ELECTROCHEMICAL BASED ASSAY PROCESSES, INSTRUMENT AND LABELS

Abstract: A method for quantitating or detecting an analyte using an electrochemical reaction, comprising a material in contact with an electrolyte in a cell or chamber but not in electronic contact with an external electronic circuit, at least some of said material having at least its surface conducting or semi-conducting, and applying a voltage gradient across at least a portion of said material, the size of said material, the conductivity of said electrolyte and/or reactant liquid and the voltage gradient being such that not only are anodic and cathodic faces established in respect of at least some of the conducting or semi-conducting material, rendering said material bipolar, the electropotentials so generated are such that said electrochemical reaction takes place on at least a portion of the surfaces of said material resulting in the production of a detectable signal or detectable material. The said bipolar material which, advantageously, are spherical or fibres, may comprise solid conducting or semi-conducting material or cores of non-conducting material with coatings of conducting or non-conducting material thereon. The material, which is preferably in suspension, may also be bound or captured directly or indirectly onto a surface or filter matrix. The said surface or filter matrix if conducting is not acting as an electrode to carry out electrochemistry. The detection of the electrochemically-generated signal or material is related to the quantity or presence of said analyte.

Description: ELECTROCHEMICAL BASED ASSAY PROCESSES, INSTRUMENT AND LABELS Field of the Invention This invention relates to an instrument, a method and labels for carrying out assavs using an electrochemical reaction on a conducting or semi-conducting material in contact with an electrolyte but not in electronic contact with an external electronic circuit. Background of the Invention The need for methods that provide rapid, sensitive, specific, preαse and low-cost detection of numerous analytes has led to the development of a large number of differing assay methods and technologies The desire and need to improve these current methods stdl exists and numerous companies are working towards the development of improved means and the exploration of new methods. The potential use of electrochemistry for the development of assays which are rapid, sensitive, specific, precise and low-cost has not escaped study due in part to this technique's ability to detect specific electronic properties direcdy caused by reactions at the surface of an electrode electronically connected to an external electronic circuit. The use of particles, beads or other structures suspended in assav buffers is now almost universal in immunoassay analyser systems available, examples are ELECSYS (Boehπnger Mannheim), copaks technology (Sienna Biotech, Columbia MD), Luminex (Austin TX) with the fluorescence bead multiplex analysis system, IMMULTTE (Diag Pro Corp), ACS:180 (Qba Coming), Cobas Core (Roche), ACCESS (Sanofi), AIA-1200 DX fTosoh), ACAplus (DuPont) and Immuno 1 (Bayer). The reasons for using particles, beads or other structures suspended in assay buffers is that they allow for rapid kinetics and also facilitate the manufacturing and automation of random access assay systems. These also present some disadvantages related to keeping the beads in suspension, washing is not easy and problems can arise from the particles, beads or other structures suspended in assay buffers interfering with the detection svstems When considering the detection and assay of analytes in gels, various methods are used to achieve a photographic-like analysis of the spaπal distribution of samples within the gel Trpicallv, this is achieved by staining the gel directly with vaaous agents to visualise the molecules in the gel, for example Coomassie Blue is used to detect proteins in gels The proteins bind the dye and are detected as blue bands Ethidium bromide is used to detect DNA in gels as illumination with UV light allows visuaksauon of the fluorescence of the DNA-bound ethidium bromide. In some cases the molecules are radiolabeled and are detected by autoradiography The analytes mav also be transferred to a membrane and analysed after they have been bound. Examples of this are hybridizations southern, northern, and lmmunoblomng westerns These methods are typically time consuming and/or lack sensitivity Other methods for assaying analytes of interest are based on the use of filter wicking methods These are used for various analytes such as glucose, cholesterol, drugs, antigens, antibodies and nucleic aαds In one form, using antibodies, these are called lmmunochromatographic assays These test formats using filter strip, wicking methods or lateral-flow offer the beauty of simplicity All that is necessary is to apply a sample, for example blood, urine or saliva, and this results in the dned and labelled antibody dissolving and mixing with the sample and starting the anπbodv/analvte binding reaction During this binding reaction the sample and labelled antibody are wicked (via capillary flow) along a strip which at a predetermined point contains an immobilised second antibody against the analyte of interest. The result is that as the sample and labelled antibody are transported along the membrane or supporting phase, the analyte binds to the antibody. This immune complex then at some point is transported in the liquid flow to the capture antibody which is immobilised at a given site within the filter or supporting phase. When the analyte-labelled antibody complex interacts with the immobilised capture antibody it is captured by binding to an alternative epitope on the analyte of interest resulting in the immobilisation of the label which is attached to the labelled antibody and complexed with the analyte. The fluid continues to wick or flow past the immobilised antibody carrying any un-complexed (not bound to analyte of interest) labelled antibody away from the immobilised capture antibody. At this point, the labelled antibody is detected. These assays use a number of different labelling methods such as particles and enzymes. In other systems based on these wicking or flow methods, additional buffer and/or solutions can be added to give other types of signal and improve the binding reactions. In such a test, the sample is added and allowed to incubate. This is then followed by a wash, and the second binding reagent (labelled) is added followed by a wash. The substrate is then added to detect the bound labelled reagent. These two extremes of the filter wicking, lateral flow or lmmunochromatographic assay systems are given here to illustrate the potential range of conditions and steps which can make up such rapid assay systems. Electrochemical-based sensors for the detection of biomolecules have been developed into highly successful commercial products. This has been exemplified by the measurement of glucose based on the detection of electrical changes that occur during an electrochemical reaction. Current glucose detectors use an enzyme such as glucose oxidase to provide the selective recognition and generation of a detectable signal by an electrode. Some of these products, such as the system manufactured by Boehrmger Mannheim, use direct electrochemical oxidation of hydrogen peroxide produced by the enzyme. In an altemaαve system, MediSense Inc. uses a modified ferrocene as a redox mediator between the enzyme and the electrode. This removes problems due to oxygen concentraoons and pH (M.G. Boutelle et al. J MoL Rec. 1996. 9, 383-388). Electrochemical technology has also been applied to the development of electrochemical methods based on the generaαon of light as a signal (Igen lnc, Gaithersburg MD). In this system, a specific laObel, typically Ru is used attached to a binding species through a spacer arm and the capture of this label is detected by the generauon of exαted-state Ru (2,2-bιpyπdyl) 3 2+ via a redox reaction at the surface of an electrode connected via an electromc circuit to a potendostat. The voltage is controlled at the surface of the externally, electronically connected electrodes within the electrochemical cell to surface potentials less than 3 volts due to the nature of the instrument and the electrochemistry of this system. This electrochemistry is conducted using a potenuostat to control the potential at a working electrode. These instruments for controlling electrochemistrv are designed to apply voltages of less than 10 volts and electrochemical methods have thus been restricted to these low voltages applied to an externally, electronically connected electrode surface. In an alternative electrochemical system which makes use of light as the detectable signal, luminol and its denvaαves can be subjected to electrochemical excitation resulting in the emission of light. The use of the luminol system typically involves combination with a peroxidase-producing enzyme which generates hydrogen peroxide for the activation of the luminol light emission on electrochemical activation. In summary, there are numerous examples of the use of electrochemistry for assaying biomolecules based on the detection of specific biomolecules directly via electrochemical methods or via the use of enzymes or other biocatalysts used to generate detectable species or via the use of electrochemiluminescent labels as in the case of the ruthenium tnsbipyπdyl label used by Igen me, Gaithersburg MD (WO 86/02734). The essential element of all these methods has been the need to bring the reagents and/or binding species in close proximity to an electrode surface which is in direct electronic contact via wires or equivalent electron conduction material to an external control electromc circuit. The electrode systems in these cases are typically made of a three-electrode system with working, counter and reference electrodes in contact with an electrolyte that contains the sample. These three electrodes are then in electromc contact outside the sample or electrolyte chamber via wire or equivalent electron conducting material to a potenttostat This configuration of electrodes linked via a potendostat allows precise control of the voltages at the working electrode. In some cases, the electrode configuration is made up of two electrodes and the counter and reference electrode are combined with some success. Thus, all electrochemical-based assay systems have been designed using electrodes that are exposed to an electrolyte containing the sample and connected by external contacts via wire or equivalent electron conducting material to a potendostat These electrochemical assay systems make use of measurable electrochemistry, for example, by measuring electromc properties or light generated at the surface of these direcdy controlled and connected electrodes. These systems suffer from the problem of not being able to detect and analyse the presence of analytes in the bulk solution. If they are able to effectively capture the analytes in bulk solution, e.g. using beads, then these beads need to be captured or otherwise brought to the surface of an externally, electronically connected electrode. This presents a significant impediment to the speed, sensitivity and simplicity of the assay and the instrumentation, for example requiring a magnet (WO 96/15440, WO 92/14139) In the case where the bead is brought to the surface of the electrode, only a small portion of the assay sample is measurable (Williams 1995 IVD Technology November 28-31). In cases where beads are not brought mto proximity of the working electrode, actual loss of signal has been descπbed when ECL labels are bound to the bead (WO 90/05301). Systems involving electrochemical synthesis or production have provided examples of electrochemistry using electrodes consisting of suspended conducting particles. These have been descπbed for the electrolysis of sea water and the production of potassium permanganate (Fleischmann et al US4124453, Agladze et al US4269689; Bharucha et al US3941669). This field of electrochemistry has been called bipolar electrochemistry as each conducting element serves as both anode and cathode ("Applications of Fluidized Beds in Electrochemistry" by P. Le Goff et al., Industrial & Engineering Chem., VoL 61 No. 10, 1969, pp. 8- 17. J.C. Bradley et aL Nature 1997, 389, 268-271). In these experiments, the electrolyte contains a suspension of conducting or semi-conducting particles that are subjected to an electrical field. This results in the generation of anodic and cathodic faces on the conducting particles and results in electrochemical reactions at the surface of the conducting particles. These methods have not been used to generate a detectable signal or material which is related to a binding event or the presence of a molecule or analvte of interest for the purpose of determining the presence or concentration of these molecules or analytes in a sample The present invention provides for the application of bipolar electrochemistry in a new way for diagnostic applications and constitutes an improvement over those currently known Various methods and examples are disclosed. Objects and Advantages of the Invention Accordingly, it is an object of the invention to provide a method for detecting molecules or analytes of interest using a conducting or semi-conducting material - not in electromc connection with an external electromc circuit - as a bipolar electrode for electrochemically generating detectable signals or material. The level of detectable signal or material being detected is related to the amount or presence of the molecules or analytes of interest It is another and related object of the invention to describe an apparatus able to detect the signal or material electrochemically generated by the conducting or semi-conducting material which is not in electromc connection with an external electromc circuit. It is another object of the invention to provide a new label for binding assays which is a conducting or semiconducting material acting as a bipolar electrode. Accordingly, the invention is an improvement over the existing art in that it allows the electrochemical reaction to occur more effectively m the bulk solution providing for more rapid assays of greater sensitivity. It is a further improvement in that it provides a means for assaying multiple analytes in an array without the need to provide multiple electrode contacts or large extended electrode surfaces. Also the invention is a method for generating light using a bipolar electrode not in electromc contact with an external electromc circuit. Summary of the Invention This invention includes an assay method for an analyte of interest using an electrochemical process The assay compnses the establishment of contact between the sample to be assayed for an analvte of interest and at least one structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit; followed by the application of a voltage gradient across at least a portion of at least one structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit, the voltage gradient bemg such that at least one electrochemical reaction takes place on at least one of at least one structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit; then the detection and/or quantitaαon of at least one electrochemical reaction directly and/or indirecdv and determination of the presence and/or quantity of the analyte of interest Variations are possible in this assay, for example, the structure of conducting and/or semiconducting material coupled to a binding species, including antibodies, avidin, biotin represents an embodiment Also, the electrochemical reactions include those generating electrochemiluminescence or chemiluminescence. It will also be appreciated that the assay method as just descnbed above in a selected embodiment includes use of additional binding species such as those free m solution and/or coupled to electrochemically detectable speαes which include compounds able to support electrocheπuluminescence or chemiluminescence. In this way a sandwich immunoassay can be constructed. Common binding speαes include, for example- antibody, antigen, nucleic aαd, receptor, kgand, lectin, nucleic aαd analogue, streptavidin, avidin, biotin, lmminobiotin, aminobiotin, digoxin, fluorescein. The use of various combinations of binding speαes is also contemplated to allow for a 'universal' capture, including the use of immobilized steptavidin with a seπes of biotinylated antibodies. The structure of conducting and/or semiconducting material includes numerous materials depending on the desired chemistπes, examples include: carbon, gold and platinum, graphitic carbon fibres, fibrils or nanotubes, graphitic particles, glassy carbon particles, carbon films, sputtered carbon, carbon pastes and carbon composites. This invention is also an assay where a sample has added to it an exogenous enzyme for a substrate in a sample or has added to it an exogenous substrate for an enzyme in a sample to form a mixture of an enzyme with a substrate This mixture can either be formed before or after contacting a sample with a structure of conducting and/or semi-conducting material not m electromc contact with an external electromc circuit, to form a mixture. Having formed this mixture, a voltage gradient is applied across the mixture, the voltage gradient being such that an electrochemical reaction takes place on the structure of conducting and/or semiconducting material not in electromc contact with an external electromc circuit, wherein an electrochemical reaction occurs with a product of the enzyme or the exogenous enzyme action, either direcdy or lndirecdy. The electrochemical reaction is detected and/or quanbtated direcdy or lndirecdy, allowing the determination of the presence or quantity of the substrate or the enzyme in the sample. Examples of enzymes and substrates include those involved m dehydrogenatton and/or oxidase enzyme reactions. Examples of electrochemistry include those linked to electrochemiluminescence or chemiluminescence. This invention is also an apparatus for the detection or assay of an analyte and compπses: an electπcal power supply able to deliver a voltage; a cell able to accept a sample containing structures of conducting and/or semi-conducting material, wherein the cell contains at least two electrodes which are externally and electromcally connected to the electπcal power supply and the cell is either an integral part of the apparatus or is a removable element The instrument also includes a detector able to detect electrochemistry and is selected from the following film, photomulαplier tube, photodiode, phototransistor, CCD camera, electrochemical cell, wherein the detector is selected and/or placed such that it optimally detects electrochemistry from structures of conducting and/or semi-conducting material and avoids detection of electrochemistry from the two electrodes which are externally and electromcaUv connected to the electπcal power supply. An example of a cell (in the above apparatus) compπses at least three functional zones- a central zone for the sample to be assayed and at least two zones which flank the central zone and which contain the two electrodes wherein each electrode of the two electrodes is contained within each of the two zones which flank the central zone. In another example, the central zone can be separated from the flanking zones by a membrane which is a semi-permeable membrane. In another example, the central zone can have a window for the detector allowing solely a view of the central zone. In another example, the apparatus can be controlled by vaπous means for example by a computer or microprocessor. This invention also concerns kits for performing an assay compπsing; a bmding speαes labelled with an electrochemically detectable speαes and a structure of conducting and/or semi-conducting material coupled to a second bmding speαes, wherein the structure of conducting or semi-conducting material not in electπcal contact with an external electromc circuit is subjected to an applied voltage in an electrolyte causing electrochemistry to occur on the structure of conducting or semi-conducnng material. These kits in one example also make use of a bifuncQonal binding speαes which would allow the bmding between structures to generate larger structures of conducting and/or semi-conducting material. In addition, the binding between structures could also generate interfaces which would allow coupling of the electrochemistry occurring on the surfaces of two proximal structures. Examples of a detectable electrochemical reaction are those generating light either direcdy or lndirecdy. This invention also concerns kits for performing an assay wherein electrochemistry is detected direcdy or lndirecdy from at least one structure of conducting and/or semi-conducting material, the kit consisting essentially of; an enzyme or substrate of an enzyme and at least one structure of conducting and/or semiconducting material, wherein the structure of conducting and/or semi-conducnng material is capable of being stimulated to carry out electrochemistry on application of a voltage to an electrolyte in contact with the structure of conducting or semi-conducting material when not in electromc contact with an external electromc control circuit This invention also concerns an immunochromatographic device compπsmg a bmding speαes labelled with an electrochemically detectable speαes and a binding speαes immobilised, and a solid phase non-conducting material containing at least one structure of conducting and/or semi-conducting material positioned such that electromc connection to an outside electπcal circuit can be avoided, wherein the solid phase is not rendered conducting and/ or semi-conducting by the structure of conducting and/or semi-conducnng material. In another embodiment of the immunochromatographic device two electrodes are able to make electromc contact with an external electromc circuit but do not make electromc contact with the solid phase. This invention also concerns the generation of electromagnetic radiation by application of a voltage gradient across at least one structure of conducting and/or semi-conducting material not in electromc contact with an external electromc αrcuit, the voltage gradient bemg such that at least one electrochemical reaction takes place on the structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit wherein the one electrochemical reaction results in the emission of electromagnetic radiation, either direcdy or lndirecdy. An electrocherniluminescent reaction is one example of an electrochemical reaction Also, stabilised dioxetanes or other chemiluminescent molecules can be activated by electrochemistry in such systems. This invention also concerns the generation of electromagnetic radiation within a separations medium and compπses the application of a voltage to a separations medium which contains or is constructed from structures of conducting and/ or semi-conducting material such that the separations medium is not rendered conducting or semi-conducting. Some examples of separations media include the following materials, styrene, dextran, agarose gels, polyacrylamide gels, cellulose fibres, and deπvaaves thereof. Examples by which electromagnetic radiation is generated include electrochemiluminescence or chemiluminescence. This invention also concerns an assay for an analyte of interest using an electrochemical process, the assay compπsmg the following. The estabhshment of contact between the sample to be assayed for an analyte of interest and at least two structures of conducting and/or semi-conducαng material not in electromc contact with an external electromc circuit, wherein the two structures of conducting and/or semi-conducting material are bound to at least one binding speαes or at least one enzyme substrate. This is followed by allowing at least one of the two structures of conducting and/or semi-conducnng material to interact with the analyte either enzymaαcally or by binding to alter at least one of the two structures of conducting and/or semi-conducting material such that it is able to bind to at least one of the two structures of conducting and/or semi-conducting material. This is followed by allowing an altered structure of conducting and/or semi-conducong material to bind to at least