Dipole-like electrostatic asymmetry of gold nanorods

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Dipole-like electrostatic asymmetry of gold nanorods by Ji-Young Kim, Myung-Geun Han, Miao-Bin Lien, Sergei Magonov, Yimei Zhu, Heather George, Theodore B. Norris, and Nicholas A. Kotov Science Volume 4(2):e1700682 February 9, 2018 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 1 Schematic description of possible electrostatic potential in AuNRs. Schematic description of possible electrostatic potential in AuNRs. (A) Typical morphology and surface facets of AuNR grown with CTAB surfactant. The top view shows possible complexity of facets composing ends of AuNR. The colored areas present possible variation of {111} facet area. (B) Expected electrostatic potential at outer surface of CTAB with equal (case 1) and unequal (case 2) capping for two ends. Ji-Young Kim et al. Sci Adv 2018;4:e1700682 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 2 Electrostatic properties of individual AuNRs. Electrostatic properties of individual AuNRs. Phase map (A and C) and profiles (B and D) along the longitudinal axis of the AuNRs supported by silicon grids with (A and B) and without (C and D) CTAB coating. Blue and red curves are extracted from their phase shift maps by EH and HAADF images, respectively. (E) Capacitance gradient (dC/dZ) image and (F) line profiles of individual (dashed) particles and average curve (solid, black) along long axis, obtained by Kelvin probe microscopy. a.u., atomic unit. Ji-Young Kim et al. Sci Adv 2018;4:e1700682 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 3 Noncentrosymmetric distribution of CTAB on AuNR. Noncentrosymmetric distribution of CTAB on AuNR. (A, D, and E) STEM-HAADF and (B, F, and G) SEM images for a same gold NR. (D to G) Atomic resolution images of the side (D and F) and end (E and G) sections of the AuNR. (C) Carbon element map and (H) carbon profile along the white arrow obtained by EF-TEM. Ji-Young Kim et al. Sci Adv 2018;4:e1700682 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 4 Computational analysis of electrostatic properties for AuNRs. Computational analysis of electrostatic properties for AuNRs. (A) Surface charge density of the CTAB layer. (B and D) Electric potential on the surface of gold and CTAB layer, respectively. (C) Electric potential line plot in the CTAB layer and cross-sectional view of electric potential of CTAB-AuNR. (E) Surface charge density on surface of gold. (F) Voltage (orange) and phase shift (violet) slope of AuNRs with various aspect ratios obtained by computation and experimental EH data, respectively. Both values are linearly fitted as dashed lines with R2 value of 0.999 (orange) and 0.971 (violet). Ji-Young Kim et al. Sci Adv 2018;4:e1700682 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

Fig. 5 Asymmetrical optical properties of AuNRs. Asymmetrical optical properties of AuNRs. (A and B) Comparison of simultaneously obtained SHG and FL images of AuNRs. Max intensity projection of same z stacks of SHG (A) and FL (B) with same gray scale. The scale bars represent 1 μm. (C) Histogram of relative intensity of SHG compared to FL from 119 of individual AuNRs. Note that blue-colored bar represents the AuNRs having zero intensity. (D) NPL from AuNRs embedded in PSS (black, decoupled; red, coupled) and PVA (blue) matrix. Ji-Young Kim et al. Sci Adv 2018;4:e1700682 Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).