeP), which proved much more reactive to H/D exchange with benzene-d6 than [(iPr3P)Ni]5H6. 1H6⸱tBu2MeP also had a triplet state only 6.1 kcal⸱mol–1 higher in energy than the ground state. This cluster is unstable at room temperature and in solution reacts via P−C bond cleavage. The smaller phosphine Cy2MeP supported the complex (Cy2MeP)3Ni (8⸱Cy2MeP), which cocrystallized with the dinitrogen complex (Cy2MeP)3Ni(N2) (8N2⸱Cy2MeP). Only partial conversion to [(Cy2MeP)2Ni](μ-H)2 (5⸱Cy2MeP) occurred under 4 atm H2. The complexes (Et2tBuP)2NiCl2 (2⸱Et2tBuP) and (2⸱iPr2EtP) were prepared but reduction gave the supporting phosphine as the major recovered product. This work shows the importance of steric factors in cluster formation and emphasizes the importance of resistance to P−C bond cleavage, both prior to and after cluster formation, for the isolation of pentanuclear complexes.
Codonopsis javanica (C. javanica) is an indigenous medicinal plant of Vietnam that possesses various valuable bioactive compounds with potential applications in multiple fields. In this study, the extraction of C. javanica tuber was carried out using ultrasound-assisted extraction with ethanol as the solvent. The effects of the solid-to-solvent ratio, extraction time, and temperature on the saponin content of the extract were investigated. The results indicated that the optimal extraction conditions were a solid-to-solvent ratio of 1:40, an extraction time of 45 min, a temperature of 50 °C, and four extraction cycles. Under these conditions, the extract exhibited a saponin content of 32.7 ± 2.5 mg/g, along with other bioactive compounds, including polyphenols (6.14 ± 0.045 mg GAE/g), flavonoids (1.906 ± 0.006 mg/g), proteins (38.78 ± 0.085 mg/g), reducing sugars (122.6 ± 0.2 mg/g), and polysaccharides (907.4 ± 2.5 mg/g). The antioxidant activity of the extract was evaluated using DPPH and ABTS assays, yielding IC50 values of 40.34 µg/mL and 228.39 µg/mL, respectively. These results demonstrate that the extract from C. javanica tuber exhibits significant antioxidant activity and has promising potential as a natural source of bioactive compounds for pharmaceutical and cosmetic applications.
The identification of complex organic molecules (COMs) in cold dark clouds like Taurus Molecular Cloud 1 has heightened interest in comprehending their chemical origins under astrochemical conditions. Notable among these is dinitrile substances such as malononitrile CH 2 (CN) 2 and maleonitrile (Z)-NC–CH=CH–CN, which are important for their possible contributions to prebiotic chemistry and molecular diversity in the interstellar medium (ISM). This work examines the possible single-step formation processes of malononitrile and maleonitrile in the gas phase at the ωB97XD/aug-cc-pVTZ level, which accurately accounts for dispersion interactions essential for weakly bound interstellar systems. Energetic and thermodynamic factors suggest that both molecules can be generated via barrierless recombination pathways involving CN, CH 2 CN, and CHCN species. Spectroscopic parameters, including dipole moments and vibrational modes were calculated to assist current astronomical detection initiatives. The results enhance the comprehension of nitrogen-heavy COMs in the ISM and provides important perspectives on the chemical evolution routes that might connect interstellar organic chemistry to the beginnings of life.
One of the challenges faced in the field of lipidomics is that approximately 75%–85% of mass spectral features are unidentified in complex liquid chromatography-tandem mass spectrometry (LC-MS) datasets, colloquially referred to as “dark matter”. Using available LC-MS data processing and characterization techniques, a protocol was developed to minimize the dark matter observed in complex lipidomic datasets and increase the number of lipids identified. Lipids were extracted from bovine liver and analyzed in both polarities via reversed phase HPLC-ESI-MS/MS. Extracted ion chromatograms for each feature in the dataset were extracted using MZmine and annotated using a modified LipidBlast library. Once a preliminary feature annotation was conducted, the data were then further analyzed using a novel protocol employing additional informatics tools including the molecular networking software global natural products social, a diagnostic fragmentation filtering tool, a Kendrick mass defect tool, as well as the LIPID MAPS database to identify additional lipid features. Through this approach, 48 more lipids were added to our list in positive ion mode (335 lipids) and 7 more lipids were added to our list in negative ion mode (214 lipids). This approach also enabled the identification of other spectral features including dimers, polymers, sodium adducts, sodium formate adducts, as well as in source fragmentation peaks. This work demonstrates that the use of multiple data processing and informatics tools reduces the percentage of a dataset that is classified as dark matter by increasing the number of lipid identifications and better characterizing non-lipid features.
