US20100109510A1 - Functionalized carbon nanotubes - Google Patents
Functionalized carbon nanotubes Download PDFInfo
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- US20100109510A1 US20100109510A1 US12/564,750 US56475009A US2010109510A1 US 20100109510 A1 US20100109510 A1 US 20100109510A1 US 56475009 A US56475009 A US 56475009A US 2010109510 A1 US2010109510 A1 US 2010109510A1
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- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/68—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving nucleic acids
- C12Q1/6813—Hybridisation assays
- C12Q1/6816—Hybridisation assays characterised by the detection means
- C12Q1/6825—Nucleic acid detection involving sensors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/68—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving nucleic acids
- C12Q1/6813—Hybridisation assays
- C12Q1/6834—Enzymatic or biochemical coupling of nucleic acids to a solid phase
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/544—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being organic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/701—Integrated with dissimilar structures on a common substrate
- Y10S977/702—Integrated with dissimilar structures on a common substrate having biological material component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/701—Integrated with dissimilar structures on a common substrate
- Y10S977/707—Integrated with dissimilar structures on a common substrate having different types of nanoscale structures or devices on a common substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/745—Carbon nanotubes, CNTs having a modified surface
- Y10S977/746—Modified with biological, organic, or hydrocarbon material
Definitions
- the present invention relates in general to carbon nanotubes, and in particular, to the functionalization of carbon nanotubes.
- Carbon Nanotubes are used in their electron emission mode for many applications.
- the CNTs are deposited on a substrate, resulting in the field emission cathode.
- the CNTs are operated at high fields, and their adherence to the cathode substrate is very important.
- CVD chemical vapor deposition
- the other method is the use of CNTs that are already manufactured, in which case, in order to secure the adherence of the CNTs to the cathode substrate, inks and pastes, etc., may be utilized. Although these inks and pastes assist in adherence of these types of CNTs to the substrate, the emission characteristics of the carbon nanotubes are changed, and an activation process may be required to free the carbon nanotubes from the adhesion layer constituted of inks or pastes. These inks or pastes are based on a mixture of organic and inorganic materials. In general, the CNTs in inks and pastes have a higher threshold voltage, their electron emission is not uniform, and as a result, it is very difficult to produce high quality CNT televisions. Furthermore, the organic materials may disturb the high vacuum necessary for electron emission operation.
- FIG. 1 illustrates carbon nanotubes grown on a substrate and having different lengths
- FIG. 2 illustrates immersion of the CNTs in streptavidin
- FIG. 3 illustrates a functionalized CNT
- FIG. 4 illustrates a substrate coated with biotin
- FIG. 5 illustrates streptavidin-absorbed CNTs having a high affinity for biotin
- FIG. 6 illustrates a field emission device
- FIG. 7 illustrates DNA utilized to bind CNTs to a substrate
- FIG. 8 illustrates another embodiment of the present invention.
- an embodiment of the present invention is described around one example of making cathodes for CNT televisions, this invention is not limited to these types of devices.
- embodiments of the present invention are applicable to other bodies, antibodies or chemicals that have specific abilities to bind between them or bind in a localized fashion along the length of the CNT.
- At least one embodiment of the present invention uses precise location functionalization of CNTs over the length of the CNTs. For example, in some cases one would like to functionalize only a small portion in one of the ends of a CNT or both ends. In other situations, one may want to functionalize the CNT in the middle part of its length. If, for example, one were able to functionalize only one end of the CNT, and not its entire length, and then find a way to anchor this localized functionalized CNT on the substrate, a situation is achieved where a multitude of CNTs are all anchored in one end to the substrate, having the majority of their length available to direct themselves toward the anode when an electric field is applied.
- This method in this case solves the issue of activation, the use of inks or pastes (improving the vacuum necessary in the device), and also can be utilized to screen the very long or very short CNTs with respect to the average desired length. Furthermore, it is easier to control the density of carbon nanotubes on the substrate.
- CNT cathode may be used for electron emission in a CNT TV or other products.
