<p>This study presents for the first time a comprehensive study of the mechanisms of interaction <span>L</span>-tryptophan (<span>L</span>-Trp) in aqueous solution with platinum (Pt) and gold nanoparticles (Au NPs) of different shapes based on <sup>1</sup>H NMR, DOSY spectroscopy, T<sub>1</sub> relaxation measurements, and data analysis. This paper introduces criteria for assessing the degree of <span>L</span>-Trp binding to Au NPs, including the probability of <i>π</i>-stacking, such as the multidirectional changes in chemical shift, the slowing of molecular motion, and the contribution of surface-induced relaxation. Based on these criteria, it is shown that the mechanism of interaction between <span>L</span>-Trp and Au NPs is critically dependent on Au NP morphology. The diffusion coefficient data set demonstrates that rod- and star-shaped Au NPs have a significantly stronger effect on translational diffusion than their spherical counterparts, reflecting differences in surface morphology, contact area, and heterogeneity of binding sites (<span>L</span>-Trp: D = (6.50 ± 0.2) × 10⁻<sup>10</sup> m<sup>2</sup>/s, <span>L</span>-Trp + Au RNP: D = (5.50 ± 0.2) × 10 ⁻<sup>10</sup> m<sup>2</sup>/s; <span>L</span>-Trp + Au SNP: D = (5.90 ± 0.20) × 10⁻<sup>10</sup> m<sup>2</sup>/s). The DFT/SAPT analysis complements the experimental <sup>1</sup>H NMR data and supplies an independent structural–energetic justification for our interpretation: in the absence of strong shielding by an organic corona, π‑stacking of the indole ring is the most plausible and energetically favorable adsorption mode of <span>L</span>-Trp on Au NPs.</p>

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Interaction of L-Tryptophan in Aqueous Solutions with Platinum and Gold Nanoparticles of Different Morphologies

  • Galina Kupriyanova,
  • Mark Smirnov,
  • Ivan Mershiev,
  • Aleksandr Zozulya,
  • Andrey Zyubin,
  • Mark Kaplanskiy

摘要

This study presents for the first time a comprehensive study of the mechanisms of interaction L-tryptophan (L-Trp) in aqueous solution with platinum (Pt) and gold nanoparticles (Au NPs) of different shapes based on 1H NMR, DOSY spectroscopy, T1 relaxation measurements, and data analysis. This paper introduces criteria for assessing the degree of L-Trp binding to Au NPs, including the probability of π-stacking, such as the multidirectional changes in chemical shift, the slowing of molecular motion, and the contribution of surface-induced relaxation. Based on these criteria, it is shown that the mechanism of interaction between L-Trp and Au NPs is critically dependent on Au NP morphology. The diffusion coefficient data set demonstrates that rod- and star-shaped Au NPs have a significantly stronger effect on translational diffusion than their spherical counterparts, reflecting differences in surface morphology, contact area, and heterogeneity of binding sites (L-Trp: D = (6.50 ± 0.2) × 10⁻10 m2/s, L-Trp + Au RNP: D = (5.50 ± 0.2) × 10 ⁻10 m2/s; L-Trp + Au SNP: D = (5.90 ± 0.20) × 10⁻10 m2/s). The DFT/SAPT analysis complements the experimental 1H NMR data and supplies an independent structural–energetic justification for our interpretation: in the absence of strong shielding by an organic corona, π‑stacking of the indole ring is the most plausible and energetically favorable adsorption mode of L-Trp on Au NPs.