Search Results (195)

The replacement of ionizable functional groups that are predominantly charged at physiological pH with neutral bioisosteres is a common strategy in medicinal chemistry; however, its impact on binding affinity is often context-dependent. Here, we investigated a series of amide derivatives of a glycomimetic E-selectin ligand, in which the carboxylate group of the lead compound is substituted with a range of amide and isosteric analogs. Despite the expected loss of the salt-bridge interaction with Arg97, several amides retained or even improved the binding affinity. Co-crystal structures revealed conserved binding poses across the series, with consistent interactions involving the carbonyl oxygen of the amide and the key residues Tyr48 and Arg97. High-level quantum chemical calculations ruled out a direct correlation between carbonyl partial charges and affinity. Instead, a moderate correlation was observed between ligand binding and the out-of-plane pyramidality of the amide nitrogen, suggesting a favorable steric adaptation within the binding site. Molecular dynamics (MD) simulations revealed that high-affinity ligands exhibit enhanced solution-phase pre-organization toward the bioactive conformation, likely reducing the entropic penalty upon binding. Further analysis of protein–ligand complexes using Molecular mechanics/Generalized born surface area (MM-GB/SA) decomposition suggested minor lipophilic contributions from amide substituents. Taken together, this work underscores the importance of geometric and conformational descriptors, beyond classical electrostatics, in driving affinity in glycomimetic ligand design and provides new insights into the nuanced role of amides as carboxylate isosteres in protein–ligand recognition. Full article

The phase-pure cubic pyrochlore of the Bi₂Cr_0.5Co_0.5Nb₂O_9+Δ composition can be successfully synthesized by a modified sol–gel method (Pecini method-PM) and a traditional solid-phase method (SPM). A feature of the solid-phase synthesis method is the formation of bismuth(VI) chromates as intermediate synthesis products, which is confirmed by X-ray spectroscopy data (NEXAFS). During the sol–gel synthesis method, bismuth chromates are not formed due to the formation of the Bi₂₈O₃₂(SO₄)₁₀ salt, which is thermally stable up to 880 °C, preventing the interaction of bismuth(III) and chromium(III) oxides. The temperature of the final pyrochlore calcination during sol–gel synthesis is reduced by 100 °C (950 °C) compared to the solid-phase method. The crystal structure of pyrochlore (sp. gr. Fd-3m, PM, a = 10.49360(5) Å, Z = 4) was refined by the Rietveld method based on X-ray powder diffraction (XRD) data. NEXAFS Cr2p and Co2p spectra of ceramics synthesized at 1050 °C correspond to the charge states of Cr(III), Co(II) and Co(III) ions. The thermal expansion coefficient of the cell was calculated from high-temperature X-ray diffraction measurements in the range of 20–1200 °C. The thermal expansion coefficient (TEC) monotonically increases from 3.92 × 10⁻⁶ °C⁻¹ (20 °C) to 9.89 × 10⁻⁶ °C⁻¹ (1020 °C). Above 1110 °C, TEC decreases due to thermal dissociation of Bi₂Cr_0.5Co_0.5Nb₂O_9+Δ with the formation of CoNb₂O₆, Bi₂O₃. The mixed pyrochlore (PM) exhibits a moderately high permittivity of ∼97, and low dielectric losses of ∼2 × 10⁻³ at 1 MHz and ∼30 °C. The activation energy of conductivity of the high-temperature region is 0.89 eV. The electrical properties of pyrochlore were synthesized by the ceramic (SPM) and Pechini methods (PM) were analyzed. The electrical properties of the samples up to 400 °C were modeled using equivalent electrical circuits Full article

Thermochemical energy storage (TCES) utilizes chemical reactions to store thermal energy, offering a promising solution for efficient energy management. However, a significant challenge in application of TCES materials, particularly with crystal-to-crystal chemical transformations, is the mechanical degradation of reactive particles during repeated cycles connected with the constant re-modeling of crystals due to consecutive hydration–dehydration steps. This degradation leads to increased pressure drops in packed beds due to swelling and fracturing of salt particles, complicating their practical application. To address this issue, this study investigates the effect of a polymeric network as stabilizing element within TCES particles to enhance mechanical stability. Using potassium carbonate hydrate (K₂CO₃·1.5H₂O) as a model thermochemical material and thermoplastic polymers for reinforcement, composite particles were developed to resist disintegration over multiple cycles. The incorporation of polymeric networks from polyamide (PA11), polyetherimide (PEI) and polyvinylidene fluoride (PVDF) resulted in improved mechanical properties at relatively high porosity, which contributes to higher hydration rate. The developed stabilization method is compatible with existing scalable particle production methods like tableting and compacting. Full article

