CN101581685B - Sensor instrument system including method for detecting analytes in fluids - Google Patents

Sensor instrument system including method for detecting analytes in fluids Download PDF

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CN101581685B
CN101581685B CN 200910152400 CN200910152400A CN101581685B CN 101581685 B CN101581685 B CN 101581685B CN 200910152400 CN200910152400 CN 200910152400 CN 200910152400 A CN200910152400 A CN 200910152400A CN 101581685 B CN101581685 B CN 101581685B
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instrument system
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CN101581685A (en
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孙一忠
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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

Sensor instrument system including and method for detection of the analyte in fluid
Invention field
The present invention relates to the sensor apparatus field, particularly relevant for 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, 887, and that authorizes the people such as Pei Na (Payne) for No. 455 on Dec 9th, 1989 is entitled as " gas sensor " (following 455 patents for wearing and receiving);
Background technology
2, United States Patent (USP) the 5th, 571, authorizes on November 5th, 1996 for No. 401 being entitled as of the people such as Lewis (Lewis) " for detection of the sensor group of the analyte in fluid " (following be Lewis's 571 patents);
3, United States Patent (USP) the 6th, 319, authorizes in November 20 calendar year 2001 for No. 724 being entitled as of the people such as Lewis " detection of using artificial sense of smell instrument to the microanalysis thing " (following be Lewis's 724 patents);
4, wear people's such as receiving document is entitled as " with the frequency measurement of alternating current high-frequency to conducting polymer composite: a kind of new technology that detects the Volatile chemical product ", detect science and technology, the 6th volume (Meas.Sci.Technol., 6), nineteen fifty-five, the 1500th to 1507 page (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 page (following is the document of Na Geer);
6, special this people's such as (Balters) of Bel document is entitled as " Subminiature electronic nose ", international electric electronic engineering field (IEEE Spectrum), in September, 1998, the 35th to 38 page (following be this document of Bel spy);
7, United States Patent (USP) the 6th, 631, authorize on October 7th, 2003 for No. 333 being entitled as of the people such as Lewis " method that is used for the remote measurement smell " and (followingly be Lewis's 333 patents, United States Patent (USP) the 7th is arranged again in addition, 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, 465, authorizes being entitled as of grandson (Sun) " for detection of sensor and the method for the analyte in fluid " on Dec 16th, 2008 for No. 425 (following be grandson's 425 patents).
455 patents that pendant is received disclose a gas sensor.The skin of this sensor has the macromolecule membrane with semiconductor property of exposed and tested gas.Use an alternating current analytical instrument and this sensor is applied 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 in being stored in computing machine.In view of resulting different Electrical Impedance Spectroscopy, this invention can detect the gas that has contacted sensor.The phenomenon of electric frequency resonance between 500 megacycles, because in this interval, can occur 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 the compound sensitivity of using macromolecular material and carbon black granules composition.Sensor has two conductive electrodes of being isolated by chemically sensitive resistor but being connected to the 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 zone that is formed by non-conductive macromolecular material of arranging in the same way with the approach of current flowing and the conductive region that is 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 has respectively different resistance values with contacting.By this type of sensor group that is formed by the sensor of chemically sensitive resistor more than at least two, different analytes is provided the dissimilarity that is showed by different resistance values like this.Change sensor chemical sensitivity can by quantitatively or the material that changes qualitatively conduction and non-conductive zone form and reach.The conductive electrode that utilizes like this an 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 the Artificial Olfactory instrument to detect the 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.When 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 the research that the Electronic Nose instrument is done till the last century late nineteen nineties and the development that obtains.This report describes the various sensors that are used for making the Electronic Nose instrument in detail, comprised metal-oxide film sensor, conducting polymer composite thin film sensor, by macromolecule membrane be coated in plane of crystal the weight induction sensor, by macromolecule material film be coated in plane of crystal saw sensor, by gate surface scribble the silicon field-effect transistor sensor of metal-oxide film, by the Fibre Optical Sensor of using many sound waves, by the corresponding sensor that forms according to gas chromatography, spectrum and mass spectrum principle.This report has also been summed up the relative merits of various sensors.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 when the 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 that is used 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 with robot system.All sensors that this patent is mentioned, also collected the sensor group of the ditch beam shape of the chunk sensor group of bleeding and micromachining in collecting in the Na Geer document.This patent also discloses the sensor of the electric conductivity of invention simultaneously, its by friendship body between two electrodes arrange by forms regional of conductive material and the zone that formed by the material that is different from conductive material.This sensor just provides the approach that a confession electric current is flowed through the different materials zone between two electrodes like this.
