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WO2003104787A1 - Capteur et procede de detection pour detection et commande de processus - Google Patents

Capteur et procede de detection pour detection et commande de processus Download PDF

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Publication number
WO2003104787A1
WO2003104787A1 PCT/GB2003/001902 GB0301902W WO03104787A1 WO 2003104787 A1 WO2003104787 A1 WO 2003104787A1 GB 0301902 W GB0301902 W GB 0301902W WO 03104787 A1 WO03104787 A1 WO 03104787A1
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WO
WIPO (PCT)
Prior art keywords
sensor
species
accordance
electrode
modifying agent
Prior art date
Application number
PCT/GB2003/001902
Other languages
English (en)
Inventor
Ritu Kataky
Neil Ronald Cameron
Original Assignee
University Of Durham
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/GB2002/002035 external-priority patent/WO2002090958A2/fr
Application filed by University Of Durham filed Critical University Of Durham
Priority to AU2003227903A priority Critical patent/AU2003227903A1/en
Publication of WO2003104787A1 publication Critical patent/WO2003104787A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Definitions

  • the present invention relates to a novel sensor for detecting a desired chemical or biochemical species, novel components thereof, a sensing method for detection of a desired species, and the use thereof in medical, environmental and industrial applications and to a method for the control of industrial processes for the reaction of a desired chemical or biochemical species. More particularly the invention relates to a sensor for use in harsh media such as whole blood and other body fluids, brackish water, industrial environments and the like, for determination and speciation of species such as heavy metals, pesticide residues and the like, steroids, neurotransmitters, metabolites, carbohydrates, pharmaceutical molecules and the like.
  • the invention comprises a sensor including a modifying agent for mobilisation and transport of a desired species, a method for determination of a desired species, as a contaminant or otherwise, a method for the control of industrial processes for the reaction thereof, and the use of the sensor and methods in medical and other bioscience applications for example for the detection of steroids, neurotransmitters, metabolites, carbohydrates, pharmaceutical molecules and the like and in environmental and industrial applications where heavy metals, pesticide residues and the like are employed and discharged into the environment.
  • a further application is envisaged in controlling industrial processes such as metal finishing, metal oxides, wood preservatives, and the leather tanning industry which uses over 750,000 tonnes of chromium chemicals per year, and the like, to optimise processes, minimising consumption of heavy metals, and eliminating at least in part the metal wastage to effluent and disposal issues.
  • industrial processes such as metal finishing, metal oxides, wood preservatives, and the leather tanning industry which uses over 750,000 tonnes of chromium chemicals per year, and the like
  • optimise processes minimising consumption of heavy metals, and eliminating at least in part the metal wastage to effluent and disposal issues.
  • electroanalytical methods described in literature for determining Cr (111) include limited references to ion-selective electrodes characterised in aqueous solutions.
  • Chromium speciation in industrial effluents has been studied using time- consuming and inadequate laboratory based techniques such as 1,5 diphenyl- carbazide based spectrophotometry, extraction with methyl isobutyl ketone and co-precipitation with iron and bismuth salts. In presence of organic complexes, all three methods gave erroneous results requiring empirical corrections. The current state of art, although extensive, is complex and inadequate for the development of a commercial instrument.
  • One potentially interesting electro-chemical sensing technique comprises programmed absorptive stripping voltammetry. This method involves accumulating species on one or more electrodes of a sensor which is then provided with electrical contact and scanned through a voltage or current range. Amperometric detection shows peak current flow, and calibration of the sensor indicates characteristic voltages at which given species are desorbed from the electrode. When the voltage applied across the electrode is held constant, measurement of the current yields a result that can be converted electronically to the concentration of the detected species.
  • the existing technologies generally involve gold or mercury electrodes and have the significant disadvantages in that they are relatively expensive, require the use of strong acids and are easily blocked in highly mixed organic and inorganic process liquors.
  • US 6,090,269 discloses a stripping voltammetry method using gold electrodes, having SAM's thereon, as a result of thiol binding to the electrode, however these are unstable in harsh media.
  • WO 96/24840 discloses an enhanced sensitivity or specificity anodic stripping voltammetry method comprising a working electrode and a chemical species incorporated in a layer over or close to the surface of the electrode or incorporated into the electrode.
  • the chemical species enables detection of metals in the presence of interfering species, e.g lead in presence of copper.
