The Royal Society of Chemistry最新文献

Aqueous two-phase system (ATPS) epitomize a remarkable phenomenon where two immiscible phases manifest through the amalgamation of at least two water-soluble components at precise concentrations. Revered as an economically sustainable and environmentally harmonious technique for liquid–liquid separation, this method boasts extensive utility in the isolation and refinement of biomolecules, owing to its innate simplicity, cost-effectiveness, and compatibility with biological systems. The principal aim of this article is to provide a comprehensive overview of the fundamental principles governing phase formation in ATPS. It endeavors to elucidate the influential factors dictating this phenomenon and expound upon the construction of phase diagrams, which serve as pivotal tools in comprehending and manipulating ATPS behavior. Furthermore, the article delves into the diverse domains that reap benefits from ATPS applications. These encompass, yet transcend, the extraction of metal ions, elimination of pharmaceutical residues, environmental restoration, strides in biomedical sciences, and the recovery of dyes. In this pursuit, it strives to illuminate the manifold strengths and limitations of ATPS, offering a holistic understanding of its potential and existing challenges.

As the demand for efficient and high-performance energy storage devices continues to rise, supercapacitors have emerged as a promising technology due to their rapid charge–discharge capabilities and long cycle life. Among the various strategies to enhance supercapacitor performance, binary and ternary transition metal-based composites have garnered significant attention. These composites offer a unique approach by combining multiple transition metals, which synergistically enhance electrochemical performance through both physical and chemical charge storage mechanisms. This review provides an in-depth analysis of the latest research on binary and ternary transition metal composites, discussing their electrochemical properties, synthesis methods, and performance metrics in supercapacitor applications. The combination of different transition metals in composite materials as energy storage electrodes allows for a broader voltage window, increased energy density, enhanced power density, and improved cycling stability. Additionally, we discuss the structural and morphological features of these composite materials, such as porosity, surface area, and conductivity, which play critical roles in determining overall performance. Furthermore, the review highlights the challenges faced in optimizing these composites, including material scalability, cost-effectiveness, and long-term stability. The paper also outlines future research directions, emphasizing the potential of binary and ternary transition metal-based composites in supercapacitor applications, providing insights into potential avenues for the next generation of high-performance energy storage systems. This review thus provides valuable insights into both the current state and future potential of these composite materials in high-performance supercapacitors.

The site-selective cleavage of peptides and proteins at specific amino acid residues is an important strategy for the modification of biomolecules as it can potentially transmute the reactivity profile of the whole molecule. Moreover, precise cleavage of a specific amide bond in peptides and proteins has enormous applications in the domains of chemical biology, genetics, and protein engineering. Among the 20 proteinogenic amino acids, tryptophan (Trp, W), tyrosine (Tyr, Y), phenylalanine (Phe, F) and histidine (His, H) are classified as aromatic amino acids that maintain the function of protein folding through hydrophobic and π–π interactions. Thus, scissoring at a specific site of an aromatic amino acid may alter the structure and function of a peptide or protein. In the last 60–70 years, great success has been achieved in the development of methods for the aromatic amino acid (AAA)-selective cleavage of peptides and proteins. Generally, aromatic side chains are derivatized in the presence of specific reagents. Consequently, either the downstream or the upstream amide bond of the aromatic side chain is activated, and hydrolysis of the amide bond splits the peptide. Unfortunately, a systematic review covering this methodological development of the AAA-selective fission of peptide is lacking to date. Thus, in this review, we aim to showcase the up-to-date progress in the site-selective rupture of peptide bonds at aromatic amino acid residues with an emphasis on the postulated mechanisms, enabling future researchers to further drive progress in this research field.

