Search Results (802)

This study examines the chemical recycling of polymethylmethacrylate (PMMA) dental waste in semi-batch fixed-bed reactors via pyrolysis, aiming to convert this waste into the valuable monomer methyl methacrylate (MMA). First, the effect of temperature is analyzed in a laboratory-scale (30 g) semi-batch reactor at 350, 400 and 450 °C. In order to visualize the combined effect of temperature and increase in bed volume, experiments conducted at 350 °C in the laboratory (30 g) and on a pilot scale (20 kg) are compared. Experiments conducted at 475°C on technical and pilot scales are also compared to elucidate this behavior. A detailed process analysis is presented, considering different experiments conducted in a semi-batch technical-scale reactor. Experiments were conducted in a 2 L reactor at temperatures of 425 °C, 450 °C and 475 °C to understand the effects of heating rate and temperature on product yield and composition. The results show that at 425 °C, MMA was the primary liquid component, with minimal by-products, suggesting that lower temperatures enhance monomer recovery. Higher temperatures, however, increased gas yields and reduced MMA yield due to intensified thermal cracking. This study also highlights that char formation and non-condensable gases increase with the reactor scale, indicating that heat transfer limitations can influence MMA purity and yield. These findings emphasize that for effective MMA recovery, lower temperatures and controlled heating rates are optimal, especially in larger reactors where heat transfer issues are more prominent. This research study contributes to scaling up PMMA recycling processes, supporting industrial applications to achieve efficient monomer recovery from waste. Full article

Effective treatment of central nervous system (CNS) infections remains a major challenge, as most therapeutic agents do not efficiently cross the blood–brain barrier (BBB) and the blood–cerebrospinal fluid barrier (BCSFB). Coumarin derivatives are of particular interest due to their broad pharmacological activity, favorable safety profile, and potential to penetrate biological barriers. Eight novel coumarin-based peptidomimetics functionalized with trifluoromethyl or methyl scaffolds were synthesized and evaluated as antimicrobial agents with the ability to cross the blood–brain barrier. Antimicrobial activity of the investigated compounds was tested against Staphylococcus aureus and multiple Escherichia coli strains (K12, R2, R3, R4) using minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) assays. Cytotoxicity was assessed in vitro in BALB/c-3T3 mouse fibroblasts and αT3-1 pituitary gonadotrope cells using the MTT assay. In vivo studies were performed in sheep to assess transfer of the compounds from blood to cerebrospinal fluid (CSF). All synthesized derivatives demonstrated antimicrobial activity and acceptable cytotoxicity, comparable to those of clinically used antibiotics. CF₃-modified coumarin peptidomimetics show promise as antimicrobial agents with the potential to penetrate the BBB/BCSFB. These findings support further investigation of coumarin-based scaffolds as a platform for the development of novel therapeutics for CNS infections. Full article

Aroma and flavor are central to consumer perception, product acceptance, and market positioning of animal-derived foods such as meat, milk, and eggs. These sensory traits arise from volatile organic compounds (VOCs) formed via lipid oxidation (e.g., hexanal, nonanal), Maillard/Strecker chemistry (e.g., pyrazines, furans), thiamine degradation (e.g., 2-methyl-3-furanthiol, thiazoles), and microbial metabolism, and are modulated by species, diet, husbandry, and post-harvest processing. Despite extensive research on food volatiles, there is still no unified framework spanning meat, milk, and eggs that connects production factors with VOC pathways and links them to sensory traits and consumer behavior. This review explores how production systems, feeding strategies, and processing shape VOC profiles, creating distinct aroma “fingerprints” in meat, milk, and eggs, and assesses their value as markers of quality, authenticity, and traceability. We have also summarized the advances in analytical techniques for aroma fingerprinting, with emphasis on GC–MS, GC–IMS, and electronic-nose approaches, and discuss links between key VOCs and sensory patterns (e.g., grassy, nutty, buttery, rancid) that influence consumer perception and willingness-to-pay. These patterns reflect differences in production and processing and can support regulatory claims, provenance verification, and label integrity. In practice, such markers can help producers tailor feeding and processing for flavor outcomes, assist regulators in verifying claims such as “organic” or “free-range,” and enable consumers to make informed choices. Integrating VOC profiling with production data and chemometric/machine learning pipelines can enable robust traceability tools and sensory-driven product differentiation, supporting transparent, value-added livestock products. Thus, this review integrates production variables, biochemical pathways, and analytical platforms to outline a research agenda toward standardized, transferable VOC-based tools for authentication and label integrity. Full article

