Search Results (632)

The transition to a sustainable chemical industry necessitates efficient valorization of biomass, with polyols serving as versatile, renewable feedstocks. This comprehensive review, focusing on advancements within the last five years, critically analyzes the selective hydrogenolysis of key biomass-derived polyols—including glycerol, erythritol, xylitol, and sorbitol—into valuable diols. Emphasis is placed on the intricate catalytic strategies developed to control C–O bond cleavage, preventing undesired C–C scission and cyclization. The review highlights the design of bifunctional catalysts, often integrating noble metals (e.g., Pt, Ru, Ir) with oxophilic promoters (e.g., Re, W, Sn) on tailored supports (e.g., TiO₂, Nb₂O₅, N-doped carbon), which have led to significant improvements in selectivity towards specific diols such as 1,2-propanediol (1,2-PD), 1,3-propanediol (1,3-PD), and ethylene glycol (EG). While substantial progress in mechanistic understanding and catalyst performance has been achieved, challenges persist regarding catalyst stability under harsh hydrothermal conditions, the economic viability of noble metal systems, and the processing of complex polyol mixtures from lignocellulosic hydrolysates. Future directions for this field underscore the imperative for more robust, cost-effective catalysts, advanced computational tools, and intensified process designs to facilitate industrial-scale production of bio-based diols. Full article

Flexible polyurethane foams (PUFs) are widely used materials whose crosslinked chemical structure hinders conventional recycling, leading to significant environmental challenges. This study presents a selective and scalable depolymerization strategy for polyurethane foam waste (PUFW), utilizing a combination of 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) as water-miscible ionic liquid (IL) and a strong organic base to enable hydrolytic cleavage of urethane bonds under mild reaction conditions (98 °C, atmospheric pressure). The approach was evaluated across different PUFW formulations and successfully scaled up to a 1 kg reaction mass, maintaining high efficiency in both the depolymerization and separation steps. The recovered polyols exhibited high purity and structural fidelity, comparable to those of virgin polyols. The recycled products were integrated into a new foam formulation, resulting in a PUF with mechanical and morphological properties, as revelated by scanning electron microscopy (SEM), which closely resemble those of virgin polyol-based references and surpass those of foams produced using commercially recycled polyols. These findings support the feasibility of closed-loop polyurethane recycling and represent the transition towards circular polymer economy strategies. Full article

Phthalic acid esters (PAEs), ubiquitously employed as a plasticizer, have been classified as priority environmental pollutants because of their persistence, bioaccumulation, and endocrine-disrupting properties. As a characterized PAE-degrading strain of marine origin, Mycolicibacterium phocaicum RL-HY01 utilizes di-(2-ethylhexyl) phthalate (DEHP) as its sole carbon and energy source. Genome sequencing and RT-qPCR analysis revealed a previously uncharacterized hydrolase gene (dehpH) in strain RL-HY01, which catalyzes ester bond cleavage in PAEs. Subsequently, recombinant expression of the cloned dehpH gene from strain RL-HY01 was established in Escherichia coli BL21(DE3). The purified recombinant DehpH exhibited optimal activity at 30 °C and pH 8.0. Its activity was enhanced by Co²⁺ and tolerant to most metal ions but strongly inhibited by EDTA, SDS, and PMSF. Organic solvents (Tween-80, Triton X-100, methanol, ethanol, isopropanol, acetone, acetonitrile, ethyl acetate, and n-hexane) showed minimal impact. Substrate specificity assay indicated that DehpH could efficiently degrade the short and long side-chain PAEs but failed to hydrolyze the cyclic side-chain PAE (DCHP). The kinetics parameters for the hydrolysis of DEHP were determined under the optimized conditions, and DehpH had a V_max of 0.047 ± 0.002 μmol/L/min, K_m of 462 ± 50 μmol/L, and k_cat of 3.07 s⁻¹. Computational prediction through structural modeling and docking identified the active site, with mutagenesis studies confirming Ser228, Asp324, and His354 as functionally indispensable residues forming the catalytic triad. The identification and characterization of DehpH provided novel insights into the mechanism of DEHP biodegradation and might promote the application of the target enzyme. Full article