  • Other techniques use ligands in the sample solution which are specific to a species to be detected and freely accumulate these species, providing some improvement in sensitivity or specificity.
  • Potentiometric ion-selective electrodes non-destructively measure ionic activities rather than concentrations.
  • the measurements are made in equilibrium conditions. In several situations, measurements of activities are more meaningful than measurements of total concentrations as these give an indication of the active form of the compound.
  • a classic example is the significance of calcium ionic activity rather than total concentration in blood electrolyte measurements.
  • the current limitation is the sensitivity of the method, which, realistically, only goes ' down to micromolar levels using established techniques. However research is underway to lower limits of detection and the present invention will contribute towards this goal.
  • Membranes of ionophore based ISEs traditionally consist of a polymeric phase (typically poly(vinylchloride)) as polymer matrix, lipophilic ion-exchanger sites, and a plasticiser which also acts as a solvent for a lipophilic ionophore.
  • the membrane is placed between two aqueous phases, the sample and the inner filling solution (usually an approximately millimolar concentration of the primary analyte ion), which is in contact with an inner reference electrode, usually Ag/AgCl in traditional ion-selective electrodes.
  • the ion-selective membranes are deposited on the conductor, replacing the conventional inner filling solution, giving coated wire electrodes. Elimination of the internal filling solution is the first step towards miniaturisation.
  • the ultimate stage in miniaturisation is deposition of the electroactive material directly on the insulator of a field-effect transistor giving an ion-selective field effect transistor (ISFET).
  • ISFET ion-selective field effect transistor
  • stripping voltammetry methods and indeed optical equivalents thereof, can be further enhanced in terms of specificity and sensitivity by modifying the electrode or optical contact with a chemical agent which is anchored securely at the electrode and which selectively and reversibly bonds to the species to be detected thereby controlling the mobilisation and transport thereof.
  • a sensor for electrochemically or optically determining a desired species comprising at least one electrode or optical path, wherein the electrode or optical path is modified for specific accumulation of the desired species, by means of a modifying agent which is adapted to selectively and substantially reversibly bind the species to be detected and to release the species at a characteristic voltage or give an absorbance measurement at a characteristic optical wavelength, wherein the modifying agent is associated with at least part of the surface of the electrode or optical path by physical or chemical anchoring.
  • the modifying agent is chosen so that it has specific binding sites for the desired species. When a potential or optical source is applied the species are loosely bound to the agents surface. Sweeping the potential or wavelength leads to desorption of the ionic species present.
  • the sensor of the invention has the additional benefit that it can distinguish between oxidation states, for example Cr (III) and the highly toxic Cr (VI), as these ions are selectively desorbed at different voltages or wavelengths.
  • the invention is particularly adapted to use in harsh media such as whole blood and other body fluids, brackish water, industrial fluids or contaminated environments and the like, or in testing samples taken directly from such harsh media without a need for remote testing or sample pre-treatment.
  • the modifying agent is adapted to bind the species to be detected and to release the species at desired moment for analysis.
  • the sensor inherently performs both a separation function, in which the target species is effectively separated from the harsh environment of the sample by the action of the modifying agent, and a sensor function.
  • the sensor may be electrochemical or optical.
  • An electrochemical sensor may be amperometric or potentiometric.
  • the role of the modifying agent in amperometric sensors is to ensure a high concentration of the analyte (species to be detected) in the vicinity of the electrode, detection occurs via a redox reaction of the analyte at the electrode surface; consequently, equilibrium conditions are not necessary and the electrode need not comprise an inner sensing chamber or region.
  • the senor of the invention serves to integrate the sensing and separation of desired species by inco ⁇ oration of separation on the sensor surface achieved by differing electrophoretic mobilities of the species. Moreover the ability of the sensor to speciate in situ revolutionises the uses thereof and provides an excellent sensor for use in process control.
  • the sensor may comprise exclusion means for excluding non desired species from the surface of the electrode or optical source, such means selected from size-specific exclusion means about the electrode or optical source and remote therefrom, to prevent access of large particles such as dust, soil, cells etc, or exclusion agents about the electrode or optical source and remote therefrom, for example pepsin for prevention of protein fouling and the like.
  • the sensor may comprise an additional layer of material such as porous polymer with tuneable porosity, preferably gradient porosity, mechanical stability and resistance to fouling.
