We describe the fabrication of asymmetric nanopores sensitive to ultraviolet (UV) light, and give a detailed account of the divalent ionic transport through these pores using a theoretical model based on the Nernst-Planck equations. The pore surface is decorated with lysine chains having pH-sensitive (amine and carboxylic acid) moieties that are caged with photo-labile 4,5-dimethoxy-2-nitrobenzyl (NVOC) groups. The uncharged hydrophobic NVOC groups are removed using UV irradiation, leading to the generation of hydrophilic “uncaged” amphoteric groups on the pore surface. We demonstrate experimentally that polymer membranes containing single pore and arrays of asymmetric nanopores can be employed for the pH-controlled transport of ionic and molecular analytes. Comparison between theory and experiment allows for understanding the individual properties of the phototriggered nanopores, and provides also useful clues for the design and fabrication of multipore membranes to be used in practical applications.

1.
K.
Healy
,
Nanomedicine
2
,
459
(
2007
).
2.
J.
Griffiths
,
Anal. Chem.
80
,
23
(
2008
).
3.
T.
Jovanovic-Talisman
,
J.
Tetenbaum-Novatt
,
A. S.
McKenney
,
A.
Zilman
,
R.
Peters
,
M. P.
Rout
, and
B. T.
Chait
,
Nature (London)
457
,
1023
(
2009
).
4.
R. B.
Schoch
,
J.
Han
, and
P.
Renaud
,
Rev. Mod. Phys.
80
,
839
(
2008
).
5.
S.-W.
Nam
,
M. J.
Rooks
,
K.-B.
Kim
, and
S. M.
Rossnagel
,
Nano Lett.
9
,
2044
(
2009
).
6.
J. M.
Perry
,
K.
Zhou
,
Z. D.
Harms
, and
S. C.
Jacobson
,
ACS Nano
4
,
3897
(
2010
).
7.
W.
Guan
,
R.
Fan
, and
M. A.
Reed
,
Nat. Commun.
2
,
506
(
2011
).
8.
C. C.
Striemer
,
T. R.
Gaborski
,
J. L.
McGrath
, and
P. M.
Fauchet
,
Nature (London)
445
,
749
(
2007
).
9.
A.
van den Berg
and
M.
Wessling
,
Nature (London)
445
,
726
(
2007
).
10.
C.
Dekker
,
Nat. Nanotechnol.
2
,
209
(
2007
).
11.
M. D.
Mager
and
N. A.
Melosh
,
Adv. Mater.
20
,
4423
(
2008
).
12.
P. Y.
Apel
,
Y. E.
Korchev
,
Z.
Siwy
,
R.
Spohr
, and
M.
Yoshida
,
Nucl. Instrum. Methods Phys. Res. B
184
,
337
(
2001
).
13.
Z.
Siwy
and
A.
Fuliński
,
Phys. Rev. Lett.
89
,
198103
(
2002
).
14.
P.
Ramirez
,
S.
Mafe
,
V. M.
Aguilella
, and
A.
Alcaraz
,
Phys. Rev. E
68
,
011910
(
2003
).
15.
Z.
Siwy
and
A.
Fuliński
,
Am. J. Phys.
72
,
567
(
2004
).
16.
Z.
Siwy
,
I. D.
Kosińska
,
A.
Fuliński
, and
C. R.
Martin
,
Phys. Rev. Lett.
94
,
048102
(
2005
).
17.
M. R.
Powell
,
M.
Sullivan
,
I.
Vlassiouk
,
D.
Constantin
,
O.
Sudre
,
C. C.
Martens
,
R. S.
Eisenberg
, and
Z. S.
Siwy
,
Nat. Nanotechnol.
3
,
51
(
2008
).
18.
E.
Garcia-Gimenez
,
A.
Alcaraz
,
V. M.
Aguilella
, and
P.
Ramirez
,
J. Membr. Sci.
331
,
137
(
2009
).
19.
X.
Hou
,
H.
Zhang
, and
L.
Jiang
,
Angew. Chem., Int. Ed.
51
,
5296
(
2012
).
20.
C. C.
Harrell
,
Z. S.
Siwy
, and
C. R.
Martin
,
Small
2
,
194
(
2006
).
21.
P. Y.
Apel
,
I. V.
Blonskaya
,
S. N.
Dmitriev
,
O. L.
Orelovitch
,
A.
Presz
, and
B. A.
Sartowska
,
Nanotechnology
18
,
305302
(
2007
).
22.
P. Y.
Apel
,
I. V.
Blonskaya
,
O. L.
Orelovitch
,
P.