Can see from document cited above and patent in the past to having dropped into great effort in the research of sensor instrument system including, 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.After the technology that comprises large scale integrated circuit, computer software technology and the data remote conveying feed technique of existing sensor apparatus in having used above-described sensor technology and having combined electronic engineering, greatly facilitate detection and discriminating to analyte.
As everyone knows, from the olfactory system of research mammal as can be known, the discriminating of a smell object is not only depended on 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 technology relevant for sensor construction develops according to following two kinds of technical schemes: use the scheme of multisensor structure and the organization plan of application single-sensor.
On the organization plan of using multisensor, as narrating in Lewis's 333 patents, developed numerous different sensor technologies.Include metal-oxide film sensor, conducting polymer composite thin film sensor, by macromolecule membrane be coated in plane of crystal the weight induction sensor, by macromolecule material film be coated in plane of crystal saw sensor, be coated in the silicon field-effect transistor sensor of gate surface by metal-oxide film.Although obtained in the past significant progress at the sensor research along this scheme, it also exists because having followed the shortcoming of using the multisensor scheme to bring.These shortcomings comprise: the sensor of a large amount of numbers of needs produces the Information Atlas that the type difference is arranged of analyte; The labyrinth of sensor and then cause inconsistency in sensor production; When chemical analyte is tested in response to the interference of the humidity that is subject to macromolecule material film; Blunt sensitivity; The instrument of necessary costliness and dark restricted operating conditions.
When using this organization plan, multi-thickness is about sensitivity and the detection limit that the macromolecule membrane of several microns has been widely used for improving sensor.This is mainly to comprise absorption and absorb compound as analyte because macromolecule membrane can be tackled because of its special chemo-selective to compound.Consequently analyte can be enriched in the surface or body of macromolecule membrane before being detected by sensor.
Classical macromolecule material film exists multiple shortcoming.The first, film has high-sensitive adsorbability to the humidity that is accompanied by 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 of using of sensor.Three, obtaining the repeatability that is placed in the macromolecule material film on sensor on producing is also a difficult problem.In particular for adopting the multisensor organization plan, thereby the problem of repeatability is particularly remarkable must use the sensor of a large amount of numbers the time.
Adopting on the single-sensor organization plan, narrating as the 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 makes 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 the medical diagnosis field.In suc scheme, patient's health maintenance comprises that medical diagnosis is that the bedside that directly reaches the patient launches in patient family.Like this, if Medical Instruments is can carry use just to have competitive power on market.Have wireless in addition as again 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 that comprises correct diagnosis for the 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 using single-sensor, the patent received of wearing and Literature Development in specific frequency range, detect from detecting electrical impedance and the electrical properties relevant with phase place thereof of using the conducting polymer composite membrane electrode 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 the electric resonance signal.Yet the electric resonance phenomenon of the device receive of wearing must just might occur in the frequency in 500 megacycle intervals at 100 megacycles.This high-frequency restriction all brings great difficulty to making and the use of instrument.The device of receiving of wearing has simultaneously still been inherited the shortcoming of using macromolecular material to bring.
The single-sensor of the new construction that scans for the not enough of the patent of Pei Na with for the invention applying frequency, grandson's 425 patents disclose the single-sensor as detecting sensor that is used for detecting and differentiating the analyte in fluid.This sensor is comprised of pair of electrodes.When having enough concentration, analyte needn't come the 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 that is provided by an alternating current instrument has been provided sensor, the interchange electrical properties of the sensor on each frequency when 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.The program of differentiating with a type is again distinguished the type of this electrical properties, and compares with the type of the electrical properties of known substance, and 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 variation of the electrical properties of the aging effect of interference, macromolecular material of humidity and the sensor that caused by temperature variation.
The function of the sensor instrument system including that Lewis's 333 patents develop to comprising that the sensor group that is comprised of macromolecular material and carbon black has been added remote information processing.Obvious positive effect is arranged for the effect of sensor instrument system including like this.
Yet in multiple occasion, be included in to detect in air and contain ozone when interior pollutant, sensing system is had an extra requirement, namely this instrument can provide the instant with geographic location of air pollutants to change and the information of variation.So just can draw the instant air-polluting distribution plan in an area, thereby can obtain better understanding and comparatively perfect control to this regional air pollution.Instrument system with this function also is conducive to study many other problems.
Thereby this has just facilitated wish of the present invention: design and develop the shortcoming that a kind of new sensor instrument system including and method overcome traditional sensor device.This new instrument has in the sensor manufacturing and the good repeatability of 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 comes deal with data, with the ability of determining the geographic position corresponding with analyte.
