CN101692061B - Sensor instrument system including method for detecting analytes in fluids - Google Patents

Abstract

A sensor instrument system and a method for detecting and identifying analytes in fluids of a region comprising a local sensor instrument and remote central station are disclosed. The instrument is comprised of a core technology employing a single sensor having two electrodes operated by an electrical frequency sweeping to generate two sets of patterned electrical information from a single measurement, a data transmission module and a GPS receiver module. The central station connects to a network means connected to a plurality of local receiving sites equipped with including the respective transceivers, so that the local analyte electrical information and geographic position information transmitted by the instrument can be wirelessly and remotely received and processed by the central station. The core technology is further comprised of a reference sensor for eliminating background influence, a temperature programming to control adsorption and desorption of analytes, and usage of all kinds of adsorbent materials having chemical selectivity including the hydrogen selectivity to enhance detection and identification of analytes in fluids.

Description

For detection of sensor instrument system including and the method for the analyte in fluid

Invention field

The present invention relates to sensor apparatus field, relate to especially the sensor instrument system including and the method thereof that detect the analyte in fluid.

Background technology

Sensor apparatus is used to the analyte in test fluid widely.Below the list of references relevant with the technology of the present invention.

1, United States Patent (USP) the 4th, authorizes being entitled as of the people such as Pei Na (Payne) " gas sensor " (following 455 patents for wearing and receiving) 887, No. 455 on Dec 9th, 1989;

2, United States Patent (USP) the 5th, authorizes being entitled as of the people such as Lewis (Lewis) " for detection of the sensor group of the analyte in fluid " on November 5th, 1996 for 571, No. 401 (below for Lewis 571 patents);

3, United States Patent (USP) the 6th, authorizes being entitled as of the people such as Lewis " detection of using artificial sense of smell instrument to microanalysis thing " in November 20 calendar year 2001 for 319, No. 724 (below for Lewis 724 patents);

4, wear and people's the document such as receive and be entitled as " frequency measurement by alternating current high-frequency to conducting polymer composite: a kind of new technology that detects Volatile chemical product ", detect science and technology, the 6th volume (Meas.Sci.Technol., 6), nineteen fifty-five, the 1500th to 1507 pages (following document for wearing and receiving);

5, the people's such as Na Geer (Nagle) document is entitled as " what kind of and Electronic Nose why ", international electric electronic engineering field (IEEE Spectrum), in September, 1998, the 22nd to 34 pages (being the document of Na Geer below);

6, the people's such as Bel special this (Balters) document is entitled as " Subminiature electronic nose ", international electric electronic engineering field (IEEE Spectrum), in September, 1998, the 35th to 38 pages (be below Bel spy this document);

7, United States Patent (USP) the 6th, 631, authorize being entitled as of the people such as Lewis " for the method for remote measurement smell " on October 7th, 2003 for No. 333 (is Lewis's 333 patents below, there is again in addition United States Patent (USP) the 7th, 359, authorize same inventor on April 15th, 2008 No. 802, this patent of invention is the division of Lewis's 333 patents); With

8, United States Patent (USP) the 7th, authorizes being entitled as of grandson (Sun) " for detection of sensor and the method for the analyte in fluid " on Dec 16th, 2008 for 465, No. 425 (below for grandson 425 patents).

455 patents that pendant is received disclose a gas sensor.The skin of this sensor has a macromolecule membrane with semiconductor property of exposed and tested gas.Apply an alternating current analytical instrument and this sensor is applied to the ac signal altered electrical impedance feature of detecting sensor afterwards with special resonant frequency, then with computing machine, this feature is compared with the reference feature being stored in computing machine.In view of obtained different Electrical Impedance Spectroscopy, this invention can detect the gas that has contacted sensor.To between 500 megacycles, because in this interval, can there is the phenomenon of electric frequency resonance at 100 megacycles in the test a-c cycle that this patent also discloses its best.

Lewis's 401 patents disclose the sensor group that is used for detecting analyte in fluid, have comprised the electric resistance sensor to compound sensitivity of application macromolecular material and carbon black granules composition.Sensor has two conductive electrodes of being isolated by chemically sensitive resistor but being connected to resistance two ends.This resistance provides the approach of current flowing between two electrodes like this.This resistance by numerous alternately and the non-conductive region being formed by non-conductive macromolecular material of arranging in the same way with the approach of current flowing and the conductive region being formed by conductive material.When this resistance has an analyte of the first concentration among contacting with fluid, when having the second concentration, this analyte there is respectively different resistance values with contacting.By at least two above these type of sensor groups that formed by the sensor of chemically sensitive resistor, different analytes is provided to the dissimilarity being showed by different resistance values like this.The chemical sensitivity that changes sensor can be formed and be reached by the material that changes quantitatively or qualitatively conduction and non-conductive region.The conductive electrode that utilizes like this electrical measurement to connect each sensor of this sensor group just can form an Electronic Nose instrument that detects the analyte in fluid.

Lewis's 724 patents disclose utilizes Artificial Olfactory instrument to detect multiclass analyte.This multiclass analyte can be used to diagnose numerous medical conditions, comprises the situation of halitosis, periodontitis and other diseases.

Pendant receive document a kind of sensor is disclosed.In the time of its contact Volatile chemical product, this sensor produce the phenomenon of electric frequency resonance than the alternating current impedance meeting of pyridine macromolecule material film.

The document of Na Geer is a specialist paper.It has collected till the research that Electronic Nose instrument is done of the last century late nineteen nineties and the development obtaining.This report describes the various sensors that are used for making Electronic Nose instrument in detail, comprised metal-oxide film sensor, conducting polymer composite thin film sensor, by macromolecule membrane be coated in the weight induction sensor of plane of crystal, by macromolecule material film be coated in the saw sensor of plane of crystal, by gate surface scribble the silicon field-effect transistor sensor of metal-oxide film, by the Fibre Optical Sensor of the many sound waves of application, by the corresponding sensor forming according to gas chromatography, spectrum and mass spectrum principle.This report has also been summed up the relative merits of various sensors.It is wherein a common shortcoming of all sensors with macromolecule material film to the high sensitivity of humidity.

Bel special this reported literature the microwafer as Electronic Nose of research and development.The principle of work of this Electronic Nose is to utilize the CMOS integrated circuit (IC) wafer that scribbles macromolecule material film in the time of contact volatile organic matter, has the change of the weight that can detect and the change of electric capacity.

Lewis's 333 patents disclose sensor construction, the system and method for remote monitoring chemical hazard thing, air quality and patient's situation.Such as search for and find explosive, land mine and chemical hazard article by robot system.All sensors that this patent is mentioned in collecting in Na Geer document, also collect the sensor group of the chunk sensor group of bleeding and the ditch beam shape of micromachining.This patent also discloses the sensor of the electric conductivity of invention, the region being made up of conductive material that it is arranged by the friendship body between two electrodes and the region being made up of the material that is different from conductive material simultaneously.This sensor just provides the approach that a confession electric current is flowed through different materials region between two electrodes like this.

From document cited above and patent, can see in the past in the research of sensor instrument system including, oneself has dropped into great effort, and this research is to study centered by the structure of sensor.This is because the structure of sensor has fundamentally determined the effectiveness that instrument detects and differentiates for analyte in fluid.Existing sensor apparatus, having applied above-described sensor technology and having combined after the technology including large scale integrated circuit, computer software technology and the data remote conveying feed technique in electronic engineering, greatly facilitates detection and discriminating to analyte.

As everyone knows, from the olfactory system of research mammal, the discriminating of a smell object is not only depended on to those has sense of smell especially targetedly to receive unit to this smell object, and to rely on those be not to receive especially targetedly unit to this gas.With another a word, be the collection of illustrative plates of confirming the characteristic type information of this object of performance to the discriminating of smell object.According to this principle, traditional having about the technology of sensor construction develops according to following two kinds of technical schemes: the scheme of application multisensor structure and the organization plan of application single-sensor.

On the organization plan of application multisensor, as narrated in Lewis's 333 patents, develop numerous different sensor technologies.Include metal-oxide film sensor, conducting polymer composite thin film sensor, be coated in the weight induction sensor of plane of crystal, be coated in the saw sensor of plane of crystal, be coated in the silicon field-effect transistor sensor of gate surface by metal-oxide film by macromolecule material film by macromolecule membrane.Although obtained in the past significant progress at the sensor research along this scheme, it also exists because having followed the shortcoming that uses multisensor scheme to bring.These shortcomings comprise: the sensor of a large amount of numbers of needs produces the Information Atlas that has type difference of analyte; The labyrinth of sensor and then cause the inconsistency in sensor production; The interference of the humidity being subject to because of application macromolecule material film in the time that chemical analyte is tested; Blunt sensitivity; The instrument of necessary costliness and dark restricted operating conditions.

In application when this organization plan, multi-thickness is about the macromolecule membrane of several microns has been widely used for improving sensitivity and the detection limit of sensor.This is mainly because macromolecule membrane can be tackled and comprise absorption and absorb the compound as analyte because of its special chemo-selective to compound.Consequently before being detected by sensor, analyte can be enriched in the surface or body of macromolecule membrane.

Classical macromolecule material film exists multiple shortcoming.The first, film has high-sensitive adsorbability to being accompanied by the humidity of analyte.Thereby humidity is the principal element that impact has macromolecule material film sensor effect.The second, high molecular film material has aging effect, thereby has influence on the long-term stability using of sensor.Three, on producing, obtaining the repeatability that is placed in the macromolecule material film on sensor is also a difficult problem.In particular for adopting multisensor organization plan, thereby the problem of repeatability is particularly remarkable must use the sensor of a large amount of numbers time.

Adopting on single-sensor organization plan, narrate as Na Geer document, be developed according to the multiple instrument of chromatogram, spectrum and mass spectrum principle.In general, these instruments are all very expensive.And their volume is all very huge, so just make the possibility miniaturization of these instruments.So these instruments lack attractive force on market, this is because on current market, and the wireless communication capability that instrument has and portably using property day are aobvious important.

For example, a kind of trend in the patient bedside diagnosis state of an illness just prevailing in medical diagnosis field.In suc scheme, patient's health maintenance comprises that medical diagnosis is directly in patient family and at patient's bedside, to launch.Like this, if Medical Instruments is can carry use just to have the competitive power on market.Have in addition as again wireless and far-end informational linkage function, this Medical Instruments will have competitive power.This is because patient's health and fitness information can send to a medical centre immediately, thereby can provide the better health maintenance including correct diagnosis for patient.In fact, the portability that instrument has and wireless messages propagation function be except medical field, at other many in such as safety, defendance, military affairs and industrial circle be also have commercioganic.

As the example of application single-sensor, the patent received of wearing and Literature Development in specific frequency range, detect from the electrical impedance and the electrical properties relevant with phase place thereof that detect application conducting polymer composite membrane electrode the technology that has gaseous analytes.This technology under characteristic frequency due to the interaction of analyte and conductive polymer material film produce can be measured electric resonance signal.But the electric resonance phenomenon of the device that pendant is received must just likely occur at 100 megacycles in the frequency in 500 megacycle intervals.Making and the use of this high-frequency restriction to instrument all brings great difficulty.The device of receiving of simultaneously wearing has still been inherited the shortcoming that uses macromolecular material to bring.

For the not enough of the patent of Pei Na be the single-sensor of the new construction of invention applying frequency scanning, grandson's 425 patents disclose and have been used for detecting and the single-sensor as detecting sensor of the analyte of discriminating in fluid.This sensor is made up of pair of electrodes.In the time that having enough concentration, analyte needn't carry out adsorption analysis thing by the additional adsorption material of filling between electrode.Otherwise filling sorbing material.After the ac-excited signal of the change frequency being provided by an alternating current instrument has been provided sensor, the interchange electrical properties of the sensor in each frequency in the time that the analyte in fluid is in or flows through between electrode can be detected.Such as electrical impedance and its component: resistance and reactance and phase place, so just set up two spectrograms with respect to the analyte electrical properties of frequency.Distinguish the type of this electrical properties by the program that a type is differentiated again, and compare with the type of the electrical properties of known substance, this invention just can detect and differentiate the analyte in fluid like this.This invention has comprised that again one is used as the single-sensor of reference sensor.Combine detect and the electrical properties of reference sensor after, this invention just can be removed the aging effect of interference, macromolecular material of humidity and the variation of the electrical properties of the sensor that caused by temperature variation.

The sensor instrument system including that Lewis's 333 patents develop has added the function of remote information processing to comprising the sensor group being made up of macromolecular material and carbon black.For effect of sensor instrument system including, there is so obvious positive effect.

But in multiple occasion, be included in to detect in air and contain ozone in the time of interior pollutant, sensing system is had to an extra requirement, this instrument can provide the instant with geographic location of air pollutants to change and the information of variation.So just can draw a regional instant air-polluting distribution plan, thereby can obtain better understanding and comparatively perfect control that this regional air is polluted.The instrument system with this function is also conducive to study many other problems.

Thereby this has just facilitated wish of the present invention: the shortcoming that designs and develop a kind of new sensor instrument system including and method and overcome traditional sensor device.This new instrument has in sensor manufacture and the good repeatability using, less negative interference factor, high sensitivity, less in the use restricted and Portability easily.In addition, this sensing system also has the ability of wireless telecommunications and carrys out deal with data, with the ability of determining the geographic position corresponding with analyte.

Summary of the invention

The present invention is conceived to found a sensor instrument system including and method detects and differentiate the analyte in fluid.This system include a sensor apparatus and with its central information station being separated by a distance.The composition of sensor apparatus has comprised the detection module being connected with a single-sensor, and it is used to obtain the electrical properties of numerous analytes; One location, global geographic position receiver module, it is used to obtain the geographic position at analyte place; With a transmission data module, it is used to wirelessly transmitting data.Single-sensor has two electrodes, is used to detect the analyte in fluid under the pumping signal effect that periodically comprises sinusoidal wave alternating current with frequency sweeping.Central information stands in the information that can process after the wireless information spreading out of of sensor apparatus with storage of analyte of receiving.And these packets of information have contained the electrical properties of detected analyte and the data of its geographic location.

An object of sensor instrument system including of the present invention and method be to provide one for detection of with differentiate the novelty of analyte in fluid and unique sensor construction.This structure has been used has two electrodes and single-sensor application AC current frequency scanning and vector analysis principle of work.In measurement, can use numerous different sweep frequencies, comprising preferred 10 kilocycles to the frequency in a megacycle interval.By the once measurement of the frequency sweeping to sensor, just can obtain two groups and include interchange electrical properties analyte internal characteristics, that have type rule, be included in each sweep frequency and can obtain two kinds of different orthogonal electrical properties.These character be by the analyte including specific inductive capacity, polarity or dipole moment feature determine.

Another object of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.This instrument comprised there are two electrodes with the single-sensor of having applied a-c cycle scanning, can be used to detect and differentiate the analyte in fluid.Discriminatory analysis thing is the type of the interchange electrical properties of the analyte that arrives according to analysis to measure, then the judgement afterwards of comparing with the type of the electrical properties of those known compounds.

The another one object of sensor instrument system including of the present invention and method is to provide a novel and unique sensor apparatus.It contains a detecting sensor with having applied ac frequency scanning with two electrodes and detects and differentiate the analyte in fluid.This instrument also includes the mechanism of a removal ground unrest.After having applied detecting sensor, also applied a reference sensor identical with detecting sensor structure.Reference sensor is used to reduce ground unrest to detecting the impact of analyte electrical properties and promoting the discriminating of the electrical properties type to analyte.Ground unrest has comprised the aging effect of impact, macromolecule membrane and the variation of the electrical properties detecting that causes by being placed in the temperature variation of the analyte between electrode of humidity.

A more object of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.It contains a single-sensor with having applied ac frequency scanning with two electrodes and detects and differentiate the analyte in fluid.This instrument has adopted the temperature of controlling the sensor storehouse including sensor and analyte including the fixing temperature controlled program with variable, and then improves detection and discriminating to analyte.

The object also having of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.It contains a single-sensor with having applied ac frequency scanning with two electrodes and detects and differentiate the analyte in fluid.This instrument has the function that can place the organic and inorganic and metal-adsorbing material of all kinds in sensor two electrodes, thereby reaches by optionally adsorbing, absorb corresponding analyte the object of improving analyte detection and discriminating.

