Search Results (927)

Hydrogel-based optical sensors have emerged as a versatile class of analytical materials that combine soft-matter processability, tunable network chemistry, and compatibility with luminescent, colorimetric, photonic, and hybrid transduction strategies. Progress in the field is driven not by a single sensing mechanism, but by the convergence of key advances in material functionalization, embedded selectivity, operation across diverse sample matrices, mechanical and analytical robustness, and usability beyond the laboratory. Current systems include framework-integrated, nanoparticle-doped, probe-functionalized, photonic-crystal, enzyme-immobilized, and device-coupled hydrogels, reflecting growing architectural diversity and application-oriented engineering. Selectivity has likewise advanced from basic interferent screening to recognition-specific, imprinted, and pattern-discriminative formats suited to complex environmental, food, biological, and wearable settings. Evidence of stability, reusability, and deformation tolerance further suggests that many platforms are moving beyond proof-of-concept demonstrations toward credible real-world operation. At the same time, translational priorities such as portability, smartphone readout, implantable and epidermal formats, and multifunctionality spanning antimicrobial action, adsorption, anti-counterfeiting, and device integration are becoming increasingly prominent. Together, these trends show that hydrogel-based optical sensing is maturing into a materially rich, application-responsive domain. The key challenge ahead is to unify materials design, selectivity control, durability, and deployability in standardized, reproducible, and clinically or environmentally credible sensing platforms. Full article

The presence of residual moisture in tetrahydrofuran (THF) greatly limits its suitability for moisture-sensitive processes, including polymerization, Grignard chemistry, and fine-chemical production, where the allowable water concentration is generally lower than 10 mg/kg. Here, a hierarchical microporous/mesoporous composite adsorbent was prepared via extrusion molding, combining an LTA-type zeolite microporous framework with an amorphous mesoporous matrix. Characterization by XRD, FTIR, SEM, and pore analysis confirmed that the LTA crystal structure was retained while mesopores provided channels for mass transport. Static dehydration tests showed that the composite reduced THF water content from 70 mg/kg to 8.3 mg/kg, compared to 23.4 mg/kg for commercial 3A molecular sieves. The enhanced performance arises from micropores supplying uniform adsorption sites for deep dehydration and mesopores accelerating diffusion. Water vapor adsorption, kinetic and isotherm analyzes, regeneration, and competitive adsorption experiments indicated improved water accessibility and high selectivity, with kinetics described by a double-exponential model. The adsorbent remained stable over six adsorption–regeneration cycles. These results demonstrate that hierarchical microporous/mesoporous structures effectively achieve deep THF dehydration. Full article

Azolium-derived metallates are well-established intermediates in metal–N-heterocyclic carbene chemistry; however, their potential as standalone therapeutic agents remains largely unexplored. Herein, we report the first systematic biological investigation of a diverse family of Au(I), Cu(I), Pt(II), Pd(II), and Ru(II) metallates paired with functionalized azolium cations. The complexes were synthesized quantitatively through a simple, atom-economical, and purification-free protocol under aerobic conditions in technical-grade green solvents. Structural characterization by multinuclear NMR spectroscopy and single-crystal X-ray diffraction confirmed metallate formation and enabled the first isolation and crystallographic characterization of unprecedented azolium-derived ruthenates. The antiproliferative activity of the complexes was evaluated against cisplatin-sensitive (A2780) and cisplatin-resistant (A2780cis) ovarian cancer cell lines, alongside non-cancerous MRC-5 fibroblasts. Backbone-functionalized derivatives emerged as the most potent compounds, displaying activities comparable or superior to cisplatin in A2780 cells and up to 1000-fold higher potency in the resistant A2780cis model. Notably, unlike cisplatin, the metallates retained nearly unchanged IC₅₀ values across both ovarian cancer lines, strongly suggesting resistance-evasive mechanisms of action. While benzylazido- and methyl guanosine-derived complexes generally exhibited lower overall potency, several members retained significant activity in resistant cells while showing markedly reduced toxicity toward normal fibroblasts, highlighting promising selectivity profiles. Ethoxide-functionalized derivatives and platinum-based metallates combined pronounced anticancer activity with favourable therapeutic windows. Overall, this work establishes azolium-derived metallates as a previously overlooked class of metal-based anticancer agents combining exceptional synthetic accessibility, broad structural tunability, and remarkable activity against platinum-resistant ovarian cancer. Full article

