Determination of Nanoparticles by UV-Vis Spectra

Transcription

1 Electronic Supplementary Material (ESI) for Nanoscale. This journal is The Royal Society of Chemistry 2015 Determination of Nanoparticles by UV-Vis Spectra Shahed Behzadi 1, Forough Ghasemi 2, Masoumeh Ghalkhani 3, Ali Akbar Ashkarran 4, Mostafa Akbari 5, Sepideh Pakpour 6, Mohammad Reza Hormozi-Nezhad 2*, Zahra Jamshidi 7, Somayyeh Mirsadeghi 5, Rasoul Dinarvand 5,8, Fatemeh Atyabi 5,8, and Morteza Mahmoudi 5,8,9,10* 1 Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz, Germany 2 Department of Chemistry, Sharif University of Technology, Tehran, Iran 3 Department of Chemistry, Faculty of Science, Shahid Rajaee Teacher Training University, Lavizan, Tehran, Iran 4 Department of Physics, Faculty of Basic Sciences, University of Mazandaran, Babolsar, Iran 5 Nanotechnology Research Center, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran 6 Department of Biology, University of British Columbia, Kelowna, BC, Canada 7 Department of Physical Chemistry, Chemistry and Chemical Engineering Research Center of Iran, Tehran, Iran 8 Pharmaceutical Nanotechnology, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran 9 Cardiovascular Institute, Stanford University School of Medicine, Stanford, California , United States 10 Division of Cardiovascular Medicine, Stanford University School of Medicine, Stanford, California , United States The authors contributed equally in this work as first author. *Corresponding Authors: (MRHN) hormozi@sharif.edu; (MM): E- mail: Mahmoudi@stanford.edu 1

2 (a) 2

3 (b) 3

4 (c) 4

5 (d) 5

6 (e) 6

7 (f) 7

8 (g) 8

9 (h) 9

10 (i) 10

11 (j) 11

12 (k) 12

13 Figure S1: (a-l) Absorbance spectrums of various pigments, with their chemical structures, before and after exposure to the different NPs (at various concentrations) at ph of (l) 13

14 Normalise Resemblance: D1 Euclidean distance Nanoparticles QDs1 QDs2 Polystyrene SPIONs Silica 100 Silica 200 Au 50 0 PCO3 (11.6% of total variation) PCO1 (25.5% of total variation) PCO2 (23.2% of total variation) Figure S2: Results of the PCoA analysis on 7 different types of nanoparticles at 6 concentrations (i.e. 10, 20, 40, 60, 80, and 100 ng/ml) 14

15 Silica Polystyrene-100 Polystyrene-80 Polystyrene-40 Polystyrene-60 Polystyrene-10 Polystyrene-20 QDs2-60 QDs2-80 QDs2-100 QDs2-40 SPIONs-60 SPIONs-40 SPIONs-10 SPIONs-20 SPIONs-80 SPIONs-100 QDs2-10 QDs2-20 Au-100 Au-60 Au-80 Au-40 Au-10 Au-20 QDs1-100 QDs1-80 QDs1-40 QDs1-60 QDs 1-10 QDs1-20 Silica Silica Silica Silica Silica Silica Silica Silica Silica Silica Silica Single linkage Normalise Resemblance: D1 Euclidean distance Nanoparticles QDs1 QDs2 Polystyrene SPIONs Silica 100 Silica 200 Au Euclidean Distance Euclidian Distance Figure S3: Results of the HCA on 7 different types of nanoparticles at 6 concentrations (i.e. 10, 20, 40, 60, 80, and 100 ng/ml) 15

16 Synthesis of Gold Nanoparticles Various gold nanoparticles (i.e., gold nanospheres (NS20; ~20 nm), gold nanospheres (NS30; ~30 nm), short gold nanorods (NR4; aspect ratio of 4), and long gold nanorods (NR20; aspect ratio of 20)) were synthesized according to the previous report. 1 Preparing of chromophore solutions. Chromophore solutions were prepared in PBS with a maximum visible absorbance of 1.0 (concentrations were in order of to M). The ph of solutions was fixed with HCl and NaOH at The absorbance measurements were done after one minute of exposure with NPs. Since the polarity of the solvent effect on the absorption spectrum 7, only the water solvent was used to prepare solutions. Results of the synthetic NPs. Aqueous solutions of all indicators were prepared in phosphate buffered saline (PBS), with peak absorbance 1.0 before the addition of the NPs. Figure S5 shows the initial normalized absorbance of the dye solutions, covering the visible range from 380 to 750 nm. Various gold NPs (i.e., spheres with various sizes (20 and 30nm), short rod, and long rod) were characterized by TEM and UV/vis spectroscopy approaches (see Figure S4). It is notable that none of NPs showed the plasmonic absorption peak at concentrations lower than 1ppm. 16

