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WO2011070572A2 - Procédé et dispositif de détection de nitroamines - Google Patents

Procédé et dispositif de détection de nitroamines Download PDF

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Publication number
WO2011070572A2
WO2011070572A2 PCT/IL2010/001033 IL2010001033W WO2011070572A2 WO 2011070572 A2 WO2011070572 A2 WO 2011070572A2 IL 2010001033 W IL2010001033 W IL 2010001033W WO 2011070572 A2 WO2011070572 A2 WO 2011070572A2
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WO
WIPO (PCT)
Prior art keywords
matrix
nanoparticles
analyte
rdx
groups
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PCT/IL2010/001033
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English (en)
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WO2011070572A3 (fr
Inventor
Itamar Willner
Ran Tel-Vered
Michael Riskin
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Yissum Research Development Co of Hebrew University of Jerusalem
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Yissum Research Development Co of Hebrew University of Jerusalem
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Priority to US13/512,380 priority Critical patent/US8597956B2/en
Priority to EP10801709A priority patent/EP2510350A2/fr
Publication of WO2011070572A2 publication Critical patent/WO2011070572A2/fr
Publication of WO2011070572A3 publication Critical patent/WO2011070572A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0057—Warfare agents or explosives
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G01N21/553—Attenuated total reflection and using surface plasmons
    • G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2600/00—Assays involving molecular imprinted polymers/polymers created around a molecular template
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/14—Heterocyclic carbon compound [i.e., O, S, N, Se, Te, as only ring hetero atom]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/14—Heterocyclic carbon compound [i.e., O, S, N, Se, Te, as only ring hetero atom]
    • Y10T436/145555—Hetero-N
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/14—Heterocyclic carbon compound [i.e., O, S, N, Se, Te, as only ring hetero atom]
    • Y10T436/145555—Hetero-N
    • Y10T436/147777—Plural nitrogen in the same ring [e.g., barbituates, creatinine, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173845—Amine and quaternary ammonium

Definitions

  • This invention relates to a method and device for detecting nitroamines.
  • the redox activity of the nitro groups associated with many of the explosives was used to develop electrochemical sensors [14], and modified electrodes such as mesoporous Si0 2 -functionalized electrodes were employed to enhance the sensitivity of detection of nitroaromatic explosives [15].
  • Other electronic devices for the analysis of explosives included surface acoustic wave (SAW) systems.
  • SAW surface acoustic wave
  • the coating of the piezoelectric devices with silicon polymers [16], carbowax [17] or cyclodextrin polymers [18] yielded functional coatings that enabled the electronic transduction of explosives adsorbed to these matrices; while the aggregation of functionalized gold nanoparticles in the presence of TNT was used to develop an optical sensor for the explosive [19].
  • NPs metallic and semiconductor nanoparticles
  • the unique electronic and optical properties of metallic and semiconductor nanoparticles, NPs added new dimensions to the area of sensors.
  • the aggregation of Au (gold) NPs as a result of sensing events and the formation of an interparticle coupled plasmon absorbance was used for the development of colorimetric sensors [31].
  • color changes as a result of aggregation of Au nanoparticles were used to detect phosphatase activity [32], polynucleotides [33], or alkali (lithium) [34] ions.
  • the shifts in the plasmonic absorption bands associated with Au nanoclusters as a result of changes in the surface dielectric properties upon sensing were used to develop optical sensors for dopamine [35], adrenaline [36], cholesterol [37], DNA hybridization
  • imprinted polymers as functional sensing matrices suffers, however, from several basic limitations.
  • the density of imprinted sites is relatively low, and thus, for sensitive sensing thick polymer matrices are required. This leads, however, to slow binding of the analytes to the recognition sites (long analysis time intervals) and to an inefficient communication between the binding sites and the transducers.
  • imprinted monolayers [47], multilayers [48] and thin films were suggested to overcome these difficulties.
  • the present invention in most general terms, provides use of nanoparticle matrices for ultra sensitive and selective detection of non-aromatic, and structurally non-planar nitroamine analyte molecules such as hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX) and other nitroamine compounds.
  • non-aromatic, and structurally non-planar nitroamine analyte molecules such as hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX) and other nitroamine compounds.
