Search Results (2,561)

Background: Fresh frozen tissues are considered the gold standard for proteomic analyses due to their superior preservation of protein integrity; however, their use is limited by the logistical and financial requirements of long-term cold storage. Formaldehyde-fixed paraffin-embedded (FFPE) tissues provide a practical alternative, owing to their stability and widespread availability in clinical settings. A critical step in FFPE proteomics is deparaffinization, which traditionally relies on organic solvents such as xylene, along with the efficient reversal of formaldehyde-induced crosslinks. Methods: In this study, we evaluated multiple FFPE protein extraction and digestion workflows including chaotropic, surfactant-based, and detergent-free approaches in combination with xylene-free deparaffinization strategies, using label-free data-independent acquisition (DIA) LC-MS/MS. Results: Among the tested methods, a chaotropic, reductant, and surfactant-free in-solution digestion workflow demonstrated robust protein and peptide recovery. A modified version of this protocol further improved peptide coverage while maintaining comparable protein depth. The applicability of the optimized workflow was assessed using FFPE needle biopsy samples from control, hepatic steatosis, and liver fibrosis groups. Exploratory proteomic patterns were observed across conditions, with hepatic steatosis associated with early activation of stress-response pathways, while fibrosis showed evidence suggesting altered lipid metabolism. Conclusions: Overall, this study presents a simple, xylene-free, and MS-compatible workflow for FFPE proteomics that is suitable for low-input clinical samples and may support broader application of archival tissues in proteomic research. Full article

Quinoline derivatives constitute a privileged class of nitrogen-containing heterocycles with extensive applications in medicinal chemistry, agrochemicals, materials science, and functional organic materials. Owing to their broad biological and industrial relevance, the development of efficient, selective, and sustainable synthetic methodologies for quinoline construction remains an active area of research. This review provides a comprehensive overview of recent advances in quinoline synthesis, with particular emphasis on catalytic strategies aligned with the principles of green and sustainable chemistry. Classical transformations, including the Friedländer, Skraup, and Povarov reactions, are revisited in the context of modern catalytic developments that improve reaction efficiency, substrate scope, selectivity, and environmental compatibility. Special attention is devoted to homogeneous and heterogeneous catalytic systems based on both platinum-group and earth-abundant transition metals, highlighting the growing importance of borrowing-hydrogen and acceptorless dehydrogenative coupling methodologies. Recent progress in nanocatalysis, photocatalysis, multicomponent reactions, ionic-liquid-mediated transformations, and metal-free protocols is also critically discussed. Furthermore, solvent-free processes, microwave-assisted synthesis, and recyclable catalytic systems are examined as practical approaches toward minimizing waste generation and energy consumption. Mechanistic aspects, catalytic design principles, substrate limitations, and sustainability metrics are evaluated throughout the review to provide a critical perspective on current methodologies. Collectively, the advances summarized herein demonstrate the rapid evolution of quinoline synthesis toward more atom-economical, environmentally benign, and operationally efficient processes, while also identifying future opportunities for the development of next-generation catalytic platforms for quinoline-based heterocycle construction. Full article

Pyrrolidinyl-substituted silacyclopentane (CH₂)₄Si(Pyr)₂ and α-amino isobutyric acid (H₂Aib) react with the release of one equivalent pyrrolidine (HPyr) and the formation of the pentacoordinate silicon bis-chelate (Aib)Si(CH₂)₄(HPyr), which features the di-anion of the amino acid as an (O,N)-chelator and one equivalent of pyrrolidine as an additional lone-pair donor. Crystallographic analyses of the chloroform solvate (Aib)Si(CH₂)₄(HPyr)·(CHCl₃), which undergoes a phase transition at 200 K, and a solvent-free modification (Aib)Si(CH₂)₄(HPyr), which features two crystallographically independent molecules of the complex, revealed that the N atom of the HPyr ligand, as well as the carboxylate of Aib, occupy the axial positions in the trigonal bipyramidal Si coordination sphere; the Si–C bonds of the silacyclopentane rest on equatorial sites. For the isolated molecule in a solvent environment, computational analyses revealed that the energy difference between this configuration and the related isomer with an equatorial HPyr and equatorial–axial positioning of the silacyclopentane motif is marginal. In DMSO solution, the adduct (Aib)Si(CH₂)₄(HPyr) decomposed, forming the hexacoordinate Si complex (HAib)₂Si(CH₂)₄ as one of the decomposition products. In a deliberate manner, this compound was accessible from the diethylamino-substituted silacyclopentane (CH₂)₄Si(NEt₂)₂ and H₂Aib with the liberation of diethylamine. (HAib)₂Si(CH₂)₄ features two mono-anions of the α-amino acid as (O,N)-chelators, their carboxylate O atoms are trans-disposed to silacyclopentane, and their NH₂ groups are mutually trans. Full article