The present invention is conceived to found a sensor instrument system including and method thereof and detects and differentiate analyte in fluid.This system include a sensor apparatus and with its central information station that is separated by at a distance.The composition of sensor apparatus has comprised a detection module that is 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 of 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 that spreads out of of sensor apparatus with storage of analyte of receiving.And these information have comprised the electrical properties of detected analyte and the data of its geographic location.
A purpose of sensor instrument system including of the present invention and method be to provide one for detection of with the novelty of differentiating the analyte in fluid and unique sensor construction.This structure used have two electrodes with the single-sensor of using AC current frequency scanning and vector analysis principle of work.Can use numerous different sweep frequencies in measurement, comprising the frequencies of preferred 10 kilocycles in the megacycle interval., just can obtain two groups and include the interchange electrical properties analyte internal characteristics, that the type rule is arranged the measurement of the frequency sweeping of sensor by once, be included in the electrical properties that can obtain two kinds of different quadratures on each sweep frequency.These character be by in the analyte that comprises specific inductive capacity, polarity or dipole moment feature determine.
Summary of the invention
Another purpose of sensor instrument system including of the present invention is to provide a novel and unique sensor apparatus.This instrument comprised have two electrodes with the single-sensor of having used a-c cycle scanning, can be used to detect and differentiate analyte in fluid.The 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 purpose 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 used ac frequency scanning that have two electrodes and detects and differentiate analyte in fluid.This instrument also includes the mechanism of a removal ground unrest.Namely after having used detecting sensor, also used a reference sensor identical with the detecting sensor structure.Reference sensor is used to reduce ground unrest to the impact that detects the analyte electrical properties and promotes discriminating to the electrical properties type of analyte.Ground unrest has comprised the aging effect of impact, macromolecule membrane of humidity and the variation of the electrical properties that detects that caused by the temperature variation that is placed in the analyte between electrode.
More purpose 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 used ac frequency scanning that have two electrodes and detects and differentiate analyte in fluid.This instrument has adopted and has comprised that fixing and variable temperature controlled program control the temperature in the sensor storehouse that includes sensor and analyte, and then improves detection and discriminating to analyte.
The purpose that also has 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 used ac frequency scanning that have two electrodes and detects and differentiate analyte in fluid.This instrument has can place the function of the organic and inorganic and metal-adsorbing material of all kinds in sensor two electrodes, thereby reaches by optionally adsorbing, absorb corresponding analyte the purpose of improving analyte detection and discriminating.
The another one purpose that also has 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 used ac frequency scanning that have two electrodes and detects and differentiate analyte in fluid.The characteristics of this instrument have: compact volume, easily the palm Portability, easily with, be not subjected to that ground unrest affects, temperature that low cost of manufacture and low power consumption are controlled the sensor storehouse that comprises sensor and analyte.
A purpose 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 analyte in fluid.This sensor has two electrodes and uses the principle of work of AC current frequency scanning and vector analysis.Being filling in the electrode of each detecting sensor at least one detecting sensor, 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 that applies is disturbed.
A purpose 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 analyte in fluid.This sensor has two electrodes and uses the principle of work of AC current frequency scanning and vector analysis.Being filling in the electrode of each at least one detecting sensor, different materials optionally adsorbs, absorbs corresponding analyte.And the pumping signal of ac frequency is closed, applied in an orderly manner, respectively to each detecting sensor in this at least one detecting sensor by electromagnetic screen, thereby the cross-inductive of eliminating the magnetic field radiation that may be caused by the AC signal that applies is disturbed.
Another purpose of sensor instrument system including of the present invention be to provide one for detection of with the novelty of differentiating the 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.
A purpose that also has 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 at a distance.And each sensor apparatus is in a corresponding area in a zone movably, is 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 ac frequency scanning and vector analysis principle of work arranged, 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 of data module, it is used to wirelessly transmitting data.The data of transmission have comprised that the electrical properties of the analyte that detects and analyte are in the geographic position of this area.
The 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 that is connected with antenna and sends the dual-purpose electronic unit.Numerous receiving stations is in numerous corresponding area in a zone, with numerous dispose movably in the sensor apparatus of this corresponding area corresponding one by one.The information exchange of each analyte that sends from each sensor apparatus is like this crossed corresponding receiving station in each department and just can be received by the central information station.The computer stored at central information station contain the global geographic position positioning map in interior application software with include authentication data type analysis method in the application software of interior analytic approach.The electrical properties information of the analyte that obtains in each department like this can be analyzed by the central information station, thereby can differentiate each analyte that is in each corresponding geographic position.After being stored in the central information station by the information in the geographic position of the analyte differentiated and analyte, all application can be arranged, comprise being plotted in this zone the instantaneous distribution plan of analyte in numerous different regions.