Methylation reactions catalyzed by S-adenosylmethionine (SAM)-dependent methyltransferases are essential to numerous biological functions, including gene expression regulation, epigenetic modifications, and biosynthesis of natural products. Dysregulation of these enzymes is associated with diseases, including cancer and neurodevelopmental disorders, making them attractive drug targets. This review explores the contribution of computational methods, particularly quantum chemical calculations and molecular dynamics (MD) simulations, in elucidating the mechanisms of SAM-dependent methyltransferases. These techniques enable detailed characterization of transition states and reaction pathways, often inaccessible by experimental methods. The review discusses molecular modeling approaches such as the quantum chemical cluster approach (QM-cluster) and hybrid QM/MM methods, emphasizing their applications in studying methyl group transfer, substrate specificity, and the roles of water molecules and metal ions in catalysis. Additionally, dynamic aspects of enzyme function are addressed using classical MD and QM/MM MD simulations. Case studies demonstrate how computational predictions align with experimental data and enable rational design of selective inhibitors and engineered enzymes with altered specificity. Overall, computational chemistry offers a powerful, atomistic view of SAM-dependent methyltransferases, not only complementing experimental studies but also providing a foundation for the design of future experiments in this field. Full article

The improved biomass-derived aldehyde compounds represent a valuable route to the production of high-value-added fuels and chemicals. However, the majority of mature catalytic systems exhibit low hydrodeoxygenation (HDO) activity, even under harsh reaction conditions. In this study, it was observed that a Pd/Fe magnetic bimetallic catalyst, in conjunction with formic acid (FA) as a hydrogen source and nitrogen-containing carbon material as a support, exhibited remarkable catalytic performance for the conversion of phenyl aldehydes in oxygenates derived from crude lignin. In the hydrogenation of vanillin, the Pd/Fe@N/C catalyst demonstrated superior catalytic activity under mild reaction conditions of 80 °C. When ethyl acetate was used as the solvent, the product was vanillyl alcohol (VA), and when cyclohexane was employed as the solvent, the product was p-methyl guaiacol (MMP). The yields achieved were 84.5% and 92.3%, respectively. It is recommended that further exploration of the FLOW reactor system be considered at a later stage due to the magnetic and easily separable characteristics of the catalyst. The excellent mass transfer and heat transfer performance of the FLOW reactor system will further ensure that the reaction conditions are moderate and will strive to achieve normal-temperature conversion. Full article

Silver nanoparticles (Ag NPs) green-synthesized using Nypa fruticans fruit husk (NF) extract were applied as catalysts for the degradation of organic dyes in water for the first time. The synthesized Ag NPs, which were well-dispersed, highly stable, and small in size with an average diameter of ~4 nm, efficiently catalyzed the degradation of methyl orange (MO) in the presence of ${\mathrm{NaBH}}_4$, achieving complete degradation (>99%) within one minute under optimized conditions. The application to a commercial synthetic dye resulted in over 89% degradation within five minutes. To elucidate the degradation mechanism at the atomistic level, molecular dynamics (MD) simulations and density functional theory (DFT) calculations were employed. MD simulations revealed the adsorption behavior of MO on the Ag(111) surface. DFT calculations clarified the reaction pathway of MO degradation, identifying direct hydride transfer from ${\mathrm{BH}}_4^{-}$ to the azo group of MO as the rate-determining step, with the subsequent step influenced by the pH conditions. These findings illustrate the potential of NF extract in the green synthesis of catalytically active Ag NPs and contribute to understanding their role in dye degradation processes relevant to environmental remediation. Full article