The Al-bearing scorodite from the Hemerdon Ball Mine (HBM) was studied using electron microscopy and microprobe analysis, single-crystal X-ray diffraction, infrared, and Raman spectroscopy. The crystal chemistry formula of Al-bearing scorodite is expressed as Fe³⁺_0.87Al³⁺_0.16(As_0.97O₄)·H₂O. The calculated d-spacings and unit-cell parameters of Al-bearing scorodite are slightly affected by the substitution of Al for Fe in the octahedral sites. The Al-bearing scorodite HBM crystalizes in the Pbca space group with the following unit-cell lattice parameters: a = 8.92882(14) Å; b = 10.02217(14) Å; c = 10.30525(15) Å; V(Å) = 922.18(2) and Z = 8. The lattice structure becomes slightly distorted by the formation of the Fe,Al-OH octahedron, which leads to a compression of the newly formed octahedron along the a* ^ b* direction and an expansion of the Fe-OH octahedron along the c* direction. The incorporation of Al³⁺ has a strong effect on the tilting angle of the Fe,Al-OH octahedron in the b* ^ c* crystallographic direction. The refined structure suggests that Al³⁺ occupies the octahedral sites alongside Fe³⁺, leading to a distortion of the Fe,Al-OH octahedron. Infrared and Raman spectroscopy exhibit a doublet at 820 and 800 cm⁻¹, and at 810 and 800 cm⁻¹ ascribed to the Fe,Al-O-OAsO₃ group. The 799–800 cm⁻¹ Raman region is assigned to the Fe–O–As group (at 798 and 803 cm⁻¹), whereas the 810–814 cm⁻¹ region is ascribed to a band resulting from the AsO₄³⁻ [υ₁ (A₁) symmetric stretching vibrational modes], indicative of the Fe,Al–OH–As group in both Al-bearing scorodite and mansfieldite. Full article

Synthesis of bifunctional cytisine–squaramide derivatives bearing a single amino acid moiety has revealed an unexpected and intriguing chemical challenge. During modification of cytisine squaramates with α-amino acids, base-sensitive amido esters readily underwent hydrolysis, forming poorly soluble amido-acid side products that resisted standard purification and initially obscured their identity. Persistent observation of these elusive precipitates prompted a deliberate co-crystallization approach, which unambiguously revealed their supramolecular nature using single-crystal X-ray diffraction. With this insight, optimized purification strategies allowed isolation of analytically pure Cyt-SQ-OH and its derivatives, which were characterized by complementary spectroscopic techniques, X-ray crystallography and computational studies. Furthermore, the DFT-optimized parameters of all compounds were determined, providing additional insight into their structural and electronic properties. This work highlights the interplay between reactivity, solubility, and supramolecular assembly in cytisine–squaramide-amino acid hybrids, providing a robust platform for future exploration of multifunctional conjugates with potential applications in medicinal chemistry, molecular recognition, and materials science. Full article

Perovskite-type oxides are among the most promising cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs) due to their mixed ionic–electronic conductivity and compositional flexibility. Many high-performance cathodes rely on Sr substitution at the A-site, often associated with surface segregation and long-term degradation. In this work, we explore an alternative strategy based on defect engineering and phase interactions in Sr-free composites. Perovskite-fluorite composites based on LaFe_0.8Co_0.2O₃ were synthesized through a one-pot route designed to promote the formation of a perovskite phase and a limited amount of fluorite-type ceria. This approach allows the introduction of small fractions of Ce into the perovskite lattice, favoring the cooperative coexistence with La-doped CeO₂. Structural, microstructural and spectroscopic characterization indicates that Ce influences the crystallization pathway and composite defect chemistry. Variations in lattice parameters and Raman features suggest modifications of perovskite structure consistent with defect formation and lattice distortion. Reduction properties and electrical conductivity measurements indicate that Ce incorporation in the perovskite and oxide interaction affect charge transport and oxygen mobility. The electrochemical results demonstrate that the optimal trade-off between activation energy (Ea) and polarization resistance (Rp) is achieved for the sample, with a nominal cerium content, Ce/(La + Ce) of 0.16. Moreover, the electrochemical properties are found to correlate with the nominal cerium content, which regulates defect chemistry and the resulting composite composition. Overall, results suggest that the one-pot synthesis promotes beneficial interactions between the perovskite and ceria phases, allowing the development of Sr-free ferrite-based materials with enhanced functional properties, minimizing the amount of ceria in the composite. Full article

