EP2909135A1 - Fonctionnalisation de surface couche-par-couche de nanostructures de fullerène dépourvues de catalyseur et ses applications - Google Patents

Fonctionnalisation de surface couche-par-couche de nanostructures de fullerène dépourvues de catalyseur et ses applications

Info

Publication number
EP2909135A1
EP2909135A1 EP12841875.3A EP12841875A EP2909135A1 EP 2909135 A1 EP2909135 A1 EP 2909135A1 EP 12841875 A EP12841875 A EP 12841875A EP 2909135 A1 EP2909135 A1 EP 2909135A1
Authority
EP
European Patent Office
Prior art keywords
layer
nanostructure
fullerene
och
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12841875.3A
Other languages
German (de)
English (en)
Inventor
Chunhong Li
David J. Ruggieri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ruggieri David J
Nanoselect Inc
Original Assignee
Ruggieri David J
Nanoselect Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/US2012/054399 external-priority patent/WO2013039819A2/fr
Application filed by Ruggieri David J, Nanoselect Inc filed Critical Ruggieri David J
Publication of EP2909135A1 publication Critical patent/EP2909135A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/154—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

Definitions

  • the disclosed system and method generally relate to a layer-by-layer surface functionalization of carbon nanostructures.
  • the disclosed system and method relate to layer-by-layer surface functionalization of carbon nanostructures and the application of such functionalized carbon nanostructures as sensing elements. More specifically, the disclosed system and method relate to the surface modification and functionalization of fullerene nanostructures produced using a Carbo Thermal Carbide Conversion process whereby exemplary fullerene nanostructures are rendered hydrophilic and free from non-specific adsorption.
  • CNT carbon nanotubes
  • One method for producing CNTs employs small particles of a metal catalyst, such as, but not limited to, nickel, cobalt and iron, to catalyze the decomposition of a carbon-containing gas thereby causing the growth of CNTs on each metal particle.
  • a metal catalyst such as, but not limited to, nickel, cobalt and iron
  • a different process named Carbo Thermal Carbide Conversion in which no metal catalyst is utilized may also produce CNTs in large quantities.
  • a carbide starting material e.g., silicon carbide, etc.
  • a reactive gas or an admixture of gases is passed through the chamber to actively remove silicon by-products.
  • the carbide is converted to carbon
  • Nanostructures such as CNTs. Nano structures produced via this method may be used as an electrode material as disclosed in patent application number 12/889,019 the entirety of which is incorporated herein by reference.
  • Pristine CNTs and CNTs grown on a carbide substrate are generally hydrophobic and individual CNTs tend to bundle together due to van der Waals forces.
  • Efforts have been made to covalently graft chemical functions to the surface of CNTs for various applications in attempts to impart new properties to these CNTs.
  • one conventional practice to impart new properties to CNTs is to first oxidize CNT powder in HNO 3 solution or oxygen plasma resulting in -OH and -COOH groups on the CNT surface. Functional groups may then be introduced via amide or ester bond formation. These as-functionalized CNTs may then be used as a powder or in a composite to enhance electrical or mechanical properties in various applications.
  • Another conventional practice to impart new properties to CNTs includes non-covalent functionalization of CNTs such as dispersion and solubilization of CNT powders using surfactants and polymers.
  • WO 03/050332 describes a preparation of CNT dispersions in liquid
  • WO 02/16257 describes a polymer wrapped, single-walled CNT
  • WO 03/102020 describes a method for obtaining peptides that bind to a CNT and other carbon nanostructures
  • WO 02/095099 describes non-covalent sidewall functionalization of CNTs
  • WO 07/013872 describes the use of non-covalently functionalized CNTs as a sensing composition.
  • non-covalent approach relies upon favorable interactions between adsorbed molecules and CNT sidewalls, namely, van der Waals, ⁇ - ⁇ , and CH- ⁇ interactions.
  • non-covalent functionalization of CNTs using these conventional approaches most likely results in little disturbance to the ⁇ system in a CNT and thus minimal alteration to the mechanical, electrical and spectroscopic properties of CNTs.
  • These non-covalent approaches typically perform well in dispersing and solubilizing CNT powders, and such approaches generally include mechanical force processes such as ultrasonication and/or mechanical milling to form such powders.
  • An additional conventional approach to impart new properties to harness the superior properties of CNTs is to grow CNTs on a substrate, functionalize these CNTs on the substrate, and then use the resulting carbon nanostmcture on the substrate as an electrode material.
  • a thin film of a metal catalyst such as nickel, cobalt or iron may first be deposited on a silicon substrate with a titanium adhesion or barrier layer. This film may then be annealed at high temperature leading to the formation of small metal particles on the substrate. Feed gases such as acetylene, hydrogen and argon are introduced and contact the surface of each particle of metal catalyst whereby CNTs grow from the particles. The metal catalyst particles may then serve as conducting contacts between the CNTs and the substrate.
  • CNT dispersion and functionalization are non-conducting and introduce an uncontrolled amount of foreign materials (e.g., conducting or non-conducting) to the respective CNT surface which may compromise any superior electrical properties of the CNT.
  • foreign materials e.g., conducting or non-conducting
  • functionalized carbon nanostructures are free from non-specific adsorption.
  • serum albumin an abundant plasma protein in mammal, forms complexes with CNT whereby the binding leads to quenching of the band gap fluorescence of CNT.
  • An uncontrolled thickness of surface deposition of polymers or proteins may effectively block access to or shield the CNT from the environment. Thus, in such instances, the CNT would cease to function as sensing element.
  • Embodiments of the present subject matter may protect and functionalize carbon nanostructures using a layer-by-layer approach. For example, various functional groups and functional moieties may be introduced onto the carbon nanostructure surface platform thereby resulting in carbon nanostructures suitable for various applications. Embodiments of the present subject matter may also control the thickness of the functionalization layer thereby resulting in minimal alteration of the intrinsic electrical and optical properties of such carbon nanostructures. Additionally, embodiments of the present subject matter may adjust the density of introduced functional groups and functional moieties and may modulate the degree of surface hydrophilicity of the functionalized carbon nanostructures.
  • Functionalized carbon nanostructures formed according to exemplary embodiments may then be stable and robust in resisting fouling (e.g., mineral deposition and biofouling) when used in aqueous applications.
  • resisting fouling e.g., mineral deposition and biofouling
  • one embodiment of the present subject matter includes a stable CNT
  • electrochemical sensor which is adaptable to determine free chlorine, bromine, chlorine dioxide and ozone concentrations in flowing tap water.
  • Another embodiment of the present subject matter finds applicability as a voltammetric pH sensor when a pH responsive redox mediator moiety is introduced onto a CNT surface.
  • This resulting CNT electrode may then be used in a buffer solution with high ionic strength and/or a non-buffered tap water solution.
  • a further embodiment of the present subject matter provides a functionalized CNT-based potentiometric pH sensor for flowing tap water with low conductivity.
  • Such an exemplary functionalized CNT electrode may be employed to monitor molecular binding or interaction events on an electrode surface in electrochemical impedance spectroscopy or in a field-effect transistor (FET) device (e.g., ion-selective FET and solution-gate FET).
  • FET field-effect transistor
  • Pristine CNTs may also be dispersed and functionalized using an exemplary layer-by-layer approach for CNT sorting, separation and purification; and, exemplary surface functionalized CNTs according to embodiments of the present subject matter may be utilized as optical sensors by harnessing the unique spectroscopic properties of CNT such as optical absorption, luminescence and Raman scattering.
  • One embodiment of the present subject matter provides a layer-by- layer protection and functionalization of a carbon nanostructure by subjecting carbon nanostmctures to a composition comprising an alkyl protective moiety under conditions that permit the formation of an alkyl protective moiety layer adjacent to the carbon nanostructure.
  • Various functional groups and functional moieties may subsequently be introduced to form a second layer above the alkyl protective moiety layer. These introduced functional groups and functional moieties may, in other embodiments, undergo further transformations to incorporate additional layers and/or functionalities to the respective carbon nanostructure surface.
  • a further embodiment of the present subject matter provides a method for the protection of carbon nanostmctures such as fullerene nanostmctures.
  • the method may include protecting the surface of such a stmcture, e.g., a carbon and metal catalyst on a substrate, by contacting the nanostmctures with a composition comprising an alkyl protective moiety under conditions that permit the formation of an alkyl protective moiety layer disposed directly adjacent to at least a portion of the metal catalyst, the carbon, or both.
  • An additional embodiment of the present subject matter provides a method for subsequent surface functionalization of carbon nanostmctures, such as fullerene nanostmctures, comprising forming a second layer and/or third layer on nanostmctures that have been protected with an alkyl protective moiety layer.
  • functionalization may include, but is not limited to, the introduction of various functional groups such as -OH, -COOH, -NH 2 , -NHR, -SH, -S-S-R, -C ⁇ CH, -N 3 , -CN, -CHO, -CONH-NH 2 , a maleimido group, epoxide, and other functional moieties such as redox mediator stmctures.
  • functional groups such as -OH, -COOH, -NH 2 , -NHR, -SH, -S-S-R, -C ⁇ CH, -N 3 , -CN, -CHO, -CONH-NH 2 , a maleimido group, epoxide, and other functional moieties such as redox mediator stmctures.
  • these functional groups may be further derivatized to form covalent bonds with other functional moieties including, but not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, proteins such as enzymes and antibodies, quantum dots and nanoparticles, cells, cell organelles, and other cellular components, either before or after the formation of the second layer on carbon
  • Embodiments of the present subject matter may also control the density of specific functional groups and functional moieties on carbon nanostmcture surfaces and may control the degree of hydrophilicity of functionalized carbon nanostmcture surfaces. Exemplary methods may be provided to constmct a hydrophilic platform on the surface of a CNT and carbon nanostmcture.
  • Functional groups and/or moieties such as redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, proteins such as enzymes and antibodies, quantum dots and nanoparticles, cells, cell organelles, and other cellular components, may then be introduced on the hydrophilic surface via covalent bond formation that is free from non-specific adsorption.
  • Exemplary devices formed using embodiments of the present subject matter may include, but are not limited to, voltametric pH sensors using a layer-by-layer functionalization of carbon nanostmcture surface having, for example, redox mediator molecules that require proton participation for their redox reactions (redox peak potential shift and the solution pH adhere to the Nernst Equation), a surface-functionalized CNT- based potentiometric pH sensor, and an amperometric pH sensor, to name a few.
  • Another embodiment of the present subject matter provides a method of functionalizing carbon nanostmctures.
  • the method may include providing a carbon nanostmcture having a first protective layer on a surface of the stmcture and forming a functional second layer over the first protective layer, where the second layer comprises a bipolar molecule with functional groups or functional moieties.
  • One embodiment of the present subject matter provides a carbon
  • nanostmcture having a substrate with one or more carbon nanotubes situated on a surface of the substrate.
  • a first protective layer may cover portions of the substrate, and a functional second layer may be situated over the first protective layer.
  • This second layer may comprise a bipolar molecule with functional groups or functional moieties.
  • a further embodiment of the present subject matter provides a method of controlling the density of functional groups or functional moieties on a surface of a carbon nanostructure.
  • the method may include providing a carbon nanostructure having a first protective layer on a surface of the structure and forming a functional second layer over the first protective layer, the second layer having a controllable density of functional groups or functional moieties.
  • the density may be controlled by applying bipolar molecules having a predetermined ratio of functional groups or functional moieties.
  • An additional embodiment of the present subject matter provides a method of modulating hydrophilicity of a carbon nanostructure.
  • the method may include providing a carbon nanostructure having a first protective layer on a surface of the structure, and forming a hydrophilic second layer over the first protective layer using compounds having one or more -OH groups, -NH 2 groups or -NH- groups.
  • electrodes comprising fullerene nanostructures may be produced via a catalyst- free process where the nanostructure surface has been modified by contacting the nanostructures with a composition comprising an alkyl moiety under conditions that permit the formation of an alkyl moiety layer and by introducing various functional groups and functional moieties to form a second layer above the first layer. These functional groups and functional moieties may further undergo transformations to covalently incorporate additional layers and/or functionalities to the fullerene
  • nanostructure surface exemplary functionalities include, but are not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, proteins such as enzymes and antibodies, quantum dots and nanoparticles either before or after the formation of the second layer on fullerene nanostructure surfaces.
  • redox mediator molecules include, but are not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, proteins such as enzymes and antibodies, quantum dots and nanoparticles either before or after the formation of the second layer on fullerene nanostructure surfaces.