one of the two structures of conducting and/or semiconducting material to form a complex of at least two structures of conductmg and/or semi-conducnng material. Following this, a voltage gradient is applied across the complex of at least two structures of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit, the voltage gradient being such that an electrochemical reaction takes place on the complex of at least two of the structures of conducting and/or semi-conducting material not in electromc contact with an external electromc errant This is then followed by the detection or quantitation of the electrochemical reactions direcdy or lndirecdy, and the determination of the presence or quantity of the analyte of interest. This invention also concerns an assay for an analyte of interest using an electrochemical process, the assay composing the following Contact is established between a sample to be assayed and a structure coated or otherwise linked to a selected compound such that an analyte interacts enzymaπcallv or by bmding with the structure via the selected compound resulting in a modified structure. This is followed bv establishing contact between the previous mixture and a binding speαes able to bind to the modified structure to form a second modified structure, wherein the bmding speαes is linked or labelled with an electrochemically detectable speαes. This is followed by establishing contact between the second modified structure and a structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit, and, applying a voltage gradient across the structure of conducting and/or semi- conducting material not in electromc contact with an external electromc circuit such that an electrochemical reaction with the electrochemically detectable speαes takes place. This is then followed by the detection or quantitation of the electrochemical reactions direcdy or lndirecdy, and the determination of the presence or quantity of the analyte of interest. Examples of these structures include polymer base beads coated with at least two binding speαes, one speαfic for the analyte and one speαfic for a complementary binding speαes on the structures of conducting and/or semi-conducting material, and the structures of conducting or semiconducting material are coated with the complementary binding species This invention also concerns an assay for an analyte of interest using an electrochemical process, the assay compπsmg the following. Contact is established between a sample and a structure coated or otherwise linked to a selected compound wherein an analyte interacts with the structure via the selected compound. This is followed by establishing contact between the previous mixture and structures of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit, wherein the structures bind or otherwise form a close contact with the structures of conducting or semi-conducting material. This is followed by subjecting the previous mixture to a voltage gradient across the structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit but bound or otherwise in close contaα with the structures, such that an electrochemical reaction takes place, wherein the electrochemical reaction either direcdy or lndirecdy involves compounds bound or associated with the structure. This is followed by detection of the electrochemical reaction involving either direcdy or lndirecdy the compounds bound or associated with the structure, whereby the analyte is detected or quanntated. Examples whereby the structures bind or otherwise form a close contact with the structures of conducting and/or semi-conducting material mclude interactions selected from the following; binding speαes to bmding speαes interactions, magnetic field interactions, charge charge interactions, dipole dipole, electπcal field interactions, hydrophobic interactions. Examples whereby the structures bind or otherwise form a close contact with the structures of conducting and/or semi-conducting material mclude concentration methods selected from the following; filtration, sedimentation, centήfugation, drying, evaporation and preαpitaαon. In addition, the structures in one embodiment are bound to both an electrochemically detectable speαes and to a bmding speαes or enzyme substrate and the structures of conducting and/or semi-conducting material are bound to a bmding speαes or enzyme substrate. Detailed Description of Invention This invention relates to electrochemical-based assay systems for analytes of interest such as molecules, ions, amme-contaimng molecules, enzymes, substrates, antibodies, antigens, nucleic aαds, receptors, kgands, hormones, biomolecules and any combmation of bmding speαes which, in operation, incorporate vaπous structures of conducting or semi-conducting material. These vaπous structures are not in electromc contact via a wire or equivalent electron conducting media to an external voltage supply The material of the subject invention is conducting or semi-conducting and acts as an electrode which has both an anodic and cathodic face under an applied electπc field. Thus, the matenal becomes bipolar with respect to the developed electπcal potential. The matenal is m electπcal contact via an electrolyte providing an ionic but not an electromc contact to an external electromc circuit The matenal is stimulated to carry out the desired electrochemical reactions by applying a voltage gradient across at least a portion of the electrolyte which is in contact with the conducting or semi-conducting material. This results in the development of anodic and cathodic portions on the conducting or semi-conducnng matenal surface such that electrochemistry occurs on at least a portion of the anodic or cathodic portions of the conducting or semi-conducting material in contact with the electrolyte. The result of the electrochemical reaction is to produce a detectable signal (such as light) or to produce a detectable molecular speαes (such as a chromophore or fluorophore or electrochemically-reacQve molecule) which allows the detection and/or quanotaαon of the analytes of interest The detailed speαfic methods by which this can be brought about to allow detection and/or quantitation of analytes of interest are further descπbed below. Electπcal contact and electrical conduction It is well understood that electncal contact can be established by vaπous methods and can be characterised by the mode of charge transfer. In one method for electπcal contact, electrons move to achieve the charge transfer This form is typically known as electromc. This electromc method of electncal contact is based on electrons as earners of charge and electπαty, as found in metals, conductors or semi-conductors. When an electrolyte is used to create electπcal contact and allow electπcal conduction, no direct electromc conduction is mvolved. When an electrolyte is used, the charge transferred during electπcal conduction is earned by ionic speαes (charged atoms and molecules) Thus, electromc conduction is not based on the movement of ionic speαes as charge earners An electrolyte is an lomc conductor capable of forming an electπcal contact in all three states of matter gases, solids and liquids With electrolytes, charged molecular speαes move at the interface between an electrolyte and an electromc conductor or semi-conductor where electrochemistry can occur. This electrochemistry is dependent on the applied voltage, chemicals (Le. electrochemically-active compounds) in the electrolyte and the nature of the electromc conductor or semi-conductor surfaces. Conducting and semi-conducting materials Examples of materials which can be used m this invention to act as electrodes to carry out electrochemistry are without limitation: conducting or semi-conducting materials, composites, mixtures, alloys, blends or other such obvious deπvatives which combme many conducting, semi-conducting and non-conducting materials to produce materials which in the final form are able to act as conductors or semi-conductors. Some examples are Si, GaAs, Pt, Ag, Au, C, Zn, Si, Ge, Sn, Pb, Hg, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Cd, In, Sb, W, Re, Ta, Os, Ir, Bi, Al, on oxide, indium/tin oxide (ITO), anαmonv/nn oxide, electronically- conductive polymers such as polypyrole and polvthiophene Mateπals used as coatings mclude, carbon, gold, Pt, ITO and the conductive polymers An example of a coated conductive material is Zelec ECP which is an electronicallv-conductive powder (DuPont, DE). Zelec is available m two forms, one as a coating of antimony doped tin oxide on an inert core (silica, mica and titanium dioxide) or as solid particles of antimony doped tin oxide In an advantageous embodiment of the invention C, Au, Pt, ITO and Ag are the most favoured conducting mateπals of interest in the invention as they present a number of ideal properties including cost, stability, availability and expeπence with these materials in a number of electrochemical systems. Also, these mateπals have already been used to manufacture numerous structures, forms and coatings. C is of particular interest because of the number of different forms available and the number of differing electrochemical systems both in electrochemical applications and also in electrochemical assay devices which have made use of this matenal in its vaπous conducting or semi-conducting forms. Carbon is also readily deπvatized to vield numerous speαficallv modified surfaces such as in WO 97/33176 and WO 98/12539 which are hereby incorporated by reference in their entirety In addition, many other methods are known m the art for modifying carbon and other mateπals to render them useful for coupling Examples are cited in the following; US 5,667,667; P Allongue et al J Am Chem Soc 1997, 119, 201; C Sellim et al Material Science and Eng.1990, A126, (1990) 235-244; C Kozlowski et al J. Chem. Soc., Faraday Trans. 1985, 81 2745-2756; B Barbier J. Electrochem. Soc. 1990, 137, 1757-1764; Au and Pt are also of special interest as these mateπals are used widely for electrochemistry, electromc fabπcation and in immunoassay systems. Au and Pt also have added advantages over many other materials in that they are relatively inert and are stable when exposed to a wide range of chemical agents. Structures Examples of structures of conducting or semi-conducting mateπals suitable for the subject mvention are numerous. These structures take numerous shapes and forms, such as beads, particles, spheres, spheroids, cylinders, cones, plates, coatings, fibres, fibrils, nanotubes, nanoparticles, colloids, splinters, filings, springs, coils, amorphous particles, amorphous plates or coatings, and as a conductive coating take the form of two dimensional shapes of squares, triangles, rectangles, circles, pentagons, hexagons, stars etc. In an advantageous embodiment, the structures of most interest will be particles that are spheπcal or spheres or similar, also fibres, fibrils and nanotubes. Coatings take the form of conductive coatings on the surface of 3 dimensional structures, but can also be in the form of 2 dimensional shapes such as those produced by the evaporation of gold onto a surface which is masked to produce a desired shape on a surface. Other examples of coating methods are without limitations, e.g. sputtering, screen printing, plating, polymensaαon, stamping and painting. Many mateπals can be coated onto surfaces of flat or shaped structures thus producing a desired conducting or semi-conducting surface to form a structure for the purposes of the invention. In the cases of evaporated gold, sputtered carbon shapes or pyrolysed carbon on a surface, the potential exists to generate an array of such gold or carbon elements where each functions as separate bipolar electrodes as descπbed for this mvention. Other coating methods, as illustrated above, could also be used in this way to generate a senes of potential bipolar electrodes. The present mvention using arrays of patterned conducting elements does not need to be in electromc contact with an outside circuit. As a result, the mvention solves a problem inherent to the apphcation of multiple electrodes or multiarray electrodes used in the development of electrochemical assay systems for multiple samples and multiple analyte detection systems. In the case of particles or beads, it is understood that particles or beads from cm to nm in size have been used in immunoassay applications ranging from tube-based assays to filter wicking assay systems. We anticipate the use of particles m these ranges as structures of the subject mvention. It is also anticipated that the structures of conducting and/or semi-conducting matenal will also be incorporated into composite mateπals by mixing with non-conducting and/or conducting and/or semiconducting mateπals. By way of an example, filters constructed by the inclusion of structures of conducting and/or semi-conducting matenal duπng manufacture are contemplated to generate a non-conducting filter material which contams dispersed structures of conducting and/or semi-conducting materials. These composite filters are valuable in the development of the lmmunochromatography methods of the mvention. When wetted with electrolyte, these composite filters can be activated to earn' out electrochemistry through 1 1 the bulk of the filter at the sites of the dispersed structures of conducting and/ or semi-conducting material. In other forms of composites the concentration of the conducting and/or semi-conducting matenal is such that the composite is itself conducting and/or semi-conducting. The composites of this type are then equivalent to the conducting and/or semi-conducting mateπals of the subject mvention. These composites can then be used to form the structures of the mvention as descπbed above forming for example fibres, particles, beads etc. Other types of composite containing conducting and/or semi-conducting structures of the subject mvention are gels and sols and hydrogels. In these composites with gels, sols and hydrogels, the conducting material is dispersed or suspended in such a way that the conducting or semi-conducting structures do not render the composite electromcally conducting. In addition, the amount of conducting or semi-conducαng structures is such that the final form of the composite is visible to vanous electromagnetic radiation and photon detection means. Also, such composites are amenable to the use of conventional electrochemical detection methods using electrochemical cells externally connected to a electromc circuit. Some examples of mateπals which are readily available and illustrate some of the forms contemplated in this mvention mclude: Aluminium powder, 20 micron; Beryllium powder, 10-20 micron; glassy carbon sphencal powder in vaπous sizes from 0.2 μm to 2,000 μm; graphite powders; graphite fibre 8 μm in diameter and 0.5 to 25 mm in length; gold powder/shot, sphencal, 2μm to 3mm; gold flake, 2-15 μm; gold wires 0.05mm to 2mm dia; nickel powders, 2-7 micron, vanous forms; palladium powder, vanous forms from 0.25-7.5 micron; platinum wire 0.025mm to 2mm dia; platinum powder/ shot, vaπous forms, 0,2μm to 3mm (Alfa Aesar, Ward Hill, MA); carbon nanotubes or fibrils (Materials and Electrochemical Research Corp, Tucson, AZ); long ordered carbon nanotubes from lOμm to 2mm have been descπbed (Pan ZW et al, Nature 1998, 394, p631 and Fan S et al, 1999, Sαence, 283, p512), Zelec ECP (DuPont, DE). In addition, the fabπcaαon of the structures of the subject mvention from the materials of the mvention is highly developed allowing a wide range of shapes and structures as outlined above. For example, so-called nanowires 55 μm long and about 250 nm in diameter have been made (Huber, CA, Sαence 1994, 263, p800). It is contemplated that nanowires of vaπous sizes and matenal be used advantageously in the present mvention as structures of the subject mvention. It is also contemplated that structures of the subject mvention, as descπbed above can be optionally coated to improve the electrochemistry or reduce interferences, for instance with gels, polymer layers or grafts and solid electrolytes layers which are known in the art. Detectable electrochemical reactions Detectable electrochemical reactions consist of electrochemistry on a speαes (a so-called electrochemically- detectable speαes) which gives πse to a direcdy detectable speαes such as photons of electromagnetic radiation or lndirecdy via production of a subsequendy-detectable speαes or molecule such as a chemiluirunescent, fluorescent or coloured molecule or a molecule with an altered absorption spectrum, and electrochemically active speαes Numerous examples of detectable electrochemical reactions exist producing electromagnetic radiation, electrochemically active molecules, chromogenic molecules and fluorogemc molecules. Advantageously, the detectable reaction is direcdy coupled (i.e. compπsmg typically no more than four to five reaction steps) to the electrochemical reaction at the electrode surface but can also be lndirecdy coupled to the reactions at the electrode surface where numerous reactions linked to an initial electrode reaction result in the production of a detectable signal, speαes and/or molecule. The electrochemical reactions that produce electromagnetic radiation, such as ECL, chem uπunescence, and electrolurmnescence, are easy to detect as they require simply a means to detect the electromagnetic radiation produced. In the case of ECL and chemiluminescence, the electromagnetic radiation is produced from electrochemical reactions αther direcdy or by coupling to other electrochemically-produced reactants. Vaπous forms of ECL are considered in this mvention, for example, ECL from Luminol with hydrogen peroxide, ECL from metal chelates and orgamc molecules which can occur in the presence of co-reactants such as oxalate (D Ege et al, 1984, Anal Chem 56, 2413-2417) and numerous amines as descπbed in WO 97/33176 and EP 0441894B1 which are incorporated by reference in their entirety. Also, the ECL from Luminol with hydroperoxides, e.g. in the measurement of lipid hydroperoxides (A. Zamburhno, Biochim Biophys Acta (1995) 1256, 233-240). ECL is also generated from a number of metal chelates and orgamc molecules where use is made of the electrochemically-generated oxidised and reduced speαes (generated at the anode(s) and cathode(s)) to produce the exαted state for light emission. Light emission is also activated electrochemically from other chemilurmnescent molecules in addition to luminol such as acndinium ester and advantageously from stabilised dioxetanes such as those sold by Tropix (Waltham, MA), In the case of the stabilised dioxetanes, these have typically been stabilised by the use of subsαtuent groups which can be removed enzymatically to destabihse the dioxetane and thus produce light In the subject mvention, dioxetanes stabilised by groups which are or can be electrochemically removable provide for a wider range of potential chemistπes; alcohols, aαds, and glycosides are contemplated as such groups (VG Mairanovsky, 1976, Angew. Chem. Int Ed. Engl. 15, 281-292). It is also contemplated that fluorescence would be used as a detectable signal or label. Fluorescence could be used either via the synthesis or the activation of a fluorescent speαes. For example, the local pH changes brought about in the proximity of a micro electrode can be sensed by the fluorescein activation caused bv the pH change in the local environment of the electrochemical reaction (BB Ratcliff et al 1996, Anal Chem 68, 2010-214). Electrogenerated fluorescent speαes are also detectable as demonstrated bv McLeod et al, (The Analyst, 1982, 107, 1-11) In another example, the electrochemical reaction, which is detectable, allows the detection of the conducting and/or semi-conducting structure. In this example, the conducting and/or semi-conducting structure becomes the detectable speαes and can be used to detect the analyte of interest. This property has been descπbed for Al which can emit light on apphcation of a voltage at anodic and cathodic surfaces (Haapakka K et al, 1988, Anal Chun Acta 207, 195-210). A conducting and/or semi-conducting structure coupled to a bmding speαes to form the electrochemically- detectable speαes is also contemplated. When bound or captured, this could subsequendy be detected using electrolytes with ECL and CL speαes such as Ru(bιpy), luminol. The capture of a structure of the subject mvention would allow for considerable enhancement of the signal as a single bmding event would provide a bipolar electrode which could generate more light in an ECL reaction than from the capture of a few ECL active molecules. Conducting and/or semi-conducαng structures made from or coated with electroluminescent matenal are contemplated. These coated structures of the subject mvention support the generation of hght from structures in the electrolyte when a suitable voltage is apphed without the need for additional chemistry. ECL labels The ECL labels of the subject mvention mclude numerous examples of both orgamc compounds and metal ion chelates. Well known examples are tπs(2-2'-bιpyπdine)ruthemum(ir) (Ru tπbipy), Ru tπs phen, Os tπbipy and numerous other metal chelates descπbed m the hterature, and luminoL Numerous examples are covered in the following publications: US5453356, US5591581, US5238808, US5221605, WO 97/33176, WO 96/28558 which are incorporated by reference in their entirety. Also, Al structures are known to luminesce when coupled to an electrochemical reaction m an electrolyte (Haapakka K et aL 1988, Anal Chun Acta 207, 195-210). Examples of other compounds that produce ECL are 9,10-dιphenylanthracene, rubrene, bιs(tn-n- hexylsιloxy)(2,3-ρhthalocyamnato)sιhcon and its dimer, bιs(tπ-n-hexvlsdoxy)(2^-naphtalocyamnato)sιhcon > tπs(4-vmyl-4'-methyl-2^'bιpyπdyI)nιthemum(II) and its polymers, luαgenin, acπdimum esters, rhodamine 6G, europium chelates, cryptates and mixed-hgand chelate/cryptand complexes (Richter MM and Bard AJ, Anal Chem 1996, 68, p2641), (7,12-dιphenyI)benzol(k]fluoranthene, bιs-4,4'-(7,12- &phenyl)benzol[k]fluoranthene, d benzo{[f,-^-4,4\7,7'-tetraphenyl}diindenol[l^ r 3-cd:r^',3'-lm]perylene and Ru(bpy) 2 (bpy(CO 2 MePEG350) 2 from Maness KM et al J. Am. Chem. Soc 1997, 119, p3987, which is incorporated by reference in its entirety. Electrolytes The electrolyte of the present mvention typically contams ionic speαes in liquids, solids and gases to allow electπcal conducting A charge passing through an electrolyte is transferred via movement of the lomc speαes m the bulk liquid, solid or gas. In addition to these basic elements, m manv cases the ionic speαes is also mvolved in the control of the ionic strength and/or the pH of the electrolyte such that it is optimal for the assay of the analyte of interest and/or the electrochemistry. Additionally, it is common to find within the electrolyte the addition of coreactants used to enhance or support the electrochemistry of the detection system. An example of an electrolyte that can be used for ECL with Ru is phosphate buffer used as electrolyte and pH control, combmed with tnpropylamine as an amine coreactant to support the ECL electrochemistry. Numerous examples of buffers exist, for example borate, phosphate, tπs, HEPES, MES, MOPS, PIPES, acetate, tπethylarrune, tnpropylamine, bicarbonate with the appropπate counter ion In some cases, the buffer would be a coreactant, such as amine-containing buffers that can act as coreactants in Ru (2,2- bιpyπdyl)3 2+ -based ECL. The ionic strength of the medium can be controlled typically by adding salts, or be established by controlling the concentrations of the buffer and/or the coreactants. Examples of salts which are used to control the ionic strength are numerous. Examples mclude salts of K, Na, Ca, ammonium, guanidinium. Typically, electrolytes of the subject mvention are based on water solutions and orgamc solvents. Advantageously electrolytes of the subject mvention are based on water solutions. Orgamc solvents in some cases are advantageous during the electrochemical reaction. It will be understood that mixed solvents are also used. For example, formamide is used advantageously in DNA probe applications. Other components are also added to improve assay conditions. Typical examples of components used to improve lmmunoassays include detergents, other proteins and hpid components. These other components are known