Sensor instrument system including of the present invention provides novel and unique sensor apparatus and method thereof to differentiate analyte in fluid.The possibility of discriminatory analysis thing be based in the analyte that detects analyte in fluid the various alternating current character that typing rule is arranged dominated of physicochemical property, form resistance and reactance such as electric current, voltage and electrical impedance and vector thereof, and the phase place that is determined by resistance and reactance.The present invention has used a paired metallic conductor as space electrode, perhaps it is disposed on ceramic substrate as thick membrane electrode, perhaps it is disposed and come the interchange electrical properties of Measurement and analysis thing as membrane electrode on silicon matrix.These analytes can rest on or flow through between two electrodes when measuring, thereby can obtain the interchange electrical properties at numerous sweep frequencies analyte that to be included in preferred frequency separation be 10 kilocycles under the frequency effect of a megacycle.
The measurement of applying frequency scanning can obtain two groups of interchange electrical properties with type rule to each analyte in numerous analytes.After the program of having used 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 from detecting the resulting corresponding numerous electrical properties that the type rule is arranged of analyte.These character are special to corresponding analyte, and are to be integrated on different dimensions.The present invention just focuses on and seeks the different electrical properties that type feature arranged relevant from the natural speciality of these analytes like this, and these electrical properties can be measured to simultaneously by using a kind of technology.
For example specific inductive capacity is one of natural speciality as the compound of detected object analyte own.Specific inductive capacity be compound be used to describe in numerous dimensions of this compound one, specific inductive capacity can be used to the 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 obtain from the electrical impedance that measures in vector category internal reactance.Reactance is a kind of in the special electrical properties that has of analyte like this, is also should be used for detecting by the present invention on a kind of dimension and differentiate compound (in the scalar category, electric capacity is directly proportional to specific inductive capacity, and is used to detection compound.See special this academic report of Bel).
When an analyte was the potpourri of gaseous compound, the specific inductive capacity of this gaseous mixture can be estimated according to several method.For example can be calculated as be the function of temperature, gas density and gas composition: Ha Wei (Harvey, A, H) to the specific inductive capacity of the inflammable gas of natural mixing; 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 the author declare, their method is to be better than traditional mixing rule.When analyte was 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, and perhaps 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 the above result of study that exemplifies as can be known, for gaseous state and liquid chemical mixture, specific inductive capacity remains a kind of dimension that is used for describing their feature.The present invention can use reactance and detects and differentiate as the gaseous state of analyte or liquid chemical mixture like this.
Except specific inductive capacity, has the composition of the chemical element of its uniqueness as the compound of analyte.And each chemical element has its corresponding electronegativity, has so just formed the peculiar molecular dipole distance of each compound or polarity.It is the another kind of natural speciality of compound.In electricity field, can use 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, compare with the reactance of the analyte that measures, as another component resistance of analyte electrical impedance also measured obtaining simultaneously.Yet compare with the amplitude of resistance value, reactance occupies leading status in electrical impedance.This is because (comprise its gas, refer under anhydrous state) that the compound as analyte is nonconducting in pure compound situation.Yet although resistance value is smaller, it has reflected the ohmic speciality of analyte.In other words, resistance is that dimension from another intrinsic property of compound reflects this compound.And the dimension of resistance is with the dimension phase quadrature of reactance.The information of resistance is also very important concerning the discriminatory analysis thing like this.
Using the change frequency, comprising the method for frequency sweeping, the present invention can obtain two groups of alternating current character that characteristic type is arranged such as resistance and reactance of each analyte, thereby can reach the purpose to detection and the discriminating of corresponding analyte.
Electrical impedance is to combine resistance and reactance.Can use Ohm law in interchange electricity obtains:
Z＝V/I [1]
Wherein Z is the 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 when using a galvanostatic technique.When the constant voltage technology of application, be inversely proportional to the electrical impedance of sensor by the current value of sensor.Detect and the purpose 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 when analyte has enough concentration, need to not placed additional material and come the adsorption analysis thing in sensor electrode.During lower than specified sensor signal to noise ratio (S/N ratio), the present invention can use absorption or absorbing material when the original concentration of analyte is enough.Thereby for the sensitivity of improvement sensor and the limit of detection, optionally adsorb or the absorption analysis thing.
Obviously in the sensor electrode filling the resulting dimension that is relevant to the electrical properties of analyte after sorbing material, comprise resistance and reactance, the dimension of resulting electrical properties when 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 purpose from the searching of the present invention electricity dimension relevant to the internal characteristics of analyte, even when analyte has enough concentration, the present invention also can detect and differentiate analyte in fluid at filling sorbing material between sensor electrode.