This study investigates the biodeterioration of mosaic surfaces in a semi-confined archaeological environment along the Phlegraean coast (Baiae, Italy), focusing on the interaction between salt efflorescence and phototrophic biofilms. A multi-analytical approach was employed, integrating in situ observations with ex situ analyses, including SEM/EDS, FTIR spectroscopy, and metabarcoding (16S and 18S rRNA), to characterize both abiotic and biotic alteration patterns. Results highlight subtle traces of spatial differentiation: samples from the more exposed sector showed a more consistent colonization by halotolerant and halophilic taxa, particularly among Halobacteria and Rubrobacter, along with abundant sodium, chloride, and sulfate signals suggestive of active salt crystallization. Protected areas exhibit a comparable presence of salts with less diverse halophilic communities that vary along a vertical gradient of light exposure. The integration of chemical and biological data supports a model in which salt stress and biofilm development are co-dependent and synergistic in driving surface degradation. These findings emphasize the need for context-specific conservation strategies that account for the combined action of environmental salinity and microbial communities on historical materials. Full article

This report focuses on the oxalate anion radical (C₂O₄^●−) formed during γ-radiolysis of polycrystalline oxalates: protonated oxalic acid (H₂C₂O₄·2H₂O), caesium oxalate (Cs₂C₂O₄), and potassium oxalate monohydrate (K₂C₂O₄·H₂O). Irradiation at 77 K generates stable radical species, revealed by EPR spectroscopy and supported by DFT calculations. In H₂C₂O₄·2H₂O, the primary axial signal (g_avg = 2.0035) is shown to arise from the structural relaxation of the HC₂O₄∙ radical into the intrinsically stable non-planar (D_2d) conformation, resolving the symmetry conflict with the planar crystal precursor. Numerical deconvolution confirmed the co-existence of this radical with the secondary HCO₂^● species, exhibiting distinct relaxation characteristics. In Cs₂C₂O₄, the broad isotropic signal (g ≈ 2.008) is attributed to the D_2d form. Quantitative analysis proved a sharp, thermodynamically driven structural conversion (D_2d→D_2h) upon annealing above 220 K, where the D₂h conformer (g_avg ≈ 2.011) becomes the dominant species (≈73%). In K₂C₂O₄·H₂O, the C₂O₄^●− radical undergoes rapid decomposition into the CO₂^●− radical (g_avg ≈ 2.0007) due to the kinetic instability of the primary species in that matrix. Our findings underscore the crucial role of computational assistance and quantitative numerical fitting in EPR studies: DFT provided crucial assistance and yielded satisfactory agreement in most cases, while clarifying the structural and kinetic stability governed by the local cationic environment. The stability of the most resistant radical forms persists up to 430 K in the caesium salt. Full article

Indium, widely used in indium–tin oxide (ITO) coatings for liquid crystal displays (LCDs), is a scarce and strategically important metal with increasing demand. Recycling waste LCD panels offers an efficient secondary source to address supply risks and environmental concerns. In this study, a hydrometallurgical flow sheet was developed under mild conditions for indium (In) recovery. Leaching trials with sulphuric acid at varying concentrations, pulp densities, temperatures, and times showed that 5% H₂SO₄ (v/v) with 100 g/L pulp density at 60 °C for 30 min achieved ~98% dissolution of In, while minimizing the co-leaching of Al and Sn. Kinetic analysis indicated a diffusion-controlled mechanism for In dissolution with an activation energy of 21.2 kJ mol⁻¹. The leached liquor was further purified through solvent extraction by 20% Cyanex 921 (v/v), achieving optimum In extraction at pH 2.5 with an organic-to-aqueous phase ratio of 1/3, reaching equilibrium within 15 min. The McCabe–Thiele plot shown indicates the complete In extraction in two stages. FT-IR studies confirmed the In-extractant bonding at optimized conditions. 10% H₂SO₄ (v/v) was used for the stripping of In from the loaded organic, ensuring nearly complete back-transfer of indium with excellent phase separation. The integrated process yielded ~97% In recovery in stripping. The pure salt of Indium could be obtained by evaporation/crystallization of pure indium solution. The developed process has the potential to be transferred for commercial exploitation after scale-up and pilot trial. Full article

