New Journal of Chemistry最新文献

Lithium-ion batteries (LIBs) are among the most widely used power storage technologies today, yet challenges such as the development of efficient anode materials persist. To address this, researchers continue to explore novel anode candidates. In this work, we investigate RuClF/AlN van der Waals heterostructures as a potential LIB anode material using density functional theory. Two distinct stacking configurations, FRuCl/AlN and ClRuF/AlN heterostructures, are examined. Their structural and dynamical stability is confirmed through binding energy and phonon calculations. Results reveal that the most favourable stacking exhibits exceptional lithium adsorption properties, suggesting promising applicability in high-performance LIB anodes. Furthermore, the measured diffusion barrier was as low as 0.33 eV, highlighting their significance in facilitating rapid ion mobility. The open circuit voltage and theoretical capacity of 0.78 V and 564.29 mAh g⁻¹, respectively, indicate that this heterostructure holds significant promise as a competitive high-capacity anode material.

Photocatalytic preferential dechlorination of high-environmental-risk 2-chlorophenol (2-CP) is highly desired. Although Bi₂O₃ has previously displayed a preferential dechlorination pathway of 2-CP, the phase-effect of Bi₂O₃ remains ambiguous. Here, one dimensional (1D) α- and β-Bi₂O₃ photocatalysts were prepared by using bismuth metal organic framework (CAU-17) microrods as the template, of which β-Bi₂O₃ microrods were obtained via a bicarbonate-induced transformation route and α-Bi₂O₃ microrods were prepared through a direct pyrolysis route. Multi-pronged characterization confirmed that β-Bi₂O₃ microrods have a larger surface area and a narrower band gap compared with α-Bi₂O₃ microrods. As expected, β-Bi₂O₃ microrods showed a 2-fold higher photocatalytic activity for degrading 2-CP under white-light LED irradiation, with higher mineralization than α-Bi₂O₃ microrods. According to liquid chromatography tandem mass spectrometry, radical trapping experiments and ion chromatography, both α-Bi₂O₃ and β-Bi₂O₃ displayed a hole-induced photocatalytic preferential dechlorination of 2-CP, resulting in the conversion of chlorine into chloride ions.

Proteins maintain a dynamic 3D structure essential for homeostasis, which is largely governed by non-covalent interactions that are sensitive to physicochemical changes. Metal nanoparticles, used for biological applications because of their unique properties in the biological milieu, adsorb proteins to form protein coronas, disrupting the intramolecular interactions governing the protein's native structure and functions. Understanding these changes is crucial for sustainable nanoparticle-based biological applications. Along this line, herein, lysozyme-zinc oxide nanoparticle (ZnONP) interactions at pH 7.4 and 9 and their effects on protein conformations are explored. Lysozymes with different molecular interacting interfaces interacted differently with the same ZnONP interface at these pH values. The native conformation of lysozyme, characterized by a melting temperature of 345.2 K, upon entropically driven interaction with the NP surface, adapted a partially unfolded conformation with a melting temperature of 343.9 K and reduced protein-mediated antibacterial activity. The partially unfolded lysozyme at pH 9 upon enthalpically driven interaction with the NP surface adapted a native-like rigid conformation and exhibited a melting temperature of 345 K, which is comparable to that of the native protein.

