ChemistryOpen最新文献

The emerging role of ionic liquids (ILs) and deep eutectic solvents (DESs) in the synthesis of cobalt-based catalysts for water splitting is reviewed. ILs and DESs can serve as solvents and templates due to their unique physicochemical properties. They can efficiently dissolve raw materials and provide a special nucleation and growth environment, obtaining catalysts with novel structures. The designability of ILs and DESs allows for the controlled preparation of catalysts, where they can participate in the reaction as reactants, providing elements such as P, S, N, simplifying the preparation system of cobalt phosphide, sulfide, and nitride. ILs and DESs in catalyst synthesis achieve structural and compositional design, impacting surface adsorption and intermediate stability, allowing precise control over reaction paths and product selectivity. This leads to improved catalytic performance and stability. The review aims to succinctly summarize recent progress and guide researchers in selecting superior solvents for catalyst preparation.

Impact of fluorination on crystal and molecular structure, heteroatom reactivity, and solid-state magnetic properties of thermally-stable π-radicals is studied experimentally and computationally with 1,3,2-benzodithiazolyl 1^· and its 4,7-difluoro, 4,5,6,7-tetrafluoro, and 4,7-difluoro-5,6-(hexafluoropropane-1,3-diyl) derivatives 2^·-4^·, respectively. Radicals 2^·-4^· are isolated by vacuum thermolysis of their unusual covalent 2:1 adducts with 7,7,8,8-tetracyanoquinodimethane. The impact of fluorination on reactivity is evidenced by transformation of 2^·-4^· and 2⁺-4⁺ into corresponding 2H-1-oxo-1,3,2-benzodithiazoles under the influence of air's or solvents' moisture; back transformation into the cations under the action of protic acids; and formation of a paramagnetic molecular complex between 3^· and naphthalene, whereas 1^· and octafluoronaphthalene do not exhibit complexation. The crystal structures of 3^· and 4^· reveal a novel packing motif featuring radical pairs linked by four-center interactions that stack into offset π-columns, forming a unique zip-π-stack synthon that incorporates head-over-tail π-pairs of radicals. Despite the formation of π-pairs, polycrystalline 3^· and 4^· display a nonzero effective magnetic moment that rises with temperature above 200 K, although the values remain significantly lower than those of the high-temperature polymorphs of magnetically-bistable 1^· and 2^·. This behavior can be rationalized by different magnetic topologies and values of spin exchange between the radicals.

As wood is still scarce in some countries, it is necessary to replace wood in the paper industry with other lignocellulosic raw materials, particularly agricultural residues. This study evaluated hemp, flax, and sisal postharvest biomass as alternative nonwoody fibrous feedstocks for pulp and paper production. Pulping was performed using soda and nitrate-alkaline methods under comparable degrees of delignification. Their suitability for papermaking was assessed in terms of mechanical properties, fiber sedimentation (rheosedimentation), and chemical parameters, including the degree of polymerization and the chemical composition of the raw material. The highest tensile strength was achieved for sisal, reaching 11.6 N m g^-1 when produced by the soda method, which was higher than that of industrially produced flax or hemp soda pulps. Regarding pulp sedimentation behavior, hemp pulp showed significantly higher sedimentation rates, while comparable values were observed for recovered paper.

2D-hybrid halide perovskites are semiconductor materials with excellent optical properties that have been widely studied due to their potential as materials applicable to green energy production. Data mining techniques are powerful tools to recognize and extract relevant patterns from databases. In this study, data mining techniques are used to extract relationships among geometric characteristics, composition, and the bandgap of 2D-hybrid halide perovskites. Our analysis reveals patterns that connect the chemical properties of the organic spacer cation with the bandgap, like the distance between the halogen in the perovskite and the terminal nitrogen of the interlayer organic cation, and the relation among the type of organic interlayer cation, the interlayer distance, and the perovskite layer phase. Furthermore, it is found that aromatic cations lead to bandgaps between 2.2 and 2.4 eV. These results are consistent with previous experimental reports and provide insight into the structure-property relationships, thus illustrating the utility of data mining techniques for extracting valuable knowledge to optimize and design new materials with improved properties.

Prostate cancer is the second most common cancer globally, causing ≈396,792 deaths in 2022. Early diagnosis and advanced drug delivery are vital to prevent its progression. This research leverages the anticancer properties of selenium nanoparticles and enzalutamide, a leading prostate cancer drug, by coencapsulating them within mesoporous silica nanoparticles (MSNPs). MSNPs offer advantages for drug delivery, including high surface accessibility and a tunable porous structure. The results indicated that MSNPs synthesized via solvent extraction, yielding a specific surface area of 1017.4 m²/g, a pore volume of 0.2531 cm³/g, and an average pore size of ≈10 nm, were superior to those obtained by calcination, which yielded a smaller pore size (≈3 nm). Enzalutamide was loaded into these selenium-embedded MSNPs, achieving a drug loading efficiency of 76.3 ± 0.5%. Separately, curcumin was encapsulated in chitosan nanoparticles with high efficiency (83.2 ± 0.7%). The combined nanosystem enables pH-responsive, gradual drug release that mimics the tumor microenvironment. MTT assays confirmed the drug-loaded system exerts significantly stronger, time- and concentration-dependent anticancer effects than the free drug. Furthermore, curcumin plays a vital role in enhancing anticancer efficacy and inducing apoptosis. This research demonstrates that the designed dual-nanoparticle system is a promising candidate for targeted prostate cancer therapy.