  • a method for determining the presence and/or concentration of non-aromatic non-planar nitroamine analyte molecules in a sample comprising contacting a matrix of a plurality of transition metal nanoparticles (TMNPs), each carrying a plurality of recognition groups, with a sample suspected of containing non-aromatic nitroamine analyte molecules, and monitoring at least one of a chemical and a physical change in said matrix, i.e., resulting from an interaction between said non-aromatic nitroamine analyte molecules and said matrix, via the recognition groups, wherein said at least one of a chemical and a physical change is indicative of at least one of presence and quantity of said non- aromatic nitroamine analyte (such as RDX or any other nitroamine compound or combination thereof) in the sample.
  • TMNPs transition metal nanoparticles
  • the matrix is composed of TMNPs associated with each other through a plurality of recognition groups being carried on their surface.
  • each nanoparticle may form more than one bond with a neighboring nanoparticle, as further disclosed below, a net is formed having a multitude of analyte-recognition fields (in the form of cavities) that are complementary in shape and/or size to the non-aromatic nitroamine analyte molecules to be detected.
  • the matrix is a three-dimensional structure.
  • the non-aromatic nitroamine analytes to be detected such as RDX, HMX and others are known to adopt a non-planar conformation (one or more such conformations may be envisaged for the main ring structure), the three-dimensional structure which forms may be distinct to each of the analytes and thus may be of greater selectively to each analyte in comparison to other methods of analyte detection, as further demonstrated hereinbelow.
  • the analyte-recognition fields constitute cavities within the matrix, suitable for holding/binding the analyte molecules therein, thereby permitting at least one interaction between the analyte molecules and the recognition groups.
  • the analyte- recognition fields may be of any size and shape.
  • the plurality of TMNPs in the matrix are associated with each other through a plurality of recognition groups, each group linking at least two TMNPs, thereby forming the boundaries of the analyte-recognition fields in the matrix.
  • the groups linking the TMNPs are referred to as "recognition groups" for having the ability to chemically and/or physically interact with the analyte molecules (RDX or other nitroamine compounds), thereby ensuing their recognition.
  • the recognition groups are so selected to permit recognition of a single molecular shape and/or size, a family of compounds having a distinct shape or chemical constitution (e.g., having triazine or tetrazine groups, or nitro groups or a combination thereof), or a class of compounds identified by their ability to undergo chemical interaction (i.e., chemical reaction) when in the matrix.
  • the purpose of the recognition groups is not only to provide a net having a plurality of analyte-recognition fields around the TMNPs, but also permit interaction (reversible or permanent) with the analyte molecules which enter the analyte-recognition fields, as further disclosed below.
  • the recognition groups are selected to undergo chemical and/or physical interaction with the analyte molecules (one or more) present in the analyte-recognition fields. Such an interaction may be through a single, double or triple bond, or through one or more of van der Waals, hydrogen bonding, electrostatic interaction, complexation, caging and other physical interactions as known in the art. In some embodiments, the physical interaction is reversible.
  • the recognition groups are selected to have certain length and substitution so as to predefine the shape and size of the non-planar analyte- recognition fields formed between the TMNPs.
  • the recognition groups are typically selected to maintain strong and, in some embodiments, permanent (irreversible) interaction (association, bonding) with the TMNPs. Such association is dependent on the nature of the TMNPs, their size and to a lesser extent, in some embodiments, also on the method employed for achieving association between the TMNPs and the recognition groups.
  • the recognition groups are residues of "electropolymerizable groups", namely groups which association (e.g., covalent bonding) with the TMNPs is achieved, at least partially, through electropolymerization.
  • the TMNPs are nanoparticles of at least one transition metal selected from the af-block of the Periodic Table of the Elements.
  • nanoparticles are of a metal selected from platinum (Pt), palladium (Pd), iridium (Ir), gold (Au), silver (Ag), nickel (Ni) and titanium (Ti), or alloys thereof.
  • the TMNPs are gold nanoparticles.
  • the TMNPs contain gold metal and at least one additional transition metal, at least one non-metal or at least one metal (not a transition metal).
  • the TMNPs forming the matrix may be a mixture of two or more nanoparticle types, each may be of a different metal or metal alloy, different size, different shape, etc.
  • the matrix is composed of a mixture of gold nanoparticles and other metallic particles.
  • the matrix is composed of nanoparticles of various metals.
  • the matrix is composed solely of gold nanoparticles.
  • the TMNPs may be of any shape, such as spherical, elongated, cylindrical, or in the form of amorphous nanoparticles.
  • the TMNPs typically have at least one dimension (diameter, width) in the range of about 1 nm to 1000 nm.