Molecular photosensitizers can use a donor–chromophore–acceptor architecture to achieve long-lived charge separated states that may more efficiently initiate the single electron transfer processes involved in photocatalysis or photovoltaic devices. These photosensitizers are typically metal complexes wherein the dominant lowest energy photon-absorbing state is a metal-to-ligand charge transfer, having molar absorptivities on the order of 104 cm−1 (mol/L)−1, and charge separation is achieved through careful redox leveling of ancillary electron donating and accepting groups. Taking advantage of direct ligand-to-ligand charge transfer states introduces new excited state pathways that can also lead to charge separated states. In this work, we present a series of heteroleptic zinc(II) 2,2′:6′,2″-terpyridine photosensitizers containing a pendant pyridyl group and carbazole or diphenylamine electron donating groups capable of undergoing direct ligand-to-ligand charge transfer with up to 42% photoluminescence quantum yields in solution or solid state, and up to 86% when arrested in a polymer matrix due to overcoming aggregation induced quenching effects.
Understanding the interactions between drugs and surfactants is crucial for improving drug delivery systems and developing successful therapeutic formulations. This investigation intends to evaluate the temperature-induced aggregation of sodium dodecyl sulfate (SDS) in combination with clocacillin sodium (ClxNa), while also examining the influence of glucose and urea on micellization. Conductivity measurements were employed to examine the interactions within the SDS–ClxNa system including aqueous glucose/urea at various temperatures. The addition of ClxNa facilitated micellization by lowering the critical micellar concentration (CMC) values of SDS. Glucose stabilizes the water structure and enhances hydrophobic interactions, hence lowering the CMC of SDS/SDS–ClxNa. Urea diminishes the hydrophobic action that promotes micellization by altering the water structure, hence increasing the CMC. A U-shaped pattern has been noticed in the correlation between temperature and the CMC of SDS–ClxNa in both aqueous and aqueous glucose/urea environments. Thermodynamic parameters (entropy of micellization, Δ S 0 m ; enthalpy of micellization, Δ H 0 m ; and Gibbs free energy of micellization, Δ G 0 m ) and physicochemical variables (CMC and counterion dissociation, α) have been used to characterize the interaction between SDS and ClxNa. The spontaneity of micellization in the SDS–ClxNa system in both water and urea/glucose conditions is depicted by the negative Δ G 0 m results. The results offer critical understanding for scholars aiming to refine parameters, including temperature, concentration, and the incorporation of glucose/urea additives, to improve the effectiveness and durability of drug delivery systems.
The hexavalent chromium [Cr (VI)] present in industrial effluent is considered to be a threat to the environment as it is highly toxic, carcinogenic, and also persist in aquatic ecosystems. Concurrently, improper disposal of wood sawdust contributes to environmental degradation, leading to soil and water contamination and air pollution from open burning. This study addresses both challenges by exploring the utilization of waste-derived materials Neem (Azadirachta indica) and Teak (Tectona grandis) sawdust chars as affordable, eco-friendly adsorbents for Cr (VI) removal from synthetically prepared chromium solution of concentration 2 mg/L through batch investigation. Experimental investigation was performed with char produced with and without chemical activation at different normality of KOH in comparison with commercially available activated carbon which are now widely used as adsorbents for a time period of 3 h. The results have shown that Neem char demonstrated high adsorption capacity of 64% even without undergoing chemical activation, highlighting its natural efficacy, and suggesting its superior potential as a biosorbent. The study involved comparing five different nonlinear kinetics model to ensure the best fit on understanding the adsorption mechanism involved. Overall, it is evident that the Elovich model is found to be the best fit with R2 for all the cases being 0.949 ± 0.032. This indicates that the adsorption proceeds primarily through chemisorption on a heterogeneous surface rather than diffusion. These findings underscore the applicability of Neem and Teak char in treating chromium-contaminated water while promoting sustainable waste management and paving a way for further research.
Produced water generated from oil and gas operations represents one of the largest and most complex industrial wastewater streams, characterized by persistent petroleum hydrocarbons that are difficult to remove using conventional separation or adsorption-based technologies. Existing treatment approaches often suffer from limited efficiency, poor regenerability, or an inability to simultaneously capture and mineralize dissolved hydrocarbons. In this context, multifunctional materials that integrate adsorption and photocatalytic degradation within a single platform have emerged as promising alternatives. La–ZnO/silica aerogel composite was synthesized using rice husk-derived silica and evaluated for the removal of petroleum hydrocarbons from aqueous systems. Structural analyses (XRD, FTIR, SEM, and BET) confirmed the uniform dispersion of La–ZnO nanoparticles within the aerogel matrix, producing a hierarchical meso–macroporous network with enhanced surface area and stability. Adsorption studies revealed pseudo-second-order kinetics and a strong fit with the Langmuir model, indicating chemisorption on homogeneous sites with a maximum monolayer capacity of ∼150 mg g−1. Under simulated solar irradiation (AM 1.5G), the composite exhibited superior photocatalytic activity compared with bare La–ZnO, achieving rapid degradation with an apparent rate constant (kapp ≈ 0.014 min−1). total organic carbon and chemical oxygen demand reduction confirmed significant mineralization (>50% within 240 min), while recyclability tests demonstrated high structural stability and sustained performance over multiple cycles. Mechanistic evaluation highlighted a synergistic “adsorb-and-degrade” pathway, supported by La-induced bandgap modification and aerogel-assisted pollutant pre-concentration. These findings demonstrate the potential of La–ZnO/silica aerogels as sustainable, high-performance materials for treating complex petroleum-contaminated waters.