  • PolyHIPE is particularly suitable for improving the analytical capabilities of electrochemical separation and detection. Physically, the material is inert, easy to manipulate, has tuneable porosity, can be cast as open or closed cell structures, and is mechanically stable.
  • the modifying agent and any exclusion means or agents may be chemically or physically anchored to the electrode or optical source or remote therefrom and thereabout.
  • Chemical anchors may include any chemical modifying groups which are known for anchoring chemical substrates to metal, composite or polymer or like surfaces.
  • Preferred anchoring groups include lipophilic groups such as C 4 - 20 aliphatic or alicyclic saturated or unsaturated hydrocarbon groups for example C 8 octyl groups and the like.
  • Physical anchors may comprise any known means for physically anchoring a chemical substrate to metal, composite, polymer or like surfaces.
  • Preferred physical anchoring means comprises a porous open or closed cell membrane or film applied at or about the surface and having electrode or optical source modifying agent anchored in turn chemically or physically within its pores.
  • Physical anchoring of modifying agent is achieved with use of pore interconnects of diameter which preclude release of modifying agent but allow access of the species to be detected.
  • Chemical anchoring of modifying agent is achieved with use of groups or substituents having an affinity for the porous material.
  • Preferred porous open cell structures include high internal phase emulsion polymers (Poly-HIPE or PHP), solgels, electrically conducting or optically transparent zeolites and the like.
  • anchoring means comprises PHP membrane of thickness 1 micron - 5 mm, preferably 0.01 - 3 mm and having pore size in the range up to 100 micron and interconnect size in the range up to 10 micron.
  • Suitably modified PolyHIPE therefore provides an excellent material for developing integrated amperometric electrochemical systems combining separation, detection and compatibility.
  • the Poly-HIPE is loaded with graphite for conductivity.
  • the Poly-HIPE includes an electron mediator to facilitate communication with the redox-active centre of biomolecules such as enzymes.
  • electron mediators include ferrocene and derivatives of ferrocene, conducting salts such as tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) and bipyridyl salts.
  • Multilayer structures for potentiometric sensing which comprise PNC or polyurethane composites with Poly-HIPE have benefits over using Poly-HIPE alone. They lower the limit of detection and can work in harsh or fouling media.
  • the mechanical anchoring means may be adapted for use with different modifying agents specific for detection of a range of different species, thereby simplifying the process for sensor manufacture.
  • a modifying agent according to the invention may be any known or novel agent which is capable of selectively and reversibly binding a desired species to be detected.
  • modifying agents are selected from ionophores, ligands, enzymes and other multi-dentate species providing reversible binding by affinity such as charge delocalisation, for example hydrogen bonding, van der Waals forces and the like.
  • More preferably modifying agents are selected from compounds of formula
  • n is 0 -2 and R is a lipophilic or other group suitable for stably binding with high affinity to the electrode surface or a surface layer such as polyHIPE or PNC surface membrane; when n is 0, the ligand is physically anchored, for example caged in membrane pores and wherein A is a C 1-36 aliphatic or alicyclic saturated or unsaturated or aromatic hydrocarbon moiety optionally including one or more heteroatoms selected from ⁇ and S and the like, and optionally substituted by functional groups including halo, hydroxy, cyano, amino, carbonyl, and the like and optionally including one or more ether, amino or thioether linkages and having m binding sites for accumulating a desired cationic species, wherein m is 1 - 6, preferably 1 - 4.
  • the sensor may be used for detection of any desired species, for example selected from the heavy metals, pesticides, oil residues and the like.
  • the sensor is adapted for the detection of chromium species and in particular for the detection of Cr(III) speciated with respect to Cr(NI).
  • Preferred modifying agents for detection of chromium include ligands comprising modified 2, 3 pyridine dicarboxylic acid of general formula I
  • Preferred modifying agents for detection of lead include ligands comprising modified N, N' substituted aliphatic diamides such as N,N'-dioctadecyl-N,N'- dipropyl-3 ,6-dioxaoctandiamide (Fluka) .
  • Preferred modifying agents for detection of potassium K include ligands selected from the class of the mycin antibiotics such as valinomycin.
  • Modifying agents may also be employed comprising ionophores for detection of hydrophilic species such as Calcium Ca 2+ , sodium Na + , magnesium Mg 2+ and the like, or for detection of hydrophobic species such as ionophores for chiral and achiral aryl and alkyl ammonium cations, or for detection of other environmental pollutant cations such as ionophores for Cd 2+ , Hg 2+ and the like.
  • hydrophilic species such as Calcium Ca 2+ , sodium Na + , magnesium Mg 2+ and the like
  • hydrophobic species such as ionophores for chiral and achiral aryl and alkyl ammonium cations