The photochemistry of 1,3,4-oxadiazoles remains poorly understood, despite their recognized importance in medicinal chemistry and materials science. In this work, we report a detailed matrix-isolation study of 2-amino-5-(4-methoxyphenyl)-1,3,4-oxadiazole, combining low-temperature infrared spectroscopy with broadband UV photolysis and quantum chemical calculations. Theoretical analysis predicts the gas-phase molecule to exist exclusively as the amino tautomer, populating two nearly isoenergetic conformers (anti and syn) defined by the relative orientation of the amino and methoxy groups. Experimental IR spectra of the compound isolated in Ar and Xe matrices at 15 K confirm sole trapping of the amino tautomer. Annealing of the Xe matrix to the highest achievable temperature induced no detectable spectral changes, consistent with the predicted isoenergetic character of the conformers. Upon broadband UV irradiation (λ > 200 nm), the compound undergoes ring opening through N−N and C−O bond cleavages, paralleling the behavior of unsubstituted 1,3,4-oxadiazole system. Isocyanates emerge as the predominant photoproducts from these photochemical pathways. Additionally, spectroscopic evidence supports an alternative reaction pathway involving early-stage amino−imino tautomerization, followed by ring-opening of the imino tautomer through isocyanic acid extrusion, leading to the formation of a nitrilimine intermediate. This reactive species subsequently photorearranges into a carbodiimide via a diazirine-mediated pathway. All photoproducts were unambiguously identified through their distinct IR signatures, supported by quantum chemical calculations and reference data from structurally related systems. These findings provide unprecedented insight into the photochemical behavior of substituted 1,3,4-oxadiazoles and unveil new reaction pathways modulated by substituent effects, expanding the understanding of their photoreactivity. Full article

Lithium/carbon fluoride (Li/CF_x) batteries are promising for specialized applications due to their high theoretical capacity (>865 mAh·g⁻¹) and energy density. However, their practical deployment is hindered by the intrinsically low conductivity of CF_x and sluggish reaction kinetics. While conventional conductive additives improve electron transport, their physical mixing with active materials yields weak interfacial contacts and fails to catalytically facilitate C–F bond cleavage. To address these dual limitations, this study proposes a dual-functional conductive-catalytic additive strategy. We engineered zinc-nickel/carbon nanotube (ZnNi/CNT) composites modified with transition metal dopants (Fe, W, Cu) to integrate conductive networks with nanoscale-dispersed catalytic sites. Fe-doped ZnNi/CNT (ZnFeNiC) emerged as the optimal system, delivering a discharge plateau of 2.45 V and a specific capacity of 810.3 mAh·g⁻¹ at 0.1 C. This performance is attributed to Fe-doping accelerates Li⁺ diffusion, and promotes reversible Ni redox transitions (Ni²⁺↔Ni⁰) that catalyze C–F bond dissociation. This work establishes a design paradigm for high-performance Li/CF_x batteries, bridging the gap between conductive enhancement and catalytic activation. Full article

Red deer fat makes up approximately 7–10% of the animal’s weight and is not currently used. Regarding sustainability in the food industry, it is desirable to look for opportunities for its processing and use, not only in the food industry. The aim of this study is the enzymatic modification of red deer fat, leading to modification of its physicochemical properties, and the study of changes in phase transitions of modified fat, its structure, color, and texture. Hydrolysis was performed using sn-1,3-specific lipase at different water concentrations (10–30%) and reaction times (2–6 h). The results showed that there was a significant decrease in melting and crystallization temperatures with an increasing degree of hydrolysis, which was confirmed by differential scanning calorimetry. FTIR spectra revealed a decrease in the intensity of the ester bonds, indicating cleavage of triacylglycerols. Texture analysis of the modified fats confirmed a decrease in hardness of up to 50% and an increase in spreadability. The color parameter values remained within an acceptable range. The results show that enzymatic modification is an effective tool for targeted modification of red deer fat properties, and this expands the possibilities of its application in cosmetic matrices and food applications as functional lipids. Full article