m the art and are typically optimised for vaπous assays under the vaπous conditions of differing assay systems. The optimisation of these components is well known in the art and forms an integral part of assay optimisations. The use of other components to enhance vanous aspects of nuclαc aαd probes is also known in the an. Instruments Basically, the instruments integrate a luminometer, a voltage control αrαnt and a cell with two externally electromcally connected electrodes. Optionally, the apparatus includes a pump or other fluid-handling components and a flow-through cell with externally electromcally conneαed electrodes. The instruments of the subject invention advantageously have a cell which contams at least one electrolyte. This cell contams at least two electrodes which are m electromc contact with an external electπcal circuit which is able to apply a voltage. These two electrodes are in contact within the cell via the electrolyte within the cell. It is possible to design cells of vaπous shapes and configurations such as flow-through cells, single- chamber cells which allow the introduction of electrolyte at desired times. It is also possible that the cell and electrodes are a single module which can be inserted into the instrument to make contact Externally electromcally connected electrodes isolated from a central zone or at least from each other by a membrane, gel or other material which is semi permeable to ions and thus maintains contact between the two externally electromcally connected electrodes via the electrolyte, are also contemplated. This use of a semi permeable membrane isolates the sample from the externally electromcally connected electrodes and from the electrolyte in which they are immersed. This method of isolating the externally electromcally connected electrodes prevents both the detectors and the sample from bemg affected by the electrochemistry occurring on the externally electronically connected electrodes Ideally, the vaπous instruments contemplated would be controlled by a microprocessor αther direcdy by incorporation of a microprocessor into the instrument and/or by an external microprocessor such as a computer. Software for controlling such mterfaces is well known to those in the art for custom applications to make use of internal and external microprocessor control e.g. Labview from National Instruments (Austin Tx) www.nattnst.com. In addition it will be understood that simple electromc circuits can be constructed to control the apphcation of the voltage to the cell. Thus, the control of such an mstrument can be achieved at vanous levels from simple mechanical systems to microprocessor controlled systems An example of an instrument of the sub j ect invention contams a cell which is able to contain an electrolyte of interest for the detection and/or quantitation of an analyte(s) of interest which further consists of three zones or functionally distinct areas. Two of the zones flank a central zone and contain externally (to the cell) electromcally connected electrodes. These two externally electromcally connected electrodes are used to apply voltages to the central zone of the cell. The two externally electtonicallv connected electrodes are externally connected to a controlled voltage source. Typically, this controlled voltage source is under the control of a computer or is controlled by other means such as a simple electncal circuit or mechanical means for triggering the apphcation of the voltage. The controlled voltage apphed to at least the central zone of the cell is initiated by an operator or by determining the presence of, or placing, the sample electrolytes in the central zone of the cell. The sample electrolyte contams the conducting and/or semi-conducting structures of the subject mvention along with the compound(s) which are able electrochemically to produce a detectable speαes allowing detection of analytes. The two externally electromcally connected electrodes electromcally connected to the controlled voltage source are thus able to apply a desired voltage gradient to the central zone of the cell controlled by electromc means including a simple electromc circuit and/or microprocessor. The apphcation of this desired voltage to the central zone of the cell allows the conducting and/or semi-conducting structures of the subject mvention to carry out electrochemistry. This desired electrochemistry results in the formation direcdy or lndirecdy of a detectable speαes which when detected allows the detection and/or quantitation of the analyte of interest The central zone of the cell is fashioned in such a way that it readily allows the detection of the detectable speαes generated by the electrochemistry. In this regard, the central zone will contain at least one window. This window will permit the detection of electromagnetic radiation from the central zone. In an alternative embodiment, the window is present and additional externally and electromcally connected electrodes are introduced through the open window into the central zone, or into a zone in a flow-path from the central zone, to allow electrochemical detection of the detectable speαes using conventional and understood electrode configurations in combmation with conventional electrochemical methods such as amperometnc or potentiometπc methods. Examples of these are glucose and oxygen sensors and oxygen electrodes. In the case of ECL and chemilu mescence, the window will permit photon detection by a means of choice to detect and/or quanπtate the photons from the central zone. In the case of a chromogenic detectable speαes, the central zone would allow a beam of photons to pass through the sample in the central zone and be analysed and/or detected and/or quanntated The analysis of this beam of photons after passing through the sample in the central zone would determine whether the intensity of the photon beam had changed and/or if the spectral properties of the photon beam had been changed. In an advantageous embodiment, the beam of photons would have a wavelength selected to interact optimally with the detectable chromogenic speαes of interest. In the case of a fluorogemc detectable speαes, the central zone would allow a beam of photons to pass through the sample and the photons emitted from fluorescent molecules present in the sample to be analysed and/or detected and/or quanntated. The analysis of these photons emitted from fluorescent molecules, in the central zone, would determine whether the spectrum had changed with respect to the lnαdent beam of photons. In an advantageous embodiment, the beam of photons would have a wavelength selected to interact optimally with the detectable fluorogemc speαes of interest and the detector would be optimised to detect and/or quanαtate the emitted photons from the detectable fluorogemc speαes. The use of time- resolved fluorescence is also a contemplated detection means. The use of fluorescence and/or other energy transfers is also contemplated as a means of signal enhancement and discrimination, as used in other assay systems known in the art Other detection means are also contemplated by this assay system and instrument, such as electrochemical means for the products of the electrochemical reactions at the surface of the structures of the subject mvention. Cells of the instrument Vaπous cells for the instrument of the subject mvention are contemplated and it is understood that numerous potential examples are possible. Examples are descπbed in detail m the section "Examples" In the case for an instrument able to analyse clinical samples, a flow-through cell with the three zones descnbed above would be advantageous. When usmg the subject mvention with rapid immunochromatography-based assays, a cell would be a section of such a device. This section could be removable and is potentially a disposable element. In a multiwell plate, the structures of the mvention could be coated onto the surface of the well in a microtitre plate, typically on the bottom or portions of this part of the well, either as a single contiguous conducting or semi-conducting structure or advantageously as multiple elements in the size range of 1 μm to 1 mm as measured between the edges of the mdividual structures m the plane between the externally electromcally connected electrodes. The wells in this multiwell format could have the externally electromcally connected electrodes within the well or these could be introduced at a suitable time to apply the electncal field needed to render the conducting or semi-conducting structures bipolar thus stimulating electrochemistry This would result in the production of a detectable signal Multiwell plates constructed using composite mateπals containing conducting and/or semi-conducnng structures of the subject invention is also contemplated. Multiwell plates so constructed would possess well surfaces of conducting and/or semiconducting structures able to act as bipolar electrodes in an apphed field. It will also be understood that the structures of the mvention used m a multiwell plate format where they do not from a integral part of the plate structure, such as in a composite, but are dispersed or included in buffers used in a multiwell plate, are also contemplated. In a multianalyte system, the conducting or semi-conducting structures of the subject mvention could take the form of multiple mdividual patterns or shapes on the surface of a non-conducting matenal forming a multitude of potential assay sites rendered bipolar in an apphed electπcal field. These bipolar structures of the subject invention would then be capable of electrochemistry m electrolytes known to the art. The result of this electrochemistry would be to allow production of a detectable signal dependent on the presence of an electrochemically active speαes m proximity to the bipolar structures of the subject mvention In this mulαanalvte cell, the surface with its multiple mdividual patterns or shapes of conducting or semi-conducting matenal form the bottom of a well in an assay plate with many other such surfaces as found in a microtitre plate or are part of a flow-through system as a means for introduction of sample and/or reagents. In these and other related cells, the surface with its multiple structures must be in contact with an electrolyte and must have at least one window to allow the detection of the detectable speαes. This provides for significant advantages over the current art which requires external electromc connections to each element. Further examples of cells are descnbed in the section "Assay formats" and the section "Examples". Waveforms and voltages Duπng analysis of the sample, a voltage is apphed to the sample. The following section descπbes some examples of these and gives examples of the apphed voltage waveforms. Apphed voltage profiles can be those seen in typical electrochemical studies and cells with the exception that these are not limited to the low voltages seen in conventional electrochemical cells (less than 5 volts). The voltages apphed to the structures of the subject mvention range from 2 volts/cm to 50,000 volts/cm or the limit of the solvent/electrolyte used. Advantageously, voltages range from 20 volts/cm to 50,000 volts/cm or the limit of the solvent/electrolyte used. More advantageously, the voltages range from 50 volts/cm to 50,000 volts/cm or the limit of the solvent/electrolyte used. Most advantageously, the voltages range from 50 volts/cm to 5,000 volts/cm or the limit of the solvent/electrolyte used. The voltage apphed to the cell of the subject mvention via the externally and electromcally connected electrodes can take multiple forms. For example, voltage apphed in a step form where the potential is raised to a given value and held for a time and then removed is also contemplated. It is also contemplated that this type of step is apphed repeatedly to give a square wave form with a wide range of frequenαes from 0.001-10,000 cycles per sec, advantageously this is from 0.001 to 1,000 cycles per sec, more advantageously this is from 0.01 to 1,000 cycles per sec. Voltage scans or waveforms containing portions of reverse potentials are also contemplated. Thus the step potential would be descπbed as having a negative and then a positive portion and this single unit repeated to give an alternating square wave form. The voltage apphed in such a way that it follows a ramp up and down in voltage with or without negative or reverse polaπty portions to the ramp is also contemplated. These ramps constructed around numerous potential waveforms such as sin waves, saw tooth waves, multiple component step waves and combinations of these are also contemplated. Also, advantageously having at least a lower voltage portion in such wave forms pπor to the exαtaπon of the electrochemically detectable speαes is contemplated. Where a single cycle of apphed voltages is used, cycles take from 0.01 to 1600 sees to complete, advantageously this is from 0.1 to 600 seconds, more advantageously this is from 1 to 300 seconds, most advantageously this is from 1 to 60 seconds. Measuring cycle The measuring cycle in the instrument consists of the introduction of the sample into the central zone of the cell either by flow (in a flow-through system), by robot arm or other manual or mechanical pipetting means, or by plaαng a cartridge and/or disposable element containing the electrodes, conducting and/or semiconducting structures and sample into the instrument The sample is then subjected to a voltage waveform or pulse as outlined above and the detectable electrochemical reaction is then detected Sub j ecting the sample to somes or ultrasonics to improve the kinetics of the bmding reaction and/or the electrochemistry is contemplated and has been descπbed previously for these reactions and is known in the art (K Suslick, Sαence, 1990, 247, 1439-1445 and D Walton et al mectrochimica Acta, 1993, 38, 307-310) Mixing achieved via the use of magnetic methods or other mechanical methods known m the art which are known to achieve significant fluid mixing is also contemplated These vanous forms of mixing are advantageous m that the mixing duπng the apphcation of the apphed voltage, activating the electrochemistry, can induce tumbling and rotation of the structures of the subject mvention is such a way that significantiy more surface of the structures is activated to carry out the desired detectable electrochemical reaction(s). It is contemplated that the voltages and waveforms descnbed above are apphed duπng mixing or sonication or ultrasomcation. In addition, multiple (advantageously from 2 to 20) externally and electromcally connected electrodes are used m a cell to achieve the apphcation of a voltage field at vaπous angles with or without the apphcation of alternating positive and negative fields to achieve activation of a greater surface of the structures of the subject mvention In one of its forms, externally and electromcally connected electrodes could be positioned at the eight positions of a sphere, or comers of a cube or rectangle defining the central zone of the cell These electrodes could then be used in pairs or other vaπous combinations to apply both negative and positive voltages to the cell These voltages could be controlled bv a computer or mechanical device to apply a sequence of voltages to the different electrodes in such a way that all faces of the conducting and/or semi-conducnng matenal are activated to carry out the desired electrochemistry to produce the detectable signal. Activation of vaπous faces of the conducting and/or semi-conducting structures of the subject mvention could also be used in combination with multiple detectors of electromagnetic radiation to permit correlation of apphed voltages and electromagnetic radiation from vaπous faces to be made thus allowing a more effective determination and elimination of background signals in the system and from the detectors and their associated circuits The vaπous forms in which the electrochemicallv-detectable signal can be detected are numerous and are known in the art, for example in the case of ECL and chemiluminescence, a light detection method based on the use of photomulαplier tubes and photodiodes (luminometers), CCD cameras, film and by eye, in the case of a fluorescent molecule generated bv the electrochemistry, a detector based on a fluonmeter would be used; m the case of a chromogenic or other molecule with a new absorption spectrum, a spectrophotometer system would be used, m the case of an electrochemically active molecule generated as the electrochemically detectable signal, an electrochemical cell with externally electromcally connected electrodes would be used to electrochemically detect the speαes generated usmg potentiometπc or amperometnc methods Binding Species Vaπous assays are descπbed for the subject mvention and these can be earned out making use of numerous bmding species The following are examples illustrative of the types and land of binding speaes contemplated in the subject mvention In this discussion, a molecular speαes mcludes chemicals from single speαes atoms or ions (I e Ca + ) to complex multiple atom compounds (I e antibodies) Most binding speαes are defined by the existence of a partner binding species since, to be a binding speαes, the molecular speαes must bmd to another molecular speαes, which mcludes the same molecular speαes. For example, an antibody developed such that it will bmd to itself. In many cases, this type of self bmding is not valuable but can be useful in certain cases, for example, where development of signal amplification is of interest. In the case of a binding speαes and its bmding partner, these two speαes can be considered to be bmdmg speαes since they are both able to bmd to another molecular speαes. For example, in the case of antibodies and antigens (well known bmdmg speαes), the antibody bmding speαes' partner is the antigen and the antigen bmding speαes' partner is the antibody. Thus, the antibody and the antigen can both be considered to be bmdmg speαes. The following is a partial list of such bmding speαes contemplated in the subject mvention: antibodies, antigens, receptors, enzymes, enzyme inhibitors, drugs, hormones, gands, receptor hgands, lectins, selectins, mtegnns, RNA, DNA, nucleic aαd analogues, nuclαc aαd bmding protons, chelating hgands. These bmding speαes are all contemplated as analytes that can be detected and/or quanntated by the subject mvention. Analytes Analytes of the subjeα mvention are numerous, including the binding speαes descnbed above, but also mclude molecules which are not bmdmg speαes or can be detected without being part of a binding-speαes to binding-speαes lnteraαion. The character which defines these groups is their ability to interact with the electrochemistry in a detectable manner, this interaction occurring because of the apphed voltage on the structures of conducting and/or semi-conducting materials not m external electromc contact. Also considered as analytes are molecules able direcdy or lndirecdy to produce, destroy or metabolise electrochemically detectable speαes. An example would be the detection and/or quantitation of amine- containing compounds which act as a coreactant in the generation of ECL from vaπous metal chelates such as Ru(bpy) 3 2+ Examples of this are contained m EP 0 441 894 Bl which is incorporated by reference in its entirety. Other examples are tnpropylamine, NAD(P)H, and hydrolysed beta lactams. It will be understood that ECL labels (as descπbed earlier) and ECL active speαes such as Ru(bpy)3 2' , ruberene, luminol, and dioxetanes are also considered as analytes No bmd g interactions occur in this reaction Also, in the case of glucose detection and/or quantitation, where glucose is acted upon by glucose oxidase, the product of this reaction (hydrogen peroxide) acts as a coreactant with luminol to electrochemicallv generate hght. It would be understood from such a reaction that in addition to glucose as an analyte, glucose oxidase and hydrogen peroxide could also be analytes. It will be understood that an analyte subjected to a seπes of reactions giving πse to a molecular speαes which can direcdy partiαpate in modifying (enhanαng or inhibiting) a detectable electrochemical reaction is contemplated. An example of this is seen in the case of a glucose assay based on a well understood assav for glucose which first kinases the glucose (with ATP and the enzyme hexose kinase) to form glucose-6-phosphate. This is then subjected to the action of glucose-6-phosphate dehydrogenase in the presence of NAD + to generate NADH This acts as a coreactant with Ru(bpy)3 2+ to generate ECL (Jameison F, et al. 1996, Anal Chem 68, 1298). Assays based on coupling multiple reactions and/or chemical reactions such as that descπbed for glucose are known and well understood and those reactants, enzymes and substrates which parπαpate to give πse to an electrochemically detectable reaction can be considered as analytes. Thus, it will be understood that many other chemicals are analvtes in addition to the binding speαes descπbed above. Some example of analytes mclude enzyme substrates, enzyme products, enzymes, whole cells, viruses, sub cellular particles, nuclαc aαds, polysacchaπdes, proteins, glycoproteins, lipoproteins, hpopolysacchaπdes, pids, fatty aαds, peptides, cellular metabolites, hormones, pharmacological agents, tranquillisers, steroids, vitamins, ammo aαds, sugars, and non biological polymers Assay formats Numerous assay formats are contemplated and are given in the form of examples below The assay formats of the subject mvention provide vaπous advantages over the current assay systems. Also provided are new ways of carrying out analyses which allow for a seπes of contemplated improvements to assay systems and sαentific exploration. One key advantage over the current electrochemically based detection or assav systems - where the electrochemistrv is confined to the surface of an externally electromcally connected electrode - is that the subject mvention does not present any such limitation. The subject invention allows for electrochemical stimulation withm a sample volume, generating a detectable signal which allows for the detection and/or quantitation of analytes within the sample volume and to a greater extent than previously possible because of the effective extension of the electrode surface area available. This ability to generate a detectable signal by stimulation of electrochemistry withm the volume of a sample provides the following advantages; 1) improved detectabihty, more of the sample is activated, 2) improved sensitivity, more signal is developed as the sample volume is significantly larger than in conventional electrochemical methods, 3) improved speed, improved kineαcs and time to analysis, 4) increased volumes for samples allows activation through the sample volume, 5) spatial discrimination, allows multiple samples to be analysed and provides the potential for photographic- ke resolution withm a sample l e. a gel This spatial discrimination can also be three dimensional. 