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Nanochannel and Its Application in Analytical Chemistry
Zenglian Yue, Guoqing Zhao, Bin Peng, Shasheng Huang*
College of Life and Environment & science
Shanghai Normal University
Shanghai, 200234, China
[email protected] http://www.shnu.edu.cn Abstract: The
nanochannels method for the separation and detection of analytes
plays an important role in the analytical chemistry and is
exhibiting the great potential advantages and promising future. In
this review we bring together and discuss a number of nanochannels
made of biological and special material. The preparation and
appli-cation of biological nanochannels are described. Compared
with the biological single channel, nanochannels pre-pared by
special material are more selective and have advantages in
practical application because these channels are less fragile and
more easily modified. Studies of the special material membrane
involve in the chemical, bio-technical, medical fields, etc. For
the increasing interest in using material channels at present, we
demonstrated the synthetic methods of different special material
nanochannels and a mount of their applications in analytical
chem-istry here. The advantages and tendency of nanochannels are
discussed as well.
Key-Words: - Nanochannels, separation, preparation,
applications
1 Introduction Traditional separation methods and techniques
such as extraction, ion-exchange, chromatography, etc. are
confronted with great challenges. How to separate and analyze
trance analytes is the focus of the challenges. With the fast
development of nanotechnology in 1999s, new thoughts and
opportunities have appeared for deep research of separation.
Nanochannels are the pores or channels with diameter from 0.1 to
100 nanometers. As an important part of nanoscience, nanochannels
tech-nique has become a new growth point. It is exhibiting the
great potential advantages and promising future due to the size
effect, chemical and physical character-istics.
At present, the studies about nanochannels mainly refer to the
biological nanochannels and material nanochannels. The biological
nanochannels such as bacterial α-hemolysin (α-HL) a heptameric
protein that spontaneously assembles in a lipid membrane has pro-
ven in the separation of peptide [1]. A single channel
(typically,an α-hemolysin channel) also can be used as the sensing
element. These sensors can detect individ-ual analyte with channel
interactions and convert these stochastic events into a current
pulse. Sutherland et al [2] demonstrated that peptide transport
through nanopores can also be used to analyze the structure of
peptides. Depending on this device, the change in cur-
rent can be used to determine size and the concentra-tion of the
analytical species.
However, lower stability and reproducibility of tra-ditional
bilayer membrane limited its practical applica-tion. In contrast
with the biological single channel, material nanochannels have
advantages in practical application, special because these channels
are less fragile.
The studies on the special material membrane have received
intensive interest since Martin et al. reported gold nanochannels
membrane for the separation of small molecules on the basis of
molecular size [3]. Generally, material nanochannels are prepared
by spe-cial materials such as carbon nanochannels, silicon
nanochannels, nanochannel array (eg. porous alumina membranes and
the polycarbonate tracketched me-branes) and so on. The templates
of material nano-channels include membrane template, emulsion /
mi-cromulsion template and other kinds of templates.
In this article, we will first introduce the general
configuration and the preparation of nanochannels. The unique
properties of gold nanochannels for chemistry and bioseparation
have been summarized. At the same time, some successful examples of
nanochanneles membrane that have been applied to chemical and
biomolecular species have been introduced. The novel bioseparation
method based on nanotubules will also
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be described. The objective of this review is to intro-duce the
extremely valuable nanochannels to the bi-ologists and chemists and
encourage them to consider nanotubules in their research.
2. Biological nanochannels 2.1 Structure and characteristics of
biological
nanochannels Biological nanochannels were first posted in 1999.