Somatic cell nuclear transfer (SCNT) holds promise for animal cloning but remains limited by low efficiency and phenotypic abnormalities, often attributed to incomplete nuclear reprogramming. This study presents an integrative genomic and epigenomic analysis of cloned buffaloes and their respective donors using long-read Oxford Nanopore sequencing. Our results showed a high degree of genomic similarity between clones and donors, with most variations located in non-coding regions and structural variants (SV) distributions highly correlated at the chromosomal level. Gene and protein level overlap of SV-affected loci revealed 70.9–73.3% gene-level and 69.7–72.5% protein-level similarity. Despite this genetic similarity, DNA methylation analysis identified differentially methylated regions (DMRs), particularly in intergenic and promoter regions. Clones exhibited slightly lower CpG methylation than the donors. The DMRs in donor vs. clone comparisons indicated higher hypomethylated regions than hypermethylated regions. Functional enrichment of DMR-associated genes highlighted pathways linked to mitochondrial function, oxidative phosphorylation, and reproductive processes. Although clones showed moderate genome-wide methylation correlation with donors, key differences in methylation suggest incomplete epigenetic reprogramming. Despite these epigenetic differences, all clones were phenotypically normal and healthy into adulthood. This study offers the first comprehensive SV and methylome profile of SCNT-derived buffaloes and emphasizes the role of epigenetic mechanisms in clone development and health, providing valuable insights to enhance cloning efficiency. Full article

Pd nanoparticles (Pd/SiC) with a main exposed plane of Pd (111) were prepared by liquid phase reduction. The use of formaldehyde as a methylation reagent for the photocatalytic methylation of aromatic nitro compounds to N,N-methylaniline resulted in one-pot methylations of aromatic nitro compounds with high photocatalytic activity and selectivity under mild reaction conditions. The high catalytic activity of Pd/SiC in N-methylation reactions arises from the Mott–Schottky contact between Pd and SiC, which promotes the transfer of photogenerated electrons to Pd. The high selectivity is ascribed to the ability of Pd nanoparticles to catalyze the hydrogenation of nitro groups to amino groups, which subsequently undergo direct methylation with formaldehyde, bypassing the intermediate formylation step. Full article

Background: Vandetanib is a clinically approved epidermal growth factor receptor (EGFR) tyrosine kinase inhibitor (TKI) used in the treatment of medullary thyroid cancer. Recent studies have also suggested potential activity against the SARS-CoV-2 main protease (Mpro), indicating dual therapeutic relevance. However, its clinical use is limited by photosensitivity side effects, the molecular basis of which remains poorly understood. This study aims to elucidate the conformational, spectroscopic, and electronic properties of vandetanib underlying its photoreactivity. Methods: Density functional theory (DFT) was employed to explore vandetanib’s conformational landscape, electronic structure, and spectroscopic behavior. Low-energy conformers were identified and compared with experimental crystal and NMR data. Time-dependent DFT (TD-DFT) calculations were used to simulate UV–Vis absorption spectra and assign key electronic transitions. Results: Eight low-energy conformer clusters, including the global minimum structure, were identified. The global minimum was validated by consistency with crystal and experimental NMR data, emphasizing the role of conformational averaging. TD-DFT simulations successfully reproduced the two main UV–Vis absorption bands, with the primary band (~339 nm) assigned to a HOMO–1 → LUMO charge-transfer excitation between the N-methyl piperidine and quinazoline rings, pinpointing a structural contributor to photoreactivity. Additionally, the N-methyl piperidine ring was identified as a major metabolic hotspot, undergoing multiple biotransformations potentially linked to phototoxicity. Conclusions: This study provides molecular-level insights into the structural and photophysical origins of vandetanib’s photosensitivity. The findings improve understanding of its adverse effects and can inform the safer design of EGFR-targeting drugs with reduced phototoxic risks. Full article