The process that analyte is adsorbed on the sorbing material surface can be accompanied by the process of absorption, perhaps adsorbs and the process that absorbs can occur simultaneously.Yet can determine according to material elements relevant for 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 specimen module, sensor storehouse module, the heating module that is used for sensor storehouse temperature control, detection module, microcomputer module, the transmission of data module, applied global positioning system.
Detection module has comprised an Analogic Electronic Circuits unit, and it is used as a detecting device.The Analogic Electronic Circuits unit has connected a connector, such as similarly being is transformed into the converter (ADC) of digital numerical value from simulation value.And then be connected to the microcomputer module by converter.This microcomputer module includes home computer's structure of a micro.The module that other are all is connected with the microcomputer module by their corresponding connector if required.In addition, also settled numerous application software in the microcomputer module, included: an application software has comprised the positioning map of global geographic position; Numerous analytic approachs of the analytic approach that comprises identification types have been comprised with an application software.Sensor apparatus can be come 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 the central information station.
Match with being in local sensor apparatus, present invention includes the central information station.It includes the central computer that is 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 zone simultaneously.Network comprised easy house network (Ethernet), at the network of an organization internal, network and the internet network that is connected area, the whole world (the Internet) in a zone.This network comprises to be used up fibre, cable, plain conductor or comprises the electromagnetic interior any mode that is wirelessly connected on.
Each local information receiving station has comprised an information that is connected with antenna and has received and sent electronic unit.This unit has connected one and has had the collection unit of digital data of 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 the central information station, includes contain global geographic position positioning map in interior application software and the type identification analytic approach arranged at the software of 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 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 to have comprised all operations of memory function performance is arranged.Word used herein " connection " has comprised electric connection, and this refers to comprise 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 used a-c cycle scanning that a plurality of frequencies are arranged and the principle of work of vector analysis.In one-shot measurement, just can obtain the electrical properties that type feature is arranged of two set of analytes like this, comprising two different electrical properties can be obtained, as resistance and reactance on each frequency that is scanned.They are the bidimensional dimensions that belongs to mutually orthogonal in exchanging 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 that obtains on one dimension time dimension and detects analyte, the present invention is applied in the character that obtains on the dimension of two orthogonal dimensions and detects analyte and have significant advantage: the present invention uses making and the use that preferred frequency sweeping below 1 megacycle has facilitated sensor apparatus; Because applying frequency scanning the present invention is not subjected to use the analyte sorbing material that conducts electricity to comprise the restriction of conductive polymer film or polymer composite on sensor design, the adsorption that therefore can use all kinds comprises absorbing material and has adaptability widely.
Sensor apparatus of the present invention has been used again the impact that reference sensor is eliminated ground unrest.In addition, also used and comprise that variable and stationary temperature control program controls the temperature in the sensor storehouse that includes sensor and analyte, 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 lower cost of manufacture, compact volume, palm Portability and easy-to-use characteristics easily.
The advantage of above-described instrument of the present invention, particularly being conducive to research and develop with dc-battery is the palm portable sensor apparatus of power supply.This is to cause corresponding little sensor storehouse to control required low power consumption to temperature because of the significant little volume of single-sensor.
Be appreciated that, one of major advantage of the present invention is to have used the single-sensor with frequency sweeping and vector analysis principle of work, thereby can produce simultaneously the collection of illustrative plates of two different alternating current character that type feature is arranged to the one-shot measurement of analyte.When making sensor apparatus of the present invention will be used 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.Caused so again might using the structure of dual sensor actually, namely except detecting sensor, also can use the reference sensor with same structure.
After having used dual sensor, when sample when namely the analyte in fluid is with ground unrest, such as being that when the humidity ground unrest is arranged, sample can be detected by detecting sensor, and detect 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.
Use the dual sensor structure and can also bring the advantage of quick test.This is because of the test to detecting sensor and reference sensor, namely 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 the research to 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 zone.
It must be understood that, present 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 purpose: namely will determine the geographic position of analyte, the present invention also can use any global geographic location positioning system, so long as this system can be for civilian use prerequisite under.
Being described in detail of chapters and sections afterwards discussed and to the request of claim and with reference to more clearly understanding being arranged to structure and the purpose of the invention after accompanying drawing.
The structural drawing of the following discloses that will point out especially is only in order to illustrate rather than limitation of the present invention.Now be described below:
Fig. 1 has shown that using 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 that obtains have simultaneously been used in analysis on each frequency of 7 frequencies.And this frequency at random is taken from the frequency that be scanned of 10 kilocycles to 500 kilocycle intervals.