One of the typical channels is a single α-hemolysin in
cross-section embedded in a lipid bilayer with a di-ameter about
1.5-2.6 nm [4]. Ions, water and other small molecules can go
through this channel .So it can be used as an ion-channel. The
structure of α-HL is shown as figure 1
Figure 1
The important structure features of α-HL are the mouth of the
channel (2.6 nm), which leads into a lar-ger vestibule, and the
stem of the channel containing a pore with an interior diameter of
2.2 nm. The opening between the vestibule and stem forms the
limiting ap-erture of 1.5 nm diameter, so it can only allow the
sin-gle strand DNA to go through the channel while the double
strand DNA can not. α-HL is composed of a ring of 14 alternating
lysine and glutamate side chain. So the channel is hydrophilic in
the interior while lyo-phobic in the exterior [5].
2.2 Applications of biological nanochannels The biophysical
characteristics of poly-nucleic acids through the channel were
first researched by Kasianowicz and his group [6]. They found that
the single molecules of DNA or RNA can be detected as they are
driven through the α-hemolysin channel by applying an electric
field. During translocation, the spread single DNA or RNA can block
the channel and transiently block the ion current, resulting in a
down-ward current pulse. The duration of the current pulses is
proportional to the length of the polymer molecules. It has proved
that this nanochannel can be used to find differing pyridine and
purine quickly [4]. The charac-teristics of DNA hairpin within
millisecond can be ana-lyzed by combining the nanochannels and the
support vector machine [7].
The interior of the α-HL pore can be modified by changing the
order of amino acids. The inner geometry
and the chemical or static characteristics of the nano-tubules
were changed due to modification. Some spe-cial analytes (e.g
nucleic acid) can transport more sen-sitively through the
nanotubules membrane because the functional group can be modified
onto the nano-tubules of membrane using the covalence bonding and
entrapment methods. Howorka et al. bonded DNA-SH to the inner pore
to detect the complementary DNA. When the isonucleoside was
modified in the inner pore, the current would be decreased by 30%
[8,9]. Szabo et al. covalenced biotin molecule with the 3.4kDa
poly-ethyleneglycol of monomer cysteine -106 radical and then
bonded with the deep area of α-HL pore. After modification, the
ionic current would be lower by 15% [10].
However, the stability of traditional bilayer mem-brane is not
so high and this membrane can not play important role in practice.
So, there is much room to improve in acquiring the carrier with
more channel selectivity and higher stability. It has been proved
that solid supported object as the carrier will be more stable than
the single channel. Cornel et al. stabled the rami-cidin on the Au
surface as a biosensor and studied the transport of electrolyte
[11]. Stora et al. studied the bacterial multipore channel on the
similar surface, and found that the R residue can close the channel
[12].
3 Nanochannels of special material Nanochannels of special
material are nanochannel ar-rays prepared by the template
-synthesized method. This kind of special material nanochannels is
more selective and producible due to the flexible nanochan-nels
membrane. The application of these nanochannels membrane was
expanded due to the modification within the pores. The templates,
preparation and ap-plication of these channels in the below were
shown in table 1.
Table 1
3.1 The templates of nanochannels Generally, the membranes such
as porous alumina membranes and the track-etched membranes
generally can be used as template to make nanochannels. The
track-etched membranes prepared by polycarbonate, polyacetate or
other polymer material membranes are broadly used. At present, it
is a general method to syn-thesize nanomaterials within the pores
of porous alu-
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mina membranes. In contrast to traditional elec-tron-etch
technology, this method can get the nanoma-terial with high aspect
ratio. Furthermore, this method described here provides a simple
means to alter the diameter of the nanosized pores easily and make
the nanomaterial with good thermal stability.
