Search Results (946)

Polymorphism critically influences the solid-state properties of organic molecules, affecting stability, solubility, and functionality. We investigated the polymorphic behavior of enantiomerically pure (+)-(6aS,11aS)-medicarpin through combined experimental and computational analyses. Single-crystal X-ray diffraction revealed two distinct chiral polymorphs: the previously reported monoclinic P2₁ form and a newly identified orthorhombic P2₁2₁2₁ form with a fully chiral packing arrangement. The discovery of this previously unreported polymorph underscores the subtle yet decisive effects of solvent and conformational flexibility in directing crystallization. Detailed structural analysis reveals that, whereas the P2₁ form is only stabilized by a single dominant electrostatic interaction, the P2₁2₁2₁ form features a more complex network comprising C-H···π contacts, bifurcated C-H···O hydrogen bonds, and aromatic edge-to-face interactions. Further investigation of a functionalized p-nitrobenzoate derivative corroborates the critical influence of molecular substituents and crystallization conditions on packing motifs. Lattice energy DFT calculations confirm that each polymorph is stabilized by distinct electrostatic and dispersive interaction patterns, illustrating the complex energetic landscape of polymorph selection. Altogether, this work provides a framework for understanding and anticipating which polymorph is likely to form under specific solvent and crystallization conditions, offering insights for future strategies in materials design and guiding the pursuit of patentable crystalline forms in pharmaceutical applications. Full article

Objectives: Invasive aspergillosis (IA) poses significant risks to patients with malignancies or transplantation; however, estimates of burden-of-illness in patients with IA are sparse. We sought to assess in-hospital and outpatient healthcare resource utilization, all-cause treatment costs, and mortality in patients admitted with IA with hematologic or non-hematologic malignancies, bone marrow transplant/hematopoietic cell transplantation (BMT/HCT), or solid organ transplantation (SOT). Methods: This claims study utilized United States IQVIA data. Adults admitted for IA were identified by diagnosis codes during the patient selection period (October 2015–November 2022). IA patients were stratified into cohorts including recent hematologic or non-hematologic malignancies, or a history of BMT/HCT or SOT. We assessed hospital and intensive care unit (ICU) length-of-stay (LOS), all-cause index hospital treatment costs, and inpatient mortality or need for hospice in each cohort, as well as the need for re-admission and total treatment costs for up to six-months after admission, and all-cause mortality at end of study follow-up. Results: Among 1190 patients admitted for IA, 317 had hematologic malignancies, 155 non-hematologic malignancies, 133 BMT/HCT and 173 SOT. Across these cohorts, IA was associated with protracted (median LOS = 12–18 days; ICU LOS = 10–13 days) and costly (median = USD 79,058–USD 172,342) index hospitalizations ending in death or hospice in 28.1% (89/317) to 36.1% (48/133) of patients. Among those surviving to discharge, between 53.1% (34/64) and 63.4% (97/153) were re-admitted within six months. Total median treatment costs at six months ranged from USD 213,378 to USD 397,857. All-cause mortality was 33.6% (52/155) to 40.6% (54/133) at end of study follow-up. Conclusions: Hospitalizations for IA in patients with malignancies or transplantation are long, costly, and end with readmission, hospice, or death in more than one-third of patients. Full article

Proteins that span cellular membranes represent around 30% of the proteome and over 50% of drug targets. A variety of synthetic and naturally-occurring small organic molecules interact with membrane proteins and up- and down-regulate protein function. The atomic details of these regulatory molecules offer important information about protein function and aid the discovery, refinement and optimization of new drugs. X-ray crystallography and cryo-electron microscopy (cryo-EM) are not always able to resolve the structures of small molecules in their physiological sites on membrane proteins, particularly if the molecules are unstable or are reactive enzyme substrates. Solid-state nuclear magnetic resonance (SSNMR) is a valuable technique for filling in missing details on the conformations, dynamics and binding environments of small molecules regulators of membrane proteins. SSNMR does not require diffracting crystals possessing long-range order and can be performed on proteins within their native membranes and with freeze-trapping to maintain sample stability. Here, work over the last two decades is described, in which SSNMR methods have been developed to report on interactions of the ATP substrate with the Na,K-ATPase (NKA), an ion-transporting enzyme that maintains cellular potential in all animals. It is shown how a combination of SSNMR measurements on membranous NKA preparations in the frozen and fluid states have provided unique information about the molecular conformation and local environment of ATP in the high-affinity nucleotide site. A combination of chemical shift analysis using density functional theory (DFT) calculations, dipolar coupling measurements using REDOR and measurements of the rates of proton spin diffusion is appraised collectively. The work described herein highlights the methods developed and challenges encountered, which have led to a detailed and unrivalled picture of ATP in its high-affinity binding site. Full article