6) Improved electrochemistry via redox cycling espeαallv when structures of the subject mvention are coupled to or linked via a binding interaction which is mediated by an analvte of mterest, thus allowing detection of the bmdmg reaction without the need for separations or washes following the bmdmg interaction. Assays in separation media These advantages of the subject mvention are significant when determining the location of labelled material localised withm a large volume or surface. Examples of this are electrophoretic separations, chromatographic separations (TLC, HPLC, FPLC), lmmunochromatography, southern blots, western blots, northern blots. In the case of electrophoretic separations, where the detection of the positions and amounts of each speαes within the gel is of mterest, vaπous methods are used for detection and quantitation, ι.e. staining with vanous dves and fluorescence Typically, this results in staining the gel direcdy with vaπous agents to visualise the molecules in the gel, e.g usmg commassie blue to detect proteins in gels. Here, the proteins bmd the dve and are detected as blue bands. Ethidium bromide is also used to detect DNA in geis followed by illumination with UV hght to visualise the fluorescence of the DNA-bound ethidium bromide. In some cases, the molecules are radiolabeled and are detected by autoradiography. In the case of this invention, it is possible to manufacture gels which contain structures (ι.e. particles, fibres, fibrils etc.) of conducting matenal which can be activated to carry out electrochemistry to allow the detection of analvtes separated by the gel electrophoresis. Numerous examples of gels, papers and other electrophoretic supports are known in the art and mclude; polvacrylamide, agarose, starch, cellulose acetate, cellulose, silica, nvlon, mtrocellulose, PVDF, etc. In an advantageous embodiment of this gel detection apphcation of the mvention, analysis of PCR products could be earned out as follows. Ohgonudeotide pπmers are labelled with an electrochemiluirunescent (ECL) label ORIGEN TAG (IGEN, Gaithersburg MD) following methods descπbed by the manufacturer (apphcation notes descnbing PCR are available on the internet at http:/ / ww.igen.com). These PCR pπmers are then used in a PCR to amplify and generate an ECL-labelled PCR produα which is dependent on the presence of DNA complementary to the labelled PCR pπmers. The PCR product can now be run on a standard agarose or polvacrylamide gel containing for example advantageously carbon nanotubes or carbon fibres (Alfa Aesar; Mateπals and Electrochemical Research Corp, Tucson, AZ, Pan ZW et al, Nature 1998, 394, p631 and Fan S et al, 1999, Sαence, 283, p512) as conducting and/or semi-conducting material. These nanotubes would be included at such a concentration that the gel is not conductive and is not totally opaque such that no ECL would be visible, advantageously 0.1-10 μg/mL It is understood that other suitable conducting or semi-conducting mateπals (as descπbed above) are also used in the gel. The gel is then loaded with the PCR products and the DNA subjected to electrophoresis at voltage gradients typical for the separation of PCR products ι.e. less than lOOv/cm. After the electrophoretic separation, the gel is then soaked in ORIGEN assav buffer (IGEN, Gaithersburg, MD) for 30-60 mm with three changes of buffer. This gel is then placed m a high voltage chamber contained withm a black box to exclude as much hght as possible with electrolyte in contact at each end of the gel as in a typical electrophoresis chamber The high voltage container has an electrode at each end as is typical of an electrophoresis chamber with the gel between these electrodes The gel is visualised by a photomultipher tube, film or CCD camera The door to the black box containing the gel, high voltage chamber and photon detection system (PMT(s) or CCD camera or photodιode(s)) is closed to create a substantially light-free environment The high voltage chamber is then subjected to a high voltage which typically mcreases at a rate of 100 v/ s to 10 kv/s but could also be in the range of lOv/s to 1,000 kv/s. This voltage ramp is apphed for 0 1 sec or longer. Duπng the apphcation of these high voltages, peak voltages are controlled to prevent arcing which would indicate an excessive voltage. The voltages reached are advantageously from 100 v/cm to 10,000 v/ cm. Duπng the high voltage sweep the light produced is detected by the CCD camera (or other hght detection means) and the location and/or amount of the PCR product is determined In a further embodiment of the above protocol, the electrophoresis buffer would also be the ECL buffer as in the case of a buffer (as descπbed earlier) which contams amines useful for the generation of ECL, for example tπpropylamine-phosphate, tnpropylamine-acetate, tnethvlamine-borate, tπpropylamme-borate, PIPES and HEPES (WO 97/33176). Commerαal examples of ECL buffers are ProCell (Boehπnger Mannheim) and ORIGEN assay buffer (IGEN). Alternative methods for ECL could also be used where different pHs are desired for electrophoresis, for example by the use of the tns(2,2-bιpyndyl) ruthenium oxalate system. In this case, where the ECL enabling buffer and/or co-reactants are present, the gel could be pulsed to the higher voltages at desired times duπng the lower voltages used for the electrophoretic separations to activate the ECL labels on the labelled molecules. The higher voltages are required to render the carbon nanotubes or fibrils bipolar (generating an anodic and cathodic face on at least some of the carbon nanotubes or fibrils, or other structures of conducting and/or semi-conducting matenal) resulting in the activation of the ECL label contained in the PCR products separated on the gel, as descnbed above, or other labelled molecules This high voltage pulse used to render the carbon nanotubes or fibπls bipolar and activate the electrochemistry on part of the surface of at least some of the carbon nanotubes or fibπls could thus be part of the electrophoresis protocol. This would allow the electrophoretic migration to be followed over time by mtermittent activation of the ECL labels attached to the labelled PCR products. This in situ momtoπng of the electrophoresis would be valuable, improvmg the speed and resolution of the electrophoresis. These electrophoretic methods, of great mterest for the analysis of biomolecules, could also be apphed in the analysis and detection of ECL labels not coupled to biomolecules. The apphcation of this method to the analysis and detecnon of ECL labels and ECL coreactants not coupled to biomolecules could also be extended to ECL active compounds such as Ru (bpy)3 2+ and to compounds able to stimulate, enhance and support ECL, such as tnpropylamine. A further modification of the above example concerning the in situ detection of an analyte of mterest withm gels or other separation media is also contemplated. This method contemplates the detection of numerous molecules able to support ECL as has been demonstrated for numerous amine-containing molecules such as TPA, TEA, PIPES, HEPES, beta-lactams, NADH, and enzymes coupled to XAD or NADP etc. This provides the potential to detect enzv es and substrates of enzymes either direcdv or mdirecdy via a seπes of enzyme reaction steps (Marun AF et al, 1 97, Biosensors and Bioelectronics 12, 4 7 9-489, GA Forbes et al Analytica Qnmica Acta 34"', (1997) 289-293) This is also possible with enzymes that give πse to hydrogen peroxide, e.g glucose oxidase, cho ne oxidase etc., the resultant hydrogen peroxide bemg detected via coupling to the ECL of luminol. This luminol ECL can also be coupled to the detection of hydroperoxides such as pid hydroperoxides In this format, the conducting or semi-conducnng matenal is precoated with an ECL active label sensitive to the presence of amines or other potential coreactants that enhance ECL, e.g. Ru (2,2-bιpyπdyl)3 2+ when these amines or other potential co-reactants are in close proximity to the dispersed conducting or semi-conducαng matenal coated with the ECL active speαes. This type of detector system would be useful in the detection of mateπals in gels, matenal eluαng from columns duπng puπfication, duπng capillary electrophoresis and obviate the problems with the application of conventional electrochemical stimulation which requires sample withm a narrow region of an externally electromcally connected electrode surface which, bemg able to analyse or activate only a verv small portion of any given sample, results in poor sensitivity for these conventional methods. Here, the coated conducting or semiconducting matenal would be exαted by the apphcation of an external voltage to generate bipolar faces on at least some of the dispersed conducting or semi-conducting matenal, and thereby allow the detection of the ECL co-reactants such as amines, beta-lactams, NADH, NADPH and peroxides. In a further variation of this method, the ECL acnve speαes are added m solution i.e. in the gel, HPLC or capillary electrophoresis buffers. This would remove the need to immobilise the ECL speαes to the conducting and/or semiconducting structures of the subject mvention. Alternatively, this system could be used to detect ECL labels direcdy or by supporting ECL with a co-reactant. In the case of the luminol peroxide system, peroxides could be detected e.g. hydrogen peroxide or lipid hydroperoxides. In an alternative embodiment of the above example, these conducting or semi-conducting materials coated with an ECL active speαes sensitive to co-reactants such as amines, peroxides, beta-lactams, NADH and NADPH, could be used as suspended electrode systems for the detection of vaπous molecules which affect the concentration of these co-reactants. For example, enzymes acting on vaπous substrates can affect the concentration of these co-reactants allowing detection of αther the enzyme or the substrates of the enzyme. An example would be dehydrogenases that generate NADH or NADPH, e.g. glucose-6-phosphate dehydrogenase which can be used in a glucose assay when coupled to hexokinase as descπbed earlier. In this system, the analyte of mterest is a molecule which can be speαfiαdly acted on by a dehydrogenase to produce NADH or ADPH. This is then detected and quanntated by the activation of ECL. In the previous example this is glucose-6-phosphate. The assay could be earned out as follows: the sample would be mixed with the appropriate dehydrogenase and the appropriate co-factor such as NAD or NADP. This enzyme/substrate/co-faαor mix would then be supplemented with particles, fibres or fibπls of conducting or semi-conducting material precoated with an ECL active label sensitive to the presence of NADH or NADPH, e.g. Ru (2,2-bιpvπdyl) 3 2+ . Alternatively, the conducting or semi-conducnng material could be added with an ECL acnve speαes such as Ru (2,2-bιpyπdyl) 3 2+ free m solution. After the conducting or semi- conducting matenal and the ECL active speαes sensitive to the NADH or NADPH co-reactant have been added, a voltage is apphed. This results in the production of bi-polar faces on the conducting or semiconducting material leading to ECL which is dependent on the concentration of the analyte of mterest In addition to the potential to immobilise the ECL active speαes, it is also possible to immobilise additionally the enzyme and the co-factor. These systems - usmg conventional electrochemical methods - have been descπbed by Marαn AF et a (1997, Biosensors and Bioelectronics 12, 479-489). It is also possible to add the ECL acnve speαes into the solution, not immobilised on the conducting or semi-conducting structures of the subject mvention. These examples of embodiments of the mvention concerning the detection of molecules withm a large volume of sample (not possible with current electrochemical detection methods) are directed at ECL but could also make use of other detectable signal systems such as fluorescence, chemilummescence or spectrometπc methods as descπbed in other sections of the mvention These alternative detectable signal systems are activated bv the EC that itself is induced by the apphcation of elevated voltages, inducing the appropriate bipolar character on the conducting or semi-conducting materials withm the bulk or volume of the sample. Assays using filter wicking and/or lmmunochromatography In an advantageous embodiment of the subject mvention, the detection of antigens, antibodies, receptors, hgands and nuclαc aαds and their analogues is possible. This embodiment relates to an immunoassay, nuclαc aαd assay or other similar bmdmg assays earned out usmg a filter stπp or wicking method and also called immunochromatographic tests or lateral-flow tests. Examples of these are found in US 5591645, US 4861711, EP 0 258 963 A2, US 4703017 and US 5008080 which are hereby incorporated by reference in its entirety. This embodiment relates to the electrochemical activation of at least part of such a filter or flow- supporting matenal such that an analyte contamed withm or bound throughout the body of the filter or flow- supporting matenal is deteαed and/or quanntated. These tests usmg a filter snip or wicking method and also called immunochromatographic tests or lateral-flow tests, offer the beauty of simphαty. They involve simply the apphcation of a sample (e.g. blood, uπne, sahva). The apphcation of the sample results in the dπed labelled antibody and the other assay reagents dissolving and mixing with the sample to start the antibody- analyte bmdmg reaction Duπng this bmding reaction, the sample and labelled antibody is wicked (via capillary flow) along a stπp which, at a predetermined point, contams immobilised second antibody for the analyte of mterest The result is that as the sample and labelled antibody is transported along the membrane or supporting phase, the analyte binds the antibody. This immune complex then at some point is transported in the liquid flow to the capture antibody which is immobilised at a given site withm the filter or supporting phase. When the analyte-labelled antibody complex interacts with the immobilised capture antibody it is captured by bmding to an available epitope on the analyte of mterest, resulting m the immobilisation of the label which is attached to the labelled antibody and complexed with the analyte. The fluid continues to wick or flow past the immobilised anubody carrying any un-complexed (not bound to analvte of mterest) labelled antibody awav from the immobilised capture antibody. At this point, typically, the labelled antibody is detected These assays use a number of different labellmg methods such as particles and enzymes In apphcation of these immunochromatographic methods, as an advantageous embodiment of this mvention, an ECL label could be bound to the antibody (IGEN, Inc, Gaithersburg, MD) although other labels are possible, and the filter matrix or supporting phase could be manufactured to mclude structures of conducting and/or semi-conducting mateπals. Examples of such conducting and/or seπu-conducαng mateπals mclude, carbon nanotubes, carbon fibres, glassv carbon particles, Au and/or Pt nanowires. These conducting materials would be mixed with the mateπals used in the manufacture of the filter membranes or fibre wicking matenal m such a way that they would be immobilised within the bulk of the membrane or supporting phase m such a way that the supporting phase or membrane is not transformed mto an electromc conducting or semi-conducting matenal. An alternative embodiment would be to immobilise the capture antibody onto a conducting or semiconducting matenal fi e. glassy carbon) and to impregnate the filter or supporting matenal with these particles at a given site (an example of this is descnbed m US 5008080, but onlv usmg plastic πucroparαcles as a solid phase for antibodies impregnated into a glass fibre filter for use as a capture phase in an enzyme based immunoassay). These antibody-coated particles could, for example, be ink jet printed onto the filter or supporting matenal or pipetted. With a suitable selection of particles or fibres, nanotube sizes or aggregates, these would not migrate from the site of impregnation due to the relative size of the antibodv-coated particles to the pores or channels m the filter or flow-supporting material Alternatively, the conducting particles or fibres could be chemically or physically trapped in the filter or flow-supporting material by impregnation of the conducting or semi-conducting particles or fibres usmg printing or injection methods followed by antibody immobilisation either onto or withm close proximity of the conducting or semiconducting matenal Potentially appropriate conducting and semi-conducting mateπals are carbon nanotubes, carbon fibres, C, Au and/or Pt nanowires With this combmation of an ECL-labelled antibody and an electrochemicallv acπvatable filter or flow-supporting material, the assay would be earned out as descπbed above for the traditional filter stnp or wicking method (also called immunochromatographic tests or lateral-flow tests) but the detection of the antibody-captured analvte/anαbodv complex would be achieved via the apphcation of a high voltage field (advantageously 2v/cm to 50 kv/ cm, most advantageously 500v/cm to 50 kv/cm) across the filter or flow-supporting matenal such as to generate electrochemically active portions of the surface resulting m the generation of hght via ECL. The ECL hght is detected via a number of understood methods for light detection and/or quantitation, including eye, photography, photodiode, photomultipher or photocell. It will be understood by those skilled in the art that this method of analyte detection usmg a bmdmg reaction between antibody and analyte could also be apphed without a labelled antibody but via the use of a labelled analyte which competes with the sample analyte for bmdmg to the capture antibody. It is also understood by those skilled m the art that these immunoassay formats are apphcable to numerous bmd g assays based on other well understood binding interactions, e g nucleic aαd - nuclαc aαd, receptor- gand, nucleic aαd analogues-nucleic aαd. and nucleic acid-protein It is also understood that these immunochromatographic assays include those developed with liquid reagents not dπed onto the immunochromatographic assay device In a further embodiment of the above method where the capture antibody or nucleic aαd is attached to the conducting or semi-conducting matenal dispersed throughout at least a portion of the flow or filter material, the assay is earned out without the need for a so-called wash step to remove the unbound or free label. In this case, the bmdmg of the labelled species modulated in the presence of the analvte is detected due to the effective concentration of the label on the surface of the conducting or semi-conducting matenal which allows selective EC activation of the bound labelled speαes over that of the unbound This method - which allows the assays to be earned out without a wash - is of great benefit in that it allows for rapid testing and simplification of the diagnostic system device In a further embodiment related to usmg a filter stπp or wicking method (also called immunochromatographic tests or lateral-flow tests), the structures of conducting or semi-conducting material - advantageously with the longest dimension bemg less then 200um - would be the label and a binding speαes attached to this label. In this embodiment, the assav would be conducted in the normal manner for such immunochromatographic tests or lateral-flow tests, resulting in the capture of the structures of conducting or semi-conducting material on the capture antibody at a predetermined site in the immunochromatographic tests or lateral-flow tests stπp or cartridge based on the presence of analyte. Such assays already exist and make use of latex beads, colloidal gold or silver as a label on the antibody (Boehπnger Mannheim) but these use visual detection of the particles and no use is made of the electrochemical properties of the conducting or semi-conducting matenal. In this mvenαon, we would carry out the immunoassay m a similar format but make use of, for example, a buffer containing ECL active speαes When the bmdmg reaction and capture to the immobilised bmding speαes (antibody) is completed, the labels - which are conducting or semi-conducnng mateπals - would be activated The activation of the bound conducting or semi-conducting material would be achieved by the apphcation of a high voltage (advantageously 2v/cm to 50 kv/cm, most advantageously 500v/cm to 30 kv/cm) across the bmding zone in the immunochromatographic tests or lateral-flow tests. This apphcation of a high voltage across the bmdmg zone results in the formation of cathodic and anodic faces on the labels of conducting or semi-conducting materials used in the immunochromatographic tests or lateral- flow tests, and generates bipolar labels The result of the formation of these bipolar labels is that they become electrochemically active and result in the activation of the ECL active speαes and the emission of light. This a be detected in numerous ways as descπbed m this mvention. It is also possible to generate other detectable signals usmg this format, e.g. fluorescence, chemilummescence using luminol or acπdimum esters which is a well understood method for the generation of hght from an electrochemical reaction. Stabihsed dioxetanes are also considered since they can be activated by electrochemical methods. Visible signals can also be generated e.g. bv electropolymeπsation to generate polypyrole and polvthiophenes Conducting or semi-conducting material used as the label can be electroluminescent or chemilum escent with or without addition of active speαes to the buffer used for the assay. An example of such an electroluminescent or chemiluminescent material, active without addition of active speαes, is Al (Haapakka K et al, 1988, Anal Chim Acta 207, 195-210). It is also contemplated that other electroluminescent compounds be used in this way. This mode of detection for the conducting or semi-conducting label is supeπor to known visual methods as the labels can be detected before they are visible or they can be amplified to become visible as in the case of electropolvmensation Thus, the mvention improves on the current immunochromatographic tests or lateral-flow tests which use conducting or semi-conducnng materials as labels In an alternative embodiment, these filter wicking assays are also apphed to the detection of analytes without the need for a binding speαes. In these assays, ECL labels or co-reactants are detected. Examples of potentially-detectable analvtes have already be descπbed above for the subject mvention. A good example would be the detection of glucose, where the apphcation of the sample to the filter-wicking substrate bπngs the glucose mto contact with glucose oxidase and luminol. The glucose m the sample is acted upon bv the glucose oxidase to generate hvdrogen peroxide and this wicks up the wicking substrate and comes mto contact with the structures of conducting and/or semi-conducting matenal of the subject invention. The wicking substrate with the sample is then subject to an apphed external voltage which activates the structures of conducting and/or semi-conducting material to generate ECL from the luminol and the hydrogen peroxide produced bv the action of glucose oxidase on the glucose in the sample This ECL is used to detect and/or quantitate the glucose in the sample The value of a glucose assay in this format is that it allows the separation of the sample pnor to the enzyme reaction and detection of the ECL This is most valuable as, for example in the case of a blood sample, it allows the removal of the red and white blood cells and other interfering substances A glucose assay earned out with dehydrogenases usmg the ECL from the Ru(bpy)3 2+ and NAD(P)H reaction based on the coupled enzyme reaction employed for glucose analysis of hexokinase and glucose-6-phosphate dehydrogenase (as descnbed above in analytes) is also an example of a filter wicking assay for glucose These filter wicking assays are thus not restπcted to the detection of bmdmg reactions but can be used to detect enzymes, substrates of enzymes, ECL co-reactants, ECL labels, ECL active molecules and EC reactive speαes as descπbed earlier for the subject mvention. Assays making use of l-2000μm carbon structures (particles /fibπls /fibres) in free solution An advantageous embodiment of the present mvention is a bmdmg assay such as an immunoassay, receptor, gand or nuclαc aαd assay where small conducting or semi-conducting structures are coated with one of the bmdmg speαes to form the αipture phase of the assay. Numerous coating formats are known in the art Advantageously, glassv carbon (or graphiuc) structures (particles/fibnls/fibres) l-2000μm in diameter are activated by standard methods to generate, for example, NHS ester-activated structures (L. Dong et al 1996 J MoL Rec. 9, 383-388). These NHS ester-activated structures are then allowed to react with the bmding speαes of mterest such as an antibody, receptor, hgand, antigen or nuclαc aαd This results in the generation of a bmdmg speαes coated onto the glassy carbon structure. Typically, any non specific bmdmg in the assay is blocked by incubation with a non speαfic proton such as BSA and/or an amino-containing compound such as erhanolamine which react with any remaining NHS groups and bmd to non-speαfic bmdmg sites on the surface of the structures These glassy carbon structures coated with a speαfic bmdmg speαes such as an antibody (or streptavidin) and blocked are now ready to be used as the sohd