It is possible to use nonaqueous emulsion template to get the
ordered macroporous molecule sieve because inorganic oxide is
easily hydrolyzed. Imhof and Pine reported a new method for
producing highly monodis-perse macroporous materials with pore
sizes ranging from 50 nm to several micrometres. The result showed
that the pore size can be accurately controlled, and that the
technique should be applicable to a wide variety of metal oxides
and even organic polymer gels [13]. Walsh and his coworkers
described a method for syn-thesizing hollow porous shells of
crystalline calcium carbonate (aragonite) that resembles the
coccospheres of certain marine algae. They showed that thin
cellular frameworks of either mesoporous or macroporous aragonite
can be formed from oil–water–surfactant microemulsions
supersaturated with calcium bicarbon-ate. Hollow spherical shells
of the honeycomb archi-tecture can be produced by using
micrometre-sized polystyrene beads as the substrate for the
microemul-sion. It proposed that these cellular frameworks
origi-nated from rapid mineralization of aragonite, with
self-organized foam of oil droplet acting as a structural template,
and similar processes could be of general importance in materials
chemistry [14].
Zhao et al. reported a morphological control ap-proach using
block copolymers, cosurfactants, cosol-vents , or the additive of
strong electrolytes to selec-tively form micrometer-sized hard
sphere-, fiber-, doughnut-, rope-, egg-sausage-, gyroid-, and
discoid-like mesoporous silica SBA-15 with highly ordered large
mesopore hexagonal structures [15].
The synthesis of mesoporous materials using sur-factants as
templates has been studied extensively since 1992 [16, 17]. In
1998, mesoporous silica mate-rials were prepared by HCl-catalyzed
sol-gel reaction of tetraethylorthosilicate in the presence of non
- sur-factant templating compounds, e.g., D-glucose, D-maltose, and
dibenzoyl-L-tartaric acid [18]. This new, versatile, low-cost,
environmentally friendly non-surfactant templating pathway leads to
mesopor-ous materials with large surface areas and pore vol-umes as
well as narrow pore size distributions. Zheng and Qiu synthesized
mesoporous titania materials us-
ing non-surfactant organic compounds, such as 2, 2-bis
(hydroxymethyl) propionic acid, glycerin and pentae-rythritol, as
templates via the HCl-catalyzed sol-gel process. The surface area
and pore volume increase slightly with increasing content of
organic template while the pore size is nearly constant (3~4 nm )
with narrow distribution about 0.5~0.8 nm [19].
Davis et al. showed how a bacterial superstructure, consisting
of a thread of coaligned multicellular fila-ments of bacillus
subtilis, can be used to extend the length scale of inorganic
materials patterning [20].
3.2 Preparation of Membrane Template-synthesized method is often
used in synthe-sizing nanochannels. It uses the porous material as
template containing pores whose diameter is varied from micron to
nanometer. Electrochemical deposition, chemical deposition,
chemical polymerization, sol-gel and chemistry gas deposition
methods can be used to deposit the atom or ion on the pore walls to
form channels and then remove away the template or leave it as
supported matter.
Potentiostatic or galvanostatic method at room tem-perature can
sputter a layer of Au onto one side of membrane to make the surface
electrically conductive. This electrodeposition method has been
used to pre-pare metal nanowire of Cu, Pt, Au and Ni. Changing the
amount of metal deposition can make the wires with different
length. A spot of metal deposition can get short wires while a mass
of metal deposition can get long and acicular wires. Zhang et al.
used electro-deposition method to fabricate the single-crystalline
anatase TiO2 nanowire arrays by anodic oxidative hy-drolysis of
TiCl3 with AAO(porous alumina mem-branes) template [21,22].The
fabrication of Au and Ni nanowire arrays is also reported. Li et
al. used this method to prepare Bi2Te3 and Bi2Te3 derived alloy
nanochannel arrays [23].
Electroless metal deposition involves the use of a chemical
reducing agent to plate a metal from solution onto a surface. Menon
and Martin described detail of electroless deposition of Au on the
nanochannels of polycarbonate membrane. The advantage of the
elec-troless method (relative to electrochemical plating) is that
the surface to be coated does not need to be elec-tronically
conductive. The key feature of the elec-troless deposition process
is that Au deposition begins at the pore wall. Changing the
deposition time can get the hollow tubules or stuffed wires. Unlike
electrode-
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position, by this method it is possible to control the inner
diameter by changing the deposition time [24]. Nishizawa et al.
synthesized many conductive poly-mers and prepare the nanochannel
or nanowire by con-trolling the deposition time [25].