Background/Objectives: Lipid-based nanocarriers have emerged as promising systems for improving the delivery of poorly soluble drugs by enhancing stability, bioavailability, and controlled release. This work aimed to formulate solid lipid nanoparticles (SLN) and nanostructured lipid carriers (NLC) containing ciprofloxacin (CIP) using solvent-free procedures. Methods: The systems were extensively characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), and atomic force microscopy (AFM) to study the nanoparticles in the solid state. Furthermore, in vitro drug release was evaluated, and mathematical modeling was applied to analyze the resulting release kinetics. Additionally, storage stability was assessed at 4 °C and 25 °C over a period of 8 months. Results: The results indicated that SLN with an average size of ~50 nm (SLN 50) and NLC with mean diameters of ~25, 50, and 100 nm (NLC 25, NLC 50 and NLC 100 respectively) were successfully prepared. DLS measurements showed narrow particle size distributions (PdI ≤ 0.2) and negative zeta potentials ranging from −3.7 to −7.7 mV. Encapsulation efficiencies were remarkably high for most systems, reaching ~98% for SLN 50, NLC 50, and NLC 100, while the smallest formulation (NLC 25) showed a lower efficiency (~80%). Both TEM and AFM confirmed the formation of spherical nanoscale structures consistent with the sizes determined by DLS. Release studies revealed a strong influence of particle size on kinetics: NLC 25 exhibited rapid release (~95% within 30 min), whereas NLC 100 showed a sustained profile (<20% after 6 h). Dissolution profiles were accurately described by the Lumped-Gonzo kinetic model (R² > 0.98), enabling estimation of dissolution efficiency. Conclusions: These findings confirm that lipid-based nanocarriers can be engineered to precisely control CIP release. Full article

A comparative density functional theory (DFT) study was performed to elucidate the mechanistic details of Schiff base formation between 3-pyridinecarboxaldehyde and the three positional isomers of aminobenzoic acid (o-, m-, and p-). Both single proton transfer (SPT) and methanol-assisted double proton transfer (DPT) pathways were systematically investigated in the gas phase and within a polarizable continuum model (PCM) for methanol. All stationary points were optimized at the B3LYP/6-31G and 6-311++G(d,p) levels, and transition states were confirmed by vibrational frequency and intrinsic reaction coordinate (IRC) analyses. The results reveal that the DPT mechanism is consistently associated with significantly lower activation free energies compared to the direct SPT pathway, particularly in methanol, where solvent-mediated proton relay markedly stabilizes the transition states. The positional effect of the amino group influences both the electrostatic potential distribution and the activation barriers, with the para isomer exhibiting enhanced nucleophilicity and improved reaction efficiency. These findings provide detailed mechanistic insight into solvent-assisted proton transfer processes in Schiff base synthesis and highlight the cooperative role of hydrogen-bond networks in reducing energetic barriers. Full article

