A combination of mechanical synthesis, solid-state analytical techniques (ssNMR, powder XRD, ATR-FTIR) and DFT calculations sheds light on the mechanisms operating in two organometallic solid-state syntheses and highlight the importance of workup protocols in mechanochemical syntheses. The data clearly indicate that product formation can occur during or post grinding.

A series of hydrazones derived from vanillin and salicylaldehyde, incorporating isoniazid (INH) and its analogues (nicotinic hydrazide and pyrazine-2-carbohydrazide), were designed, synthesized, and evaluated for anti-mycobacterial activity. The INH-bearing derivatives demonstrated significant activity against Mycobacterium tuberculosis (Mtb), with MIC values of 0.078-0.625 μg/ml. Salicylaldehyde-based hydrazones exhibited the highest potency (MIC = 0.078 μg/ml), whereas vanillin analogs showed marginally reduced activity, potentially due to linker length effects. All compounds were non-toxic to THP-1 macrophages at concentrations <10 μg/ml, suggesting a favourable safety profile. UV-vis studies showed that the salicylaldehyde-based hydrazone 5d is stable under mildly acidic conditions, suggesting that pH-triggered release of INH is unlikely inside Mtb infected cells. Additionally, their lack of activity against INH-resistant Mtb KatG mutants (MIC >10 μg/ml) implies a KatG-dependent activation mechanism, analogous to INH. These findings highlight the promise of Schiff base dimerization in developing safe and potent anti-tubercular agents, warranting further chemical optimization.

We discovered a brucite, quartz and moissanite bearing natural rock of mantle affinity containing relics of two now decomposed minerals, so far known from meteorites only, constituting 4 vol

Multicationic nitrides are emerging as a new class of high-performance electrode materials for micro-supercapacitors (MSCs), yet their synthesis and structural control remain challenging. Here, we report the fabrication of VWN nanolaminates using reactive magnetron sputtering deposition method. The deposition pressure and Ar/N2 ratio are systematically tuned to optimize morphology and electrochemical performance. The 100 nm resulting films, composed of alternating 2 nm-thick VN and W2N layers, achieve a high volumetric capacitance of 1400 F·cm−3 at 5 mV·s−1 in 1 mol/L KOH, among the best reported multicationic materials for MSCs. We demonstrate that preferred-oriented nanolaminate growth and interface stabilization occur when VN is used as the initial layer, with a critical VN layer thickness of ≤50 nm. Structural characterization via TEM and XRD reveals the formation of a cubic Fm3¯m phase, while electrochemical analyses confirm exceptional rate capability and cycling stability. Post-annealing treatments further elucidate the stabilization mechanism of the nanolaminate architecture. This work provides a rational design strategy for engineering multicationic nitrides with tailored electrochemical properties, offering a promising pathway for next-generation energy storage devices.

The growing demand for miniaturized autonomous microdevices within the Internet of Things (IoT) ecosystem necessitates compact, high-voltage, on-chip energy storage solutions. This work presents a systematic characterization of the electrochemical properties of atomic layer deposition (ALD)-grown Al2O3 and Ta2O5 dielectric films deposited on various current collector for electrolytic micro-capacitor operating in aqueous electrolyte. Four planar electrode configurations, namely Pt / Al2O3, Al / Al2O3, Pt / Ta2O5 and TaN / Ta2O5, were compared to select the most suitable current collector. The Pt-based electrode exhibited a stability window of ca. 1 V versus Ag/AgCl, constrained by oxygen evolution at 1.2 V vs Ag/AgCl. This work shows as well that Al / Al2O3 and TaN / Ta2O5 electrodes have a greater stability (0-10 V versus Ag/AgCl), attributed to self-healing anodic oxidation, due to a good cation-matched interfacial chemistry, and reduced leakage currents. High temperature X-ray diffraction and X-ray reflectivity revealed that annealing temperatures of sputtered TaN / ALD grown Ta2O5 films should be restricted to 500 degrees C under N2 / H2 to both ensure film densification and to prevent oxidation and increased resistance in TaN.