Chemical polymerization is performed by immers-ing the membrane
template into the solution including polymeric monomer and
polymeric reagent. The inner diameter can be controlled by changing
the polyreac-tion time. The outside diameter is decided by the
di-ameter of template pore. Parthasarathy et al. produced
polyacrylonitrile nanochannel by immersing the porous alumina
membranes into the solution containing acry-lonitrile momomer
[26].
Sol-gel chemistry has recently been evolved into a general and
powerful approach for producing inorganic materials [27, 28]. This
method typically entails hy-drolysis of a solution of a precursor
molecule to obtain a suspension of colloidal particles (the sol)
and then a gel composed of aggregated sol particles. The gel is
then thermally treated to yield the desired material. It occurred
to us that sol-gel chemistry could be done within the pores of the
nanoporous template mem-branes to obtain tubules and fibrils of a
variety of in-organic materials. Martin used this method to make
tubules and fibrils composed of polymers, metals, semiconductors,
carbon, and Li ion intercalation mate-rials [29-31]. Lakshmi et al.
combined the sol-gel and template methods to prepare fibrils and
tubules of a variety of inorganic semiconducting materials
includ-ing ZnO, WO3 and TiO2 using alumina membrane as a template.
They found that single-crystal anatase-phase TiO2 nanostructures
can be obtained via this approach and that these nanostructures can
be used as efficient photocatalysts [32]. Like other template
synthesis methods, changing the immersion time can get the
nanochannels or nanofibrils.
Chemical vapor deposition (CVD) is a way to de-posit the
material onto the template in the vapor. The problem is that the
material may block the pores of surface and cannot deposit inside
because of the fast deposition speed. Li et al. developed a method
for producing pure carbon nanochannel fibers which in-volved direct
spinning of continuous fibers from an aerogel of carbon
nanochannels formed by CVD [33]. This process was realized through
the appropriate choice of reactants, control of the reaction
conditions and continuous withdrawal of the product with a
rotat-ing spindle used in various geometries.
3.3 Applications of special material nanochan-nels 3.3.1
Separation of the small molecule
The nanochannels can be acted as the molecular siev-ing and the
filtration. In 1995, Menon and Martin first reported a commercially
available microporous poly-carbonate filter with cylindrical
nanoscopic pores. The gold nanotubules are prepared via electroless
deposi-tion of Au onto the pore walls; i.e., the pores act as
templates for the nanotubules [24]. By controlling the Au
deposition time, Au nanotubules that have effective inside
diameters of molecular dimensions (
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(Au nanochannel membrane). Water and electrolyte are forbidden
from entering these very hydrophobic pores/nanochannels. The
transition to the “on” state was induced by partitioning a
hydrophobic ionic spe-cies (e.g., a drug or a surfactant) into the
membrane. The membrane switches to the “on” state because at a
sufficiently high concentration of this ionic analyte species, the
pores/nanochannels flood with water and electrolyte. A
pH-responsive membrane was also pre-pared by attaching a
hydrophobic alkyl carboxylic acid silane to the alumina membrane.
Steinle et al. investi-gated the transport of amiodarone,
amitriptyline and bupivacaine in the hydrophobic channels [38].
3.3.3 Separation of protein and DNA
Huang et al. prepared the gold nanotubule with about 55 nm of
diameter by chemical deposition of gold on polycarbonate templates
membrane. After being modi-fied by cysteine and guanide
thiocyanate, the nanomembranes were studied with BSA and IgG as the
model molecules. The results showed that guanide thiocyanate
facilitated transporting of BSA by 30 to 50 times because of
hydrophilic and denaturalization ef-fects whereas IgG almost
retained its transporting speed, indicating that gold nanotubule
membranes had a good separating capability for protein [39]. The
bo-vine IgG modified onto the pores of nanomembrane greatly impacts
the transport of detecting antibody through the Au nanotubules.