Fluoroalkyl-substituted organoboron compounds are valuable building blocks for organic synthesis and for the development of functional molecules in medicinal chemistry, agrochemicals, and materials science. Building on our previous work on difluoromethyl-substituted borates, we report the synthesis and structural characterization of trifluoromethylated borates, 2-aryl-4,4,5,5-tetramethyl-2-(trifluoromethyl)-1,3,2-dioxaborolan-2-uide salts ([pinB(Aryl)CF₃]⁻). Treatment of pinB–Aryl boronates (pinB = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane) with trimethyl(trifluoromethyl)silane (Ruppert–Prakash reagent) in the presence of potassium tert-butoxide and 18-crown-6 ether (18-C-6) afforded the corresponding trifluoromethylated borates as isolable crystalline compounds. Compared with the related difluoromethylated borates, the CF₃ substituent increases the tendency of [pinB(Aryl)CF₃]⁻ to exhibit hygroscopic behavior, as supported by a hydrated crystal structure and the formation of a hygroscopic product. The isolable trifluoromethylborates can serve as reservoirs of electrophilic trifluoromethyl radicals upon oxidation. Full article

Shape memory polymers (SMPs) can undergo reversible shape transformations, yet most conventional one-way SMPs recover only a single programmed shape. Reported bidirectional SMPs frequently rely on complex chemistries or continuous external loads or tolerate pronounced losses in mechanical robustness, largely because microphase separation, crystallization and internal stress are difficult to regulate in an integrated fashion. Here, we propose a UV-programmed internal-stress-locking strategy to construct a crosslinked polyurethane (UV-SMPU) that simultaneously achieves high toughness and stable, stress-free bidirectional actuation. Using polycaprolactone (PCL) as the soft segment, hexamethylene diisocyanate (HDI) as the hard segment and triallyl isocyanurate (TAIC) as a photocrosslinker, in-situ UV curing under pre-stretch fixes a tunable three-dimensional network while “freezing” the microphase-separated morphology and pre-oriented internal stress. Covalent crosslinks stabilize PCL crystallites as reversible actuation domains, whereas hydrogen-bonded hard segments provide elastic restoring force; the coordinated regulation of crosslink density, crystallinity and locked-in internal stress enables efficient CIE/MIC-type transitions without compromising mechanical integrity. The optimized UV-SMPU (3 wt% TAIC, 10 min UV) exhibits excellent thermal stability, a rare strength–ductility balance (26.6 MPa tensile strength; ~1700% elongation) and robust bidirectional actuation, with reversible strain stabilizing at 15.73% after six cycles. This work offers a simple, scalable route to tough bidirectional SMPUs and furnishes mechanistic design principles for next-generation adaptive and soft-actuated materials. Full article

Ultra-high-temperature ceramics (UHTCs), including transition-metal carbides, nitrides, and diborides, have emerged as a class of promising structural materials for applications in extreme aerospace and energy environments. Their strong covalent–metallic bonding endows them with exceptionally high melting points, elastic moduli, and thermal stability. Nevertheless, intrinsic brittleness, limited oxidation resistance, and poor sinterability remain key challenges for the engineering application of conventional UHTCs. Recently, novel material design strategies such as multiphase composites, microstructural engineering, and compositional complexity have emerged. Among these, high-entropy UHTCs (HE-UHTCs) have attracted significant attention due to their configurational entropy, lattice distortion, and sluggish diffusion effects, which collectively enhance oxidation resistance, thermal stability, sinterability, and mechanical performance. This review summarizes the crystal chemistry, mechanical behavior, oxidation, and ablation properties of conventional UHTCs and HE-UHTCs. The four core effects of HE-UHTCs—configurational entropy, lattice distortion, sluggish diffusion, and cocktail effects—are discussed in relation to their mechanical properties and oxidation resistance. The roles of computational materials science, including density functional theory (DFT), molecular dynamics (MD), and machine learning, in composition screening and property prediction are critically reviewed. Finally, key challenges and future directions for the rational design and engineering application of UHTCs are discussed. Full article