Objectives: This study aimed to find salts with similar pharmacological effects designed as cocrystals to improve the aqueous solubility and bioavailability of dihydromyricetin (DMY). Methods: A salt-cocrystal solvate (DMY-CIP·C₂H₆O) of dihydromyricetin and ciprofloxacin hydrochloride (CIP) was successfully prepared via solvent evaporation method, and further characterized using powder X-ray diffraction, thermal analysis, and infrared spectroscopy. The solubility, stability, bioavailability, and in vitro antimicrobial efficacy of the cocrystal were also studied. Results: The cocrystal could increase the solubility of DMY in water and greatly improve the absorption of DMY in vivo (8-fold enhancement in relative bioavailability). In addition, the in vitro antimicrobial efficacy of the cocrystal was comparable to that of CIP, which is a great improvement for DMY. However, due to the formation of cocrystals with salts, the humidity stability of DMY is reduced and it should not be stored in high-humidity environments. Conclusions: These findings demonstrate that cocrystallization with water-soluble salts represents an effective strategy for optimizing the pharmaceutical properties of poorly soluble compounds. Full article

Pazufloxacin is a fluoroquinolone antibiotic synthesized by Toyama Chemical Co., Ltd. (Tokyo, Japan) in the 1990s. Up until now, the X-ray crystal structure of its mesylate salt had not been determined. The dissolution and recrystallization of pazufloxacin mesylate from different solvents afforded the salts pazufloxacinium mesylate (1), pazufloxacinium mesylate dihydrate (2), pazufloxacinium mesylate hydrate (3) and pazufloxacinium mesylate bis(peroxosolvate) (4), which were all crystallographically characterized. Molecular and crystal structures of these compounds, as well as their thermal behavior, were studied. For all compounds, single-crystal X-ray diffraction confirmed that a proton migrates from methanesulfonic acid to the amino group of pazufloxacin to form a salt. Dehydration of two hydrates occurs as a two-step single-crystal-to-powder process, leading to the formation of two metastable polymorphs of the anhydrous salt. In the solid state, the peroxosolvate compound is stable under ambient conditions for several months, thus making this drug–drug solid suitable for topical application. Full article

All-solid-state lithium batteries (ASSLBs) employing Li-rich layered oxide (LLO) cathodes are regarded as promising next-generation energy storage systems owing to their outstanding energy density and intrinsic safety. Polymer-in-salt solid electrolytes (PISSEs) offer advantages such as high room-temperature ionic conductivity, enhanced Li anode interfacial compatibility, and low processing costs; however, their practical deployment is hindered by poor oxidative stability especially under high-voltage conditions. In this study, we report the rational design of a bilayer electrolyte architecture featuring an in situ solidified LiClO₄-doped succinonitrile (LiClO₄–SN) plastic–crystal interlayer between a Li_1.2Mn_0.6Ni_0.2O₂ (LMNO) cathode and a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based PISSE. This PISSE/SN–LiClO₄ configuration exhibits a wide electrochemical stability window up to 4.7 V vs. Li⁺/Li and delivers a high ionic conductivity of 5.68 × 10⁻⁴ S cm⁻¹ at 25 °C. The solidified LiClO₄-SN layer serves as an effective physical barrier, shielding the PVDF-HFP matrix from direct interfacial contact with LMNO and thereby suppressing its oxidative decomposition at elevated potentials. As a result, the bilayer polymer-based cells with the LMNO cathode demonstrate an initial discharge capacity of ∼206 mAh g⁻¹ at 0.05 C and exhibit good cycling stability with 85.7% capacity retention after 100 cycles at 0.5 C under a high cut-off voltage of 4.6 V. This work not only provides a promising strategy to enhance the compatibility of PVDF-HFP-based electrolytes with high-voltage cathodes through the facile in situ solidification of plastic interlayers but also promotes the application of LMNO cathode material in high-energy ASSLBs. Full article