Concern over the presence of pharmaceutical waste in the environment has prompted research into the management of emerging organic micropollutants (EOMs). In response, sustainable technologies have been applied as alternatives to reduce the effects of these contaminants. This study investigated the capacity of filamentous fungi isolated from iron mine soil in the Amazon region to biodegrade the drug chloroquine diphosphate. An initial screening assessed the growth of four fungal strains on solid media containing chloroquine diphosphate: Trichoderma pseudoasperelloides CBMAI 2752, Penicillium rolfsii CBMAI 2753, Talaromyces verruculosus CBMAI 2754, and Penicillium sp. cf. guaibinense CBMAI 2758. Among them, Penicillium sp. cf. guaibinense CBMAI 2758 was selected for further testing in liquid media. A Box–Behnken factorial design was applied with three variables, pH (5, 7, and 9), incubation time (5, 10, and 15 days), and chloroquine diphosphate concentration (50, 75, and 100 mg·L⁻¹), totaling 15 experiments. The samples were analyzed by gas chromatography–mass spectrometry (GC-MS). The most effective conditions for chloroquine biodegradation were pH 7, 100 mg·L⁻¹ concentration, and 10 days of incubation. Four metabolites were identified: one resulting from N-deethylation M1 (N4-(7-chloroquinolin-4-yl)-N1-ethylpentane-1,4-diamine), two from carbon–carbon bond cleavage M2 (7-chloro-N-ethylquinolin-4-amine) and M3 (N1,N1-diethylpentane-1,4-diamine), and one from aromatic deamination M4 (N1-ethylbutane-1,4-diamine) by enzymatic reactions. The toxicity analysis showed that the products obtained from the biodegradation of chloroquine were less toxic than the commercial formulation of this compound. These findings highlight the biotechnological potential of Amazonian fungi for drug biodegradation and decontamination. Full article

Plasma-activated water (PAW), enriched with reactive oxygen and nitrogen species (RONS), presents oxidative and antimicrobial characteristics with potential in cosmetic applications. This study examined the effects of two PAW formulations—nitrate-rich (PAW-N) and peroxide-rich (PAW-P)—on human hair types classified as straight (Type 1), wavy (Type 2), and coily/kinky (Type 4). The impact of PAW on hair structure and chemistry was evaluated using Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), UV–Vis spectrophotometry, and physicochemical analyses of the liquids (pH, ORP, conductivity, and TDS). PAW-N, with high nitrate content (~500 mg/L), low pH (2.15), and elevated conductivity (6244 µS/cm), induced significant damage to porous hair types, including disulfide bond cleavage, protein oxidation, and lipid degradation, as indicated by FTIR and EDS data. SEM confirmed severe cuticle disruption. In contrast, PAW-P, containing >25 mg/L of hydrogen peroxide and exhibiting milder acidity and lower ionic strength, caused more localized and controlled oxidation with minimal morphological damage. Straight hair showed greater resistance to both treatments, while coily and wavy hair were more susceptible, particularly to PAW-N. These findings suggest that the formulation and ionic profile of PAW should be matched to hair porosity for safe oxidative treatments, supporting the use of PAW-P as a gentler alternative in hair care technologies. Full article

Fungal lytic polysaccharide monooxygenases (LPMOs) have revolutionized the field of biomass degradation by introducing an oxidative mechanism that complements traditional hydrolytic enzymes. These copper-dependent enzymes catalyze the cleavage of glycosidic bonds in recalcitrant polysaccharides such as cellulose, hemicellulose, and chitin, through the activation of molecular oxygen (O₂) or hydrogen peroxide (H₂O₂). Their catalytic versatility is intricately modulated by structural features, including the histidine brace active site, surface-binding loops, and, in some cases, appended carbohydrate-binding modules (CBMs). The oxidation pattern, whether at the C1, C4, or both positions, is dictated by subtle variations in loop architecture, amino acid microenvironments, and substrate interactions. LPMOs are embedded in a highly synergistic fungal enzymatic system, working alongside cellulases, hemicellulases, lignin-modifying enzymes, and oxidoreductases to enable efficient lignocellulose decomposition. Industrial applications of fungal LPMOs are rapidly expanding, with key roles in second-generation biofuels, biorefineries, textile processing, food and feed industries, and the development of sustainable biomaterials. Recent advances in genome mining, protein engineering, and heterologous expression are accelerating the discovery of novel LPMOs with improved functionalities. Understanding the balance between O₂- and H₂O₂-driven mechanisms remains critical for optimizing their catalytic efficiency while mitigating oxidative inactivation. As the demand for sustainable biotechnological solutions grows, this narrative review highlights how fungal LPMOs function as indispensable biocatalysts for the future of the Circular Bioeconomy and green industrial processes. Full article