Celestine (SrSO₄) is the principal ore of Sr and a sensitive tracer of diagenetic fluid–rock interaction in carbonate–evaporite successions. This study presents integrated petrographic mineral chemistry and Sr–S isotopic data for epigenetic celestine hosted by Asmari carbonates at Jabal Hafit, Al Ain (UAE), to constrain fluid source, and mechanisms of SrSO₄ precipitation during basin diagenesis. Field and SEM observations show celestine as stratabound, vug- and fracture-filling euhedral to subhedral crystals within dolomitised limestone, suggesting precipitation after initial lithification during early-to-mid burial diagenesis. Electron microprobe analyses show nearly stoichiometric SrSO₄ (55.15–57.30 wt.% SrO; 42.43–44.35 wt.% SO₃) with very low Ba and Ca. The characteristically high Sr/Ba signature of the celestine reflects a complex diagenetic history driven by efficient Sr remobilisation during carbonate recrystallisation within an inherently Ba-poor marine sequence. Measured ⁸⁷Sr/⁸⁶Sr ratios are tightly clustered (0.707841–0.707854) with a high degree of isotopic homogeneity, which indicates a stable, well-buffered fluid reservoir, while the absolute values align with an Oligocene marine signature. Sulphur isotope values (δ³⁴S = +27.3 to +29.1‰) are enriched relative to coeval marine sulphate, which could be attributed to closed-system Rayleigh fractionation driven by bacterial sulphate reduction. We propose that celestine precipitated from stable, marine-buffered burial brines, where supersaturation was achieved through coupled Sr enrichment from carbonate diagenesis and microbial modification of the sulphate reservoir. Full article

Background: A lean crystal engineering study was performed on the early pre-clinical POLθ inhibitor MSC178 to enable sufficient exposure for high-dose PK studies. Methods: COSMOquick-derived excess enthalpies in combination with a toxicological assessment of co-formers were used for the selection of four co-formers. Experimental crystallization trials were performed in a staged approach from a 15 mg scale, over a 50 mg upscale, to a final g-scale upscale of the most promising co-crystal form with 2,4-DHBA. Results: The 2,4-DHBA co-crystal form revealed more enhanced and sustained supersaturation plateaus in FaSSIF compared to the amorphous free base form, the 3,4-DHBA co-crystal form, and the 1,2-EDSA salt form. Moreover, the 2,4-DHBA co-crystal form was shown to be physically stable in the suspension vehicle for the PK study. The high physical stability toward physical-form conversion in the suspension vehicle as well as the more sustained supersaturation plateau in the non-sink dissolution profile could be attributed to the intrinsic features of the crystal structure as well as the assessed surface hydrophilicity of the co-crystal particles, both suggesting that rather hydrophobic surfaces are present that help preferentially attract stabilizing surfactants from the dissolution medium (taurocholate) and from the suspension vehicle (polysorbate, methocel), respectively. Successful upscale of the 2,4-DHBA co-crystal form was achieved in the small g-scale, revealing mainly isotropic crystal growth in primary particles as well as a pronounced tendency toward isotropically shaped dendrite-like secondary particles, both favored by a multi-dimensional hydrogen bonding network being present. Excellent agreement was shown for the extent of in vitro supersaturation behavior and in vivo exposure gain in the high-dose PK study for the 2,4-DHBA co-crystal form versus the amorphous free form. Conclusions: The co-crystal strategy can be successfully developed in early pre-clinical industrial research with lean methodologies to optimize sub-optimal phys.-chem. properties of a free base compound to achieve improved and less variable in vivo exposure between animals in high-dose PK studies. Full article

