Nanoparticle-based Indicator-Displacement Assay for Pyrophosphate
(s, 2H), 7.10–7.15 (m, 4H), 7.50 (d, 4H), 7.58–7.70 (m, 4H), 8.53 (d, 4H),
10.95 ppm (s, 1H); 13CNMR (CDCl3, 75 MHz): d=30.38, 36.27, 51.68,
54.91, 59.95, 122.12, 123.09, 124.20, 129.02, 130.28, 136.69, 149.02, 154.45,
159.39, 173.75 ppm; MS (FAB+) [M+H]+: 603.2; HRMS (FAB+)
[M+H]+ calcd for C36H39N6O3: 603.3005; found: 603.3088.
Acknowledgements
This work was supported by grants from the Center for Electro-Photo
Behaviors in Advanced Molecular Systems (R11-2008-052-01001).
3-(3,5-Bis
hydroxyphenyl)propanoic acid (6)
ACHTUNGTRENNUNG{bis[(pyridin-2-yl)methyl]aminomethyl}-4-
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A solution of bis(DPA)-methyl ester 5 (350 mg, 0.58 mmol) in MeOH/
ACHTUNGTRENNUNG
water (3:1, 5 mL), was treated with NaOH (23 mg, 0.58 mmol), and the
mixture was stirred for 24 h at room temperature. Most of the methanol
was evaporated under reduced pressure, and the aqueous solution was
washed with CH2Cl2 (3ꢃ20 mL). The aqueous solution was neutralized
with 1 n HCl and extracted with CH2Cl2 (3ꢃ30 mL). The combined or-
ganic layer was dried over anhydrous Na2SO4 and concentrated in vacuo
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to give bisACHTUNGTRENNUNG(DPA)-acid 6 (290 mg, 85%), which was used for the nanopar-
ticle functionalization. 1HNMR (CDCl3, 300 MHz): d=2.57 (t, 2H), 2.91
(t, 2H), 3.79 (s, 4H), 3.85 (s, 8H), 7.08 (s, 2H), 7.12–7.16 (m, 4H), 7.50
(d, 4H), 7.59–7.65 (m, 4H), 8.53 ppm (d, 4H); 13CNMR (CDCl3,
75 MHz)): d=31.48, 37.83, 55.07, 59.57, 122.39, 123.52, 123.81, 129.95,
130.51, 137.06, 148.83, 154.54, 159.08, 176.25 ppm; MS (FAB+) [M+H]+:
589.2; HRMS (FAB+) [M+H]+ calcd for C35H37N6O3: 589.2849; found:
589.2930.
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Preparation of bis-Zn
ACHTUNGTRENNUNG(DPA)-silica nanoparticle 8
A solution of bis(DPA)-acid 6 (185 mg, 0.315 mmol), aminopropyl-termi-
ACHTUNGTRENNUNG
nated silica nanoparticles (2.5 mg; available as 25 mg/1 mL, 50 nm;
0.315 mmol) in water/DMF (2 mL, 1:1) was stirred at room temperature
for 3 days. After centrifugation twice (12000 rpm, 30 min, 208C), the
nanoparticles were subjected two times to dialysis (membrane pore
3500 MW, 2000 mL waterꢃ2) to remove any remaining reagents. As dial-
ysis proceeded, nanoparticles became solid and subsided onto the bottom
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of the membrane. Then, bisACTHNUTRGNEUG(N DPA)-functionalized nanoparticles were dis-
solved in water/MeOH (1:1) and treated slowly with an aqueous solution
(10 mL) of ZnClO4·6H2O (235 mg, 0.63 mmol), and the resulting solution
was stirred at room temperature for 24 h. The reaction mixture was sub-
jected to centrifugation (5000 rpm, three times) and then dialysis to
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afford bis-ZnACHTUNGTRENNUNG(DPA)-functionalized silica nanoparticle 8. For sensing pur-
poses, a solution of nanoparticles (0.02 mgmLꢀ1) was prepared from a
stock solution of the nanoparticles (0.1 mgmLꢀ1, water). The functional-
ized nanoparticle was characterized by IR and TEM.
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UV/Vis Titration of the Nanoparticle Ensemble System with PPi
Received: February 14, 2011
Published online: May 19, 2011
The nanoparticle ensemble system was prepared by mixing bis-ZnACTHNUTRGNEU(GN DPA)-
silica nanoparticle 8 and pyrocatechol violet in HEPES buffer (pH 7). A
nano-ensemble solution (1.0 mL) containing the functionalized nanopar-
ticle (0.02 mgmLꢀ1) and pyrocatechol violet (50 mm) in HEPES buffer
(pH 7, 10 mm) was titrated with pyrophosphate aliquots (in the final con-
centration range of 0–200 mm) and the corresponding absorption changes
were followed by UV/Vis spectrometry.
Chem. Asian J. 2011, 6, 2034 – 2039
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2039