All-solid-state lithium batteries (ASSLBs) are emerging as a promising alternative to conventional lithium-ion batteries, offering solutions to challenges related to energy density and safety. Their core advancement relies on breakthroughs in solid-state electrolytes (SEs). SEs can be broadly grouped into two main types: inorganic solid electrolytes (ISEs) and organic solid electrolytes (OSEs). ISEs offer high ionic conductivity (0.1~1 mS cm⁻¹), a lithium-ion transference number close to 1, and excellent thermal stability, but their intrinsic brittleness leads to poor interfacial wettability and processing difficulties, limiting practical applications. In contrast, OSEs exhibit good flexibility and interfacial compatibility but suffer from poor ionic conductivity (10⁻⁴~10⁻² mS cm⁻¹) due to high crystallinity at room temperature, in addition to poor thermal stability and weak mechanical integrity, making it difficult to match high-voltage cathodes and suppress lithium dendrite growth. Against this backdrop, the stability of the organic–inorganic interface plays a crucial role. However, challenges such as low overall conductivity and unstable interfaces still limit their performance. This review provides a microscopic perspective on lithium-ion transport pathways across the polymer phase, the inorganic filler phase, and their interfacial regions. It categorizes inert fillers and active fillers, analyzing their structure–performance relationships and emphasizing the synergistic effects of filler dimensionality, surface chemistry, and interfacial interactions. In addition, cutting-edge analytical methods such as time-of-flight secondary ion mass spectrometry (TOF-SIMS) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) have also been employed and are summarized into their roles for revealing the microstructures and dynamic interfacial behaviors of OICSEs. Finally, future directions are proposed, such as hierarchical pore structure design, surface functionalization, and simulation-guided optimization, aiming to provide theoretical insights and technological strategies for the development of high-performance composite electrolytes for ASSLBs. Full article

This study reports the successful synthesis of pure cobalt-substituted calcium molybdate powders (Co-doped CaMoO₄) through a co-precipitation method conducted at room temperature, without the use of surfactants or hazardous organic solvents. The formation of solid solutions with x values ranging from 0.00 to 0.08 was confirmed by X-ray diffraction, Rietveld refinement, and Raman spectroscopy analyses. Elemental analysis using energy-dispersive X-ray spectroscopy showed a strong correlation between the experimental and nominal stoichiometries. The synthesized molybdate powders consist of micrometer-sized particles exhibiting diverse morphologies, including microspheres, flower-like architectures, and dumbbell-shaped particles. These agglomerates are composed of primary particles smaller than 43 nm. The specific surface area increased from 3.59 m²/g for the undoped CaMoO₄ to 10.74 m²/g for the 6% Co-doped CaMoO₄. These nanostructured powders represent promising host materials for 4f ions, making them potential candidates for solid-state lighting applications. Full article

Mechanochemical methods have received much attention in the synthesis and design of all-solid-state battery materials in recent years due to their advantages of being green, efficient, easy to operate, and solvent-free. In this review, common mechanochemical methods, including high-energy ball milling, twin-screw extrusion (TSE), and resonant acoustic mixing (RAM), are introduced with the aim of providing a fundamental understanding of the subsequent material design. Subsequently, the discussion focuses on the application of mechanochemical methods in the construction of solid-state electrolytes, anode materials, and cathode materials, especially the research progress of mechanical energy-induced polymerization strategies in building flexible composite electrolytes and enhancing interfacial stability. Through the analysis of representative work, it is demonstrated that mechanochemical methods are gradually evolving from traditional physical processing tools to functional synthesis platforms with chemical reaction capabilities. This review systematically organizes its development and research trends in the field of all-solid-state battery materials and explores potential future breakthrough directions. Full article