The another one object also having of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.It contains a single-sensor with having applied ac frequency scanning with two electrodes and detects and differentiate the analyte in fluid.The feature of this instrument has: compact volume, easily palm Portability, easily with, be not subject to that ground unrest affects, temperature that low cost of manufacture and low power consumption are controlled the sensor storehouse including sensor and analyte.

An object of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.This instrument application at least one sensor of the present invention that is used as detecting sensor detect and differentiate the analyte in fluid.This sensor has two electrodes and uses the principle of work of AC current frequency scanning and vector analysis.In the electrode of the each detecting sensor at least one detecting sensor, being filling, different materials optionally adsorbs, absorbs corresponding analyte.And this each detecting sensor is by electromagnetic screen, thereby the cross-inductive of eliminating the magnetic field radiation that may be caused by the AC signal applying is disturbed.

An object of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.This instrument application at least one sensor of the present invention that is used as detecting sensor detect and differentiate the analyte in fluid.This sensor has two electrodes and uses the principle of work of AC current frequency scanning and vector analysis.In the electrode of each at least one detecting sensor, being filling, different materials optionally adsorbs, absorbs corresponding analyte.And each detecting sensor in this at least one detecting sensor is closed, applied in an orderly manner, respectively the pumping signal of ac frequency by electromagnetic screen, thereby the cross-inductive of eliminating the magnetic field radiation that may be caused by the AC signal applying is disturbed.

Another object of sensor instrument system including of the present invention be to provide one for detection of with differentiate the novelty of analyte in fluid and unique sensor apparatus.This instrument includes at least one sensor.One of them sensor is the sensor that has two electrodes, uses the principle of work of ac frequency scanning and vector analysis of the present invention.Remaining sensor is to select from existing sensor technology.

The object also having of sensor instrument system including of the present invention is to provide numerous identical, above-mentioned novel and unique sensor apparatus.They and central information station are separated by a distance.And each sensor apparatus is in a corresponding area in a region movably, be used to detect the analyte in fluid of this area.The composition of sensor apparatus comprises: a detection module has connected a single-sensor that has ac frequency scanning and a vector analysis principle of work, and it is used to obtain numerous electrical properties of analyte; One location, global geographic position receiver module, it is used to obtain the geographic position at analyte place; With a transmission data module, it is used to wirelessly transmitting data.The data of transmission have comprised the electrical properties of the analyte detecting and the analyte geographic position in this area.

Central information station has comprised a central computer.It is to connect numerous identical local information receiving stations by existing information network.Each receiving station includes the reception being connected with antenna and sends dual-purpose electronic unit.Numerous receiving stations is in corresponding areas numerous in a region, with numerous dispose movably in the sensor apparatus of this corresponding area corresponding one by one.The information exchange of the each analyte sending from each sensor apparatus is like this crossed and just can be received by central information station in the receiving station of each department accordingly.The computer stored at central information station contain global geographic position positioning map in interior application software with include the application software of authentication data type analysis method in interior analytic approach.The electrical properties information of the analyte obtaining in each department like this can be analyzed by central information station, thereby can differentiate the each analyte that is in each corresponding geographic position.The information in the analyte of being differentiated and the geographic position of analyte can have all application after being stored in central information station, comprises and is plotted in this region the instantaneous distribution plan of analyte in numerous different regions.

Sensor instrument system including of the present invention provides novelty and unique sensor apparatus and method thereof to differentiate the analyte in fluid.The possibility of discriminatory analysis thing be based on detect in fluid in the analyte of analyte the various alternating current character that have typing rule dominated of physicochemical property, such as electric current, voltage and electrical impedance and vector composition resistance and reactance, and the phase place being determined by resistance and reactance.The present invention has applied a paired metallic conductor as space electrode, or is disposed on ceramic substrate as thick membrane electrode, or is disposed the interchange electrical properties that carrys out Measurement and analysis thing on silicon matrix as membrane electrode.In the time measuring, these analytes can rest on or flow through between two electrodes, thereby can obtain that to be included in preferred frequency separation be 10 kilocycles to the interchange electrical properties of the analyte under the frequency effect of a megacycle in numerous sweep frequencies.

The measurement of applying frequency scanning can obtain the interchange electrical properties that has a type rule to two of each analyte in numerous analytes groups.After having applied the program of a discriminating type, just can differentiate the corresponding type of electrical properties of each analyte again.Through the type feature of the electrical properties of the type feature that relatively detects and known compound, just can differentiate each analyte so again.

As mentioned above, the discriminating to analyte in fluid of the present invention is to depend on to set up the corresponding numerous electrical properties that have type rule that obtain from detecting analyte.These character are special to corresponding analyte, and are to be integrated in different dimensions.The present invention just focuses on and finds the different electrical properties that there be type feature relevant from the natural speciality of these analytes like this, and these electrical properties can be measured to by a kind of technology of application simultaneously.

For example specific inductive capacity is as one of natural speciality of the compound of detected object analyte own.Specific inductive capacity is in the numerous dimensions that are used to describe this compound of compound, and specific inductive capacity can be used to discriminatory analysis thing like this.Exchanging in electricity field, specific inductive capacity can be that capacitive reactance obtains with the condensive reactance of Measurement and analysis thing.Concerning short sensor electrode, capacitive reactance is the Main Components of reactance, so reactance is a good approximate value of capacitive reactance.Can from the electrical impedance measuring, obtain in vector category internal reactance.Reactance is the one in the special electrical properties that has of analyte like this, is also in a kind of dimension, should be used for detecting by the present invention and differentiate compound (in scalar category, electric capacity is directly proportional to specific inductive capacity, and is used to detection compound.See special this academic report of Bel).

In the time that an analyte is the potpourri of gaseous compound, the specific inductive capacity of this gaseous mixture can be estimated according to several method.It is the function of temperature, gas density and gas composition: Ha Wei (Harvey, A, H) that the specific inductive capacity of the inflammable gas of for example natural mixing can be calculated as; Lei Meng (Lemmon, E, W); " estimate the specific inductive capacity of natural mixed combustible gas body ", hot physical world periodical (International Journal of Thermophysics), the 26th volume, the first phase, 31 pages to 46 pages, in January, 2005.This article author declare, their method is to be better than traditional mixing rule.In the time that analyte is the liquid of a mixing, the specific inductive capacity of mixing material can be according to triumphant Hughes-Mo Su Supreme Being (Calausius Mosotti) theory of strangling, or Olympic Competition lattice (Onsager) theory is calculated: plug (Sen, A.D.); An Nixike (Anicich, V.D.); Ai Yakai rem (Ayakeliam, T.); " specific inductive capacity of the potpourri of liquid-state silicon alkanes and hydrocarbon ", applied physics periodical, physics D (J.Phys.D; App.Phys.), the 25th volume, 516 pages to 521 pages.

From above exemplified result of study, for gaseous state and liquid chemical mixture, specific inductive capacity remains a kind of dimension of the feature that is used for describing them.The present invention can apply reactance and detect and differentiate gaseous state or the liquid chemical mixture as analyte like this.

Except specific inductive capacity, there is the composition of the chemical element of its uniqueness as the compound of analyte.And each chemical element has its corresponding electronegativity, the peculiar molecular dipole distance of each compound or polarity are so just formed.It is the another kind nature speciality of compound.In electricity field, can apply resistance measurement and reflect this feature.For example existing experimental result shows, volatile organic compounds comprises that those compounds that are rich in hydrogen and oxygen element can change the conductivity (resistivity) of metal-oxide film sensor (seeing special this report of Na Geer and Bel).And hydrogen and oxygen have corresponding larger electronegativity value.

Exchanging in electricity field, compared with the reactance of the analyte measuring, as another component resistance of analyte electrical impedance also measured obtaining simultaneously.But compared with the amplitude of resistance value, reactance occupies leading status in electrical impedance.This is because (comprise its gas, refer under anhydrous state) to be nonconducting as the compound of analyte in pure compound situation.But although resistance value is smaller, it has reflected the ohmic speciality of analyte.In other words, resistance is to reflect this compound from the dimension of another intrinsic property of compound.And the dimension of resistance is mutually orthogonal with the dimension of reactance.The information of resistance is also very important concerning discriminatory analysis thing like this.

Applying change frequency, comprising the method for frequency sweeping, what the present invention can obtain each analyte has the alternating current character of characteristic type such as resistance and reactance two groups, thereby can reach detection to corresponding analyte and the object of discriminating.

Electrical impedance is to combine resistance and reactance.In interchange electricity, can apply Ohm law obtains:

Z＝V/I [1]

Wherein Z is electrical impedance vector, and V is voltage vector, and I is current phasor.From above formula, be appreciated that the added voltage on sensor is proportional to the electrical impedance of sensor in the time of application one galvanostatic technique.In the time of application one constant voltage technology, be inversely proportional to the electrical impedance of sensor by the current value of sensor.Detect and the object of discriminatory analysis thing to reach as a kind of replacement scheme, the measurement that can adopt voltage or electric current (replacing electrical impedance) like this.

Sensor instrument system including of the present invention and method thereof in the time that analyte has enough concentration, need to not placed additional material and carry out adsorption analysis thing in sensor electrode.When the original concentration of analyte is enough, during lower than specified sensor signal to noise ratio (S/N ratio), the present invention can apply absorption or absorbing material.Thereby for improving the sensitivity of sensor and the limit of detection, optionally adsorb or absorption analysis thing.

Obviously in sensor electrode filling the dimension of the electrical properties that is relevant to analyte that obtains after sorbing material, comprise resistance and reactance, the dimension of the electrical properties obtaining while being different between sensor electrode not filling sorbing material.This be because in filling after sorbing material, this single-sensor can be recorded in the electrical properties of the special similar compound of an a kind of or class in analyte specially.And this kind or this compounds are because the Specific Interactions between itself and sorbing material is adsorbed on this material.

Thereby be appreciated that, spirit and the object of the electricity dimension relevant to the internal characteristics of analyte from searching of the present invention, even, in the time that analyte has enough concentration, the present invention also can detect and differentiate the analyte in fluid at filling sorbing material between sensor electrode.

The process that analyte is adsorbed on sorbing material surface can be accompanied by the process of absorption, or the process of absorption and absorption can occur simultaneously.Can determine according to material elements but have about the actual conditions which kind of process occurs.This factor comprised the kind of material, the quantity that is added in the material between electrode comprise material layer thickness, allow to produce the time of adsorption phenomena and the concentration of detected analyte.So the adsorption phenomena of discussing in this article also may comprise absorbing phenomenon.

The sensor apparatus that is positioned in movably an area of the present invention is a complete device.From a structural point, formed by eight modules.Comprising global geographic position location receiver module and the power module of collecting test sample block, sensor storehouse module, heating module for the temperature control of sensor storehouse, detection module, microcomputer module, transmission data module, applied global positioning system.

Detection module has comprised an Analogic Electronic Circuits unit, and it is used as a detecting device.Analogic Electronic Circuits unit has connected a connector, such as similarly being the converter (ADC) that is transformed into digital numerical value from simulation value.And then be connected to microcomputer module by converter.This microcomputer module includes home computer's structure of a micro.The module that other are all, is connected with microcomputer module by their corresponding connector if required.In addition, in microcomputer module, also settled numerous application software, included: an application software has comprised the positioning map of global geographic position; The numerous analytic approachs including the analytic approach of identification types are comprised with an application software.Sensor apparatus can be carried out in its location the electrical properties of the analyte that instant analysis detects like this, thereby differentiates the analyte in fluid.Then the result of this discriminating can be transferred to central information station.

Match with being in local sensor apparatus, present invention includes central information station.It includes the central computer being connected with a servocomputer.And one of function of servocomputer is storage data.Central station and central computer are connected with existing information transfer network.Network has also connected numerous each local information receiving stations that is distributed in different regions in a region simultaneously.Network comprised easy house network (Ethernet), at the network of an organization internal, network and the internet network (the Internet) that is connected area, the whole world in a region.This network packet contains with optical fiber, cable, plain conductor or comprises any mode in electromagnetic being wirelessly connected on.

Each local information receiving station has comprised the information being connected with antenna and has received and sent electronic unit.This unit has connected a collection unit of digital data with central processing unit (CPU).Being placed in so the local receiving station that information that the sensor apparatus in an area sends just can be positioned in identical area receives.This is because local receiving station and sensor apparatus are all followed the technical standard of same transmission information.Then under the effect of network, the information in the information of analyte and the geographic position at its place can be transferred to central information station at a distance.

Identical application software has also been installed at central information station, includes and contains global geographic position positioning map in interior application software and have the software of type identification analytic approach in interior numerous analytic approachs.The information of the original electrical properties of analyte can be in a local sensor apparatus and processes like this, also can stand in the information of receiving and processes afterwards by being in central information at a distance.

" computing machine " mentioned in this article, has comprised microcomputer module, central computer and servocomputer.According to the concept of the common approval in electromechanical engineering field, " computing machine " has its all primary element, so be including there being an all operations performance memory function.Word used herein " connection ", has comprised electric connection, and this refers to and comprises that code, data, instruction and program are that the digital electric signal of form can circulate in a device.This device has comprised sensor apparatus, local information receiving station, network and central information station connected to the network.

Sensor apparatus of the present invention and method have many novelties and unique performance and advantage concerning detection and discriminating the analyte in fluid.It can be summarized as follows: core technology single-sensor of the present invention has been applied the principle of work that has the scanning of the a-c cycle of multiple frequencies and vector analysis.In one-shot measurement, just can obtain the electrical properties that has type feature of two set of analytes like this, comprising two different electrical properties can be obtained in each frequency being scanned, as resistance and reactance.They are the bidimensional dimensions that belongs to mutually orthogonal exchanging in electricity.

Resistance and reactance are again the sweep frequency functions of (sweep time).It has described the different inherent speciality of analyte.Than the existing multisensor method that is applied in the character obtaining in one dimension time dimension and detects analyte, the present invention is applied in the character obtaining in the dimension of two orthogonal dimensions and detects analyte and have significant advantage: the present invention applies preferred frequency sweeping below 1 megacycle and facilitated making and the use of sensor apparatus; Because applying frequency scanning the present invention is not subject to use the analyte sorbing material of conduction to comprise the restriction of conductive polymer film or polymer composite in sensor design, the adsorption that therefore can apply all kinds comprises absorbing material and has adaptability widely.

Sensor apparatus of the present invention has been applied again reference sensor and has eliminated the impact of ground unrest.In addition, also applied the temperature of controlling the sensor storehouse including sensor and analyte including variable and stationary temperature control program, thereby the process of the sorption and desorption of control analysis thing is well improved detection and discriminating to analyte.In addition, instrument of the present invention has volume, easily palm Portability and the easy-to-use feature of lower cost of manufacture, compactness.

The advantage of above-described instrument of the present invention, is particularly conducive to the palm portable sensor apparatus that research and development are power supply with dc-battery.This is to cause the corresponding little sensor storehouse low power consumption required to temperature control because of the significant little volume of single-sensor.

Be appreciated that, one of major advantage of the present invention is to have applied the single-sensor with frequency sweeping and vector analysis principle of work, thereby can produce the collection of illustrative plates of two different alternating current character that have type feature to the one-shot measurement of analyte simultaneously.In the time that making sensor apparatus of the present invention will be applied a little several sensor, can easily reach the repeatability of making sensor like this.In addition, because single-sensor has significant little volume, and caused controlling the required low power consumption in small size sensor storehouse.Cause so again likely applying actually the structure of dual sensor,, except detecting sensor, also can apply the reference sensor with same structure.

After having applied dual sensor, when sample is when the analyte in fluid is with ground unrest, such as being that while having humidity ground unrest, sample can be detected by detecting sensor, and detects the fluid with ground unrest by reference sensor.Again by the relatively output of detection and reference sensor, the impact that just can remove ground unrest and fluid.Similarly, can eliminate other ground unrest, such as if be used in the aging effect of the macromolecule membrane in sensor, and cause the fluctuation of the electrical properties of detection because of temperature fluctuation.

Application dual sensor structure can also be brought the advantage of quick test.This is because the test to detecting sensor and reference sensor completes at synchronization to sample with to the test with noisy fluid.

Moreover, combining existing wireless data transmission technology, by determining the technology in geographic position after application global geographic location positioning system, with used numerous corresponding sensor apparatus that is distributed in different regions in to the research of analyte after, sensor instrument system including of the present invention and method thereof can provide the information of analyte instantaneous distribution of different regions in a region.