Herein, we propose a paper-based colorimetric biosensor as an analytical device for glucose sensing (g-PAD), which is fabricated via a two-step process consisting of the inkjet printing of a barrier of carbon onto a filter paper to form a working zone for the g-PAD and the immobilization of reagents, including ferric hydroxide/nitrogen-doped graphene quantum dots (FN-GQDs) as a peroxidase nanozyme, 3,3′,5,5′-tetramethylbenzidine (TMB) as a cosubstrate color indicator and glucose oxidase (GOx) as a capture probe, onto the working zone of the g-PAD by drop-casting. Glucose sensing is conducted by adding a drop of an analyte sample onto the working zone. In this proposed g-PAD, the GOx will oxidise glucose into gluconic acid and hydrogen peroxide (H₂O₂), and then, the FN-GQDs, as a peroxidase nanozyme, will catalyse the reaction of H₂O₂ and TMB, which will convert the reduced TMB state (TMB_red) to the oxidized TMB state (TMB_ox), appearing as a color change from colorless to blue in the working zone. The blue intensity reflects the concentration of glucose in the sample, which can be recognized directly by the naked eye or by measuring the gray intensity (GI). The developed g-PAD biosensor can detect glucose in a linear range from 0.025 mM to 0.5 mM, with a limit of detection of 18.75 µM. This developed g-PAD has been tested for glucose monitoring in human blood plasma samples with high accuracy.

This work demonstrates a synergistic strategy combining molecular engineering and heterojunction construction to significantly enhance the visible-light photocatalytic performance of perylene diimide (PDI) polymers. Two novel sulfonyl-functionalized PDI polymers, 3,3′-DS-PPDI and 4,4′-DS-PPDI, were designed and synthesized for the first time, with the unmodified biphenyl-linked polymer 4,4′-B-PPDI for comparison. The introduced sulfonyl groups effectively broadened the visible-light absorption and, more importantly, enhanced the molecular dipole moments to facilitate intramolecular charge separation which was demonstrated based on experimental measurements and molecular simulation. In order to combine the strong molecular dipole-induced built-in electric field with an interfacial S-scheme charge transfer mechanism of sulfonyl-functionalized PDI polymers and at the same time adjust their aggregation state, a heterojunction of 3,3′-DS-PPDI with TiO₂ was fabricated. Consequently, this synergy markedly improved charge separation and migration, leading to a visible-light photocatalytic degradation rate constant for Congo red of 0.462 h⁻¹, which was 8.34 and 2.05 times higher than that of the pristine polymer and pure TiO₂, respectively. This study thereby demonstrates a multilevel strategy that spans the molecular and material scales for developing high-performance organic photocatalysts.

With the growing severity of energy and environmental issues, the development of efficient water splitting photocatalysts has emerged as a promising research direction. This work develops Co²⁺-modified Mn_0.5Cd_0.5S solid solutions as an efficient photocatalyst for solar hydrogen production. Through hydrothermal synthesis and room-temperature cobalt deposition, a series of Co²⁺/Mn_0.5Cd_0.5S composites exhibiting volcano-type activity dependence on Co²⁺ loading was engineered. The optimal catalyst achieves a maximum hydrogen evolution rate of 8146.2 µmol g⁻¹ h⁻¹ under visible light, which is 6.9 times that of pristine Mn_0.5Cd_0.5S. Mechanistic studies reveal that surface-anchored cobalt species provide additional active sites for proton reduction. Electrochemical analysis confirms reduction in charge transfer resistance and lower overpotential versus unmodified controls. This work demonstrates transition-metal surface engineering as a scalable strategy for designing high-performance sulfide photocatalysts.

Dichlorvos and Cr(VI) are widespread environmental contaminants that pose significant risks to water quality, ecosystems, and human health. Therefore, the development of rapid, sensitive, and reliable detection methods for these pollutants is critically important. Although various techniques have been employed for the individual detection of these substances, achieving simultaneous and selective detection of both remains a considerable analytical challenge. In this study, iron-doped poly(amidoamine) carbon dots (PAMAM-Fe CDs) were synthesized, exhibiting multiple enzyme-mimetic activities, including peroxidase-, oxidase-, superoxide dismutase-, and catalase-like functions. Notably, dichlorvos and Cr(VI) were found to selectively influence the catalase-like and oxidase-like activities, respectively. Based on these findings, a dual-mode fluorescence and colorimetric sensing platform was developed, enabling rapid, sensitive, and selective detection of dichlorvos and Cr(VI), with detection limits of 1.69 × 10⁻⁵ µg mL⁻¹ and 0.0418 µM, respectively. The applicability of this platform was validated through analysis of real-world samples, demonstrating satisfactory recovery rates and reproducibility. This work not only establishes a new approach for detecting dichlorvos and Cr(VI) for food safety and environmental monitoring but also provides new insights into designing multienzyme-active nanomaterials with significant practical potential.