Here we investigated the electrochemical performance of molybdenum nitride films as an efficient electrode for asymmetric micro-supercapacitors. Molybdenum nitride films were successfully deposited and optimized by reactive magnetron sputtering. On the one hand, the tuning of several deposition parameters (pressure, gas flow rates) allows obtaining molybdenum nitride electrode with high porosity and high electrical conductivity. On the other hand, Operando X-ray diffraction, operando Raman spectroscopy and operando X-ray absorption spectroscopy are combined to unveil the charge storage process in 1 M KOH aqueous electrolyte. These measurements clearly reveal the role of molybdenum oxide species in the pseudocapacitive mechanism at the oxide/electrolyte interface. High volumetric capacitance up to 624 F & sdot;cm-3 with excellent capacitance retention of 95 % over 20 000 cycles was achieved in 1 M KOH.

Iron-based perovskites are of increasing interest for applications in symmetrical reversible solid oxide cells used for hydrogen production via steam electrolysis and power generation in a fuel cell configuration. We synthesize La _0.72 Sr _0.18 Fe _0.9 Ni _0.1 O _3– _δ as a potentially new candidate for this application, employing rapid nonequilibrium auto-combustion synthesis. Using powder x-ray diffraction and electron microscopy, we reveal that the material is an ABO _3 -type perovskite with an orthorhombic crystal structure. This compound exsolves small FeNi particles upon thermal treatment in a hydrogen-containing reductive atmosphere. These particles exhibit a cubic crystal structure with predominantly exposed [001] facets. The exsolution is assisted by the structural transformation of the parent orthorhombic ABO _3 -type perovskite into a Ruddlesden–Popper A _2 BO _4 -type perovskite with a tetragonal structure. Conveniently, the exsolution can be tailored to be either partially or completely reversible, depending on the temperature of the subsequent thermal treatment in an oxidative atmosphere. This correspondingly affords either the formation of a perovskite/nickel-ferrite spinel composite or reversion to the parent La _0.72 Sr _0.18 Fe _0.9 Ni _0.1 O _3– _δ perovskite. The newly synthesized Co-free La _0.72 Sr _0.18 Fe _0.9 Ni _0.1 O _3– _δ material is electrochemically investigated as an air electrode in a symmetrical solid oxide fuel cell, demonstrating good performance, with total polarization resistances of 2.42 and 0.33 Ω cm ^2 at intermediate (650 °C) and conventional (800 °C) operating temperatures, respectively. Finally, we show that the polarization resistance at the intermediate temperature is significantly reduced from 2.42 to 1.63 Ω cm ^2 through the observed formation of nickel-ferrite spinel upon redox cycling.

A homo- and a hetero-dinuclear organometallic complex, [(Cp)Fe(Cp)-CH(Tz)-(Cp)M(Cp)] (M = Fe (3a), Ru (3b); Cp- = cyclopentadienyl, Tz = 1,2,4-triazole), were prepared from carbinol precursors [(Cp)Fe(Cp)-CH(OH)(Cp)M(Cp)] (M = Fe (2a), Ru (2b), and 1,2,4-triazole. Complexes 3a-b were characterized by 1H and 13C NMR spectroscopy, mass spectrometry (MS), and elemental analysis. The X-ray crystal structure of 3a reveals two ferrocenyl units, whereas 3b exhibits two Fe/Ru mixed-occupancy metal sites in a 1:1 ratio, along with disorder in the pendant Cp units in both structures. These findings are consistent with the MS data, which clearly show the [M]+ ion for 3a (Fe/Fe) and 3b (Fe/Ru), but no Fe/Fe or Ru/Ru species for 3b. The antiproliferative activities of 3a and 3b were evaluated against HeLa, MCF-7, and HT-29 cancer cell lines, with IC50 values ranging from 14 to 95 mu M. For comparison, cisplatin exhibited IC50 values between 0.33 and 22 mu M under the same conditions.

A promising way to address environmental problems caused by plastic waste is through its upcycling into renewable energy and resources.With annual production reaching millions of tons,one of the most widely single-use daily plastics,polyethylene terephthalate(PET),has recently been investigated in terms of chemical recycling to reduce its environmental impact and generate renewable fuels.This study intro-duces an innovative electrochemical method for the specific conversion of PET hydrolysate into high-value compounds utilizing CoCuOx@MXene/NF catalyst.Our findings revealed that the electrocatalyst was capable of facilitating the conversion of water into hydrogen(H2),while simultaneously oxidizing ethylene glycol(EG),obtained from PET plastic waste hydrolysis,into formate with a high selectivity and lower initial potential compared to water oxidation.Notably,the exceptional performance was attributed to the synergistic interfacial electronic coupling effect between CoCuOx and MXene,which results in a low overpotential(1.24 V@10 mA cm-2)and a high yield of formate product(87.6％).In addi-tion,the electrolyzer could be operated using solar energy panel for upcycling of PET to formic acid and hydrogen fuels by using CoCuOx@MXene catalyst.