The conventional production of waterborne polyurethane (WPU) typically relies on organic solvents to regulate viscosity; additionally, traditional ionic WPU systems still utilize volatile neutralizers, raising environmental and health concerns. To overcome these limitations and reduce dependence on petrochemical resources, this study presents a solvent-free approach for WPU synthesis using isophorone diisocyanate (IPDI), polytetrahydrofuran (PTMG), and the nonionic PEG derivative Ymer^TM A-130. In addition, castor oil (CO), a renewable and hydroxyl-rich bio-based material, was incorporated as a partial substitute for PTMG to improve both sustainability and material performance. The effects of varying substitution ratios of castor oil on the physical properties of the resulting dispersions, dried films, and coatings were initially investigated. The results indicate that increasing the castor oil content from 0 wt% to 11.8 wt% led to an enhancement in tensile strength, rising from 1.45 MPa to 2.40 MPa. Concurrently, the temperature at 5% weight loss (Td_5%) shifted upward from 263.84 °C to 285.36 °C, indicating a favorable trend in thermal stability. Furthermore, the preliminary solvent resistance, surface wetting characteristics, and environmental durability of the prepared coatings were evaluated and discussed. 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

Toluene, as a common organic solvent in academic laboratories in university campuses, poses potential exposure concerns to students and staff in university campuses. Hence, by using a computational fluid dynamics simulation, we investigated the dispersion characteristics of toluene at a campus in Guangzhou under meteorological conditions and the impact of newly constructed buildings on toluene concentrations. The numerical simulation results reveal that toluene is readily accumulated in the free movement area under the prevailing east wind, in the administrative area under the prevailing north-northeast wind, and in the teaching area under the prevailing south wind. Therein, the teaching buildings (TB3–TB6) possess the highest average concentration of toluene compared with other functional areas. In the presence of newly constructed buildings, the toluene concentrations are decreased under the south-southeast wind but are aggravated under the southeast wind. As the height increases, under south-southeast winds, the merging of vortex structures continuously reduces toluene concentrations at TB3 and TB4 and the expansion of the wake region rebounds the toluene pollution at TB5 and TB6; under southeast winds, the expanding vertical vortex structures aggravate toluene pollution at TB3 and TB5 but attenuate toluene pollution at TB4 and TB6. Our results reveal that the teaching areas of the target campus represent a critical zone for potential student exposure during summer and require particular attention. This study provides new insights into the coupled effects of prevailing wind conditions and campus morphology on VOC dispersion characteristics and improves the understanding of airflow pollutant interactions in complex campus environments. Full article

SiO_x anodes are highly promising for next-generation lithium-ion batteries due to their superior theoretical capacity. However, issues such as drastic volume expansion and low initial Coulombic efficiency (ICE) impede their practical use. While macroporous architectures can mitigate these challenges, traditional fabrication often depends on tedious hard templating methods and significant organic solvent consumption. In this work, we report a sustainable, emulsion-self-templated and organic solvent-free strategy to synthesize a carbon-coated 3D macroporous SiO_x/C composite (3DM-SiO_x/C@C). Our approach uniquely integrates radical polymerization with a water-in-oil emulsion and sol–gel process, followed by chemical vapor deposition (CVD). The 3D macroporous framework is generated via in-situ emulsion droplets acting as self-templates, effectively eliminating the need for external sacrificial templates and toxic etchants. Notably, this organic solvent-free process achieves an exceptional precursor to (precursor + organic solvent) mass ratio of 1.0, contrasting sharply with conventional methods (0.0044–0.17). The resulting hierarchical structure, characterized by interconnected macropores and a uniform carbon coating, significantly enhances structural integrity and electronic conductivity. Electrochemical evaluations reveal that 3DM-SiO_x/C@C exhibits an improved ICE of 74.32% and long-term cycling stability even at a high current density of 1.0 A g⁻¹ compared to non-porous and uncoated counterparts. This integrated synthesis offers a green and scalable pathway for developing high-performance silicon-based anodes for large-scale energy storage. Full article