Phenytoin is an anticonvulsant drug that suffers from low aqueous solubility. The formation of phenytoin salts is a strategy employed to address this issue. A phenytoin–piperidine salt (PPD–PNT) was synthesized by solvent-assisted grinding and characterized by infrared (IR) spectroscopy, ¹H and ¹³C Nuclear Magnetic Resonance (NMR), and powder and single crystal X-ray diffraction. The IR and NMR spectra obtained differed from those of the starting compounds, showing shifts in the N-H and C=O group signals, as well as the appearance of NH⁺ signals, indicating proton transfer and salt formation. Powder X-ray diffraction confirmed the formation of a new solid phase corresponding to the salt. Single crystal X-ray diffraction showed the molecular structure of the PPD–PNT salt. Full article

Acrylic resin is a polymer with strong crosslinking density and strength, and it is commonly used as a matrix in water-based coatings. Barium europium phosphate (Ba₃Eu(PO₄)₃) is a novel functional filler that is expected to provide anti-corrosive effects to coatings. In this study, Ba₃Eu(PO₄)₃ was prepared by the high-temperature solid-phase method and applied to acrylic anti-corrosion coatings. The influence of the molar ratio of reactants on Ba₃Eu(PO₄)₃ purity was studied. The anti-corrosion performance of the coating was investigated. It was found that, when BaCO₃:Eu₂O₃:(NH₄)H₂PO₄ = 3:0.5:3 and the reaction was carried out at 950 °C for 1000 min, high-purity Ba₃Eu(PO₄)₃ can be obtained, according to XRD and EDS tests. SEM shows that Ba₃Eu(PO₄)₃ has good crystal morphology and a porous morphology. TEM revealed that its structure was intact. When Ba₃Eu(PO₄)₃ was added to a relative resin content of 5 wt%, the anti-corrosion performance of the coating was the best after 168 h, with the lowest Tafel current density of 9.616 μA/cm² and the largest capacitance arc curvature radius. The salt spray resistance test showed that the corrosion resistance of the 5 wt% Ba₃Eu(PO₄)₃ coating was also the best, which is consistent with the results of the electrochemical test. Ba₃Eu(PO₄)₃ as a pigment and filler can effectively improve the anti-corrosion performance of water-based industrial coatings. Full article

Aminotris(methylene phosphonic acid) (ATMP) and poly(acrylic acid) sodium salt (PAA) have shown favorable results in the treatment of porous building materials against weathering damage, showing promising potential as mixed-in additives during the production of lime-based mortars. This study investigates the impact of these additives on microstructure and mechanical properties. Additives were introduced in various concentrations to assess their influence on CaCO₃ crystallization, porosity, strength, and carbonation behavior. Results revealed significant modifications in the morphology of CaCO₃ precipitates, showing evidence of nanostructured CaCO₃ aggregates and vaterite stabilization, thus indicating a non-classical crystallization pathway through the formation of amorphous CaCO₃ phase(s), facilitated by organic occlusions. These nanostructural changes, resembling biomimetic calcitic precipitates enhanced mechanical performance by enabling plastic deformation and intergranular bridging. Increased porosity and pore connectivity facilitated CO₂ diffusion towards the mortar matrix, contributing to strength development over time. However, high additive concentrations resulted in poor mechanical performance due to the excessive air entrainment capabilities of short-length polymers. Overall, this study demonstrates that the optimized dosages of ATMP and PAA can significantly enhance the durability and mechanical performance of lime-based mortars and suggests a promising alternative for the tailored manufacturing of highly compatible and durable materials for both the restoration of cultural heritage and modern sustainable construction. Full article