The effect of growth temperature and subsequent annealing on the epitaxy of both single- and few-layer TaSe2 on Se-terminated GaP(111)B substrates is investigated. The selective growth of the 1T and 1H phases is shown up to 1 ML according to X-ray and ultraviolet photoelectron spectroscopies. The 1H monolayer, favored at low temperatures, exhibits a very homogeneous coverage after annealing, while the 1T ML, grown at high temperatures, is characterized by a better in-plane orientation. Moreover, X-ray photoelectron diffraction spectroscopy performed on 1T submonolayers shows a negligible amount of mirror twins. By contrast, in multilayers, scanning transmission electron microscopy always reveals a mixture of 2Ha and 3R polytypes with very few 1T. In addition, the multilayers become Se-deficient above 500 °C, and a new interfacial phase identified as Ta1+xSe2 or TaP appears. Finally, the optimized multilayers grown between 250 and 500 °C exhibit a similar metallic behavior with a resistivity comparable to the bulk one with valuable outcomes in the formation of electrical contacts for two-dimensional (2D) material-based devices.

Triple-negative breast cancer (TNBC) is a highly aggressive subtype marked by pronounced intra-tumoral heterogeneity and frequent therapeutic resistance. In this study, we report the design, synthesis, and biological evaluation of a novel series of triazolopyrimidine-isatin hybrids against the TNBC cell lines MDA-MB-231 and MDA-MB-468. Among them, 9h emerged as the most promising candidate, exhibiting potent cytotoxic activity against TNBC cell lines. Notably, 9h demonstrated 5.7-fold greater potency than tamoxifen and slightly better efficacy than the reference drug cisplatin against MDA-MB-231 cells. Further, 9h induced a significant reduction in MDA-MB-231 cell viability through caspase-mediated apoptosis. Preliminary ADMET predictions were also carried out to assess pharmacokinetic properties.

Poly(ethylene terephthalate) (PET), a common single-use plastic, significantly contributes to CO2 emissions when discarded or incinerated. In this study, we have employed an innovative approach by combining electrochemical PET hydrolysate oxidation and CO2 reduction reaction (CO2RR) to simultaneously produce formate in a single electrochemical cell. Utilizing simple electrochemical methods, a porous 3D carbon felt (CF) electrode was anodically oxidized to produce activated carbon felt (aCF). The latter was used as a support for the electrochemical deposition of bismuth oxide carbonate (Bi2O2CO3) and nickel cobalt phosphate (NiCoPOx) for CO2RR and anodic PET hydrolysate oxidation, respectively. In situ Raman analysis indicated that MOOH (M = Ni, Co) intermediates acted as active sites for PET hydrolysate oxidation, with the ability to regenerate into lower-valence nickel species post-reaction. Both electrodes exhibited Faradaic efficiencies (FEs) exceeding 90% in their respective half-cell reactions. When implemented in a two-electrolyzer setup, a combined FE of up to 158% for both reactions was recorded at a remarkably low cell voltage of 1.8 V. This research highlights the use of non-noble metals to transform PET plastic waste and CO2 into valuable fuels.

The urgent challenge of climate change drives the need for sustainable and environmentally friendly practices, such as recycling, upcycling, and sustainable chemistry. Despite their importance, these practices are rarely integrated into undergraduate chemistry laboratories. Here, we describe a hands-on approach suitable for a second-semester organic chemistry lab that incorporates waste management principles, guiding students to recognize the value of repurposing chemical waste. The precursors for this experiment are discarded CDs and DVDs, which are readily available in most households. This not only helps reduce waste but also demonstrates how everyday materials can be transformed into high-value chemicals (HVCs). In this lab, students extract a carbonyl group from old CDs and DVDs, using a process called "carbonyl harvesting," to show how waste can be turned into valuable materials. The recycled bisphenol A (BPA) is monitored using thin layer chromatography (TLC) and collected separately, while the N,N'-diphenylethylurea is purified by simple filtration and characterized using 1H, 13C NMR, IR, XRD, and melting point analysis. This approach not only reinforces fundamental organic lab techniques but also provides hands-on training in sustainability lab practices, showing students how to integrate waste management, resource recovery, and sustainability into their experimental work. Its versatility allows it to be integrated into chemical engineering, general chemistry, and biotechnology curricula. It serves as a valuable learning tool by demonstrating sustainable process design, functional group preservation, and selective chemical transformations.