  • each TMNP is, on average, of a nanometer scale (size), ranging between 1 nanometer to 1000 nanometer; between 1 nanometer and 500 nanometers; between 1 nanometer and 250 nanometers; between 1 nanometer and 250 nanometers; between 1 nanometer and 150 nanometers; between 1 nanometer and 100 nanometers; between 1 nanometer and 50 nanometers; between 1 nanometer and 25 nanometers; between 1 nanometer and 10 nanometers and between 1 nanometer and 5 nanometers.
  • size ranging between 1 nanometer to 1000 nanometer; between 1 nanometer and 500 nanometers; between 1 nanometer and 250 nanometers; between 1 nanometer and 250 nanometers; between 1 nanometer and 150 nanometers; between 1 nanometer and 100 nanometers; between 1 nanometer and 50 nanometers; between 1 nanometer and 25 nanometers; between 1 nanometer and 10 nanometers and between 1 nanometer and 5 nanometers.
  • each TMNP is, on average, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 nanometers in diameter, or any intermediate diameter, e.g., 1.1, 1.2, 1.3...2.1, 2.2, 2.3...3.1, 3.2, 3.3...etc.
  • the matrix comprises a plurality of TMNPs, each being associated with one another through one or more recognition moieties.
  • recognition moieties may have one or more reactive groups which are capable of undergoing interaction with the nanoparticles.
  • Non-limiting examples of such reactive groups are -S, -NH 2 and -C0 2 _ .
  • the recognition groups may be selected to have one or more reactive groups which are capable of undergoing interaction with the gold nanoparticles.
  • the one or more reactive groups are sulfur containing groups, particularly thiols.
  • the thiols are selected amongst aromatic thiols or alkyl thiols having at least one aromatic substituent.
  • Non- limiting examples of such sulfur containing recognition groups are thioaniline, thioaniline dimer and oligomers thereof.
  • the recognition groups having one or more sulfur- containing groups are selected from -thioaniline and the oligo-thioanilines having 2, 3, 4, 5, 6, 7, 8, 9 or 10 / ⁇ -thioaniline monomer units.
  • the recognition groups are electorpolymerized thioanilines.
  • the recognition groups is the thioaniline dimer 4-amino-3-(4-mercaptophenylamino) benzenthiol, i.e., wherein the terminal -S-aryl groups undergo association with the gold nanoparticles.
  • each TMNP may further be functionalized to affect a change (increase, decrease or substantially maintain an intrinsic property of the nanoparticle) in one or more property associated with the nanoparticles, such property may be physical or chemical and may be selected from solubility, film forming properties, aggregation, reactivity, stickiness, stabilization, reusability, adhesion, charge, interaction with a medium, and other known properties.
  • the TMNPs are functionalized to increase their solubility in a liquid medium, e.g., an aqueous medium.
  • the TMNPs are functionalized to increase their shelf-life and reusability in the matrix of the invention.
  • the TMNPs are functionalized with negatively or positively charged functional groups.
  • the TMNPs are functionalized with sulfonic acid containing groups.
  • a non-limiting example of a sulfonic acid group is 2-mercaptoethane sulfonic acid or an anion thereof.
  • the TMNPs are functionalized with monomers of the recognition groups which have not undergone polymerization and subsequent association with neighboring TMNPs.
  • the TMNP matrix is bound to an active surface which, in some embodiments, is conductive and thus capable of reporting at least one chemical and/or physical change resulting from an interaction between the TMNP matrix and the analyte molecules in the sample.
  • the active surface may be a metal body or a metallic surface of a metal selected from gold, platinum, silver, and alloys thereof.
  • the active surface is a non-metallic body, such as graphite, Indium-Tin- Oxide (ITO), glass and others, which may or may not be coated with a metallic coating.
  • the active surface is an electrode. In other embodiments, the active surface is a metal (or alloy) coated glass.
  • the active surface may be a two-dimensional surface on top of which the matrix is formed or may be a three-dimensional body having, e.g., a circumference which is fully or partially associated with the matrix.
  • the matrix completely covers the active surface.
  • the matrix is formed on spaced-apart regions of the active surface.
  • the matrix is associated with said active surface through one or more surface-binding moieties.
  • the surface-binding moieties may or may not be the same as the recognition groups used to associate the plurality of TMNP in the matrix.
  • the surface-binding moieties and the recognition groups compose sulfur containing groups, such as thiols, as further disclosed hereinabove.
