Supplementary information

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1 Supplementary information Gold Nanoparticle Silica Nanopeapods Vu Thanh Cong, Erdene-Ochir Ganbold, Joyanta K. Saha, Joonkyung Jang, Junhong Min, Jaebum Choo, Sehun Kim, Nam Woong Song, Sang Jun Son, *, Sang Bok Lee, *, and Sang-Woo Joo *, Department of Chemistry, Gachon University, Seongnam, , Korea and Gachon Medical Research Institute, Gil Medical Center, Inchon, 45-76, Korea, Department of Nanomaterials Engineering, Pusan National University, Miryang , Korea, ǂ School of Integrative Engineering, Chung-Ang University, Seoul Korea, Department of Bionano Engineering, Hanyang University, Sa-1-dong 1271, Ansan , South Korea, Molecular-level Interface Research Center and Department of Chemistry, KAIST, Daejeon, 35-71, Korea, Center for Nano-Bio Convergence Research, Korea Research Institute of Standards and Science 29 Gajeong-Ro, Yuseong-Gu, Daejeon 35-34, Korea, Department of Chemistry & Biochemistry, University of Maryland, College Park, Maryland 2742, U.S.A *Corresponding-Author S1

2 Figure S1. The TEM images of the AuNPs and the single-line linear AuNP chains inside 1.7 µm the SNTs. S2

3 (a) (b) (c) Frequency (%) AuNP size (nm) Frequency (%) SNT length (um) Frequency (%) SNT diameter (nm) (d) (e) Frequency (%) Gap Junction (nm) Figure S2. (a) Size distribution of the AuNPs for the 1.7 µm single-line linear AuNP chain SNTPs. Size distributions of (b) lengths and (c) orifice diameters of the singleline linear AuNP chain SNTPs. (d) The histogram of measured nanogap distances between AuNPs. The recorded distances between the AuNPs showed that subnanometer gaps were formed shown in the image. (e) The number distribution of AuNPs inside a single SNT, S3

4 Figure S3. The TEM images of the 1.7 µm double-line linear AuNP chain SNTPs Figure S4. (a) Size distribution of AuNPs for double-line linear AuNP chain SNTPs. (b) Size distributions of orifice diameters of double-line linear AuNP chain SNTP. (c) The histogram of measured nanogap distances between AuNPs inside double-line linear AuNP chain SNTP. The recorded distances between the AuNPs showed the subnanometer gaps, some of which can generate the hot spots. (d) The number of distribution of AuNPs inside a double-line linear AuNP chain SNTPs. The histogram of SNT length is omitted because the same length SNTs as in Fig. S2(b) were used only with a difference of orifice diameters. S4

5 Figure S5. The DFM image of the single-line linear AuNP chain SNTPs. (a) Nanopeapod Mica (b) 1 15 o 9 o 18 o 27 o 36 o Raman Intensity Theta (Degree) S5

6 (c) 8 o 9 o Raman Intensity W a v e n u m b e r ( c m - 1 ) Theta (Degree) Figure S6. (a) Schematic diagram of probing a single SNTP. Raman spectra at different polarization angles for (b) single-line and (c) double-line chain linear AuNP chain SNTP. 3 2 a) um um Figure S7. (a) SERS spectra of single-line 5 nm SNTPs and b) dark-field microscopy image inside the single cell. The arrow indicate the point, where the SERS spectra were obtained. Please note that the bands at 998, 12, and 1575 cm -1, which can be ascribed to the thiophenol peaks were observed inside the cell. (c) TEM image of a single-line SNTP. S6

7 (a) (b) 2 Frequency (%) Frequency (%) Frequency (%) SNT Diameter (nm) SNT Length (nm) Number of AuNPs per SNT Figure S8. (a) The TEM images of 5 nm SNTPs. (b) Size distributions of orifice diameters (left) and lengths (middle) of SNTPs. The number of distribution of the AuNPs in a single SNT (right). S7

8 25 2 ph ph ph 6.5 ph 7.4 ph 7.2 ph 6.5 ph 6.2 Figure S9. Infrared spectra of p-mba-coated AuNPs after coating with serum proteins ph 7.4 ph 7.2 ph 6.5 Figure S9. SERS spectra of p-mba-coated AuNP-embedded SNTPs in a single A549 mammalian cell and the corresponding DFM image after the uptake of SNTPs. S8

9 ν as (COO - ) Absorbance (Arbitr. Unit) ν s (COO - ) ν (C=O ) Amide I Amide II p-mba-aunps p-mba-aunps RPMI (1% FBS) RPMI (1% FBS) W avenumber (cm -1 ) Figure S1. Infrared spectra of p-mba-coated AuNPs after coating with serum proteins. Figure S11. Confocal image of (a) AuNPs in K562 cells and (b) SNTP encapsulated A549 cells by staining the lysomal marker of DND 16. The blue arrow indicates the AuNPs and SNTPs without endosomal encapsulation. S9