Magnesium hydroxide is attracting growing interest as a versatile, halogen-free flame retardant, and this review surveys its production routes, structure–property relationships and use in polymer systems from commodity polyolefins to advanced bio-based materials. Industrial Mg(OH)₂ is still predominantly obtained from mining or hydration of MgO, but increasing attention is being devoted to recovery from seawater and saltwork brines, where precipitation from Mg²⁺-rich streams followed by controlled rehydration or direct precipitation yields fine, high-purity powders suitable for flame retardant use and simultaneously valorizes saline wastes. In parallel, hydrothermal synthesis has been extensively explored to tailor particle size and morphology by adjusting the precursor, solvent, temperature and time, enabling high-surface-area Mg(OH)₂ or MgO with narrow size distributions that are attractive for high-performance composites also evaluated via ball milling, crushing and refining. More recently, process intensification strategies such as microwaves and ultrasounds have been proposed to shorten reaction times, lower temperatures and better control nucleation and growth, opening paths toward energy efficient production of structured Mg(OH)₂ from both conventional and brine-derived precursors. The second part of the review analyzes how the intrinsic endothermic decomposition and basic character of Mg(OH)₂ can be utilized across a broad range of polymer matrices and how surface functionalization strategies extend its applicability. In addition to “as received” powders, stearic acid and other fatty acids, metal soaps and various organic coupling agents are widely used to render the surface more hydrophobic, enhance dispersion and interfacial adhesion, and in some cases introduce additional char-forming or barrier functionality. In terms of the application, the review methodically synthesizes and contrasts fire and mechanical data for Mg(OH)₂-containing polyolefins (HDPE, LLDPE, PP and EVA) utilized in cables and building products, expandable polymers and foams, biopolymers (PLA and PBS), and elastomers. The review places particular emphasis on the balance between loading level, processability, flame performance and mechanical integrity. This review aims to provide a comprehensive framework for designing next-generation Mg(OH)₂-based flame-retardant systems for both conventional and emerging polymer technologies. To this end, it integrates advances in sustainable feedstocks, controlled synthesis and surface engineering with the rapidly expanding application space. Full article

Chemical warfare agents (CWAs) pose severe threats to human health and the environment because of their extreme toxicity. Conventional liquid-phase decontamination processes can present limitations, including potential equipment corrosion, generation of secondary liquid waste, and increased operational complexity. To overcome these challenges, we report a solar-assisted process intensification strategy for solvent-free decontamination of toxic organophosphorus compounds using UiO-66-NH₂@carbon nanotube (CNT) hybrid platforms. Incorporation of CNTs (optimized at 5 wt%) enables efficient solar-to-thermal conversion, resulting in rapid photothermal self-heating to 85 °C under simulated solar irradiation (1000 W m⁻²). This localized thermal effect contributes to accelerated DMMP removal within the MOF-based hybrid structure, thereby partially alleviating the kinetic limitations typically associated with solvent-free reactions. Consequently, the optimized hybrid achieves 94% removal of dimethyl methylphosphonate (DMMP), a representative sarin simulant, within 10 min under humidity-conditioned, solvent-free conditions, representing a 27% improvement compared with pristine UiO-66-NH₂. This decontamination platform eliminates the need for chemical solvents and external energy input, thereby mitigating secondary contamination and reducing the environmental footprint. By integrating the catalytic framework of Zr-based MOFs with the photothermal capability of CNTs, this study presents a sustainable engineering strategy for advanced defense and environmental protection. Full article

(1) Background: Grape pomace (GP), a major by-product of winemaking, is a sustainable source of bioactive polyphenols with antioxidant, anti-inflammatory, and antimicrobial properties, although their instability limits cosmetic applications. This study aimed to valorize GP through a green extraction process and improve its incorporation and apparent stability in cosmetic formulations through SLN-based systems. (2) Methods: GP extracts were obtained using an eco-friendly extraction method and encapsulated using a W/O/W double emulsion-solvent evaporation technique; nanoparticles were characterized (size, polydispersity, zeta potential) and incorporated into cosmetic formulations compared with a blank and a formulation containing free extract. (3) Results: GP-SLNs exhibited suitable physicochemical properties and preserved antioxidant activity, as confirmed by DPPH and ORAC assays; SLN incorporation appeared to preliminarily improve the photostability profile of the formulation under UVA irradiation conditions; in vivo tests showed enhanced skin hydration and moderate occlusivity, while stability studies confirmed consistent color, odor, pH, and viscosity over 60 days; microbiological analyses demonstrated safety and concentration-dependent antimicrobial activity. (4) Conclusions: SLN encapsulation preserved GP bioactivity and improved formulation stability and performance, supporting its potential use in multifunctional cosmetic products. Full article