  • a method for functionalizing a fullerene nanostructure may include producing a fullerene nanostructure on a substrate using a catalyst- free process and forming a first protective layer on a surface of the fullerene nanostructure.
  • a functional second layer may be formed over the first protective layer where the second layer comprises a bipolar molecule with functional groups or functional moieties.
  • a nanostructure having a substrate with one or more fullerene structures situated on a surface of the substrate and a first protective layer covering portions of the fullerene structures and the substrate.
  • a functional second layer is provided over the first protective layer where the second layer comprises a bipolar molecule with functional groups or functional moieties.
  • An additional embodiment provides a nanostructure having a substrate with one or more fullerene structures situated on a surface of the substrate.
  • a first protective layer covers portions of the fullerene structures and the substrate, and a functional second layer covers the first protective layer where the second layer comprises a bipolar molecule with functional groups or functional moieties.
  • One embodiment provides a method for sensing an electrochemical species in an environment.
  • the method may include providing an electrochemical sensor, the sensor having a reference electrode and a sensing electrode with a fullerene
  • the sensing electrode is disposed between a first contact and a second contact.
  • a potential may be applied across the reference and sensing electrodes, and current resulting from the applied potential measured.
  • electrochemical species in the environment may then be determined as a function of the measured current.
  • Yet another embodiment provides a device for measuring electrochemical species in a fluid.
  • the device includes sensing and reference electrodes in
  • the sensing electrode may be disposed between a first electrical contact and a second electrical contact, and the sensing electrode may include one or more fullerene nano structures functionalized with a chemically stable moiety that measures concentration of an electrochemical species when a potential is applied across the first and second electrical contacts.
  • Figure 1 is a schematic illustration of an exemplary layer-by-layer approach to provide surface functionalization to a CNT and carbon nanostructure.
  • Figure 2 is an illustration of a general structure for a molecule with an attached anthraquinone functional moiety for CNT surface functionalization.
  • Figure 3 is an illustration of a hydrophilic CNT nanostructure surface with controllable density of anthraquinone moieties.
  • Figure 4 is a graphical depiction of a square wave voltammogram overlay of CNT nanostructures functionalized with different ratios of polyoxyethylene alkyl ether anthraquinone 2-carboxylic acid conjugate and C12EG30 for the formation of a second layer, demonstrating the control of functional moiety (anthraquinone) density on functionalized CNT nanostructure surface.
  • Figure 5 is a schematic illustration of controlling the number of -OH groups in a bipolar molecule used for the formation of a second layer on a functionalized CNT surface.
  • Figure 6 is a schematic illustration of depositing a polyoxyethylene dialkyl ether on a CNT surface to form a second layer on a functionalized CNT surface.
  • Figure 7 is an illustration of an exemplary structure of a hydrophilic CNT nanostructure surface and a covalent functionalization of surface -OH groups with an activated anthraquinone ester.
  • Figure 8 is a graphical depiction of a square wave voltammogram overlay of differently functionalized CNT nanostructure electrodes.
  • Figure 9 is a schematic illustration of an exemplary layer-by-layer introduction of various functional groups onto a CNT nanostructure surface.
  • Figure 10 is a graphical depiction of a square wave voltammogram overlay for various embodiments of the present subject matter.
  • Figure 11 is a graphical depiction of a square wave voltammogram overlay of a CNT nanostmcture electrode functionalized with anthraquinone in buffer solutions at various pHs.
  • Figure 12 is a plot of anthraquinone square wave voltammogram redox peak potential versus buffer solution pH for a CNT nanostmcture electrode
  • Figure 13 is a graphical depiction of an open circuit potential of a CNT nanostmcture electrode functionalized using an embodiment of the present subject matter.
  • Figure 14 is a plot of open circuit potential versus pH for flowing tap water using an embodiment of the present subject matter.
  • Figure 15 is a depiction of how untreated CNTs exhibit poor wettability.
  • Carbon nanotubes possess high tensile strength and elastic modulus but are somewhat subject to oxidation reactions. Such oxidation reactions may arise from the vulnerability of covalent sp bonds between individual carbon atoms in CNTs to oxidation when the bonds are not part of aromatic conjugation system. Further, defects in CNT nanostmctures are especially prone to oxidative damage and the electronic properties of CNTs may be severely affected by stmctural damages in CNTs.
  • CNTs are generally regarded as a superior electrode material
  • grown CNTs are typically hydrophobic.
  • CNTs are generally regarded as a superior electrode material
  • grown CNTs are typically hydrophobic.
  • CNTs are generally regarded as a superior electrode material
  • MWCNT multi-walled CNTs
  • conductive, semi-conductive, or insulated CNTs and chiral, achiral, open headed, capped, budded, coated, uncoated
  • FIG. 15 is a depiction of how untreated CNTs exhibit poor wettability. With reference to Figure 15, as-grown CNT patterns may trap air bubbles rendering the surfaces of individual CNTs inaccessible to an electrolytic aqueous solution. As a result, it may be difficult to control the effective electrode surface area for electrochemical detection.
  • a low current response may result in difficult calibration of an associated sensor or device and difficult quantification of analyte concentration in a respective aqueous solution.
  • CNTs may be necessary to control their surface hydrophobicity.
  • hydrophobicity may make such CNTs unsuitable for aqueous applications, especially in aqueous solutions with low ionic concentrations.
  • Embodiments of the present subject matter may chemically modify a CNT surface to impart a certain degree of hydrophilicity.
  • the use of CNTs as an electrode material is challenging as good contact between the CNT and a conductive surface or electric lead structure must be established.
  • CNTs have been used in a composite format with carbon powder on glassy carbon as an electrode material; however, such a mixture of CNT with carbon powder and a composite binder may result in uncertain electrical properties for the CNT.
  • hydrophobic CNTs Another issue with hydrophobic CNTs is non-specific adsorption. For example, as foreign material is non-specifically and uncontrollably adsorbed onto the nanostructure surface, electrical and optical properties of the nanostructure may be altered thus resulting in poor long-term stability for a respective sensing element. Further, an uncontrolled thickness of surface deposition of polymers or proteins (e.g., protein multi-layers) may also effectively block access to or shield a CNT from the environment thereby rendering the CNT inoperable as a sensing element.
  • polymers or proteins e.g., protein multi-layers
  • Embodiments of the present subject matter may grow CNTs on a substrate with an established electric contact.
  • a metal catalyst such as, but not limited to, nickel on top of a titanium adhesion/barrier layer may be deposited on a silicon substrate and annealed at a high temperature to form small catalyst particles.
  • any type of metal catalyst may be employed in embodiments of the present subject matter and the claims appended herewith should not be limited to the example above.
  • CNTs may grow from the catalyst particles and establish electric contact between the grown CNT and substrate.
  • Figure 1 is a schematic illustration of an exemplary layer-by-layer approach to provide surface functionalization to a CNT and carbon nanostructure. With reference to Figure 1, to exploit the superior electrical and optical properties of CNTs,
  • embodiments of the present subject matter may covalently attach additional functional groups or functional moieties such as redox mediators and enzyme molecules on top of an exemplary protective layer for the detection of other analytes of interest using a layer- by-layer approach.
  • grown CNTs 10 on a substrate 12 may be contacted with a composition comprising an alkyl protective moiety under conditions that permit the formation of an alkyl protective layer 15 disposed directly adjacent to at least a portion of the metal catalyst 14 and/or the carbon nanotubes 16.
  • An exemplary alkyl protective moiety may include, but is not limited to, a compound such as an alkane.
  • alkanes include n-octadecane, n-dodecane, eicosane and hexatriacontane. Of course, these examples of alkanes should not limit the scope of the claims appended herewith.
  • the alkyl protective layer 15 may have a thickness in the range of, for example, from about 1 nm to about 500 nm, about 10 nm to about 300 nm, about 50 nm to about 250 nm, or about 50 nm to about 100 nm.
  • the CNT surface having the first protective layer 15 may be hydrophobic.
  • One non-limiting method for the deposition of the first hydrophobic protective layer on an exemplary CNT nanostructure on a substrate may include depositing a solution comprising n-octadecane (10 mM in tetrahydrofuran (THF), 2 x 5 ⁇ ) onto CNTs on a silicon substrate using standard procedures. Upon drying the solvent in air, the treated sample may be placed in a small vial (I.D. ⁇ 2.5 cm) and the vial purged with an Argon stream for 30 seconds and then securely capped. This capped vial may be heated at 120°C for 16-24 h, and the sample then cooled to ambient temperature in the capped vial.
  • THF tetrahydrofuran
  • the sample may then be removed from the vial with forceps and rinsed with THF before drying in air.
  • the CNT may be highly hydrophobic with the alkyl protective layer (first layer) in place.
  • step two other functional groups 17 and functional moieties may then be introduced above this first protective, hydrophobic layer 15, leading to the formation of a second layer 18.
  • One non-limiting method for the second layer functionalization of a CNT nanostructure on a substrate may include providing a CNT nanostructure on a silicon substrate with the first alkyl protective layer in place, followed by depositing a solution of bipolar molecules or a mixture of bipolar molecules with desired functional groups or functional moieties onto the first layer (e.g., 10 mM in THF, 2 x 5 ⁇ ). Upon drying the solvent in air, the treated sample may be placed in a small vial (I.D. ⁇ 2.5 cm) and the vial purged with an Argon stream for 30 seconds and then securely capped.
  • a small vial I.D. ⁇ 2.5 cm
  • This capped vial may be heated at 80 ⁇ 120°C for 16-24 h, and the sample cooled to ambient temperature in the capped vial. The sample may then be removed from the vial with forceps and rinsed with a solvent to remove excess deposition before drying in air.
  • the CNT nanostmcture on the substrate may be used as an electrode if no additional functional groups derivatization is required.
  • bipolar molecule or a mixture of bipolar molecules where favorable hydrophobic-hydrophobic interaction assists the anchoring of the bipolar molecule onto the first layer 15 with the polar groups exposed for additional manipulation if necessary.
  • An exemplary bipolar molecule may be represented by a compound having the general formula (I):
  • Ri represents hydrogen or a Ci -50 straight or branched alkyl or alkenyl, which is optionally substituted with one or more halogen atoms;
  • R 2 represents a single bond, an aromatic or alicyclic group, -(OCH 2 CH 2 ) m -,
  • R may be R h R J CCH ⁇ R, or -(CH 2 ) N R 2 X;
  • R, R", R" may each be independently hydrogen, alkyl, cycloalkyl, alkyl and cycloalkyl substituted by one or more hydroxyl groups, alkyl and cycloalkyl substituted by one or more carboxylic groups, - (CH 2 CH 2 O) n R, - (CH 2 CH 2 CH 2 O) n R, or -[CH 2 CH(CH 3 )O] n R;
  • p, q may each be independently an integral number between 0 and 10;
  • Any polyol may be selected for use as the X substituent in a compound of the formula (I) above.
  • Polyols are compounds having multiple hydroxyl functional groups and may be, for example, diols, triols, tetrols, pentols, and the like.
  • Non-limiting examples of polyols also include polyethylene glycol, pentaerythritol, ethylene glycol, glycerin pentaerythrityl, polyglycerol, sorbitan, polyethylene oxide derivatives of sorbitan, sugar alcohols, trimethylolethane, and trimethylolpropane, among others.
  • the bipolar molecule may be represented by a compound having the eneral formula (II) with two sub-units connected by a linker:
  • Ri represents hydrogen or a Ci -50 straight or branched alkyl or alkenyl, which is optionally substituted with one or more halogen atoms;
  • R 2 represents a single bond, an aromatic or alicyclic group, -(OCH 2 CH 2 ) m -, - (OCH 2 CH 2 CH 2 ) m -, or -[OCH 2 CH(CH 3 )] m -, where m and n are each independently 0 to 500;
  • R may be R h R ⁇ CH ⁇ R, or -(CH 2 ) n R 2 X;
  • R, R", R" may each be independently hydrogen, alkyl, cycloalkyl, alkyl and cycloalkyl substituted by one or more hydroxyl groups, alkyl and cycloalkyl substituted by one or more carboxylic groups, - (CH 2 CH 2 O) n R, - (CH 2 CH 2 CH 2 O) n R, or -[CH 2 CH(CH 3 )O] n R;
  • p, q may each be independently an integral number between 0 and 10;
  • t, v may each be an integral number between 1 and 3
  • u and w may each be an integral number between 0 and 2
  • Y represents a single bond or a divalent linker that comprises: C 1-50 alkyl, alkenyl or aromatic group which is optionally substituted with one or more X; - (OCH 2 CH 2 ) m - -(OCH 2 CH 2 CH 2 ) m - or - [OCH 2 CH(CH 3 )] m - where m and n may each be independently 0 to 500.
  • Any polyol may be selected for use as the X substituent in a compound of the formula (II) above.
  • Exemplary polyols may be, but are not limited to, diols, triols, tetrols, pentols, polyethylene glycol, pentaerythritol, ethylene glycol, glycerin
  • pentaerythrityl polyglycerol, sorbitan, polyethylene oxide derivatives of sorbitan, sugar alcohols, trimethylolethane, and trimethylolpropane, and the like.
  • the bipolar molecule may be a compound similar to the compound represented by formula (II) above but may include more than two sub- units connected with multiple linker groups.
  • a bipolar molecule having three sub-units connected with two linker groups in a linear manner may be utilized. It should be appreciated by those skilled in the art that a bipolar molecule with three or more sub-units may be connected with three or more linker groups to form a macro-ring structure as well and such examples should not limit the scope of the claims appended herewith.
  • embodiments may introduce an array of functional groups onto a CNT surface above the hydrophobic alkyl protective layer 15.
  • the functionalized CNT surface should, however, be resistant to non-specific adsorption.
  • the functionalized CNT surface should also be highly hydrophilic.