Two nitrogen-modified mesoporous MCM-41-type silicas were synthesized by the sol–gel route and post-grafting surface modification procedure, obtaining an aminopropyl-modified MCM-41 (denoted MCM-41-N) and an aminoethyl-aminopropyl-modified MCM-41 (denoted MCM-41-NN). Hexavalent chromium removal from acidified water by adsorption and reduction to Cr(III) on the solid mesophases was analyzed. The modified silicas were characterized by powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FT-IR), nitrogen adsorption–desorption measurements at −196 °C, X-ray photoelectron spectroscopy (XPS), ²⁹Si solid state Nuclear Magnetic Resonance (²⁹Si-RMN), and thermogravimetric analysis (TGA). Both samples exhibited very high capacities for decreasing Cr(VI) concentrations in water, according to the Langmuir isotherm model: 129.9 mg·g⁻¹ for MCM-41-N and 133.3 mg·g⁻¹ for MCM-41-NN. The chromium speciation in the supernatant after 24 h indicates that MCM-41-N had a higher capacity to reduce Cr(VI) to the less toxic Cr(III) species than MCM-41-NN: 92.9% vs. 72.5% when the initial Cr(VI) concentration was 10 mg·g⁻¹. These differences were related to the different capacity of nitrogen atoms in MCM-41-N and MCM-41-NN to interact with the surrounding surface silanols which are required for the chemical reduction in the hexavalent species to take place, as evidenced by FT-IR and XPS analysis. Also, the Cr(III)/Cr(VI) atomic ratios on the solid’s surfaces were higher for MCM-41-N. These results highlight the characteristics that nitrogen atoms incorporated into silica matrices must possess in order to maximize the transformation of Cr(VI) into the trivalent species, thereby reducing the generation of toxic waste harmful to living organisms. Full article

Lanthanide hydrogen-bonded organic frameworks (Ln-HOFs) integrating luminescent and proton-conductive properties hold significant promise for multifunctional sensing and energy applications, yet their development remains challenging due to the difficulty of balancing structural stability and functional diversity. In this context, this study successfully synthesized a novel neodymium(III)-based hydrogen-bonded framework material, formulated as {Nd(H₂O)₃(4-CPCA)[H(4-CPCA)]∙H₂O}ₙ (SNUT-15), via hydrothermal assembly using 1-(4-carboxyphenyl)-4-oxo-1,4-dihydropyridazine-3-carboxylic acid (H₂(4-CPCA)) as the ligand. Single-crystal X-ray diffraction analysis revealed a rare two-dimensional hydrogen-bonded bilayer structure stabilized by π-π stacking interactions and intermolecular hydrogen bonds. Hirshfeld surface analysis further corroborated the structural characteristics of this material. Moreover, leveraging the superior luminescent properties of lanthanide elements, this crystalline material exhibits dual functionality: selective fluorescence quenching toward Fe³⁺, La³⁺, and Mn²⁺ (with detection limits of 1.74 × 10⁻⁴, 1.88 × 10⁻⁴, and 3.57 × 10⁻⁴ mol·L⁻¹, respectively), as well as excellent proton conductivity reaching 7.92 × 10⁻³ S cm⁻¹ under conditions of 98% relative humidity and 353 K (80 °C). As a multifunctional neodymium(III)-based HOF material, SNUT-15 demonstrates its potential for applications in environmental monitoring and solid-state electrolytes, providing valuable insights into the rational design of lanthanide-containing frameworks. Full article

The citrus processing industry is an economically important agro-industrial sector worldwide; however, it produces significant amounts of waste annually. The biorefinery concept and the recovery of bio-based materials from agro-industrial residues, including citrus processing waste, are emphasized in the European Green Deal, reflecting the EU’s commitment to fostering circularity. Biotreatment of citrus processing waste, including bioconversion into biomethane, biohydrogen, bioethanol and biodiesel, has been applied to valorize biomass for energy recovery. It can also be composted into a valuable soil conditioners and fertilizers, while raw and fermented citrus residues may exhibit phytoprotective activity. Citrus-derived residues can be converted into materials such as nanoparticles with adsorptive capacity for heavy metals and recalcitrant organic pollutants, and materials with antimicrobial properties against various microbial pathogens, or the potential to remove antibiotic-resistance genes (ARGs) from wastewater. Indeed, citrus residues are an ideal source of industrial biomolecules, like pectin, and the recovery of bioactive compounds with added value in food processing industry. Citrus processing waste can also serve as a source for isolating specialized microbial starter cultures or as a substrate for the growth of bioplastic-producing microorganisms. Solid-state fermentation of citrus residues can enhance the production of hydrolytic enzymes, with applications in food and environmental technology, as well as in animal feed. Certain fermented products also exhibit antioxidant properties. Citrus processing waste may be used as alternative feedstuff that potentially improves the oxidative stability and quality of animal products. Full article