There was a larger differ-ence of transport rate between goat
anti-bovine IgG and goat anti-cat IgG through the B-IgG-Au-Mem.
Therefore, goat anti-bovine IgG and goat anti-cat IgG can permeate
through the nanotubules membrane se-lectively as shown in Figure2
[40]. DNA and proteins also were reported [41, 42]. Kohli et al.
prepared gold nanochannels with inside diameters of 12 nanometers.
A "transporter", DNA-hairpin molecule, was attached to the inside
walls of these nanochannels. These DNA-functionalized nanochannel
membranes selec-tively recognize and transport the DNA strand that
is complementary to the transporter strand. Under opti-mal
conditions, single-base mismatch transport selec-tivity can be
obtained [43]. The nanochannels with uniform pores can be prepared
by the template of po-rous alumina membranes. These nanomaterials
include metal, metal alloy, metal of oxide, semiconductor, and
polymer so on [44-49]. This template is also used to prepare DNA
and protein nanochannels and then detect them [50-51].
Figure2
3.3.4 Separation of chiral drug
Synthetic bio-nanochannel membranes were developed and used to
separate two enantiomers of a chiral drug. Lee et al. used alumina
films that had cylindrical pores with monodisperse nanoscopic
diameters (for example, 20 nanometers). Silica nanochannels were
chemically synthesized within the pores of these films, and an
an-tibody selectively bindings one of the enantiomers of the drug
was attached to the inner walls of the silica nanochannels. These
membranes selectively transport the enantiomer specifically binded
to the antibody. The enantiomeric selectivity coefficient increases
as the inside diameter of the silica nanochannels decreases
[52].
3.3.5 Separation based on different charge
Because Au nano template membranes (Au-NTMs) are electronically
conductive, they can be charged electro-statically in an
electrolyte solution. The inner walls of the metal tubules can be
charged by modification. The membranes reject ions with the same
sign and trans-port ions of the opposite sign. Because the sign of
the excess charge on the tubule can be changed potentio-statically,
a metal nanotubule membrane can be either cation selective or anion
selective depending on the potential applied to the membrane [25,
53].
In addition to transmembrane potential and nano-channel
diameter, solution pH value plays an important role in determining
the transport selectivity. This is because pH determines the net
charge on the protein molecule and this, in turn, determines the
importance of the electrophoretic transport term. Yu et al.
investi-gated the transport properties of four proteins (ly-sozyme,
bovine serum albumin, carbonic anhydrase and bovine hemoglobulins)
with different sizes and pI values [54].
3.3.6 Sensors based on the nanochannels
The nanochannel membranes can also be used as sen-sors. Martin
and his coauthors have shown that elec-trically conductive polymers
with fibrillar supermo-lecular structures can be prepared by
synthesizing the polymer within the pores of a microporous
membrane. They compared charge transport rates in fibrillar
polypyrrole with the corresponding rates in conven-tional
polypyrrole films. The results showed that the charge transport
rates in the fibrillar versions can be significantly higher
[55].
Martin et al. described an electroless deposition pro-cedure for
filling the pores in nanoporous filtration
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membranes with metal (gold) nanowires. This method prepared
ensembles of gold nanodisk electrodes in which the nanodisks have
diameters as small as 10 nm. Cyclic voltammetric detection limits
for electroactive species at ensembles containing 10-nm-diameter
gold disks can be as much 3 orders of magnitude lower than those at
large-diameter gold disk electrodes26. Moretto et al. described the
construction and characterization of an electrochemical nitrate
biosensor based on the ul-trathin-film composite membrane concept.