  • Polyethylene glycol may generally resist non-specific adsorption when deposited on a surface and may render a respective surface hydrophilic to a certain degree.
  • Polyoxyethylene alkyl ethers may also be suitable to be deposited above the hydrophobic alkyl protective layer or first layer 15 on an exemplary CNT to form a hydrophilic polyethylene glycol layer or second layer 18.
  • polyoxyethylene alkyl ethers possess the general formula:
  • Pv 3 represents an optionally substituted, linear or branched, saturated or unsaturated, carbo- or heteroalkyl chain bearing 4 to 50 carbon atoms;
  • n represents an integer of 1 to 500, and preferably 4 to 200.
  • Exemplary polyoxyethylene alkyl ethers include, but are not limited to, tetraethyleneglycol monooctyl ether (designated as C8EG4), hexaethyleneglycol monododecyl ether (C12EG6), heptaethyleneglycol monohexadecyl ether (C16EG7) and commercially available detergents, identified by the trade names Brij®30 (C12EG4), Brij®52 (C16EG2), or Brij®56 (C16EG10), Brij®58 (C16EG20), Brij®35 (C12EG30), Brij®78 (C18EG20), Brij®S 100 (C18EG100), Brij®S 200 (C18EG200) (Croda
  • Embodiments of the present subject matter may employ a myriad of processes to synthesize exemplary bipolar molecules having various functional groups and functional moieties. It should be noted, however, that the subsequent processes detailed below are exemplary only and should not limit the scope of the claims appended herewith.
  • a first process may be used to synthesize N-( 6-hydroxy-n-hexyl)7-decylbenzamide represented by the general formula:
  • a portion of the this filtrate (0.71 1 mmol) may be mixed with 6-aminohexan-l-ol (0.1755 g, 1.5 mmol) upon stirring. After approximately 2 hours, the reaction mixture may be loaded onto a SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 . The fractions containing the desired product may be combined and concentrated to yield a white solid (0.239 g, 93%).
  • a second process may be used to synthesize N, N'-[2,2'-(ethylenedioxy) bis(ethyl)] di(/?-decylbenzamide) represented by the general formula:
  • the process may include adding 2,2'-(ethylenedioxy) bis(ethylamine)
  • a third process may be used to synthesize N-( 1 1 -hydroxy-3 ,6,9- trioxaundecyl) /?-decylbenzamide represented by the general formula:
  • the process may include adding 1 l-amino-3,6,9-trioxaundecan- l-ol (0.2 g, 1.0 mmol) to a CH 2 C1 2 solution (7 mL) ofp-decylbenzoic acid NHS ester (1.0 mmol) and Et 3 N (0.14 mL, 1.0 mmol).
  • the mixture may be stirred at room temperature for approximately 1 hour before loading onto an SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 .
  • the fractions containing the desired product may be combined and concentrated to yield a solid with a low melting point (0.31 g, 71%).
  • a fourth process may be used to synthesize N-( 1 1 -hydroxy-3 ,6,9- trioxaundecyl) octadecanamide represented by the general formula:
  • the process may include adding DCC (2.512 g, 12.173 mmol) to a CH 2 C1 2 solution (30 mL) of stearic acid (3.463 g, 12.173 mmol), NHS (1.429 g, 12.416 mmol) and Et 3 N (1.7 mL, 12.173 mmol) resulting in an opaque solution, which may slowly turn into a white slurry. After approximately 16 hours at room temperature, a white solid may be filtered using a Buchner filter funnel and rinsed with additional CH 2 C1 2 (30 mL) whereby the filtrate (stearic acid NHS ester) may be combined and used for subsequent reaction without further purification.
  • a portion of the filtrate (2.815 mmol) may be mixed with 1 l-amino-3,6,9-trioxaundecan-l-ol (0.483 g, 2.5 mmol) and Et 3 N (0.39 mL, 2.82 mmol) upon stirring.
  • the mixture may then be concentrated to ⁇ 5 mL and then loaded onto an SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 .
  • the fractions containing the desired product may be combined and concentrated to yield a white solid (0.772 g, 72%).
  • a fifth process may be used to synthesize C16EG10CH 3 represented by the general formula:
  • the process may include dissolving waxy solid Brij®56 (a mixture designated as C16EG10) (1.808 g, 2.65 mmol) in anhydrous DMF (6 mL). Upon the addition of NaH (57% oil dispersion, 0.223 g, 5.29 mmol), the mixture may turn slightly foamy with gas evolution. After introduction of CH 3 I (0.66 mL, 10.6 mmol), the reaction may become warm and gas evolution subside. After approximately 5 hours, the solvent may be removed in vacuo and the resultant white residue suspended in CH 2 C1 2 (2 mL) and then loaded onto an SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 and then 5% MeOH in CH 2 C1 2 . After removal of the solvent, the desired product may be obtained as a white waxy solid (0.963 g, 53% yield).
  • a sixth process may be used to synthesize C16EG10C6 represented by the general formula: [0067]
  • the process may include dissolving waxy solid Brij®56 (C16EG10) (3.53 g, 5.17 mmol) in anhydrous DMF (10 mL), followed by adding NaH (57% oil dispersion, 1.088 g, 25.84 mmol).
  • 1-bromohexane (4.354 mL, 31.02 mmol) may then be introduced to the mixture resulting in a slurry which may be stirred at room temperature in a sealed flask after gas evolution subsides.
  • the solvent may be removed in vacuo and the resultant white residue mixed with an ethyl acetate/hexanes mixture solvent (EtO Ac/hex, 1 : 1 v/v, ⁇ 5 mL).
  • This mixture may then be loaded onto an SiO 2 column and eluted with EtO Ac/hex (1 : 1 v/v) and then 3% MeOH in CH 2 C1 2 .
  • the fractions containing the product may be combined to yield a waxy solid (-3.15 g) and may then be subjected to a second SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 to yield a white waxy solid (2.872 g, 72% yield).
  • a seventh process may be used to synthesize heptaethylene glycol dihexadecyl ether (C16 rmula:
  • the process may include dissolving waxy solid heptaethylene glycol monohexadecyl ether (pure compound from Sigma- Aldrich, designated as C16EG7) (0.11 g, 0.2 mmol) in anhydrous DMF with NaH (57% oil dispersion, 42 mg, 1.0 mmol), followed by the addition of 1-bromohexadecane (0.366 g, 1.2 mmol).
  • the resulting mixture may be stirred at room temperature for approximately 16 hours in a sealed flask before removal of the solvent in vacuo and suspension of the resultant white residue in an ethyl acetate/hexanes mixture solvent (EtO Ac/hex, 1 : 1 v/v, ⁇ 2 mL).
  • EtO Ac/hex 1 : 1 v/v, ⁇ 2 mL
  • the suspension may then be loaded onto an SiO 2 column and eluted with EtO Ac/hex (1 : 1 v/v) and then 3% MeOH in CH 2 C1 2 to afford the desired product as a waxy film (0.147 g, 95% yield).
  • the process may include mixing waxy solid Brij®78 (a mixture designated as C18EG20) (2.302 g, 2.0 mmol) with anhydrous DMF (10 mL), followed by the addition of NaH (57% oil dispersion, 0.21 g, 5.0 mmol).
  • the mixture may be heated whereby gas evolution may commence and the mixture may become free-flowing.
  • 1-bromohexadecane (1.832 g, 6.0 mmol) may be introduced and the resulting slurry stirred at room temperature in a sealed flask. After approximately 16 hours, the solvent may be removed in vacuo and the white residue mixed with 3% MeOH in CH 2 C1 2 (5 mL) and SiO 2 (2 g).
  • the slurry may then be loaded onto an SiO 2 column, and eluted with 3% MeOH in CH 2 C1 2 and then 5% MeOH in CH 2 C1 2 . Less polar fractions of the product may be discarded, and the more polar fractions of product may be combined and concentrated in vacuo to afford a white waxy solid (1.619 g, 59%).
  • a ninth process may be used to synthesize C12EG30C12 represented by the general formula:
  • the process may include mixing white solid Brij®35 (a mixture designated as C12EG30) (2.624 g, 1.741 mmol) with anhydrous DMF (10 rnL), followed by adding NaH (57% oil dispersion, 0.183 g, 4.35 mmol). The mixture may be heated whereby gas evolution may commence and the mixture may become free-flowing.
  • l-bromododecane (1.252 mL, 5.223 mmol) may be introduced and the resulting slurry stirred at room temperature in a sealed flask. After approximately 16 hours, the solvent may be removed in vacuo and the white residue was mixed with 3% MeOH in CH 2 C1 2 (5 mL) and SiO 2 (2 g). The slurry may then be loaded onto an SiO 2 column, and eluted with 1 % MeOH in CH 2 C1 2 , 5% MeOH in CH 2 C1 2 and then 8% MeOH in CH 2 CI 2 . The fractions containing the desired product may be combined and concentrated in vacuo to afford a white solid (2.91 g, 100%).
  • a tenth process may be used to synthesize C16EG9CH 2 CH 2 N 3 represented by the general formu
  • the process may include dissolving waxy solid Brij®56 (C16EG10) (6.20 g, 9.078 mmol) in anhydrous THF (30 rnL), followed by adding Et 3 N (1.9 mL, 13.62 mmol) thereto.
  • Toluenesulfonyl chloride (1.904 g, 10.0 mmol) may be introduced to the mixture resulting in a slurry which may be stirred at room temperature in a sealed flask. After approximately 3 days, a solid may be filtered using a Buchner filter funnel and the filtrate concentrated to afford a milky liquid (8.16 g).
  • Anhydrous DMF (10 mL) and NaN 3 (0.649 g, 10.0 mmol) may be mixed with the milky liquid and then stirred at 80°C in a sealed flask for approximately 24 hours.
  • the solvent may then be removed in vacuo and the residue mixed with EtO Ac/hex (1 : 1 v/v) ( ⁇ 10 mL) and SiO 2 (5 g).
  • the resulting slurry may be loaded onto an SiO 2 column and eluted with EtO Ac/hex (1 : 1 v/v), 3% MeOH in CH 2 C1 2 and then 5% MeOH in CH 2 C1 .
  • Fractions containing the desired product may be combined to afford a light yellow waxy solid (5.3 g, 82%).
  • the process may include dissolving a light yellow waxy solid (a mixture designated as C16EG9CH 2 CH 2 N 3 ) (1.87 g, -2.63 mmol) in THF (20 mL), followed by adding a Raney Ni suspension (50% slurry in H 2 O, ⁇ 1 mL). Upon gas evolution subsiding, the solid may be filtered using glass wool in a pipette and rinsed with THF. The filtrate may then be concentrated and loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 , then 10% MeOH in CH 2 C1 2 and then MeOH/CH 2 Cl 2 /saturated NH 3 aqueous solution (1 :5:0.1 v/v/v). The desired product may be obtained as a white solid (1.006 g, 56%).
  • a light yellow waxy solid a mixture designated as C16EG9CH 2 CH 2 N 3
  • Raney Ni suspension 50% slurry in H 2 O, ⁇ 1 mL
  • a twelfth process may be used to synthesize (C16EG9CH 2 CH 2 S) 2 represented by the general formula:
  • the process may include dissolving waxy solid Brij®56 (C16EG10) (1.282 g, 1.877 mmol) in anhydrous CH 2 C1 2 (10 mL), followed by adding Et 3 N (0.53 mL, 3.75 mmol) thereto.
  • Methanesulfonyl chloride (0.22 mL, 2.82 mmol) may be introduced to the mixture at 0°C resulting in a suspension which may be stirred at room temperature in a sealed flask for approximately 30 min.
  • This reaction mixture may then be loaded onto an SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 .
  • the fractions may be combined and concentrated to afford a waxy solid (1.27 g), which may be mixed with anhydrous DMF (5 mL) and KSAc (0.381 g, 3.338 mmol). This mixture may be stirred at 80°C in a sealed flask for approximately 24 hours resulting in a gel-like suspension.
  • the suspension may be cooled to room temperature and mixed with 5% MeOH in CH 2 C1 2 (5 mL) and SiO 2 (5 g) and then loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 .
  • Fractions containing the product may be combined and concentrated into a red oil, and the red oil subjected to a second SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 to afford a pale yellow waxy solid (1.186 g).
  • This solid may then be dissolved in MeOH (5 mL) and then treated with NaOH (0.134 g, 3.34 mmol), stirred at room temperature in a sealed flask for approximately 16 hours, and then stirred in open air for approximately 16 hours to oxidize any free thiol -SH to its corresponding disulfide.
  • the resulting solid may then be mixed with 3% MeOH in CH 2 C1 2 (3 mL) and SiO 2 (2 g) resulting in a slurry.
  • This slurry may be loaded onto a SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 .
  • the product may be obtained as a pale yellow solid (1.04 g, 79% yield).
  • a thirteenth process may be used to synthesize CI6EGIOSO 3 " represented by the general formula:
  • the process may include mixing solid Brij®56 (C16EG10) (0.8829 g, 1.293 mmol) with a solid sulfur trioxide trimethylamine complex (SO 3 NMe 3 , 0.201 g, 1.44 mmol) in a sealed flask under Argon.
  • the mixture may then be warmed at 90°C for approximately 16 hours resulting in a white slurry which slowly turns into a clear oil, indicating the consumption of SO 3 NMe 3 .
  • the oil may then turn into a white solid upon cooling.
  • As the solid is not soluble in THF, this indicates conversion of C16EG10 to its sulfate C16EG10SO 3 " .
  • the resultant solid is soluble in a THF/MeOH (1 : 1 v/v) mixture solvent and may be employed for CNT nanostmcture surface functionalization without further purification.
  • a fourteenth process may be used to synthesize C18EG20SO 3 " represented by the general formula:
  • the process may include mixing Brij®78 (C18EG20) (1.331 g, 1.157 mmol) with a solid sulfur trioxide trimethylamine complex (SO 3 NMe 3 , 0.177 g, 1.272 mmol) in a sealed flask under Argon.
  • the mixture may then be warmed at 90°C for approximately 16 hours turning into a clear oil which indicates the consumption of SO 3 NMe 3 .
  • the oil may then turn into a white solid upon cooling which is soluble in a THF/MeOH (1 : 1 v/v) mixture solvent for CNT nanostmcture surface functionalization.
  • a fifteenth process may be used to synthesize C12EG30SO 3 " represented by the general formula:
  • the process may include mixing Brij®35 (C12EG30) (1.574 g, 1.044 mmol) with a solid sulfur trioxide trimethylamine complex (SO 3 NMe 3 , 0.16 g, 1.149 mmol) in a sealed flask under Argon.
  • the mixture may then be warmed at 90°C for approximately 16 hours turning into a clear oil which indicates the consumption of SO 3 NMe 3 .
  • the oil may then turn into a white waxy solid upon cooling which is soluble in a THF/MeOH (1 : 1 v/v) mixture solvent for CNT nanostructure surface
  • a sixteenth process may be used to synthesize C16EG7SO 3 ⁇ represented by the general formula:
  • the process may include mixing solid heptaethylene glycol monohexadecyl ether (C16EG7, 0.712 g, 1.293 mmol) with a solid sulfur trioxide trimethylamine complex (SO 3 NMe 3 , 0.198 g, 1.42 mmol) in a sealed flask under Argon.
  • the mixture may then be warmed at 90°C for approximately 16 hours turning into a clear oil which indicates the consumption of SO 3 NMe 3 .
  • the oil may then turn into a white waxy solid upon cooling which is soluble in a THF/MeOH (1 :1 v/v) mixture solvent for CNT nanostructure surface functionalization.
  • a seventeenth process may be used to synthesize C8EG3CH 2 CH 2 N 3 represented by the general formula:
  • the process may include adding toluenesulfonyl chloride (0.482 g, 2.53 mmol) to a THF solution (8 mL) of tetraethylene glycol monooctyl ether (pure compound from Sigma- Aldrich designated as C8EG4) (0.646 g, 2.11 mmol) and Et 3 N (0.593 mL, 4.22 mmol) resulting in a slurry.
  • This slurry may be stirred in a sealed flask at room temperature for approximately 24 hours whereby an additional 0.2 eq of toluenesulfonyl chloride may be introduced followed by additional stirring at 40°C for approximately 16 hours.
  • the solvent may then be removed, and the residue loaded onto an SiO 2 column and eluted with EtO Ac/hex 1 :2 then 1 : 1 to yield an oil (0.865 g, 89%).