It must be understood that, current except the global geographic location positioning system of having set up in the U.S., worldwide, among other some GPS are being built.Like this according to one of spirit of the present invention and object: will determine the geographic position of analyte, the present invention also can apply any global geographic location positioning system, under prerequisite that can be for civilian use in this system.

Describing in detail of chapters and sections afterwards, discusses and to the request of claim and with reference to having more clearly understanding to the structure of the invention and object after accompanying drawing.

Accompanying drawing explanation

The structural drawing of the following discloses that will point out is especially only in order to illustrate rather than limitation of the present invention.Now be described below:

Fig. 1 has shown that applying principal component analysis (PCA) distinguishes the distribution plan that the analyte of five kinds of analytes distributes by major component.Resistance and the reactance numerical value of the analyte simultaneously obtaining in analysis, have been applied in each frequency of 7 frequencies.And this frequency is at random taken from the frequency that be scanned of 10 kilocycles to 500 kilocycle intervals.

Fig. 2 has shown that applying principal component analysis (PCA) distinguishes the distribution plan that the analyte of five kinds of analytes distributes by major component.Resistance and the reactance numerical value of the analyte simultaneously obtaining in analysis, have been applied in each frequency of 11 frequencies.And this frequency is at random taken from the frequency that be scanned of 500 kilocycles to 1 megacycle interval.

Fig. 3 is the schematic diagram of single-sensor, and it includes the pair of electrodes of making of metal wire rod or a capacitor of making of two sheet metals.

Fig. 4 A has shown the dual sensor structure of applying two identical sensors 1.One of them sensor is used as detecting sensor 2 (being simply denoted as: A).Another is used as reference sensor 3 (R).The dual sensor structure showing in figure does not have integrated form.

Fig. 4 B has shown the integrated dual sensor structure of applying two identical sensors 1.

Fig. 5 is the schematic diagram that a single-sensor 1 and an alternating current analyser 9 are electrically connected.

Fig. 6 has shown that any adsorption material 8 is filled between two electrodes or a capacitor.

Fig. 7 A is used for explanation and forms single-sensor schematic diagram with different structure 4.Wherein an electrode is used as the first electrode of single-sensor.The structure of another conduction is such as the wall of an object is used as the second electrode.

Fig. 7 B shown in the time that same alternating current analyser 9 connects, and the wall of conduct the second electrode in single-sensor 4 is connected with ground zero potential.

Fig. 8 is the schematic diagram of sensor instrument system including structure of the present invention, has comprised sensor apparatus and the central information station being connected with local information receiving station by network.This figure has also shown sensor apparatus transmitting information wirelessly central information station a long way off everywhere.In information, comprised the geographic position at instrument place, this geographic position with the effect of global geographic location positioning system after obtain.

Fig. 9 collects the front elevational schematic that test sample block is connected with sensor storehouse module.In figure, the top of sensor storehouse intermediate structure is removed, so can see two sensors that are placed in respectively in two sensors time storehouse.

Figure 10 has shown the transverse cross-sectional view of the sensor storehouse intermediate structure in Fig. 9.

Figure 11 is except being presented at the same structure in Fig. 9, also shown that adsorption material 8 disposed the front position in a sensor time storehouse.Adsorption material is used to be adsorbed on the analyte in fluid.Only have like this fluid can pass through to dispose the sensor electrode in this sensor time storehouse.

Figure 12 is the schematic diagram of another embodiment of sensor instrument system including of the present invention.In figure, central information station is connected with numerous local information receiving stations that are in different regions by network.Numerous like this sensor apparatus that is in different local areas can with the central information station wireless messages communication being at a distance.

Figure 13 has shown that applying principal component analysis (PCA) distinguishes the distribution plan that the analyte of three kinds of analytes distributes by major component.Resistance and the reactance numerical value of the analyte simultaneously obtaining in analysis, have been applied in each frequency of 7 frequencies.And this frequency is at random taken from the frequency that be scanned of 10 kilocycles to 500 kilocycle intervals.

specific implementation method

Although concrete enforcement of the present invention can be in following narration after with reference to accompanying drawing, must be clear and definite be that these concrete enforcements only represent a few in many kinds of concrete manifestations of the spiritual and object of the present invention.Numerous is apparent to this concrete distortion of implementing and improvement for having the people of same ken.These distortion and improvement are all related with the present invention, thereby these distortion and improvement are all confirmed to be and are included among the expressed spiritual object of the claim of the present patent application and imagination.

Sensor instrument system including of the present invention and method are applicable to detect and differentiate the analyte in fluid in each department in a region.The present invention has three objects.Shown in Fig. 3 and Fig. 5, first object is to have followed the single-sensor 1 by the invention theory of single-sensor with two electrodes.This kind of sensor can be used to effectively differentiate the numerous analytes in fluid.And this kind of discriminating to be multiple electrical properties by detecting these analytes reach, this is because these electrical properties and unique physics of analyte, chemical feature, such as specific inductive capacity, electronegativity, polarity or dipole moment are relevant.

First object of the present invention is that the method for applying again electric vector analysis after to the scanning of the single-sensor that contains analyte by application ac frequency realizes.The scanning of implementing electric frequency can connect the single-sensor 1 that contains analyte by the analyser 9 with an alternating current and complete.The present invention just can obtain two groups of electrical properties that have about analyte internal characteristics with respect to numerous sweep frequencies of analyte in one-shot measurement like this, and can in the frequency of each scanning, obtain these two kinds of different electrical properties.Measure after multiple analytes by such structure, then the program of applying a discriminating type is analyzed the data of the electrical properties of these obtained analytes.This just can identify the special type of each analyte electrical properties, its correspondence the specific type of corresponding analyte.Then by the type of having differentiated of each analyte, compare with the type of known substance, thereby can differentiate each analyte.Known, first object has embodied core technology of the present invention.

Second object of the present invention has been to provide a kind of structure of sensor and the method for sensing.The ground unrest that it can be used to eliminate sensor, comprise humidity in test sample impact, be applied in the aging effect of the macromolecular material in single-sensor and the fluctuation of the electrical properties of the tested analyte that caused by temperature fluctuation.

Shown in Fig. 4 A and 4B, second object is that the structure of having applied dual sensor reaches.This structure includes two 1, one identical of sensors and is used as detecting sensor 2, and another is used as reference sensor 3.The making of this dual sensor can be followed two schemes, the scheme 13 of first integral structure, and it two is schemes 12 of the absolute construction of two separation.Dual sensor scheme of the present invention also can be used to detect a kind of compound of obtaining or the electrical properties of multiple similar compound when analyte is a chemical mixture, thereby reaches the object of this analyte of discriminating.The scheme of this dual sensor can be used for detecting the relevant mark compound biochemical marker of one or more and organ disease in a biological sample especially in the time of medical diagnosis.

Must be clear and definite, the actuality of applying this dual sensor structure comes from special benefits of the present invention: the information that has type rule that has the single-sensor of small size and its and can obtain two serial analytes in test once.

The 3rd object of the present invention is in core technology of the present invention, to have engaged current existing wireless communication technique and global physical location location technology forms a sensor instrument system including.This system by a central information station and with its away from the numerous identical sensor apparatus that is distributed in different regions, region formed.Each identical sensor apparatus includes a detection module, a global geographic position location receiver module and a transmission data module.This central information station is connected with global information network.And this network has also connected numerous identical local information receiving stations.These numerous receiving stations are distributed in the corresponding area distributing with numerous instruments.Be in like this regional information receiving station that a regional sensor apparatus can be transferred to the information wireless in the geographic position at the information of the analyte detecting and this analyte place one correspondence.Then the information in the geographic position of the information synergism analyte of the electrical properties of analyte is differentiated after can being received by central information station again.Apply system of the present invention and can detect simultaneously and differentiate all analytes that are in different regions in the same area, thereby can obtain the instantaneous distribution plan of the analyte in this region.

Of the present inventionly two parts are openly comprised.Part I discloses core technology of the present invention: i.e. single-sensor and the a-c cycle scanning having and the principle of work of vector analysis method.Part II openly combines existing wireless information transfer and the global geographic position of this core technology and locates the sensor instrument system including of the present invention forming after reception technique.

In sensor instrument system including of the present invention and the method that comprises thereof, analyte is defined as a compound of numerous same moleculars.This analyte also can be defined as a kind of special chemical mixture being made up of different compounds.In this kind of potpourri, each compound all has numerous identical molecules, that a kind of potpourri of for example coffee smell representative.Analyte can not have smell, for resembling hydrogen.And for example resemble the potpourri of the inflammable gas that is used as coal gas that industry makes, and in this kind of potpourri, be not added gas odorous.Analyte also can scent of.As if compound acetic acid, or as if containing sewage odorous.One analyte group refers to analyzed numerous different compound, or numerous different chemical mixtures.This analyte or analyte group can be gaseous state or liquid.

Studying interested analyte group with the present invention haply can derive from following all: the material (including for example hemp) that contains violated thing, relevant with environmental protection (includes and for example monitors air, water, pollutant with soil, as if the ozone containing in the air of earth's surface), (such as the biological sample that include oral cavity smell) relevant including medical diagnosis with medical care, comprise with scientific research (such as resembling the quality of air in research spaceship) that space research interest is relevant, relevant with the interest of each industry, comprise that food industry (as includes meat, the detection of fish freshness), beverage industry (such as the odor detection including lemon beverage), agro-industry (such as including the detection of the degree of ripeness to fruit), chemical industry (such as including the monitoring that hydrogen chloride gas is produced), petroleum industry (such as the detection including combustible gas leakage), plastics industry (such as the control including production run and product quality), building industry (such as the monitoring including the air quality in New Dwelling), medical industry (such as including the research and development of new medicine), auto industry (such as the supervision including lubricating oil and various liquid), biochemical industry (such as including the synthetic of biochemical article by enzymic catalytic reaction), with transportation industry (such as including the monitoring of the waste gas to discharge), relevant with daily life, such as including perfume, cosmetics, wine, and spices, for safety consider (such as including explosive, set on fire, and the investigation of the liquid of leakage on road surface), with (such as be used as the chemical substance of weapon) relevant with military affairs.

Fluid in this article refers to gaseous state or liquid background compound, and it is not the interest place of research.Fluid is for analyte or the analyte group of lodging.Under a pure state, analyte itself can be used as fluid.In the time of analyte and fluid mixing all-in-one-piece state, fluid can be a kind of compound, or a kind of chemical mixture.For example, in research when air pollutants, the air that itself is chemical mixture is as the fluid multiple gaseous contaminant of lodging.And for example in gas chromatography, be the multiple compounds in gas chromatographic column that transports separated as fluid as the hydrogen of carrier gas or helium or nitrogen.This multiple compounds has formed the initial chemical mixture as analyte in chromatographic column that is injected into.

Fluid group refers to numerous different compounds, or numerous different chemical mixture.For example research numerous patients by the caused halitosis of odontopathy time, sulfuretted hydrogen as a kind of biochemical marker be research interest place analyte.Its halitosis to numerous patients is common.Obviously except sulfuretted hydrogen symbolic gas, what in patient's oral cavity gas, also have other is not the gas of research interest.Those gases are fluid.But the composition of this kind of fluid because of different patients different.For example in fluid, have by patient and breathe the carbon dioxide causing and the oxygen not consuming.Their corresponding number percent is that the patient's corresponding with it health condition comprises that the function of lung is relevant with the function of hematological system.The sample of all like this patients' the oral cavity gas detecting, has identical symbolic gas and different fluid.In this case, just draw into a kind of sample sets of the present disclosure, can be referred to as: a kind of analyte in fluid group.

Analogize according to above-mentioned example, the numerous patients of research suffer from numerous Different Organs diseases as the oral cavity gas sample of pneumonia, ephritis and enteritis time, this sample packages contains the different symbolic gas relevant with research in numerous different fluid.This situation is referred to as: the analyte group in fluid group.

Contrary with above-mentioned situation, there is another kind of sample group to be: the analyte group in a fluid.For example an identical carrier gas (or liquid) is held different compounds as continuous fluid.These compounds be in the detachment process of gas phase (or liquid phase) chromatogram by an initial analyte, one chemical mixture separate form.It must be understood that, the analyte group's in a fluid who produces in chromatographic process sample is a special case.Separate the numerous different compound in this potpourri just because of the detachment process of chromatogram, made these compound sequentialities ground, be respectively contained in the identical fluid in chromatographic column.Another sample is the air pollution case from a region.In this case, in the same air in whole region, hold corresponding to the different pollutant in different regions in region.

But it must be understood that, as on the whole, there is the differentiation of the sample sets of analyte group, the analyte group in single fluid and the single analyte in fluid group in fluid group, but no matter be which kind of sample sets, in the step of the sequentiality of testing process, each sample must be to be detected by sensor apparatus individually.So, in the moment of a test, always there is the situation of an analyte in a kind of fluid.

As everyone knows, compound has the specific inductive capacity of feature corresponding thereto.Each compound includes again number of chemical element.And various elements have the electronegativity of characteristic of correspondence.In addition, on molecular level, each compound has unique molecular structure, size, weight, shape and dipole moment including symmetry.These key elements have determined the feature as the physics and chemistry of each compound of analyte.Also just affect each compound or chemical mixture simultaneously and made mutually the process of the sorption and desorption of used time with sensor electrode.

When these analytes are in the time being encouraged by an ac signal that has a frequency, the feature of their physics and chemistry can exchange electrical properties with some and describe: such as electric current, voltage, electrical impedance Z and its phase sensitivity element comprising: reactance X, resistance R and phase theta (runic is expressed as vector here).This ac-excited signal refers to that one has sine-shaped alternating voltage or electric current.

As shown in Figure 5, these exchange electrical properties and can connect single-sensor 1 by the analyser 9 of application one electrical impedance analytical instrument or other known alternating currents and obtain.This single-sensor has the simplest form, be pair of metal conductor as a pair of space electrode, or pair of metal plate is as a space electric capacity.This also can be placed on and on ceramic substrate or on silicon matrix, form corresponding thick membrane electrode or membrane electrode electrode.When the analyte in a fluid is to be placed on or by between two electrodes of single-sensor, or between two battery lead plates of electric capacity time, the interchange electrical properties of analyte just can be detected.

In plural system, electrical impedance can be described to:

Z＝R+X [2]

Phase theta can be calculated by the numerical value of resistance R and reactance X.

The reactance X of sensor of the present invention combines capacitive reactance X _cwith induction reactance X _l.They can be described to respectively:

X _C＝j(-1/2πf C) [3]

X _L＝j(2πf L) [4]

Wherein C is electric capacity, and it is proportional to the specific inductive capacity that is in one medium between two electrodes.L is the inductance of electrode.For application short electrode in the present invention, the numerical value of electric capacity is much larger than inductance.So reactance presents capacitive reactance substantially.Like this, reactance is a good approximate representation of capacitive reactance.

If in the time of the analyte having between electrode in a fluid, reactance is X (2).If only have this fluid between electrode time, reactance is X (1), and their difference DELTA X is:

ΔX＝X(2)-X(1) [5]

It is the change of reactance, is because of the contribution of disposing the analyte between electrode.

Because analyte determined by its specific inductive capacity at interelectrode electric capacity, and capacitive reactance is the main contributions person's of reactance cause, so reactance can be used to detect and differentiate this analyte.This means that reactance provides the information of the finger-print type of each compound or chemical combination potpourri.In one-shot measurement, as applied the method for the frequency that changes AC signal, the present invention just can construct a reactance spectrogram and be recorded in the inherent chemical feature of this analyte in each frequency.This reactance spectrogram has just comprised the interchange electrical properties that has type rule of a series of these analytes like this.

As everyone knows, analyte can be attracted to by the mechanism of chemisorption and physisorption the surface of test component.This mechanism has caused diffusion process and the dynamics of analyte on device surface of complicated analyte.Or the surface resistance of the device having been affected by analyte, so this resistance is the significant characterization of molecules that combines analyte.For example, while metal-oxide film sensor being exposed in volatile organic compound, comprise that those compounds that are rich in hydrogen and oxygen element have changed the conductivity of this sensor (seeing Na Geer and Bel Te Siwen chapter) significantly.

