nanochannel and its application in analytical chemistrytively form micrometer-sized hard sphere-,...

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

RECENT ADVANCES in BIOLOGY, BIOPHYSICS, BIOENGINEERING and COMPUTATIONAL CHEMISTRY

ISSN: 1790-5125 80 ISBN: 978-960-474-141-0

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-


ISSN: 1790-5125 81 ISBN: 978-960-474-141-0

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-


ISSN: 1790-5125 82 ISBN: 978-960-474-141-0

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 (

(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


ISSN: 1790-5125 84 ISBN: 978-960-474-141-0

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).

References

[1] Stefureac, R., Long, Y.T., Kraatz, H.B. et al. Transport of α-helical peptides through α- Hemo-lysin and aerolysin pores. Biochemistry, Vol.45, No.12, 2006, 9172-9179

[2] Sutherland T C., Long Y T., Stefureac R I .et al. Structure of peptides investigated by nanopore analysis. Nano letters, Vol.4, No.7,2004, 1273-1277

[3] Jirage K.B., Hulteen J.C., Martin C.R.et al. Nano-tubule-Based Molecular-Filtration Membranes. Science,Vol. 278,No.5338,1997, 655-657


ISSN: 1790-5125 85 ISBN: 978-960-474-141-0

[4] Song, L., Hobaugh, M.R., Shustak, C. et al. Struc ture of staphyloco cal-hemolysin, α- heptameric transmembrane pore. Science, Vol.274,No.5294, 1996, 1859 -1865

[5] Deamer, D.W., Akeson, M. Nanopores and nucleic acids: prospects for ultrarapid sequencing. Trends in Biotechnol, Vol. 18,No.4, 2000, 147-151

[6]Akeson, M., Branton, D., Kasianowicz, J.J. et al. Microsecond time-scale discrimination Among poly-cytidylic acid, polyadenylic acid, and polyuridylic acid as homopolymers or as segments withinsingle RNA. J. Mol. Bio, Vol.77,No.6, 1999, 3227-3233

[7] Meller, A., Nivon, L., Branton, D. Voltage driven DNA translocation through a nanopore. Phys. Rev. Lett, Vol.86, No.15, 2001, 3435–3438

[8]Howorka, S., Cheley, S., Bayley, H. Squence - spe-cific detection of individual DNA strands using en-gineered nanopores. Nature, Vol.19, No.7, 2001, 636-639

[9] Howorka, S., Movileanu, L., Braha, O. et al. Ki-netics of duplex formation for individual DNA strands within a single protein nanopore. Proc. Natl. Acad. Sci, USA, Vol.98, No.23,2001, 12996-13001

[10] Szabo, I., Bathori, G., Tombola, F. et al. DNA translocation across planar bilayers containing bacillus subtilis ion channels. J. Bio. Chem., Vol.272, No.40, 1997, 25275-25282

[11] Cornell, B.A., Braach-Maksvytis, V.L., King, L.G. et al. A biosensor that uses ion-channel switches. Nature, Vol.387,No.6633,1997,580-583

[12] Stora, T., Lakey, J.H. Ion-channel gating in trans-membrane receptor proteins: functional activity in tethered lipid membranes. Angew. Chem. Int. Ed., Vol. 38, No.3, 1999, 389-392

[13] Imhof, A., Pine, D.J. Ordered marcoporous mate-rials by emulsion templating. Nature, Vol. 389, No. 6654, 1997, 948-951

[14] Walsh, D., Mann, S. Fabrication of hollow porous shells of calcium carbonate from self-organizing media. Nature, Vol.377, No.28, 1995, 320-323

[15] Zhao, D., Sun, J., Li, Q. et al. Morphological con-trol of highly ordered mesoporous silica SBA-15. Chem. Mater, Vol.12, No.2, 2000, 275-279

[16]Raman, N.K., Anderson, M.T., Brinker, C.J. Template-based approaches to the preparation of

amorphous, nanoporous silicas. Chem. Mater, Vol.8, No.8, 1996, 1682-1701.

[17] Kresge, C.T., Leonowicz, M.E., Roth, W.J. et al. Ordered mesoporous molecular sieves synthe-sized by a liquid-crystal template mechanism. Nature, Vol. 359, N0.22, 1992, 710-712

[18] Wei, Y., Jin, D., Ding, T. et al. A non-surfactant templating route to mesoporous silica materials. Adv. Mater, Vol.3, No.4, 1998, 313-316

[19] Zheng,J.Y., Qiu, K.Y. Synthesis of mesoporous titania materials with Non-surfactant organic compounds as templates. Chem. J. Chinese Univ., Vol.21, No.4, 2000, 647-649