  • This oil 0.865 g, 89%).
  • the process may include mixing an oil C8EG3CH 2 CH 2 N 3 (0.156 g, 0.469 mmol) with THF (3 mL), H 2 O (20 ⁇ ) and triphenyl phosphine (0.185 g, 0.704 mmol). The resulting mixture may then be stirred at room temperature under Argon in a sealed flask for approximately 16 hours. The solvent may be removed and residue loaded onto an SiO 2 column and eluted with 10% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 with a 1 % saturated NH 3 aqueous solution to afford the desired product as a clear film (0.11 g, 77% yield).
  • a nineteenth process may be used to synthesize 12-(n-octyl)-12-aza-3,6,9- trioxa-l-eicosanol represented b the general formula:
  • the process may include mixing dioctylamine (0.71 mL, 2.37 mmol) with tetraethylene glycol monotosylate (0.412 g, 1.18 mmol) in a sealed flask. The mixture may be stirred and warmed at 80°C for approximately 16 hours resulting in a slurry. Upon cooling, the slurry may be suspended in CH 2 C1 2 (5 mL), followed by adding Et 3 N (0.164 mL, 1.18 mmol) and acetic anhydride (0.112 mL, 1.18 mmol) at 0°C.
  • a twentieth process may be used to synthesize N, N-di-( «-octyl)-N-(l 1- hydroxy-3,6,9-trioxaundec l) succinamide represented by the general formula: (XXIII)
  • the process may include mixing dioctylamine (0.302 mL, 1.0 mmol) with succinic anhydride (0.1 1 g, 1.1 mmol) and diisopropylethylamme (DIPEA, 0.348 mL, 2.0 mmol) in CH 2 CI 2 (2 mL). After approximately 16 hours, the solution may be treated with l l-amino-3,6,9-trioxaundecan-l-ol (0.193 g, 1.0 mmol) and 3-diethoxyphosphoryloxy- l,2,3-benzotriazin-4(3H)-one (0.329 g, 1.1 mmol) resulting in a light yellow solution.
  • DIPEA diisopropylethylamme
  • This solution may be stirred at room temperature for approximately 4 hours before quenching with ethylene diamine (0.1 mL) to form a yellow suspension.
  • the suspension may be loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 to afford the desired product as a clear oil (0.306 g, 59% yield over two steps).
  • a twenty first process may be used to synthesize N, N-di-( «-octadecyl)-N - (1 l-hydroxy-3,6,9-trioxaundecyl) succinamide represented by the general formula:
  • the process may include mixing dioctadecylamine (0.261 g, 0.5 mmol) with succinic anhydride (0.055 g, 0.55 mmol) and diisopropylethylamme (DIPEA, 0.174 mL, 1.0 mmol) in CH 2 C1 2 (1 mL). After approximately 16 hours, the solution may be treated with 1 l-amino-3,6,9-trioxaundecan-l-ol (0.0966 g, 0.5 mmol) and 3- diethoxyphosphoryloxy-l,2,3-benzotriazin-4(3H)-one (0.165 g, 0.55 mmol) resulting in a light yellow solution. This solution may be stirred at room temperature for
  • a twenty second process may be used to synthesize N, N-di-(n-octadecyl)- N'-(6-hydroxyhexyl) succinamide represented by the general formula:
  • the process may include mixing dioctadecylamine (0.261 g, 0.5 mmol) with succinic anhydride (0.055 g, 0.55 mmol) and diisopropylethylamme (DIPEA, 0.174 mL, 1.0 mmol) in CH 2 CI 2 (1 mL). After approximately 16 hours, the solution may be treated with 6-amino-hexan-l-ol (0.0585 g, 0.5 mmol) and 3-diethoxyphosphoryloxy- l,2,3-benzotriazin-4(3H)-one (0.165 g, 0.55 mmol) resulting in a light yellow solution.
  • DIPEA diisopropylethylamme
  • This solution may be stirred at room temperature for 16 hours before quenching with ethylene diamine (0.15 mL) to form a yellow suspension.
  • the suspension may be loaded onto a SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 to afford the desired product as a clear oil (0.305 g, 86% yield over two steps).
  • a twenty third process may be used to synthesize 12-(n-octadecyl)-12-aza- 3,6,9-trioxa-l-triacontanol represented by the general formula:
  • the process may include mixing solid dioctadecylamine (0.367 g, 0.703 mmol) with tetraethylene glycol monotosylate (0.223 g, 0.639 mmol) in a sealed flask. The mixture may then be stirred at 90°C for approximately 16 hours to form an amber oil. Upon cooling, the resultant yellow solid may be suspended in 3% MeOH in CH 2 C1 2 (5 mL) followed by adding Et 3 N (0.21 mL, 1.5 mmol) and acetic anhydride (0.0354 mL, 0.375 mmol) resulting in a clearly slurry.
  • reaction mixture may be quenched with ethylenediamine (0.15 mL) and loaded onto an S1O 2 column and eluted with 3% MeOH in CH 2 C1 2 , 5% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 to yield the desired product as a waxy solid (0.212 g, 48% yield).
  • ethylenediamine (0.15 mL)
  • S1O 2 S1O 2 column
  • the process may include introducing diisopropylethylamine (0.082 mL, 0.472 mmol) and 3-diethoxyphosphoryloxy-l,2,3-benzotriazin-4(3H)-one (77.7 mg, 0.26 mmol) to a slurry of 3a, 7a, 12a-trihydroxy-5P-cholan-24-oic acid (96.5 mg, 0.236 mmol) and dioctadecylamine (123.3 mg, 0.236 mmol) in CH 2 CI 2 (5 mL) turning the slurry into a clear yellow solution after approximately 16 hours of stirring.
  • Ethylenediamine (0.025 mL) may then be added to the slurry and mixed with SiO 2 (1 g) and then loaded onto a SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 to yield the desired product as a white solid (0.186 g, 86% yield).
  • a twenty fifth process may be used to synthesize (2,2,2- trimethylol) azidoethane tri(3 -tetraoxaeicosanyl) ether represented by the general formula: (XXVIII)
  • the process may include stirring (2-bromomethyl)-(2-hydroxymethyl)- 1,3- propanediol (2.5747 g, 12.93 mmol) with aN 3 (1.163 g, 17.9 mmol) in anhydrous DMF (10 mL) in a sealed flask at 85°C for approximately three days.
  • the solvent may be removed in vacuo, and the resulting white slurry purified by loading onto an SiO 2 column and eluted with 10% MeOH in CH 2 C1 2 and then 20% MeOH in CH 2 C1 2 to yield the desired product (2-azidomethyl)-(2 -hydro xymethyl)-l,3-propanediol as a white soft solid upon standing (2.059 g, 99% yield).
  • (2-azidomethyl)-(2-hydroxymethyl)- 1,3 -propanediol (57.4 mg, 0.357 mmol) may then be mixed with NaH (57% oil dispersion, 68 mg, 1.61 mmol) in anhydrous DMF (5 mL).
  • Tetraethylene glycol monooctyl ether tosylate (0.525 g, 1.14 mmol) may then be introduced into the mixture resulting in a slurry. The slurry may then be stirred in a sealed flask at room temperature for approximately 24 hours, and additional NaH (57% oil dispersion, 42 mg) introduced followed by the addition of tetraethylene glycol monooctyl ether tosylate (0.10 g).
  • This reaction mixture may then be stirred at room temperature for approximately three days whereupon the solvent may be removed and residue loaded onto an SiO 2 column and eluted with EtO Ac/hex (1 :2 v/v) then 5% MeOH in CH 2 C1 2 to yield the desired product (2,2,2-trimethylol) azidoethane tri(3,6,9,12 tetraoxaeicosanyl) ether as a clear oil (0.37 g).
  • a twenty sixth process may be used to synthesize (2,2,2-trimethylol) ethylamine tri(3,6,9,12-tetraoxaeicosan l) ether represented by the general formula:
  • the process may include subjecting the clear oil (2,2,2-trimethylol) azidoethane tri(3,6,9, 12-tetraoxaeicosanyl) ether (0.37 g, -0.357 mmol) to reduction with triphenyl phosphine (0.14 g, 0.536 mmol) in THF (3 mL) with H 2 O (10 mg) in a sealed flask under Argon upon stirring for approximately 24 hours. The solvent may then be removed and the residue mixed with CH 2 C1 2 (1 mL) and then loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 , and then a mixture solvent of
  • a twenty seventh process may be used to synthesize
  • the process may include mixing pellets of Brij®35 (C12EG30) (9.042 g, 6.0 mmol) with Et 3 N (1.254 mL, 9.0 mmol) in THF (4 mL). The mixture may be heated to a clear solution and toluenesulfonyl chloride (1.258 g, 6.6 mmol) introduced thereto resulting in a milky slurry. The slurry may be stirred at room temperature for approximately three days and a solid filtered using glass wool in a glass pipette.
  • the solid may then be rinsed with THF (-1 0 mL) and the filtrate concentrated to a viscous oil in vacuo which may then be mixed with ethanolamine (3.62 mL, 60 mmol) in a sealed flask upon stirring at 90°C for approximately 16 hours resulting in a slightly yellow reaction mixture.
  • the mixture may become a waxy solid whereupon the solid may be dissolved in 5% MeOH in CH 2 C1 2 , loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 , 10% MeOH in CH 2 C1 2 , and then a mixture solvent of MeOH/CH 2 Cl 2 /saturated aqueous ammonia (10:90: 1 followed by 20:80:2 v/v/v) to yield the desired product as a slightly yellow waxy solid (6.408 g, 69%).
  • a twenty eighth process may be used to synthesize N-(C 16EG9CH 2 CH 2 ) ( ⁇ )-a-lipoic (XXXI)
  • the process may include introducing C16EG9CH 2 CH 2 NH 2 (0.1076 g, 0.1577 mmol) to a solution of ( ⁇ )-a-lipoic acid (39 mg, 0.189 mmol) and
  • a twenty ninth process may be used to synthesize N-(C16EG9CH 2 CH 2 ) anthraquinone-2-carboxylic acid amide represented by the general formula: (XXXII) [001 13]
  • the process may include introducing C16EG9CH 2 CH 2 NH 2 (0.101 g, 0.149 mmol) to a solution of anthraquinone-2-carboxylic acid (45 mg, 0.178 mmol) and diisopropylethylamine (52 ⁇ ⁇ , 0.297 mmol) in CH 2 C1 2 (2 mL), followed by adding 3- diethoxyphosphoryloxy-l,2,3-benzotriazin-4(3H)-one (53.4 mg, 0.178 mmol) resulting in a yellow solution.
  • ethyl enediamine (10 ⁇ ⁇ ) may be added to the solution resulting in a slurry which may be loaded onto an SiO 2 column and eluted with 3% MeOH in CH 2 C1 2 , 5% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 to afford the desired product as a light yellow waxy solid (93 mg, 68% yield).
  • a thirtieth process may be used to synthesize N-(C 12EG29CH 2 CH 2 )-N-(2- hydroxyethyl) anthraquinone-2-carboxylic acid amide represented by the general formula:
  • the process may include introducing C 12EG29CH 2 CH 2 NHCH 2 CH 2 OH (0.203 g, 0.131 mmol) to a solution of anthraquinone-2-carboxylic acid (33 mg, 0.131 mmol) and diisopropylethylamine (46 ⁇ ⁇ , 0.262 mmol) in CH 2 C1 2 (1 mL), followed by adding 3-diethoxyphosphoryloxy-l,2,3-benzotriazin-4(3H)-one (39.2 mg, 0.131 mmol) resulting in a yellow solution.
  • ethyl enediamine (10 ⁇ ⁇ ) may be added to the solution resulting in a slurry which may be loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 to afford the desired product as a light yellow waxy solid (172 mg, 75% yield).
  • a thirty first process may be used to synthesize N-(C 12EG29CH 2 CH 2 )-N- (2-hydroxyethyl) 3-(2,5-dimethoxyphenyl)propionic acid amide represented by the general formula:
  • the process may include introducing C12EG29CH 2 CH 2 NHCH 2 CH 2 OH (0.576 g, 0.371 mmol) to a solution of 3-(2,5dimethoxyphenyl) propionic acid (78.08 mg, 0.371 mmol) and diisopropylethylamine (129 ⁇ ⁇ , 0.742 mmol) in CH 2 CI 2 (4 mL), followed by adding 3-diethoxyphosphoryloxy-l,2,3-benzotriazin-4(3H)-one (1 1 1 mg, 0.371 mmol) resulting in a yellow solution. After approximately 16 hours,
  • ethylenediamine (30 ⁇ ⁇ ) may be added to the solution resulting in a slurry which may be loaded onto an SiO 2 column and eluted with 5% MeOH in CH 2 C1 2 and then 10% MeOH in CH 2 C1 2 to afford the desired product as a light yellow waxy solid (0.42 g, 65% yield).
  • an exemplary CNT nanostructure can be functionalized using a layer-by- layer approach, i.e., forming a first protective (e.g., alkyl) layer followed by a second layer of
  • polyoxyethylene alkyl ether or other layer may be employed as an electrode for free chlorine concentration determination in tap water, as a potentiometric pH sensor, an amperometric pH sensor, a biometric sensor or electrode, or a voltammetric pH sensor or other sensor or electrode.
  • polyoxyethylene alkyl ethers may be derivatized to form bipolar molecules with additional functionalities.
  • the -OH group in polyoxyethylene alkyl ethers may react with SO 3 or P 2 O 5 to create a bipolar molecule which can be used to introduce -OSO 3 " or -OPO 3 H 2 groups onto an exemplary CNT electrode surface.
  • an -OH group can form esters with various carboxylic acids and may undergo a variety of transformations to be replaced by groups such as, but not limited to, -N 3 , -NH 2 and -SH or -S-S-, to name a few.
  • polyoxyethylene alkyl ether may be converted to a respective mesylate or tosylate, which could then be substituted with nucleophilic groups including, but not limited to, halide, azide, sulfide or masked thiol such as thioacetate, NH 3 , primary amine, secondary amine and tertiary amine.
  • polyoxyethylene alkyl ether may react in the presence of NaH with activated acetate such as tert-butyl bromoacetate followed by deprotection of tert-butyl ester to yield polyoxyethylene alkyl ether with a terminal -COOH group.
  • Another embodiment may employ polyoxyethylene alkyl ether with a terminal -NH 2 group to react with succinic anhydride to introduce a terminal -COOH group.
  • a terminal -NH 2 or -NH- group in derivatized polyoxyethylene alkyl ether may react with various carboxylic acids via an amide bond formation.
  • a range of exemplary redox mediator moieties may be covalently linked to polyoxyethylene alkyl ether.
  • Exemplary, non-limiting mediators include anthraquinone 2-carboxylic acid, 3- (2,5-dimethoxyphenyl) propionic acid and ( ⁇ )-a-lipoic acid.
  • the hydroquinone moiety may be protected with methyl groups and hence the hydroquinone/benzoquinone redox pair would not be present after the second layer deposition. After a few scans of cyclic voltammetry, the 2,5-dimethoxyphenyl moiety may then be oxidized to generate a desired
  • hydroquinone/benzoquinone redox pair for electrochemical sensing of solution pH. It should be noted that many other masked/protected functional groups or functional moieties may be unmasked/deprotected electrochemically once they are introduced onto an exemplary CNT electrode surface, thus, such examples should not limit the scope of the claims appended herewith.
  • FIG. 2 is an illustration of a general structure for a molecule with an attached anthraquinone functional moiety for CNT surface functionalization.
  • a molecule 20 is provided having a polyoxyethylene alkyl ether covalently attached with redox mediators [e.g., anthraquinone (AQ)] or another functional group (e.g., polyoxyethylene alkyl ether conjugate) to form an exemplary second layer 18 above the first protective layer 15 on a CNT structure (see Figure 1). Peak potential of the respective redox mediators may be used to determine solution pH according to the Nernst Equation.
  • redox mediators e.g., anthraquinone (AQ)
  • another functional group e.g., polyoxyethylene alkyl ether conjugate
  • FIG 3 is an illustration of a hydrophilic CNT nanostructure surface with controllable density of anthraquinone moieties.
  • the density of exemplary functional groups may be, in one embodiment, controlled by mixing polyoxyethylene alkyl ether containing a first functional group with polyoxyethylene alkyl ether containing a second functional group.
  • polyoxyethylene alkyl ether derivatized with a terminal -NH 2 or -NH- group can be mixed with a non- derivatized polyoxyethylene alkyl ether to control the density of the surface -NH 2 or - NH- group.
  • polyoxyethylene alkyl ether anthraquinone 2-carboxylic acid conjugate may be diluted with non-derivatized polyoxyethylene alkyl ether to control the density of anthraquinone functional moieties on a CNT surface as illustrated in Figure 3.
  • Figure 4 is a graphical depiction of a square wave voltammogram overlay of CNT nanostructures functionalized with different ratios of polyoxyethylene alkyl ether anthraquinone 2-carboxylic acid conjugate and C12EG30 for the formation of a second layer.