Because each chemical element of analyte, such as oxygen, hydrogen, nitrogen and carbon, has its determined electronegative numerical value, Yin Er has facilitated polarity or the dipole moment of this analyte.The experimental fact that conductivity (resistivity) changes has like this pointed out resistance can be used to record this as the chemical speciality of the analyte inherence of polarity or dipole moment.

In above-mentioned application one-shot measurement of the present invention, except the reactance information of a series of analyte that obtains, the information of the resistance of a series of analyte is in addition also simultaneously available.Like this, than reactance change form, in each frequency, the change Δ R of resistance can confirm as:

ΔR＝R(2)-R(1) [6]

Wherein R (1) is the resistance of the sensor while not containing any analyte in fluid.R (2) is the sensor resistance while containing analyte in fluid.The change of known resistance is the contribution because of analyte.

The relatively resistance of an analyte and the reactance size to electrical impedance contribution, known reactance accounts for leading status in electrical impedance.This is that the analyte in fluid is nonconducting because under anhydrous state, thereby the dimension axle of electrical impedance vector deflection reactance.Secondly, phasing degree θ can be calculated and be obtained by resistance R and reactance X, also just can obtain the change of phase place and the change of electrical impedance.Combine like this information that in each frequency resistance changes Δ R and reactance and change Δ X, or they one of with the information of phase change Δ θ, or the change of electrical impedance, just can be built into a curve map.Wherein comprise with respect to the change of the scanned multifrequency resistance of crowd, change, the change of phase place or the corresponding curve of the change of electrical impedance of reactance.This each curve has shown unique inherent chemical speciality of analyte.

In the research of common this curve of analysis, can first study this and recorded the curve of analyte speciality, comprise and compare at the curve of the existing known analyte of lane database.Like this, the similarity of analyte electrical properties and known sample or dissimilarity or type probably can by this Direct Analysis curvilinear characteristic by way of and differentiated.

Continuing to use the numerous analyte of above-mentioned program can be detected one by one.So just obtain the curve map of the interchange electrical properties that has type rule of numerous each analytes of correspondence.

Except the curve of above-mentioned drafting, it,, as outside the mode that has a kind of continuous type of electrical properties of type rule to express analyte, also has the mode that the discrete type of this character is expressed.As the mode of expressing with the matrix that builds this analyte feature electrical properties.

This matrix has the perpendicular hurdle of even number.Adjacent every two perpendicular hurdles are used to be filled in the corresponding electrical properties of the analyte obtaining in same frequency, such as resistance and reactance.Under this structure, the perpendicular column number that this matrix is maximum is the number (look into analytical instrument and have the technical stipulation about the sweep frequency number of record) that doubles the frequency of scanning; Or the number on this perpendicular hurdle can be decided by the number of random frequency of taking out from scanned frequency; Or can be decided by the number of the specific frequency of choosing.One horizontal bar of this matrix is for inserting the electrical properties with respect to each analyte is detected in selected frequency.Obviously, same analyte can be measured over and over again in once testing.In matrix, just have like this to should analyte measured multiple horizontal bars repeatedly.

According to above-mentioned step, can set up a matrix that has comprised numerous analyte electrical properties.As supposed, each analyte is only once measured, and each horizontal bar of this matrix has represented the electrical properties of each analyte with respect to selected frequency.

Because the change of interchange electrical properties of analyte and the relation of sweep frequency are non-linear, so difference that the electrical properties of the feature of the tested analyte of login in above-mentioned matrix changes, can apply numerous analytic approachs and comprise that multivariate element analytic approach (Multivariate) analyzes, such multivariate element analytic approach has comprised the analytic approach that type is differentiated.Applied the above-mentioned analytic approach including type is differentiated the matrix of showing numerous analyte electrical properties is analyzed, the feature of various analytes comprises that their type can easily be identified.This easiness be compare with above-mentioned attempt by more various analytes directly perceived corresponding curve draw the difficulty of their corresponding type.

Like this, then the type of the electrical properties of the analyte obtaining is compared with the type of the electrical properties of the numerous known substances in built database, this analyte just can be identified.

Be understandable that, although the interval of the preferred sweep frequency of the present invention between 10 kilocycles and 1 megacycle, according to spirit of the present invention and object, other the frequency that is different from this optimized frequency also can be employed.But apply this preferred frequency, not only can discriminatory analysis thing but also increased the convenience in the time of Instrument Design and practical application.

In the design of sensor of the present invention, do not need given application conductive polymer film or other conduction sorbing materials to detect or differentiate the numerous analytes that contain enough concentration.This is because the pumping signal of alternating current can in vacuo be propagated, so it can cross over the spatial domain that does not have conductive materials between two electrodes.This structure of the present invention is extremely suitable for being used as the detecting device and the detection method that comprise gas chromatography and liquid chromatography.This is because each compound in potpourri is under the centrifugation of chromatogram, is separated one by one and concentrates gradually, thereby just created the Fundamentals that each compound can be detected respectively in chromatographic column.New detecting device and the method for the present invention not only can provide the information of the quantity of analyte after application single-frequency like this, and after having applied multiple sweep frequencies, can provide to differentiate it is the information of which kind of analyte.In addition, apply this detecting device and detection method and can not damage sample in the time detecting sample, this is another advantage of the present invention.

As shown in Figure 6, because ac signal can propagate in a vacuum, so the present invention can use absorption any conduction or nonconducting or absorbing material 8.Detect again afterwards this analyte by the step that concentrates or be optionally concentrated in the analyte of content rareness in fluid.Because this speciality, the present invention can be utilized numerous existing and develop perfect technology and concentrate and be concentrated in selectively chemical marker or the mark group in analyte, thereby reach high sensitivity and the selectivity of sensor.

This class technology be usually directed to apply macromolecule material film, macromolecular material and inorganic material compound substance, the compound substance that contains platinum metal-type metallic particles, be applied in Gas Phase Adsorption chromatogram as the solid mineral material of stationary phase fraction and be applied in the macromolecular material of the stationary phase fraction in the chromatographic column that is used for making filled type chromatographic column and capillary type in gas phase distribute type chromatogram.

For example hydrogen is a kind of important gas being applied in numerous industry.For the purpose of using hydrogen completely, detect and differentiate that hydrogen is particularly crucial.The present invention can apply and contains metallic palladium particles and concentrated after hydrogen selectively by compound substance organic or that inorganic filling material forms for this reason, then carrys out the method to its measurement.This design has utilized hydrogen in Metal Palladium, to have the feature of great solubleness, as can absorbing, Metal Palladium holds up to 900 times of hydrogen to own vol (chemistry and physics handbook: Hand Book of Chemistry and Physics, CPC publishing house, the 24th edition, 4-12 page, 1993 to 1994 versions).Because this cause, palladium metal is referred to as " trap of hydrogen " conventionally.Again because can not be subject to the detection of analyte the restriction whether sorbing material conducts electricity, so the present invention has great dirigibility, can decide the ratio that contains palladium particle in composite adsorbing material according to the variable concentrations of hydrogen in fluid, comprise the shape of particle.After having tackled the hydrogen in fluid, detect the hydrogen in fluid.

In addition, Metal Palladium is one of metal in platinum group.Platinum group is made up of ruthenium, Rhodium, palladium, osmium, iridium and platinum.They have the similar character including the physics and chemistry to the solubleness of hydrogen (chemistry and physics handbook, the 24th edition, 4-15 page is to 4-12 page).Like this, each metal in platinum group is all suitable and can be applied among the present invention.

Gas Phase Adsorption chromatographic applications solid particle optionally adsorbs various gas as stationary phase material.Solid particle has comprised numerous different solid mineral materials.Wherein most often molecular sieve, silica gel, aluminium oxide, glass, cavernous carbon granules and calcium carbonate.In addition, the carbon granule of fluoridizing is also suitable, and such as tetrafluoroethylene macromolecule material particle, (the above-mentioned application of setting forth this type of material is seen everywhere, and comprises bohr and bohr: Poole, C.F.and Poole, S.K.; Today chromatogram: Chromatography Today, 199 pages to 209 pages, Ai Er Seville Science Press: Elsevier Scientific Publisher, 1991 and the document wherein quoted).

For example molecular sieve is a kind of material that contains accurate dimension and be uniformly distributed micropore.In molecular sieve making process, can control and generate this kind of micropore.Molecular sieve is by widely cognitive and be applied to adsorbed gas and liquid.Between molecular sieve and absorbate, there is strong physical action.It can carry out separate analytes according to the size of analyte molecule, configuration, polarity and unsaturation.For example molecular sieve is easy to adsorb carbon monoxide and surpasses in absorption helium, and can preferentially adsorb the polar molecule or the asymmetric molecule that comprise aerobic, sulphur, chlorine and nitrogen element.Molecular sieve can adsorb and retain water and carbon dioxide effectively, and catches the unsaturated hydrocarbon compounds such as ethene and propylene.

Resolve in the detachment process of chromatogram in gas phase, the separation of the each compound in a mixture be according to the vapor pressure of each compound and its be used as being optionally used between the macromolecular material of the fixing phase in chromatographic column and carry out.In filled type chromatographic column, this stationary phase material is coated over the surface of solid filling particle.In the chromatographic column of capillary type, this stationary phase material is the inside surface that is coated in capillary hollow post.

As will be understood above-mentioned selectively acting in the degree of molecular action, this kind of effect is that building is on the intermolecular effect between each compound and the stationary phase material as analyte, such as dispersion force, induction force, dipole-dipole force and the acting force between donor and acceptor.In order to help to understand above-mentioned mechanism, the metaphor of one " alike and mix " is approximately the result that contributes to understand this intermolecular interaction.Selectivity is one of this interactional result, and it comes from the similarity of certain compounds and chromatographic column fixed phase material and causes.For example polarity is the character of a feature for compound.It can be used to describe this alike property: the compound of polarity tends to the stationary phase material for chromatographic column of polarity; And nonpolar compound trends towards nonpolar stationary phase material.

According to the above-mentioned principle representing with metaphor, can use a kind of stationary phase material and reach the object of dividing selectively molten certain compounds.The polarity of this fixing phase is the polarity that approaches or mate corresponding compound.Such as polymer siloxane is a kind of non-polar polymeric material.It is widely used as the host material into chromatographic column fixed phase most.This is to change because its chemical constitution is easy to derived reaction, and for example, by methyl, vinyl, phenyl, two phenyl, 3,3,3-tri-fluoridizes propyl group, 21 cyanoethyls or a cyanogen propyl group and changes.Thereby the polarity of the change polymer siloxane of leading: from nonpolar to polarity.This kind of derivatization reaction be well-known (bohr and bohr, today chromatogram, chapter 2, and the list of references wherein quoted; Western Buddhist: Hyver, volume is seized; The mulberry rank of nobility: Sandra, author is invited; High resolving power gas chromatograph: High Resolution Chromatography, 2-1 page is to 2-16 page, the 3rd original text, Xi Laite-Pan Kate company: Hewlett-Packard, 1989, and the list of references of wherein quoting).With regard to the similarity of polarity, the polymer siloxane macromolecule that has changed polarity via specific derivatization reaction is applicable to being permitted accordingly eurypalynous compound like this.

Be below all derivants of well-known siloxane polymer, it is often used to and optionally divides the classes of compounds being dissolved in fluid.

1, contain 100% pair of methyl polymer siloxane, for numerous analytes, comprising: two phenyl polymer of solvent, petrochemical industry goods fuel, oils, hydrocarbon, medicine, seasoning thing, spices, sulfocompound and chlorination.

2, contain 5% pair of phenyl and 95% methyl or contain 35% pair of phenyl and 65% methyl or contain 14% cyanogen propyl group and 86% methyl polymer siloxane, for the biphenyl of analysis of analytes including the hydrocarbon of pesticide, aromatic hydrocarbon, multiple chlorination, saturated oxygen compound, aminated compounds, aromatics oil, pharmaceutical compound, the compound herbicide that comprises to the influential compound of environment and Nitrogen element.

3, the polymer siloxane that contains 20% pair of phenyl and 80% pair of methyl, includes aromatic compounds and the alcoholic drink compounds of seasoning effect for detection of analyte.

4, the polymer siloxane that contains 50% phenyl and 50% methyl or three and fluoridize propyl group methyl, comprises the influential compound of environment, solvent, ketone compounds, drugs compounds, steroids and halogen-containing compound for detection of analyte.

The polymer siloxane of the two methyl that 5, contain two phenyl of 65% and 35%, includes phenol compound and fatty acid compound for detection of analyte.

6, the polymer siloxane that contains 50% cyanopropyl methyl and 50% phenyl methyl, comprises carbohydrates and natural steroid compound for detection of analyte.

It must be noted that, the derivative siloxane high molecular polymer of above elaboration can optionally act on multiple target compound including aminated compounds mutually.And amine comprises that derivative aminated compounds is as confessed biochemical marker in patient's pathology sample comprises oral cavity smell sample in numerous researchers' the research report for diagnosis various diseases.Oneself is listed in the result of study of above-mentioned part in Lewis's 333 patents.For shortening length disclosed by the invention, show the result of study that those are enumerated and be all incorporated in of the present invention disclosing.

Except above-mentioned siloxane high molecular polymer with and derivant, between the phenylethanol polymkeric substance, the ester of phthalic acid that connect of position, the polymkeric substance of ester, such as similarly being that polymerization ethanol and the liquid organic salt of polymerization glycol and so on is all polymkeric substance conventional in gas chromatography.It is used to the Compound Phase effect similar with its polarity.For example polymerization glycol is the fixing phase of polarity, and it can be used to analyze acid, alcohol, acetaldehyde, acrylates, ketonates, aromaticity oil plant, glycol and solvent based compound.Liquid organic salt is also polarity, is conventionally composed of by organic ammonium or organophosphorus positive ion and protophilic negative ion.This kind of ion ratio sulfate root in this way, or the negative ion of inorganic salts, as if halide ion and nitrate radical ion.The example of liquid organic salt just like tetrabutyl ammonium sulfate and tetrabutyl nitric acid phosphorus (bohr and bohr, today chromatogram, 114 pages to 118 pages, and the document of wherein quoting; Western Buddhist and the mulberry rank of nobility, high resolving power gas chromatograph, 2-9 page).

High molecular polymer including above-mentioned macromolecular material is to be painted on solid to support the outside surface of particle while being used in filled type chromatographic column, or is the inside surface that is painted on hollow pipe column while being used in hollow capillary chromatographic column.But, before implementing coating step, solid is supported particle surface or is a common well-known step to the depolarization of hollow chromatographic column inside surface.Implementing this step is in order to keep or to strengthen the wellability of coated article surface to macromolecular material, thus desirable uniform surface coating.

Generally speaking, depolarization is that the silanol of solid surface is changed into silicon ether through chemical reaction.This chemical reaction has been applied the two chlorinated silane (DMCS) of two methyl, [dimethyl-(trimethyl silyl amino) silicyl] methane (hexamethyldisilazane), trimethyl chlorinated silane (TMCS) or has been formed or also can use the two methyl chlorinated silane (octadecyldimethylchlorosilane) of 18 ring (Bohr and bohr, today chromatogram) by above-mentioned chemical agent combination.

In the making of gas chromatographic column, solid is supported to the modification of particle surface and open hole capillary column inside surface and forms with being connected of high polymer material chemical key to be also conventional means.Scheme relates to a surface for simple function group or multi-functional alkyl or cyclic silane reagent and elemental silicon or diatomaceous support particle, or the chemical reaction of the hollow chromatographic column inside surface made of fused quartz.In reaction, the connection of high molecular polymer may produce high molecular polymer and solid and supports being connected of the surface of particle or the firmly chemical bond of chromatographic column inside surface by form the chemical bond of silane key and macromolecular polymerization reaction simultaneously.

Another kind of scheme is that the surface of support particle or the inside surface of chromatographic column that oneself is coated with to macromolecular material have been applied the cross-linking polymerization of the free-radical generating of being brought out by superoxide or ozone and formed fixing siloxane polymer.The siloxane polymer of for example making middle polarity is to have applied the siloxane of the vinyl that contains varying number, tolyl, octyl group and promoted to have formed crosslinked polymkeric substance (bohr and bohr, today chromatogram, 122 pages to 127 pages, 132 pages to 152 pages).

The present invention can apply above-mentioned successful prior art and processes the corresponding single-sensor being made up of ceramic substrate or silicon matrix like this thick film or thin-film electro pole plate surface, or be used in the surface of the solid support particle on space electrode, the coating of the macromolecule membrane of agreeing.

