<p>The use of natural plant extracts as multifunctional reducing and stabilizing agents provides a sustainable alternative to conventional chemical routes for metal–organic framework (MOF) synthesis. Herein, we report the first green synthesis of mesoporous Ag@ZIF-67, AgZn@ZIF-67, and Zn@ZIF-67 using aqueous tuber and leaf extracts of <i>Crinum wattii</i> as dual bio-reducing and capping agents. The green-synthesized samples were systematically compared with the composite prepared via a conventional NaBH<sub>4</sub> reduction route. Comprehensive analyses (XRD, XPS, FT-IR, SEM, TEM, and N<sub>2</sub> adsorption–desorption) confirmed that the <i>C. wattii</i>-mediated synthesis produced highly crystalline ZIF-67 frameworks with uniformly dispersed Ag nanoparticles (&lt; 5&#xa0;nm) and enhanced mesoporosity, exhibiting BET surface area in the range of 820–1170 m<sup>2</sup>/g. Interestingly, the plant extract selectively reduced Ag<sup>+</sup> to Ag<sup>0</sup> while Zn<sup>2+</sup> remained unreacted, suggesting a distinct phyto-reduction selectivity corresponding to metal reduction potential. In contrast, NaBH<sub>4</sub>-reduced samples exhibited significant Ag aggregation (particle size &gt; 5&#xa0;nm) and lower surface areas (350–440 m<sup>2</sup>/g). The leaf-extract-mediated nanocomposite (Ag<sub>1.0</sub>@ZIF-67-L) demonstrated remarkable antibacterial activity against <i>Staphylococcus epidermidis</i>, <i>Bacillus subtilis</i>, and <i>Escherichia coli</i> with MIC/MBC values of 2/8&#xa0;mg/mL and inhibition zone diameters of 13–24&#xa0;mm, along with potent antifungal effects against <i>Diaporthe phaseolorum</i>, <i>Schizophyllum commune</i>, and <i>Alternaria alternate</i>, producing inhibition zones of 29–33&#xa0;mm, comparable to ketoconazole. The correlation between phyto-induced mesoporosity, selective metal reduction, and increased bioactivity offers new insight into plant-mediated MOF engineering. This study highlights a bio-inspired and eco-friendly route for synthesizing Ag@ZIF-67, AgZn@ZIF-67, and Zn@ZIF-67 nanomaterials with enhanced nanostructural control and antimicrobial performance, offering potential for biomedical coatings and infection-resistant materials.</p> Graphical Abstract <p></p>

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Phyto-Mediated Synthesis of Ag-, Zn-, and AgZn-Decorated ZIF-67 Using Crinum wattii Extract for Antimicrobial Applications

  • Piaw Phatai,
  • Jiyapa Sripirom,
  • Anong Promsorn,
  • Orrasa Prasitnok,
  • Pongtanawat Khemthong,
  • Saran Youngjan,
  • Teera Butburee,
  • Cybelle Morales Futalan,
  • Agarat Kamcharoen,
  • Sirilak Kamonwannasit

摘要

The use of natural plant extracts as multifunctional reducing and stabilizing agents provides a sustainable alternative to conventional chemical routes for metal–organic framework (MOF) synthesis. Herein, we report the first green synthesis of mesoporous Ag@ZIF-67, AgZn@ZIF-67, and Zn@ZIF-67 using aqueous tuber and leaf extracts of Crinum wattii as dual bio-reducing and capping agents. The green-synthesized samples were systematically compared with the composite prepared via a conventional NaBH4 reduction route. Comprehensive analyses (XRD, XPS, FT-IR, SEM, TEM, and N2 adsorption–desorption) confirmed that the C. wattii-mediated synthesis produced highly crystalline ZIF-67 frameworks with uniformly dispersed Ag nanoparticles (< 5 nm) and enhanced mesoporosity, exhibiting BET surface area in the range of 820–1170 m2/g. Interestingly, the plant extract selectively reduced Ag+ to Ag0 while Zn2+ remained unreacted, suggesting a distinct phyto-reduction selectivity corresponding to metal reduction potential. In contrast, NaBH4-reduced samples exhibited significant Ag aggregation (particle size > 5 nm) and lower surface areas (350–440 m2/g). The leaf-extract-mediated nanocomposite (Ag1.0@ZIF-67-L) demonstrated remarkable antibacterial activity against Staphylococcus epidermidis, Bacillus subtilis, and Escherichia coli with MIC/MBC values of 2/8 mg/mL and inhibition zone diameters of 13–24 mm, along with potent antifungal effects against Diaporthe phaseolorum, Schizophyllum commune, and Alternaria alternate, producing inhibition zones of 29–33 mm, comparable to ketoconazole. The correlation between phyto-induced mesoporosity, selective metal reduction, and increased bioactivity offers new insight into plant-mediated MOF engineering. This study highlights a bio-inspired and eco-friendly route for synthesizing Ag@ZIF-67, AgZn@ZIF-67, and Zn@ZIF-67 nanomaterials with enhanced nanostructural control and antimicrobial performance, offering potential for biomedical coatings and infection-resistant materials.

Graphical Abstract