Mixed anion compounds have attracted growing interest in solid-state chemistry as a way to tailor physical properties. In this work, we synthesized new silver niobium and tantalum pyrochlore oxyfluorides by an ion-exchange reaction from Na2M2O5F2 (M = Nb or Ta). Instead of a classical Na+/Ag+ cation exchange, a less conventional dual cation and anion exchange reaction (2 Na+ + F-)/(Ag+ + H2O) takes place. Indeed, chemical and thermal analyses, as well as Rietveld refinement and 19F NMR, reveal the formation of AgTa2O5F·H2O and Na0.4Ag0.8Nb2O5F1.2·0.8H2O leading to a significant band gap narrowing of approximately 0.4 eV, as determined by diffuse reflectance spectroscopy. DFT calculations show that Ag 4d-O 2p states are located at the edge of the valence band and that the presence of fluorine in the coordination sphere of Ag promotes the hybridization and hence contributes to the band gap narrowing.

In this work, we present a new cell design for miniaturized energy storage devices by realizing a hybrid microcapacitor, which uses for the first time a TaN/ Ta2O5 thin film electrode in combination with a MnO2 composite electrode. In this proof of concept study, the electrochemical performance of the dielectric material Ta2O5 was of main interest. Therefore, various tantalum oxide films with different thicknesses from 23 to 80 nm have been tested in combination with a pseudocapacitive oversized MnO2 composite electrode. This was done with two model electrolytes, namely the ionic liquid Emim FSI and the solid-state ionogel Emim FSI: PVdF 80:20. Surface capacitance values up to 1.94 mu F cm-2 in Emim FSI and 2.84 mu F cm-2 in IG Emim TFSI: PVdF 80:20 have been reached at high scan rates (100 mV s-1) with no significant distortion of the voltammograms. When films of 47 and 80 nm thickness of Ta2O5 are used, stable cycling with scan rates of up to 5000 mV s-1 at a cell voltage of 20 V can be achieved even in solid-state ionogel electrolyte. This performance highlights the promising characteristics of these materials and cell concept for miniaturized high power energy storage application and opens the way for further investigations to improve this needed technology.

Photocatalytic performance of titanium dioxide under visible light was optimized by preparing heterophase compounds (containing two or more phases) by hydrolysis method using TiCl4 as a precursor with different concentrations (0.5, 0.7, 1, and 2) to adjust condensation modes of Ti4+. The structural and textural properties of the synthesized TiO2 multiphase were fully characterized by XRD, Raman scattering, FTIR, BET, MEB-EDX, XPS, diffuse UV-vis, and EIS spectroscopy. The increase of TiCl4 amount precursor has a significant effect on the heterophase junctions of TiO2 structure and more especially on textural and structural properties. The best specific surface area (131 m(2)/g) is observed for the sample at high Ti-content (2 in Ti4+). The anatase phase (79%) is detected only for 0.5 in Ti4+ sample. However, both rutile (R) and brookite (B) phases are present in 0.7, 1, and 2 Ti-contents. On the one hand, the band gap of 2.9 eV allows titanium dioxide to be active under visible light. In addition, the presence of rutile/brookite heterophase junction contributes significantly to the improvement of active sites for photocatalytic reaction. The separation efficiency of photogenerated electrons and holes contributes to photocatalytic evolution performance under visible light for hydrogen production. The optimal sample (0.7 content in Ti+4 species) which presents in its structure 52% of rutile and 46% of brookite phases presented the highest photocatalytic activity with a 230 mu mol/h of hydrogen generation, attributed to the heterophase junctions R52/B46, highly pore size 20.60 nm, and relatively small bandgap energy 2.974 eV. This work opens new horizons on the creation and study of a multiphase TiO2 that works under visible light in the fields of renewable energies and various other fields.