The technology of application single-sensor and ac frequency scanning, the present invention not only can obtain the electrical properties with type feature of analyte, and can in sensor design, obtain the distinguished advantage including undersized sensor and sensor storehouse.And this undersized sensor and sensor storehouse make the present invention in fact in sensor production, particularly, in the time manufacturing the palm type electronic nose instrument being driven by battery power, can apply the structure of dual sensor.

In dual sensor organization plan, the present invention has applied two identical sensors, and one of them is used as detecting sensor, and another is used as reference sensor.Work as ground unrest, when resembling humidity and so on and have influence on the serviceability of detecting sensor, detected by detecting sensor with the analyte being in fluid of ground unrest, and detected by reference sensor with the fluid of ground unrest.And then deducting the processing that is obtained electrical properties by reference sensor by the electrical properties being obtained by detecting sensor, ground unrest comprises that the impact of humidity just can be excluded.So just guarantee can not obtain the information of the wrong analyte that contains ground unrest.

One of application of dual sensor is particularly conducive to the medical diagnosis of the loss mode of operation to patient, such as if in patient's ear and the diagnosis of mouth disease.In such diagnosis, the characteristic gas potpourri being produced by the bacterium that causes disease, be the analyte of Electronic Nose instrument, covered by the humidity in the breathing gas sample of oral cavity, this is because cause the concentration of the moisture of humidity to be normally greater than significantly the concentration of analyte.Apply dual sensor structure of the present invention and just can in the time detecting oral cavity gas sample, remove the impact of humidity on analyte.

In the gas sample of detection patient oral cavity, application includes the dual sensor structure of eliminating moisture effect, the present invention can also have by detection selectively and numerous diseases the gaseous compound of the corresponding biochemical object of conduct of corresponding relation, or compound group is that biochemical object group fast and effeciently diagnoses the illness.The strategy of applying this medical diagnosis is the corresponding relation that is to set up biochemical object (group) and relevant disease.In this research, analyte is a chemical mixture normally.In numerous compounds of this potpourri, including one is biochemical object group with multiple biochemical objects.Application dual sensor strategy is in the time detecting biochemical object (group), and available detecting sensor removes to detect the sample with the analyte in fluid of ground unrest.Go to detect the analyte in fluid that is comprised in same ground unrest with reference sensor in addition, but now in analyte, do not contain this biochemistry object (group).This has utilized suitable sorbing material to come selectively hurdle and has cut this biochemistry object (group) and cause (seeing Figure 11) before reference sensor.This hurdle cut before reference sensor detects and completes.Then electrical properties detecting sensor being obtained deducts and on reference sensor, obtains electrical properties, just can obtain the electrical properties of this biochemistry object (group).

Below enumerate the biochemical object corresponding with known organ disease for medical diagnosis:

(1) corresponding to the methyl amine of kidney and liver disease.See the American National Standard of news report of " biochemical drug ": BioMed on the 25th February in 2008 and technical institute and the result of study the researchist of the University of Colorado of U.S. baud city (Boulder)." biochemical drug " be one on the internet at line mechanism.

(2) ruin relevant ammonium and Trimethylamine with kidney.It is reported in respectively " biochemical drug ", and " chemistry and Engineering News Record ": Chemical & Engineering News have about the Pittsburg world holding in U.S. Pittsburg for 2004 analyze and the periodical of the special topic introduction of spectrochemistry annual meeting on.

(3) acetone relevant with diabetes.Be reported in respectively " biochemical medicine ", and " modern science " of publishing in January, 2008: Current Science, the 94th volume, No. 2.

(4) comprise with respiratory disease the nitrogen monoxide that asthma is relevant with tuberculosis.Be reported in " biochemical medicine ", the people such as and Charltons: Choi are reported in " for the biological study of nursing ": Biological Research for Nursing, the 7th volume, No. 4,241 pages to 255 pages, 2006, and Fo Manike: the people such as Formanek are reported in " respiratory system ": Respiratory Journal, 2002,19 phases, 487 pages to 491 pages.

(5) ammonium relevant with blood urine nitrogen disease.By that La Ximuha: it is upper that the people such as Narasimhan are published in NAS's journal: PNAS, April 10 calendar year 2001, the 98th volume, No. 8,4917 pages to 4921 pages.

(6) pentane relevant with enteritis.By Ke Hasaka: the people such as Kohoszka are published in " intestinal disease ": Diseases of the Colon & Rectum, the 36th volume, No. 6,597 pages to 602 pages, in June, 1993.

(7) carbonyl sulfide relevant with lung qi bubble fiberization: cysticfibrosis.By Ou Fang branch school, University of California: UC, the press room newpapers and periodicals report of Irvine, on October 17th, 2005.This result of study is also reported in the online bulletin of NAS, in October, 2005.

(8) iso pentane two floride relevant with cholesterol disease.By Jie Kebi: Jacoby report to Pittsburg annual meeting in 2004 on " chemistry and Engineering News Record ".

(9) with the Cancer-Related six carbon alkane of lung, methyl five carbon alkane and the aniline including contraposition toluidine.By O 'Neill: the people such as O ' Neil are reported in " medical clinic chemistry ": Clinical Chemistry, 34 phases, 1988 years, the 1613rd page.

Meanwhile, have been reported the physiological basis to some biochemical objects.For example acetaldehyde is the product of alcohol metabolism; The decarboxylic reaction of acetacetate has produced acetone; The metabolism of protein has caused the generation of ammonia; Reaction by heme oxygenase catalysis has produced carbon monoxide; Carbonyl sulfide, sulfuration two carbonyls, ethanol, hydrogen and methane are the products of intestinal bacterium; The peroxidation of lipides has produced ethane and pentane; The metabolic product of lipid is hydrocarbon; Iso pentane two floride derives from the biosynthesizing of cholesterol; Methyl mercaptan is the product of methyl mercaptan metabolism; The metabolism of fruit has produced methyl alcohol; Methylamine derives from the metabolism of protein; Derive from reaction of formation (the Li Si ratio: Risby, T.H. by the catalysis of nitrogen monoxide biosynthesizing institute with nitrogen monoxide; Suhl lattice: Solga, S.F.; Applied physics B:Appl.Phys.B, the 85th volume, 421 pages to 426 pages, 2006).

Multiple biochemical object is for the chemical examination of medical clinic in addition.For example acetic acid esters, glycosyl uride are used for detecting the fringe time of you effect: orocecal of Continental Europe fork clip; Amino pyrene, caffeine, erythromycin, N-acetyl-anisidine and galactose etc. are used for testing liver function; Glucose is used for detecting the degree that produces insulin that hinders; Ketoisocaproic acid and methionine are as the function that detects hepatic mitochondria; Olein is as detecting fatty malabsorption; Uracil is used for testing the activity of dihydro-pyrimidin deoxidation hydrogen enzyme; With urea as catching as inner: the test of H.Pylori inflammation (Li Si than and Suhl lattice).

Must be clear and definite, biochemical object exists in the urine of sufferer, ight soil, serum, blood and saliva sample simultaneously.The strategy that the present invention includes like this dual sensor also can be used to detect the gas that these samples come out and reach the object of medical diagnosis.

Oral cavity gaseous sample has report to be used to diagnose of trends of mammary gland (Ai Erfolazi: Alvarez, american fox news: Fox News, the result of study of the University of Michigan--Ann Arbor reporting on February 28th, 2008 recently; Du flutters inferior: Dobson, " the online mail " of Britain: Mail Online Internet enterprises, the result of the London's Imperial College reporting on June 5th, 2008).

Except being used to medical diagnosis, oral cavity breathing gas sample is also used to monitoring anesthetic content in patient's body in operation.This is in the gaseous sample of oral cavity, to have anesthetic Propofol: Propofol and two metabolins (people: the Harrison such as Harrison, the G.R. relevant with it in view of once finding; Anesthesia institute periodical of Britain: British Journal of Anaesthesia, the 91st volume in 2003, No. 6,797 pages to 799 pages).

In medical diagnosis field, the body odour that how to utilize the mankind is also a problem receiving much concern.For example find there is the compound Sai Qie Fo Ruiniya of family: Schizophrenia from the taste of one or two people's a kind of special epidermis after testing (people: the Smith such as Smith, K.; Science: Science, 969,166 phases, 398 pages).So at present by applying electronic nose instrument to the research of skin smell comprised detection to this compound (the people such as that special youngster: Di Natale, C.; Sensor and drive mechanism B:Sensors and Actuators B, 2000, No. 65,216 pages).

Except applying the sample detecting at random, the method and apparatus of collecting in advance gaseous state sample is also already by cognitive (special resistance to people: the Gardiner that waits of loud, high-pitched sound, the disease in virgin child period: Archives of Disease in Childhood, 1981 years, 56,125 pages to 127 pages).The present invention also just can be used to human body body odour like this.In detection, can use to detect at random, or the sample of the patient's body odor being collected into.Comprise the sample of the body odour that those foots from human body, oxter and thigh root collect, this is the generation that causes disease because bacterium is most likely at that those positions are assembled.

Structure at application dual sensor is come in the impact of correcting background noise, and except humidity, the present invention can also be used to compensate other ground unrest.Fluctuate such as the aging effect of macromolecule membrane and the electrical properties that caused by temperature fluctuation.Accuracy and the accuracy of the electrical properties of analyte are so just guaranteed to detect.

The sorption and desorption process of analyte can be subject to the impact of temperature.In gas chromatography, often adopt temperature controlled program, comprise that the control program of thermograde separates the various compounds in a chemical mixture effectively.Because the little volume that single-sensor of the present invention and its corresponding sensor storehouse have, this has just caused required few power consumption to control the temperature to the sensor storehouse including sensor and analyte.The program that the present invention also just in fact can application of temperature control like this, comprises that the control program of thermograde carrys out the sorption and desorption process in control analysis thing and sensor electrode mechanism.This temperature control be particularly conducive to by application the present invention make, the battery-powered portable Electronic Nose instrument of palm.After having used above-mentioned temperature controlled program, the present invention likely carrys out to show fully the inherent chemical speciality of analyte and reaches detection and the discriminating of the high-quality to analyte.

Owing to there being above-mentioned all features, the present invention can design and develop into has that volume is little, cost is low and the sensor of Portability easily.As an example, in the time of design Electronic Nose instrument, due to particularly because low sensor production cost, so single-sensor of the present invention is to be extremely suitable for for making disposable sensor.

example

The example and the experiment situation that relate to core technology of the present invention and apply the single-sensor of the principle of work of ac frequency scanning and vector analysis of following discloses.It is to be only used as elaboration of the present invention that this example is provided, and not as limitation of the present invention.

Pair of electrodes as simple sensor is made of pure gold round wire rod.Long 12 millimeters of this electrode, electrode separation is about 1 millimeter.Connect this electrode and an alternating current analytical instrument with the concentric cable of standard, such as Ai Jielun 4294 electrical impedance instrument: Agilent4294A (Ai Jielun companies: Agilent; California, USA Borrow Ao Erduo city: Palo Alto).Before test sample, first this electrode is carried out to electricity demarcation.In the time that test resistance is anti-, apply the method for ac frequency scanning and vector analysis, thereby in the frequency being scanned at each, can obtain two kinds of electrical properties of the various combination such as electrical impedance and phase place or reactance and resistance simultaneously.

In first experiment, apply the frequency sweeping of 10 kilocycles to 500 kilocycle intervals.In second experiment, use the frequency sweeping of 500 kilocycles to 1 megacycle interval.Five kinds of different compounds are used as corresponding analyte, comprise acetone, acetic acid, positive six carbon alkane, toluene and water, and indoor air are to be fluid as referred to herein as their carrier.In first experiment, each compound is to hand over body ground tested six times.In the test of stating on the implementation, each compound is packaged in six little glass sample bottles, until this bottle while being full of by half for extremely.Except being used in test, this sample is the state that is in sealing.

Before each sample of test, first the air in test cabinet is fluid, and records its electrical properties such as electrical impedance, reactance and resistance.And with them as with reference to numerical value.In test when sample, open a sample plasma bottle that holds this sample, then this electrode is put in bottle until electrode front end approaches the liquid level of this chemical example.Now also clog with a cotton ball space that cable occurs simultaneously mutually with bottleneck, prevent the fluctuation of this chemical compound gas concentration in bottle.Before the electrical properties of test sample gas, again with the time of ten seconds as wait.After sample is tested, immediately this sample bottle is removed from electrode, and by capping upper bottle cover again.The sample of this tested mistake is no longer reused in experiment.

Before upper once sample test, this sensor electrode is exposed in room air about ten minutes.The order of testing these compounds is toluene, acetone, positive six carbon alkane, water and acetic acid.Be the test of second and follow-up bout with such an order, until complete the test of whole six bouts.

In the time of data analysis, the change of a kind of electrical properties of this sensor electrode to each tested analyte can be by following formula.It has represented the electrical properties under this electricity frequency of this test compound.

The electrical properties [7] of the electrical properties-air of the change=sample of electrical properties

Collect the data that electrical properties that corresponding compound obtains under different frequency changes, and construct thus the matrix of a raw data.And the frequency of these collections is to be at random taken from all frequencies being scanned.

In matrix, the data on every two adjacent perpendicular hurdles have represented a change for compound resistance and the change of reactance (or the change of available electrical impedance and change of phase place) selected in frequency at one.The data that each in matrix is walked crosswise represent this test compound through once test after in all changes that are selected the corresponding electrical properties in frequency.And all walking crosswise represented the electrical properties data of the samples that is repeated test all in experiment.Analyze the data in this matrix by application principal component analysis (PCA) again, this analysis is that the application software of store in a home computer realizes.

Fig. 1 has shown the result of application principal component analysis (PCA).It is the compound to above-mentioned five kinds: the result that the corresponding resistance that acetic acid, acetone, positive six carbon alkane, toluene and water obtain in each frequency of seven scanned frequency 10,20,50,100,200,300 and 500 kilocycles of taking out arbitrarily and reactance are analyzed.After having applied principal component analysis (PCA), the type of the electrical properties of many compounds has been distinguished, and arranges according to the orthogonal number axis of the two major component F1 that calculate and F2.It must be noted that in application principal component analysis (PCA) and analyze before the reactance and resistance data in matrix, those data have first been passed through normalized.

Can be clear that from Fig. 1, the result of the Analysis on Electrical Properties that the repeated test of same compound is obtained for six times is the specific region concentrating in the plane that major component F1 and F2 determine, and five kinds of different compounds are respectively disposed at F1 and F2 and determined the corresponding zones of different in plane.In other words, under the analysis of principal component analysis (PCA), five kinds of compounds have embodied them and have been distributed in a kind of type feature in the first and second major components decision planes.The result of being described by the first and second major components has shown that many compounds can be used the electrical properties relevant to them to be identified.This kind of electrical properties comprised sweep frequency interval 10 kilocycles between 500 kilocycles, in each frequency, obtain comprise all as if composition reactance and the resistance of electrical impedance and its phase sensitive.

Fig. 2 shown second experiment utilization principal component analysis (PCA) and obtain distinguishing the result of many compounds.It is to above-mentioned identical compound after by frequency sweeping, the result that the corresponding resistance obtaining in each frequency of frequency 502,550,600,651,700,750,801,850,901,949 and 1000 kilocycles of being taken out arbitrarily and reactance are analyzed.Second experiment repeated in the step described in first experiment, and different is only each compound is only by repeated test alternately three times.In the time of the data processing of application principal component analysis (PCA), in matrix, the resistance of compound and the raw data of reactance are done the analysis of type difference after normalized again.Experimental result has shown that electrical impedance and mutually responsive component thereof can be used to identify corresponding compound.This is to have feature and be distributed on by the first and second major components according to five kinds of different compounds to be determined that one type of different region in plane judges.

The 3rd experiment detected three kinds of analytes: acetone, toluene and a kind of alcohol content are about 44% white wine.The situation of this experiment conforms to substantially with above-mentioned experiment.Difference is: it is that 13 millimeters and electrode separation are about 0.5 millimeter that (1) two electrode is about.This two electrode is made by the wiring of shearing resistor two ends.Wiring is the copper wire rod that is coated with tin film; (2) each analyte is to be stored in a little glass sample bottle, and is repeatedly used in experiment; (3) each analyte is alternately repeated test 5 times; (4) the corresponding resistance and the reactance that in each frequency of 7 frequency 10,20,50,100,200,300 and 500 kilocycles of application, obtain.These frequencies are to be at random taken from interval 10 kilocycles of sweep frequency to all frequencies being scanned in 500 kilocycles.