- These cathodes may be made such that the CNTs are strongly attached to the substrate only at one of their ends and when they bend in the field they are substantially the same length, achieving in such a way a very uniform electron emission pattern, and as a result light emission uniformity from the anode.
- a process of the present invention begins with CNTs 101 grown on a wafer 102 by one of various methods known in the industry.
- perpendicular CNTs 101 may be grown by a CVD process on a wafer 102 such that the CNTs 101 are parallel to each other having more or less an average height, h, with CNTs 101 longer and shorter than h.
- the maximum length is L and the minimum length is l.
- the wafer 102 with the CNTs 101 grown on it may be immersed into a functionalizing agent 203 with nanometric precision through a precise immersion apparatus, and wafer holder 204 as shown in FIG. 2 . Because it may be desired to have the height of the CNTs 101 on the final cathode to be approximately h in the electric field, the wafer 102 may be immersed such that only the ends of the CNTs 101 having a length h or greater will be immersed in the functionalizing agent 203 .
- streptavidin may be used, which has very specific binding properties to another chemical, biotin. Referring to FIG.
- streptavidin homogeneously covers the immersed parts of the CNTs by adsorption as was indicated by fluorescence microscopy (see, Braun et al., DNA - Templated Carbon Nanotube Field - Effect Transistor, Science, Vol. 302, Nov. 21, 2003).
- fluorescence microscopy see, Braun et al., DNA - Templated Carbon Nanotube Field - Effect Transistor, Science, Vol. 302, Nov. 21, 2003.
- the CNTs 101 on the water 102 are harvested by controlled chemical etching (using piranha and ammonium persulfate solutions), laser, microtome or other method.
- a substrate 301 e.g., glass
- a material that has high affinity to streptavidin in the present example, biotin 302 may be used.
- biotin 302 may be used.
- These coating can be covalently attached to the substrate surface through thiol-, sulfhydryl- or amine-based surface modifications.
- a silanized glass or indium-tin oxide (ITO) surface presenting amine groups can be reacted with the N-hydroxysuccinimide (NHS) ester group of biotin-NHS creating a covalent linkage between the substrate and biotin.
- ITO indium-tin oxide
- the substrate 301 coated with biotin 302 localizes the streptavidin-adsorbed CNTs 401 to the cathode surface.
- the functionalized CNTs are deposited on the cathode substrate. Due to the strong specific binding between streptavidin and biotin, all the CNTs that were functionalized with streptavidin will bind to the substrate while all the CNTs not functionalized with streptavidin will not be bound to the substrate and will be washed off as shown in FIG. 5 .
- height h is defined and controlled by the depth of precise wafer insertion into the functionalizing agent (e.g., streptavidin), and is effectively uniform across the population of CNTs harvested from the wafer.
- the functionalized area of the free-end region of the CNTs is variable due to the variable native length of the CNTs as grown on the wafer.
- This variable functionalized region will adhere to the surface (e.g., at biotin layer), leaving h available to bend in the electric field toward the anode, as depicted in FIG. 6 .
- the streptavidin-biotin linkage 601 is depicted as a simplified rectangle on the surface of the substrate.
- the rectangle 601 illustrates the variable area of binding between the CNT 401 and the biotin layer.
- FIG. 6 also illustrates how a field emission device, such as a display, may be created.
- a phosphor (not shown) may be added to the anode.
- biotin-streptavidin linkage may be reversed in this process so that the streptavidin is on the second substrate in FIG. 4 .
- this process can be modified, for example by using complementary strands of short deoxyribonucleic acid (DNA) oligomers.
- DNA short deoxyribonucleic acid
- One single-stranded oligomer (Strand 1 ) is covalently attached to the cathode surface using numerous available chemistries including but not limited to disulfide bonding, esterification, or amidation.
- DNA oligomers generally of length less than 100 nucleotides, can be designed with assorted 3′ or 5′ end-modifications that allow for covalent attachment to surfaces, for example a 5′ amine (NH2) terminus.
- NH2 5′ amine
- the substrate is derivatized with a carboxyl(COOH)-terminated silane, a condensation reaction will covalently link the DNA oligomer to the surface through an amide bond.