  • other environmental pollutant cations such as ionophores for Cd 2+ , Hg 2+ and the like.
  • the modifying agent is selected from known enzymes, ionophores, sequestering agents, oligomeric species and the like.
  • agents also provide moderate selectivity, either by means of specificity or by means of stripping potential or wavelength of each species being adequately separated or having "finger print" patterns.
  • the agent provides sufficient affinity, or lipophilicity to minimise leaching of the agent from the electrode or optical source surface.
  • the sensor of the invention may comprise any known or novel electrode or optical source and detection arrangement.
  • an electrochemical sensor comprises one or more electrodes.
  • Electrodes may be screen printed on to a suitable carrier such as a plastic carrier using conductive inks as known in the art or may comprise a composite electrode as known in the art. Electrodes are typically comprised of carbon, such as graphite.
  • the sensor may be multi use or may be for disposable single use.
  • the sensor may be suited for immersing in a sample cell, or may be in the form of a probe for inserting directly into material to be determined.
  • the senor may be mounted as an array for example in a liquid effluent stream to provide continuous measurement of heavy metal concentrations or in a reaction vessel to provide continuous measurement of heavy metal concentrations in the course of their reaction.
  • This sensor may advantageously be based on end of capillary, electrochemical detection combined with capillary electrophoresis. In a particular advantage this combination is well suited to on-line and field based instrumentation, whereby the instrument may be suitable for portable electroanalytical systems.
  • a detector cell may be of any suitable geometry and is typically of wall-jet configuration which reduces contamination of the electrode surface by minimising the impact time of the analyte solution plug. This allows simultaneous detection of pH.
  • Optical sensors may similarly comprise any single or multi use sensor which may be disposable or otherwise.
  • An optical sensor may comprise a cell having optical source and detection means or may comprise an optical fibre for conducting light of desired wavelength into a sample to be detected. Preferably optical sensing is with UN light.
  • a method for the manufacture of a sensor as hereinbefore defined comprising providing at least one electrode or optical path, applying a layer of modifying agent thereabout, and anchoring by chemical or physical means, applying exclusion means thereabout and anchoring, and providing electrical contacts or optical source.
  • the sensor may be provided as an array or as a single contact sensor.
  • a novel electrode modified with use of a modifying agent as hereinbefore defined, preferably with use of a Cr (III) selective agent, for Cr (III) detection or with use of a Cr (NI) selective agent, for Cr (NI) detection.
  • Cr (NI) is highly toxic and therefore of environmental concern.
  • a method for species detection with use of a sensor as hereinbefore defined comprising providing or obtaining a sample to be detected in fluid phase, applying an electrical current or optical source and scanning through a pre-determined range to a stripping potential or wavelength, maintaining the current or optical source at that potential or wavelength and detecting or measuring the current evolved or absorbance, optionally with conversion thereof to indicate concentration of species.
  • the method is suitable for the measurement of species as hereinbefore defined down to 0.1 ppm of heavy metal or 10 "9 mg/litre of pesticides such as organophosphate.
  • the method is suitable for detection of heavy metals such as chromium, arsenic, elemental cadmium, lead or zinc and other metals, for the detection of pesticides such as organophosphates, for the detection of oil residues and the like.
  • Measurement may be of liquid samples directly or of analyte extracted from soil or from industrial process streams or effluent and made up as a sample. Extracts may be conveniently obtained by subjecting to ultrasound to break down signal distorting contaminants, and to break down polymerised species to detectable form.
  • detection is with use of a solid phase adso ⁇ tive column as sample cell.
  • a method for the regeneration or priming of a sensor as hereinbefore defined comprising the (re)introduction of modifying agent.
  • the method may be useful for changing the specificity of the sensor to detect a different species, or simply regenerating the existing sensor for prolonged lifetime.
  • a method for process control of an industrial process for the introduction and reaction of a given species comprising monitoring the species with use of the sensing method and sensor as hereinbefore defined, in situ in real time operation, periodically obtaining values for the concentration of species in a given location and deriving parameters to maintain or alter the process controls for continued efficient operation.
  • the method involves the, use of suitable software and instrumentation to receive and process signals and relate to a calibration logarithm to produce concentration values.
  • Ligands were selected in turn and made up in a solution with the desired species, Cr(III). Binding Constraints ⁇ t and ⁇ 2 for CrIII were determined by potentiometric titrations and compared with literature values.