To investigate the influence of Ag and the loading of Ni species, Ni-Ag type catalysts were synthesized with varying Ni/Ag ratios (1, 1.5 and 2) using the coprecipitation method. The catalysts were extensively characterized using various techniques such as TG-DSC-SM, XRD, ICP, BET, SEM-EDX and TPR and subsequently tested in the CH4/CO2 reaction without any pretreatment. Regardless of the ratio employed, a phase mixture containing NiO and Ag was observed after calcination under air between 600 °C and 1200 °C. SEM analysis confirmed the presence of a close interface between Ag and NiO. The specific surface area was found to be significantly higher for the catalyst with lower Ni content (R = 1). TPR analysis demonstrated that the inclusion of Ag facilitated the reduction of Ni at lower temperatures. XRD analyses of the spent catalyst confirmed catalyst reduction during the reaction. Among the samples, a catalyst with Ni/Ag = 1 exhibited superior catalytic activity without any pretreatment under a reduction atmosphere, in which case the conversions of methane and CO2 at 650 °C amounted to 38 and 45 mol%, respectively, with H2/CO = 0.7 and 71 mol% of H2. The presence of Ag species enhances the stability of the Ni catalyst and improves catalytic performance in the dry reforming of methane.

Ruddlesden-Popper LaxSr2−xMnO4−δ materials are interesting symmetric solid oxide fuel cell electrodes due to their good redox stability, mixed ionic and electronic conducting behavior and thermal expansion that matches well with common electrolytes. In reducing environments - as at a solid oxide fuel cell anode - the x = 0.5 member, i.e. La0.5Sr1.5MnO4−δ, has a much higher total conductivity than compounds with a different La/Sr ratio, although all those compositions have the same K2NiF4-type I4/mmm structure. The origin for this conductivity difference is not yet known in literature. Now, a combination of in-situ and ex-situ 3D electron diffraction, high-resolution imaging, energy-dispersive X-ray analysis and electron energy-loss spectroscopy uncovered clear differences between x=0.25 and x=0.5 in the pristine structure, as well as in the transformations upon high-temperature reduction. In La0.5Sr1.5MnO4−δ, Ruddlesden-Popper n=2 layer defects and an amorphous surface layer are present, but not in La0.25Sr1.75MnO4−δ. After annealing at 700°C in 5% H2/Ar, La0.25Sr1.75MnO4−δ transforms to a tetragonal 2D incommensurately modulated structure with modulation vectors q1 = 0.2848(1) · (a* +b*) and q2 =0.2848(1) · (a* -b*), whereas La0.5Sr1.5MnO4−δ only partially transforms to an orthorhombic 1D incommensurately modulated structure, with q = 0.318(2) · (a* - b*). Perovskite domains grow at the crystal edge at 700°C in 5% H2 or vacuum, due to the higher La concentration on the surface compared to the bulk, which leads to a different thermodynamic equilibrium. Since it is known that a lower degree of oxygen vacancy ordering and a higher amount of perovskite blocks enhance oxygen mobility, those differences in defect structure and structural transformation upon reduction, might all contribute to the higher conductivity of La0.5Sr1.5MnO4−δ in solid oxide fuel cell anode conditions compared to other La/Sr ratios.

Alternative energy sources require the search for innovative materials with promising functionalities. Systems with unusual chemical properties represent an insufficiently explored domain, concealing unexpected features. Using diffraction and Raman spectroscopy over a wide temperature range, supported by first-principles simulations, a rare phenomenon is unveiled: phase-dependent chemical interactions between binary components in the NaCl-Ga2S3 system. In this unique occurrence, previously intact binary crystalline species transform upon melting into mixed liquid structural isomers, forming bonds with new partners. The chemical combinatorics appears to be fully reversible for stable crystals and liquids. Despite this, rapidly frozen glasses out of thermodynamic equilibrium remain in a metastable isomeric state, offering remarkable properties, particularly a high room-temperature Na+ conductivity, comparable to the best sodium halide superionic conductors and therefore encouraging for sodium solid-state batteries and energy applications. A rigidity paradigm is responsible for the observed phenomenon, as the extremely constrained Ga2S3 crystal lattice does not survive viscous flow, breaking up at a short-range level. The removal of rigidity constraints and dense packing leads to a significant increase in empty space, which is the origin of high sodium diffusivity. Broadly, the rigidity-driven structural isomerism opens up an inspiring path to the discovery of atypical materials.