- the ability of each derivatized surface to attach nucleic acid oligomers varies, depending on the functional groups and the attachment condition. The chemistries of these interactions can be exploited following well-established genetic microarray and biosensor techniques (Beier and Hoheisel, Versatile derivatization of solid support media for covalent bonding on DNA-microchips, Nucleic Acids Research, Vol. 27, pp. 1970-1977).
- This strand can even be patterned on the cathode if needed by DNA microarray printing techniques which utilize automated micro-volume printers to achieve high-density gridded arrays of DNA or similar biological material; mask fabrication which can control patterning of an e-beam deposited oxide to protect specified regions from DNA or biotin conjugation; or other method.
- the complementary “sequence” oligomer (Strand 2 ) is covalently attached specifically to the CNT terminus by “precise insertion” method by the process described in FIG. 2 , where the functionalizing solution is DNA oligomer.
- the CNTs can be carboxyl-functionalized (CNT-COOH) by acid treatment via precise insertion described here in H 2 SO 4 —HNO 3 solution or commercially purchased as-modified.
- the NH 2 -terminated DNA can be covalently linked to the CNT-COOH by condensation reaction, resulting in CNT-Strand 2 complexes.
- the DNA Strand 2 functionalized CNTs can now be localized to the Strand 1 derivatized cathode by the inherent annealing of complementary nucleic acid strands. In this case, the length of the double-stranded DNA complex is on the nanometer scale, while the CNT itself is microns in length.
- an alternate mechanism using long DNA may be designed using homologous DNA recombination via the RecA protein, as partially described by Erez Braun and associates (Braun et al., DNA-Templated Carbon Nanotube Field-Effect Transistor, Science, Vol. 302, Nov. 21, 2003.)
- ssDNA single-stranded DNA
- PCR polymerase chain reaction
- linear double-stranded lambda phage genome is covalently attached to the cathode surface through standard surface chemistry, examples of which are described above.
- the RecA polymerized ssDNA is incubated with the ds-lambda-DNA-derivatized cathode and homologous recombination occurs, mediated by RecA. Now the RecA resides with the dsDNA complex on the cathode surface.
- anti-RecA antibody is added to the cathode-dsDNA-RecA complex. The anti-RecA antibody binds RecA.
- a biotinylated secondary antibody e.g., commercially available anti-mouse, anti-rabbit, etc.
- Streptavidin-adsorbed CNTs (as in FIG. 2 ) are then localized to the cathode via the biotin moiety, and the process continues accordingly.
- the length of the double-stranded DNA-antibody complex is similar to the CNT itself.
Abstract
Carbon nanotubes are grown on a first substrate. The CNTs grown on the first substrate are immersed in a biological solution at a predetermined depth to functionalize ends of the CNTs with a biological molecule. The functionalized CNTs are harvested from the first substrate. A second substrate is functionalized with a complementary biological modification, which is a complementary binding partner to the biological molecule functionalized to the ends of the CNTs. The functionalized CNTs are attached to the second substrate by way of the complementary binding partner.
Description
- This application is a divisional of U.S. application Ser. No. 11/625,653 filed Jan. 22, 2007 and claims priority to U.S. provisional patent application Ser. No. 60/761,113 filed Jan. 23, 2006, both of which are incorporated by reference herein.
- The present invention relates in general to carbon nanotubes, and in particular, to the functionalization of carbon nanotubes.
- Carbon Nanotubes (CNTs) are used in their electron emission mode for many applications. In some of these applications, the CNTs are deposited on a substrate, resulting in the field emission cathode. In their electron emission mode, the CNTs are operated at high fields, and their adherence to the cathode substrate is very important. There are mainly two methods for CNTs to be deposited on cathodes. One is direct deposition by chemical vapor deposition (CVD) on the substrate that requires, in general, high temperatures, and as a result, is not compatible with low cost substrates. The other method is the use of CNTs that are already manufactured, in which case, in order to secure the adherence of the CNTs to the cathode substrate, inks and pastes, etc., may be utilized. Although these inks and pastes assist in adherence of these types of CNTs to the substrate, the emission characteristics of the carbon nanotubes are changed, and an activation process may be required to free the carbon nanotubes from the adhesion layer constituted of inks or pastes. These inks or pastes are based on a mixture of organic and inorganic materials. In general, the CNTs in inks and pastes have a higher threshold voltage, their electron emission is not uniform, and as a result, it is very difficult to produce high quality CNT televisions. Furthermore, the organic materials may disturb the high vacuum necessary for electron emission operation.