Description of drawings
Fig. 2 has shown that using 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 that obtains have simultaneously been used in analysis on each frequency of 11 frequencies.And this frequency at random is 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 using two identical sensors 1.One of them sensor is used as detecting sensor 2 and (simply is denoted as: A).Another is used as reference sensor 3 (R).The dual sensor structure that shows in figure does not have integrated form.
Fig. 4 B has shown the integrated dual sensor structure of using two identical sensors 1.
Fig. 5 is the schematic diagram that a single-sensor 1 and an alternating current analyser 9 are electrically connected to.
Fig. 6 has shown that any adsorption material 8 is filled between two electrodes or a capacitor.
Fig. 7 A is used for illustrating and forms the 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 has shown that the wall of conduct the second electrode in single-sensor 4 is connected with the ground zero potential when connecting with alternating current analyser 9.
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 that is connected with local information receiving station by network.This figure has also shown sensor apparatus transmitting information wirelessly a long way off central information station everywhere.The geographic position that has comprised the instrument place in information, this geographic position with the effect of global geographic location positioning system after obtain.
Fig. 9 collects the front elevational schematic that the specimen module 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.
The same structure of Figure 11 in being presented at Fig. 9, shown that also adsorption material 8 disposed the front position in a sensor time storehouse.The adsorption material is used to be adsorbed on the analyte in fluid.Only have like this fluid can be by disposing 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, the 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 that is at a distance.
Figure 13 has shown that using 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 that obtains have simultaneously been used in analysis on each frequency of 7 frequencies.And this frequency at random is 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 the reference 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 purpose of the present invention.Numerous is apparent to this concrete distortion of implementing and improvement for the people who has at same ken.These distortion and improvement all are related with the present invention, thereby these distortion and improvement all are confirmed to be among the expressed spiritual purpose of the claim that is included in 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 zone.The present invention has three purposes.By Fig. 3 and shown in Figure 5, first purpose is to have followed the single-sensor 1 that has two electrodes with the invention theory of single-sensor.This kind sensor can be used to effectively differentiate the numerous analytes in fluid.And this kind discriminating is to reach by the multiple electrical properties that detects these analytes, and this is the feature because of the physics of the uniqueness of these electrical properties and analyte, chemistry, such as specific inductive capacity, electronegativity, polarity or dipole moment are relevant.
First purpose of the present invention is to realize by using the method for using again the electric vector analysis after the scanning of ac frequency to the single-sensor that contains analyte.The scanning of implementing electric frequency can have been connected the single-sensor 1 that contains analyte and complete by the analyser 9 with an alternating current.The present invention just can obtain two groups of electrical properties relevant for the analyte internal characteristics with respect to numerous sweep frequencies of analyte in one-shot measurement like this, and can obtain these two kinds of different electrical properties on the frequency of each scanning.After measuring multiple analytes with such structure, then use data of differentiating the electrical properties of these analytes that the program analysis of type obtains.This just can identify the special type of each analyte electrical properties, its correspondence the specific type of corresponding analyte.Then with the type of having differentiated of each analyte, compare with the type of known substance, thereby can differentiate each analyte.As can be known, first purpose has embodied core technology of the present invention.
Second purpose 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 specimen 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 purpose is that the structure of having used dual sensor reaches.This structure includes 1, one of two identical sensor 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 the electrical properties of when analyte is a chemical mixture resulting a kind of compound or multiple similar compound, thereby reaches the purpose of differentiating this analyte.The scheme of this dual sensor can be used for detecting one or more relevant to the organ disease sign compound biochemical marker in a biological sample especially when medical diagnosis.
Must be clear and definite be that the actuality of using this dual sensor structure comes from special benefits of the present invention: have the single-sensor of small size and its and can obtain the information that the type rule is arranged of the analyte of two series in test once.
The 3rd purpose of the present invention is to have engaged current existing wireless communication technique and global physical location location technology forms a sensor instrument system including in core technology of the present invention.This system by a central information station and with its away from the numerous identical sensor apparatus that is distributed in regional different regions formed.Each identical sensor apparatus includes a detection module, global geographic position location receiver module and a transmission of 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 that distributes with numerous instruments.The sensor apparatus that is in like this an area can be transferred to the information wireless in the geographic position at the information of the analyte that detects and this analyte place the regional information receiving station of 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 the central information station again.Use system of the present invention and can detect simultaneously and differentiate that all are in the analyte of different regions in the same area, thereby can obtain the instantaneous distribution plan of the analyte in this zone.
Of the present inventionly two parts have openly been comprised.First discloses core technology of the present invention: i.e. the principle of work of single-sensor and the a-c cycle that has thereof scanning and vector analysis method.Second portion openly combines the sensor instrument system including of the present invention that forms after the existing wireless information transfer of this core technology and location, global geographic position reception technique.