[20] Davis, S.A., Burkett, S.L., Mendelson, N.H. Bact erial templating of ordered macrostructures in sil-ica and silica-surfactant mesophases. Nature, Vol.385, No.6615, 1997, 420-423

[21] Zhang, X.Y., Zhang, L.D., Chen, W. et al. Elec-trochemical fabrication of highly ordered semi-conductor and metallic nanowire arrays. Chem. Mater, Vol.13, No.8, 2001, 511-2515

[22] Zhang, X.Y., Zhang, L.D., Meng, G.W. et al. Syn-thesis of ordered single crystal silicon nanowire arrays. Adv. Mater, Vol.13, No.16, 2001, 1238 - 1241

[23] Li, X.H., Zhou,B., Pu,L. et al. Electrodeposition of Bi2Te3 and Bi2Te3 Derived Alloy Nanotube Arrays.Crystal Growth &Design, Vol.8, No.3, 2008, 771-775

[24] Menon, V.P., Martin, C.R. Fabrication and evalua-tion of nanoelectrode ensembles. Anal.Chem, Vol.67, No.13, 1995, 1920- 1928

[25] Nishizawa, M., Menon, V.P., Martin, C.R. Metal nanotubule membranes with electrochemically switchable ion-transport selectivity. Science, Vol.268, 1995, 700 – 702

[26] Parthasarathy, R.V., Phanikln, K.L., Martin, C.R. Template synthesis of graphitic nanotubules. Adv. Mater, Vol.7, No.5211, 1995, 896-897

[27]Regan, B.O., Gratzel, M. A low-cost, high - effi-ciency solar cell based on dye - sensitized colloi-dal TiO2 films. Nature, Vol.353, No.6346, 1991, 737-740

[28] Hench, L.L., West, J.K. The sol-gel process. Chem.


ISSN: 1790-5125 86 ISBN: 978-960-474-141-0

Rev, Vol.90, No.1, 1990, 33-72.

[29] Martin, C.R. Membrane-based synthesis of nano-materials. Chem. Mater, Vol.8, No.8, 1996, 1739-1746.

[30] Martin, C.R. Template synthesis of electronically conductive polymer nanostructures. Acc. Chem. Res, Vol.28, No.2, 1995. 61-68.

[31] Martin, C.R. Nanomaterials: A membrane-based synthetic approach. Science, Vol. 266, No.5193, 1961-1966.

[32]Lakshmi, B.B., Dorhout, P.K., Martin, C.R. Sol-gel

template synthesis of Semiconductor Nanostructures. Chem. Mater, Vol.9, No.11, 1997, 857-862

[33] Li, N.C., Yu, S.F., Harrell, C.C. et al. Conical nanopore membranes preparation and transport properties. J. Anal. Chem, Vol.76, No.7, 2004, 2025-2030

[34] Yu, S.F., Lee, S.B., Kang, M.et al. Size-Based Protein Separations in Poly(ethylene gly-col)-Derivatized Gold Nanotubule Membranes. Nanoletters. Vol.1, No.9, 2001,495-498

[35] Huang, S.S., Yin, Y.F. Transport and separation of small organic molecules through nanotubules. Anal. Sci, Vol.22, No.7, 2006, 1005-1009

[36] Shen, J., Huang, S.S., Peng, B. et al. Separation and detection of rutin based on gold nanotubule membrane. Acta. Chimica. Sinica, Vol.22, No.65, 2007, 2533-2538

[37] Hulteen, J.C., Jirage, K.B., Martin, C.R. Intro-ducing chemical transport selectivity into gold nanotubule membranes. J. Am. Chem. Soc, Vol.120,No.26, 6603-6604

[38] Steinle, E.D., Mitchell, D.T., Wirtz, M. et al. Ion channel mimetic micro-pore and nanochannel membrane sensors. Anal.Chem, Vol.74, No.10, 2002, 2416-2422

[39] Huang, S.S., Yin, Y.F., Wang, K.M. et al. A new biochemical method for protein separation based on gold nanotules membrane. Chem. J. Chinese Univ., Vol.25, No.12, 2007, 2238-2242

[40] Huang, S.S., Sheng, C., Yin, Z.F. et al. Immuno-reaction-based separation of antibodies using gold nanotubules membrane. J. Mem. Sci., Vol.305, No.1-2, 2007, 257–262

[41] Huang, S.S., Yin, Z.F., Yang, X.H. et al. Detection of target deoxyribo nucleic acid based on gold nanochannel membranes. Anal. Chem. (Chinese), Vol.34, No.11, 2006, 1515-1518

[42] Huang, S.S., Xu, G.M., Wang, K.M., et al. Studies of determination of IgG based on the nanotubules. Chinese. Sci. Bulletin., Vol.49, No.14, 2004, 1368-1370