phase in a bmdmg assay Typically, these particles are added to a mixture of sample and another bmdmg speαes which is labelled with an EC acαvatable label and able to bind to the analyte of mterest This mixture is allowed to incubate typically for 1-60 mm During this time, the labelled bmdmg speαes, for example an antibody, binds to the analyte of mterest and this complex is then captured by the binding speαes immobilised on the surface of the glassy carbon structures This senes of binding reactions results in the immobilisation of the EC acuvatable label on the surface of the glassy carbon structure which is then available to be activated. In one method for the activation, detection and/or quantitation of the bound label, the sample is now direcdy activated by the apphcation of a voltage such that bipolar faces are generated on at least part of at least some of the glassy carbon structures The bipolar faces so generated are of suffiααit voltage that thev are able to activate the EC activatable label(s) Typically, the EC acovatable label is an ECL label which is detected usmg standard methods for the detection of hght, e g PMT, photodiode, film, eve, CCD etc In an alternative method of the above assay, the glassy carbon structures are first washed with a suitable buffer pnor to the activation of the EC activatable labels as descnbed above. The washing of the glassy carbon structures could be achieved in vanous ways Usmg magnetic structures as the basis for the assay would allow for a method based on magnetic capture, but centnfugation and filtration are potentially valuable methods which could be apphed. In the case of filtration, the structures could be readily collected and washed on the surface of a filter which could form the matrix on which the structures could be activated by the apphcation of a voltage across the filter. Contemplated is the apphcation of a voltage across a filter making use of any axis and wherein the axis of apphed voltage is also optionally changed, rotated or scanned and the polaπtv of the field changed such that more of the captured structures and /or more of the structures coated with immobihsed EC activatable labels are activated. For example, it is contemplated that an alternating voltage is apphed with vaπous frequenαes and waveforms (or pulses). Additionally, the apphcation of somes used to improve signal generation, bmdmg kinetics (i.e. antigen and antibody) and electrochemistry is contemplated and has been demonstrated previously (Malms et al 1997, J Phys Chem, 101, 5063-8). These somes are from 1 to 100,000 Hz (cycles per sec), covering the range from sub-somcs to ultrasonics. Additionally, somes can improve signals by inducing tumbling of the structures. This results in more of the surface bemg subjected to electrochemical activation. This assay format is ideal for all sandwich lmmunoassays and DNA probe sandwich assay formats. Also, the structures of conducting and/or semi-conducting matenal hav g a paramagnetic component allowing capture for washing and/or optimal positioning of the structures with respect to the voltage field and/or detector are contemplated. Also, the structures of conducting and/or semi-conducnng matenal havmg a magnenc component allowing capture for washing and/or optimal positioning of the structures with respect to the voltage field and/or detector are contemplated. An alternative embodiment of the assay descnbed above for glassy (and graphitic) carbon structures is an assay that detects an analvte which is in competition with the structure-bound bmdmg speαes for bmding with a labelled equivalent of the analvte. The label in this example is the same as descπbed above, bemg an EC activatable label which results in the production of a detectable signal or EC detectable speαes. In such an assay, the- sample typically will have added to it the labelled equivalent of the analvte followed bv the addition of the structures or other conducting or semi-conducting matenal coated with a bmdmg speαes speαfic for the analyte of mterest or capable of bmding to a bmdmg speαes speαfic for the analyte of mterest This mixture is then allowed to react typically for 1-90 mm duπng which the analvte and the labelled analyte equivalent compete for binding to the immobihsed binding speαes. Duπng this competition step, the amount of bound labelled analyte equivalent is inversely proportional to the level of the analvte in the sample. Following this bmding step, the bound electrochemically activatable and/or detectable label or moiety is detected as outlined in other of the two methods given above. An example of such an assav for oestradiol is outlined below in the examples. Scanning or alteration of the polaπty and position of the bipolar faces to speαfically generate ECL by rapidly generating oxidised and reduced speαes (i.e. Ru 3+ and Ru + ) is also contemplated. These are then able to react to yield the exαted state which then emits electromagnetic radiation. Varying the frequency of the apphed voltage from 0 to 200,000 cycles per second, and advantageously from 0 to 5,000 cycles per second to enhance certain reaction mechanisms, is contemplated. This is demonstrated in the double potential step mode of ECL (Edge et al), and in luminol hydrogen peroxide electrochemically activated cheπuluπunescence. It will be understood by those skilled in the art that numerous combmations of conducting and semiconducting structures are possible and numerous assays are possible ranging from immunoassays, receptor kgand assays and nucloc aαd probe assays to those used to detect substrates for NAD- and NADP- dependent enzymes, oxidases amines peroxides, oxalates and other ECL active molecules or co-reactants. In the case of the bmding assay, the vaπous formats give nse to the followmg compositions in the presence of analyte duπng the speαfic bmdmg step(s); 1) structure-SA-Bio-Ab-At-Ab-El + Ab-El 2) structure- Ab-At-Ab-El + Ab-El 3) structure-At-Ab-El + At(ιn sample)-Ab-El 4) structure-Ab-At-El + structure- Ab-At + At + At-El 5) structure-SA -Bio- At- Ab-El + Ab-El + At(ιn sample)-Ab-El 6) structure-SA-Bio-Ab-At-El + structure-SA-Bio-Ab-At Where: Ab; is selected from at least one of the followmg; antibody, nucloc aαd, mole ilar speαes capable of bmding in a sequence-dependent fashion to a nucloc aαd sequence, a so-called nucloc aαd analogue or other nuclαc analogue, or a receptor or hgand. SA; is selected from at least one of the followmg; streptavidin, avidin or a molecular speαes able to bind biotin or At is selected from at least one of the followmg; the analyte of mterest such as a hgand or nucloc acid. EL is the electrochemically active label. is bioαn, ammo biotin, lmminobioon pepode or a molecular speαes able to bmd to SA. Structure; is selected from examples of structures of the subject mvention descnbed earher. An example of such assays is descπbed below in the examples for TSH, HCG, oestradiol and nucloc aαd assays. Multiple assays usmg arrays Spatial arrays of multiple zones or elements are also contemplated by this invention. This consists of conducting and/or semi-conducting structures of the subject mvention spatially arranged such as on the surface of a non conducting surface such as glass or plastics The methods for putting down or coating multiple elements or zones of conducting and/or semi-conducting materials are well known in the art, e.g. sputtering, evaporation, electron beam evaporation, screen printing, painting, ink jet printing, other printing methods, photocopying, stamping, physically placing elements and fixing them in place, etc. It is also well known in the art that methods for coating, etching and recoaαng with conducting and/or semi-conducting and non conducting materials are able to produce complex structures with exposed and masked regions which contain elements that are also connected electromcally via a conducting and/or semi-conducting matenal. It is also contemplated that spatial multi arrays of conducting and/or semi-conducting materials of the subject mvention could also be arranged in a 3 dimensional array, e.g. fabπcated into a macroporous support or woven mto a 3 dimensional array of supporting fibres. The mterest m generating such spatial arrays of structures of conducting and/or semi-conducting material of the subject invention is to allow for the construction of an analyte-detection device for multiple analytes where each of the structures of conducting and/or semi-conducting matenal is a potential electrode capable of carrying out an assay for a predetermined analyte. In this way, the spatial arrays are able to carry out multiple analyte assays without the need for mdividual reaction chambers or tubes, or the need for multiple electromc conducting contacts to the structures of conducting and/or semi-conducnng material. In the array of structures of conducting and/or semi-conducting matenal, vanous materials can be mixed (see above) te. Pt, Au, Ag, Cu, C (and its vanous forms). Also, vanous methods for making the contemplated structures can be used in combination to achieve the optimal combmations of structures. The use of combinations of coating methods can also be used to develop combinauon mateπals such as platinized carbon by vacuum- deposition methods for Pt onto screen-printed Carbon structures. In addition, vanous sizes of structures of conducting and/or semi-conducting matenal are used to allow the sequential activation of vaπous elements to provide an addition means for determining which assay is bemg read in addition to the spatial information from the structures' position withm the spatial array This use of vaπous sizes of structures of conducting and/or semi-conducting material - which will develop the potential required to activate the detectable electrochemistry of the subject mvention - is achieved through the dependence of the structure size and the apphed voltage m determining the voltage developed across a given structure within the apphed voltage gradient For example, a multi arrav device might be constructed with stπps of carbon paste, (glassy carbon particles for example from l-2000μm in size, m a plastic or resin b der) or conducting composite. Alternatively, the methods used bv Iwasaki may be used to generate dun patterned films of graphitic and conducting carbon (Y Iwasaki, Current Separations (1995) 14, 2-8 and O Nrwa, Electroanalysis (1995) 7, 606- 613) These stπps of composite carbon could be vaπous lengths such as 0.1, 0.2, 04, 0.8, 1 6 mm. These stπps then placed mto an instrument of the subject mvention with the vaπous lengths aligned such that the vanous long dimensions of the stπps (0 1, 0 2, 0 4, 0.8, 1 6 mm) are lined up along an axis advantageously defined bv the shortest distance between the externally and electromcaUv conneαed electrodes. This array of potential bipolar electrodes when subjected to an increasing apphed voltage in a solution of electrolyte within the central zone of an instrument of the subject mvention would sequentially become electrochemically acnve. As the externally apphed voltage is raised, the longest conducting structure or carbon composite will become active as it reaches the required voltage across the structures. This will be followed by the next length, and so on. When using a senes of potential bipolar electrodes 0 1, 0.2, 0 4. 0 8, 1.6 mm long to induce an electrochemical reaction involving ECL with Ru (2, 2' bypyπdyl)3 2+ , the voltage apphed by the externally electromcally connected electrodes to the central zone of the mstrument will double as each electrode becomes activated. In bmding reactions, these vanous structures of conducting and/or semi-conducting mateπals of the subject invention would be coupled to bmdmg speαes with the potential to present a different bmding speαes on each element, thus enabling multiple analyte detection. The detection and/or quantitation of multiple analytes on a single surface or with a single container is an advantageous embodiment of the subjett mvention. In these multiple assay applications, multiple zones or elements are fabπcated onto a surface followmg conventional methods descnbed for externally electromcally connected lnterdigitated array microelectrodes (Y Iwasaki, Current Separations (1995) 14, 2-8 and O Niwa, Electroanalysis (1995) 7, 606-613) or constructed within a three dimensional structure such as a filter or fabnc. Thus, it is envisaged that a sample would be introduced mto a container, and within this container multiple zones or elements containing structures of conducting and/or semi-conducting matenal of the subject mvention not electromcally connected to an external electromc circuit would allow multiple assays to be earned out. These assays would be based on the electrochemistry produced by the structures of conducting and/or semi-conducting material of the subject mvention not electromcally connected to an external electromc circuit when subjected to a voltage gradient in a suitable electrolyte. Further applications of this embodiment are descπbed below. The multiple zones or elements for these multiple assays consist of other a single structure of conducting and/or semi-conducnng matenal forming the zone, or multiple structures of conducting and/or semiconducting material grouped to form the zone or element in a defined region or portion of an assay component (surface or three dimensional array) In the case of the single structures, an example can be given where gold, carbon or other conducting or semi-conducting matenal is evaporated, sputtered, deposited, printed, painted or formed onto a surface making a defined shape based on a mask or printing device used in the process or by the use of resist patterning and selective etching These defined shapes are electromcally conducting and/or semi-conducting throughout the denned shape and form the zone or element in which an assay for an analyte can be conducted. In the alternative format, the multiple structures of conducting and/or semi-conducting material are used to form a zone or element for performing a given assay Examples of this are the same as for the previous example but here, the mask or printing device, or the use of resist patterning and the selective etching used in the process, allows multiple structures to be deposited or formed in a given zone or element Alternatively, the multiple structures of conducting and/or semi-conducting matenal are already made and are simply apphed to the surface such as with carbon fibres, fibrils, nanotubes or particles. These vanous methods result in the formanon of multiple zones or elements (each able to carry out an assay) and each zone or element contams multiple structures of conducting and/or semi-conducting matenal In the case where multiple structures of conducting and /or semi-conducting materials are already formed and are then apphed to create zones or elements containing multiple structures, these could be apphed using vaπous printing methods known in the art with or without binding material to bond the structures to the surface by physical immobilisation within a matπx (such as descnbed m example 15 for the filter wicking assays). In the case where no bmding matenal is used to physically trap the structures of conducting and/or semi-conducnng matenal, these are coupled to the surface either covalendy or non-covalendy. Usmg multiple structures of conducting and/or semi-conducting matenal within a zone or element to carry out an assay creates multiple bipolar electrode elements when subjected to an apphed voltage field in the presence of electrolyte and provides for improved electrochemistry. In the case of physical immobilisation within a matπx, such as a filter, multiple analytes can be analysed in a flow-through or wicking format. It is also contemplated that multi arrays can also be formed in a three dimensional array, e.g. usmg arrays of fibres incorporating structures of conducting and/or semi-conducnng materials of the subject invention. In its simplest form, the structures of conducting and/or semi-conducting material could be woven mto a fabnc to form a filter or wicking material. The incorporation of structures mto a fabnc or filter is another example of physical immobilisation. These fibres can be made of fibre optical matenal allowing the rumination and/or collection of electromagnetic radiation from these conducting mateπals withm a sample or withm a matπx of such fibres. In this example, the structures of conducting and/or semi-conducang material can be advantageously coated onto the optical fibres. For example, a surface can be patterned with gold and/or other conducting and/or semi-conducting materials as descπbed above usmg vaπous methods which are known, to form an array of single structures each of which acts as a potential bipolar electrode element for a given assay. In this case the gold forms a single structure of the subject mvention which is also a single zone or region able to be become electrochemically activated by the apphcation of a voltage field m the presence of a suitable electrolyte. Also, the surface can have zones which, rather than havmg a single structure of conducting matenal forming the zones or elements, can be composed of multiple structures withm a defined zone or element for the means of conducting a speαfic assay By way of an illustration, in a practical example, a zone or element for carrying out a given assay might be defined as havmg a size of 5 mm by 5 mm; on a given surface these zones or elements are spaced 2 mm apart Thus, when constructing an assav device with 6 such zones, the surface would be at least 12 mm by 19 mm with the zones or elements m a 2 by 3 array In this form, the 5 mm bv 5 mm zones could be made of evaporated gold, etched carbon, glassy carbon particles or printed carbon nanotubes The 5 mm bv 5 mm zones may be a continuous electromcally conducting structure but could also be composed of multiple structures of 5 μm bv 5 μm contamed within the 5 mm by 5 mm zones with spacing of 5 μm This would create an arrav within the 5 mm by 5 mm zones of structures of conducting matenal A 5 mm by 5 mm zone could contain 250,000 5 μm bv 5 μm structures of conducting matenal spaced at 5 urn intervals. The following example is to further illustrate the detection and/or quantitation of multiple analytes In the case of glassv carbon particles, there is no need to define the structures of the conducting matenal on the surface as the particles already define the structures of the conducting material. Glassy carbon particles 1% (w/v) m polystyrene (10% w/v) dissolved in chloroform are apphed to a polystyrene surface (15 mm by 20 mm by 2 mm thick) to generate the six 5 mm by 5 mm zones as descnbed above. This surface, containing the 5 mm by 5 mm zones, is then etched usmg vaπous methods to better expose the carbon and activate it for coupling to antibodies usmg vaπous methods known m the art such as abrasion followed by chemical activation (see examples) or a plasma such as oxygen (O Niwa, Electroanalysis (1995) 7, 606-613). Antibodies are coupled to the oxidised carbon surface as descnbed in the followmg examples. Speαfic antibodies are coupled to the 6 zones by spotting the speαfic antibody onto each zone. Following coupling of the antibodies to the zones, the polystyrene surface is blocked with a solution of bovine serum albumin and washed ready for use m an assay. The surface is then covered with the sample of mterest and incubated for 1 hr followed by washing. The surface is then incubated with antibodies labelled with Ru(bpy) 3 2+ for 1 hr followed by washing in PBS. The surface is then placed in a cell containing an electrolyte able to support ECL as descπbed in the examples, and is subjected to a voltage field. The light emitted from each of the zones is detected usmg a CCD camera. The apphed voltage field is advantageously apphed in a dun film cell such that the surface of the polystyrene coated with the glassy carbon particles is parallel to the voltage field. The hght generated at each of the zones is proportional to the concentranon of the analytes of mterest in the sample. In this way, multiple analytes are detected and/or quantitated. Nucloc aαd assays In an alternative embodiment, an assay for nucloc aαds is contemplated. Here, a specific bmdmg speαes for the nucloc aαd is used, typically a nucleic aαd sequence but this also could be a nucloc aαd analogue. Numerous examples of bmding assay formats are known for vaπous nuclαc aαd-based assays and all are amenable to the assay system of the subject mvention. Some are outlined above in the schematic for bmding assays. In its simplest form, the nucleic aαd or DNA of mterest (the sample containing the analyte of interest) can be coupled to the surface of the structures of conducting and/or semi-conducung material usmg methods known in the art via phosphate, amme, aldehyde or thiol groups on the nucloc aαd. The DNA modified structures would then form the basis of the specific bmdmg surface for the complementary bmdmg nuclαc aαd or nucloc aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy) 3 2+ The DNA modified structures are then subjected to a so-called pre-hybπdisation reaction which effectively blocks the non-speαfic binding sites on the structure of conducting and/or semt- conducting material. Followmg this pre-hybπdisation, the DNA modified structures are then subjected to the speαfic hybπdisation reaction with complementary bmdmg nucloc aαd or nuclαc aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy) 3 2+ . This hybπdisation reaction between the structure-bound DNA and the complementary bmding nuclαc aαd or nucleic aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy) 3 2+ , can last for 1 mm to 24 hrs and depends on the concentration of the complementary bmding nucleic aαd or nucloc acid analogue labelled with the electrochemically detectable speαes, for example Ru(bpy) 3 2+ , the temperature and the ionic strength of the hybndisaαon buffer known in the art After the hybndisaαon step, the structures are washed into an electrolyte able to support the detectable electrochemistry of the electrochemically detectable speαes. The structures are then introduced mto the cell of an mstrument of the subject mvention and subjected to the voltage field apphed to the central zone of the cell by the externally electromcally connected electrodes. The detectable electrochemical reaction is then detected, for example by a PMT, CCD camera or photodiode in the case of a detectable electrochemical reaction based on ECL or chemilummescence. The detection and/or quantitation of the detectable electrochemical reaction is used to determine the presence and/or quantity of a nucloc aαd sequence of mterest in the analyte or sample nuclαc aαd. In the case of Ru(bρy)3 2+ and DNA, the ECL hght level is used to determine the presence of a given DNA sample and/or the number of genes present in the sample. It will be understood that the complementary bmdmg nuclαc aαd or nuclαc aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy)3 2+ , may instead be labelled with a bmding speαes such as biotin and then rendered detectable by binding of a bmding speαes such as streptavidin coupled to an electrochemically detectable speαes, for example Ru(bpy) 3 2+ In an alternative format, known as sandwich hybndisation, a specific nucloc aαd sequence (or nuclαc aαd analogue) for the analyte nucloc aαd of mterest is coupled to the surface of the structures of conducting and/or semi-conducting matenal using methods known in the art via phosphate, amme, aldehyde or thiol groups on the nuclαc aαd The nucloc aαd modified structures would then form the basis of the speαfic binding surface for the analyte nucloc aαd of mterest The nuclαc aαd modified structures are then subjected to a so-called pre-hybπdisation reaction which effecnvely blocks the non-speαfic bmdmg sites on the structure of conducting and/or semi-conducting matenal. Following this step, the sample nucloc acid containmg the analyte nuclαc aαd is added to these pre-hybπdised structures other with, before or after the addition of a nucloc aαd or nucloc aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy) 3 2+ , which is similarly complementary to the analyte of mterest, and subjected to hybndisauon The nuclαc aαd coupled to the structure and the nucloc aαd labelled with the electrochemically detectable speαes are selected such that