This study investigated the aerobic biodecolorization of azo dyes by Shewanella oneidensis MR-1. S. oneidensis MR-1 can rapidly degrade azo dyes under aerobic conditions, even at high concentrations of up to 270 mg/L, demonstrating remarkable dye decolorization capabilities. This decolorization efficiency persists even under high concentrations of oxygen. The introduction of different environmental metal ions led to either inhibitory or stimulatory effects on the decolorization of Methyl Orange and Amaranth. Furthermore, the addition of extracellular electron shuttles and electron scavengers confirmed that dyes were being reduced via electron transfer, and the decolorization capability of S. oneidensis MR-1 correlated with electron density. Our study unveils the rapid degradation ability of S. oneidensis MR-1 for dyes under aerobic conditions, which is closely linked to its electron transfer capacity. This research holds significant implications for a deeper understanding of the biodegradation mechanisms of azo dyes under aerobic conditions. Full article

Structure–property relationships in imidazolium-based hybrid Sb(III) chlorides provide critical guidance for designing high-performance materials. Three zero-dimensional metal halides, namely, [C₃mmim]₂SbCl₅ (1, [C₃mmim]⁺ = 1-propyl-2,3-dimethylimidazolium), [C₅mmim]₂SbCl₅ (2, [C₅mmim]⁺ = 1-pentyl-2,3-dimethylimidazolium), and [C₅mim]₂SbCl₅ (3, [C₅mim]⁺ = 1-pentyl-3-methylimidazolium), are synthesized by ionothermal methods. These compounds exhibit markedly distinctly photophysical properties at their optimal excitation wavelengths. Structural analyses reveal that elongated alkyl chains in compounds 2 and 3 increase Sb–Sb distances compared to that in 1, effectively isolating [SbCl₅]²⁻ units, suppressing inter-center energy transfer, and reducing non-radiative transitions, thereby enhancing the photoluminescence quantum yield (PLQY). Furthermore, methyl substitution at the C2-position of the imidazolium ring in compounds 1 and 2 induces asymmetric coordination environments around the [SbCl₅]²⁻ emission centers, leading to pronounced structural distortion. This distortion promotes non-radiative decay pathways and diminishes luminescent efficiency. Furthermore, temperature-dependent spectroscopy analysis and fitting of the Huang–Rhys factor (S) reveal significant electron–phonon coupling in compounds 1–3, which effectively promotes the formation of self-trapped excitons (STEs). However, compound 1 exhibits extremely high S, which significantly enhances phonon-mediated non-radiative decay and ultimately reduces its PLQY. Overall, compound 3 has the highest PLQYs. Full article

In this study, a selection of active materials were coated onto commercially available intermediate modulus carbon fibers to form and analyze the performance of novel composite cathodes for structural power composites. Various slurries containing polyvinylidene fluoride (PVDF), active material powders, 1-methyl-2-pyrrolidone (NMP) and carbon black (CB) were used to coat carbon fiber tows by immersion. Four active materials—lithium cobalt oxide (LCO), lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), and lithium nickel cobalt aluminum oxide (NCA)—were individually tested to assess their electrochemical reversibility. The cells were prepared with a polymer separator and liquid electrolytes and assembled in 2025-coin cells. Electrochemical analysis of the cathode materials showed that at C/5 and room temperature the measured capacities ranged from 39.8 Ah kg⁻¹ to 64.7 Ah kg⁻¹ for the LFP and NCA active materials, respectively. The full cells exhibited capacities of 18.1, 23.5, 27.2, and 28.2 Ah kg⁻¹ after 55 cycles for LFP, LCO, NCA, and NMC811, respectively. Finally, visual and elemental analysis were performed via scanning electron microscope (SEM) and energy-dispersive x-ray (EDX) confirming desirable surface coverage and successful transfer of the active materials onto the carbon fiber tows. Full article