During food intake, small amounts of antioxidants are absorbed and distributed to the extracellular matrix, from which they are made available to all types of cells. They protect against various free radicals generated in the extracellular and intracellular environments. They also protect against ionising radiation or UV directly. Some of the most abundant antioxidants in food are the proanthocyanidins, a form of condensed tannin found in tea, cocoa, and grape seeds. They also bestow various other health benefits as apoptosis inducers. The present study examines the vertical and adiabatic ionisation potentials and electron affinities of flavan, (−)-epicatechin, procyanidin B2, procyanidin C1, and cinnamtannin A2, and discusses the influence of non-equilibrated solvent–solute interactions on their electronic properties. The analysis employs the M06-2x/aug-cc-pVTZ//M06-2x/6-31++G** level of theory in the aqueous phase. Procyanidin C1 was found to have the lowest ionisation potential (6.08 eV) and the highest adiabatic electron affinity (1.15 eV); also, all (−)-epicatechin derivatives demonstrated a lower IP than guanine (6.42 eV), suggesting a potential genome-protective effect. These findings were confirmed by the global reactivity descriptor, the Fukui reactivity index, and the spin density distribution. The theoretical results presented here support the experimental results which predict that nutrients can help maintain a delicate redox balance which is crucial for the extra- and intracellular matrix. Full article

UV-curable polymer composites are attractive for fabricating complex components by digital light processing (DLP), but improving thermal transport while preserving printability remains challenging at high filler loadings. In this work, solvent-free UV-curable formulations filled with hexagonal boron nitride (h-BN) and h-BN/graphite hybrids were developed for DLP 3D printing using commercially available equipment. The effects of filler composition on viscosity, printability, microstructure, through-thickness thermal conductivity, electrical conductivity, and tensile behavior were investigated. Viscosity increased markedly with filler loading, yet reliable DLP printing was achieved up to 40 wt% h-BN through composition-dependent adjustment of build parameters. Thermal analysis supported negligible macroscopic sedimentation during printing, while optical and FE-SEM observations revealed generally uniform platelet dispersion, visible 50 μm layer stratification, and limited phase segregation in the hybrid systems. The through-thickness thermal conductivity increased from ~0.25 W/mK for the neat resin to ~1.95 W/mK at 40 wt% h-BN. At a fixed 20 wt% h-BN, graphite addition led to a smaller increase in thermal conductivity, up to ~1.16 W/mK, while increasing electrical conductivity and reducing mechanical performance. A phenomenological percolation-type model captured the thermal-conductivity trend of the h-BN series. Overall, h-BN-rich formulations provided the most effective route to enhance thermal conductivity while preserving electrical insulation. Full article

Thermoplastic starch (TPS) and polyvinyl alcohol (PVA) blends were prepared over the full compositional range (0–100 wt% PVA) by solvent-free twin-screw extrusion and injection molding. This enabled a systematic evaluation of structure–performance–disintegration relationships under industrially relevant conditions. The blends exhibited clear composition-dependent trends in thermal and mechanical behavior. Increasing PVA content from 0 to 100 wt% raised the onset degradation temperature (T5%) from 160.5 °C to 290.5 °C and increased crystallinity from near zero to 12.24%. Mechanically, the response evolved from a rigid TPS-rich state to a ductile PVA-rich one. FTIR and SEM analyses indicated partial compatibility, with limited molecular-level interactions leading to morphologically homogeneous but only partially miscible blends. Under simulated composting conditions, all formulations showed substantial physical disintegration. PVA-rich blends (≥60 wt%) disintegrated rapidly (>80% mass loss within two days), primarily by dissolution rather than microbial degradation. Overall, this work provides a comprehensive, scalable assessment of solvent-free TPS/PVA blends, clarifies their limited compatibility under melt processing, and demonstrates how composition can be used to tailor structure, performance, and disintegration behavior across the full compositional range. Full article