they hvbπdise to the analyte nucloc aαd in such a way that the analyte nucloc aαd in the sample links the structure-bound nuclαc aαd to the nucloc aαd labelled with the electrochemically detectable speαes For example, the nuclαc aαd coupled to the structure and the nuclαc aαd labelled with the electrochemically detectable speαes might be selected to bmd to the same strand of the analyte nucloc aαd without interfering with bmding of each other to the analyte strand, typically within 1 kilobase of each other, and advantageously within 200 bases, most advantageously within 50 bases. This hybπdisation reaction of the structure-bound nuclαc aαd or nucloc aαd analogue and the nucloc aαd or nucloc aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy)3 2+ , to the analyte nucleic aαd m the sample can last for 1 nun to 24 hrs and depends on the concentration of the nuclαc aαd or nucloc aαd analogue labelled with the electrochemically detectable speαes, for example Ru(bpy) 3 2+ , the temperature and the ionic strength of the hybndisation buffer. After the hybπdisation step, the structures are washed mto an electrolyte able to support the detectable electrochemistry of the electrochemically detectable speαes The structures are then subjected to a voltage field apphed to the central zone of the cell by the externally electromcally connected electrodes. The detectable electrochemical reaction, in the case of a detectable electrochemical reaction based on ECL or chemiluminescence, is then detected for example by a PMT, CCD camera or photodiode. The detecnon and/or quantitation of the detectable electrochemical reaction is used to determine the presence and/or quanπty of a nucloc aαd sequence of mterest in the analyte or sample nuclαc aαd. In the case of Ru(bpy)^ 2 ^ and DNA, the ECL light level is used to determine the presence of a given DNA sample and/or the number of genes present in the sample. In a further embodiment of the above example, the structures of conducting and/or semi-conducting material are coated, coupled or deπvatized with a bmdmg speαes which bmds to a bmding speαes on a nucloc aαd or nucloc aαd analogue. For example, streptavidm could be coupled to the structure and the nucloc aαd coupled to biotin. These two reagents replace the structures coated or coupled to a specific capture nuclαc aαd in the previous example and allow the hybndisation reaction to occur in solution concurrent with or followed by the capture of the hybπd complex of the three nucloc aαds (the bmding speαes-labelled analyte-speαfic nuclαc aαd, the analyte nuclαc aαd and the nucloc aαd labelled with the electrochemically detectable speαes). This method also allows for the use of a universal structure and a speαfic capture o gonucleoαde which provides for greater flexibility in the development of a random access analyser to assay a number of different analytes. This pπnαple forms the basis of the Roche Boehπnger Mannheim Elecsys system where the structures (paramagnetic beads) are coated with streptavidin. Other formats of nucloc aαd detection which differ from the traditional bmding reaction-based tests are those where the sample containing the analyte nucloc aαd is subjected to an enzymatic step which allows amplification of the amount of the analyte nuclαc aαd m the sample and/or labelling of the analyte nuclαc aαd with other a bmding speαes or an electrochemically detectable speαes The followmg are some examples known in the art In the case of the polvmerase chain reaction (PCR), one or more ohgonucleoπde sequences (pπmers) are used to prime the synthesis of nuclαc aαd resulting m the amplification of the analvte nuclαc aαd which is adjacent to the pnmers used in the PCR The product of such a PCR is nucloc aαd which can be detected and/or quanntated by the above methods. Alternatively, the pπmers used to amplify the analyte nucloc aαd could be labelled with other a bmding speαes or an electrochemicallv detectable speαes In the case where the PCR mcludes a pnmer labelled with an electrochemically detectable speαes, the products of this reaction are detected and/or quanntated by hybπdisation usmg structures coupled to a nuclαc aαd sequence speαfic (and complementary) to the analyte nucloc aαd sequence which is amplified by the pnmer labelled with the electrochemically detectable speαes. These structures coupled to a nuclαc aαd sequence are prepared as descnbed above for the sandwich hybndisation. Also, it will be understood that these nuclαc aαd-coupled structures are able to be substituted with a combmation of a structure coupled to a bmd g speαes (stteptavidin) and a nuclαc aαd sequence speαfic (and complimentary) to the analyte nuclαc aαd sequence labelled with a complementary bmdmg speαes (biotin) to the bmdmg speαes coupled to the structure, as descnbed above It will be understood that the format j ust descπbed could be modified such that the bmding speαes is incorporated mto the PCR and the electrochemically detectable speαes can be attached to the nudαc aαd sequence specific (and complementary) to the analyte nudoc aαd sequence which is amplified. It will also be understood that m addition to the PCR amplification descnbed, the enzymatic synthesis of nudoc aαd usmg pπmers is also used to label nudoc aαd analytes of mterest with bmding speαes and/or electrochemically detectable speαes usmg the pnmer. In addition, it is also well known that the labelling of nudαc aαd with vaπous speαes is possible via the use of direct incorporation of labelled NTPs and chemical modification of the nudαc aαd (US5512433). In an alternative format, the sample nudoc aαd is hybπdised to a nudoc aαd or nudαc aαd analogue which is able to form an antigen sigmficandy different from other nuclαc aαd in the hybπdised form such that an antibody will bmd the hybπd and allow assay of the analyte nudoc aαd. In this format, it is contemplated that the analyte can be labelled with vaπous speαes and/or the nudαc aαd and/or the antibody specific for the analyte nudoc aαd to probe the nudoc aαd hybπd which is formed. An example of such a system is based on the formanon of a DNA:RNA hybπd which is recognised by an annbody speαfic for the hybnd such as those descπbed in US 4833084. It will be understood that vaπous combinations of bmding speαes and labels are possible. It will also be understood that by analogy, the use of tπple helix bmding may also achieve a substantially equivalent result by recognition of a speαfic hybnd. In another nudoc aαd assay format, it is contemplated that the structures are coupled to a nudαc aαd sequence which is able to hybπdise to an analyte nudαc aαd other direcdy from a sample or after amplification using for example PCR, NASBA or other target-amplification systems. In addition to these nudαc aαd sequences, a probe sequence labelled with an electrochemically detectable speαes complementary to the structure-coupled nudαc aαd is contemplated. The analyte nudαc aαd competes with the bmdmg of the probe sequence labelled with an dectrochemically detectable speαes for the structure-bound nudαc aαd. A loss of structure-boimd electrochemically detectable speαes results from hybndisation to the analvte nudαc aαd This results m a signal decrease. An obvious modification to this method would be to use a bmding speαes on the structure (streptavidm) and a bmding speαes on the capture nudoc aαd (biotin) such that the nuclαc aαd is captured onto the structure at the desired time. The hybπdisation steps, wash steps and analysis are as descπbed m the examples above It is understood by those skilled m the art that the types of sample containing analvte nudoc aαd of mterest indude, cells, biological fluids such as serum, plasma, urine, saliva, stool, semen, sputum, cell lysates, viruses, bactena, plant tissue, animal nssues, fungi, achea bacteπa, DNA, cDNA, RNA, mRNA, tRNA, rRNA, plasmids, phage, mitochondria! nudαc aαd. Examples of the above formats for nucloc aαd assays based on conventional dectrochemical activation using externally dectromcally connected electrodes have been descnbed (Kenten et al 1991 Chn Chem 37, 1626; Kenten et al 1992 Chn Chem 38, 873; and Van Gemen et al 1994 J Virol Methods 49, 157) Flow-through analysis systems In an alternative embodiment of the subject mvention, a flow-through assay system is contemplated. This method is related to methods used for cell counting and fluorescent cell analysis but provides a novd solution to improving assay sensitivity and simphαty. In this assay system, an mstrument is constructed which contams the basic dements descnbed above containmg a voltage control αrcuit designed to apply a voltage usmg the externally connectable dectrodes which are contamed in a cell, a detector for dectromagnenc radiation which is a photomulαpher tube (PMT), a computer for the control of the voltage circuit, a detector and a pump. In addition to the dements descnbed previousl y , the mstrument contains a pump which controls - with the aid of the computer - the flow of the sample, and a cell which is designed to have a narrow zone (the central zone of the subject mvention) through which will flow the structures of the subject mvention which are advantageously conducting partides. The cell of this mstrument m its basic form could be a simple tube with a neck or narrow portion such that the flow of sample containing the conducting particles results m the separation of the particles allowing mdividual partides to be present m this neck or narrow zone. This basic cell would have externally connected electrodes positioned other side of the central zone composed of the neck or narrow portion of the flow cell. This would place these dectrodes up stream and down stream of the central measuring zone around the neck or narrow portion of the flow cell- Narrowing the flow path in this way creates a flow of smgle partides past the PMT which is positioned to view the narrow or neck portion of the flow cell. This narrowing of the flow cell to form a neck also creates an increase in the voltage gradient at this point such that the voltage across the conducting parades reaches a point at which a detectable electrochemical reaction can take place. Typically, this reaction generates light The other advantage to a cell configured to form a gradual narrowing of the flow path is that the voltage gradient will increase across the conducting parades as they flow through this narrow neck- ke region. This gradual increase m the voltage would allow the cell to acuvate parades of different sizes at different points as they flow through the narrowed portion of the cell. For example, the larger parades require a lower voltage gradient than do the small parades to achieve the required surface voltage to activate any given dectrochemical process. Thus, as the larger parades travel in the flow of dectrolyte through the narrowed portion of the cell they will be activated earher than the smaller particles to carry out a given dectrochemical reaction. This differential activation of partides withm the flow cell under a given voltage apphed from the externally connected dectrodes also allows this mstrument configuraπon to detect multiple analytes by determination of the position at which the parades become activated. For example, an assay would be constructed with partides of vanous sizes such that each bmding speαes for each assay would be bound to a different size parade. Each group of different size particles would be activated at different positions in the flow cell as the sample flowed through under the voltage apphed from the externally connected dectrodes. This mixture of vanous size particles coated with a number of different bmding speαes would be mixed with a sample of mterest and with labelled bmdmg speαes to effect a bmdmg of the labelled bmdmg speαes proportional to the concentration of the analytes of mterest m the sample of mterest. For example, each size of conducting parade would be coated with a different antibody. This would result in a mixture of parades of vaπous sizes where a given parade size would have a given antibody coated on it This mixture of coated conducting particles would then be added to a sample which contams a senes of analytes to which the antibodies coated on the conducting particles could bmd In addition to the beads, labelled antibodies or labelled anngen (labelled with an electrochemilummescent or chemiluminescent speαes) would be added to the sample either with the coated conducting parade, before or after. This mixture of coated conducting particles, sample and labelled antibodies and/or antigens would then be allowed to bmd. This would result in the formanon of antibody-anαgen complexes on the surfaces of the vanous size conducting parades and thus the immobilisation of the labds attached to the antibodies and/or antigens m amounts related to the amounts of the analytes m the sample. At this point, the sample is analysed with or without addition of further buffers Further buffers may be needed to assist in the optimal flow by dilution, and/or dectrochermlummescence and/or chemilummescence of the coated conducting parades the apphed voltage fidd, This mixture would then be aspirated mto the flow cell of the mstrument as outhned above m this example. As it flows through the narrow poraon of the flow cell, the sample will generate light from the vanous size parades at speαfic positions in the flow cell path depending on the size of the parade The location of the light is determined by the use of light detectors positioned such that light is detected at denned positions m the flow path This detection of light can be achieved advantageously by the use of a diode arrav or similar as descnbed earlier. In addition, the light emitted is opttonally subjected to spectral analysis. This flow-through assay system based on conducting partides thus offers great value as it provides multiple analyte detection and/or quantitation using parade size. This advantage of the flow-through system is enhanced by its ability to carry out multi-analyte detection usmg multiple wavdengths Here, each parade's light emission is analysed spectrally, and a spectral signature is all that is required to identify and thus assay a given parade Smce each parade is spectrally analysed as it passes the detectors, labds with overlapping spectra are readily detectable using, for example, in its simplest form, a 2 spectral window detection system. Such a system based on two spectral windows can readily detect multiple labds with minor differences in peak emissions when the labds are exαted and analysed separately Such a system has been used to detect the presence of at least 4 labels in a DNA sequencing system produced bv DuPont In the case of the system used by Luminex 64, different beads are detected based on two fluorescent dyes, one orange and one red. An alternative cell configuration consists of electrodes which flank the narrow portion of the flow cell with a voltage apphed across the path of the particle as it flows through the cell In an additional embodiment of the flow-through system descπbed above, detection of the parade is optionally incorporated mto the mstrument A number of methods could be used based on methods currendy employed for particle analysis or cell analysis An example of this is the svstem used m the copahs technology (Sienna Biotech, Columbia MD) where size is determined by light scattering Examples of such methods which could be advantageously incorporated m the flow-through system are given hereafter. Light or advantageously a laser could be used to detect and analyse the parades as thev pass through the detection zone. This could be enhanced bv the use of coloured or fluorescent structures of conducting and/or semi- conducting matenal of the subject mvention to enable additional parade identification for multiple analyte detection in addition to the use of particle size and ECL wavelength Such a svstem is used by Lu inex (htroV/www luminexcorp com, Fulton et al Chn Chem, 1997, 43, 1749) where two fluorescent dyes are used to code beads mto 64 different groups and a single green fluorescent dye is used for the vaπous assays. The flow-through system of the subject mvention could also make use of this method for parade identification and also make use of an electrochemically detectable speαes, advantageously an ECL label. The addition of a light source to the flow-through mstrument may not require a supplementary deteαor but could make use of the existing detector used for the ECL emission. In order to detect the ECL with the light from the hght source, this hght source could be pulsed at a given frequency such that the ECL and fluorescent light emission could be multiplexed and then (discriminated by the light detector and analysis system. The advantage of this system is that it would provide information concerning the size and spectral properties of the structure of conducting and/or semi-conducting matenal of the subject mvention and correlate this with the ECL for the parade. Thus, this system would allow for multiple analyte detection and/or quantitation. Based on results obtained with the Luminex system, 64 to 500 assays may be readily earned out with this type of system. Altemaαvdy, the parades are detected and the analysis is made as they flow through the neck or narrow zone by analysis of the resistance across the neck. This method has been widely used for parade and cell analysis invented by Coulter and is often called the aperture impedance or dectncal method. An alternative embodiment of the subject invenuon, wherein structures of the subjett invenuon coupled to binding speαes are used to bmd to cells resulting m aggregation or the formation of multiple beads around a cell or multi-cell collection such as an embryo or micro-organism is contemplated. These aggregates of more than one bead would then be detected based on the intensity of the light emitted as they pass through the devated voltage zone which acnvates the dectrochemisrry on the surface of the structures. Advantageously, this analysis would make use of the structures as labds and most advantageously the detectable dectrochemisrry would be ECL. Thus, after bmdmg the structures, the cells would be added to a buffer containing an ECL speaes and a coreactant if needed to allow ECL at the surface of the structures as they pass the activation and detecπon zone. Advantageously, the structures used in this embodiment would be beads, parades, nanotubes or fibπls. More advantageously, the structures would be nanotubes or fibnls. Most advantageously, the structures would be graphitic carbon nanombes or fibπls In an alternative embodiment of the flow-through cell configurauon of the subject mvention, analytes are detected form duates of gels, HPLC, FPLC, chromatography and dectrophoreπc separation methods. In this embodiment, a flowing stream from the separation method would be mixed with a flowing stream of buffer, containing structures of the subject mvention. This mixture would then flow through a cell as descπbed m the above embodiments This would result m the activation of the structures of the subject mvention to carry out electrochemistry The results of the activation of electrochemistry would generate a detectable signal An example could be the detection of amines from HPLC as has been descnbed (Forbes et al 1997, Analvtica Chimica Acta 347, 289- 293) usmg conventional dectrochemical methods. For the detection of amines from an HPLC eluate, a flowing stream of Ru(bpy) 3 2+ with the structures of the subject mvention would be mixed with the HPLC duate and then passed through a cell where the voltage gradient is apphed as described above. Advantageously, the structures would be carbon fibres or nanombes. It will be understood that this mode of detection can be apphed to any detectable dectrochemical reaction by judiάous choice of the known buffers and coreactants. In general, the methods used to construct flow cells able to create a flow of individual partides through a zone or neck in the flow are well understood. Thus, the construction of variations which draw on the current knowledge for particle and cell analysers is understood. In situ binding assays In a further embodiment of the subject invention, an alternative use of the structures of conducting and/or semi-conducting materials as labels attached to a binding spe es is considered. In this example, advantageously, the structure is a carbon nanotube or fibril (advantageously 0.02 μm to 2 mm, most advantageously 1 to lOOOμm in length) which is advantageously labelled with a binding spedes such as an antibody, nudoc add, or receptor hgand. This binding spedes-attached carbon nanotube or fibril is then used as a reagent in binding to samples of binding spedes present on a surface. This may be the surface of a synthetic material but advantageously the surface is a biological material grown or deposited onto a surface such as a glass microscope slide. Examples of such are tissue sections, cell cultures, immobilised arrays of nudoc acid, smears of tissue which are processed to preserve the biological material of interest, stabilise the biological material and improve the presentation of the biological material After specific binding of the binding spedes on the carbon nanotube or fibril to the biological sample, the surface is washed thoroughly and placed in the central zone of a cell which contains ECL reagents that may be in organic solvents. Advantageously, the ECL reagents are other tnpropylamine and Ru(bpy) 3 2+ or hydrogen peroxide and luminol or luminol, hydrogen peroxide and ferrocene. This cell, which contains the two externally connectable dectrodes flanking the central zone, is place in an instrument as described earlier for the apphcation of the external voltage and detection of the ECL light emission. In this case, the use of a microscope and CCD camera has certain advantages in the instrument in that this provides a spatial determination of the position of the bound carbon nanotubes or fibrils on the surface of the sample. This use of the subject invention allows for sensitive detection of binding spedes on a surface and also provides the potential to determine spatial information concerning the distribution of a given bmding spedes on a cell or within a celL or the counting of the given cell type within a population. Assays based on structure to structure binding In a further embodiment of the subject invention, assays based on the binding of at least two structures of conducting and/or semi-conducting material is also contemplated. Such assays consist of detecting the formation of induced proximity of two conducting and/or semi-conducting material by methods of the subject invention. In its simplest from, a binding spedes and/or pair of binding spedes are coated onto structures of conducting and/or semi-conducting material such that they are able to bind a given analyte in such a way that at least two structures of conducting and/or semi-conducting material are linked via the binding to the analyte. By way of an illustration the readers attention is drawn to assays which involve latex agglutination such as blood typing assays where the latex parades coated with a bmding speαes are linked together by the presence of analyte. Havmg formed a complex between two structures of conducting and/or semi-conducnng material they are detected by the apphcation of a voltage across the complex. This apphcation of a voltage across the parades mduces the parades to become bipolar and allows the formation of a redox couple between the two faces of the bound parade pair when suitably disposed m the apphed voltage fidd. This formanon of a redox couple allows for effective channelling of reactants from the anode face of one parade to the cathode face of the other, thus allowing the generation of an dectrochemical reaction only effectivdy seen when the at least two parades are linked in this way An example of such a coupled reacnon would be where ECL is generated from the oxidised and reduced speαes of ECL labels, te. when Ru + and Ru 3+ react they generate light. In this form, an assay would allow bmdmg to be caused by the bmding speαes and the bmding of the structures of conducting and/or semi-conducnng matenal in proximity would allow the detection of the bmding reaction via the induction of EC of the subject mvention. For example, induction of EC would occur m the