Journal of Chemical Sciences最新文献

Peptide self-assembly continuously manifests the transcendence of supramolecular chemistry into bioinspired functional materials. In a pioneering discovery, researchers unveil how a tripeptide, YYY (Y = tyrosine), with water as co-architect, self-assembles into a transparent, rigid, amorphous ‘peptide glass’. The glass thus obtained offers optical clarity, strong adhesion, humidity-responsive flexibility, and rapid self-healing through reversible hydrogen bonding. This discovery blurs the boundary between the living and the synthetic, exemplifying the formation of glass-like materials grown in water, rather than forged in fire, utilizing elementary biomolecules, heralding to a future of self-healing, recyclable and sustainable designs.

Graphical abstract

A minimal tripeptide, YYY, forms a transparent, rigid, amorphous peptide glass. This bioinspired condensed-phase material exhibits optical clarity, strong adhesion, humidity-responsive flexibility, and rapid self-healing driven by reversible hydrogen bonding, demonstrating how simple biomolecules can form glass-like materials in water and redefine sustainable, recyclable soft matter.

Actinide elements pose a two-fold risk once they enter the human body. On the one hand, the major risk is due to their nuclear radiation, and on the other hand, it is a consequence of their heavy metal toxicity. Irrespective of the intake pathway, i.e., inhalation, ingestion, or cutaneous absorption, actinides are resorbed and transported by the bloodstream prior to deposition in target organs or tissues. The actinides exhibit long biological lifetimes of 20–50 years and are excreted at slower rates. They link with different biological ligands (proteins, free amino acids, etc.) and mimic natural biological elements (iron, calcium etc.), although the phenomenon remains largely unexplored in the research community. Actinide interaction and transport within the body are important to study for a better understanding of the mechanisms controlling their specific target deposition and the toxic effects. The present report reviews the major studies carried out in the field of actinide interaction and speciation with biomolecules. It summarizes the actinide behaviour within biological fluids and with serum proteins viz. human serum albumin and serum transferrin. The report also gives a brief description of various tools and techniques used for studying actinide interaction with biomolecules, with special emphasis on computational tools.

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This review highlights interactions of actinides with biomolecules in body fluids. Computational tools, namely, MD, QM/MM, enhanced sampling methods, and DFT provide atomic-level insights into binding, speciation, and conformational changes of serum protein. Integrating simulations with experiments advances the understanding of actinide biochemistry and guides design of effective decorporation strategies.

This study explores the adsorptive removal of Ni (II) ions using laboratory–synthesized graphene oxide (GO), thoroughly characterizing the adsorbent before and after adsorption. The impact of key operational variables, including initial Ni (II) concentration, solution pH, adsorbent dosage, contact time, and temperature, is systematically analysed. Experimental data indicate that the pseudo-second-order kinetic model (R² > 0.99) and the Langmuir isotherm model (R² > 0.98) best describe the adsorption process, with GO achieving a maximum adsorption capacity of 32.95 mg/g at pH 6.5 and 318 K. Further mathematical analysis determines the effective diffusivity (5 × 10^–16 m²/s) and external mass transfer coefficient (8.583 × 10^–11 m/s) for an initial Ni (II) concentration of 50 mg/L. Fourier transform infrared spectroscopy (FTIR) and NaNO₃ interference studies highlight the role of electrostatic interactions, with C=O and O–H functional groups serving as active adsorption sites. Thermodynamic analysis confirms that the adsorption process is endothermic (ΔH = 14.88 kJ/mol) and spontaneous (ΔG = –3.88 kJ/mol at 318 K). Moreover, density functional theory (DFT) calculations justify that Ni (II) ions preferentially bind to oxygen-containing functional groups on GO. Reusability studies reveal a 22.89% decrease in adsorption capacity after five successive adsorption–desorption cycles, underscoring the material’s potential for practical wastewater treatment applications.

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Synopsis Being synthesized using Tours’ method, Graphene oxide (GO) is used as an adsorbent for the removal of Ni (II) from aqueous solutions. Oxygenated functional groups on the GO surface are primarily responsible for Ni (II) adsorption.

Zinc aluminate (ZnAl₂O₄) is projected as a versatile compound with excellent thermal and chemical stability, which makes it a suitable material in various applications. Motivated by recent experimental observation that doping of Er into ZnAl₂O₄ makes it as a potential phosphor material for bio-imaging, I have investigated the role of Er doping using density functional theory as a tool. I have also investigated the effect of doping with Er into ZnAl₂O₄, aiming to improve its optical behavior to a greater extent. In contrast to the experimental study, the present study revealed that doping of Er is thermodynamically feasible in both the Al and Zn sites, with Al site energetically more favorable. Electronic structure investigation indicates that the presence of Er(4f) impurity states in the band gap region is mainly responsible for the improvement of optical properties of ZnAl₂O₄. Thus, the present study provides valuable insight for further improvement of the luminescence behavior of these types of materials.