Interaction of benzimidazole-2-thione (MBI) with a typical π-type charge transfer (CT) acceptor, 2,3-dicholo-5,6-dicyano-1,4-benzoquinone (DDQ) has been studied by using several spectral techniques, viz., UV/Visible, FT-IR, 1 H, and 13 C NMR and Mass spectra. Electronic absorption spectra of the system MBI–DDQ in methanol, a protic solvent, have indicated initial formation of an outer-sphere CT complex (MBI.DDQ). Formation constant ( K CT ), molar absorption coefficient (ε CT ), and the thermodynamic properties, ΔH, ΔS, and ΔG, of this CT complex have been determined and discussed. The first formed CT complex (MBI.DDQ) has led to a substitution reaction involving a nucleophilic replacement catalyzed by methanol.
In this investigation, we present a combined density functional theory and molecular docking study to explore the structural, reactivity, spectroscopic properties, and anticancer activity of new Cu(II) and Zn(II) complexes with 1,3-dimesitylpropane-1,3-dione (LMes) in both the gas phase and ethanol solvent. Geometric parameter scanning elucidates the intramolecular interactions, revealing the steric and electronic effects of the metal centers on the molecular geometry. A good correlation is observed between the experimental and calculated geometric parameters, validating the theoretical model. The obtained results indicate that the Cu(II) complex adopts a square–planar geometry, whereas the Zn(II) complex exhibits a tetrahedral geometry. Molecular reactivity descriptors and the molecular electrostatic potential maps were calculated to identify the most reactive sites within the molecular framework. Moreover, a good agreement is found between the experimental and theoretical vibrational frequencies, confirming the reliability of the computational approach. The UV–visible absorption spectra were also analyzed, revealing that the metal center significantly influences the electronic transitions, with a notable shift in λmax to 424.71 nm for the Cu-complex and 320.84 nm for the Zn-complex. Finally, the Cu(II) complex demonstrates superior stability, specificity, and structural reinforcement within the epidermal growth factor receptor active site, supported by stronger hydrogen bonding, π–π interactions, and reduced protein flexibility. In contrast, the Zn(II) complex adopts a more hydrophobic and flexible binding mode, indicating weaker stabilization and lower inhibitory potential. These findings suggest that both complexes possess promising anticancer potential, warranting further experimental validation and pharmacological evaluation to confirm their therapeutic efficacy.
In this study we have explored the structure, elastic, optoelectronic, and thermodynamic properties of cubic NaXO 3 (X = Cr, Mo) perovskites, using first-principles calculations with the density functional theory within Wien2k frame work. Structural optimization is used in the cubic phase to confirm the lattice stability and its mechanical stability is checked by calculating the elastic constants. Phonon dispersion and quasi-harmonic thermodynamic studies establish the existence of localized soft modes in cubic NaCrO 3 , whereas NaMoO 3 is dynamically stable; both compounds have strong vibrational properties and show no signs of thermal phase transitions in the temperature range studied. Elastic constants demonstrate mechanical stability and brittle nature for NaCrO 3 while ductile behavior for NaMoO 3 , which is backed up by Cauchy pressures and Pugh ratio analysis. Both compounds are suggestively metallic in nature according to electronic band structure and density of states calculations, and highly spin polarized. NaCrO 3 has strong magnetism and NaMoO 3 has weak magnetism. Optical analysis shows high reflectivity in the low-energy regime and dielectric response of a metallic type. The results offer theoretical understanding of the multifunctional nature of the NaXO 3 (X = Cr, Mo) perovskites and their use in spintronic and energy storage applications.
