文献速递 | 青岛科技大学白强/王丽娜/朱之灵/隋凝Angew :石墨炔辅助构建三维结构纳米酶构建及其环境催化

Angew. Chem. Int. Ed. 2025, e202418707. 

第一作者：Yujian Sun

通讯作者：Lina Wang, Qiang Bai, Zhiling Zhu, Ning Sui

通讯单位：青岛科技大学

DOI：10.1002/anie.202418707

这项工作中，我们首次提出了一种利用石墨炔辅助构建具有几何和电子结构纳米酶的通用仿生策略，制备出的G/Cu/GDY三维纳米酶表现出优秀的类漆酶活性，实现了对天然漆酶的仿生模拟。通过紫外光谱实验我们研究了其漆酶活性，这种具有三维结构的 G/Cu/GDY类漆酶纳米酶比活性达到82.53 × 10⁻⁴ U mg^-1，是天然漆酶的4.72倍，证明了构建轴向电子不对称策略在提高纳米类酶活性中的巨大潜力。而密度泛函理论(DFT)计算证明了石墨炔能够调节活性中心与O₂之间的电子排布，改善氧气的吸附和脱附过程并降低反应能垒，从而加快反应速率。此外，本研究实现了真实水中污染物的快速检测，并表现出对微塑料高效降解的巨大潜力。

Figure 1. Synthesis and characterization of G/Cu/GDY nanozyme.  (a) Schematic illustration of the synthesis of G/Cu/GDY and the image of final product.  (b) Transmission electron microscopy (TEM) image of G/Cu/GDY.  (c) High-magnification TEM image of G/Cu/GDY.  (d) High-resolution TEM image (HRTEM) of G/Cu/GDY.  (e) Energy-dispersive X-ray spectroscopy (EDS) elemental spectrum of G/Cu/GDY.  (f) X-ray diffraction (XRD) patterns of G/Cu/GDY and G/Cu.  (g) Raman spectra of G/Cu/GDY and G/Cu.  (h) Particle size distribution of G/Cu/GDY.  (i) X-ray photoelectron spectroscopy (XPS) survey spectra of G/Cu/GDY and G/Cu.  (j) XPS C 1s spectra of G/Cu/GDY and G/Cu.  (k) XPS Cu 2p spectra of G/Cu/GDY and G/Cu.

Figure 2. Construction of LEF in G/Cu/GDY nanozyme.  (a) Schematic diagram of the structure of the G/Cu/GDY nanozyme.  (b, c) Differential charge density maps of G/Cu/GDY from different perspectives.  (d, e) Magnetization versus temperature curves for (d)G/Cu/GDY and (e)G/Cu, fitted according to Curie-Weiss law.  Insets show the electron occupancy of t2g and eg anti-bonding orbitals.  (f) X-ray absorption near-edge structure (XANES) spectra for G/Cu/GDY, G/Cu, CuO, Cu2O, and Cu foil.  (g) Fourier-transform extended X-ray absorption fine structure (FT-EXAFS) spectra for G/Cu/GDY, G/Cu, CuO, Cu2O, and Cu foil.  (h−j) EXAFS quantitative curve fitting analysis for (h) Cu foil, (i) G/Cu, and (j) G/Cu/GDY.  (k−o) Wavelet-transform EXAFS (WT-EXAFS) contour plots for (k) Cu foil, (l) CuO, (m) Cu₂O, (n) G/Cu, and (o) G/Cu/GDY.

Figure 3. Laccase-like activity of G/Cu/GDY nanozyme.  (a) Schematic diagram illustrating the colorimetric reaction mechanism of 2,4-dichlorophenol (2,4-DP) and 4-aminoantipyrine (4-AP).  (b) UV-Vis spectra and color changes of the 4-AP, 2,4-DP, and 4-AP + 2,4-DP + G/Cu/GDY systems.  The appearance of a distinct absorption peak at 510 nm and the color change from colorless to wine-red indicate the laccase-like activity of G/Cu/GDY.  (c) Comparison of laccase-like activity among different materials: G/GDY, G/Cu, Cu/GDY, and G/Cu/GDY.  (d) Effect of varying concentrations of G/Cu/GDY on laccase-like activity.  (e) Effect of varying concentrations of G/Cu on laccase-like activity.  (f) Michaelis-Menten kinetic curves for G/Cu/GDY and G/Cu.  (g) Lineweaver-Burk plots for G/Cu/GDY and G/Cu.  (h) Relative activity comparison of G/Cu/GDY, G/Cu, and natural laccase.  Values represent mean ± standard deviation (S.D.), n = 3.  *P < 0.05, **P < 0.01, ***P < 0.001.

Figure 4. Laccase mimetic mechanism of G/Cu/GDY nanozyme. (a) Schematic illustration of the G/Cu/GDY nanozymes catalyzed reaction process. (b) DMPO/O2•⁻ EPR spectra and (c) DMPO/•OH EPR spectra for the G/Cu/GDY system. The system containing only 2,4-DP and G/Cu/GDY was used as a control, with values reported as mean ± standard deviation, n = 3. (d) Comparison of the adsorption energies of oxygen on G/Cu/GDY, G/Cu/G, and G/Cu. (e) and (f) Differential charge density plots for G/Cu and G/Cu/GDY. (g) PDOS plots for G/Cu/GDY and G/Cu. (h) In situ infrared spectroscopy of G/Cu/GDY. (i) Gibbs free energy diagram of the catalytic processes of G/Cu/GDY and G/Cu nanozymes.

Figure 5. Electrochemical detection of hydroquinone. (a) CV curves of bare GCE, Cu/GDY, G/Cu/GDY, and G/Cu in 5.0 mM [Fe(CN)6]3-/[Fe(CN)6]4- solution containing 0.1 M KCl. (b) CV cyclic curves of G/Cu/GDY at scan rates ranging from 20 to 100 mV s-¹. (c) Impedance plots for different materials. (d) DPV curves for the detection of 20 µM hydroquinone on various modified electrodes in pH 7 PBS buffer. (e) CV curves of the G/Cu/GDY modified electrode in pH 7 PBS buffer containing 20 µM hydroquinone at different scan rates, with the inset showing the linear relationship between the redox peak current and the square root of the scan rate. (f) DPV curves for hydroquinone detection using the G/Cu/GDY modified electrode. (g) Reproducibility of hydroquinone detection with the G/Cu/GDY modified electrode. (h) Selectivity of G/Cu/GDY for hydroquinone, catechol and resorcinol. detection. (i) Stability of G/Cu/GDY. (j) Schematic diagram of practical application detection. (k) Real-time I−t curve for hydroquinone detection. Values represent mean ± standard deviation (S.D.), n = 3. *P < 0.05, **P < 0.01, ***P < 0.001.

Figure 6. Catalytic degradation of microplastics by G/Cu/GDY. Degradation of polyethylene by G/Cu/GDY, G/Cu, and natural laccase under (a) different reaction times and (b) various temperatures and conditions. (c) Total organic carbon (TOC) values in the residual solution at different reaction times. The experiment was repeated three times and the optimal results were taken and displayed in the figure. (d) Gel permeation chromatography (GPC) of polyethylene degradation. (e) Fourier transform infrared (FT-IR) spectra of products after polyethylene degradation at 90 °C, pH 6, 20 hours. (f) Magnified FTIR spectra. (g−i) SEM images of microplastics after reaction times of (g) 2 h, (h) 8 h, and (i) 20 h. (j) Roadmap of the LDPE degradation catalyzed by G/Cu/GDY.