  • the surface-binding moieties and the recognition groups are p- thioaniline or a dimer or oligomer thereof.
  • the matrix In order to associate the matrix with the active surface, it is not necessary to have all nanoparticles of the matrix associated with the surface. It is merely required that a portion of the matrix is associated with the surface through the surface-binding groups. It should be noted, that in embodiments where electropolymerization is employed for the construction of the matrix, the matrix may contain elecotropolymerized recognition groups and electropolymerized surface-binding groups of various lengths (a varying number of monomers, e.g., /?-thioaniline monomers).
  • the matrix may be composed of nanoparticles which are associated with each other via dimers of ?-thioaniline and nanoparticles which are associated via a different oligomer, e.g., trimer, quartermer, etc.
  • the matrix is inhomogeneous, i.e., not arranged from a single type of recognition group nor is it arranged in an ordered multilayered structure.
  • non-aromatic nitroamine analyte molecules which may be detected, using a method according to the invention, are numerous.
  • the "non-aromatic, non-planar" analyte molecules are organic nitroamines which do not have one or more aromatic (benzene) ring as their main ring structure.
  • the analytes detected according to the method of the invention are different from aromatic nitro compounds.
  • the method of the invention may be both generic and, as desired, analyte-specific.
  • the non- aromatic nitroamine analyte to be assayed is an organic material.
  • the non-aromatic nitroamine analyte is selected from hexahydro-1,3,5- trinitro-l,3,5-triazine (RDX), octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX), and 2,4,6,8, 10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20).
  • the analyte is RDX or HMX or a combination thereof.
  • the method of the invention may be carried out by bringing into contact the matrix comprising the TMNPs, as defined herein, with a sample (control or the so- called field-sample suspected of comprising the analyte) in such a way to permit interaction between the recognition groups of the matrix and the non-aromatic nitroamine analyte molecules.
  • the matrix may be introduced into the sample (e.g., by dipping) for a period of time sufficient to achieve (not necessarily complete) interaction. The dipping may be repeated.
  • the sample may be added onto the matrix (e.g., dripping). Other methods are suitable alternatives.
  • the matrix and the sample are brought into contact at room temperature.
  • the interaction between the matrix, i.e., the recognition groups, and the analyte molecules, e.g., RDX molecules, may be probed by monitoring at least one measurable change, the change being associated with a change in at least one property or structure of the target molecule or one or more component of the matrix (or the matrix as a whole) caused by said interactions.
  • the measurable change may be, for example, in any one electric property or any one electrochemical property or any one spectroscopic property.
  • the at least one change is in at least one electric property of the analyte and/or the matrix.
  • the change may be measured by determining, e.g., current-voltage relationship, impedance, and other parameters, prior to and after the matrix and the sample have been brought into contact with each other. For quantitative measurements, calibration curves may be used.
  • the at least one change is in at least one optical property of the analyte and/or the matrix.
  • optical property may be detected by Surface Plasmon Resonance (SPR), infra-red (IR) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), photonic detection, evanescent detection, and cantilever detection.
  • SPR Surface Plasmon Resonance
  • IR infra-red
  • Raman spectroscopy Raman spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • photonic detection evanescent detection
  • evanescent detection evanescent detection
  • cantilever detection cantilever detection.
  • the qualitative and/or quantitative analysis of the non- aromatic nitroamine analyte is achieved by employing SPR to probe a change in a dielectric property of the analyte and/or the matrix or a combination thereof.
  • the active surface to which the matrix is bound is a gold-coated glass, e.g., an SPR cell (chip).
  • the method of the invention comprises:
  • nanoparticles of a transition metal carrying a plurality of recognition groups capable of undergoing interaction with non-aromatic nitroamine analyte molecules, e.g., RDX molecules;
  • the invention provides an electrode for carrying out the method of the invention.
  • the electrode has a conductive surface connected to a matrix, said matrix comprising a plurality of transition metal nanoparticles (TMNPs), wherein substantially each of said nanoparticles is connected to another by at least one recognition group capable of mediating electron transfer between nanoparticles of the matrix; at least a portion of said plurality of nanoparticles is connected to said conductive surface by at least one surface binding group, capable of mediating electron transfer between the matrix and said conductive surface.
  • TMNPs transition metal nanoparticles
  • each of the TMNPs is selected as defined above.
  • the matrix is produced by molecular imprinting.