This film separated the analyte solution from an internal sensing
solution which contained the enzyme nitrate reductase and an
electrocatalyst (methyl viologen). The sensor showed good
sensitivity to nitrate, with a detection limit of 5.4 µM and a
dynamic range which extended up to 100µM NO3- [56]. Brunetti et al
prepared gold nanoelectrode ensembles (NEEs) used for biosensors
based on reductase enzymes — two phenothiazines (Azure A and B) and
methylviologen. Compared with macro electrode, NEE can obtained
lower detection limits without adsorption of the reduced forms to
the electrode surface .And it is the first use of the NEEs for the
determination of standard heterogeneous rates constants [57].
A new kind of nanochannels membrane with coni-cally shaped pores
was developed based on the mem-branes with cylindrical pores. The
conically pores membranes can provide dramatically higher rates of
transport than analogous cylindrical pore membranes. Apel et al.
showed that conical nanopores can be chemically etched into
radiation-tracked polymeric membranes [58]. Li et al. investigated
plasma etching the surface of a track-etched (vide infra) polymeric
membrane (schema1) to obtain conical pores as shown in Fig.3
[33].
Figure 3
Martin research group described resistive-pulse sensing of two
large DNAs, a single-stranded phage DNA (7250 bases) and a
double-stranded plasmid DNA (6600 base pairs), using a conically
shaped nanopore in a track-etched polycarbonate membrane as the
sensing element. The conically shaped nanopore had a small-diameter
(tip) opening of 40 nm and a large-diameter (base) opening of
1500nm. The phage DNA was driven electrophoretically through the
nanopore (from tip to base), and these translocation events were
observed as transient blocks in the ion current. They found that
the frequency of these cur-
rent-block events scales linearly with the concentration of the
DNA and with the magnitude of the applied transmembrane potential.
Increasing the applied transmembrane potential also led to a
decrease in the duration of the current-block events [59].
Sexton et al. added a protein analyte to the solution containing
antibody that selectively binds the protein. The complex formed
upon binding of the Fab to BSA is larger than the free BSA
molecule. So the cur-rent-pulse signature for the BSA/Fab complex
can be easily distinguished from the free BSA. Furthermore, the
BSA/Fab pulses can be easily distinguished from the pulses obtained
for the free Fab and from pulses obtained for a control protein
that does not bind to the Fab. The current-pulse signature for the
BSA/Fab complex can provide information about the size and
stoichiometry of the complex [60].
4 Conclusions Nanotubules technology is exhibiting the great
poten-tial advantages and promising future due to the size effect
and chemical physical characteristics. The ap-plications of
nanochannels in many fields, such as analytical chemistry,
biochemistry, materials science, environmental science, and so on,
will undergo more development although some reports on the
nanochan-nels have been published.
Acknowledgment
This work was supported by the National High-tech R&D
program (863 program, 2007AA06Z402), Pro-ject of Shanghai Municipal
Government (08520510400), Shanghai Leading Academic Disci-pline
Project (S30406), and Leading Academic Disci-pline Project of
Shanghai Normal University (DZL706).
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Table1.Templates, preparation and application of material
nanochannels
Different templates Membrane preparation applications of special
material
of nanochannels nanochannels in analytical
chemistry
membrane template electrochemistry deposition separate the
molecular with
emulsion template electroless deposition different size
micromulsion template chemical polymerization separate mixtures
containing
other kinds of templates sol-gel chemistry hydrophobic and
hydrophilic
chemical vapour deposition molecules
separate the molecular with differ-ent charge
separate protein,DNA
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Figure legends
Figure 1. Cross-section of single α-hemolysin channel embedded
in a lipid bilayer.4
Figure 2 The transport of goat anti-bovine IgG and goat anti-cat
IgG through Au-Mem and B-IgG-Au-Mem, respectively. 41
Figure 3. Surface SEM images of the membrane after (A) chemical
etching and (B) after 5min (C) 10min (D) 20 min of plasma
etching.34
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Figure 1
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Figure 2
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Figure 3
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