¹
2
purified by silica gel column chromatography with chloroform.
The eluate was concentrated under reduced pressure to afford
bandpass filter ( = 365 nm). The intensity was 25 mW cm ,
as determined with a UIT-201 power meter equipped with a
UVD-365PD UV sensor (Ushio). The irradiated substrates
were rinsed with chloroform, sonicated in chloroform for
3 min, and then dried under a nitrogen stream.
0
.232 g (0.202 mmol, 44%) of 5 as a whitish yellow solid.
1
H NMR (400 MHz, CDCl ): ¤ 7.55 (s, 1H), 7.20 (s, 1H), 5.27
3
(t, J = 4.6 Hz, 1H), 4.234.08 (m, 4H), 2.412.28 (m, 4H),
2
6
.212.14 (m, 5H), 2.051.97 (m, 1H), 0.96 and 0.94 (d, J =
.8 Hz, 6H).
Patterning of SAM Prepared from 7. To prepare SAM,
¹2
UV irradiation of 2 J cm (80 s) was carried out through a
photomask (10-μm line and space pattern or 5-μm line and
original shape pattern) composed of Cr patterns on quartz glass
in acetone. Then, the substrate was cleaned with an ultrasonic
cleaner in chloroform for 3 min and dried under a nitrogen
stream.
1
-[2-Nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroundecyl-
oxy)phenyl]-2-methylpropyl N-succinimidyl carbonate (6):
Di(N-succinimidyl) carbonate (0.206 g, 0.804 mmol) and tri-
ethylamine (0.159 g, 1.57 mmol) were added to a solution of
5
(0.602 g, 0.525 mmol) in THF (10 mL) and acetonitrile (10
mL). The solution was stirred at room temperature for 72 h,
then concentrated in a rotary evaporator. Water (30 mL) and
Selective Deposition of Ag Nanoparticle Ink.
Ag
nanoparticle ink was deposited on the patterned substrate by
spin-coating at 300 rpm for 3 s, and then at 3000 rpm for 30 s.
The patterned surface was observed with a VH-Z500R digital
microscope (KEYENCE).
2
M aqueous HCl (5 mL) were added, and the solution was
extracted with ethyl acetate (30 mL © 3). The organic layer was
washed twice with saturated aqueous NaCl, dried over MgSO4,
and evaporated under reduced pressure. The crude product was
purified by silica gel column chromatography with hexane/
ethyl acetate (4/1), and the eluate was concentrated under
Selective Chemical Modification. The patterned SAM
¹
1
was soaked in DMSO containing 0.1 mg mL of 5-(and-6)-
carboxytetramethylrhodamine succinimidyl ester (5(6)-
TAMRA) for 20 h at room temperature. The modified substrates
were rinsed with chloroform, and then dried under a nitrogen
stream. The patterned surface was observed with a BX-FLA
fluorescence microscope (Olympus).
reduced pressure to afford 0.278 g (0.216 mmol, 41%) of 6 as a
1
pale yellow solid. H NMR (400 MHz, CDCl ): ¤ 7.65 (s, 1H),
3
6
.96 (s, 1H), 6.38 (d, J = 4.8 Hz, 1H), 4.374.12 (m, 4H), 2.79
3
(
(
s, 4H), 2.392.14 (m, 9H), 1.07 (d, J = 6.8 Hz, 6H). 1 C NMR
400 MHz, CDCl ): ¤ 168.4, 153.1, 151.1, 147.6, 140.2, 129.4,
3
Results and Discussion
1
1
09.5, 109.4, 83.4, 77.2, 67.7, 67.5, 33.4, 25.4, 20.5, 19.4,
6.5.