In sensor instrument system including of the present invention and the method that comprises thereof, analyte is defined as having a compound of numerous same moleculars.This analyte also can be defined as a kind of special chemical mixture that is comprised of different compounds.In this kind potpourri, each compound all has numerous identical molecules, for example that a kind of potpourri of 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 be not added gas odorous in this kind potpourri.But analyte is scent of also.As if compound acetic acid, perhaps as if contain sewage odorous.One analyte group refers to numerous different compound of analyzing 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 that contains in the air of earth's surface), comprise with medical care (such as the biological sample that includes oral cavity smell) that medical diagnosis is relevant, comprise with scientific research (such as the quality that resembles research spaceship Air) that space research interest is relevant, relevant with each industrial interest, comprise that food industry (as includes meat, the detection of fish freshness), beverage industry (such as the odor detection that includes lemon beverage), agro-industry (such as the detection that includes the degree of ripeness of fruit), chemical industry (such as including the monitoring that hydrogen chloride gas is produced), petroleum industry (such as the detection that includes combustible gas leakage), plastics industry (such as the control that includes production run and product quality), building industry (such as the monitoring that includes the air quality in New Dwelling), medical industry (such as the research and development that include new medicine), auto industry (such as the supervision that includes lubricating oil and various liquid), biochemical industry (such as including the synthetic of biochemical article by enzymic catalytic reaction), with transportation industry (such as the monitoring that includes the waste gas of discharging), 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 revealing the liquid on the road surface), with (such as the chemical substance that be used as 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 lodge analyte or analyte group.Analyte itself can be used as fluid under a pure state.When 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 during 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 that is injected in chromatographic column.
The fluid group refers to numerous different compounds, perhaps numerous different chemical mixtures.For example the numerous patients of research by the caused halitosis of odontopathy the time, sulfuretted hydrogen is the analyte at research interest place as a kind of biochemical marker.Its halitosis to numerous patients is common.Obviously except the sulfuretted hydrogen symbolic gas, what also have other in patient's oral cavity gas is not the gas of research interest.Those gases are fluid.Yet the composition of this kind fluid is different because of different patients.For example have in fluid by the patient and breathe the carbon dioxide that causes and the oxygen that does not consume.Their corresponding number percent is to comprise that with its corresponding patient's health condition the function of the function of lung and hematological system is relevant.The sample of all patients' the oral cavity gas that detects, have identical symbolic gas and different fluid like this.In this case, just drawn into a kind of sample sets of the present disclosure, can be referred to as: a kind of analyte in the fluid group.
Analogize according to above-mentioned example, the numerous patients of research suffer from the oral cavity gas sample of numerous Different Organs diseases such as pneumonia, ephritis and enteritis the 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 the fluid group.
Opposite 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, namely a chemical mixture separates and to form.It must be understood that, the analyte group's in a fluid who produces in chromatographic process sample is a special case.Separated numerous different compound in this potpourri just because of the detachment process of chromatogram, made these compound sequentialities ground, respectively be contained in an identical fluid in chromatographic column.Another sample is the air pollution case from a zone.In this case, held corresponding to the different pollutant in different regions in the zone in the same air in whole zone.
Yet it must be understood that, as on the whole, the differentiation of the sample sets of analyte group, the analyte group in single fluid and the single analyte in the fluid group in the fluid group is arranged, 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 have the situation of an analyte in a kind of fluid.
As everyone knows, compound has the specific inductive capacity of the feature corresponding with it.Each compound includes again the number of chemical element.And various elements have the electronegativity of characteristic of correspondence.In addition, each compound has unique molecular structure, size, weight, the shape that comprises symmetry and dipole moment on molecular level.These key elements have determined the feature as the physics and chemistry of each compound of analyte.Also just affect simultaneously each compound or chemical mixture and made mutually the process of the sorption and desorption of used time with sensor electrode.
When being encouraged by the ac signal that a frequency is arranged, the feature of their physics and chemistry can exchange electrical properties with some and describe when these analytes: such as electric current, voltage, electrical impedance Z and its phase sensitivity element that comprises: 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 interchange electrical properties can be obtained by the analyser 9 connection single-sensors 1 of using an electrical impedance analytical instrument or other known alternating currents.This single-sensor has the simplest form, be namely the pair of metal conductor as a pair of space electrode, perhaps the pair of metal plate is as a space electric capacity.This also can be placed on ceramic substrate to electrode or form corresponding thick membrane electrode or membrane electrode on silicon matrix.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 the 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 LThey can be described to respectively:
X C＝j(-1/2πfC) [3]
X L＝j(2πfL) [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 the short electrode of using in the present invention, the numerical value of electric capacity is much larger than inductance.So reactance presents capacitive reactance basically.Like this, reactance is a good approximate representation of capacitive reactance.