Background/Objectives: Increasing the solid-state landscape of an active pharmaceutical ingredient (API) by generating new crystalline forms (e.g., polymorphs, cyclodextrin (CD) inclusion complexes, co-crystals, and salts) can yield products with significantly enhanced biopharmaceutical properties (especially increased water solubility), thereby improving API delivery and extending its lifetime. The aim of this study was the isolation of new solid forms of the poorly water-soluble non-steroidal anti-inflammatory drug fenbufen (FBF), for which relatively few solid phases have been reported to date. Further motivation for the study is the recent finding that it has potential for repurposing to treat acute pancreatitis. Methods: Interventions for generating new solid forms of FBF included (a) polymorph screening with a variety of solvent media, (b) attempts to form solid inclusion complexes with the native cyclodextrins α-, β-, and γ-CD using various preparative methods, and (c) co-crystallization with a series of coformers to produce co-crystals and/or molecular salts. Results: No new polymorphic forms of FBF were identified, but screening with CDs resulted in isolation and characterization of a new solid inclusion complex with γ-CD. However, co-crystallization of FBF with the water-soluble coformer isonicotinamide yielded two new products, namely a 1:1 co-crystal and an unusual multi-component ionic co-crystal, whose aqueous solubility indicated significant enhancement of FBF solubility. Conclusions: Due to its extremely low water solubility, FBF presented challenges during the study aimed at modifying its crystalline form. However, two new supramolecular forms, a co-crystal and an ionic co-crystal, were isolated, the latter phase having potential for further formulation owing to its significantly enhanced solubility. Full article

This study investigates the impact of various nucleating agents on the crystallization behavior, thermal stability, and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HBHHx) with 6 mol% 3-hydroxyhexanoate (3HHx) units. Nucleating agents, including boron nitride (BN), poly(3-hydroxybutyrate) (PHB), talc, ultrafine cellulose (UFC), and an organic potassium salt (LAK), were incorporated to enhance the crystallization performance. Differential scanning calorimetry (DSC) revealed that BN and PHB significantly increased the crystallization temperature and reduced the crystallization time by half, with BN exhibiting the highest nucleation efficiency. Isothermal kinetics modeled using the Avrami and Lauritzen–Hoffman theories confirmed faster crystallization and reduced nucleation barriers in nucleated samples. Polarized optical microscopy (POM) revealed that the nucleating agents altered the spherulite morphology and increased the growth rates. Under fast cooling, only BN induced crystallization, confirming its superior nucleation activity. Thermogravimetric analysis (TGA) indicated minimal changes in thermal stability, while mechanical testing showed a slight reduction in stiffness without compromising the tensile strength. Overall, BN emerged as the most effective nucleating agent for enhancing the P3HBHHx crystallization kinetics, providing a promising strategy for improving processing efficiency and reducing the cycle times in industrial applications. Full article

Unconventional heavy oil reservoirs are particularly susceptible to steam breakthrough, which significantly reduces crude oil production. Profile control is a crucial strategy used for stabilizing oil production and minimizing production costs in these reservoirs. Conventional plugging agent systems used in the thermal recovery of heavy oil currently fail to meet the high-temperature, high-strength, and deep profile control requirements of this process. Precipitation-type calcium salt blocking agents demonstrate long-term stability at 300 °C and concentrations up to 250,000 mg/L, making them highly effective for profile control and channeling blockage during the steam injection stages of heavy oil recovery. This study proposes two types of precipitation-type calcium salt blocking agents: CaSO₄ and CaCO₃ crystals. The precipitation behavior of these agents was investigated, and their dynamic growth patterns were examined. The calcium sulfate blocking agent exhibits a slower crystal precipitation rate, allowing for a single-solution injection, while the calcium carbonate blocking agent precipitates rapidly, requiring a dual-solution injection. Both systems incorporate scale inhibitors to delay the growth of calcium salt crystals, which aids in deep profile control. Through microscopic visualization experiments, the micro-blocking characteristics of the calcium salt blocking agent systems within pores were compared, elucidating the blocking positions of the precipitated calcium salts under porous conditions. Calcium sulfate crystals preferentially precipitate in and block larger pore channels, whereas calcium carbonate crystals are more evenly distributed throughout the pore channels, reducing the reservoir’s heterogeneity. The final single-core displacement experiment demonstrated the sealing properties of the precipitation-type calcium salt blocking agent systems. The developed precipitation-type calcium salt blocking agent systems exhibit excellent profile control performance. Full article