Herein, we depict the stability, and bonding studies of bis-(dichloro-aluminium) oxides Cl₂Al–O–AlCl₂ supported by a pair of homo-/hetero-leptic donor base ligands L, L′ [L, L′ = cyclic alkyl(amino) carbene (cAAC^Me; 1); N-heterocyclic carbene (NHC^Me; 2); di-amido carbene (DAC^Me; 3); L = cAAC^Me, L′ = NHC^Me; (4)] with a general formula (L)Al(Cl)₂–O–Al(Cl)₂(L′) (1–4) by NBO, QTAIM and EDA-NOCV analyses. Theoretical calculations suggest that 1–4 possess favorable interaction energies (ΔE_int), and bond dissociation energies between L/L′, and Al(Cl)₂–O–Al(Cl)₂ fragments via the formation of two dative L→Al bonds [1 > 4 > 2 > 3]. This trend is rationalized by the σ-donor ability of the ligands L/L′. Moreover, we depict the first successful solid-state isolation of the colorless compound (cAAC)Al(Cl)₂–O–Al(Cl)₂(cAAC) (1′) by reacting cAAC and AlCl₃ in the presence of a controlled amount of H₂O, where two equiv. of cAAC is being utilized as the base. 1′ has been structurally characterized by single-crystal X-ray diffraction, and further studied by NMR spectroscopy.

Immune checkpoint blockade (ICB) inhibitors have shown great promise for the treatment of numerous types of cancers, including triple-negative breast cancer (TNBC), by interrupting immunosuppressive checkpoints. Herein, programmed cell death ligand 1 (PD-L1) blockade peptide-functionalized NaGdF₄ nanodots (designated as PDL1-NaGdF₄ NDs) were prepared for magnetic resonance imaging (MRI)-guided TNBC immunotherapy through covalent conjugation of the PD-L1 blockade peptide (sequence, CALNNCVRARTR) with tryptone-capped NaGdF₄ NDs (designated as Try-NaGdF₄ NDs). MDA-MB-231 tumor could be easily tracked using in vivo MRI with PDL1-NaGdF₄ ND enhancement because the as-prepared PDL1-NaGdF₄ NDs have a high longitudinal relaxivity (r₁) value (22.8 mM⁻¹ S⁻¹) and accumulate in the tumor site through binding with programmed cell death ligand-1 (PD-L1)-overexpressed cells. A series of in vitro/in vivo results demonstrated that the PDL1-NaGdF₄ NDs could effectively suppress MDA-MB-231 tumor growth in mice (66% volume ratio) by inhibiting migration and proliferation of tumor cells. In addition, the results of pharmacokinetic study showed that the PDL1-NaGdF₄ NDs were excreted from the body through the kidneys. These results highlight the potential of PDL1-NaGdF₄ NDs as a biocompatible nanomedicine for TNBC diagnosis and immunotherapy.

Transition metal sulphides have been widely studied in the field of thermal batteries, but their low decomposition temperature, low conductivity, and discharge capacity are still pressing issues hampering their practical application. Inspired by the strategy of entropy increase in sodium-ion and lithium-ion batteries, herein, we propose an Fe_0.5Co_0.2Ni_0.3S₂ cathode material possessing the advantages of electrochemically active elements Fe, Co, and Ni. Fe_0.5Co_0.2Ni_0.3S₂ exhibited a thermal decomposition temperature of 591 °C, which was significantly higher than that of FeS₂. Furthermore, the wettability of the LiCl–KCl molten salt on the surface of Fe_0.5Co_0.2Ni_0.3S₂ was improved and its contact area was 1.1 times that of FeS₂, providing more active sites for electrochemical reactions and effectively improving the electrochemical performance of the material. Moreover, it exhibited a specific capacity (cutoff voltage ≥1.5 V) of 584 mA h g⁻¹ at 500 °C with a discharge current of 100 mA cm⁻², representing an increase of approximately 96.5% compared to that of CoS₂. Thus, this work presents a new strategy for the design of high-performance cathode materials for thermal batteries.