Silane coupling agent 7 was synthesized from 1,2-di-
methoxybenzene in 7 steps (Figure 2). Synthesis of 1, 2, and
35 with different fluoroalkoxy groups was performed accord-
1
-[2-Nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroundecyl-
oxy)phenyl]-2-methylpropyl N-[3-(trimethoxysilyl)propyl]-
carbamate (7): 3-Aminopropyltrimethoxysilane (0.0351 g,
2
8
ing to the previously reported method. 1-[2-Nitro-4,5-di-
(1H,1H,2H,2H,3H,3H-perfluoroundecyloxy)phenyl]-2-methyl-
propyl N-succinimidyl carbonate (6) was synthesized by the
reaction of the hydroxy functionality of 5 with di(N-succini-
midyl) carbonate. The relatively low yield of 41% was proba-
bly due to steric hindrance of the isopropyl group at the benzyl
position of 5. The synthesized 6 was reacted with 3-amino-
propyltrimethoxysilane to obtain 7. Tetramethoxysilane (1%
v/v) was added to the eluent in column chromatography to
0
0
.196 mmol) was added dropwise to a solution of 6 (0.229 g,
.178 mmol) in dry THF (10 mL). The solution was stirred at
room temperature for 2 h, and then evaporated under reduced
pressure. The crude product was purified by silica gel column
chromatography with hexane/ethyl acetate/tetramethoxysilane
(3/1/0.04), and the eluate was concentrated under reduced
pressure to afford 0.166 g (0.123 mmol, 69%) of 7 as a pale
1
yellow solid. H NMR (400 MHz, CDCl ): ¤ 7.58 (s, 1H), 6.88
3
3
0
(
4
(
s, 1H), 6.20 (d, J = 5.6 Hz, 1H), 4.96 (t, J = 5.8 Hz, 1H),
.154.10 (m, 4H), 3.56 (s, 9H), 3.183.08 (m, 2H), 2.422.26
m, 4H), 2.202.10 (m, 5H), 1.611.55 (m, 2H), 0.98 (d, J =
prevent adsorption on the silica gel. The substrate was modi-
fied under various conditions (solvent, concentration of 7, and
time for preparation of the smooth silanized surface).
6
¤
6
6
.9 Hz, 6H), 0.620.58 (m, 2H). 13C NMR (400 MHz, CDCl3):
155.7, 152.3, 147.0, 140.8, 132.5, 110.4, 109.4, 77.2, 75.7,
7.5, 67.4, 50.6, 43.4, 33.3, 27.8, 27.7, 23.1, 20.5, 19.4, 17.2,
.3. Anal. found: C, 34.53; H, 2.95; N, 2.04%. Calcd for
Table 1 summarizes the silanization conditions and water
contact angle on the silanized surface, and Figure 3 shows AFM
images and average roughness (R ). The average roughness of
a
the modified substrate surface in the case of 1 mM toluene
C H F N O Si: C, 34.63; H, 2.83; N, 2.07%.
solution of 7 at 100 °C for 1 h (Entry 1) was very large (R =
39
38 34
2
9
a
Preparation of SAM. A silicon wafer bearing a 150 nm
6.5 nm). This might be due to aggregation of the silane coupling
agent. The water contact angle was smaller, despite the rough
surface, probably owing to the short modification time. When a
lower concentration of 0.1 mM (Entry 2) and longer modifica-
tion time of 24 h was used to avoid aggregate formation, the
contact angle of water was higher (115°) and the roughness was
thermal oxide film was cleaned with an ultrasonic cleaner in
water, methanol, and acetone for 5 min each, and dried under a
nitrogen stream. The substrate was further cleaned and
hydroxy-terminated with a UV-ozone cleaner (UV253, Filgen),
and then soaked in a solution of 7 in dry toluene or 1,3-bis-
(trifluoromethyl)benzene (HFX) under a nitrogen atmosphere.
smaller (R = 1.5 nm) than that of Entry 1. Nevertheless, the
a
The resulting modified substrate was rinsed with chloroform,
sonicated in chloroform for 5 min, and then dried under a
nitrogen stream.
surface was still rough as a monolayer. When HFX was used as
a solvent (Entry 3 in Table 1), the contact angle of water was
108° and the roughness was the lowest (R = 0.13 nm) among
a
Photodeprotection of 2-Nitrobenzyl Groups on Substrate.
The prepared substrates were irradiated with an ultrahigh-
pressure mercury lamp (USH-500SH, Ushio) through a
the three conditions. Aggregation of the silane coupling agent
in solution was prevented because 7 containing fluoroalkoxy
groups had higher solubility in HFX than in toluene.
© 2016 The Chemical Society of Japan