The liquid-phase method is the most commonly utilized strategy for synthesizing fluorescent carbon quantum dots (CQDs). However, the liquid-phase synthesis of CQDs faces challenges such as low yield, complex purification, and the use of toxic solvents, which limit large-scale production and practical applications. In this study, fluorescent CQDs with a high product yield of 78% were synthesized using glucose as a carbon source through a green and facile one-step solid-phase approach, without solvents or post-treatment. A systematic study of the structure and fluorescence properties of the synthesized CQDs was conducted using various characterization techniques. The results indicated that the mean size of obtained CQDs was 4.1 nm, and that their surface had abundant oxygen-containing functional groups, resulting in favorable water solubility. The synthesized CQDs exhibited excitation-dependent fluorescence, with optimal excitation and emission wavelengths at 358 and 455 nm, respectively. Additionally, the CQDs solution showed bright blue fluorescence under 365 nm UV light, with a quantum yield of 6.21% and a fluorescence lifetime of 3.02 ns. This study offers valuable insights into the green and efficient synthesis of fluorescent CQDs powder.
Photocatalytic NO removal is usually accompanied by the generation of NO2, an intermediate with a higher toxicity than NO. Therefore, it is critically important to develop new photocatalysts capable of NO selective conversion. Herein, we report on the synergistic roles of cyano and hydroxyl functional groups in photocatalytic NO removal. According to the results, the NO2 production efficiencies on cyano/hydroxyl-group-modified g-C3N4 (DCN-O-R) was limited to 4.8%, which was lower than that of cyano-group-modified g-C3N4 (DCN, 38.6%) and pure g-C3N4 (CN, 50.0%). Meanwhile, the photocatalytic NO conversion efficiency over DCN-O-R was higher than that of DCN and g-C3N4. It was found that the insertion of cyano groups favorably changes the energy band of g-C3N4 towards the generation of •O2−. NO can only be oxidized to NO2 by the photogenerated holes. When NO2 is adsorbed on the surface of hydroxyl groups, it can be further oxidized to the product NO3− by •O2−. The synergistic effect of bifunctional groups regulates the conversion pathway from NO→NO2 to NO→NO2→NO3−. This work provides a strategy to abate toxic intermediates during the NO removal process, underlining the importance of surface/interface molecular engineering in regulating catalytic reaction pathways.
A novel (E)-1-(4-methylbenzylidene)-4-(3-isopropylphenyl) thiosemicarbazone was synthesized in a one-pot four-step synthetic route. Fourier transform infrared spectroscopy (FTIR), 1H and 13C nuclear magnetic resonances (NMR), single-crystal X-ray diffraction, and UV-visible absorption spectroscopy were utilized to confirm the successful preparation of the title compound. Single-crystal data indicated that the intramolecular hydrogen bond N(3)-H(3)···N(1) and intermolecular hydrogen bond N(2)-H(2)···S(1) (1 − x, 1 − y, 1 − z) existed in the crystal structure and packing of the title compound. Besides the covalent interaction, the non-covalent weak intramolecular hydrogen bond N(3)-H(3)···N(1) discussed by atoms in molecules (AIM) theory also functioned in maintaining the title compound’s crystal structure. The strong intermolecular hydrogen bond N(2)-H(2)···S(1) (1 − x, 1 − y, 1 − z) discussed by Hirshfeld surface analysis played a major role in maintaining the title compound’s crystal packing. The local maximum and minimum electrostatic potential of the title compound was predicted by electrostatic potential (ESP) analysis. The UV-visible spectra and HOMO-LUMO analysis revealed that the title compound has a low ΔEHOMO–LUMO energy gap (3.86 eV), which implied its high chemical reactivity due to the easy occurrence of charge transfer interactions within the molecule. Molecular docking and in vitro antifungal assays evidenced that its antifungal activity is comparable to the reported pyrimethanil, indicating its usage as a potential candidate for future antifungal drugs.