  • exemplary functionalized CNT nanostructures is important for such nanostructures to be used as electrodes since many electrochemical reactions in aqueous solutions require the participation of H + or OH " . It follows that one may then control the degree of surface hydrophilicity at the molecular level. Thus, by increasing the number of terminal -OH groups in the polyoxyethylene alkyl ether chain, the degree of hydrophilicity of the subsequently functionalized CNT surface may be increased.
  • the tosylate of polyoxyethylene alkyl ether may be treated with ethanolamine, 2-amino-l,3-propandiol, 3-amino-l ,2-propandiol and tris(hydroxymethyl) amino methane to introduce 1 , 2 and 3 terminal -OH groups onto the polyoxyethylene alkyl ether chain.
  • Figure 5 is a schematic illustration of controlling the number of -OH groups in a bipolar molecule used for the formation of a second layer on a functionalized CNT surface.
  • aminopolyols may be used in embodiments of the present subject matter including, but not limited to, amino saccharides that can be covalently linked to polyoxyethylene alkyl ether chain in similar fashion and such an example should not limit the scope of the claims appended herewith.
  • these derivatized polyoxyethylene alkyl ethers may lead to a surface having various degrees of hydrophilicity due to the presence of different numbers of terminal -OH groups.
  • primary aminoalcohols may also provide for subsequent derivatization of a resulting secondary amino group with various carboxylic acids including anthraquinone 2-carboxylic acid, 3-(2,5-dimethoxyphenyl) propionic acid and ( ⁇ )-a-lipoic acid via amide bond formation.
  • carboxylic acids including anthraquinone 2-carboxylic acid, 3-(2,5-dimethoxyphenyl) propionic acid and ( ⁇ )-a-lipoic acid via amide bond formation.
  • redox mediator molecules such as, but not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, proteins such as enzymes and antibodies, quantum dots and nanoparticles, cells, cell organelles, and other cellular components, may be covalently attached to the hydrophilic surface via ester or amide bond formation.
  • the tosylate of polyoxyethylene alkyl ether may react with various alcohols in the presence of NaH to afford polyoxyethylene alkyl ether with 0, 1, 2, 3, 4 or more -OH groups per polyoxyethylene alkyl ether chain.
  • exemplary, non-limiting alcohols may be any monoalkyl alcohol, ethylene glycol, glycerol, erythritol, threitol, pentaerythritol, inositol, xylitol, mannitol and other sugar alcohols.
  • Certain embodiments may also glycosylate the terminal -OH group in polyoxyethylene alkyl ether to covalently link various sugar alcohols or polyols to the polyoxyethylene alkyl ether chain.
  • the density of -OH groups may be controlled and the surface hydrophilicity modulated as desired.
  • One embodiment may modulate and/or control the density of various surface functional groups and functional moieties by mixing a bipolar compound containing the functional groups and/or functional moieties described herein with a similar bipolar compound containing no such functional groups and/or functional moieties according to a specific ratio (e.g., 1 : 1, 1 :2, etc.) in a solution used for the second layer functionalization of an exemplary CNT surface. Further, more than two compounds may also be utilized to simultaneously introduce functional groups with desired density.
  • a specific ratio e.g. 1 : 1, 1 :2, etc.
  • FIG. 6 is a schematic illustration of depositing a polyoxyethylene dialkyl ether on a CNT surface to form a second layer on a functionalized CNT surface.
  • the surface of an exemplary functionalized CNT nanostructure electrode 60 having a protective first layer 62 and a polyoxyethylene dialkyl ether C18EG20C16 in the second layer 64, may be hydrophilic thereby providing an indication that the polyoxyethylene portion thereof is exposed on the outermost surface.
  • the prospective functional group when the prospective functional group is relatively unstable under the conditions for the formation of the second layer, it may be desirable that the functional group be covalently attached after the second layer structure is established on the CNT surface.
  • Figure 7 is an illustration of an exemplary structure of a hydrophilic CNT nanostructure surface and a covalent functionalization of surface -OH groups with an activated anthraquinone ester.
  • an exemplary method may establish a hydrophilic platform on a CNT nanostructure 10 amenable for subsequent covalent attachment of various functional groups regardless of their size, polarity, hydrophobicity/hydrophilicity, and/or stability under elevated temperatures.
  • an exemplary CNT nanostructure electrode 10 may be protected with n- octadecane to form the first protective layer, followed by the deposition of molecules such as C12EG30, (2,2,2-trimethylol) ethylamine tri(3,6,9,12-tetraoxaicosanyl) ether or dioctadecylamine [(n-Ci 8 H 38 ) 2 NH] to form a second layer with -OH groups (see Figure 7) or -NH 2 or -NH- groups.
  • exemplary groups may be useful for covalent attachment of other functional groups or functional moieties.
  • carboxylic acids may be introduced to the surface via ester and amide bond formation, and other functional groups and functional moieties including, but not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, peptides and proteins such as enzymes and antibodies, quantum dots and nanoparticles, cells, cell organelles, and other cellular components, may also be covalently linked to the amino and/or hydroxyl groups on the hydrophilic surface.
  • Figure 8 is a graphical depiction of a square wave voltammogram overlay of differently functionalized CNT nanostructure electrodes. With reference to Figure 8 and continued reference to Figure 7 to illustrate certain principles underlying
  • a series of CNT nanostructures 10 were used to demonstrate the covalent nature of an exemplary functionalization process with functional groups such as -OH and -NH 2 in the second layer.
  • These CNT nanostructures 10 were first protected with n-octadecane in the first layer 62 and then deposited with C12EG30 to form the second layer 64 with -OH groups on the surface thereof.
  • the CNT nanostructure electrode 10 yielded a strong redox signal for the AQ as graphically illustrated by a first trace 82.
  • AQ methyl ester anthraquinone 2-carboxylic acid methyl ester
  • nanostructure electrode 10 subsequently yielded a considerably smaller redox signal for the AQ as graphically illustrated by a second trace 84.
  • a CNT nanostructure 10 was only protected with n-octadecane and no deposition of C12EG30 occurred for the second layer (hence no -OH groups on the nanostructure surface)
  • subsequent treatment of the electrode with activated AQ ester under identical condition resulted in no redox signal for the AQ as illustrated by a third trace 86.
  • another CNT nanostructure 10 having n-octadecane and then C12EG30 deposition was treated with only
  • FIG. 9 is a schematic illustration of an exemplary layer-by-layer introduction of various functional groups onto a CNT nanostructure surface.
  • ring opening reactions of epoxide may be advantageously employed using a CNT surface having a second layer with -OH groups or -NH 2 or -NH- groups that readily react with polyetheneglycol diglycidyl ether and trimethylolpropane triglycidyl ether.
  • Other glycidyl ethers can also be used including trimethylolethane triglycigyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol
  • Exemplary cross-linking 92 may result in a new polymeric layer (e.g., third layer) 94 with excess epoxide groups.
  • amino alcohols such as ethanolamine, 2-amino-l,3-propandiol, 3-amino-l,2-propandiol and
  • tris(hydroxymethyl)aminomethane, secondary amine -NH- and 1, 2 or 3 terminal -OH groups may be introduced onto the CNT surface.
  • aminopolyols including, but not limited to, aminosaccharides may be employed in similar fashion and such a disclosure should not limit the scope of the claims appended herewith.
  • the resulting amino and/or hydroxyl groups may also be derivatized with various carboxylic acids including 3-(anthracen-9-yl) propionic acid, anthraquinone 2-carboxylic acid, 3- (2,5-dimethoxyphenyl) propionic acid and ( ⁇ )-a-lipoic acid.
  • redox mediator molecules including, but not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, peptides and proteins such as enzymes and antibodies, quantum dots and nanoparticles, cells, cell organelles, and other cellular components, may also be covalently linked to the amino and/or hydroxyl groups on the hydrophilic surface layer 96.
  • the CNT nanostmcture may be treated with reagents in an appropriate solvent, e.g., activated AQ ester in CH 2 C1 2 for a predetermined period as described in examples above.
  • an appropriate solvent e.g., activated AQ ester in CH 2 C1 2
  • the CNT nanostmcture on the respective substrate may be rinsed with a solvent (e.g., THF), dried in air, and then wire- bonded and assembled for testing.
  • a solvent e.g., THF
  • a CNT nanostmcture functionalized with the first layer and second layer may be treated with reagents to form a third layer (e.g., via cross-linking) followed by subsequent transformations to incorporate additional functional groups or functional moieties.
  • a CNT nanostmcture on a substrate may be treated with a mixture solution of polyethylene glycol diglycidyl ether
  • PEGDGE polymethylolpropane triglycidyl ether
  • TMPTGE trimethylolpropane triglycidyl ether
  • THF 25mM/25mM, 2 x 5 ⁇
  • the CNT nanostmcture on the substrate may then be cooled to room temperature, rinsed with THF to remove excess PEGDGE and TMPTGE on the substrate.
  • the CNT nanostmcture may then be dried in air and placed in a tightly capped vial with a mixture of Tris (121 mg) in DMF (1 mL) under Argon atmosphere and warmed at 80°C for approximately 24 hours before removal from the DMF solution.
  • This nanostructure may then be rinsed with MeOH and THF and dried in air.
  • anthraquinone 2-carboxylic acid (9 mg, 0.0356 mmol) may be mixed with diisopropylethylamine (10.4 ⁇ ⁇ , 0.071 mmol) and 3-diethoxyphosphoryloxy- 1,2,3- benzotriazin-4(3H)-one (10.6 mg, 0.0356 mmol) resulting in a yellow solution.
  • the CNT nanostructure may then be placed in the yellow solution for approximately 16 hours and rinsed with THF and dried.
  • An exemplary CNT nanostructure functionalized in this manner may then, for example, be used as voltammetric pH sensor with long-term stability.
  • such a process is exemplary only and should not limit the scope of the claims appended herewith.
  • embodiments of the present subject matter may be employed as an electrochemical sensor to detect analytes in a fluid.
  • Analytes of interest may include, but are not limited to, hydrogen ions, hydroxide ions, free chlorine, total chlorine, chlorine dioxide, bromine, iodine, ozone, dissolved oxygen, sulfide, sulfite, nitrite, hydrogen peroxide, dopamine, uric acid, ascorbic acid, /?-aminophenol, 1-naphthol, oxidized 3,3 ',5,5'- tetramethylbenzidine, quinones, and combinations thereof.
  • Exemplary fullerene nanostructures may be, but are not limited to, buckminsterfullerenes, nanowires, nanorods, nanotubes, branched nanowires, nanotetrapods, nanotripods, nanohorns, nanobipods, nanocrystals, nanodots, nanoparticles, nanoribbons, 2D graphene structures, 3D graphene structures, and combinations thereof.
  • an auxiliary electrode, a reference electrode, and a working or sensing electrode any of which comprise exemplary fullerene nanostructures fabricated according to embodiments of the present subject matter may be exposed to a solution with an electrochemically active analyte of interest.
  • a voltage (e.g., about -0.5 V to about 1 V) may then be applied between the working electrode and the reference electrode for a suitable period of time or continuously whereby a current can be generated between the working electrode and the auxiliary electrode.
  • Current generated as a result of the application of voltage may then be measured, and the analyte concentration in the sample solution determined using methods known to those skilled in the art.
  • Other analytes such as trace metal ions including, e.g., Cd 2+ , Hg 2+ , Pb 2+ and Tl 3+ may also be detected in a similar fashion or by other
  • SWV measurements may be recorded using a Reference 600 potentiostat 5.61 with a standard three-electrode configuration having a Ag/AgCl reference electrode, a carbon rod auxiliary counter electrode, and a fullerene
  • the fullerene nanostructure may be functionalized with redox mediator molecules via a layer-by-layer process and then exposed to different pH solutions in the electrochemical cell.
  • SWV may be performed with the appropriate parameters to obtain the redox peak potential at various pH. Plotting the peak potential against solution pH would then generate a linear, Nerstian response.
  • embodiments of the present subject matter may be employed as a potentiometric pH sensor.
  • OCP may be used to sense solution pH whereby exemplary fullerene nanostructures can be functionalized via a layer-by-layer approach with polyethylene glycol alkyl ether, and then exposed to flowing tap water (after filtration over activated carbon to remove free chlorine in tap water) at different pH.
  • OCP may be measured between the fullerene nanostructure working electrode and the Ag/AgCl reference electrode whereby a plot of the OCP against flowing tap water pH would produce a linear response.
  • Figure 10 is a graphical depiction of a square wave voltammogram overlay for various embodiments of the present subject matter.
  • a series of bipolar molecules having -OH, -NH 2 and secondary amine groups may be used for the deposition of the second layer on an exemplary CNT surface.
  • (2,2,2-trimethylol) ethylamine tri(3,6,9,12-tetraoxaeicosanyl) ether was employed for this purpose as schematically illustrated by the generic process depicted in Figure 9.
  • Dialkyl amine including dioctadecylamine may also be applied to achieve a similar level of layer-by-layer surface functionalization.
  • Polyoxyethylene alkyl ethers such as, but not limited to, C12EG30 and C12EG30NHCH 2 CH 2 OH may also be used as the second layer material for crosslinking to construct an exemplary third layer on a CNT surface.
  • a strong redox signal may be observed by a first and second trace 1010, 1012 in Figure 10.
  • a cross-linked third layer may also stabilize the anchoring of functional groups and functional moieties on an exemplary CNT surface and may maintain the structural integrity of the surface layers thereby rendering the surface less prone to non-specific adsorption.
  • Exemplary CNT surfaces functionalized in this fashion may provide excellent long-term stability and are suitable for subsequent introduction of proteins and enzymes.
  • cross-linking and polymerization approaches may be employed by embodiments of the present subject matter for the construction of a third layer and such an example should not limit the scope of the claims appended herewith.
  • polymer brushes may be grown on top of the second or third layer of an exemplary CNT surface following the layer-by-layer approach and, with the appropriate chemistries, construction of a multilayer, organized structure possessing a controlled layer thickness may be performed.
