Programmed Fabrication of Bimetallic Nanobarcodes for Miniature ...
Supporting Information for
Programmed Fabrication of Bimetallic Nanobarcodes for Miniature Multiplexing Bioanalysis Wei-Ming Zhanga, Jin-Song Hu, Hai-Tao Ding, Li-Jun Wan*, Wei-Guo Song*
Institute of Chemistry, Chinese Academy of Sciences (ICCAS), Beijing 100190, China
and Beijing National Laboratory for Molecular Sciences (BNLMS), Beijing 100190, China;
a
Also in Graduate School of CAS, Beijing, 100064, China.
*Corresponding author. Fax: (+86) 10-62558934; E-mail: [email protected]; [email protected]
Fabrication of other nanobarcodes The Au-Co-Pt nanobarcodes are Co-Pt nanobarcodes with long gold starting segments instead of platinum. Prior to the electrodeposition of Co-Pt segments, a gold starting segment was initially electrodeposited to the membrane in 30mM KAu(CN)2 plating solution. The NiCo-Pt nanobarcodes were electrodeposited at the same condition as Co-Pt nanobarcodes expect to use 250 mM cobalt sulfate and 250 mM nickel sulfate instead of 500 mM cobalt sulfate. The Au-Fe nanobarcodes were fabricated in a plating solution consisted of 500mM FeSO4•7H2O, 30mM KAu(CN)2 and 500mM boric acid. The solution was quite unstable because of the oxidation of Fe2+, so the presence of some gentle reducing agent (such as citric acid) is helpful. Constant potentials of -1100 mV (vs. SCE) and -900 mV (vs. SCE) were alternatively applied to deposit iron segments (“spaces”) and gold segments (“bars”), respectively. The resulting Au-Fe barcode nanorods were shown in Figure S4. Details of the multiplexing bioanalysis For example, we loaded HS-Probe 3 on the surface of the nanobarcodes coded with Morse “D”. About 1e8 nanobarcodes (corresponding to about 0.05cm2 AAO membranes) were added to 0.5 mL HS-Probe 3 solution with a final concentration of 3 µM in 1 M KH2PO4 buffer, and the incubation takes about an hour in a swing bed at 25 oC. Then the barcodes were centrifuged and wash by 1x TBE Buffer with 1 M NaCl to remove the unattached probes. And finally, the probe loaded nanobarcodes were hybridized with 0.5 mL target 3 solution with a concentration of 0.5 µM in 1M NaCl - TBE Buffer. The hybridization was performed in a swing bed at 25 oC for about 2 hours. After that, the nanobarcodes were centrifuged and wash S1
by 1M NaCl - TBE Buffer to remove the uncombined fluorescently labeled target molecules. The resulting optical image and corresponding fluorescence image of the nanobarcodes were shown in Figure S5. And we load different probes on the surfaces of different nanobarcodes to form a suspension array in the same conditions, and the array was added to a mixing target solution with 0.25 µM Target 2 and 0.25 µM Target 3. The resulting nanobarcodes were imaged by a disk-spinning confocal microscopy system consisted of Olympus microscope (Olympus IX71, Japan), argon ion laser (MG, 488.0 nm), CSU10 (Yokogawa) and EMCCD (Andor), using a 100x oil immersion lens.
Figure S1. Different Co-Pt barcode nanorods encoded by Morse “A” (a), “B” (b), “C” (c) and “D” (d). Each figure contains 4 panels, which are program generated voltage versus time curve, corresponding current versus time curve, FE-SEM image and optical image of the resulting coded nanowire from top to bottom. All scale bars above are 1 µm.
S2
Pt
Si 0
Pt
Co
O 2
4
6
8
10
Pt 12
Energy(keV)
Figure S2. Large scale FE-SEM image of the Co-Pt nanobarcode array, the inset shows the EDX spectrum of the same sample.
Co (200)
Pt (111)
4000
2000
Pt (220)
Pt (200)
Intensity (CPS)
6000
0 30
40
50
60
70
80
2-Theta (deg)
Figure S3. XRD pattern of the coded Co-Pt nanobarcode array in AAO membranes. The peaks are in good agreement with face-centered cubic (fcc) platinum (JCPDS No. 87-0646) and S3
face-centered cubic (fcc) cobalt (JCPDS No. 15-0806).
Figure S4. Au-Fe barcode nanorods coded with More “SCIENCE”, the barcode nanowires are composed of brighter Au segments (the bars) and darker Fe segments (the spacers).