As shown in Figure 13, the result of experiment shows that electrical impedance and mutually responsive component thereof can be used to distinguish compound, and this judgement is to be distributed in diacritically the fact in the plane being determined by the first and second major components according to three kinds of different analytes.Analyte white wine is to belong to a kind of chemical mixture in addition, and it contains water, alcohol take ethanol as Main Ingredients and Appearance and the organic compound of other many easy gasifications.In the gas on white wine liquid level top, comprise too like this compound of these mixing.The result of this experiment proved that electrical properties can be used to distinguish and belonged to the analyte of chemical mixture, belongs to because the region of its distribution on F1 and F2 face is different from the corresponding region that simplification compound acetone and toluene distribute.

Must be clear and definite, apply above-mentioned frequency just for the validity of the principle of the invention and object is described.Rather than attempt goes to limit the application in the present invention of other frequencies, other frequencies refer to from published frequency in the present invention and different frequencies.

Again can be clear and definite, be used for confirming that according to well-known the step by the result that obtains of application principal component analysis (PCA) just can set up an experiment having stipulated model.Many factors has been contained in this experiment, comprises the step such as first experiment of the present disclosure, the step of the step of data analysis and included display data.Then can set up a database.This database has comprised numerous raw data and the model corresponding to numerous known analytes.

Once set up above-mentioned database, identification one unknown analyte, can be by stipulating that according to model the result of the principal component analysis (PCA) obtaining compares and reach with the result of the known analyte in database by this unknown analyte.Like this relatively can be according to well-known step, wherein also including one of principal component analysis (PCA) feature diagram intuitively relatively.

In addition can also be clear and definite be to identify unknown material in order to set up model, the present invention is not restricted to just differentiate to analyze the electrical properties of analyte and the result of confirmation analysis in fluid by the type of above-mentioned principal component analysis (PCA).The present invention can apply any known analytic approach, comprises multivariate element analytic approach and analytic approach that the type that comprises is differentiated is classified and is identified in the analyte in fluid.Because can, after the different emphasis point of more various analytic approachs, select an analytic approach to the experienced analysts of these analytic approachs, it is the most rightly for the problem of a certain specific research interest.

Those well-known other analytic approachs include: the similarity analysis method of simulating separately conditionally classification: SIMCA (Soft Independent Modeling of Class Analogy); The most contiguous factor analysis: KNN (K Nearest Neighbor); The group's of system analytic approach: HCA (Hierarchical Cluster Analysis); The analytic approach of canonical discriminate analysis: CDA (Canonical Discriminant Analysis); Classical Least-Squares: CLS (Classical Least Squares); Main composition returns: PCR (Principal Component Regression); Partial least square method: PLS (Partial Least Squares Regression); There is backbone network technology guidance and guideless cognitive-ability: Supervised and Unsupervised Learning Neural Network; With fuzzy backbone network technology: Fuzzy Neural Network (skin finish: Beebe, K.R.; Pan Er: Pell, R.J.; Uncommon Si Huoerzi: Seasholtz, M.B.; Chemical Measurement: actual guidance: Chemometrics:A Practical Guide, Wiley Publishing Company: Wiley, New York, 1988; Chemical Measurement periodical: J.of Chemometrics, John Willie and thereafter generation publishing company: John Wiley & Son, Ltd.).

From above-mentioned experimental result, differentiate the analyte in fluid except the detection of applying frequency scanning, the present invention can also apply a frequency and detect whether there is interested analyte.For example, in the analysis of gas chromatography, a chemical mixture is as initial analyte.And numerous compound in this potpourri is separated in chromatographic column, and taken out of chromatographic column by carrier (normally hydrogen or helium or the nitrogen) compartment of terrain of a gaseous state.The present invention just can detect the existence of each compound like this.This is in this detected frequency, to have the different electrical properties that exchanges like an elephant electrical impedance because of the carrier of gaseous state with detected compound.

Above-mentioned chemical separation process also occurs in liquid chromatography equally.It is by a kind of solvent or have the potpourri of several solvent to deliver as each compound in the potpourri of initial analyte as carrier.Can be applicable to like this in the above-mentioned electrical properties detecting in a frequency a kind of come those separated compounds of alleged occurrence.

In the time that application single-sensor of the present invention designs the detecting device of a gas chromatography, a preferred structure is that a space electrode of single-sensor can like the columniform axle sleeve of a hollow.The cylindrical electrode of this hollow is the one end that is placed in the jet mouth of pipe of a hollow, and the other end of this jet mouth of pipe is the tail end that is connected to chromatographic column.And this columniform electrode is to be coaxially connected with the tail end of chromatographic column with air jet pipe.Another space electrode of single-sensor of the present invention can be tiny linear structure always.It is positioned to consistent with the turning axle orientation of this cylindrical electrode, and within can being positioned in cylindrical electrode, or outside cylindrical electrode.With existing flame ionization detector (FID), thermoelectricity conductance detecting device (TCD) is compared with electron capture detector (ECD), and chromatographic detector of the present invention has numerous advantages.These advantages comprise that its detection to analyte is non-damageability, are blanket, simple in structure and bring easy making by it, and feature cheaply.

In addition, above-mentioned use in chromatogram carried out to the detecting device whether detection compound exists with electrical impedance or voltage or electric current, the pumping signal that can apply periodic alternating voltage or electric current is added on the detecting device of gas chromatography of the present invention.This pumping signal includes the non-sinusoidal shape ripple of square wave, triangular wave and the zigzag wave of single-frequency.

As another example of applying single-frequency test, for the safety that mine is produced, detect inflammable gas in well, be very important such as liking gas and so on.Detect this type of gas and can apply equally single-sensor of the present invention.The pumping signal of added single-frequency can have and comprises that the form of square wave, triangular wave and sawtooth wave detects a kind of electrical properties of this gas.

The ac-excited signal that produces single-frequency can be applied well-known oscillator, include capacitance-resistance phaseshift oscillator, Wien bridge oscillator: Wien-Bridge Oscillator, Ku Er splits time oscillator: Colpitts Oscillator, Tim Hartley oscillator: Hartley Oscillator and square-wave oscillator (A Mingniya: Aminian, A.; Triumphant plucked instrument Mick fork clip: Kazimierczuk, M.; Electron device, from design: Electronic Devices, a design approach; Bi Yaxun, Pan Tesi room printing firm: Pearson, Prentice Hall, 2004).For example on market, there is the integrated package AB-112 (Analog Devices Inc: Analog Devices, Massachusetts, United States: Massachusetts, USA) of application Wien bridge oscillator.Like this electrical impedance of single-sensor can be used as this integrated package output load voltage divider some and can be detected.The phase sensitivity component of electrical impedance is also available.The method in another body generation is in the time of the instrument of application scanning frequency, and setting beginning and stopping frequency is same frequency, also can obtain the pumping signal of single-frequency.

Fig. 7 A and 7B disclose single-sensor of the present invention, and its electrode can have the combination of various ways.The first electrode of for example this sensor is to be placed to the wall that approaches a container, or other structure.This wall or structure are made and be connected with ground zero potential by conductive material.The wall of container or other structures can be used as the second electrode of this sensor like this.In the time detecting, the detected analyte in fluid can be directed and by the gap by the first electrode and this container wall or other structures.

Single-sensor of the present invention has been applied the electric excitation signal of the periodicity with frequency sweeping performance including sinusoidal wave and the method for vector analysis, thereby has numerous advantages.It can just obtain two kinds of collection of illustrative plates of the alternating current character that has type law characteristic of record analysis thing in one-shot measurement.The little volume that sensor has only needs the sensor storehouse of small size and the low power consumption required to the temperature control of brief biography sensor storehouse.These features make can adopt actually the structure of dual sensor, in application one detecting sensor, add the reference sensor that application is consistent with its structure.Application dual sensor structure, can eliminate the impact of ground unrest, the variation including the electrical response of sensor in test that comprises the impact, macromolecule membrane aging effect of humidity in various degree and cause because of temperature variation.

The principle of work of single-sensor of the present invention and method has been applied frequency sweeping, is included in the frequency sweeping of preferred low frequency interval from 10 kilocycles to 1 megacycle.The method of applying frequency scanning can obtain with the single-sensor of small size size the electrical properties that has type rule of analyte.This undersized sensor only needs undersized sensor storehouse.This only needs low power consumption to control the temperature in sensor storehouse with regard to having determined, and the temperature of the analyte in fluid between the inner sensor electrode of storehouse.Palm portable sensor apparatus of the present invention is like this entered you and can practical application is comprised fixing and have the temperature control program of gradient to optimize detection and the discriminating to analyte in fluid.

In addition, application periodically includes sine-shaped alternating current driver signal, and the present invention has just possessed the application adsorption of all kinds and the ability of absorbing material, and described material comprises material organic, inorganic and metal.Combine above-mentioned various advantages, make sensor of the present invention there is the volume of low manufacturing cost, compactness, flexibly Portability and the convenient feature using.

Above open introduced core technology of the present invention: i.e. the alternating current driver signal of the frequency sweeping including sinusoidal waveform of single-sensor and periodic thereof and the method for vector analysis.Following discloses sensor instrument system including of the present invention.

This sensor instrument system including has comprised a portable sensor apparatus and a central information station, and they are separated by each other at a distance.The function that sensor apparatus has has comprised detection and has differentiated the analyte in fluid; Determine the geographic position of analyte; And transmitting information wirelessly.Central information station has connected a local information receiving station by a network.The structure that this receiving station has comprised transmitting information wirelessly, can receive mutually and transmission information with sensor apparatus.This system just has the ability of wireless telecommunications analyte information and determines the ability about analyte geographic position like this.On this framework, instrument system of the present invention can provide to the full extent detect movably, at a distance and differentiate the analyte in fluid.This kind of performance worked in coordination with simultaneously and can have been determined the performance about the geographic position of analyte.In addition, if applied numerous identical portable sensor apparatus, it is distributed in different regions accordingly numerous in a region, and system of the present invention can be set up the instantaneous distribution plan to this region inner analysis thing.

The composition of sensor apparatus combines the technology that can obtain geo-localisation information after core technology of the present invention, the at present known so-called hardware technology including the electronic component for wirelessly transmitting data and the so-called software engineering including calculation procedure and applied global positioning system.

What can feel glad favour is that the structure of the analytical instrument that contains microcomputer has just been known by people a long time ago, can be for example " chemical apparatuses: set forth on series ground " from title: Chemical Instrumentation ": A Systematic Approach; the third edition; chapter 5; this csepal: Strobel, H.A.; Hai Na alliance: Heineman, W.K.; John Willie and thereafter generation publishing company: John Wiley & Sons, lnc., cognitive this special topic over 1989.In a broad aspect, analytical instrument is by one being analyzing and testing device mimic channel used part, has connected and has included the connecting portion of an analog quantity to digital quantity converter.The digital circuit part that this connecting portion contains a built-in microcomputer with one is again connected.Specifically, this mimic channel part is to be connected with the input and output numerical data transfering channel of microcomputer by converter.

Have outside the structure of the analytical instrument with built-in microcomputer, designing the necessary element of this instrument comprises: analog quantity is to digital quantity converter, logic, multiplexer, wave filter, amplifier, data address element, include calculating, the central microprocessor of logical block and register, the numerical data transfering channel that memory cell is special, digital quantity is to analog quantity converter, direct memory, 488 numerical value parallel connection structures of the Institution of Electrical Engineers's rules, numerical value input and output interface, additional peripheral equipment comprises: the input structure that resembles keyboard or contact screen formula, random access memory, readout memory, counter, integrated circuit, binary bit connect in series structure (RS232), obtain digital data modules, code, instruction, data, program, operating system, rudimentary and higher level lanquage, application software, and display element.Of the present invention open in order to simplify, all above-mentioned well known elements all comprehensively arrive among of the present invention disclosing.

Fig. 1,2 and 13 have shown the result that detects and differentiate analyte in fluid.Obtain this result and be and applied single-sensor and connected all as if alternating current analytical equipment of Ai Jielun 4294 electrical impedance analysers and used and obtain after home computer.In computing machine, store the application software that contains principal component analysis (PCA) that is used for analyzing the electrical properties data that obtain.Like this, just drawn the instrument into a combination if connect instrument Ai Jielun 4294 with the cascaded structure of digital transmission or parallel-connection structure with home computer.And this combination has just embodied the basic structure of sensor apparatus of the present invention.In combined instrument, this alternating current analyser is as the analyzing and testing device of combined instrument, is used to measure in the fluid sample of analyte and obtains the data of sample electrical properties.Be equipped with and stored the hardware and software of the suitable use for data transmission in this home computer, the drive software that comprises the use for connecting be used as combined instrument digital circuit part.It is used to analyze data and discriminatory analysis thing.

In addition, in the article of delivering at Na Geer, also there is its this structure of the Electronic Nose instrument of narration.Its composition has three unit: a sample memory, a gas sensor group and a signal processing system.After connecting, these three units in series are used to detect gaseous sample odorous.

By shown in Fig. 8 and Fig. 9, sensor instrument system including 16 of the present invention is made up of following parts like this: the sensor apparatus of an integration 18, has central information station 90, a local information receiving station 96 and a network 130 of central computer and servocomputer 92.This central station is connected with local receiving station by interconnection network.

The sensor apparatus 18 of integration is made up of the module of eight connections.Comprising a collection test sample block 20, it includes a sample drive unit 24, a sensor storehouse module 28, pastes the external heater 82, a detection module 40, a microcomputer module 50, a transmission data module 68, global geographic position location receiver module 72 and the power module 76 that have added a heating module 80 on its shell.

Microcomputer module 50 includes built-in display screen 52 and a whole set of button 54.It is equivalent to a small-sized home computer.The major function of this module comprises promising discriminatory analysis thing and the electrical properties digitized processing of doing and the work order that gives other modules in instrument 18.Such as the Preprocessing Algorithm of application data obtains liking at above-mentioned formula [5,6, the change of the electrical properties in each frequency with respect to each analyte of discussing 7], and and be established as the raw data matrix of use of the follow-up data analysis of differentiating each analyte with it.Except applying above-mentioned formula, the algorithm of other public Fabric also can be used as the pre-service of signal.In addition, this module 50 has the function of making Data processing for other modules simultaneously.

Module 50 has for self operating required necessary element, including a central microprocessor, note Yi component information transfering channel, comprise note Yi element data, instruction and digital address and the passage of numerical data input and output.This module 50 also comprises a computer operating system.In the preferred case, this system is the commercial computer operating system of a window type.

Microcomputer module 50 is also built-in one for detection of application software, include positioning map that principal component analysis (PCA) is used for the software encrypted and includes the applied global positioning system for determining geographic position at the software, one of interior numerous analytic approachs in the time needing numeral with secret formal output at interior software.Because module 50 has the push-button unit 54 of the use of the data of being included as and instruction input, the user of instrument can key in data or the instruction into instrument work by operating corresponding button, thereby selects the work functions of required sensor apparatus.For example, show the application software of this detection use.Except with button, the display screen 52 of module itself also has the function of input message.User can input for example instruction by the domain of dependence on screen by finger pressure like this.In addition, module 50 can demonstrate the data that measure, and has comprised the electrical properties that shows an instantaneous analyte obtaining according to scanned time or scanned frequency.Module 50 also has general order interface (USB), series connection (RS-232) and (IEEE488) transmission interface in parallel and meets the needs including data wire transmission.

In the preferred situation of one, the application software of this detection use is window type, and it has comprised numerous programs.These programs are the each duties for instructing analytical instrument 18, comprise detect analyte, collection is with storage data and be connected other above-mentioned application software.For example its instruction that has operation to collect test sample block 20 and operation detection module 40 detects the analyte in fluid and records data; The instruction of geographic position data is checked and approved in receiver module 72 work of indication location; Carry out the instruction of wirelessly transmitting data with indication transmission data module 68.This software can comprise following disclosed basic part.

First part is the identity for registering many analytes, comprises type and the title of analyte.If an analyte is to belong to the biological sample getting from patient, the identity of this sample has comprised patient's name, sex, family's property and the age of encrypting.If analyte is not relevant with patient, login this real sample type.In order to ensure authenticity, the date and time of analyte testing by instrument onboard clock data and login.