  • Figure 11 is a graphical depiction of a square wave voltammogram overlay of a CNT nanostmcture electrode functionalized with anthraquinone in buffer solutions at various pHs.
  • Figure 12 is a plot of an anthraquinone square wave voltammogram redox peak potential versus buffer solution pH for a CNT nanostmcture electrode fimctionalized via an embodiment of the present subject matter.
  • exemplary functionalized carbon nanostructures may be used as sensing elements in various applications.
  • a voltammetric pH sensor was fabricated using a CNT nanostructure on a silicon substrate functionalized using an exemplary layer-by-layer approach with anthraquinone 2-carboxylic acid.
  • SWV square-wave voltammetry
  • a 0.05 M phosphate buffer solution with 0.1 M NaClO 4 as a supporting electrolyte at various pHs (2.0, 4.36, 7.0, 10.0 and 11.88)
  • the sensor electrode generated symmetrical redox peaks for the respective pHs.
  • SWV measurements were recorded using a Reference 600 potentiostat 5.61 with a standard three-electrode configuration, consisting of a Ag/AgCl reference electrode, a carbon rod auxiliary counter electrode, and a CNT nanostructure on Si substrate as working electrode in a specially designed electrochemical cell.
  • the exemplary CNT nanostructure was functionalized with redox mediator molecules using an exemplary layer-by-layer approach, and then exposed to different pH solutions (about 5 mL) in an electrochemical cell.
  • NaClO 4 may be added into these solutions as a supporting electrolyte to a concentration of 0.1 M.
  • the pH values of these solutions may be obtained using a pH meter.
  • SWV were performed with the following parameters:
  • a plot of redox peak potential against pH illustrated in Figure 12 provides a linear, Nernstian response having a slope of -55.8 mV/pH and linearity R of 0.9993, substantially close to the theoretical slope of -59.1 mV/pH.
  • Figure 12 thus reflects the plot of the AQ redox peak potential versus solution pH demonstrating a linear response from pH 2 to pH 1 1.88 with a slope of -55.788 mV per pH unit. It is apparent that an exemplary CNT nanostmcture electrode functionalized using a layer-by-layer approach with redox mediator molecules such as, but not limited to, AQ may be advantageously utilized as pH sensors for aqueous solutions.
  • Figure 13 is a graphical depiction of an open circuit potential of a CNT nanostmcture electrode functionalized using an embodiment of the present subject matter.
  • Figure 14 is a plot of open circuit potential versus pH for flowing tap water using an embodiment of the present subject matter.
  • a potentiometric pH sensor was fabricated using a CNT nanostmcture on a silicon substrate functionalized using an exemplary layer-by-layer approach with n-octadecane for the first layer and then polyoxyethylene alkyl ether Brij®35 (C12EG30) for the second layer.
  • PDMS polydimethylsiloxane
  • OCP open circuit potential
  • fullerene nanostructures may be employed as sensing elements in various applications.
  • Exemplary fullerene nanostructures may be, but are not limited to, buckminsterfullerenes, nanowires, nanorods, nanotubes, branched nanowires, nanotetrapods, nanotripods, nanohorns, nanobipods, nanocrystals, nanodots, nanoparticles, nanoribbons, 2D graphene structures, 3D graphene structures, and combinations thereof.
  • buckminsterfullerenes nanowires, nanorods, nanotubes, branched nanowires, nanotetrapods, nanotripods, nanohorns, nanobipods, nanocrystals, nanodots, nanoparticles, nanoribbons, 2D graphene structures, 3D graphene structures, and combinations thereof.
  • polyethylene glycol alkyl ethers may be used as an electrode to detect hydrogen ions, hydroxide ions, free chlorine, total chlorine, chlorine dioxide, bromine, iodine, ozone, sulfide, sulfite, nitrite, hydrogen peroxide, dopamine, uric acid, ascorbic acid, p- aminophenol, 1-naphthol, oxidized 3,3',5,5'-tetramethylbenzidine, quinones, trace metal ions (e.g., Cd 2+ , Hg 2+ , Pb 2+ , Tl 3+ , etc.), and combinations thereof in a fluid.
  • Such an exemplary electrode may resist non-specific adsorption and fouling on the electrode surface leading to an electrode possessing long-term stability.
  • An exemplary fullerene nanostmcture on a substrate functionalized via a layer-by-layer approach with a pH-dependent redox mediator may also be used as a voltammetric pH sensor.
  • a sensor electrode when subjected to SWV in aqueous buffer solutions at various pH, such a sensor electrode may generate well defined, symmetrical redox peaks.
  • a plot of the redox peak potential against pH may thus produce a linear, Nernstian response with a slope close to the theoretical slope of -59.1 mV/pH.
  • an exemplary fullerene nanostmcture on a substrate functionalized via a layer-by-layer approach with n-octadecane (first layer) and then polyoxyethylene alkyl ether Brij®35 (C12EG30) (second layer) may also be used as a potentiometric pH sensor for flowing tap water with low conductivity.
  • the OCP may be measured against a Ag/AgCl reference electrode placed above the fullerene nanostructure electrode and may thus produce a linear response to pH in flowing tap water.
  • Such an exemplary potentiometric pH sensor may find broad applications in water with low ionic concentrations as well as under pressure.
  • Exemplary starting materials may be comprised of a variety of materials including, but not limited to, carbide ceramic, aluminum carbide, boron carbide, chromium carbide, iron carbide, silicon carbide, and combinations thereof.
  • electrodes comprising fullerene nanostructures may be produced via a catalyst- free process where the nanostructure surface has been modified by contacting the nanostructures with a composition
  • exemplary functionalities include, but are not limited to, redox mediator molecules, crown ethers, catalysts, boric acids, carbohydrates, oligonucleotides (DNAs and RNAs), DNA or RNA aptamers, peptide aptamers, proteins such as enzymes and antibodies, quantum dots and nanoparticles either before or after the formation of the second layer on fullerene nanostructure surfaces.
  • exemplary electrodes may be included in a sensing element, a
  • voltammetric pH sensor a potentiometric pH sensor, an electrode, an amperometric pH sensor, a biometric sensor, a biometric electrode, an intracorporeal sensor, and/or an intracorporeal electrode.
  • an exemplary method may be provided to detect electrochemical species in a fluid.
  • the method may include applying a voltage between a working or sensing electrode and a reference electrode to produce a current between the sensing electrode and an auxiliary electrode where the working electrode may include exemplary fullerene nanostructures produced via a catalyst-free process.
  • the fullerene nanostructures may include an alkyl moiety layer adjacent the nanostructure surface and a second layer with various functionalities on top of the first layer whereby measured current may be proportional to a concentration of the
  • an exemplary method may be provided for detecting electrochemical species in an aqueous fluid.
  • the method may include forming a solution comprising said aqueous fluid and a reagent and contacting a working or sensing electrode, an auxiliary electrode, and a reference electrode with the solution.
  • An exemplary sensing electrode may include fullerene nanostructures as described herein.
  • the method may further include applying a voltage between the sensing electrode and the reference electrode to generate a current between the working electrode and the auxiliary electrode. This current may be measured and correlated to an amount of the
  • electrochemical species present in the fluid include, but are not limited to, hydrogen ions, hydroxide ions, free chlorine, total chlorine, or both, chlorine dioxide, bromine, iodine, ozone, dissolved oxygen, sulfide, sulfite, nitrite, hydrogen peroxide, dopamine, uric acid, ascorbic acid, /?-aminophenol, 1-naphthol, oxidized 3,3',5,5'-tetramethylbenzidine, quinones, and trace metal ions including Cd , Hg 2+ , Pb 2+ and Tl 3+ , to name a few.
  • a method is provided to detecting electrochemical species in a fluid in a two-electrode system.
  • the method may include applying a voltage between sensing and auxiliary electrodes to produce a current between the sensing electrode and an auxiliary electrode.
  • An exemplary sensing electrode may include fullerene
  • an exemplary monitoring system may collect information from a sensor monitoring the pH of a remote or local fluid system and may provide such information to a user or to a database for real-time or stored use.
  • an exemplary monitoring system may collect information transmitted wirelessly from an intracorporeal sensor or matrix of sensors or electrodes. Such provision (i.e., transmission) of information may be via any known mode of transmission (e.g., wireless or wire-line, as applicable).
  • any known mode of transmission e.g., wireless or wire-line, as applicable.
  • embodiments may be implemented using a general purpose computer programmed in accordance with the principals discussed herein. It is also envisioned that embodiments of the subject matter and the functional operations described in this specification may be implemented in or utilize digital electronic circuitry, or in computer software, firmware, or hardware, including the structures disclosed in this specification and their structural equivalents, or in combinations of one or more of them.
  • embodiments of the subject matter described in this specification can be implemented in or utilize one or more computer program products, i.e., one or more modules of computer program instructions encoded on a tangible program carrier for execution by, or to control the operation of, data processing apparatus.
  • the tangible program carrier can be a computer readable medium.
  • the computer readable medium can be a machine-readable storage device, a machine-readable storage substrate, a memory device, or a combination of one or more of them.
  • processor encompasses all apparatus, devices, and machines for processing data, including by way of example a programmable processor, a computer, or multiple processors or computers.
  • the processor can include, in addition to hardware, code that creates an execution environment for the computer program in question, e.g., code that constitutes processor firmware, a protocol stack, a database management system, an operating system, or a combination of one or more of them.
  • a computer program (also known as a program, software, software application, script, or code) can be written in any form of programming language, including compiled or interpreted languages, or declarative or procedural languages, and it can be deployed in any form, including as a standalone program or as a module, component, subroutine, or other unit suitable for use in a computing environment.
  • a computer program does not necessarily correspond to a file in a file system.
  • a program can be stored in a portion of a file that holds other programs or data (e.g., one or more scripts stored in a markup language document), in a single file dedicated to the program in question, or in multiple coordinated files (e.g., files that store one or more modules, sub programs, or portions of code).
  • a computer program can be deployed to be executed on one computer or on multiple computers that are located at one site or distributed across multiple sites and interconnected by a communication network.
  • processors executing one or more computer programs to perform functions by operating on input data and generating output. These processes may also be performed by special purpose logic circuitry, e.g., a field programmable gate array (FPGA) or an application specific integrated circuit (ASIC).
  • FPGA field programmable gate array
  • ASIC application specific integrated circuit
  • processors suitable for the execution of an exemplary computer program include, by way of example, both general and special purpose microprocessors, and any one or more processors of any kind of digital computer.
  • a processor will receive instructions and data from a read only memory or a random access memory or both.
  • the essential elements of a computer are a processor for performing instructions and one or more data memory devices for storing instructions and data.
  • a computer will also include, or be operatively coupled to receive data from or transfer data to, or both, one or more mass storage devices for storing data, e.g., magnetic, magneto optical disks, or optical disks.
  • mass storage devices for storing data
  • a computer need not have such devices.
  • a computer can be embedded in another device, e.g., a mobile telephone, a personal digital assistant (PDA), a mobile audio or video player, a game console, a Global Positioning System (GPS) receiver, to name just a few.
  • PDA personal digital assistant
  • GPS Global Positioning System
  • instructions and data include all forms of data memory including no n- volatile memory, media and memory devices, including by way of example semiconductor memory devices, e.g., EPROM, EEPROM, and flash memory devices; magnetic disks, e.g., internal hard disks or removable disks; magneto optical disks; and CD ROM and DVD- ROM disks.
  • semiconductor memory devices e.g., EPROM, EEPROM, and flash memory devices
  • magnetic disks e.g., internal hard disks or removable disks
  • magneto optical disks e.g., CD ROM and DVD- ROM disks.
  • the processor and the memory can be supplemented by, or incorporated in, special purpose logic circuitry.
  • exemplary systems may be implemented on a computer having a display device, e.g., a cathode ray tube (CRT) or liquid crystal display (LCD) monitor, for displaying information to the user and a keyboard and a pointing device, e.g., a mouse or a trackball, by which the user can provide input to the computer.
  • a display device e.g., a cathode ray tube (CRT) or liquid crystal display (LCD) monitor
  • keyboard and a pointing device e.g., a mouse or a trackball
  • Other kinds of devices can be used to provide for interaction with a user as well; for example, input from the user can be received in any form, including acoustic, speech, or tactile input.
  • Embodiments of the subject matter described in this specification may also be implemented in a computing system that includes a back end component, e.g., as a data server, or that includes a middleware component, e.g., an application server, or that includes a front end component, e.g., a client computer having a graphical user interface or a Web browser through which a user can interact with an implementation of the subject matter described is this specification, or any combination of one or more such back end, middleware, or front end components.
  • the components of the system may be interconnected by any form or medium of digital data communication, e.g., a
  • the computing system may also include clients and servers as the need arises.
  • a client and server are generally remote from each other and typically interact through a communication network. The relationship of client and server arises by virtue of computer programs running on the respective computers and having a client-server relationship to each other.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Abstract