17 Figure S4. UV-Vis absorbance of (a) Au nanospheres and (b) Au nanorods (AR 4); (c f ) transmission electron microscopy images of gold nanospheres (NS20; 20 nm), gold nanospheres (NS30; 30 nm), short gold nanorods (NR4; aspect ratio of 4), and long gold nanorods (NR20; aspect ratio of 20), respectively. Reproduced with permission from reference 1. 17

18 Figure S5. Normalized absorbance overlay of selected indicators in water (at ph of 7.41). 18

19 Each type of the employed gold NPs, at various concentrations (i.e., 10, 25, 50, 100, 250, 500, 1000, 2500, and 5000 ng/ml) was exposed to various indicator solutions and the spectra of solutions were recorded after one minute (see Figure S6). The spectral changes of indicators after interaction with gold NPs provide a facile and rapid way for identification of NPs. Spectral changes for all indicators produce a specific pattern for each NP at different concentrations. As can be seen from Figure S6, responses of various dyes to the existence of different NPs are not similar. (A) (B) (C) (D) (E) A B C D (a) 19

20 (A) (B) (C) (D) A B C D (E) (b) 20

21 (A) (B) (C) (D) (E) A B C D (c) 21

22 (A) (B) (C) (D) (E) A B C D (d) 22

23 (A) (B) (C) (D) (E) A B C D (e) 23

24 (A) (B) (C) (D) (E) A B C D (f) 24

25 (A) (B) (C) (D) (E) A B C D (g) 25

26 (A) (B) (C) (D) (h) Figure S6. Absorbance spectrums of various dyes (a-h) before and after exposure to the different NPs (A-D; at various concentrations) at ph of

27 Concentrations(ng/mL) A color difference map, which is a useful approach for visualization of the achieved data was performed by subtraction of the light absorbance before and after exposure between 3 selected visible wavelengths (i.e. 558, 590 and 616 nm). As shown in Figures 5, the resulting color difference pattern provides a robust fingerprint for each NPs at different concentrations. According to the maps, one can easily distinguish the type of NPs without need to any statistical technique. Color change profiles for four different gold NPs as a function of concentration are also in Figure 6. The colorimetric sensor array has also been tested against interference of Au 3+, CTAB and ph changes (range of 0.1), as a control cases. In this case, no responses were observed in the selected wavelengths. The values of limits of detection (LOD) and limit of quantification (LOQ), based on the colorimetric maps, were presented in Table S Dyes Bromocresol green Bromophenol blue Bromopyrogallol red Congo red Eriochrome black T Eosin Y Rhodamine B NR 20 NR 4 NS 20 NS 30 Control Figure S7. Color difference maps for various nanoparticles and 4 controls. 27

28 Nanoparticles Dyes Bromocresol green Bromophenol blue Bromopyrogallol red Congo red Eriochrome black T Eosin Y Rhodamine B NR20 NR4 NS20 NR ng/ml 2500 ng/ml 1000 ng/ml 500 ng/ml 250 ng/ml 100 ng/ml 50ng/mL 25ng/mL 10ng/mL Control Figure S8. Color difference maps of nanoparticles (at different concentration) and 4 control done in triplicate. Table S1. The value of LOD and LOQ for the nanoparticles according to the results of color difference maps. NR 20 NR 4 NS 20 NS 30 LOR(ng/mL) LOQ(ng/mL) <

29 (A) (B) (C) (D) (a) 29

30 (A) (B) (C) (D) (b) 30

31 (A) (B) (C) (D) (c) 31

32 (A) (B) (C) (D) (d) 32

33 (A) (B) (C) (D) (e) 33

34 (A) (B) (C) (D) (f) 34

35 (A) (B) (C) (D) (g) 35

36 (A) (B) (C) (D) (h) Figure S9. Absorbance spectrums of various dyes (a-h) before and after exposure to the different NPs (at 5μg/mL concentrations) at ph of A) Long rod B) Short rod C) Sphere20nm, and D) Sphere30nm 36

37 References 1. S. Mirsadeghi, R. Dinarvand, M. H. Ghahremani, M. R. Hormozi-Nezhad, Z. Mahmoudi, M. J. Hajipour, F. Atyabi, M. Ghavami, and M. Mahmoudi, Nanoscale, 2015, in press DOI: /c4nr06009a 37