The second part is for logining the numerical value for the alternating current that uses of test, for example, comprise the amplitude of pumping signal and apply the type of frequency.The type of frequency has comprised the single-frequency type of application particular frequencies and has had the type that starts and stop the sweep frequency of frequency.In the type of sweep frequency, the multiple choices of how carrying out collection analysis thing electrical properties according to frequency are comprised again.Wherein there are some frequencies that are captured in arbitrarily in scanned frequency, or have some particular frequencies that are chosen in arbitrarily in scanned frequency, or in sweep frequency interval, collect the frequency of all numbers that were in fact scanned.In the second part, also comprise that selectable "Yes" and "No" determine whether to start location, global geographic position receiver module 72, be also included as the running parameter of determining the driving sample unit 24 in operation collection test sample block 20.

The 3rd part is for selecting to process the scheme of testing the analyte electrical properties data that arrive.After being completed, the electrical properties data that obtain are to be processed by sensor apparatus, or are processed by central information station.These two kinds of different schemes have determined that corresponding two kinds of embodiments export the data that obtained by sensor apparatus 18.

A kind of embodiment is by local the data transmission to of analysis result information receiving station.These data have comprised the data of the original electrical properties of the analyte detecting, the data of analyte result and the data in the geographic position that display analysis thing is positioned differentiated.In this embodiment, as shown in Figure 8, in locality, data wireless as above is transferred to a local information receiving station 96 by sensor apparatus 18, and then is transferred to central information station 90 a long way off by network 130.This central station has been equipped with the servocomputer that includes memory function at interior central computer 92.In this computing machine, also store and identical included global geographic position positioning map at interior software.The result in the analyte of being differentiated like this and their corresponding geographic position can be stored and be presented on central computer 92.

In another embodiment, the original electrical properties of analyte in fluid obtaining according to sweep frequency and the information data in analyte geographic position can be wirelessly transmitted to the central computer 92 at central information station.Because stored the application software of using in the identical definite geographic position including global location map in this computing machine and included the application software of principal component analysis (PCA) in interior numerous analytic approachs, received like this electrical properties can be processed in central information station.And store and show result detected and analyte that identify, comprise their residing geographic position.

If select the first embodiment, by sensor apparatus detection site come analyzing and testing to the electrical properties of analyte, after detection is complete, this testing software can automatically show that including principal component analysis (PCA) differentiates each analyte in the application software of interior numerous analytic approachs like this.

The 4th part is to select how to carry the scheme of the information detecting including the result of the analyte of discriminating.It has comprised the scheme of automatically result being exported after corresponding selected embodiment completes, and keys in the manually operated output scheme of exporting again after the instruction that allows output according to instrument user.

The application software that starts this detection use be be positioned in the last mark " RUN " of software clicked after, so also just started sensor apparatus 18 simultaneously and make it be in duty.

Must be clearly, above disclosed for detection of the component part of application software, only comprised the running parameter that makes this instrument work very basic instruction once and need input.Formulate a set of complete instruction and running parameter, apparent for the people who sees service in this field, particularly they are with reference to open narration of the present invention, and the job applications software of numerous known apparatus is included in that a kind of software of applying in gas chromatography and after the inspiration obtaining.

Shown in Fig. 9 and Figure 10, collect test sample block 20 and be physical construction and connected the sensor storehouse 30 of the hollow in sensor storehouse module 28.

Collect the sample 10 that act as collection and then carry the analyte in fluid of test sample block 20.It is in the driving sample unit 24 in centre position by one and is connected to the Sample introduction at its two ends simultaneously and derives 22 and 26 of parts and forms.Under the preferred structure of one, this sample drive unit 24 is small-sized or miniature pumps that driven by electric energy.Certainly it also can drive by mechanical energy or by the manual energy of user.This Sample introduction and derive parts 22 and 26 and can be made up of corresponding pipeline, or by one in multi-channel structure, or anyly has inner passage and forms for the structure that is controlled at fluid analyte flow.Under the preferred structure of one, Sample introduction and derivation parts are made up of flexible pipe.But in the time that sample is tested the inner passage of sample block by collection, this importing and derive parts 22 and 26 and driver element 24 all must possess the performance that has strong adsorption sample not to comprise analyte.

The derived type structure 26 of collecting test sample block be physical construction connected the front portion structure 32 in the sensor storehouse 30 of hollow.Sensor storehouse 30 is to be made such as liking copper or metal alloy by metal material, and it is also connected and fetches the radiation interference into sensor mask electromagnetic field with ground zero potential.

The conditional thickness in sensor storehouse 30 of hollow, is connected and (has been comprised electrical connection) intermediate structure 34 by front portion structure 32 physical constructions.This intermediate structure machinery and be electrically connected a tail structure 36 again.Tail structure again physical construction connected one such as if the structure 38 of the discharge of discharge tube.Under this structure, be in sample 10 near near the analyte in fluid of outside Sample introduction parts 22 under the driving of pump 24, enter into Sample introduction parts 22, flow through pump 24 and enter into sensor storehouse 30 with deriving parts 26, finally flow out by discharge structure 38.

As shown in Figure 9, the front portion structure 32 in sensor storehouse has the shape of an isosceles triangle.The tip of front portion structure 32 is connected with derived type structure 26 physical construction ground, and the roomy horizontal afterbody of front portion structure 32 is connected with the front end of the intermediate structure 34 of flat rectangular parallelepiped.According to hydromechanical principle, when sample 10 enters into after front portion structure 32, with the narrow interior profile than derived type structure 26, this sample 10 can reduce flow velocity because of the transverse-longitudinal cutting face increasing gradually of front portion structure 32 like this.In this case, add the effect of the limited thickness in upper sensor storehouse 30, sample 10 can be with the form flows through sensor storehouse 30 of a laminar flow.And the circle in this storehouse or arc afterbody 36 have reduced the stream of breathing heavily that forms sample and flow, also just facilitate the Laminar Flow of sample 10 in sensor storehouse.And the Laminar Flow of sample has been dominated sample 10 being uniformly distributed numerous sensor electrodes in storehouse.

Shown in Fig. 9 and Figure 10, the inside of sensor storehouse intermediate structure 34 is by wall 33 even partitions upwards.The direction that this wall is disposed is parallel to the mobile direction of sample 10.The first and second identical sensors time storehouse 34a and 34b in storehouse, are just formed like this.In each storehouse, settling an identical sensor with two electrodes 1.The orientation of this electrode spread is consistent with the direction of sample flow.But can be clear and definite, each sensor 1 with two electrodes can be positioned to and become any angle including 90 degree with sample flow direction.Again as shown in Figure 8, the lines 4 and 5 in figure have represented that two identical sensors 1 are electrically connected to detector module 40 separately.

As previously mentioned, two electrodes of sensor can be placed on space and form space electrode, or can be placed on pottery and silica substrate 86 and 88 and form corresponding thick film and membrane electrode.Shown in Fig. 9 and Figure 10, in the time of application thick film or membrane electrode, corresponding ceramic substrate 86 or silica substrate 88 are to be attached on the inside surface 31 of base plate 34C of the intermediate structure in sensor storehouse.Under this structure, because pottery, silicon and metal are all hot good conductors, if an external heater 82 of heating module 80 is attached on the outside surface of sensor storehouse base plate 34C, and well heater 82 is the words that heated by the control of heating schedule by the electronic circuit of heating module 80, just can and easily control the temperature of sensor storehouse module 28, comprise in sensor storehouse 30 and storehouse the temperature of the sensor with polytype electrode 1 of placing, and in the temperature of the interelectrode sample 10 with analyte in fluid.

Moreover because the little volume size of sensor, thereby only need undersized sensor time storehouse, and then determined the low power consumption required to the temperature control of sensor storehouse.

From the above mentioned, after 30 ground connection of the sensor storehouse of metal, shielded and be coupled with the caused electromagnetic field radiation of ac sweep frequency when first sensor 1.Same reason, the electromagnetic field radiation being caused by second sensor 1 also can conductively-closed.Like this after having applied sensor storehouse, can prevent that the intersection that the possible electromagnetic field radiation effect by the first and second sensors causes from disturbing.

But must be clear and definite be, the example being connected with detection module by containing above the sensor of two maskable interference of electromagnetic field, the disclosure has been narrated one of the present invention and has been implemented structure: apply at least one sensor and detect and differentiate the analyte in fluid.Fulfiling this enforcement structure is according to spirit of the present invention and object: the dimension of finding to be described in analyte feature in fluid.

Implement, in structure, as shown in Figure 6, sorbing material 8 to be placed among the paired electrode of the sensor at least one sensor at this.In the time that this sensor of application carrys out the analyte in test fluid, after completing adsorption process this filling the sensor of sorbing material can record a kind of compound of being adsorbed or several similar compound be compound group including resistance and the electrical properties that exchanges reactance, as the information being detected.

Obvious, in the time that each analyte is a chemical mixture, from filling the sensor electrode of sorbing material obtain relevant including the electrical properties resistance and reactance reflected that compound being adsorbed potpourri or the feature of compound group, and the compound being adsorbed (group) is this chemical mixture having represented as analyte.The known this electrical properties obtaining is to be different from the electrical properties including resistance and reactance obtaining on the sensor of filling sorbing material never.They have represented an overall feature of all compounds in analyte, and they have comprised different intensions, describe this analyte from different dimensions.

In another case, if when each analyte is all a simple compound, compared with the electrical properties obtaining in the sensor electrode of filling sorbing material never, from filling the electrical properties that obtains of the sensor electrode of sorbing material there is high signal to noise ratio (S/N ratio).The electrical properties of this kind of high s/n ratio is to be conducive to be used to detect and discriminatory analysis thing all the time.Like this according to spirit of the present invention and object: find analyte feature can be measured dimension, the structure that the present invention can apply at least one sensor when needed detects and differentiates the analyte in fluid better.

By above-mentioned and analogize, between the electrode that another enforceable structure of the present invention is the each sensor at least one sensor, fill different sorbing materials.

Still from increasing the spirit and the object that are used for being described in the different dimensions of analyte fluid, an enforceable sensor construction in addition of the present invention is to select one or more known sensor of summing up in Na Geer article and Lewis's 333 patents to be used as the one or more sensors in this structure, and then a multiple or sensor of the present invention can serve as remaining sensor in this structure.This is because compared with the core technology of sensor of the present invention, those known sensor technologies are the detected information that detects analyte in different dimensions.

Figure 11 has set forth the another kind of structure of application dual sensor.The sensor being wherein positioned in sensor time storehouse 34b is used as described detecting sensor 2, and another sensor being positioned in sensor time storehouse 34a is used as described reference sensor 3.They can be by filling or not filling the space electrode of sorbing material 8 or thick membrane electrode or membrane electrode formed.But identical sorbing material 8 is but the front end that is positioned in sensor time storehouse 34a be used for being adsorbed in an analyte of chemical mixture normally, be a compound (group) of research interest.Only having like this those is not that the compound (group) of studying interest could can continue to pass through between two electrodes as reference sensor 3 afterwards by sorbing material 8.

Known from the foregoing, after combining the corresponding electrical properties obtaining in detection and reference sensor 2 and 3, can only obtain those including the corresponding electrical properties for the interested compound of research institute or compound group as biochemical object or object group.The present invention can be used to detect known compound or the compound group including known biochemical object or object group effectively like this, and detection known compound (group) or biochemical object (group) are the unknown analytes that contains known substance (group) in order to differentiate.Wherein the method known biochemical object of detection (group) is the use for medical diagnosis disease.

Except the embodiment of the dual sensor structure in this kind of integration shown in Figure 11, also can apply sensor as described in Fig. 4 A independent scheme separately.Under this scheme, detecting sensor 2 and reference sensor 3 can have special separately collection test sample block.

As previously mentioned, because of its little size, simple structure and low cost, sensor of the present invention can adopt interchangeable, the disposable electrode structure that contains or do not contain stuff actually.In the time of this kind of alternative electrode of design, if this electrode is that while being placed in corresponding sensor time storehouse 34a and 34b, the front-end architecture 32 in this sensor storehouse can be designed to detachable.Front-end architecture 32 can connect in a kind of mode of insertion the intermediate structure 34 in (comprising electrical connection) sensor storehouse like this.This detachable electrode comprises space, thick film also can be connected corresponding metal connector in the way to insert with electrode film, and connector coated outside has suitable electrically insulating material.These are positioned in sensor time storehouse 34a and are connected with detection module 40 with the corresponding connector in 34b.

According to such structure theory, for those veterans in sensor field, the detailed construction that designs this sensor is apparent thing.The present invention can apply interchangeable, disposable sensor like this.This is also unique distinction of the present invention.

The effect of detection module 40 similarly is aforesaid alternating current analyser 9.It includes an assembly, and the electronic circuit of this assembly can produce the ac-excited signal with sweep frequency.This signal can be added to the single-sensor that includes analyte sample in a fluid, thereby obtains the electrical properties of this sample.Then this electrical property mass-energy is arrived by another component detection of detecting device module 40.

This detector module can be made by numerous well-known electronic line structures.Such as applying electronic integrated package AD5933 (simulation device company, Massachusetts, United States).Integrated package has a built-in interchange oscillator, by the synthetic core cell (DDS) of a Direct Digital and a digital quantity to analog quantity converter just form one have can sweep frequency ac-excited voltage.The AC signal producing after this voltage is added on sensor is connected to a discrete type Fourier transform unit through an analog quantity after digital quantity converter.Fourier's series of plural form can be from analog quantity to digital quantity converter and the synthetic core cell of Direct Digital obtain.After being stored in respectively in different registers, the real component resistance being obtained by Fourier transform unit and the reactance of imaginary part component can be read out.This integrated package can be carried out by calculation procedure initial frequency, frequency increment and the frequency number in scanning of gated sweep.

As according to Ai Jielun 4294 structures, there is digitized controller, signal source, transducer and vector ratio detector.Wherein signal source provides the ac-excited signal with all sweep frequencies and degree of amplitude modulation being applied on sensor.Transducer converts the electrical impedance measuring to two kinds of ac signal voltages.Vector ratio detector changes into numerical data by two kinds of ac signal voltages again.And digitized controller comprises and processes numerical data and export the test result of sample.

This detection module 40 also can be from designing according to the electronic circuit of the locking principle of simulation volume, and be connected to digitizing part (the Princeton applied research company: Princeton Applied Research of collecting data in interior syndeton to digital quantity converter through including simulation volume, tennessee,USA Ou Ke Ritchie city: Oak Ridge, Tennessee, USA).In addition also can Applied Digital similar in appearance to above-mentioned simulation volume locking principle, i.e. digitized correlation principle (Su Leqiang company: Solartron, Pu Junfadu pressgang city is breathed out by Britain: Fardoroagh, Hampshire, UK).

Above-mentioned technology has been applied the principle of single sinusoidal wave alternating current driver signal.In addition the principle of many sine wave exciting signals also can be used to and make detector module 40, and (Cha Na-Ai Er is the strange company of Ke Jiemubu and Cook but: Zahner-Elektrik Gmbh & CokG more can to apply Fourier frequency switch technology, Luo Nake coughs up in Germany: Kronach, Germany).

Can determine like this structure of this detection module 40.Its part by detecting comprising can be made up of in above-described detection principle, it such as similarly being after analog quantity is connected to digital quantity converter, then has connected the digital unit of a collection numerical data that contains main central microprocessor with suitable syndeton.In the structure of sensor apparatus 18, detection module has connected sensor 1 and microcomputer module 50.The advantage of the detection module 40 that contains said structure is data analysis fast.This is because this detection module 40 has additionally been born the task of comprising the information that analyzing and testing arrives for the essential processing of discriminatory analysis thing.And one of task that this information processing is just microcomputer module 50 bears.

Under this enforcement structure, the central microprocessor in microcomputer module 50 can be mainly used to the work of other modules of instruction in instrument.This sensor apparatus can obtain rapid data analysis in interior good function like this.

Select as another kind, after utilizing the collection numerical data function of microcomputer module 50, detection module 40 can only include the Analogic Electronic Circuits that is used as detection of one of numerous detection principles according to above-mentioned, then with including analog quantity is connected to the connector digital quantity converter.