Reducing nitroarenes to aromatic amines is a valuable method in both industrial and synthetic organic chemistry for producing amine compounds. Recently, magnetite-based nanocatalysts have attracted attention as promising, eco-friendly alternatives to conventional noble-metal catalysts in this transformation. Magnetite nanoparticles, with their large surface area, strong catalytic performance, and inherent magnetic properties, enable easy separation and reuse, significantly supporting the sustainability of the process. Fe₃O₄@graphene oxide nanocatalysts are regarded as highly promising due to their straightforward synthesis, affordability, excellent superparamagnetic behavior, good biocompatibility, and low toxicity. Utilizing environmentally friendly reducing agents such as sodium borohydride or H₂, alongside these adaptable nanocatalysts, enables fast and selective transformation of nitroarenes under moderate reaction conditions. This study emphasizes the promise of Fe₃O₄@graphene oxide magnetic nanocatalysts as an economical, recyclable, and environmentally friendly catalyst for the hydrogenation of nitroarenes, offering a valuable approach toward a more sustainable chemical industry. This review provides an overview of the synthesis and applications of Fe₃O₄@graphene oxide magnetic nanocatalysts, highlighting their effectiveness and eco-friendliness in the hydrogenation of nitro compounds, with coverage extending through 2025.

This research focused on structural, electronic, and interaction properties of fluorouracil (5-FU) adsorbed on transition metal (TM)-doped ZnO nanoclusters (XZn₁₁O₁₂, where X = Zn, Cu, Fe, Ni) using density functional theory (DFT) at the B3LYP/LANL2DZ level of calculations in the gas phase. Among the studied nanocomplexes, 5-FU@NiZn₁₁O₁₂ exhibited the highest dipole moment (8.08 D), indicating strong polarization and potential surface reactivity though it has a less negative adsorption energy (-20.97 kcal/mol) compared to 5-FU@FeZn₁₁O₁₂ (-35.51 kcal/mol) and 5-FU@CuZn₁₁O₁₂ (-28.69 kcal/mol). TM doping significantly reduced the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, with 5-FU@NiZn₁₁O₁₂ showing the lowest value (2.44 eV), followed by 5-FU@FeZn₁₁O₁₂ (2.53 eV) and 5-FU@CuZn₁₁O₁₂ (3.18 eV), suggesting enhanced charge transfer and chemical reactivity. The results from molecular electrostatic potential, quantum theory of atoms in molecules, and non-covalent interaction/reduced density gradient analyses were also in favor of Ni-doped ZnO nanocomplex. Based on the DFT results, 5FU@NiZn₁₁O₁₂ was selected to analyze its interactions with human serum albumin (HSA). From molecular docking of 5-FU@NiZn₁₁O₁₂, binding energy (-5.36 kcal/mol) and inhibition constant (117.15 μM) exhibited stronger interactions with HSA, so that it acts as a potential candidate of drug delivery system for anticancer therapy. However, these predictive insights require further experimental validation.

The present study describes the synthesis of an analog of the anti-inflammatory drug fenbufen, a compound which has recently attracted of renewed interest in the treatment of chronic degenerative diseases such as cancer and rheumatoid arthritis. The molecule under consideration, 4-(4-methoxyphenyl)-4-oxobutanoic acid, is distinguished from fenbufen by the absence of the biphenyl moiety. This characteristic results in the generation of nontoxic metabolites during biotransformation. The incorporation of aromatic amino acid residues (phenylalanine and tyrosine) led to the modulation of the hybrid NSAID-amino acid and NSAID-peptide derivatives, thereby altering their biological activity and safety profile. The inhibitory activity against the dual cyclooxygenase-2/5-lipoxygenase system was evaluated using molecular docking, free energy calculations, and per-residue decomposition analysis based on molecular dynamics simulations. Compounds containing a tyrosine residue or the Tyr-Phe dipeptide exhibited strong drug-receptor binding affinities and long-term stability during our simulations, in some cases outperforming the reference drugs celecoxib and zileuton. The values of the free energy (ΔG) obtained through the Boltzmann equation demonstrated a strong correlation with the energy decomposition data, particularly for the lead compounds, which exhibited stabilizing interactions with the heme prosthetic group and the Fe²⁺ ion. These findings provide substantial support for the identification of these molecules as promising candidates for further preclinical development.

We herein report the direct fluoroformylation of indoles and other heteroaromatic cycles. Acyl fluorides are very useful moieties in coupling reactions with or without metal. However, they are usually obtained from the corresponding carboxylic acids or from aryl halides in pallado-catalyzed carbonylation/fluorination reactions. Our method uses fluorophosgene generated in situ from 2,4-dinitro(trifluoromethoxy)benzene (DNTFB) as a fluoroformylating agent without any metal and from carboxylic acid-free heteroaromatic rings. Moreover, our method can be telescoped with amidification reactions in a one-pot process.

Our recently proposed Electronically Confined Space Analogy (ECSA) postulate offers a unified framework for interpreting the structure, stability, and photochemical behavior of 18-valence-electron (18-VE) molecules composed of second-row elements. We show that bent triatomic 18-VE isomers, such as ozone, exhibit strong ultraviolet absorption due to delocalized π systems and low-energy electronic transitions, whereas their cyclic counterparts are photochemically inert. Bent structures are consistently more stable than cyclic analogs, with stability governed by electronic polarization and symmetry rather than electronegativity. This thermodynamic preference ensures the dominance of UV-absorbing species under atmospheric conditions. Applying ECSA provides a molecular-level explanation for ozone's unique role as Earth's stratospheric UV filter, complementing and extending the traditional Chapman mechanism. We further propose a UV-driven ozone cycle that incorporates excited states and intermediates, offering an improved description of ozone photophysics and atmospheric resilience.