-
FIG. 1 illustrates carbon nanotubes grown on a substrate and having different lengths; -
FIG. 2 illustrates immersion of the CNTs in streptavidin; -
FIG. 3 illustrates a functionalized CNT; -
FIG. 4 illustrates a substrate coated with biotin; -
FIG. 5 illustrates streptavidin-absorbed CNTs having a high affinity for biotin; -
FIG. 6 illustrates a field emission device; -
FIG. 7 illustrates DNA utilized to bind CNTs to a substrate; and -
FIG. 8 illustrates another embodiment of the present invention. - In the following description, numerous specific details are set forth such as specific cathode materials, etc. to provide a thorough understanding of the present invention. However, it will be obvious to those skilled in the art that the present invention may be practiced without such specific details. In other instances, well-known circuits have been shown in block diagram form in order not to obscure the present invention in unnecessary detail. For the most part, details concerning timing considerations and the like have been omitted inasmuch as such details are not necessary to obtain a complete understanding of the present invention and are within the skills of persons of ordinary skill in the relevant art.
- Refer now to the drawings wherein depicted elements are not necessarily shown to scale and wherein like or similar elements are designated by the same reference numeral through the several views.
- It has been demonstrated that CNTs align in an electric field toward an anode when a high electric field is applied. As a result, the theories that CNTs must be previously aligned are not adequate.
- Furthermore, it has been demonstrated that electron emission uniformity is improved if carbon nanotubes are substantially equal in length such that no hot spot of higher electric fields are created destroying the uniformity.
- Although, an embodiment of the present invention is described around one example of making cathodes for CNT televisions, this invention is not limited to these types of devices. In addition to making CNT TV cathodes, embodiments of the present invention are applicable to other bodies, antibodies or chemicals that have specific abilities to bind between them or bind in a localized fashion along the length of the CNT. By functionalizing the CNTs on specific locations along the axis of the CNT, a multiple of to optoelectronic devices can be realized solving some of the processing and reliability issues created by the use of usual types of microelectronic processes.
- At least one embodiment of the present invention uses precise location functionalization of CNTs over the length of the CNTs. For example, in some cases one would like to functionalize only a small portion in one of the ends of a CNT or both ends. In other situations, one may want to functionalize the CNT in the middle part of its length. If, for example, one were able to functionalize only one end of the CNT, and not its entire length, and then find a way to anchor this localized functionalized CNT on the substrate, a situation is achieved where a multitude of CNTs are all anchored in one end to the substrate, having the majority of their length available to direct themselves toward the anode when an electric field is applied.
- This method in this case solves the issue of activation, the use of inks or pastes (improving the vacuum necessary in the device), and also can be utilized to screen the very long or very short CNTs with respect to the average desired length. Furthermore, it is easier to control the density of carbon nanotubes on the substrate.
- As an example, the following describes how a CNT cathode may be used for electron emission in a CNT TV or other products. These cathodes may be made such that the CNTs are strongly attached to the substrate only at one of their ends and when they bend in the field they are substantially the same length, achieving in such a way a very uniform electron emission pattern, and as a result light emission uniformity from the anode.