A convenient and metal-free one-pot sustainable procedure has been devised for the synthesis of fluorescent quinaldic acid derivatives from (Z)-alkyl 2-chloro-4-oxobut-2-enoates and aromatic amines. By employing this strategy, a library of 29 molecules of 2-quinaldic acid derivatives with diverse substitution patterns was created. We have also demonstrated the scope of strategy for the synthesis of heterocycles like oxabicyclo[2.2.1]hept-5-enes, oxazole, and diverse building blocks, including quinoline-2-carbaldehyde, quinoline-2-carbohydrazide, quinoline-2-amides, allylic alcohol, as well as azido aldehyde. Moreover, quinaldic acid derivatives exhibited significant luminescent properties with a quantum yield (Φ_F) up to 33%.

Conventional copper based antifouling coatings suffer from a “burst release” of biocides, which significantly reduces their service life and increases environmental toxicity. Herein, we designed and synthesized an innovative composite antifoulant, Cu₂O@bentonite, through the in situ intercalation of Cu₂O nanoparticles within the lamellar structure of organo-modified bentonite. When integrated into an acrylic self-polishing copolymer, this composite exhibited a novel “ion buffering” mechanism, attributed to the inherent cation exchange capacity of the bentonite matrix, which effectively reduced the initial 24 h burst release by over 76% and promoted a sustained, long-term release profile. This controlled release mechanism enhanced the coating's biocidal efficacy, achieving over 99% effectiveness against marine bacteria and over 90% against algae in laboratory tests. Notably, after 120 days of exposure to real-sea fouling conditions, the coating maintained a clean surface, largely free of macrofouling, thereby demonstrating significantly superior performance compared to traditional Cu₂O-based coatings. Moreover, the integration of the nanocomposite significantly improved the coating's adhesion, hardness, and impact resistance, thereby enhancing its overall durability. This study presents an efficient and reliable methodology for developing advanced biocidal reservoirs, offering a novel and viable strategy for designing high-performance marine antifouling coatings with prolonged service life and a more environmentally benign release profile.

The potential of conjugated oligoelectrolyte (COE) derivatives to mitigate corrosion in mild steel remains unexplored. This paper presents a detailed description of the preparation and characterization of a Schiff base-conjugated oligoelectrolyte (BTC-SBCOE), followed by its investigation as a corrosion inhibitor. The Schiff base (SB) synthesized from benzene-1,3,5-tricarbaldehyde with 4-aminophenol is functionalised with an ionic polar pendant at the terminal oxyl position to afford BTC-SBCOE and is characterized by FTIR, ¹H-NMR, and ¹³C-NMR measurements, as well as mass spectrometry. In acidic media, quaternary ammonium bromide groups improve the stability and effectiveness of BTC-SBCOE by creating a steric-electrostatic barrier. The gravimetric technique, electrochemical impedance spectroscopy, and potentiodynamic polarization are utilized to assess the anticorrosion effectiveness of BTC-SBCOE towards the dissolution of mild steel in 2 M HCl (7.2%) at different concentrations and in the temperature range of 25–80 °C. The gravimetric investigations suggest an inhibition efficiency of 90.38% at 5 mM. Surface examination employing scanning electron microscopy and atomic force microscopy validated the formation of a protective layer on the surface. The thermodynamic analysis results indicate that the binding of BTC-SBCOE is governed by physical and chemical adsorption on the mild steel surface, which prevents corrosion. The overall finding indicates that BTC-SBCOE is a long-lasting and efficient corrosion inhibitor for mild steel in acidic media.