This study aims to evaluate eco-innovative solutions in the fertilizer industry that allow for waste valorization in the context of a resource-efficient circular economy. A comprehensive reuse strategy was developed for low-rank peat and post-cultivation horticultural mineral wool, involving the extraction of valuable humic substances from peat and residual nutrients from used mineral wool, followed by the use of both post-extraction residues to produce organic–mineral substrates. The resulting products/semifinished products were characterized in terms of their composition and properties, which met the requirements necessary to obtain the admission of this type of product to the market in accordance with the Regulation of the Minister for Agriculture and Rural Development of 18 June 2008 on the implementation of certain provisions of the Act on fertilizers and fertilization (Journal of Laws No 119, item 765). Elemental analysis, FTIR spectroscopy, and solid-state CP-MAS ¹³C NMR spectroscopy suggest that post-extraction peat has a relatively condensed structure with a high C content (47.4%) and a reduced O/C atomic ratio and is rich in alkyl-like matter (63.2%) but devoid of some functional groups in favor of extracted fulvic acids. Therefore, it remains a valuable organic biowaste, which, in combination with post-extraction waste mineral wool in a ratio of 60:40 and possibly the addition of mineral nutrients, allows us to obtain a completely new substrate with a bulk density of 264 g/m³, a salinity of 7.8 g/dm³ and a pH of 5.3, with an appropriate content of heavy metals and with no impurities, meeting the requirements of this type of product. A liquid fertilizer based on an extract containing previously recovered nutrients also meets the criteria in terms of quality and content of impurities and can potentially be used as a fertilizing product suitable for agricultural crops. This study demonstrates a feasible pathway for transforming specific waste streams into valuable agricultural inputs, contributing to environmental protection and sustainable production. The production of a new liquid fertilizer using nutrients recovered from post-cultivation mineral wool and the preparation of an organic–mineral substrate using post-extraction solid residue is a rational strategy for recycling hard-to-biodegrade end-of-life products. Full article

Mushrooms are eukaryotic organisms with absorptive heterotrophic nutrition, capable of feeding on organic matter rich in cellulose and lignocellulose. Since ancient times, they have been considered allies and, in certain cultures, they were seen as magical beings or food of the gods. Of the great variety of edible mushrooms identified worldwide, less than 2% are traded on the market. Although mushrooms have been valued for their multiple nutritional and healing benefits, some cultures perceive them as toxic and do not accept them in their culinary practices. Despite the existing skepticism, several researchers are promoting the potential of edible mushrooms. There are two main methods of mushroom cultivation: solid-state fermentation and submerged fermentation. The former is the most widely used and simplest, since the fungus grows in its natural environment; in the latter, the fungus grows suspended without developing a fruiting body. In addition, submerged fermentation is easily monitored and scalable. Both systems are important and have their limitations. This article discusses the main methods used to increase the performance of submerged fermentation with emphasis on the modes of operation used, types of bioreactors and application of morphological bioengineering of filamentous fungi, and especially the use of intelligent automatic control technologies and the use of non-invasive monitoring in fermentation systems thanks to the development of machine learning (ML), neural networks, and the use of big data, which will allow more accurate decisions to be made in the fermentation of filamentous fungi in submerged environments with improvements in production yields. Full article

Alperujo, a solid by-product from the two-phase olive oil extraction process, poses significant environmental challenges due to its high organic load, phytotoxicity, and phenolic content. At the same time, it represents a promising feedstock for recovering value-added compounds such as phenols and volatile fatty acids (VFAs). When used as a substrate for white rot fungi (WRF), it also produces ligninolytic enzymes. This study explores the use of two native WRF, Anthracophyllum discolor and Stereum hirsutum, for the biotransformation of alperujo under solid-state fermentation conditions, with and without supplementation of copper and manganese, two cofactors known to enhance fungal enzymatic activity. S. hirsutum stood out for its ability to release high concentrations of phenolic compounds (up to 6001 ± 236 mg gallic acid eq L⁻¹) and VFAs (up to 1627 ± 325 mg L⁻¹) into the aqueous extract, particularly with metal supplementation. In contrast, A. discolor was more effective in degrading phenolic compounds within the solid matrix, achieving a 41% reduction over a 30-day period. However, its ability to accumulate phenolics and VFAs in the extract was limited. Both WRF exhibited increased enzymatic activities (particularly Laccase and Manganese Peroxidase) with the addition of Cu-Mn, highlighting the potential of the aqueous extract as a natural source of biocatalysts. Phytotoxicity assays using Solanum lycopersicum seeds confirmed a partial detoxification of the treated alperujo. However, none of the fungi could entirely eliminate inhibitory effects on their own, suggesting the need for complementary stabilization steps before agricultural reuse. Overall, the results indicate that S. hirsutum, especially when combined with metal supplementation, is better suited for valorizing alperujo through the recovery of bioactive compounds. Meanwhile, A. discolor may be more suitable for detoxifying the solid phase strategies. These findings support the integration of fungal pretreatment into biorefinery schemes that valorize agroindustrial residues while mitigating environmental issues. Full article