We experimentally and numerically investigate the aggregation structure of cationic wormlike micelles in the presence of graphene oxide (GO), in connection with the change in the rheological properties of their aqueous dispersion. We first confirm that the macroscopic viscoelastic properties under oscillatory shear vary non-monotonically with the addition of GO flakes. We then carried out three distinct experiments—small-angle X-ray scattering (SAXS) measurements, time-domain nuclear magnetic resonance (TD-NMR) measurements, and molecular dynamics (MD) simulations—to elucidate the structural modifications likely responsible for the rheological changes. The results of the SAXS and TD-NMR measurements suggest that surfactant molecules preferentially remain in a worm-like microparticle form when bonded to the GO surface but not completely covering the GO surface. Moreover, using MD simulations, we confirmed that the attractive interaction between negatively charged functional groups on the GO surface and cationic surfactants indeed leads to adsorption. Together with the results of the rheology measurements, the SAXS, TD-NMR, and MD simulation results suggest that GO flakes tend to form three-dimensional aggregates bridged by the wormlike micelles. Our results can be utilized to control the rheological properties of micellar solutions and provide a new paradigm for designing microscopic structures of GO.

An excessive utilization of tetracycline antibiotics (TCs) in aquaculture and livestock farming significantly threatens human health and the vitality of aquatic environments. In this work, we used a one-pot hydrothermal approach with APT@MIL53-X hybrid material to achieve the selective removal of TC and OTC from agricultural wastewater. APT@MIL53-X showed significant chemical stability in the 3–10 pH range. Analysis of the adsorption results using adsorption kinetics, adsorption isotherm studies and adsorption thermodynamics indicated the presence of a monolayer physicochemical adsorption process with a maximum equilibrium adsorption of 600.43 mg g⁻¹ for TC (removal efficiency of 93.5%) and 537.71 mg g⁻¹ for OTC (removal efficiency of 91.4%). The elimination of TCs was not significantly impacted by the common buffer system of solution or the presence of water. Furthermore, a number of characterization techniques, including FT-IR and XPS, suggested that electrostatic interactions, π–π stacking, and hydrogen were potential adsorption processes. APT@MIL53-X showed stable recycling performance, maintaining a stable adsorption amount and chemical stability after six adsorption–desorption cycles of use, which proved that APT@MIL53-X has application possibilities for the agricultural wastewater treatment process. This study illustrates that APT@MIL53(Fe)-X hybrid material offers a novel method for the selective and effective elimination of agricultural wastewater.

Zerumbone, along with its various derivatives and structurally related compounds, has attracted significant scientific interest due to its broad-spectrum pharmacological properties, particularly its anticancer potential. In this study, novel zerumbone-secondary amide hybrids were successfully designed and synthesized with high yields using both conventional and ultrasonic methods. Reactions performed under ultrasonic conditions required significantly shorter reaction times than those conducted without ultrasound while maintaining comparable product yields. The cytotoxicity of the synthesized derivatives was evaluated against four human cancer cell lines: hepatocellular carcinoma (HepG2), lung carcinoma (A549), acute leukemia (HL-60), and gastric carcinoma (AGS). Most derivatives exhibited significant cytotoxic activity, with those derived from azazerumbone 2 demonstrating greater potency than those derived from azazerumbone 1. The incorporation of secondary amide groups has been confirmed to enhance the cytotoxic activity of the newly synthesized derivatives against cancer cells. Notably, compounds 4c, 4g, and 4i displayed the strongest cytotoxicity across all tested cell lines, with IC₅₀ values ranging from 0.81 ± 0.04 to 4.14 ± 0.44 μg mL⁻¹, comparable to those of zerumbone and ellipticine. Docking studies revealed a strong correlation between the biological activity of zerumbone-secondary amide hybrids and their binding affinity to EGFR tyrosine kinase, further highlighting the crucial role of secondary amide groups in enhancing their anticancer potential. Furthermore, pharmacokinetic predictions indicate that compounds 4c, 4g, and 4i possess favorable drug-like properties, reinforcing their potential as lead candidates for anticancer drug development.

Correction for ‘SERS-assisted characterization of cell biomass from biofilm-forming Acinetobacter baumannii strains using chemometric tools’ by Arslan Yousaf et al., RSC Adv., 2025, 15, 4581–4592, https://doi.org/10.1039/D4RA06267A.