  • Suitable ligands were immobilised on a robust polymer of controllable porosity (Poly HIPE) and attached to ceramic screen-printed electrodes to enable usage even in harsh media or as a monolith in a dip-type sensor.
  • Poly HIPE polymer of controllable porosity
  • An SEM of the Poly HIPE material is shown in figure 4, and a schematic of the sensor in Figure 5.
  • Layer 1 Non-functional poly(styrene-DNB) PHP membranes with controlled porous mo ⁇ hology to exclude large particles such as dust, soil, cells, etc.
  • Layer 2 A layer of PHP modified with pepsin for prevention of protein fouling.
  • Layer 3 A layer containing a sensing species.
  • Ionophores, ligands and enzymes are inco ⁇ orated either by physical entrapment or chemical modification to provide and ensure an optimum supply of ligand material.
  • the polymer was made conducting by inco ⁇ oration of graphite particles, metallic particles or electron mediators such as ferrocene or TTF- TC ⁇ Q.
  • PolyHIPE materials are selected according to the porosity of the material, whereby sensors are constructed which can be used in adverse media such as industrial processing media, whole blood and brackish water.
  • modified polyHIPE Styrene (4.5 g), divinylbenzene (0.5 g), ligand (ca 0.02g) and Span 80 (1.0 g) were mixed in a three-necked round-bottomed flask with a D-shaped PTFE paddle connected to an overhead stirrer at 300 ⁇ m under nitrogen. To this was added dropwise 45ml of an aqueous solution containing potassium persulfate (0.1 g) and calcium chloride dihydrate (0.5 g). The HIPE developed as a viscous white fluid, which was stirred for a further hour following addition of the aqueous phase. It was then transferred to PTFE moulds which were heated at 60 °C in an oven for 48 hours. The resulting modified PolyHIPE membranes were immersed in de-ionised water then z ' s ⁇ -propyl alcohol for 24 hours each, to remove salts and surfactant respectively, and were dried in vacuo to constant mass.
  • the lower sensing layer is a conventional nonporous polymer membrane e.g. PNC, containing the ligand and plasticiser.
  • the plasticiser makes the membrane flexible and solvates the ligand. It is necessary to have a non-porous layer in potentiometric mode as equilibrium conditions need to be established, which will only occur if the analyte is transported through the membrane to the inner filling solution or electrode by the ligand.
  • porous PolyHIPE materials are used to prepare the other layers as shown in fig. 2.
  • Ligands used are valinomycin to detect clinically relevant K + and a lead ionophore such as ⁇ , ⁇ '-dioctadecyl- ⁇ , ⁇ '-dipropyl-3,6-dioxaoctandiamide (Fluka) to detect Pb 2+ , a source of environmental pollution.
  • Ionophore modified PolyHIPE provides a new material for improving the analytical applications of current ion-selective electrode systems.
  • the optimum thickness for each layer is determined by iteration. Once prepared, the composite membrane is cut to the appropriate size and fitted in a Philips electrode-type body.
  • the inner-filling solution is the appropriately buffered analyte solution in a sol-gel matrix. This configuration helps in preventing the leaching of the electrolyte from the inner-filling solution thereby achieving the conditions required to obtain pico-molar limits of detection.
  • Membranes containing ionophores for hydrophilic (e.g. Ca 2+ , Na + , Mg 2+ , etc.) and hydrophobic (e.g. chiral and achiral aryl and alkyl ammonium) cations are also prepared by corresponding methods.
  • Sensor of Example 2 above are made up as arrays and installed in the reaction chamber and effluent streams of an industrial process using a heavy metal.
  • Periodic stripping voltammetry linked by suitable instrumentation and software gives real time readings of heavy metal concentration in each case, whereby adjustment can be made of the inlet rate of metal for optimum stoichiometric reaction or for minimum effluent content.
  • the electrodes comprise mediator immobilised in graphite or gold conducting particles and an appropriate enzyme relay which may be prepared by either of the following methods:
  • G-HIPE Graphite inco ⁇ orated high internal phase emulsions
  • Ferrocene or ferrocene monocarboxylic acid were dissolved into ethanol. A certain amount of the solution was cast onto graphite polyHIPE membranes. The membranes, absorbed with solution in the pores only, were left to dry in the air.
  • Ferrocene was dissolved in tetrahydrofuran. A certain amount of the solution was cast onto graphite polyHIPE membranes(depending on membrane dimensions). The membranes,absorbed with solution in the pores and in the polymer skeleton, were left to dry in the air.
  • a response showing the reduction of hydrogen peroxide at 0.4 mV shows that this transducer is suitable for constructing biosensors with established relay systems such as for cholesterol and acetylcholine.
  • test fluids that mimic blood electrolyte (test fluids containing bovine or human serum albumin)
  • the composite membrane 2 did not show any evidence of fouling in presence of proteins such as serum albumin whereas the PNC membrane showed an immediate decrease in sensitivity in contact with serum albumin evident as a 1-3 mN/ min drift in electrode potential.
  • the log K data defines the selectivity coefficient which again is seen to be improved for the composite systems. Use of composite membranes led to: Lower detection limits Less Interference Improved selectivity No protein interference