10 4 3 2 a) Double Line SNTPs (5 nm Length) Double Line SNTPs (1.7 µm Length) 5 b) AuNPs without Silica Nanotube Encapsulation c) Double Line SNTP (1.7 um) Double Line SNTP (5 nm) AuNP Aggregates Individual SNTP or AuNP aggregate Sample Figure S12. SERS spectra of 2 different (a) 5 nm, (b) 1.7 µm length double-line SNTPs, and (c) AuNP aggregates without silica encapsulation. (d) Plot of normalized SERS intensites The spectral intensity gave relatively uniform intensities. The SERS intensities of SNTPs and AuNP aggregates were normalized with respect to those showing the strongest signals. We selected 2 SNTPs (or AuNPs) among the 23 spots. Normalized SERS intensity 1. d) S1

11 1. 46 % Normalized Raman Intensity % 1 %. SNTPs (1.7 µm) SNTPs (5 nm) AuNP Aggregates Figure S13. Stick diagram of SERS intensities for 1.7 µm SNTP, 5 nm SNTP, and AuNP aggregates without any encapsulation. The intensities are normalized with respect to one of the highest peaks of the double-line SNTPs. The standard deviations of the SERS intensities from 2 samples were measured as 15 %, 1 %, and 46 %, respectively. Please note that we used the 5 nm SNTPs for the intracellular ph measurements in the presented work. Figure S14. Stick diagram of additional nanogap measurements of (a) 1.7 µm and (b) 5 nm SNTPs used for the examination of the reproducibility shown in Figure S1 and S2. S11

12 a) [K + ] = 1mM ph 1 ph 7 ph b) [K + ] = 1mM ph 1 ph 7 ph B 15 5 c) [K + ] = 1mM ph 1 ph 7 ph 4 I( 1423) /I( 159) d) No treatment K+ (1mM) K+ (1mM) K+ (1mM) ph 4 ph 7 ph 1 Figure S15. SERS spectra of double line 5 nm SNTPs in the presence of (a) 1 mm, (b) 1 mm, and (c) 1 mm K + ions at ph values of 4, 7, and 1. (d) The intensity ratios of the SERS band at 1423 cm -1 with respect to those at 159 cm -1. The ratios with 159 cm -1 were not changed significantly those with 176 cm -1. Three independent measurements were performed to yield the standard deviations. The variations were within the standard errors. Please note that the ph dependent SERS behaviors did not change significantly in the presence of K + ions in the concentration range between 1-1 mm. S12

13 15 5 a) [Na + ] = 1mM ph 1 ph 7 ph 4 15 [Na + ] = 1mM b) 5 ph 1 ph 7 ph c) [Na + ] = 1mM ph 1 ph 7 ph 4 I( 1423) /I( 159).25 d) No treatment Na+ (1mM) Na+ (1mM) Na+ (1mM) ph 4 ph 7 ph 1 Figure S16. SERS spectra of double line 5 nm SNTPs in the presence of (a) 1 mm, (b) 1 mm, and (c) 1 mm Na + ions at ph values of 4, 7, and 1. (d) The intensity ratios of the SERS band at 1423 cm -1 with respect to those at 159 cm -1. Three independent measurements were performed to yield the standard deviations. The variations were within the standard errors. Please note that the ph dependent SERS behaviors did not change significantly in the presence of Na + ions in the concentration range between 1-1 mm. S13

14 Figure S17. (a)-(d) Confocal fluorescence microscope images of SNTP encapsulated A549 cells by staining the lysosomal marker of DND 16 obtained by a Leica 71 microscope with 45 nm excitation and nm emission filter. We observed the fluorescence intensities considerably decreased within a few miniatures. S14

15 Figure S18. Confocal fluorescence microscope images of SNTP encapsulated A549 cells by staining the ph marker of BCECF-AM obtained by a Leica 71 microscope with either 458 nm (left) or 488 nm (middle) excitation along with the same nm emission filter. The merged images of 458 nm and 488 nm excitation (right). It was not straightforward to determine the intracellular ph values by taking a ratio of the two images as in the previous reports. 1,2 References (1) Chu, J.; Chu, S; Montrose, M. H. Am. J. Physiol. Cell Physiol. 22, 283, C358 C372. (2) Xinhan, L.; Matsushita, M.; Numaza, M.; Taguchi, A.; Mitsui, K.; Kanazawa, H. Am J. Physiol. Cell Physiol. 211, 31, C1431 C1444 S15

16 Table S1. Size distributions of the 1.7 µm single-line and double-line linear AuNP chain SNTPs and the AuNPs. The units are nm if not specified. Type Dimension N total Mean SD Minimum Maximum SNTP length (μ m) Single line Double line SNTP diameter Au size SNTP length (μ m) SNTP diameter Au size Table S2. Numbers of the AuNPs in 1.7 µm single-line and double-line linear AuNP SNTPs. Type N total Mean SD Minimum Maximum Median Single Double Table S3. Size distribution of the 5 nm SNTPs and the AuNPs. The units are nm. N total Mean SD Minimum Maximum SNTP length SNTP diameter AuNPs Table S4. Number distribution of the 5 nm long AuNPs in SNTs. N total Mean SD Minimum Maximum Median S16