A nanoparticle formulation was generated from distiller dried grains with solubles (DDGS), and its effect on the production of anthraquinones (AQs) was evaluated on Rubia tinctorum hairy roots. The DDGS material was washed with water and ethyl acetate to remove mainly the soluble organic/inorganic molecules and reduce the fat content, respectively, followed by an alkaline treatment to remove the polysaccharides. The resulting alkaline solutions were then lyophilized and redispersed in deionized water to generate a monodispersed nanoparticulate formulation (DDGS-NP) with a hydrodynamic diameter and zeta potential of 227 ± 42 nm and −53 ± 7 mV, respectively. The formulation demonstrated good colloidal stability over time, and sterilized DDGS-NPs maintained comparable physicochemical properties. The nanoparticles were enriched in protein fractions, unsaturated fatty acids, and orthophosphate anion components from DDGS, as determined by solid-state Nuclear Magnetic Resonance (NMR), X-ray photoelectron spectroscopy (XPS), organic elemental analysis (OEA), and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The DDGS-NPs were tested at different concentrations on Rubia tinctorum hairy roots, in comparison to or in combination with methyl jasmonate (MeJ), for their capacity to induce the production of AQs. All DDGS-NP concentrations increased the production of specific AQs to 7.7 (100 mg L⁻¹), 7.8 (200 mg L⁻¹), and 9.3 µmol/gFW (500 mg L⁻¹), with an extracellular AQ accumulation of 18 µM for the highest DDGS-NP concentration, in comparison with the control hairy roots (~2 µM AQ). The plant growth was not affected at any of the tested nanoparticle concentrations. Interestingly, the combination of DDGS-NPs and MeJ resulted in the highest extracellular AQ accumulation in R. tinctorum root cultures. Full article

The natural sunlight driven photocatalytic degradation of organic pollutants is a sustainable solution for water purification. The use of heterojunction nanocomposites in this process shows promise for improved photodegradation efficiency. In this work, nanocrystalline Zn₂SnO₄/SnO₂ obtained by the solid-state synthesis method was tested as a heterojunction photocatalyst material for the degradation of methylene blue (MB) and Rhodamine B (RhB) dyes as single and multicomponent systems in natural sunlight. Characterization of the structure and morphology of the synthesized nanocomposite using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDS), and photoluminescence (PL) spectroscopy confirmed the formation of Zn₂SnO₄/SnO₂ and heterojunctions between Zn₂SnO₄ and the SnO₂ nanoparticles. A photodegradation efficiency of 99.1% was achieved in 120 min with 50 mg of the photocatalyst for the degradation of MB and 70.6% for the degradation of RhB under the same conditions. In the multicomponent system, the degradation efficiency of 97.9% for MB and 53.2% for RhB was obtained with only 15 mg of the photocatalyst. The degradation of MB occurred through N-demethylation and the formation of azure intermediates and degradation of RhB occurred through sequential deethylation and fragmentation of the xanthene ring, both in single and multicomponent systems. Full article

Four novel crystalline architectures based on benzo[c]cinnolininium trifluoromethanesulonate salts, [C₁₂H₉N₂]⁺[CF₃SO₃]⁻, have been isolated as single-crystals, and their structures have been determined by X-ray diffraction analysis. The formation of the new salts results from reactions involving the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu₂Sn(OH)(H₂O)(CF₃SO₃)]₂ (1) and benzo[c]cinnoline (C₁₂H₈N₂, BCC). Organic salts I, II, III, and IV were crystallized through slow evaporation at room temperature from a mixture of toluene/dichloromethane. The cystallographic structures of I, II, and IV exhibit the presence of monoprotonated benzo[c]cinnolinium cations in interactions with a free benzo[c]cinnoline molecule through N–H···N hydrogen bonding, while for salt III, the monoprotonated cation directly interacts with the CF₃SO₃⁻ anion via an N–H···O interaction. For all four salts, aromatic π-π interactions involving rings of various components (free benzo[c]cinnoline molecule, benzo[c]cinnolinium cation, toluene molecule), combined with weak C–H···O and C–H···F interactions implying the trifluoromethanesulfonate anion, promote the solid-state self-assembly of supramolecular stacks. In parallel to the formation of benzo[c]cinnolinium based-salts, organotin(IV) 1 was converted into a distannoxane compound, ²_∞{[n-Bu₂(μ-OH)SnOSn(μ-η²-O₃SCF₃)n-Bu₂]₂[n-Bu₂(η¹-O₃SCF₃)SnOSn(μ-OH)n-Bu₂]₂} (3), which was also isolated as a single crystal and whose crystallographic structure was previously established by us. Full article