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The present study revealed that doping of Er is thermodynamically feasible in both the Al and Zn sites, with Al site energetically more favorable. Electronic structure investigation indicates that the presence of Er(4f) impurity states in the midgap region is mainly responsible for the improvement of optical properties of ZnAl₂O₄.

In this study, we investigate the encapsulation mechanism of small alkane molecules, cyclo-pentane and neo-pentane, within the supramolecular host cucurbit-[6]-uril. Using a combination of computational methodologies, including molecular docking, molecular dynamics simulations, and well-tempered metadynamics, we evaluated structures and computed the energetic barrier associated with the encapsulation/decapsulation processes. Our findings indicate that the guest binding at the cavity requires prior removal of water molecules, leading to high energetic barriers. Nevertheless, the hydrophobic nature of the ligand stabilizes the encapsulated state significantly, making the binding feasible at the cavity. The free energy surface reveals that neo-pentane experiences a slightly higher energy barrier to exit the cucurbit-[6]-uril cavity compared to cyclo-pentane, possibly due to the higher molecular volume causing greater hindrance at the portal.

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The encapsulation mechanism of cyclo-pentane and neo-pentane to cucurbit-[6]-uril is investigated. The desolvation of bound water molecules inside the host drives the guest encapsulation, followed by hydrophobic stabilization. Within the two pentane isomers, neopentane shows a higher exit barrier to cyclo-pentane, in line with the experimental binding trends.

This study presents the development of a highly efficient magnetic nanocatalyst made of Cu₂O-CuO nanoparticles (NPs) supported on silica-coated iron oxide nanoparticles (Cu₂O-CuO@Fe₃O₄-SiO₂-imine nanostructure). SiO₂ was employed to stabilize Fe₃O₄ by preventing aggregation and offering the potential for surface functionalization to immobilize catalysts. The grafting of imine over Fe₃O₄-SiO₂ reduces the leaching of Cu₂O-CuO NPs. The catalyst's composition and structure were confirmed using various techniques, such as FT-IR, SEM-EDX, elemental mapping, HR-TEM, PXRD, XPS, ICP-AES, TGA-DTA, and VSM. The potentiality of the as-prepared catalyst was examined in synthesizing quinazolinone scaffolds via a reaction between 2-amino benzonitrile and various alcohol substrates. It was observed that 2-aminobenzonitrile with electron-donating groups afforded isolated yields of the desired products ranging from 92 to 94% and was found to be recyclable up to five cycles without apparent loss in activity.

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Silica-coated iron oxide supported Cu2O-CuO heteronanostructure is an efficient magnetic catalyst for the facile synthesis of quinazolinone scaffolds via a reaction between 2-amino benzonitrile and alcohol substrates. It can be recycled up to 5 cycles without apparent loss in catalytic activity.

Ionic liquids (ILs) have garnered significant attention in CO₂ capture and separation due to their tunable physicochemical properties, enabling precise control over CO₂ affinity. While previous studies emphasize the critical role of anions, particularly fluorinated species, for enhancing CO₂ solubility and selectivity, the influence of cationic structure remains largely unexplored. In this work, we investigate the effect of different cations on CO₂ capture efficiency by impregnating ILs into a robust metal-organic framework (MOF). UiO-66, with its strong Zr–O coordination, provides exceptional structural stability, making it an ideal host for IL incorporation. We selected butyl(triethyl)azanium ([N₂₂₂₄]⁺), 1-butyl-3-methylimidazolium ([BMIM]⁺), and butylpyridinium ([BuPy]⁺) cations, all paired with a common tetrafluoroborate (BF₄⁻) anion, to systematically assess cation effect. The ILs were confined within the octahedral pores of UiO-66, and their gas adsorption performance for CO₂, CH₄, and N₂ was evaluated using the grand canonical Monte Carlo (GCMC) simulations. It is interesting to note that aromatic cation enhances the CO₂ selectivity when compared to the aliphatic cation. This is due to the steric hindrance arisen from the aliphatic cation of IL. This study provides critical insights into cation-dependent CO₂ capture mechanisms, establishing key design criteria for optimizing IL@MOF composites in gas separation technologies.

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[2,1]-Azaboranaphthalenes belong to an important class of compounds that display enhanced therapeutic activities courtesy of their unique boron–nitrogen (BN) bonds which are an isostere of naphthalene-based systems. Recently, Ravindra and co-workers¹ reported a three-component synthesis of ring fused BN-isosteres with BN-2,1-azaboranaphthalenes that subsequently undergoes a ring expansion of unstrained cyclic ketones via a Wolff-type rearrangement. This commentary emphasizes the efficient and scalable preparation of these potentially high value azaborine analogues.

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The boron-nitrogen (BN) isosteres, including BN-azaboranaphthalenes, represent an important class of compounds due to their enhanced therapeutic potential; however, their synthesis often demands harsh reaction conditions. In this news story, we highlight recent work by Ravindra and co-workers demonstrating the facile one-pot synthesis of azaborine congeners via a Wolff-type rearrangement.