  • the invention also provides a method for molecular imprinting of a matrix for detecting a non-aromatic nitroamine analyte, said method comprising:
  • said matrix is thereby composed of a plurality of nanoparticles associated with each other through recognition groups;
  • the imprinting method increases, together with the complementary ⁇ -donor-acceptor interactions, the association of the non-aromatic nitroamine analyte molecules, e.g., RDX, to the sensing electrode (active surface of the solid support), thereby enhancing the sensitivity of the analysis.
  • the non-aromatic nitroamine analyte molecules e.g., RDX
  • the at least one guest molecule is selected to have at least one of shape, size, substitution and electronic structure and distribution as that of the non-aromatic nitroamine analyte molecule, e.g., RDX, to be detected.
  • the at least one guest molecule is identical to the non-aromatic nitroamine analyte molecule, e.g., RDX.
  • the at least one guest molecule has the same substituents and substituent pattern as the non-aromatic nitroamine analyte molecule.
  • the at least one guest molecule is larger in its overall space occupying volume than that of the analyte molecule.
  • the at least one guest molecule is a mixture of two or more guest molecules, one of which may or may not be the same as the analyte molecule.
  • the guest molecule is selected from RDX, Kemp's acid, cis-1,3,5- tricarboxycyclohexane and cis-l,3-dicarboxycyclohexane.
  • the imprinting method of the invention provides for the removal of the guest molecule from the matrix, to thereby form the analyte-recognition fields.
  • the at least one guest molecule may be removed from the matrix in the imprinting process by contacting, e.g., washing the matrix with a suitable solvent, such as an organic solvent or an aqueous solution at a desired pH.
  • a suitable solvent such as an organic solvent or an aqueous solution at a desired pH.
  • the washing solution is an aqueous solution or a buffer at a substantially neutral pH (-6.5-7.5).
  • the buffer used has an acidic or basic pH.
  • the method of imprinting further comprises the step of verifying the total removal of the guest molecules.
  • the method may further comprise the step of determining the base-line property of the matrix to be used in the calibration of the matrix or device.
  • the base-line property is typically identical to the electric, electrochemical and/or optical property used to probe the change in the matrix after contact with the analyte sample. For example, if SPR measurements are used to assay the presence of RDX molecules in a sample, the dielectric properties of the matrix prior to coming in contact with the sample will be determined as the base-line property of the matrix.
  • the solid support is an electrode or a coated glass slide (cell or chip). In some further embodiments, the glass cell is coated with gold.
  • the matrix is formed by electropolymerization.
  • the matrix produced by the imprinting method of the invention may be used in a method for detecting a non-aromatic nitroamine analyte, e.g., RDX, using the molecularly-imprinted matrix, the method comprising exposing the molecularly- imprinted matrix to a sample suspected of containing said analyte and detecting the interaction of the analyte, as disclosed herein, with the matrix.
  • RDX non-aromatic nitroamine analyte
  • the matrix may be produced by any other process provided that it follows the definition and characteristics provided herein.
  • the interaction is detected using electric or optical methods, e.g., SPR or voltammetric measurements.
  • a device for carrying out the detection of an analyte in a sample comprising at least one assay unit having a plurality of nanoparticles of a transition metal, said nanoparticles carrying recognition groups capable of undergoing interaction with the analyte molecule(s), under predetermined assay conditions.
  • the device may further comprise means to probe the interaction between said recognition groups and the analyte molecule(s) and means for detecting at least one change in at least one measurable property (electric or optical).
  • the assay unit may comprise an electrode.
  • the assay unit may, for example, be in the form of an SPR cell or chip.
  • the invention also provides a sensor comprising an electrode according to the invention.
  • Figs. 1A-1C are (A) Schematic presentation for the electropolymerization of a bis-aniline-crosslinked Au nanoparticles composite for the sensing of RDX by ⁇ -donor- receptor interactions. (B) SPR curves corresponding to the bis-aniline Au nanoparticles composite: (a) before the addition of RDX, and (b) after the addition of RDX, 20 nM.
  • Fig. 2 is a graph showing the evaluation of the association constant between RDX and the bis-aniline-crosslinked Au NPs-functionalized electrode upon interaction of the electrode with the different bulk concentrations of RDX.
  • the functionalized electrode was immersed in the different solutions of RDX for ca. 4 min.