This study investigates the influence of cellulose nanofibrils (CNFs) on the polymerization kinetics of methyl methacrylate (MMA) during in situ suspension polymerization at 70 °C (343.15 K). Four CNF concentrations were evaluated and compared to a reference system without CNFs. Polymerizations were carried out in a thermostatted flask immersed in an ethylene glycol bath and covered to ensure thermal stability. The temperature profiles of both the reaction medium and the surrounding bath were continuously recorded, allowing for the calculation of heat flow, polymerization rate (R_p), and monomer conversion. The incorporation of CNFs led to a significant increase in R_p and faster MMA conversion. This effect was attributed to the presence of nanocellulose within the polymerizing medium, which restricted diffusion and contributed to the onset of the phenomenon of autoacceleration. Additionally, CNFs promoted a higher total heat release, underscoring the need for thermal control during scale-up. The resulting material qualifies as a biocomposite, as biobased nanofibrils became integrated into the polymer matrix. These findings demonstrate that CNFs act as effective kinetic promoters in MMA polymerizations and may serve as functional additives to enhance both reaction performance and sustainability. However, safety considerations remain critical when transferring this approach to industrial processes. Full article

Methionine residues in proteins and peptides are frequently oxidized by losing one electron. The presence of nearby amide groups is crucial for this process, enabling methionine to participate in long-range electron transfer. Hydroxyl radical (HO^•) plays an important role being generated in aerobic organisms by cellular metabolisms as well as by exogenous sources such as ionizing radiations. The reaction of HO^• with methionine mainly affords the one-electron oxidation of the thioether moiety through two consecutive steps (HO^• addition to the sulfur followed by HO⁻ elimination). We recently investigated the reaction of HO^• with model peptides mimicking methionine and its cysteine-methylated counterpart, i.e., CH₃C(O)NHCHXC(O)NHCH₃, where X = CH₂CH₂SCH₃ or CH₂SCH₃ at pH 7. The reaction mechanism varied depending on the distance between the sulfur atom and the peptide backbone, but, for a better understanding of various suggested equilibria, the analysis of the flux of protons is required. We extended the previous study to the present work at pH 4 using pulse radiolysis techniques with conductivity and optical detection of transient species, as well as analysis of final products by LC-MS and high-resolution MS/MS following γ-radiolysis. Comparing all the data provided a better understanding of how the presence of nearby amide groups influences the one-electron oxidation mechanism. Full article

Photosynthesis in plants and the electron transport chain in mitochondria are examples of life-sustaining electron transfer processes. The benzoquinones plastoquinone and ubiquinone are key components of these pathways that cycle through their oxidized and reduced forms. Previously, we reported direct photoreduction of biologically relevant quinones mediated by photosensitizers, red light and electron donors. Herein we examined direct photoreduction of the quinone imine 2,6-dichlorophenolindophenol (DCPIP) using red light, methylene blue as the photosensitizer and ethylenediaminetetraacetic acid (EDTA) as the electron donor. Photoreduction of DCPIP by methylene blue and EDTA was very pH-dependent, with three-fold enhanced rates at pH 6.9 vs. pH 7.4. Photochemical redox cycling of DCPIP produced hydrogen peroxide via singlet oxygen-dependent reoxidation of reduced DCPIP. Histidine enhanced photoreduction by scavenging singlet oxygen, whereas increased molecular oxygen exposure slowed DCPIP photoreduction. Attempts to photoreduce DCPIP with pheophorbide A, a chlorophyll metabolite, and triethanolamine as the electron donor in 20% dimethylformamide were unsuccessful. Photoreduced benzoquinones including 2,3-dimethoxy-5-methyl-p-benzoquinone (CoQ₀), methoxy-benzoquinone and methyl-benzoquinone were used to examine electron transfer to DCPIP. For photoreduced CoQ₀ and methoxy-benzoquinone, electron transfer to DCPIP was rapid and complete, whereas for reduced methyl benzoquinone, it was incomplete due to differences in reduction potential. Nonetheless, electron transfer from photoreduced quinols to DCPIP is a rapid and sensitive method to investigate quinone photoreduction by chlorophyll metabolites. Full article