The analysis of steroids by liquid chromatography–tandem mass spectrometry (LC-MS/MS) is associated with several analytical challenges, including difficulty in confirming their structures in complex samples, due to structural similarities. Collision-induced dissociation is commonly employed but many aspects of the fragmentation behavior of steroids remain unexplored. In this study, we report the systematic high-resolution-MS/MS (HR-MS/MS) characterization of 33 endogenous steroid standards analyzed using a micro-LC-HR-MS/MS workflow on a quadrupole-time-of-flight platform in positive mode, while varying collision energies, for their native forms and Girard P (GP) derivatives. For underivatized steroids, intermediate collision energies produced the most interpretable spectra, enabling the identification of many class-specific diagnostic ions. The multiple collision energies tested revealed strong dependence of both precursor persistence and diagnostic fragment presence related to structural features present in the steroids. GP derivatization increased signal intensities and altered their chromatographic retention, with the signal enhancement depending on the presence of specific structural features. Higher collision energies applied to GP-derivatized steroids revealed diagnostic fragments, useful for structural characterization. Fragmentation patterns and collision energy-dependent profiles provide increased confidence for steroid structural classification and isomer discrimination.
Squalene epoxidase (SQLE), a rate-limiting enzyme in cholesterol biosynthesis and a validated antifungal–anticancer target, was probed with four boswellic-acid derivatives isolated from Boswellia sacra. After purification and NMR-based structure elucidation, the compounds were tested in vitro, revealing that 9,11-dehydro-β-boswellic acid and its acetyl analogue inhibit SQLE with low-micromolar IC50 values (∼2 µmol L−1) and noncompetitive kinetics, surpassing the reference inhibitor tris-norsqualene cyclopropylamine. Two more heavily substituted analogues were weaker, one acting noncompetitively and the other showing mixed-type inhibition with a dominant competitive component. Docking and 200 ns molecular-dynamics simulations showed that the potent Δ9,11 scaffold targets an allosteric vestibule defined by Ser531/Gln500, whereas the mixed inhibitor occupies the FAD entrance channel. Free-energy-landscape mapping and molecular mechanics/Poisson–Boltzmann surface area calculations confirmed that the allosteric complexes display the deepest energetic minima and most favorable binding enthalpies (≈−24 kcal mol−1), while dynamic descriptors (RMSD, RMSF, Rg, SASA, hydrogen bonding, and interaction energies) indicated that ligand binding leaves the global fold intact but stabilizes local loops. In silico absorption, distribution, metabolism, excretion, and toxicity profiling suggested acceptable drug-likeness, low hERG and CNS liabilities, and manageable CYP2C9 interaction for the Δ9,11 derivatives, although extremely low aqueous solubility and moderate genotoxic alerts remain hurdles for optimization. Collectively, these findings establish boswellic acids—particularly the 9,11-dehydro core—as promising natural allosteric modulators of SQLE and illustrate a streamlined phytochemical–biochemical–computational workflow for repurposing natural products against challenging enzymatic targets.
The emergence of multidrug-resistant microbes and oxidative stress due to free radicals poses a serious threat to human health, rendering conventional antibacterial therapies ineffective. Hence, developing eco-friendly strategies to counter these issues is essential. In this study, an environmentally benign route was adopted for the phytofabrication of barium oxide (BaO) and stannous oxide (SnO 2 ) nanoparticles (NPs) using Thymus serpyllum leaf extract. The synthesized NPs were characterized by UV-Vis spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analysis to confirm their purity, morphology, and optical properties. The X-ray diffraction analysis was carried out to study the crystalline nature, whereas Fourier transform infrared spectroscopy verified the effective capping of NPs by T. serpyllum phytochemicals. The antimicrobial activity of the biosynthesized SnO 2 and BaO NPs was tested against Klebsiella pneumoniae using the disc diffusion method, while their antioxidant potential was evaluated using ABTS and DPPH assays. Both nanomaterials exhibited excellent antibacterial and radical-scavenging activities. The results highlight T. serpyllum as a promising biotemplate and reducing agent for nanoparticle synthesis. To the best of our knowledge, this is the first report on the phytosynthesis of BaO NPs and the dual biofabrication of BaO and SnO 2 NPs using T. serpyllum leaf extract.
Detection of infrared (IR) spectrum features of target molecules can be achieved by comparison of experimentally measured spectra to template spectra within a database. The focus of this study is the scalability of density functional theory (DFT)-calculated IR spectra with respect to macroscales, characteristic of dielectric response as measured using IR spectroscopic methods, and demonstration that IR-spectrum databases can be constructed with respect to classes of target molecules, where DFT-calculated spectra provide a complementary extension of experimentally measured IR spectra. A case study analysis concerning IR-spectra scalability for a set of energetic materials is described. This analysis provides an example of calculating template spectra for potential detection of target molecules, where DFT-calculated IR spectra are frequently more convenient than laboratory measurements using IR spectroscopic methods. We have shown that DFT-calculated spectra can be included within template-spectrum databases, and their ability to show very good correlation with measured spectra.