The majority of studies of fungal utilization of chitosan are associated with the production of a specific enzyme, chitosanase, which catalyzes the hydrolytic cleavage of the macrochain. In our opinion, the development of approaches to obtaining materials with new functional properties based on non-destructive chitosan transformation by living organisms and their enzyme systems is promising. This study was conducted using a wide range of classical and modern methods of microbiology, biochemistry, and physical chemistry. The ability of the ascomycete Fusarium oxysporum Schltdl. to modify films of chitosan with average-viscosity molecular weights of 200, 450, and 530 kDa was discovered. F. oxysporum was shown to use chitosan as the sole source of carbon/energy and actively overgrew films without deformations and signs of integrity loss. Scanning electron microscopy (SEM) recorded an increase in the porosity of film substrates. An analysis of the FTIR spectra revealed the occurrence of oxidation processes and crosslinking of macrochains without breaking β-(1,4)-glycosidic bonds. After F. oxysporum growth, the resistance of the films to mechanical dispersion and the degree of ordering of the polymer structure increased, while their solubility in the acetate buffer with pH 4.4 and sorption capacity for Fe²⁺ and Cu²⁺ decreased. Elemental analysis revealed a decrease in the nitrogen content in chitosan, which may indicate its inclusion into the fungal metabolism. The film transformation was accompanied by the production of extracellular hydrolase (different from chitosanase) and peroxidase, as well as biosurfactants. The results obtained indicate a specific mechanism of aminopolysaccharide transformation by F. oxysporum. Although the biochemical mechanisms of action remain to be analyzed in detail, the results obtained create new ways of using fungi and show the potential for the use of Fusarium and/or its extracellular enzymes for the formation of chitosan-containing materials with the required range of functional properties and qualities for biotechnological applications. Full article

Vanillin photoinduced deprotonation was evaluated and analyzed. Vibronic states and transitions were computationally investigated. Optimizations and vertical electron transitions in the gas phase and with the continuum solvation model were computed using the time-dependent density functional theory. Static absorption and emission (photostatic optical) spectra were statistically averaged over the excited instantaneous molecular conformers fluctuating on quantum–classical molecular dynamic trajectories. Photostatic optical spectra were generated using the hybrid quantum–classical molecular dynamics for explicit solvent models. Conical intersection searching and nonadiabatic molecular dynamics simulations defined potential energy surface propagations, intersections, dissipations, and dissociations. The procedure included mixed-reference spin–flip excitations for both procedures and trajectory surface hopping for photodynamics. Insignificant structural deformations vs. hydroxyl bond cleavage followed by deprotonation were demonstrated starting from different initial structural conditions, which included optimized, transition state, and several other important fluctuating configurations in various environments. Vanillin electronic structure changes were illustrated and analyzed at the key points on conical intersection and nonadiabatic molecular dynamics trajectories by investigating molecular orbital symmetry and electron density difference. The hydroxyl group decomposed on transition to a σ-molecular orbital localized on the elongated O–H bond. Full article

Our work introduces a facile and efficient metal-free [3+3] annulation approach for the synthesis of polysubstituted pyridines via the reaction between β-enaminonitriles and β,β-dichloromethyl peroxides. This strategy operates under mild conditions, demonstrating broad substrate scope and excellent functional group tolerance. Mechanistic investigations suggest that the reaction proceeds through a Kornblum–De La Mare rearrangement followed by S_NV-type C-Cl bond cleavage and intramolecular cyclization/condensation. By circumventing the need for transition metal catalysts or radical initiators, our method offers practical utility in organic synthesis and provides a new avenue for the rapid construction of complex pyridine scaffolds. Full article