Ramirez
, and
B. A.
Sartowska
,
Nanotechnology
22
,
175302
(
2011
).
23.
M.
Ali
,
P.
Ramirez
,
H. Q.
Nguyen
,
S.
Nasir
,
J.
Cervera
,
S.
Mafe
, and
W.
Ensinger
,
ACS Nano
6
,
3631
(
2012
).
24.
E. B.
Kalman
,
O.
Sudre
,
I.
Vlassiouk
, and
Z. S.
Siwy
,
Anal. Bioanal. Chem.
394
,
413
(
2009
).
25.
S.
Mafe
,
J. A.
Manzanares
, and
P.
Ramirez
,
J. Phys. Chem. C
114
,
21287
(
2010
)
26.
S.
Nasir
,
M.
Ali
, and
W.
Ensinger
,
Nanotechnology
23
,
225502
(
2012
).
27.
W.
Guo
,
H.
Xia
,
L.
Cao
,
F.
Xia
,
S.
Wang
,
G.
Zhang
,
Y.
Song
,
Y.
Wang
,
L.
Jiang
, and
D.
Zhu
,
Adv. Funct. Mater.
20
,
3561
(
2010
).
28.
M.
Ali
,
P.
Ramirez
,
S.
Mafe
,
R.
Neumann
, and
W.
Ensinger
,
ACS Nano
3
,
603
(
2009
).
29.
M.
Ali
,
S.
Mafe
,
P.
Ramirez
,
R.
Neumann
, and
W.
Ensinger
,
Langmuir
25
,
11993
(
2009
).
30.
X.
Hou
,
Y.
Liu
,
H.
Dong
,
F.
Yang
,
L.
Li
, and
L.
Jiang
,
Adv. Mater.
22
,
2440
(
2010
).
31.
X.
Hou
,
W.
Guo
,
F.
Xia
,
F.-Q.
Nie
,
H.
Dong
,
Y.
Tian
,
L.
Wen
,
L.
Wang
,
L.
Cao
,
Y.
Yang
,
J.
Xue
,
Y.
Song
,
Y.
Wang
,
D.
Liu
, and
L.
Jiang
,
J. Am. Chem. Soc.
131
,
7800
(
2009
).
32.
Y.
He
,
D.
Gillespie
,
D.
Boda
,
I.
Vlassiouk
,
R. S.
Eisenberg
, and
Z. S.
Siwy
,
J. Am. Chem. Soc.
131
,
5194
(
2009
).
33.
M.
Ali
,
R.
Neumann
, and
W.
Ensinger
,
ACS Nano
4
,
7267
(
2010
).
34.
M.
Ali
,
M. N.
Tahir
,
Z.
Siwy
,
R.
Neumann
,
W.
Tremel
, and
W.
Ensinger
,
Anal. Chem.
83
,
1673
(
2011
).
35.
I.
Vlassiouk
and
Z.
Siwy
,
Nano Lett.
7
,
552
(
2007
).
36.
E. B.
Kalman
,
I.
Vlassiouk
, and
Z.
Siwy
,
Adv. Mater.
20
,
293
(
2008
).
37.
M.
Ali
,
P.
Ramirez
,
M. N.
Tahir
,
S.
Mafe
,
Z.
Siwy
,
R.
Neumann
,
W.
Tremel
, and
W.
Ensinger
,
Nanoscale
3
,
1894
(
2011
).
38.
X.
Hou
,
F.
Yang
,
L.
Li
,
Y.
Song
,
L.
Jiang
, and
D.
Zhu
,
J. Am. Chem. Soc.
132
,
11736
(
2010
).
39.
K.
Healy
,
B.
Schiedt
, and
A. P.
Morrison
,
Nanomedicine
2
,
875
(
2007
).
40.
C. R.
Martin
and
Z. S.
Siwy
,
Science
317
,
331
(
2007
).
41.
W.
Guo
,
L.
Cao
,
J.
Xia
,
F.-Q.
Nie
,
W.
Ma
,
J.
Xue
,
Y.
Song
,
D.
Zhu
,
Y.
Wang
, and
L.
Jiang
,
Adv. Funct. Mater.
20
,
1339
(
2010
).
42.
J.
Cervera
,
P.
Ramirez
,
S.
Mafe
, and
P.
Stroeve
,
Electrochim. Acta
56
,
4504
(
2011
).
43.
P.
Ramirez
,
M.
Ali
,
W.
Ensinger
, and
S.
Mafe
,
Appl. Phys. Lett.
101
,
133108
(
2012
).
44.
Y.
Jiang
,
N.
Liu
,
W.
Guo
,
F.