In addition as previously mentioned, detect if only apply a kind of frequency, for detection module, the pumping signal of periodic has been enough to be competent at.This signal has comprised the wave mode of square wave, triangular wave and sawtooth wave.

As shown in Figure 8, transmission data module 68 includes an antenna or antenna eliminator structure 70 removes to connect a reception and transmitter.This receiving-transmitting device is connected with a digital unit that contains small-sized central microprocessor again.Transmission data module 68 is connected with microcomputer module 50, and module 68 can be carried in the information of the analyte being encoded on a high-frequency electromagnetic wave and the numerical data of its geographic location information by antenna structure 70 transmission like this.Apply this structure, can obtain two-way information communication.

Be placed in so the movably sensor apparatus 18 of a local area 102, not only can send data but also can be received in the instruction that send at the central information station 90 of remote position 94.This communication form is to complete under local information receiving station 96 collaborative.The communication of instrument 18 and local receiving station 96 is the media 120 that utilized a communication, is the electromagnetic field being produced by the high-frequency electromagnetic wave signal of transmission data module 68 (or this locality receiving station 96) transmission.Corresponding so local receiving station 96 (or transmission data module 68) just can receive the signal sending.In addition, this locality receiving station 96 is connected with the network structure 130 that has been connected central information station 90.And local information receiving station 96 is the areals 102 of disposing disposing with instrument 18.

As shown in Figure 8, location, global geographic position receiver module 72 includes an antenna or antenna structure 74.Its antenna connected a main global geographic position location receivers and include a central microprocessor and an additional clock at other interior necessary digitalized electron circuits.And this electronic circuit is connected with microcomputer module 50.This module 74 is by acting on mutually with the global geographic location positioning system 110 that contains numerous satellites the geographic position 112 (being the position of sensor apparatus 18) receiving about analyte in a fluid.Because be used for determining that the positioning map of applied global positioning system in geographic position is also stored in microcomputer module in interior application software, the on-site post-11.2 of instrument being detected like this can be displayed in instrument screen 52.Or the data of this post-11.2 can be transferred in the central computer 92 of central station by transmission data module 68, then are displayed on this computer screen.

Heating module 80 includes external heater 82 and the electronic circuit including digital circuit part.So heating module can be made by the commercial element of these existence.In the connection of instrument, the digital circuit part in heating module has connected microcomputer module.

Power module 76 by a switch 78, to each module in instrument 18 provide electric energy can recharge dc-battery, for alternating current 79 rectifications in city's being exported to galvanic electronic circuit and other electronic circuit is formed.The effect of other electronic circuit is under the instruction of computer module 50, controls the DC voltage for other modules including heating module 80 and collection test sample block 20.For example, it can control the work by power-actuated pump 24 and well heater 82.Power switch 78 has been controlled the state of sensor apparatus " have power supply supply with " and " non-transformer supply ".Once after instrument is in the state of " having power supply to supply with ", microcomputer module 50 has just been dominated the energy-saving power supply of electric heater 82 and pump 24 has been supplied with.This power consumption for the sensor apparatus driving with battery power is very important.

Must be clear and definite, above open in, the each suitable syndeton that connects microcomputer module for each module is very important, it has guaranteed the normal work of each module.

As mentioned above, the sensor storehouse 30 of metal can shield electromagnetic prevents that it is to there being the interference of sensor apparatus effect of at least one sensor.In addition, can also apply additional electronic line structure and eliminate the impact of electromagnetic field.As shown in Figure 8, such as applying the connection of an electronic switch 56 between at least one sensor 1 and detection module 40, and the duty of electronic switch 56 is controlled by computer module 50.Like this under the instruction of microcomputer module 50, the ac-excited signal with sweep frequency producing from detection module 40 can be added to each sensor of at least one sensor in an orderly manner and periodically, only has a sensor be energized and work thereby formed in a moment.Under this situation, just can thoroughly eliminate the intersection of electromagnetic field and disturb.Such line construction is feasible actually.This is because the speed of electric frequency sweeping is very fast, so can complete the frequency sweeping to the each sensor defined at least one sensor in the time of a detection.

As shown in Figure 8, local information receiving station 96 includes an antenna or antenna structure 100 has connected a sending and receiving device 98, and this receiving-transmitting device 98 is connected with a digital module with central microprocessor again.The high-frequency signals of the digital information that is loaded with analyte and its geographic position of raising the price that received like this station 96 receives can be decoded into numerical data.This is because the data transmission module 68 of local receiving station 96 and instrument is followed the technical stipulation of same transmission information.This numerical data can be transferred to the central computer 92 of central station 90 like this.In transmission in this data by network 130, a kind of preferred embodiment is, in the time that network is the form of internet, this digital information can comprise that by the service of internet file is enjoyed mutually or Email postal delivery is passed with the form of a file or Email.

In addition, Figure 12 has shown another embodiment of the present invention, its have numerous identical local information receiving station 96a, 96b ..., 96n.Each receiving station be equipped with corresponding antenna or antenna structure 100a, 100b ..., 100n.They be positioned in one have numerous local area 142a, 142b ..., 142n a region 140.These numerous local receiving stations are connected with network 130.In this embodiment, a sensor apparatus 18a who includes antenna or antenna structure 70a and global geographic position location receivers antenna or antenna structure 74a is positioned in a local area 142a movably.Like this this instrument 18a can with the 96a of receiving station wireless telecommunications.Because the 96a of this local destination disposes at the identical local area 142a disposing with this instrument 18a, and this area is the medium 120a that belongs to local wireless telecommunications.

In addition this instrument 18a also can be associated with Global Positioning System (GPS) structure 110 and the geographic position 112a of instrument be detected.This is because positioning system structure 110 has covered whole region 140.Under such structure, this geographic position 112a and the electrical properties detecting can be transferred to after the 96a of this local destination, continue to be transferred to central station 90.According to this logic, this instrument 18a can be positioned in this region any local area 142a, 142b ..., 142n come be connected with central station.

Figure 12 has shown again the embodiment of another system.Numerous identical, contain wireless communication antenna or antenna structure 70a, 70b ..., 70n and global geographic position location receivers antenna and antenna structure 74a, 74b ..., 74n instrument 18a, 18b ..., 18n be moved numerous local area 142a, the 142b that are placed in this region 140 ..., 142n can be in an orderly manner and central station 90 communications.

And this communication be medium (electromagnetic field) 120a, 120b by corresponding local wireless telecommunications ..., 120n come with the corresponding 96a of local destination, 96b ..., 96n links.Again as shown in Figure 12, corresponding geographic position 112a, the 112b of numerous instruments ..., 112n can be detected.Comprise like this post-11.2 a, 112b ..., 112n can receive by central station 90 at the electrical properties of the interior corresponding analyte detecting in each department.Thereby can construct instantaneous, at the distribution plan of the analyte of this region.

Must be clear and definite, the wireless data of above narration is propagated the restriction that is not subject to the region on a celestial body.In fact, this type of propagation can occur between interspace.As long as communication media be electromagnetic field 120 (120a, 120b ..., 120n) can relate to two spaces between celestial body, such as the space between the earth and Mars.If this sensor apparatus 18 is to be positioned in a kind of mode of robot on Mars like this, just can detect and differentiate the gaseous analytes in Mars atmosphere according to the embodiment of two kinds of above-mentioned data transmission.In this embodiment, connection local destination 96 (96a, 96b ..., 96n) central station 90 be to settle on earth.

Though certainly there be above disclosing, the present invention is not intended to by any special shape or arrangement or any special specialize or any special application limits.Because under the spirit of the present invention and object that do not depart from above narration, they can be changed into multiple special form and relation.And the apparatus and method of above narration are only in order to narrate and disclose a kind of the or several exercisable specific change of not showing all numerous forms that the present invention can show and operate.

Claims (10)

1. One for detection of with the sensor apparatus of differentiating analyte in fluid, it is characterized in that:

   A) there is a detecting sensor, this sensor contains i.e. first and second electrodes of two space electrodes of being isolated by a space, the first electrode is the structure of the cartridge sleeve shape of a hollow, the second electrode is tiny linear structure always, the second electrode of described linear structure is positioned to consistent with the turning axle orientation of the first electrode of this cartridge sleeve shape, and within being positioned in this first electrode, or outside this first electrode, this detecting sensor provides the character of measurable alternating current;

   B) have an alternating current analytical equipment to provide the alternating current driver signal of a frequency, it measures the character of this measurable alternating current after being connected with this detecting sensor;

   C) in one-shot measurement, detect at least one analyte comprising in a mobile fluid, in this measuring process, this mobile fluid is continuously to have contacted this first and second electrode, and each mobile analyte at least one analyte in this fluid has just once contacted this first and second electrode with orderly with the mode at interval;

   D) this detecting sensor is to be applied in all the time this to have the alternating current driver signal of a frequency in this measuring process; With

   E) in the time that each the mobile analyte at least one described analyte touches this first and second electrode, according to this alternating current driver signal that has a frequency applying, detect that this fluid includes the character of an alternating current of corresponding each analyte, the character of this alternating current detecting is for detecting each the described analyte at least one analyte in this mobile fluid.
2. 2. sensor apparatus according to claim 1, is characterized in that:

   F) when only have this fluid be its when not comprising any analyte and touching this first and second electrode, the character of an alternating current of this fluid detected;

   G) character that this fluid that the character of this fluid detecting alternating current detects with this includes an alternating current of corresponding each analyte combines to obtain the character of an alternating current combining of each analyte accordingly; With

   H) character of the alternating current combining of this each analyte is for detecting each the described analyte at least one analyte in this mobile fluid.
3. 3. sensor apparatus according to claim 2, is characterized in that:

   I) have the columniform jet pipe of a hollow, the first described electrode is the one end that is placed in this jet pipe, and this first electrode is to be coaxially connected with this jet pipe;

   J) described detecting sensor is the control that is subject to fixed temperature;

   K) described sensor apparatus is a gas chromatographicanalyzer, each analyte in described at least one analyte in mobile fluid is gaseous state and flows through a chromatographic column in this chromatograph, the tail end of described chromatographic column has coaxially connected the other end of this jet pipe, and described detecting sensor is the detecting device being used as in this gas chromatographicanalyzer;

   L) each described analyte is a compound; With

   M) described mobile fluid is hydrogen or nitrogen or helium.
4. 4. sensor apparatus according to claim 3, is characterized in that:

   N) described gas chromatographicanalyzer includes a database, include at this lane database the character that known fluid is its alternating current while not comprising any analyte, the character of the alternating current that this known fluid comprises a known analyte, and the character of the alternating current combining of this known analyte;

   O) character that this fluid detecting is included to the alternating current in this frequency of corresponding each analyte compares to detect each analyte with the character of the alternating current of corresponding this known fluid; Or

   P) character that this fluid detecting is included to the alternating current in this frequency of corresponding each analyte compares to detect each analyte with the character that this known fluid includes the alternating current of corresponding this known analyte; Or

   Q) character of the alternating current combining in this frequency of each analyte detecting is compared to detect each analyte with the character of the alternating current combining of corresponding known analyte.
5. 5. sensor apparatus according to claim 2, is characterized in that: the character of the alternating current described in when described alternating current driver signal includes the form of the square wave of single-frequency or the non-sinusoidal wave of triangular wave or sawtooth wave comprises voltage, electric current and electrical impedance; Or the character of the alternating current of described alternating current driver signal described in while including the sinusoidal wave form of single-frequency comprises voltage, electric current, electrical impedance, resistance, reactance and phase place.
6. 6. sensor apparatus according to claim 2, it is characterized in that: have a sensor to be used as reference sensor, described reference sensor is identical with described detecting sensor structure, described reference sensor is measured the character that this fluid is its alternating current while not comprising any analyte after being connected with this alternating current analytical equipment, the character of an alternating current of described fluid combines to obtain the character of an alternating current combining of each analyte accordingly with the character that this described fluid includes an alternating current of corresponding each analyte.
7. One for detection of with the sensor apparatus of differentiating analyte in fluid, it is characterized in that:

   A) there is a detecting sensor, this sensor contains i.e. first and second electrodes of two space electrodes of being isolated by a space, the first electrode is the structure of the cartridge sleeve shape of a hollow, the second electrode is tiny linear structure always, the second electrode of described linear structure is positioned to consistent with the turning axle orientation of the first electrode of this cartridge sleeve shape, and within being positioned in this first electrode, or outside this first electrode, this detecting sensor provides the character of measurable alternating current;

   B) have an alternating current analytical equipment to provide multifrequency alternating current driver signal, it measures the character of this measurable alternating current after being connected with this detecting sensor;

   C) in one-shot measurement, detect at least one analyte comprising in a mobile fluid, in this measuring process, this mobile fluid is continuously to have contacted this first and second electrode, and each mobile analyte at least one analyte in this fluid has just once contacted this first and second electrode with orderly with the mode at interval, what this alternating current analytical equipment provided has multifrequency alternating current driver signal to be repeatedly added in this detecting sensor;

   D) be that it is not when comprising any analyte and touching this first and second electrode when only having this fluid, according to the character of this corresponding numerous alternating current that has this fluid that multifrequency alternating current driver signal obtains detecting applying, be included in the character that obtains two kinds of different alternating currents in each frequency, in the time including corresponding each analyte in this at least one analyte at this fluid and touch this first and second electrode, include the character of numerous alternating current of corresponding each analyte according to this this fluid that has multifrequency alternating current driver signal to obtain detecting applying, be included in the character that obtains two kinds of different alternating currents in each frequency,

   E) character that this fluid that the character of numerous alternating current of this fluid detecting detects with this includes numerous alternating current of corresponding each analyte combines to obtain the character of numerous alternating current combining of each analyte accordingly; With

   F) application is differentiated described each analyte at least one analyte according to the character of the corresponding many alternating currents that combine in many frequencies of each analyte.
8. 8. sensor apparatus system according to claim 7, is characterized in that:

   G) have the columniform jet pipe of a hollow, the first described electrode is the one end that is placed in this jet pipe, and this first electrode is to be coaxially connected with this jet pipe;

   H) described detecting sensor is the control that is subject to fixed temperature;

   I) described sensor apparatus is a gas chromatographicanalyzer, each analyte in described at least one analyte in mobile fluid is gaseous state and flows through a chromatographic column in this chromatograph, the tail end of described chromatographic column has coaxially connected the other end of this jet pipe, and described detecting sensor is the detecting device being used as in this gas chromatographicanalyzer;

   J) each described analyte is a compound;

   K) described mobile fluid is hydrogen or nitrogen or helium; With

   What l) this alternating current analytical equipment provided has multifrequency alternating current driver signal, it is characterized in that: have the multifrequency alternating current driver signal of single sine wave or have many sinusoidal wave multifrequency alternating current driver signals, the multifrequency alternating current driver signal of described single sine wave comprises and obtaining by frequency sweeping, the alternating current driver signal of this frequency sweeping includes the sweep frequency that starts frequency and stop frequency, amplitude with alternating current driver signal, the character of this alternating current detecting comprises voltage, electric current, electrical impedance, resistance, reactance, and phase place.
9. 9. sensor apparatus according to claim 8, is characterized in that:

   M) described gas chromatographicanalyzer has the software of the analytic approach the analytic approach of differentiating including type, it is used to analyze each described analyte, and described analytic approach includes principal component analysis (PCA), simulates separately conditionally the similarity analysis method of classification, analytic approach, Classical Least-Squares, principal component regression and the partial least square method of the group's of the most contiguous factor analysis, system analytic approach, canonical discriminate analysis, have backbone network technology guidance and guideless cognitive-ability and fuzzy backbone network technology;

   N) described gas chromatographicanalyzer includes a database, include at this lane database the character that known fluid includes numerous alternating currents of corresponding known analyte, the character of numerous alternating currents that combine of corresponding known analyte, the type of the character of the alternating current combining of corresponding known analyte; With

   O) applying analytic approach that the type differentiates and analyzing the type that obtains the character of the alternating current combining of this analyte after the character of the corresponding many alternating currents that combine in these many frequencies of each described analyte.
10. 10. sensor apparatus according to claim 9, is characterized in that:

    P) character of the character of the corresponding many alternating currents that combine in these many frequencies of each analyte detecting and the alternating current combining of known analyte is compared to differentiate each analyte; Or

    The type of the character of the alternating current q) each analyte detecting being combined compares to differentiate each analyte with the type of the character of known analyte alternating current.

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