S4
Programmed Fabrication of Bimetallic Nanobarcodes for Miniature Multiplexing Bioanalysis Wei-Ming Zhanga, Jin-Song Hu, Hai-Tao Ding, Li-Jun Wan*, Wei-Guo Song*
Institute of Chemistry, Chinese Academy of Sciences (ICCAS), Beijing 100190, China
and Beijing National Laboratory for Molecular Sciences (BNLMS), Beijing 100190, China;
a
Also in Graduate School of CAS, Beijing, 100064, China.
*Corresponding author. Fax: (+86) 10-62558934; E-mail: [email protected]; [email protected]
Fabrication of other nanobarcodes The Au-Co-Pt nanobarcodes are Co-Pt nanobarcodes with long gold starting segments instead of platinum. Prior to the electrodeposition of Co-Pt segments, a gold starting segment was initially electrodeposited to the membrane in 30mM KAu(CN)2 plating solution. The NiCo-Pt nanobarcodes were electrodeposited at the same condition as Co-Pt nanobarcodes expect to use 250 mM cobalt sulfate and 250 mM nickel sulfate instead of 500 mM cobalt sulfate. The Au-Fe nanobarcodes were fabricated in a plating solution consisted of 500mM FeSO4•7H2O, 30mM KAu(CN)2 and 500mM boric acid. The solution was quite unstable because of the oxidation of Fe2+, so the presence of some gentle reducing agent (such as citric acid) is helpful. Constant potentials of -1100 mV (vs. SCE) and -900 mV (vs. SCE) were alternatively applied to deposit iron segments (“spaces”) and gold segments (“bars”), respectively. The resulting Au-Fe barcode nanorods were shown in Figure S4. Details of the multiplexing bioanalysis For example, we loaded HS-Probe 3 on the surface of the nanobarcodes coded with Morse “D”. About 1e8 nanobarcodes (corresponding to about 0.05cm2 AAO membranes) were added to 0.5 mL HS-Probe 3 solution with a final concentration of 3 µM in 1 M KH2PO4 buffer, and the incubation takes about an hour in a swing bed at 25 oC. Then the barcodes were centrifuged and wash by 1x TBE Buffer with 1 M NaCl to remove the unattached probes. And finally, the probe loaded nanobarcodes were hybridized with 0.5 mL target 3 solution with a concentration of 0.5 µM in 1M NaCl - TBE Buffer. The hybridization was performed in a swing bed at 25 oC for about 2 hours. After that, the nanobarcodes were centrifuged and wash S1
by 1M NaCl - TBE Buffer to remove the uncombined fluorescently labeled target molecules. The resulting optical image and corresponding fluorescence image of the nanobarcodes were shown in Figure S5. And we load different probes on the surfaces of different nanobarcodes to form a suspension array in the same conditions, and the array was added to a mixing target solution with 0.25 µM Target 2 and 0.25 µM Target 3. The resulting nanobarcodes were imaged by a disk-spinning confocal microscopy system consisted of Olympus microscope (Olympus IX71, Japan), argon ion laser (MG, 488.0 nm), CSU10 (Yokogawa) and EMCCD (Andor), using a 100x oil immersion lens.
Figure S1. Different Co-Pt barcode nanorods encoded by Morse “A” (a), “B” (b), “C” (c) and “D” (d). Each figure contains 4 panels, which are program generated voltage versus time curve, corresponding current versus time curve, FE-SEM image and optical image of the resulting coded nanowire from top to bottom. All scale bars above are 1 µm.
S2
Pt
Si 0
Pt
Co
O 2
4
6
8
10
Pt 12
Energy(keV)
Figure S2. Large scale FE-SEM image of the Co-Pt nanobarcode array, the inset shows the EDX spectrum of the same sample.
Co (200)
Pt (111)
4000
2000
Pt (220)
Pt (200)
Intensity (CPS)
6000
0 30
40
50
60
70
80
2-Theta (deg)
Figure S3. XRD pattern of the coded Co-Pt nanobarcode array in AAO membranes. The peaks are in good agreement with face-centered cubic (fcc) platinum (JCPDS No. 87-0646) and S3
face-centered cubic (fcc) cobalt (JCPDS No. 15-0806).
Figure S4. Au-Fe barcode nanorods coded with More “SCIENCE”, the barcode nanowires are composed of brighter Au segments (the bars) and darker Fe segments (the spacers).
S4