L'invention concerne des nanostructures de fullerène produites à l'aide d'un procédé de Conversion de Carbone Carbothermique dépourvu d'un catalyseur pouvant être protégées et fonctionnalisées à l'aide d'un procédé couche-par-couche, des groupes fonctionnels sur la surface de nanostructure pouvant être modifiés ultérieurement pour incorporer des fractions fonctionnelles supplémentaires. Des fractions à titre d'exemple comprennent des molécules de médiation rédox, des éthers de couronne, des catalyseurs, des acides boriques, des glucides, des oligonucléotides, des aptamères d'ADN ou d'ARN, des aptamères peptidiques, des protéines telles que des enzymes et des anticorps, des points quantiques et des nanoparticules, des cellules, des organelles cellulaires ou d'autres composants cellulaires. La densité de groupes fonctionnels ou fractions fonctionnelles sur des surfaces nanostructurelles carbonées peut également être régulée, ainsi que le degré d'hydrophilie de surface de la nanostructure. Les nanostructures de fullerène fonctionnalisées à l'aide d'un procédé couche-par-couche peuvent être utilisées pour disperser, trier, séparer et purifier des nanostructures de fullerène et peuvent également être utilisées comme éléments de détection, tels que des capteurs de pH voltamétrique, ampérométrique et potentiométrique ou en tant qu'éléments et électrodes capteurs biométriques et capteurs et électrodes intracorporels.
EP12841875.3A 2011-10-18 2012-10-15 Fonctionnalisation de surface couche-par-couche de nanostructures de fullerène dépourvues de catalyseur et ses applications Withdrawn EP2909135A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201161548559P 2011-10-18 2011-10-18
PCT/US2012/054399 WO2013039819A2 (fr) 2011-09-12 2012-09-10 Fonctionnalisation couche par couche de surface de nanostructures de carbone
PCT/US2012/060197 WO2013059107A1 (fr) 2011-10-18 2012-10-15 Fonctionnalisation de surface couche-par-couche de nanostructures de fullerène dépourvues de catalyseur et ses applications