- Referring to
FIG. 1 , a process of the present invention begins withCNTs 101 grown on awafer 102 by one of various methods known in the industry. For example,perpendicular CNTs 101 may be grown by a CVD process on awafer 102 such that theCNTs 101 are parallel to each other having more or less an average height, h, withCNTs 101 longer and shorter than h. Assume that the maximum length is L and the minimum length is l. - The
wafer 102 with theCNTs 101 grown on it may be immersed into a functionalizing agent 203 with nanometric precision through a precise immersion apparatus, and wafer holder 204 as shown inFIG. 2 . Because it may be desired to have the height of theCNTs 101 on the final cathode to be approximately h in the electric field, thewafer 102 may be immersed such that only the ends of theCNTs 101 having a length h or greater will be immersed in the functionalizing agent 203. As an example of a functionalizing agent 203, streptavidin may be used, which has very specific binding properties to another chemical, biotin. Referring toFIG. 3 , streptavidin homogeneously covers the immersed parts of the CNTs by adsorption as was indicated by fluorescence microscopy (see, Braun et al., DNA-Templated Carbon Nanotube Field-Effect Transistor, Science, Vol. 302, Nov. 21, 2003). After the functionalization as described above, theCNTs 101 on thewater 102 are harvested by controlled chemical etching (using piranha and ammonium persulfate solutions), laser, microtome or other method. - Referring to
FIG. 4 , a substrate 301 (e.g., glass), which will be the base of the cathode, is coated with a material that has high affinity to streptavidin (in the present example, biotin 302 may be used). These coating can be covalently attached to the substrate surface through thiol-, sulfhydryl- or amine-based surface modifications. In one example, a silanized glass or indium-tin oxide (ITO) surface presenting amine groups can be reacted with the N-hydroxysuccinimide (NHS) ester group of biotin-NHS creating a covalent linkage between the substrate and biotin. Referring toFIG. 5 , thesubstrate 301 coated with biotin 302 localizes the streptavidin-adsorbedCNTs 401 to the cathode surface. Each streptavidin protein has four binding sites for biotin. The interaction of this binding pair results in extremely tight binding affinity, Kd=10−14 (Savage et al., 1992, Avidin-Biotin Chemistry: A Handbook, Rockford, Ill.: Pierce Chemical Company). - At this stage, the functionalized CNTs are deposited on the cathode substrate. Due to the strong specific binding between streptavidin and biotin, all the CNTs that were functionalized with streptavidin will bind to the substrate while all the CNTs not functionalized with streptavidin will not be bound to the substrate and will be washed off as shown in
FIG. 5 . Here, height h is defined and controlled by the depth of precise wafer insertion into the functionalizing agent (e.g., streptavidin), and is effectively uniform across the population of CNTs harvested from the wafer. The functionalized area of the free-end region of the CNTs is variable due to the variable native length of the CNTs as grown on the wafer. This variable functionalized region will adhere to the surface (e.g., at biotin layer), leaving h available to bend in the electric field toward the anode, as depicted inFIG. 6 . Here, the streptavidin-biotin linkage 601 is depicted as a simplified rectangle on the surface of the substrate. Therectangle 601 illustrates the variable area of binding between theCNT 401 and the biotin layer.FIG. 6 also illustrates how a field emission device, such as a display, may be created. A phosphor (not shown) may be added to the anode. - Alternatively, the biotin-streptavidin linkage may be reversed in this process so that the streptavidin is on the second substrate in
FIG. 4 . - Referring to
FIG. 7 , this process can be modified, for example by using complementary strands of short deoxyribonucleic acid (DNA) oligomers. One single-stranded oligomer (Strand 1) is covalently attached to the cathode surface using numerous available chemistries including but not limited to disulfide bonding, esterification, or amidation. DNA oligomers, generally of length less than 100 nucleotides, can be designed with assorted 3′ or 5′ end-modifications that allow for covalent attachment to surfaces, for example a 5′ amine (NH2) terminus. If the substrate is derivatized with a carboxyl(COOH)-terminated silane, a condensation reaction will covalently link the DNA oligomer to the surface through an amide bond. The ability of each derivatized surface to attach nucleic acid oligomers varies, depending on the functional groups and the attachment condition. The chemistries of these interactions can be exploited following well-established genetic microarray and biosensor techniques (Beier and Hoheisel, Versatile derivatization of solid support media for covalent bonding on DNA-microchips, Nucleic Acids Research, Vol. 27, pp. 1970-1977). This strand can even be patterned on the cathode if needed by DNA microarray printing techniques which utilize automated micro-volume printers to achieve high-density gridded arrays of DNA or similar biological material; mask fabrication which can control patterning of an e-beam deposited oxide to protect specified regions from DNA or biotin conjugation; or other method. The complementary “sequence” oligomer (Strand 2) is covalently attached specifically to the CNT terminus by “precise insertion” method by the process described inFIG. 