Achieving superior circularly polarized luminescence brightness (BCPL) is an important subject and continuous challenge for chiroptical materials. Herein, by applying a binary molecular design for the synthesis of chiral organo-Tb3+ molecules, a novel pair of mononuclear chiral tris-pyrazolate-Tb3+ enantiomers, [Tb(PMIP)3(R,R-Ph-PyBox)] (2) and [Tb(PMIP)3(S,S-Ph-PyBox)] (5), have been synthesized and characterized. The three 1-phenyl-3-methyl-4-(isobutyryl)-5-pyrazolone (HPMIP) ligands play the role of efficient luminescence sensitizers and strong light-harvesting antennas, while the enantiopure 2,6-bis(4-phenyl-2-oxazolin-2-yl) pyridine ligand (R,R/S,S-Ph-PyBox) is employed as the strong point-chiral inducer. With the proper combination of the HPMIP and Chiral-Ph-PyBox within the Tb3+ enantiomers, strong (PMIP)−-centered π-π* electronic absorption (ε263 nm = 38,400–39,500 M−1 cm−1) and brilliant high-purity ligand-sensitized Tb3+-centered green luminescence (ΦPL = 47–48%) were observed. In addition, a clear circularly polarized luminescence (CPL) activity (|glum| = 0.096–0.103) was also observed, resulting in a strong BCPL (610–623 M−1 cm−1) for the two Tb3+ enantiomers from the hypersensitive transitions. Our results offer an effective path to develop high-performance chiroptical organo-Tb3+ luminophores.
Breast cancer remains the most common and leading cause of cancer deaths among women worldwide. The efficacy of conventional therapies is often hampered by off-target effects and multidrug resistance. Phototherapy, encompassing photodynamic therapy (PDT) and photothermal therapy (PTT), has gained significant attention due to its non-invasiveness, high spatiotemporal selectivity, and minimal side effects. However, its application is hindered by several obstacles, including the tumor hypoxic microenvironment, insufficient light penetration depth, and acquired heat resistance. Metal–organic frameworks (MOFs) have adjustable structures, enormous specific surfaces, and facile functionalization, providing an ideal platform to overcome these limitations. This review summarizes the latest research progress in the application of MOFs for precision phototherapy in breast cancer treatment. It emphasizes their role as a direct photosensitizer (PS), photothermal agent (PTA), or multifunctional nanocarrier for PDT, PTT, and synergistic phototherapy (including PDT/PTT, chemo/phototherapy, and immunotherapy/phototherapy). The design strategy and therapeutic effect of MOFs for phototherapy of breast cancer are critically discussed. In addition, the current bottlenecks and future perspectives are outlined to facilitate the clinical translation of MOF-based breast cancer treatment platforms.
Water-soluble alanine-functionalized perylene diimide derivatives (PDI-Ala) were synthesized by introducing alanine units at the imide positions of the PDI framework. Their photoluminescence properties and supramolecular aggregation behavior were investigated in solvents of varying polarity. Chiral L-PDI-Ala displayed distinct solvent-dependent emission colors and intensities, whereas the achiral PDI-Ala showed negligible emission under the same conditions. Poor solvents such as acetone and ethyl acetate promoted relatively efficient emission with hypsochromically shifted bands, while good solvents such as N, N-dimethylformamide and dimethyl sulfoxide induced bathochromically shifted emission with much lower quantum yields. The results indicate that strong face-to-face π-π stacking in the solid-state leads to aggregation-caused quenching (ACQ), whereas ordered aggregates formed by intermolecular forces such as hydrogen bonds or stacking in solution can recover luminescence. On the basis of the spectroscopic and structural results, a solvent-regulated emission mechanism involving excimer/exciplex formation together with H-type and J-type aggregation is proposed. This work provides useful insight into the aggregation-controlled optical behavior of chiral amino-acid-modified PDI materials and offers guidance for the design of chiroptical and self-assembled luminescent systems.