Publications (1)

Publication Number Publication Date
EP2909135A1 true EP2909135A1 (fr) 2015-08-26

Family

ID=48141264

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12841875.3A Withdrawn EP2909135A1 (fr) 2011-10-18 2012-10-15 Fonctionnalisation de surface couche-par-couche de nanostructures de fullerène dépourvues de catalyseur et ses applications

Country Status (2)

Country Link
EP (1) EP2909135A1 (fr)
WO (1) WO2013059107A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012603A (zh) * 2018-10-25 2018-12-18 济南大学 一种处理碱性废水中六价钼的吸附剂及其制备方法
US11932539B2 (en) 2020-04-01 2024-03-19 Graphul Industries LLC Columnar-carbon and graphene-plate lattice composite

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160102210A (ko) 2013-12-27 2016-08-29 노버스 인터내쇼날 인코포레이티드 에톡시화 계면활성제
CN106146544B (zh) * 2015-04-28 2019-02-26 东北林业大学 一种硅质体前体有机硅烷的制备方法
CN104914150B (zh) * 2015-06-15 2018-11-20 上海交通大学 一种基于石墨烯/聚苯胺复合膜的pH检测电极
US10584306B2 (en) 2017-08-11 2020-03-10 Board Of Regents Of The University Of Oklahoma Surfactant microemulsions
CN108586391B (zh) * 2017-12-15 2021-09-24 温州医科大学 一种蒽醌改性的石墨烯量子点aag及其制备方法与制备赖氨酸荧光检测试剂上的应用
US12119462B2 (en) * 2018-01-04 2024-10-15 Lyten, Inc. Sensing device for detecting analytes in batteries
CN110492115B (zh) * 2019-08-26 2021-03-16 东莞理工学院 石墨烯/碳纳米管框架包裹Fe3C催化剂、制备及应用
CN110498412B (zh) * 2019-09-06 2021-01-01 浙江恒澜科技有限公司 一种有机功能化氧化石墨烯的制备方法
CN112656409B (zh) * 2021-01-08 2022-03-01 嘉兴学院 一种纺织离子传感器及其制备方法与应用
CN117682945B (zh) * 2024-02-01 2024-07-05 苏州博研医药科技有限公司 一种聚多卡醇的制备方法及其中间体

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007089550A2 (fr) * 2006-01-26 2007-08-09 Nanoselect, Inc. Capteurs a base de nanotubes de carbone : dispositifs, processus et leurs utilisations
US20090278556A1 (en) * 2006-01-26 2009-11-12 Nanoselect, Inc. Carbon Nanostructure Electrode Based Sensors: Devices, Processes and Uses Thereof
US20110102002A1 (en) * 2008-04-09 2011-05-05 Riehl Bill L Electrode and sensor having carbon nanostructures
EP2499662A1 (fr) * 2009-11-11 2012-09-19 NanoSelect, Inc. Protection et modification de surface de nanostructures de carbone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013059107A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012603A (zh) * 2018-10-25 2018-12-18 济南大学 一种处理碱性废水中六价钼的吸附剂及其制备方法
US11932539B2 (en) 2020-04-01 2024-03-19 Graphul Industries LLC Columnar-carbon and graphene-plate lattice composite

Also Published As

Publication number Publication date
WO2013059107A1 (fr) 2013-04-25

Similar Documents

Publication Publication Date Title
EP2909135A1 (fr) Fonctionnalisation de surface couche-par-couche de nanostructures de fullerène dépourvues de catalyseur et ses applications
WO2013039819A2 (fr) Fonctionnalisation couche par couche de surface de nanostructures de carbone
WO2013039858A2 (fr) Capteur électrochimique à nanostructures de carbone et procédé
Hira et al. Ultrasensitive detection of hydrogen peroxide and dopamine using copolymer-grafted metal-organic framework based electrochemical sensor
Chen et al. Preparation of highly sensitive Pt nanoparticles-carbon quantum dots/ionic liquid functionalized graphene oxide nanocomposites and application for H2O2 detection
Wei et al. Stripping voltammetric determination of mercury (II) based on SWCNT-PhSH modified gold electrode
Li et al. Electrochemical behavior of graphene doped carbon paste electrode and its application for sensitive determination of ascorbic acid
Qian et al. Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor
Song et al. Disposable biosensor based on graphene oxide conjugated with tyrosinase assembled gold nanoparticles
Baghayeri et al. Monitoring of hydrogen peroxide using a glassy carbon electrode modified with hemoglobin and a polypyrrole-based nanocomposite
Jeykumari et al. A novel nanobiocomposite based glucose biosensor using neutral red functionalized carbon nanotubes
Liu et al. Highly sensitive and selective dopamine biosensor based on a phenylethynyl ferrocene/graphene nanocomposite modified electrode
Li et al. Electrostatic self-assembly for preparation of sulfonated graphene/gold nanoparticle hybrids and their application for hydrogen peroxide sensing
Muthuchamy et al. Enhanced photoelectrochemical biosensing performances for graphene (2D)–Titanium dioxide nanowire (1D) heterojunction polymer conductive nanosponges
Thanh et al. Electrochemical sensor based on reduced graphene oxide/double-walled carbon nanotubes/octahedral Fe 3 O 4/chitosan composite for glyphosate detection
Baghayeri et al. Facile synthesis of PSMA-g-3ABA/MWCNTs nanocomposite as a substrate for hemoglobin immobilization: application to catalysis of H2O2
Chen et al. Voltammetric sensing of bisphenol A based on a single-walled carbon nanotubes/poly {3-butyl-1-[3-(N-pyrrolyl) propyl] imidazolium ionic liquid} composite film modified electrode
Xu et al. Amperometric biosensor based on carbon nanotubes coated with polyaniline/dendrimer-encapsulated Pt nanoparticles for glucose detection
Qi et al. Functionalization of single-walled carbon nanotubes with protein by click chemistry as sensing platform for sensitized electrochemical immunoassay
WO2014042660A1 (fr) Détecteur de nanostructure carbonée et procédé de détection de biomolécule
Li et al. Synthesis of 1, 3-di (4-amino-1-pyridinium) propane ionic liquid functionalized graphene nanosheets and its application in direct electrochemistry of hemoglobin
Choi et al. The electrochemical glucose sensing based on the chitosan-carbon nanotube hybrid
US20150246814A1 (en) Layer-by-layer surface functionalization of catalyst-free fullerene nanostructures and the applications thereof
Wei et al. Fe3O4/SiO2/CS surface ion-imprinted polymer modified glassy carbon electrode for highly sensitivity and selectivity detection of toxic metal ions
JP2011514439A (ja) カーボンナノチューブと該カーボンナノチューブを分散させるための電解重合可能な界面活性剤とを含む水性組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150401

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20151106