presence of an ECL speαes as illustrated above It will be appreαated that numerous methods can be used to achieve the linking or mduce proximity of structures of conducting and/ or semi-conducting material. For example, the structures may be coated or linked to an enzyme substrate which when acted on by an enzyme results m the linking or mduced proximity of the coated structures. In this way an assay for the enzyme and/or its substrate may be constructed. Enzyme assays using structure-bound labels The assays descnbed are directed at the detection of bmding reactions, or the detection of a soluble analyte direcdy or generated by a chemical or enzymatic reaction. It will also be understood that other chemical and enzymatic assays can also be earned out using a number of the formats outhned above These chemical and enzymatic assays would be based on both synthesis reactions and degradation reactions For example, a synthesis reacnon would be the action of DNA polymerase on a template nudαc aαd initiated by a pnmer. In this example, the pnmer could be labelled with an dectrochemicallv detectable speαes such as an ECL labd and duπng the polymerase reaction a bmding speαes could be mcorporated such as biotin usmg a biotinylated NTP The result of such a polymerase reaction would be a nucloc aαd strand containing both a bmding speαes and an dectrochemically detectable speαes. This nudαc aαd strand could then be captured onto a structure of the subject invention and analysed to determine the levd of polymerase activity Examples of synthetic enzymes are DNA, RNA polymerase, glyco-transferases, terminal transferases. In the case of a degradation reaction, for example a protease or other hydrolase, the substrate could be coupled to the structure of the subject mvention m such a way that it contams an dectrochemically detectable speαes which is removable by the action of the speαfic protease or hydrolase These modified structures are then incubated with the protease or speαfic hydrolase. Incubanon m the presence of an enzyme able to hydrolyse the substrate, and thus remove the electrochemically detectable speαes, results m a loss of signal. Examples of hydrolases are glycosidases, nudeases, protease and pases which may be used in assays as above. It will be understood that other the enzyme or the substrate may be assayed using the methods outlined above. Generauon of light by bipolar electrochemistry A further embodiment of the subject mvention is a new way of generating hght from an dectrochemical reaction usmg for example compounds from Maness KM et al J. Am. Chem. Soc 1997, 119, p3987 (see above reference m ECL labds). In this embodiment it is contemplated that the structures of conducting and/or semi-conducting materials of the subject mvention are mixed with for example [Ru(bpy) 2 (bpy(Cθ2MePEG350) 2 ](Clθ4)2 in for example a methanol water mixture and drop cast onto a non conductive surface such as glass or Si/Siθ2 between two dectrodes formed on the glass or Si/Siθ 2 using conventional methods. This forms a film with embedded conducting and/or semi-conducting material such that on apphcation of an apphed voltage light emission is generated within the film between the adjacent structures of conducting and/or semi-conducnng material. This illustrated the potential of this mvention to generate hght m emitting devices where light can be generated within a bulk of matenal The following non-hmiαng examples are given by way of illustrations and are not to be considered a limitation of this mvention, many apparent variations of which are possible without departing from the spirit or scope thereof. Examples Example 1 Example of ECL apparatus and a method for obtaining a detectable signal from dectrolyte-suspended conducting partides. Basically, the apparatus integrates a computer-controlled programmable voltage source (Kdthley 230), a photomultiplier (Hamamatsu H5323) connected to a photon counter, a digital multimeter (Philips PM 2422A) and a custom-made cell. The cell is the heart of the instrument and is illustrated in frontal view in schematic 1, in top view in schematic 2 and in side view m schematic 3. The cell is constructed from a block of PVC 1 mto which is cut channd 2. Channd 2 contams two platinum dectrodes 13 and 14 fixed to other end. Two holes 3 and 4 are drilled mto each side of PVC block 1 for platmum electrodes 13 and 14 to be externally dectromcally connected via connectors 5 and 6 to the voltage source through leads 7 and 8. Two holes 9 and 10 are drilled perpendicular to channel 2 for insertion of a fibre optic tube 16. A lens 15 is placed between the end of fibre opnc tube 16 and channd 2 in such a manner than fibre optic tube 16 views soldy the central poraon of channd 2. A PVC hd of the same dimensions as PVC block 1 fits onto two lugs 11 and 12 situated on the upper surface of PVC block 1 to prevent extenor light from entering channd 2. The test sample is placed in channd 2 and a voltage is apphed via dectrodes 13 and 14 across channd 2. light generated withm the sample is detected by fibre optic tube 16 and earned to the photomultiplier. The data from this photometer is digitised and analysed by a computer (Dell Corporation XPS 200, software: National Instruments, Ausαn Tx). The voltage apphed to the two external plaunum dectrodes (from a Kdthley 230 programmable voltage source) is controlled by the computer in such a way that the voltage apphed to the channd duπng a measurement cycle is corrdated with the light level detected at the PMT. For safety reasons, the voltage control is constructed to prevent arcing with high current. The general layout of the experimental mstrument is illustrated m schematic 4 where 17 is the voltage generator, 18 is the digital multimeter set to monitor the current, 19 is one of the leads connecting the voltage source to the platinium dectrodes, 20 is the reaction cell, 21 is the fibre optic tube, 22 is the luminometer/PMT and 23 is the controlling computer This mstrument is designed for multiple cell configurations to be used. Cell l One cell has a continuous channel from one end to the other which allows samples to be mtroduced using a pump or other flow control method. In this case, the two externally dectromcallv connected dectrodes are attached to the channd via a porous fnt, permeable or semi-permeable diaphragms or membranes such that electncal contact is made through an electrolyte to the channel which forms the measuring zone. This cell configuration allows samples to be placed in the measuring zone and then exαted via the apphed dectnc fidd between the two externally electromcally connected dectrodes. The hght emitted is detected and the sample then flushed from the system followed by cleaning and introduction of the next sample for analysis. This cell configuration has windows in the measuring zone which would also permit fluorescence and spectrophotometπc measurements to be made. Cell 2 The second cell (illustrated m schematics 1, 2 and 3) is configured as in the first cell with respect to the externally dectronically connected dectrodes but does not have a continuous channd from one side to the other. Instead, the sample is mtroduced via the top of the channd cut mto the PVC block. The externally dectromcallv connected dectrodes are isolated from this channd via a porous fnt or semi-permeable membrane This cell allows manual washing and introduction of the sample followed by a measurement cyde Cell 3 The third cell is designed as for the second cell but the central channd is modified such that it is able to accept or hold a filter paper or immunochromatographic filter element or gel. This channel is able to accept the filter paper or immunochromatographic filter element or gd in such a wav that dectrolyte is in contact with the filter paper or immunochromatographic filter dement or gd and with the externally electromcally connected electrodes This channd with the filter element also has a window to hold the filter element in place and to allow dose proximity of the PMT or fibre optic tube to the filter element, improvmg photon capture by the PMT. The window dement is vanously glass, plastic, and plastic wrap which is transparent to the photon wavdengths of mterest The above mstrument is also configured to allow the use of a photodiode in place of the PMT To test the above ECL apparatus and cells (cell 2), a suspension of chopped carbon fibres lOOOμm x 7μm (Goodfellow Cambndge) at 3-15μg/ml in ECL buffer (100 mM tnpropylamine, 002% (w/v) Tween 20, pH adjusted to 7 2 with 85% orthophosphoπc acid) and 10-lOOnM Ru (2^-bιpvπdvl) 3 2+ [Ru (bρy)3 + ] was introduced manually mto cell 2 through the top of the channel. The electrodes at each end of the channd were then connected to the voltage source (Kothley 230 generator) and the fibre opαc tube was inserted mto the cell to view the central portion o the channd m which the electrochemistry occured. A ramp voltage from 0 to 100 V was then apphed to the platinum electrodes for 20 seconds. The PMT (Hamamatsu H5323) monitored the hght produced duπng the ramp and the current flow was monitored using a digital multimeter (Philips PM 2422A). The current mcreased in a linear manner with the voltage ramp apphed across the cell until a sudden current surge was noted at 75 V on the ramp, showing that detectable dectrochemisrry occurred at this voltage. Light was emitted at this same pomt, showing that detectable ECL occurred at this voltage. Samples of cell contents were taken before and after apphcation of the ramp voltage for spectrophotometπc measurement These showed that TPA concentrations decreased by approximatdy 30% duπng the reaction (initial TPA 100 mM) while a new chromophore was produced, absorbmg at about 210 nm. The dectrochemistry, and therefore an analyte, can be detected other amperometπcally through the determination of the resultant current with respect to the apphed voltage potential, spectrophotometncally by the production of a new chromophore, or through the generation of ECL. Tests usmg different reagent concentrations showed that the ECL signal detected by the PMT mcreased with mcreasmg numbers of fibres and with increasing concentrations of Ru (2^-bιpyπdyl) 3 2+ Example 2 Chemical activation of fibnls, fibres, particles and other structures Carbon mateπals (parades, fibres, nanotubes, fibrils) are obtained from Alfa Aesar (Ward HilL MA), Goodfellow Cambπdge and MER corporation. Altemativdy carbon fibπls are made using methods known in the art (Pan ZW et al, Nature 1998, 394, p631 and Fan S et al, 1999, Sαence, 283, p512 these references are mcorporated by reference in their entirety). These carbon materials are made mto an aqueous slurry by mixing 0.1% w/w with dαonized water and dispersing by sonication using a 400 watt sonication probe for 0.5 to 1 hour These carbon mateπals are then ready for chemical activation by oxidation usmg chromic aαd, perchloπc aαd (Dong et al 1996, J Mol Rec. 9, 383-388) (to mtroduce carboxyl groups) or for direct coattng with biomolecules. This oxidation is achieved followmg standard protocols as follows. For example, 10 g of the carbon fibπls, parades, fibres or other structures are mixed with 450 ml of cone. H2SO . This preparation is then mixed with 8.68 g of NaClθ 3 under argon by adding small amounts over a 24 hr peπod. The mixture is then added to ice and followed by extensive washing. The final carboxylated structures are dned and a portion used to determme the carboxyhc aαd content by Qtration of these groups. The chromic aαd protocol is similar except that the reaction is not conducted under argon. Example 3 Immobilisation of proteins on carbon particles, fibres and fibrils and other structures using non covalent methods Carbon matenal suspensions as descπbed in example 2 are added to PBS to generate a 0.1-1 mg/ml suspension of carbon. These are washed once then antibody or streptavidm is added at a concentration of 100-300μg/ml in a pH 9 6 100 mM sodium carbonate/bicarbonate buffer. The fibπl mix is left to mix at 48°C for 16-20 hours. Followmg this incubation, the fibπls are washed by centrifugation and resuspended in 3% BSA, 0.1% Tween 20 PBS and incubated for 2 hours to block any uncoated sites. These fibπls are then washed 5 times m the 3% BSA, PBS with 0.05% sodium azide and finally resuspended in this buffer for storage. Pnor to use, the fibπls are washed mto PBS 0.1% Tween 20 to a concentration of 0.1-1 mg/ml. In the case of other carbon parades, these are prepared by a quick wash m PBS followed by addition of the anαbody-containmg solution and apphcation of the protocol above. Example 4 Immobilisation of proteins on carbon (structures) particles, fibres and fibrils using covalent methods Carbon parades, fibres and fibπls are obtained from MER corporation and Alfa Aesar (Ward HilL MA). These are activated using oxidative methods such as perchloπc aαd, chromic aαd treatment, oxygen plasma or other methods known in the art to generate -COOH functional groups on the surface of carbon, glassy carbon and graphitic carbon (see example 2). These carbon surfaces - deπvaαzed with COOH groups - are suspended in anhydrous dioxane with mixing to concentrations of between 0.1 and 10 mg/ml. An estimate of the moles of COOH groups per mg of parades is made by titrating the COOH groups on a sample with NaOH. To this mixture is added a 5-30 fold molar excess of N-hydroxysuccimmide followed by mixing to obtain dissolution. When the N- hydroxysucαnimide has dissolved, an equivalent molar amount of ethyl- diammo-propyl-carbodiimide (ED AC) is added and the- mixture incubated with mixing for 1-4 hours at room temperature (20-24°C). Following this incubation, the particles are separated from the mixture other by filtration or by centπfugation. The partides are washed with anhydrous dioxane several times followed by an anhydrous methanol wash. These resultant NHS ester-activated parades are then dπed under vacuum and stored under anhydrous conditions until used for coupling For coupling, between 10 and 1 mg of dπed NHS-ester parades are washed with PBS and added to a solution of the biomolecules to be coupled, typically streptavidin, anπbodv and ammo-modified DNA or ohgonudeotide. In the case of streptavidin, a 5-10 mg/ml solution in PBS is used. For anubodv, between 05 and 1 mg/ml of antibody is used to couple to 1-3 mg of particles For ammo-modified o gonucleoπdes, between 0 1 and 1 mg/ml of ohgonudeoαde between 15 and 40 bases long is used The parades and biomolecules are mixed to form a suspension and this is then incubated for 1-2 hours at room temperature. The coupling reacnon between the ammo groups on the biomolecules and the NHS-ester groups on the parades forms an amide bond between the biomolecule and the particle These particles are then resuspended in 3% BSA, 0.1% Tween 20, PBS and incubated for 2 hrs Thev are then washed and resuspended in the same buffer. Example 5 Labelling of protems with ECL labels 1 mg of protem is labelled with Ru (2,2-bιpyndyl) 3 2+ (Ru(bpy) 3 2+ ) The protein is buffer-exchanged usmg Centπcon 30 microconcentrators (Amicon) mto 0 15M potassium phosphate buffer, 0 15M NaCl pH 7.8, the final volume bemg 0.5 mL Immediately pnor to use, 0 5 mg of Ru(bpy)-s 2+ -NHS (Ru(2,2-bιpyπdyl)2(4-[3- (l,3-dιoxolan-2-yl)propyι]-4-metnyl-2,2-bιpynαine) 2+ ) is dissolved with 125μl of anhydrous dimethyl sulfoxide (Aldnch). A molar ratio of about 25.1 should be achieved between the Ru(bpy) 3 2+ and the protein, based on molecular weights of 1057 for Ru(bpy) 3 2+ -NHS and 150,000 for antibodies. The Ru(bpy) 3 2+ -NHS (45μl) is added to the protem solution while shaking. The ranges for labelling can be from 3:1 to 30:1 molar ratios depending on the protem bemg labelled. The reaction tube is mcubated in the dark at room temperature for 30 minutes while shaking. The reaction is terminated by the addition of 25μl of 1M glyαne and lnαibaαon for 10 minutes. The reaction mixture is punfied by passage through a Sephadex G-25 column (1 X 20 cm in 0.15M potassium phosphate, 0.15M NaCl with 0.05% sodium azide pH 7.2). The Ru(bρy)3 2+ - labelled protem fractions are collected and pooled. These labelled proteins are then diluted mto PBS buffer with azide to give protem concentrations between 1.6μg/ml and 32μg/ml. Example 6 HCG assay Immunoassay for the quantitative determination of human choπonic gonadotropin. This electrochemiluπunescent assay demonstrates the pπnαples of the subject mvention. The measurement of HCG concentrations can be used to diagnose pregnancy just one week after conception. Reagents are obtained from Boehπnger Mannheim, ι.e. HCG STAT immunoassay reagents (Cat #1731 289) suffiαoit for 100 tests. This test kit is used to provide the two antibodies, one being labelled with an dectrochemically detectable speαes (Ru(bpy) 3 2+ ), the other bemg a bifuncαonal bmding speαes composed of an antibody conjugated to biotin. The sohd phase corresponds to the glassy carbon beads prepared m examples 3 and 4 and coated with streptavidm. In addition, the HCG STAT cahbrator set (Cat # 1731670), the buffer to provide optimal ECL, i.e. ProCell (Cat # 1662988) (this buffer is equivalent to the ECL buffer used in example 1 and to ORIGEN assay buffer) and Elecsys Diluent Umversal (Cat # 1732277) are obtained from Boehnnger Mannheim. The samples are prepared from the HCG STAT cahbrator set bv dilution in Elecsys Diluent Umversal One of the calibrators m the HCG STAT cahbrator kit consists of about 10 mlU/ml and the other about 5000 mlU/ml The highest cahbrator is used to make a seπes of samples bv senal dilution in the Elecsys Diluent Umversal to give a sequence of HCG values which form the basis of the demonstration. The result of the dilutions is a seπes of HCG values 5000 (from the oπginal cahbrator), 1250, 625, 156, 78 and 20 mlU/ml. The assay is performed as follows, 40 μl of the diluted cahbrator descπbed above is added to 220 μl of the biotinylated antibody and 220 μl of the Ru(bpy) 3 2+ -labelled antibody This is mixed and mcubated for 5-10 mm followed by addition of lOOμg (100 μl) of streptavidin-coated 10-lOOOμm glassy carbon parades as prepared in examples 3 and 4 This mixture is mcubated for 5-10 nun with mixing This mixture of assav components is then centnfuged and resuspended in the ProCell buffer and washed again before final resuspension in 600 μl of the ProCell buffer. These samples m the ProCell buffer are then mtroduced mto the cell of the instrument as descπbed in example 1 and the hght given off for each sample is determined. The values are background-subtracted usmg the 0 HCG level sample and normalised to a value of 1000 for the 5000 mlU/ml cahbrator sample. The results demonstrate an increase in hght detected with increasing HCG levels m the samples. Example 7 17-beta Oestradiol (oestradiol) assay Immunoassay for the quantitative determination of oestradiol This electrochemilummescent assay demonstrates the pπnαples of the subject mvention m a competitive assay format. Measuring oestradiol concentrauons is important in the determination of fertility disorders deπved from the hypothalamus-pituitary-gonad axis, gynecomastia and tumours. Reagents are obtained from Boehπnger Mannheim Oestradiol immunoassay reagents (Cat #1776002) which contams reagents for 100 tests. This test kit is used to provide the two bmding speαes for the assay: oestradiol with a pepαde linker labelled with an electrochemically-detectable speαes (Ru(bpy) 3 2+ ), an antibody used as a bifuncπonal binding speαes and another antibody conjugated to biotin. The sohd phase corresponds to the glassv carbon beads prepared m examples 3 and 4 and coated with streptavid . The Oestradiol CalSet (Cat # 1776037), the buffer to provide optimal ECL, ProCell (Cat # 1662988) and Elecsys Diluent Umversal (Cat # 1732277) are obtained from Boehπnger Mannheim. The test samples are prepared from Sigma reference standard oestradiol (Cat E 1132) made up in Elecsys Diluent Umversal. In addition, test samples from the Oestradiol CalSet (Cat — 1776037) are run in some experiments. The assay is performed as follows; 100 μl of the sample are added to 180 μl of the bioπnylated polydonal anti-oestradiol antibody from the kit and mcubated for 10-15 mm followed bv addition of 180 μl of the oestradiol-pepαde hnker-(Ru(bpy) 3 2+ ) and 100 μl of streptavidin-coated glassy carbon parades (lOOμg of 10- lOOOμ coated glassy carbon parades prepared as m examples 3 and 4) This mixture is mcubated for 10-15 mm with mixing This mixture of assay components is then centπfuged and resuspended in the ProCell buffer and washed again before final resuspension in 600 μl of the ProCell buffer These samples in the ProCell buffer are then mtroduced mto the cell of the mstrument as descπbed in example 1 and the light given off for each sample is determined. The values are background-subtracted usmg a sample not containmg anv oestradiol The results demonstrate an increase m hght detected with increasing oestradiol levels in the samples Example 8 TSH assay lOOμl serum calibrators for TSH, 25μl of ECL-labelled mouse anti-TSH prepared as in example 5 (typically the amount of antibody added to a test is between 40 ng and 800 ng) and 25μl (between 3 and lOOμg) of glassy carbon structures (10-1000μm) coated with sheep anti-TSH in ECL buffer followmg the protocols given in examples 3 and 4, are combined and mcubated in polypropylene tubes for 15 minutes at room temperature with mixing The glassv carbon structures are then washed twice bv centπfugation and resuspended in ECL buffer to a final volume of 1 ml These samples are then analysed for ECL usmg the instrument as descπbed in example 1 The ECL signals from the vaπous samples are then plotted against the serum cahbrator values to generate a standard curve This demonstrates that the method allows the determination of analytes usmg simple binding interactions as seen in antibodv-anagen, receptor-hgand and nuclαc aαd-nudoc aαd bmdmg reactions This standard curve can then be used to determine the levd of unknown samples of the TSH analyte This assay was repeated without washing the glassy carbon structures and demonstrated the use of this format for a no-wash, one-step assay without parade separations and/or washings Example 9 DNA probe assays Ohgonudeotides are obtained from Ohgo etc (Wilsonville, OR, USA) Ammo-modified ohgonudeotides are labelled with Ru (2,2-bιpvndyI) 3 2+ usmg the NHS ester or made direcdy during synthesis usmg Ru (2,2- bιpyπdyl)3 2+ phosphoramidite obtained from IGEN Inc Beta-actin PCR, nuclαc aαd probe assav The PCR detection of beta-aeon mRNA is achieved by the conversion of mR mto cDNA followed by a PCR which mcludes a bioαnvlated pnmer and an ECL labelled pnmer In this protocol, the ECL labd used is ORIGEN TAG (IGEN, Gaithersburg MD) The followmg pπmers are used to amplify the beta-actin cDNA bv PCR, 5' Biotin-GCC ACA GGA TTC CAT ACC CAA-3' and 5'ORIGEN TAG-GAG AAG AGC TAT GAG CTG CCT GAC-3' From 0 1 to 5 micrograms of mouse hver total RNA, including controls not containmg any beta-actin, are reverse-transcπbed m a 20μl reaction for 1 hr at 42°C with Superscπpt II RNase H- reverse transcπptase, ohgo dT, and lOmM dNTP mix as recommended by the manufacturer (Life Technologies) to generate the cDNA One microhtre of cDNA is amplified in a 100 μl reaction containmg 1XPCR buffer (Perkin Elmer), 200 μM dNTPs (LIT), 20 pmoles of each pnmer, and 4 units of Amphtaq DNA polymerase (PE) pre-mixed 1 1 with TaqStart Antibodv (Clontech) Amplification is performed on a Perkin Elmer Model 480 Thermal Cvder usmg the followmg conditions 10 mmutes at 50 C C, 10 mmutes at 94°C. 20 cycles of 45 seconds at 94°C, 45 seconds at 64°C, 2 mmutes at 72°C followed bv a final extension of ~ minutes at 72°C Followmg the PCR, 3 μl of the reaction mixture are added to 2 40 μg of streptavidin-coated glassv carbon structures (as prepared in examples 3 and 4) in 50μl of ECL buffer This mix of PCR products and the streptavidin-coated glassy carbon structures is mixed for 30 mmutes at room temperature followed bv the addition of 250 μl of ECL buffer Followmg this dilution step, the glassy carbon structures are washed in ECL buffer and then placed mto the central section of the ECL instrument descπbed in example 1 for ECL excitation and detection The results demonstrate an ECL signal dependent on the level of the beta-acαn DNA in the samples Example 10 Cholesterol