  • Fig. 3 is a schematic representation of the imprint of molecular recognition sites for RDX in bis-aniline-crosslinked Au NPs film polymerized at the Au electrode.
  • Fig. 7 is a graph showing the evaluation of the associated constant between RDX and the Kemp's acid-imprinted bis-aniline-crosslinked Au NPs-functionalized electrode upon interaction of the electrode with different bulk concentrations of RDX.
  • the functionalized electrode was immersed in the different solutions of RDX for ca. 4 min.
  • Electrochemical sensors for the analysis of RDX with enhanced sensitivities are herein disclosed.
  • the enhanced sensitivities are achieved by tailoring ⁇ -donor-acceptor interactions between RDX and 7r-donor modified electrodes or 7r-donor-cross-linked Au nanoparticles linked to the electrode.
  • a j p-aminothiophenolate monolayer-modified electrode leads to the analysis of RDX with a sensitivity corresponding to 12 fM.
  • the cross-linking of Au nanoparticles by oligothioaniline bridges to the electrode yields a functionalized electrode that detects RDX with a sensitivity that corresponds to 460 ppt (2 nM).
  • SPR Surface Plasmon resonance
  • Numerous SPR sensors and biosensors were developed [52-54], and metal nanoparticles (NPs) were implemented to enhance the SPR response and to amplify SPR-based sensors [55,56].
  • the electronic coupling between the localized Plasmon of the metallic NPs (e.g., Au) and the surface plasmon wave enhances the SPR response, and thus, the labeling of a recognition complex with metallic NPs amplifies the sensing events.
  • Different biosensing processes such as DNA hybridization [57], formation of immune-complexes [58], and the probing of biocatalytic transformations
  • Au NPs 2-mercaptoethane sulfonic acid and p- aminothiophenol
  • the solution was stirred for 1 additional hour in an ice bath and then for 14 hours at room temperature.
  • the particles were successively washed and centrifuged (twice in each solvent) with methanol, ethanol, and diethyl ether.
  • An average particle size of 3.5 nm was estimated using Transmission Electron Microscopy (TEM). Nanopure (Barnstead) ultrapure water was used in the preparation of the different solutions.
  • Au-coated semi-transparent glass plates (Mivitec GmbH, Analytical ⁇ -Systems, Germany) were used as working electrodes. Prior to modification, the Au surface was cleaned in ethanol (at 50°C) for 30 min.
  • p-Aminomiophenol-functionalized electrodes were prepared by immersing the Au plates for 24 hours into a p-aminothiophenol ethanolic solution, 50 mM.
  • the resulting films were washed with the background electrolyte solution to exclude any residual monomer from the electrode.
  • Kemp's acid, cis-l,3,5-tricarboxycyclohexane and cis-l,3-dicarboxycyclohexane- imprinted bis-aniline-crosslinked films were prepared by adding 10 mg mL "1 of the corresponding imprint analog molecule to the Au NPs mixture prior to the electropolymerization process.
  • the full removal of the imprint molecules from the electropolymerized film was verified by monitoring the restoration of the SPR curve shift to the baseline value in 0.1 M HEPES solution.
  • >-Aminothiophenol-functionalized electrodes were prepared by immersing the Au slides for 24 hours into a p-aminothiophenol ethanolic solution, 50mM.
  • the polymerization was performed by the application of 10 potential cycles between - 0.35 and 0.8 V vs.
  • the SPR sensograms (time-dependent reflectance changes at a constant angle) represent real-time changes and these were measured in situ using a home-built fluid cell.
  • Au-coated semi-transparent glass slides (Mivitec GmbH, Analytical ⁇ -Systems, Germany) were used for the SPR measurements. Prior to modification, the Au surface was cleaned in a hot ethanol, at 60°C, for 30 min.
  • Au nanoparticles 3.5 nm, were functionalized with a capping mixed monolayer consisting of thioaniline electropolymerizable units, and with mercaptoethane sulfonic acid, to enhance the solubility of the NPs in an aqueous medium.
  • the functionalized Au NPs were electropolymerized onto a mercaptoaniline monolayer-modified Au electrode, to yield the bis-aniline-crosslinked Au NPs matrix, Fig. 1A. Ellipsometry and coulometric analyses of the bis-aniline crosslinked Au NPs matrix, generated by the application of 10 electropolymerization cycles, indicated that the thickness of the matrix corresponded to ca. 10 nm, and that ca.