Rare-earth hydroxycarbonates and oxycarbonates are attractive functional materials because their crystal chemistry and optical response can be tailored through controlled cation substitution. In this work, Eu-doped lanthanum hydroxycarbonates with nominal europium contents of 1, 3, and 5 mol% were synthesized by combining co-precipitation and hydrothermal treatment at 140 °C for 24 h and subsequently calcined at 500 °C for 0.5 h to obtain the corresponding oxycarbonates. X-ray diffraction showed that the as-synthesized powders consist of single-phase hexagonal LaCO₃OH, while the calcined products are single-phase La₂O₂CO₃. In both structural families, systematic peak shifts with increasing Eu content indicated the formation of homogeneous substitutional solid solutions. Thermal analysis revealed a clear two-step decomposition pathway for the hydroxycarbonate precursors, with endothermic events at about 530 and 850 °C, consistent with the sequential transformation from hydroxycarbonate to oxycarbonate and, finally, to oxide. UV-Vis absorption measurements highlighted a dopant-dependent shift in the absorption edge in both hydroxycarbonate and oxycarbonate systems. Kubelka–Munk analysis showed that the estimated band-gap energy increases with Eu content, from 4.9 to 5.4 eV for LaCO₃OH-based samples and from 4.7 to 5.1 eV for La₂O₂CO₃-based samples. These results demonstrate that europium incorporation is an effective strategy for tuning the structural evolution and optical properties of lanthanum carbonate-derived materials, thus supporting their potential use in UV-responsive rare-earth-based functional systems. Full article

Rising environmental concerns have intensified interest in waste valorisation and the development of sustainable, bio-based materials through green chemistry approaches. In this study, proteins extracted from waste lentil and chickpea seeds were used to develop protein-based films using a range of carboxylic acids as cross-linkers. The acids facilitated protein unfolding and promoted intermolecular interactions, allowing tunable control over mechanical strength, barrier performance, and water resistance. In addition to their structural role, the inherent bioactivity of selected carboxylic acids imparted added functionality to the resulting materials. Physical characterisation and FTIR secondary structure analysis revealed that the acid-type, plasticiser, and, in some cases, protein fraction composition influenced the final material performance. Liquid monocarboxylic acids produced cohesive and flexible films, with tensile strength ranging from ~1 to 23 MPa, with formic acid yielding the strongest films. Lactic acid and its blends improved flexibility and reduced permeability, achieving water vapour permeability (WVP) of 5.76 ± 0.7 × 10⁻¹² g m m⁻² s⁻¹ Pa⁻¹ and oxygen permeability (OP) of 5.8 ± 0.0 × 10⁻¹³ mL m m⁻² s⁻¹ Pa⁻¹ at low acid loadings. In contrast, solid di- and polycarboxylic acids tended to crystallise at higher concentrations. Citric acid was an exception, exhibiting behaviour distinct from the other solid acids and producing clear, crystal-free films with excellent flexibility, showing elongation at break (EAB) up to ~326%. Preliminary proof-of-concept application testing demonstrated the suitability of selected films for vegetable shelf-life extension for up to 17 days and for gradual lactic acid release, supporting their potential use as biodegradable cosmetic mask/patch platforms. Full article

Quartz crystal microbalance (QCM) technology provides a powerful, label-free platform for monitoring molecular interactions in real time with nanogram sensitivity. Recent advances in compact instrumentation have enhanced analytical performance while reducing energy consumption, aligning with the principles of Green Analytical Chemistry. In parallel, the European Union has recommended the replacement of animal-derived antibodies with non-animal alternatives, creating an urgent need for sustainable affinity receptors. In this study, we present an innovative application of polynorepinephrine (PNE)-based molecularly imprinted polymers (MIPs) with a compact QCM sensing. PNE, a bioinspired polymer formed under mild aqueous conditions, offers strong adhesive properties and biocompatibility, enabling robust immobilization of imprinted receptors on gold-coated quartz disks. The resulting PNE-MIP/QCM platform combines the ultrasensitivity of quartz microbalances with the selectivity of molecular imprinting, delivering a reproducible and environmentally responsible affinity sensor. The sensor showed a limit of detection of 11.2 nM and enabled accurate IgG quantification in diluted human serum samples. As a proof of concept, the system was applied to Human Immunoglobulin G (IgG1) detection, demonstrating its potential for sustainable clinical diagnostics. Full article