advances.sciencemag.org/cgi/content/full/2/8/e1600902/DC1
Supplementary Materials for
Artificial cilia as autonomous nanoactuators: Design of a gradient selfoscillating polymer brush with controlled unidirectional motion
Tsukuru Masuda, Aya Mizutani Akimoto, Kenichi Nagase, Teruo Okano, Ryo Yoshida
Published 31 August 2016, Sci. Adv. 2, e1600902 (2016)
DOI: 10.1126/sciadv.1600902
The PDF file includes:
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fig. S1. Mechanism of saATRP.
fig. S2. AFM observation for the flat surface.
fig. S3. AFM observation for the gradient surface.
fig. S4. Spatiotemporal analysis of the BZ reaction.
Mechanism for the BZ reaction (Field-Körös-Noyes model)
Legend for movie S1
Other Supplementary Material for this manuscript includes the following:
(available at advances.sciencemag.org/cgi/content/full/2/8/e1600902/DC1)
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movie S1 (.mov format). Chemical wave propagation.
Supplementary Materials
fig. S1. Mechanism
of saATRP.
(A) Illustration of the mechanism of sacrificial anode ATRP.
Supplementary
Materials
(B) Relationship between the gap distance (D) and the thickness.
AFM observation for flat surface in air
20.0
100 nm
10.0
0
10.0
Position / µm
50 nm
0 nm
0
20.0
Position / µm
fig. S2. AFM observation for the flat surface. T height images of the flat self-oscillating
polymer brush prepared by saATRP.
A
Height / nm
95
0
-95
0
2.5
5.0
7.5
10.0
7.5
10.0
Position / µm
100
Height / nm
B
0
-100
0
2.5
5.0
Position / µm
fig. S3. AFM observation for the gradient surface. The height images and the cross sections of
the gradient self-oscillating polymer brush (A) of the region around the top of the gradient (B) of the
region with lower Ru(bpy)3 amount.
Supplementary Materials
BZ reaction for (A) flat and (B) gradient surface
A
B
200 µm
Length
Length
100 s
100 s
200 µm
Initial stage
stable stage
Time
Time
← Derangement in
← Ru large region
fig. S4. Spatiotemporal analysis of the BZ reaction. The spatiotemporal analysis for (A) the flat
surface and (B) for the gradient surface (long duration).
Mechanism of the BZ reaction (FKN model) (27)
Process A (consumption of bromide ion)
Br- + HOBr + H+ → Br2 + H2O (A1)
Br- + HBrO2 + H+ → 2HOBr (A2)
Br- + BrO3- + 2H+ →HOBr + HBrO2 (A3)
Process B (oxidization of Ru(bpy)32+, autocatalytic reaction)
2 HBrO2 → HOBr + BrO3- + H+ (B1)
HBrO2 + BrO3- + H+ → 2BrO2 + H2O (B2)
BrO2 + Ru(bpy)32+ + H+ → HBrO2 + Ru(bpy)33+ (B3)
Process C (reduction of Ru(bpy)33+, production of bromide ion)
BrO2 + Ru(bpy)33+ + H2O → BrO3- + Ru(bpy)32+ + 2H+ (C1)
Br2 + CH2(COOH)2 → BrCH2(COOH)2 + Br- + H+ (C2)
6Ru(bpy)33+ + CH2(COOH)2 + 2H2O → 6Ru(bpy)32+ + HCOOH + 2CO2 + 6H+
(C3)
4Ru(bpy)33+ + BrCH2(COOH)2 + 2H2O → 4Ru(bpy)32+ + HCOOH + Br- + 2CO2 +
5H+ (C4)
movie S1. Chemical wave propagation on the gradient self-oscillating polymer brush.