2 , where the functionalizing solution is DNA oligomer. For example, the CNTs can be carboxyl-functionalized (CNT-COOH) by acid treatment via precise insertion described here in H2SO4—HNO3 solution or commercially purchased as-modified. The NH2-terminated DNA can be covalently linked to the CNT-COOH by condensation reaction, resulting in CNT-Strand 2 complexes. TheDNA Strand 2 functionalized CNTs can now be localized to theStrand 1 derivatized cathode by the inherent annealing of complementary nucleic acid strands. In this case, the length of the double-stranded DNA complex is on the nanometer scale, while the CNT itself is microns in length. - Referring to
FIG. 8 , an alternate mechanism using long DNA may be designed using homologous DNA recombination via the RecA protein, as partially described by Erez Braun and associates (Braun et al., DNA-Templated Carbon Nanotube Field-Effect Transistor, Science, Vol. 302, Nov. 21, 2003.) In this scenario, a single-stranded DNA (ssDNA) on the order of hundreds of nucleotides in length corresponding to the terminal sequence of the lambda phage genome is generated by polymerase chain reaction (PCR). This PCR fragment is polymerized with the RecA protein. RecA functions to homologously recombine ssDNA with complementary double-stranded DNA (dsDNA). In a separate reaction, linear double-stranded lambda phage genome is covalently attached to the cathode surface through standard surface chemistry, examples of which are described above. The RecA polymerized ssDNA is incubated with the ds-lambda-DNA-derivatized cathode and homologous recombination occurs, mediated by RecA. Now the RecA resides with the dsDNA complex on the cathode surface. Next, anti-RecA antibody is added to the cathode-dsDNA-RecA complex. The anti-RecA antibody binds RecA. A biotinylated secondary antibody (e.g., commercially available anti-mouse, anti-rabbit, etc.) is then added to the cathode complex which binds specifically to the anti-RecA antibody. Streptavidin-adsorbed CNTs (as inFIG. 2 ) are then localized to the cathode via the biotin moiety, and the process continues accordingly. In this case, the length of the double-stranded DNA-antibody complex is similar to the CNT itself. These materials are examples and there are many other possibilities depending on the adherence of the chemical layers to the cathode substrate and the strength of the binding between the functionalized CNTs and the intermediate layers. - Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (16)
1. A method comprising:
growing carbon nanotubes (CNTs) on a first substrate;
immersing the CNTs grown on the first substrate in a biological solution at predetermined depth to functionalize ends of the CNTs with a biological molecule;
harvesting the functionalized CNTs from the first substrate;
functionalizing a second substrate with a complementary biological modification, which is a complementary binding partner to the biological molecule functionalized to the ends of the CNTs; and;
to attaching the functionalized CNTs to the second substrate by way of the complementary binding partner.
2. The method as recited in claim 1 , wherein the biological solution comprises a protein.
3. The method as recited in claim 1 , wherein the biological solution comprises DNA.
4. The method as recited in claim 1 , wherein the biological solution comprises a carbohydrate.
5. The method as recited in claim 2 , wherein the complementary biological modification comprises a protein.
6. The method as recited in claim 3 , wherein the complementary biological modification comprises DNA.
7. The method as recited in claim 4 , wherein the complementary biological modification comprises a carbohydrate.
8. The method as recited in claim 1 , wherein the CNTs gown on the first substrate have varying lengths, and only CNTs having lengths of at least a predetermined length are functionalized with the biological molecule.
9. The method as recited in claim 1 , further comprising:
Positioning an anode a predetermined distance from the second substrate with the attached functionalized CNTs.
10. A field emission device comprising a cathode comprising a substrate with functionalized CNTs attached thereto by way of biological complementary binding pairs.