The Mo:BiVO₄/FeOOH photoelectrode was synthesized through the deposition of FeOOH onto the surface of the Mo:BiVO₄ photoelectrode. The composite photoelectrode demonstrated a photocurrent of 1.8 mA·cm⁻², which is three times greater than that observed for pure BiVO₄. Furthermore, the glycerol conversion rate was recorded at 79 μmol·cm⁻²·h⁻¹, approximately double that of pure BiVO₄, while the selectivity for glyceraldehyde reached 49%, also about twice that of pure BiVO₄. The incorporation of Mo has been shown to enhance the stability of the BiVO₄. Additionally, Mo doping improves the efficiency of electron-hole transport and increases the carrier concentration within the BiVO₄. This enhancement leads to a greater number of holes participating in the formation of iron oxyhydroxide (FeOOH), thereby stabilizing the FeOOH co-catalyst within the glycerol conversion system. The FeOOH co-catalyst facilitates the adsorption and oxidation of the primary hydroxyl group of glycerol, resulting in the cleavage of the C−H bond to generate a carbon radical (C). The interaction between the carbon radical and the hydroxyl group produces an intermediate, which subsequently dehydrates to form glyceraldehyde (GLAD). Full article

Background/Objectives: PEGylated liposomes are widely recognized for their biocompatibility and capacity to extend systemic circulation via “stealth” properties. However, the PEG corona often limits tumor penetration and cellular internalization. Targeting matrix metalloproteinase-2 (MMP-2), frequently upregulated in breast cancer stroma, presents an opportunity to enhance tissue-specific drug delivery. In this study, we engineered MMP-2-responsive GPLGVRG peptide-modified cleavable PEGylated liposomes for targeted paclitaxel (PTX) delivery. Methods: Molecular docking simulations employed the MMP-2 crystal structure (PDB ID: 7XJO) to assess GPLGVRG peptide binding affinity. A cleavable, enzyme-sensitive peptide-PEG conjugate (Chol-PEG_2K-GPLGVRG-PEG_5K) was synthesized via small-molecule liquid-phase synthesis and characterized by ¹H NMR and MALDI-TOF MS. Liposomes incorporating this conjugate (S-Peps-PEG_5K) were formulated to evaluate whether MMP-2-mediated peptide degradation triggers detachment of long-chain PEG moieties, thereby enhancing internalization by 4T1 breast cancer cells. Additionally, the effects of tumor microenvironmental pH (~6.5) and MMP-2 concentration on drug release dynamics were investigated. Results: Molecular docking revealed robust GPLGVRG-MMP-2 interactions, yielding a binding energy of −7.1 kcal/mol. The peptide formed hydrogen bonds with MMP-2 residues Tyr A:23 and Arg A:53 (bond lengths: 2.4–2.5 Å) and engaged in hydrophobic contacts, confirming MMP-2 as the primary recognition site. Formulations containing 5 mol% Chol-PEG_2K-GPLGVRG-PEG_5K combined with 0.15 µg/mL MMP-2 (S-Peps-PEG_5K +MMP) exhibited superior internalization efficiency and significantly reduced clonogenic survival compared to controls. Notably, acidic pH (~6.5) induced MMP-2-mediated cleavage of the GPLGVRG peptide, accelerating S-Peps-PEG_5K dissociation and facilitating drug release. Conclusions: MMP-2-responsive, cleavable PEGylated liposomes markedly improve PTX accumulation and controlled release at tumor sites by dynamically modulating their stealth properties, offering a promising strategy to enhance chemotherapy efficacy in breast cancer. Full article

Herein a rapid, metal-free, and highly efficient synthesis of aryl ynamides from aryl alkynyl acids has been described. This approach, utilizing tertiary amines as an amino source via metal-free C-N cleavage, enabled the construction of a diverse range of aryl ynamides with medium to excellent yields (33 examples, up to 95% yield). This reaction exhibits significantly enhanced efficiency compared to the conventional stepwise approach involving aryl alkynyl acids and secondary amines. It can be successfully scaled up, providing a practical and environmentally benign strategy for alkynamide synthesis. Full article