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Abstract

L'invention concerne un capteur permettant de déterminer par voie électrochimique ou optique une espèce souhaitée. Ce capteur comprend au moins une électrode ou un chemin optique modifié, en vue d'une accumulation spécifique de l'espèce souhaitée, par un agent de modification qui est conçu pour se lier de manière réversible, sélectivement et sensiblement à l'espèce à détecter et pour libérer celle-ci à une tension caractéristique ou pour donner une mesure d'absorbance à une longueur d'onde optique caractéristique, ledit agent de modification étant associé à au moins une partie de la surface de l'électrode ou du chemin optique par fixation physique ou chimique. L'invention concerne également un procédé de fabrication et d'utilisation dudit capteur, en particulier dans des milieux hostiles de type sang total et autres liquides biologiques, eau saumâtre, environnements industriels et analogues.
PCT/GB2003/001902 2002-05-03 2003-05-06 Capteur et procede de detection pour detection et commande de processus WO2003104787A1 (fr)

Priority Applications (1)

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AU2003227903A AU2003227903A1 (en) 2002-05-03 2003-05-06 Sensor and sensing method for detection and process control

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PCT/GB2002/002035 WO2002090958A2 (fr) 2001-05-05 2002-05-03 Detecteur, procede de detection et commande de procede
GBPCT/GB02/02035 2002-05-03

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Cited By (4)

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GB2442105A (en) * 2006-09-13 2008-03-26 Rtc North Ltd Biological fluid analysis system
WO2012112611A3 (fr) * 2011-02-15 2012-10-18 Silveri Michael A Système de capteur ampérométrique
US8845905B2 (en) 2012-03-19 2014-09-30 Tongji University Polypyrrole copolymer nanoparticles-based compositions and methods for detecting lead ions
CN111533948A (zh) * 2020-04-20 2020-08-14 北京邮电大学 一种温和条件下利用有机分子导体制备多孔三维有机力学传感元件的方法

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US4582589A (en) * 1984-06-30 1986-04-15 Terumo Kabushiki Kaisha pH sensor
EP0484865A2 (fr) * 1990-11-07 1992-05-13 Hewlett-Packard Company Détecteur à fibres optiques d'ions potassium
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US6090269A (en) * 1995-08-04 2000-07-18 Yissum Research Development Company Of The Hebrew University Of Jerusalem Determination of chromium

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2442105A (en) * 2006-09-13 2008-03-26 Rtc North Ltd Biological fluid analysis system
GB2442105B (en) * 2006-09-13 2009-03-18 Rtc North Ltd Biological fluid analysis system
US20100044224A1 (en) * 2006-09-13 2010-02-25 Ritu Kataky Biological fluid analysis system
WO2012112611A3 (fr) * 2011-02-15 2012-10-18 Silveri Michael A Système de capteur ampérométrique
US10481117B2 (en) 2011-02-15 2019-11-19 Halogen Systems, Inc. Amperometric sensor system
US8845905B2 (en) 2012-03-19 2014-09-30 Tongji University Polypyrrole copolymer nanoparticles-based compositions and methods for detecting lead ions
CN111533948A (zh) * 2020-04-20 2020-08-14 北京邮电大学 一种温和条件下利用有机分子导体制备多孔三维有机力学传感元件的方法

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