11. The field emission device as recited in claim 10 , further comprising an anode positioned a predetermined distance from the cathode.
12. The field emission device as recited in claim 11 , wherein the anode further comprises a phosphor deposited on a substrate that emits light in response to bombardment of electrons emitted from the cathode under an influence of an electric field.
13. The field emission device as recited in claim 10 , wherein the biological complementary binding pairs comprise DNA.
14. The field emission device as recited in claim 10 , wherein the biological complementary binding pairs comprise biotin and streptavidin.
15. The method as recited in claim 1 , wherein the biological solution comprises streptavidin, and the complementary binding partner comprises biotin.
16. The method as recited in claim 1 , wherein the biological solution comprises biotin, and the complementary binding partner comprises streptavidin.
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US12/564,750 US20100109510A1 (en) | 2006-01-23 | 2009-09-22 | Functionalized carbon nanotubes |
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JP (1) | JP2009523699A (en) |
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Families Citing this family (15)
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US9056783B2 (en) | 1998-12-17 | 2015-06-16 | Hach Company | System for monitoring discharges into a waste water collection system |
US7454295B2 (en) | 1998-12-17 | 2008-11-18 | The Watereye Corporation | Anti-terrorism water quality monitoring system |
US8958917B2 (en) | 1998-12-17 | 2015-02-17 | Hach Company | Method and system for remote monitoring of fluid quality and treatment |
US8920619B2 (en) | 2003-03-19 | 2014-12-30 | Hach Company | Carbon nanotube sensor |
US20100159366A1 (en) * | 2008-08-15 | 2010-06-24 | Massachusetts Institute Of Technology | Layer-by-layer assemblies of carbon-based nanostructures and their applications in energy storage and generation devices |
US8702897B2 (en) * | 2009-05-26 | 2014-04-22 | Georgia Tech Research Corporation | Structures including carbon nanotubes, methods of making structures, and methods of using structures |
US8426842B2 (en) * | 2010-02-02 | 2013-04-23 | The Invention Science Fund I, Llc | Doped graphene electronic materials |
US8354323B2 (en) | 2010-02-02 | 2013-01-15 | Searete Llc | Doped graphene electronic materials |
US8455981B2 (en) * | 2010-02-02 | 2013-06-04 | The Invention Science Fund I, Llc | Doped graphene electronic materials |
US8563965B2 (en) | 2010-02-02 | 2013-10-22 | The Invention Science Fund I, Llc | Doped graphene electronic materials |
US8278643B2 (en) * | 2010-02-02 | 2012-10-02 | Searete Llc | Doped graphene electronic materials |
US8557956B2 (en) | 2010-06-11 | 2013-10-15 | Southwest Research Institute | Aligned polymers including bonded substrates |
JP5826047B2 (en) * | 2012-01-19 | 2015-12-02 | セイコーインスツル株式会社 | Method for producing multilayer structure |
CN104380469B (en) * | 2012-04-12 | 2018-06-22 | 索尔伏打电流公司 | Nano wire functionalization, dispersion and adherence method |
US9806265B1 (en) | 2016-04-07 | 2017-10-31 | International Business Machines Corporation | Heterogeneous nanostructures for hierarchal assembly |
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- 2007-01-23 JP JP2008552540A patent/JP2009523699A/en active Pending
- 2007-01-23 TW TW096102549A patent/TW200744945A/en unknown
- 2007-01-23 CN CN2007800028363A patent/CN101473445B/en not_active Expired - Fee Related
- 2007-01-23 WO PCT/US2007/060881 patent/WO2008057614A2/en active Application Filing
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Also Published As
Publication number | Publication date |
---|---|
CN101473445A (en) | 2009-07-01 |
CN101473445B (en) | 2011-06-29 |
WO2008057614A2 (en) | 2008-05-15 |
JP2009523699A (en) | 2009-06-25 |
US7611906B2 (en) | 2009-11-03 |
WO2008057614A3 (en) | 2008-11-06 |
US20070172851A1 (en) | 2007-07-26 |
TW200744945A (en) | 2007-12-16 |
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