  • ⁇ -donor bis-aniline units bridging the Au NPs associate RDX (that includes ⁇ -acceptor nitro groups), via ⁇ -donor-acceptor interactions.
  • the resulting charge transfer complexes alter the dielectric properties in the Au NPs matrix, resulting in an amplified shift in the surface Plasmon resonance spectrum, due to the coupling between the localized NPs plasmons and the surface plasmon wave.
  • Fig. IB shows the SPR curves of the Au NPs-crosslinked composite-modified surface (curve a) and after (curve b) treatment with RDX, 20 nM. The SPR curve is shifted, suggesting that the association of RDX to the matrix can be monitored by the reflectance changes of the SPR spectrum.
  • Fig. 1C shows the sensogram corresponding to the reflectance changes of the modified surface upon treatment with variable concentrations of RDX, and the resulting calibration curve, Fig. ID.
  • the reflectance changes increase upon elevating the concentration of RDX and they level off to a saturation value at RDX concentration corresponding to ca. 100 nM. This result is consistent with the fact that saturation of the ⁇ -donor sites with RDX leads to a constant reflectance value.
  • the association constant of RDX to the bis-aniline bridging units was estimated to be K a N -3.4x10 7 M "1 (Fig. 2).
  • the detection limit for analyzing RDX was 4 nM.
  • a two-layer structure of AuNPs was constructed, that lacked the ⁇ -donor sites on the Au surface.
  • a thiopropionic acid-capped Au NPs layer was assembled on a cystamine-modified Au surface [60].
  • a second layer of the thiopropionic acid-capped Au NPs was linked using 1,4-butane dithiol as bridging units.
  • the resulting two layers assembly showed a minute response only at elevated concentrations of RDX (>10 ⁇ ), implying that the ⁇ -donor-acceptor interaction between RDX and the bis-aniline units are, indeed, essential to concentrate the explosive at the surface.
  • FIG. 4A shows the SPR curves corresponding to the imprinted bis-aniline-crosslinked Au NPs composite before, curve (a), and after, curve (b), the addition of RDX, 300 fM.
  • Fig. 4B depicts the sensogram corresponding to the reflectance changes of the (analog l)-imprinted bis-aniline-crosslinked Au NPs composite upon sensing variable concentrations of RDX, and the resulting calibration curve. As the concentration of RDX increases, the reflectance changes become higher, and they level-off at a concentration corresponding to ca. 1 pM.
  • the detection limit for analyzing the (analog l)-imprinted Au NPs matrix is 12 fM.
  • the imprinted composite reveals a 4xl0 5 -fold lower detection limit for RDX, as compared to the non-imprinted sensing matrix.
  • the enhanced sensitivity of the imprinted composite is attributed to the improved association of RDX to the imprinted sites, resulting from the steric confinement of the explosive molecules to the imprinted molecular contours consisting of the ⁇ -donor bridging units.
  • the (analog l)-imprinted matrix demonstrates impressive selectivity for detecting RDX, and provides quantitative SPR response for analyzing RDX up to a concentration of 1 pM, with a detection limit of 12 fJVl. Furthermore, the (analog 1)- imprinted composite response to TNT concentrations which are only higher than 30 pM. It was also found that the Kemp's acid-imprinted Au NPs matrix is highly selective. Nitroaromatic substrates of weaker acceptor properties such as 2,4-dinitrotoluene or 4- nitrotoluene exhibit small reflectance changes at concentrations higher than 10 ⁇ .
  • Fig. 4C depicts the calibration curves corresponding to the analysis of RDX by the (l)-imprinted and the (2)-imprinted Au NPs composites.
  • the analysis of RDX by the (2)-imprinted composite reveals a less effective detection limit, 500 fM, and a substantially lower saturation value of the reflectance changes.
  • Fig. 6, curve (a), depicts the reflectance changes observed for the (l)-imprinted matrix under different bias potentials. Only minute reflectance changes are observed upon transferring the oxidized quinoid-bridged state (at E>0.1 V) to the reduced bis-aniline state (EO.l V).
  • Fig. 6, curve (b) shows the effect of the applied potential on the reflectance values of the modified surface in the presence of RDX, 120 fM.

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Abstract

La présente invention concerne un procédé ultrasensible de détection d'analytes nitroamine non planaires non aromatiques dans un échantillon.
PCT/IL2010/001033 2009-12-07 2010-12-07 Procédé et dispositif de détection de nitroamines Ceased WO2011070572A2 (fr)

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