Xia
, and
L.
Jiang
,
J. Am. Chem. Soc.
134
,
15395
(
2012
)
45.
M.
Ali
,
S.
Nasir
,
P.
Ramirez
,
I.
Ahmed
,
Q. H.
Nguyen
,
L.
Fruk
,
S.
Mafe
, and
W.
Ensinger
,
Adv. Funct. Mater.
22
,
390
(
2012
).
46.
M.
Zhang
,
X.
Hou
,
J.
Wang
,
Y.
Tian
,
X.
Fan
,
J.
Zhai
, and
L.
Jiang
,
Adv. Mater.
24
,
2424
(
2012
).
47.
See supplementary material at http://dx.doi.org/10.1063/1.4775811 for materials and methods employed for nanopore fabrication, synthesis of “caged” Lysine molecules, and functionalization of nanopore surface.
48.
P.
Ramirez
,
P. Y.
Apel
,
J.
Cervera
, and
S.
Mafe
,
Nanotechnology
19
,
315707
(
2008
).
49.
M.
Ali
,
B.
Yameen
,
J.
Cervera
,
P.
Ramirez
,
R.
Neumann
,
W.
Ensinger
,
W.
Knoll
, and
O.
Azzaroni
,
J. Am. Chem. Soc.
132
,
8338
(
2010
).
50.
P. Y.
Apel
,
I. V.
Blonskaya
,
O. L.
Orelovitch
,
B. A.
Sartowska
, and
R.
Spohr
,
Nanotechnology
23
,
225503
(
2012
).
51.
N.
Li
,
S.
Yu
,
C. C.
Harrell
, and
C. R.
Martin
,
Anal. Chem.
76
,
2025
(
2004
).
52.
C. C.
Harrell
,
P.
Kohli
,
Z.
Siwy
, and
C. R.
Martin
,
J. Am. Chem. Soc.
126
,
15646
(
2004
).
53.
J. A.
Manzanares
,
S.
Mafe
, and
J.
Pellicer
,
J. Chem. Soc., Faraday Trans.
88
,
2355
(
1992
).
54.
A. D.
MacGillivray
,
J. Chem. Phys.
48
,
2903
(
1968
).
55.
I.
Rubinstein
,
Electro-Diffusion of Ions
, SIAM Studies in Applied Mathematics (
SIAM
,
Philadelphia
,
1990
).
56.
K.
Kontturi
,
L.
Murtomäki
, and
J. A.
Manzanares
,
Ionic Transport Processes
(
Oxford University Press
,
Oxford
,
2008
).
57.
M.
Burger
,
Inverse Probl.
27
,
083001
(
2011
).
58.
M.
Burger
,
R. S.
Eisenberg
, and
H.
Engl
,
SIAM J. Appl. Math.
67
,
960
(
2007
).
59.
R. A.
Robinson
and
R. H.
Stokes
,
Electrolyte Solutions
(
Butterworths
,
London
,
1955
).
60.
J.
Cervera
,
B.
Schiedt
, and
P.
Ramírez
,
Europhys. Lett.
71
,
35
(
2005
).
61.
J.
Cervera
,
B.
Schiedt
,
R.
Neumann
,
S.
Mafe
, and
P.
Ramirez
,
J. Chem. Phys.
124
,
104706
(
2006
).
62.
J.
Cervera
,
A.
Alcaraz
,
B.
Schiedt
,
R.
Neumann
, and
P.
Ramirez
,
J. Phys. Chem. C
111
,
12265
(
2007
).
63.
C. K.
Mathews
and
K. E.
Van Holde
,
Bioelectrochemistry
(
Benjamin
/Cummings
,
Redwood City, CA
,
1990
).
64.
S. B.
Lee
and
C. R.
Martin
,
Anal. Chem.
73
,
768
(
2001
).
65.
J.
Pellicer
,
S.
Mafe
, and
V. M.
Aguilella
,
Ber. Bunsenges. Phys. Chem.
90
,
867
(
1986
).
66.
N.
Lakshminarayanaiah
,
Equations of Membrane Biophysics
(
Academic
,
New York
,
1984
).
67.
J.
Cervera
,
P.
Ramirez
,
J. A.
Manzanares
, and
S.
Mafe
,
Microfluid. Nanofluid.
9
,
41
(
2010
).
68.
G. L.
Wang
,
A. K.
Bohaty
,
I.
Zharov
, and
H. S.
White
,
J. Am. Chem. Soc.
128
,
13553
(
2006
).
69.
R. S.
Eisenberg
,
J. Membr. Biol.
150
,
1
(
1996
).

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