assav Solutions containing cholesterol (30μl of 2 50μM), cholesterol oxidase (lOμl of 48 umts/ml) and buffer (120μl of 100 mM NaPhosphate, pH5 containmg 0 05% Tπton X-100) are prepared and mcubated for 30 nun The mixture is then rendered 02 mM with respect to luminol usmg a solution of luminol in 005M sodium borate buffer pH 10.0. In an alternative assay format, followmg the 30 mm incubation step, the mixture is rendered lOOμM ferrocene, lOOuM luminol and 0.1 M Tns buffer. To these mixtures are added 2-80ug of glassy carbon parades (Alfa). The samples are then placed mto the ECL mstrument descπbed in example 1 followed by exαtanon and detection of the ECL light The samples show an increasing signal with increasing cholesterol, forming the basis of a cholesterol assay. Stock solutions of cholesterol are prepared by dissolving cholesterol m a mixture of Tnton XI 00 and ethanol (3:2 v/v). The parades used m this assay are untreated 10-lOOOμm glassy carbon beads. Example 11 Glucose assay The basic reagent mix for the glucose assay contams 16.8 μg/ml hexokinase, 20 ug/ml glucose-6-phosphate dehydrogenase, 1 mM ATP, 1 mM NAD + , 2 mM MgSO* and 25 mM Tπs HCL, pH 7 5. Ahquots of this reagent mix are prepared (270μl) and 30μl of vaπous glucose standards are added to give a final concentration range of 5 to 35μM. These samples are mcubated for 10 mm at room temperature. Followmg this incubation, 30 μl of lOmM Ru(bpy) 3 2+ is added followed by 2-40μg of glassy carbon parades (Alfa). The samples are then placed mto the ECL mstrument descnbed m example 1 followed by exαtation and detection of the ECL light The samples show an increasing signal with increasing glucose, forming the basis of a glucose assay. The parades used m this assay are untreated 10-1000μm glassy carbon beads. Example 12 Betalactamase assay A solunon of benzylpemcDhn (1 mM) is prepared in 0.1 M phosphate (sodium salt), 0.05% Tnton X-100 pH 7.5. This solunon is rendered lOμM with respect to ruthemum (II) tπs (bipyπdyl) (Ru(bpy)3 2+ ). This mixture is used as the buffer for the detection of betalactamases. To 1 ml ahquots of this mixture are added E. coh beta lactamase RTEM to a concentration of between 1 and 10 nM. The enzyme reaction is allowed to proceed for about 10 min at room temperature (about 20°C). After the enzyme lnαibaαon, 2-40μg of glassy carbon parades (Alfa) are added and the mixture is placed m the central zone of the cell of the mstrument descnbed in example 1. The sample is then subjected to an apphed voltage and the ECL signal is measured. It is found that ECL signal is sigmficandy higher in the presence of the beta-lactamase enzyme. This allows a method to be developed for the detection of beta-lactams and betalactamases. The particles used in this assay are untreated 10-lOOOμm glassy carbon beads. Example 13 Preparation of Antibody-Coated Carbon Structures Carboxylate-modified carbon structures prepared as m example 2, (2.5μg) are added to 1.0 milhhtre (ml) of methyl ethyl sulfonate (MES) buffer (5 milhmolar (mM), pH 4.75) and 75 micrometres of antibody solution (antibody to beta-hCG, Biogenesis UK) (2 milligrams per milhhtre (mg/ml)). The solution is stirred and 100 ml of 1 -Ethyl 3(3-Dιmethyl-amιnopropyl) carbodimide HCl (EDAC) (2 mg per 10 ml H2O) are added. The solution is stirred overnight at 2-8°C, after which the structures are isolated by centnfugaπon, washed twice with 0 1% "Tween-20" solution, and resuspended in "PBS" Phosphate Buffered Saline (001 M KH2PO4, 0.15 M NaCl pH 7.2) to yield a 0.125% solution. After resuspension in PBS, the structures are stored at 2- 8°C for subsequent use in the followmg procedures. Example 14 Preparation of Solid-Phase Reaction Matrix 50 microhtres of the anαbody-coated structures from Example 13 are added dropwise to the centre of a Whatman GF/D glass filter, 100 microhtres of pig sera are then added and the filter and rmcropartides mcubated for 30 mmutes in a humidity chamber at room temperature. After this time, the filter - now containmg the microparades - is washed three times m 300 microhtres of PBS buffer. The filter is then stored in a humidity chamber for use m the following lmmunoassav example. The microparades are observed, by scannmg electron microscopy, to have been trapped or agglomerated on the glass fibres of the filter matenal. It should be noted that, m addition to the techniques descnbed in the foregomg example, antibody, antigen, hgand, receptor and nudαc aαd bmdmg sequences may be attached to the parades by a vaπety of methods, e.g., adsorption or use of vaπous chemical activators. Also, it is to be appreciated that the partides can be added to the fibrous matπx after, for example, animal sera or other blockmg agents have been added, and that the use of such sera is not of cntical importance. Therefore, the order of addition of the parades to the matnx and treatment thereof after or before incorporation mto the matπx is not cntical to the present mvention. Moreover, it will be appreciated that fibrous mateπals can be used in place of the glass filter matnx matenal specifically descπbed heron, and the advantages of the mvention can also be realised thereby. Example 15 Immunochromatographic Immunoassay Protocol (Determination of beta-hCG) The glass fibre material containmg the antibody-coated structures as previously descπbed (example 14), is cut mto substantially circular "disks", and the disks - forming reaction matnces - are placed m contact with a blotter matenal to absorb excess fluid from solutions used m the assav. Thereafter, five drops of test samples of human uπne (about 280 microhtres) containmg zero, and 50 and 100 mlU/ml levels of beta-hCG are added to each matnx after passage of the sample drops through a prefilter situated above each matπx. Three drops of an antibody labelled with an ECL active speαes, as used in example 6, are then added to each matnx through the prefilter, and each matπx is mcubated at room temperature for about two mmutes. The prefilter is then removed and 1 0 ml of PBS, 0 1% Tween 20 wash solution is added to each matnx to remove an excess anπbodv-enzyme con j ugate One drop of ProCell buffer is then added to each matnx. After two mmutes, each matπx is placed in a cell (example 1, cell 3) containmg two externally and dectromcallv connected dectrodes (see above descnpπon of ECL instruments). The matπx placed in the cell forms an dectncal contact between the externally connected electrodes via the ProCell buffer which forms the electrolyte. Each matnx is then sub j ected to an externally apphed voltage This voltage is apphed at such a voltage gradient up to 10 kv/cm that at least some of the structures trapped in the glass fibre filter are rendered bipolar These bipolar structures activate the ECL from the captured antibody labelled with an ECL active speαes and hght is deteαed for the test samples which contams beta-hCG The amount of light is correlated to the level of beta-HCG in the sample. Example 16 Chromatographic assay with particles as labels Glassy carbon parades are puπfied by centnfugation washes to parades of between 10 to 2000μm m diameter. These parades are then activated usmg the oxidation reactions descnbed above and activated to form the NHS ester as descπbed. These beads are then reacted with BSA biotin from Pierce (Rockford, IL, cat # 29130). The resultant parades are then reacted with excess BSA to block any remaining bmding sites and the beads are washed 5 times over a peπod of 3 days. Large pore nitrocellulose FF85 from Schlαcher and Schuell (Ecquevilly, France) is cut mto stπps 1 cm by 10 cm and a stπp of streptavidin apphed 3 cm from one end of the mtrocellulose membrane. These membranes are then washed in water and mcubated m 3% BSA m PBS overnight followed by washing in water and air-dπed. These membranes are then placed mto tubes containmg 0.3 ml of the above bioαnylated glassy carbon parades with and without added biotin and allowed to stand for 2 hrs such that the glassy carbon parades wick up the dry membrane. The membranes are then washed with a solution of 0.1 mM lummol, 1 mM hydrogen peroxide, 0.1 mM ferrocene monocarboxyhc aαd (Sigma) and 0.05M Tπs buffer pH 8. The membranes are then trimmed to remove the lower and upper portions of the stnp to leave the site of stteptavidin stπp. The streptavidin stπp poraon is placed mto a cell designed to provide dectrolyte contact to two externally electromcally connected dectrodes attached to a voltage control αrcuit contamed withm the mstrument as descnbed m example 1. These membranes are then subjected to the voltage field and the ECL is detected. The stπps run m the absence of added biotin show higher ECL signals than those run m the presence of free biotin which blocks the bmding of the bioαnylated glassy carbon parades and prevents the bmding of these to the immobihsed streptavidin on the mtrocellulose membrane. The bmdmg of the glassy carbon parades immobilises a conducting structure of the subject mvention which is then able to activate ECL when an external voltage is apphed This therefore demonstrates the potential of this system to form the basis of a svstem used to carry out speαfic bmding reactions with enhanced sensitivity

Claims: CLAIMS We claim: 1. An assay compπsing; a) the estabhshment of contact between a sample and a structure of conducting and/or semi-conducting material not m electromc contact with an external electromc circuit, and; b) the apphcation of a voltage gradient across said structure of conducting and/or semi-conducting matenal not m electromc contact with an external dectronic circuit, said voltage gradient bemg such that an dectrochemical reaction takes place on said structure of conducting and/or semi-conducting matenal not m dectronic contact with an external dectronic circuit, and; c) the detection and/or quantitation of said electrochemical reaction direcdy or indirecdv, and; d) the determination of the presence and/or quantity of an analyte. 2. An assay method as m claim 1 wherem said structure of conducting and/or semi-conducnng material is coupled to a bmding speαes. 3. An assay method as in claim 1 wherem said electrochemical reaction results in electrochemilummescence or chemiluminescence. 4. An assay method as in claim 2 wherem a second binning speαes free m solunon and a third bmdmg speαes coupled to an dectrochemically detectable speαes free m solunon are also added to said sample other together, before or after said structure of conducting or semi-conducting matenal coupled to a bmdmg speαes, wherem said second bmding speαes and said third bmdmg speαes may be the same or different 5. An assay as in claim 4 wherem said electrochemically detectable speαes is able to support electrochemilummescence or chemilummescence other direcdy or mdirecdy. 6. An assay as in claim 5 wherem said bmdmg speαes, said second bmding speαes and said third bmding speαes are sdected from the group consisting of; antibody, antigen, nucleic aαd, receptor, hgand, lecαn, nudαc aαd analogue, streptaviαm, avidin 7. An assay as m claim 5 wherem said second bmding speαes is coupled to a fourth binding species sdected from the group consisting of, biotin, lmmmobioαn, aminobioαn, digoxin, fluorescαn, wherem said bmding speαes is capable of bmding said fourth bmdmg speαes. 8. An assay as m daim 6 wherem said structure of conducting and/or semi-conducnng matenal contams matenal sdected from the group consisting of, carbon, gold and platinum. 9. An assav as in claim 8 wherem said structure of conducting and/or semi-conducnng matenal is made from carbon in a form selected from the group consisting of, graphitic carbon fibres, fibπls or nanotubes, graphitic particles, glassv carbon parades, carbon films, sputtered carbon, carbon pastes and carbon composites 10. An assav as in claim 9 wherem said structure of conducting and/or semi-conducnng matenal is a glassy carbon parade. 11. An assav compπsmg; a) the estabhshment of contact between a sample and an exogenous enzyme for a substrate m said sample or an exogenous substrate for an enzyme in said sample to form a mixture, other before or after bringing mto contact said sample with a structure of conducting and/or semi-conducting material not m dectromc contact with an external dectromc circuit, to form a mixture and; b) the apphcation of a voltage gradient across said mixture, said voltage gradient being such that an dectrochemical reaction takes place on said structure of conducting and/or semi-conducnng matenal not m dectromc contact with an external dectromc circuit, wherem said dectrochemical reaction occurs with a product of said enzyme or said exogenous enzyme action, other direcdy or mdirecdy, and; c) the detection and/or quantitation of said dectrochemical reacnon direcdy or mdirecdy, and; d) the determination of the presence or quantity of said substrate or said enzyme. 12. An assay as m claim 11 wherem said substrate and said exogenous substrate for an enzyme is a substrate for other a dehydrogenase or oxidase, and said enzyme and said exogenous enzyme is an enzyme with dehydrogenase or oxidase activity. 13. An assay as m claim 12 wherem said dectrochemical reacnon results m dectrcK-heπmuminescence or chemilummescence other direcdy or mdirecdy. 14. An apparams for the detection or assay of an analyte compπsmg: a) an dectπcal power supply able to deliver a voltage; b) a cell able to accept a sample containing structures of conducting and/or semi-conducting material, wherem said cell contains at least two dectrodes which are externally and dectromcally connected to said dectπcal power supply and said cell is other an integral part of the apparatus or is a removable dement, c) a detector able to detect electrochemistry, said detector sdected from the following; film, photomultiplier tube, photodiode, phototransistor, CCD camera, electrochemical cell, wherem said detector is sdected and/or placed such that it optimally detects dectrochemisrry from structures of conducting and/or semiconducting material and avoids detecnon of electrochemistry from said at least two dectrodes which are externally and dectromcally connected to said electncal power supply 15. The apparams of claim 14 wherem the cell compnses at least three functional zones, a central zone for the sample to be assayed and at least two zones which flank the central zone and contain said at least two electrodes wherem each electrode of said at least two dectrodes is contamed within each of said at least two zones which flank the central zone. 16. The apparams of claim 15 wherem the cell contams a wmdow for the detector such that only the central zone is observable by the detector. 17. The apparatus of claim 15 wherem the central zone of the cell is separated from the flanking zones by a membrane which is a semi-permeable membrane. 18. The apparatus of claim 16 wherem said detector and electncal power supply are controlled by a computer or microprocessor. 19. The apparams of claim 18 wherem said voltage is in the range of 5V/cm to 30 kV/c 20. A kit for performing an assay compπsmg, (i) a bmding speαes labelled with an electrochemically detectable speαes, and; (ά) a structure of conducting and/or semi-conducting material coupled to a second bmding speαes, wherem said structure of conducting or semi-conducting material not m electncal contact with an external dectromc αrcuit is subjected to an apphed voltage m an electrolyte causmg electrochemistry to occur on said structure of conducting or semi-conducting matenal. 21. A kit for performing an assay as m claim 20 further containing a bifunctional bmding speαes. 22. A kit for performing an assay as m claim 20 and 21 where said dectrochermcallv detectable speαes is able to support electrochemilummescence or chemilummescence other direcdy or mdirecdy. 23. A kit for performing an assay wherem dectrochemistry is detected direcdy or mdirecdy from at least one structure of conducting and/or semi-conducting material, which kit consists essentially of; (ϊ) and enzyme or substrate of an enzyme, and; (ii) at least one structure of conducting and/or semi-conducting, wherem said at least one structure of conducting and/or semi-conducting material is capable of bong stimulated to carry out electrochemistry on apphcation of an apphed voltage to an electrolyte m contact with said at least one structure of conducting or semi-conducting material when not in electromc contact with an external electromc control αrαut. 24. An immunochromatographic device compπsmg; a) a bmding speαes labelled with an electrochemically detectable speαes, and; b) a bmding speαes immobihsed, and; c) a sohd phase non-conducting matenal containing at least one structure of conducting and/or semi- conducting matenal positioned such that dectromc connection to an outside electncal αrcmt can be avoided, wherem said sohd phase is not rendered conducting and/or semi-conducting by said at least one structure of conducting and/or semi-conducting material 25. An immunochromatographic device as descnbed m 24 additionally containing at least two electrodes which are able to make dectromc contact with an external dectromc circuit and do not make electromc contact with said sohd phase 26. The generation of dectromagnetic radiation by apphcation of a voltage gradient across at least one structure of conducting and/or semi-conducnng material not m electromc contact with an external dectromc circuit, said voltage gradient bemg such that at least one electrochemical reaction takes place on said at least one structure of conducting and/or semi-conducting material not in electromc contact with an external electromc circuit wherem said at least one electrochemical reaction results m the emission of dectromagnetic radiation, other direcdy or lndirecdy 27. The generation of dectromagnetic radiation as m claim 26 wherem said at least one electrochemical reaction is an dectrochemilummescent reaction 28. The generation of dectromagnetic radiation as m claim 26 wherem said dectrochemical reaction is a reaction of a stabihsed dioxetane or other chemilummescent molecule 29. The generanon of dectromagnetic radiation withm a separations media which compπses applying a voltage to a separations media which contams or is constructed from structures of conducting and/or semiconducting material such that said separations media is not rendered conducting or semi-conducnng. 30. The generation of dectromagnetic radiation as m claim 29 wherem said separations media is made from the following mateπals: styrene, dextran, agarose gds, polyacrylamide gds, cellulose fibres, and denvatives thereof. 31. The generation of dectromagnetic radiation as m claim 29 wherem said dectromagneuc radiation is generated by electrochemilummescence or chemilummescence. 32. An assay for an analyte of mterest usmg an dectrochemical process, the assay compnsing; a) the estabhshment of contact between the sample to be assayed for an analyte of mterest and at least two structures of conducting and/or semi-conducting matenal not m dectromc contact with an external dectromc circuit, wherem said at least two structures of conducting and/or semi-conducting matenal are bound to at least one bmding speαes or at least one enzyme substrate, and; b) allowing at least one of said at least two structures of conducting and/or semi-conducttng matenal to interact with said analyte other enzymatically or by bmding to alter said at least one of said at least two structures of conducting and/or semi-conducting matenal such that it is able to bmd to at least one of said at least two structures of conducting and/or semi-conducting material, and; c) allowing the altered said at least one of said at least two structures of conducting and/or semi-conducting matenal from b) to bmd to said at least one of said at least two structures of conducting and/or semi- conducting matenal to form a complex of at least two structures of conducting and/or semi-conducting material, and; d) applying a voltage gradient across said complex of at least two structures of conducting and/or semiconducting material not in dectromc contact with an external dectromc circuit, said voltage gradient being such that an electrochemical reaction takes place on said complex of at least two of said structures of conducting and/or semi-conducting matenal not m electromc contact with an external electromc αrcuit, and; c) the detection and/or quantitation of said electrochemical reacπons direcdy or mdirecdy, and, d) the determination of the presence or quantity of said analyte of mterest 33. An assay for an analyte of mterest usmg an dectrochemical process, the assay compnsing; a) the estabhshment of contact between a sample to be assayed and a structure coated or otherwise linked to a sdected compound such that an analyte mteracts enzymatically or bv bmdmg with said structure via said sdected compound resulting m a modified structure, and; b) the estabhshment of contact between the mixture m a) and a bmding speαes able to bmd to said modified structure to form a second modified structure, wherem said bmdmg species is hnked or labelled with an dectrochemically detectable speαes, and, c) the estabhshment of contact between said second modified structure and a structure of conducting and/or semi-conducting material not m electromc contact with an external electromc circuit, and; d) the apphcation of a voltage gradient across said structure of conducting and/or semi-conducting matenal not in dectromc contact with an external dectromc circuit such that an dectrochemical reaction with said dectrochemically detectable speαes takes place, and, c) the detection and/or quantitation of said dectrochemical reaction direcdy or mdirecdy, and, d) the determination of the presence and/or quantity of said analyte 34. The assay as m claim 33 wherem said structures are polymer base beads coated with at least two bmding speαes one specific for said analyte and one specific for a complementary bmdmg speαes on said structure of conducting and/or semi-conducting material and said structures of conducting or semi-conducting material are coated with said complementary bmding speαes. 35 An assay for an analyte of mterest using an dectrochemical process, the assay comprising a) the establishment of contact between a sample and a structure coated or otherwise linked to a sdected compound wherem an analvte mteracts with said structure via said selected compound, and; b) the estabhshment of contact between the mixture from a) and structures of conducting and/or semiconducting matenal not in dectromc contact with an external dectromc circuit, wherem said structures bmd or otherwise form a dose contact with said structures of conducting or semi-conducting matenal, and, c) the apphcation to the mixture from b) of a voltage gradient across said structure of conducting and/or semi-conducαng matenal not in dectromc contact with an external dectromc αrcmt but bound or otherwise in dose contact with said structures, such that an dectrochemical reaction takes place wherem said dectrochemical reaction other direcdy or mdirecdy mvolves compounds bound or associated with said structure, and, b) the detection of said dectrochemical reaction that is mvolved other direcdy or mdirecdy with compounds bound or associated with said structure, whereby said analyte is detected or quanntated 36. The assay as m claim 35 wherem said structures bmd or otherwise form a dose contact with said structures of conducting and/or semi-conducting material, based on lnteracuons sdected from the group consisting of, bmding speαes to bmding speαes mteractions, magnetic fidd mteractions, charge charge mteractions, dipole dipole, dectπcal field mteractions, hydrophobic lnteracuons 37 The assay as m claim 35 wherem said structures bmd or otherwise form a dose contact with said structures of conducting and/or semi-conducnng matenal, based on concentration methods sdected from the group consisting of, filtration, sedimentation, centnfuganon, drying, evaporanon, preαpitation 38 The assay as m claim 35 wherem said structures are bound to both an electrochemically detectable speαes and a bmding speαes or enzyme substrate and said structures of conducting and/or semi-conducting material are bound to a bmdmg speαes or enzyme substrate

Inventors: JONES MARK HOWARD, JONES, MARK, HOWARD
Applicants: JONES MARK HOWARD, JONES, MARK, HOWARD
Application year: 1999
Main classification: G01N33
IPC codes: G01N33