[43] Zhang, Y., Li, G.H., Wu, Y.C. et al. Antimony nanowire arrays fabricated by pulsed electrode-position in anodic alumina membtanes. Adv. Ma-ter, Vol.14, No.17, 2002, 1227-1230

[44]Kohli, P., Harrell, C.C., Cao, Z.H. et al. DNA-functionalized nanochannel membranes with single-base mismatch selectivity. Science, Vol.305, No.5686, 2004, 984-986

[45] Evans, P.R., Yi, G., Schwarzacher, G. Current per-pendicular to plane giant magnetoresistance of multilayered nanowires electrodeposited in anodic aluminum oxide membranes. Vol.76, No.4, Appl. Phys. Lett, 481-483

[46] Sander, M.S., Gronsky, R., Sands, T. et al. Struc-ture of bismuth telluride nanowire arrays fabri-cated by electrodeposition into porous anodic alumina templates. Vol.15, No.1, Chem. Mater, 2003, 335-339

[47]Zhou, Y.K., Li, H.L. Sol-gel template synthesis of highly ordered LiCo0.5Mn0.5O2 nanowire arrays and their structural properties. J. Solid State Chem, Vol.165, No.2, 2002, 247-253

[48] Jeong, S.Y., Kim, J.Y., Yang, H.K. et al. Synthesis of silicon nanochannels on porous alumina using molecular beam epitaxy. Adv. Mater, Vol.15, No.14, 2003,1172-1176

[49]Ai, S .F., Lu, G., He, Q. et al. Highly flexible polyelectrolyte nanochannels. J. Am. Chem. Soc., Vol.125, No.37,2003,11140-11141

[50]Hou, S.F., Wang, J.H., Martin, C.R. Tem-plate-synthesized DNA nanochannels. J. Am. Chem. Soc., Vol.127.No.24, 2005, 8586-8587

[51]Hou, S.F., Wang, J.H., Martin, C.R. Tem-plate-synthesized protein nanochannel. Nano.Lett., Vol.5,No.2,2005,231-234

[52] Lee, S.B., Mitchell, D.T., Trofin, L. et al. 2002. Antibody-based bio-nanochannel membranes for enationmeric drug separations. Science, Vol.296,


ISSN: 1790-5125 87 ISBN: 978-960-474-141-0

No.5576, 2198-2200

[53]Lee,S.B., Martin, C.R. Electromodulated molecu-lar transport in gold-nanochannel membranes. J. Am. Chem. Soc., Vol.124, No.40, 2002, 11850-1158

[54]Yu, S.F., Lee, S.B., Martin, C.R. Electrophoretic protein transport in gold nanochannel membranes. Anal. Chem., Vol.75, No.9, 2003, 1239-1244

[55] Van, D., Leon, S., Martin, C.R. Electrochemical investigations of electronically conductive poly-mers. 4. controlling the Supermolecular Structure Allows Charge Transport Rates To Be Enhanced. Lannuir ,Vol.6,No.709,1990, 1118-1123

[56] Moretto, L M., Ugo, P., Zanata, M.et al. Nitrate biosensor based on the ultrathin-film composite membrane concept. Anal. Chem. Vol.70.No.10, 1998, 2163-2166

[57] Brunetti, B., Ugo, P., Moretto, L M. et al. Elec-trochemistry of phenothiazine and methyl-viologen biosensor electron-transfer mediators at nanoelectrode ensembles.J. Elec. Chem., Vol.491, No.1-2, 2000, 166–174

[58]Apel, P.Y., Korchev, Y.E., Siwy, Z. et al. Di-ode-like single-ion track membrane prepared by electro-stopping. Nucl.Inst.Meth.Phys. Res. B., Vol.184, No.3, 2001. 337-346.

[59] Harrell, C.C., Choi, Y., Horne, L.P., et al. Resis-tive-pulse DNA detection with a conical nanopore sensor. Langmuir, Vol.22, No.25, 2006, 10837 - 10843

[60]Sexton, L.T., Horne, L.P., Sherrill, S.A. et al. Re-sistive-pulse studies of proteins and pro-tein/antibody complexes using a conical nano-channel sensor. J. Am. Chem. Soc., Vol.129, No.43, 2007, 13144-13152


ISSN: 1790-5125 88 ISBN: 978-960-474-141-0

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


ISSN: 1790-5125 89 ISBN: 978-960-474-141-0

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


ISSN: 1790-5125 90 ISBN: 978-960-474-141-0

Figure 1


ISSN: 1790-5125 91 ISBN: 978-960-474-141-0

Figure 2


ISSN: 1790-5125 92 ISBN: 978-960-474-141-0

Figure 3


ISSN: 1790-5125 93 ISBN: 978-960-474-141-0

nanochannel and its application in analytical chemistrytively form micrometer-sized hard sphere-,...

Documents