If when an analyte that has between electrode in a fluid, reactance is X (2).If when only having this fluid between electrode, 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 used the method that changes the frequency of AC signal, the present invention just can construct the chemical feature that a reactance spectrogram is recorded in the inherence of this analyte on each frequency.This reactance spectrogram has just comprised the interchange electrical properties that the type rule is arranged 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.The surface resistance of the device that has perhaps been affected by analyte is so this resistance is the significant characterization of molecules that combines analyte.When for example being exposed to the metal-oxide film sensor 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 changes of conductivity (resistivity) has pointed out resistance can be used to record the chemical speciality of this analyte inherence as polarity or dipole moment like this.
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 in addition is also simultaneously available.Like this, than the form that reactance changes, the change Δ R of resistance can confirm as on each frequency:
ΔR＝R(2)-R(1) [6]
Wherein R (1) is the resistance of the sensor when not containing any analyte in fluid.R (2) is the sensor resistance when containing analyte in fluid.The change of resistance is the contribution because of analyte as can be known.
Compare the resistance of an analyte and the size that reactance is contributed electrical impedance, reactance accounts for leading status in electrical impedance as can be known.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 on each frequency resistance and change the information that Δ R and reactance change Δ X, perhaps they one of with the information of phase change Δ θ, the perhaps change of electrical impedance just can be built into a curve map.The change with respect to scanned many multifrequency resistance, the change of reactance, the change of phase place or the corresponding curve of change of electrical impedance have wherein been comprised.This each curve has shown the speciality of chemistry of inherence of the uniqueness of analyte.
In the research of common this curve of analysis, can first study the curve that this has recorded the 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 obtained the curve map of the interchange electrical properties that the type rule is arranged of numerous each analytes of correspondence.
Except the curve of above-mentioned drafting, outside its mode as a kind of continuous type expression of the electrical properties that analyte is had the type rule, the mode that the discrete type of this character is expressed is arranged also.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 that obtains on same frequency, such as resistance and reactance.Under this structure, the perpendicular column number that this matrix is maximum is the number (check the mark and analyse instrument relevant for the technical stipulation of the sweep frequency number of record) that doubles the frequency of scanning; Perhaps the number on this perpendicular hurdle can be decided by the number of random frequency of taking out from scanned frequency; Perhaps can be decided by the number of the specific frequency of choosing.One horizontal bar of this matrix is to insert the electrical properties that is detected with respect to each analyte on selected frequency.Obviously, same analyte once can measured in experiment over and over again.Just have in matrix like this to should analyte measured a plurality of horizontal bars repeatedly.
According to above-mentioned step, can set up a matrix that has comprised numerous analyte electrical properties.As suppose that each analyte is only once measured, each horizontal bar of this matrix has represented the electrical properties of each analyte with respect to selected frequency.
Because the change of the 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 use 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.Used the above-mentioned analytic approach that type is differentiated that comprises 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 an analyte that will obtain compares with the type of the electrical properties of numerous known substances in built database, and 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 purpose, other the frequency that is different from this optimized frequency also can be employed.Yet use this preferred frequency, not only can the discriminatory analysis thing but also increased convenience when 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 extremely is suitable for being used as detecting device and the detection method that comprises gas chromatography and liquid chromatography.This is because under each compound in potpourri is centrifugation in chromatogram, is separated one by one and concentrate gradually in chromatographic column, thereby just having created the Fundamentals that each compound can be detected respectively.New detecting device and the method for the present invention not only can provide the information of the quantity of analyte after using single-frequency like this, and can provide to differentiate it is the information of which kind of analyte after having used a plurality of sweep frequencies.In addition, use this detecting device and detection method and can not damage sample when test 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.By detecting again this analyte after the step that concentrates or optionally be concentrated in the analyte of content rareness in fluid.Because this speciality, make the present invention to utilize numerous existing and develop perfect technology and concentrate and be concentrated in selectively chemical marker or mark group in analyte, thereby reach high sensitivity and the selectivity of sensor.
This class technology be usually directed to use macromolecule material film, macromolecular material and inorganic material compound substance, contain the platinum metal-type metallic particles compound substance, be applied in the 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 that is applied in numerous industry.For the purpose of using hydrogen fully, detect and differentiate that hydrogen is particularly crucial.After the present invention can use and contain metallic palladium particles and concentrate hydrogen selectively by compound substance organic or that inorganic filling material forms for this reason, then come method to its measurement.This design has utilized hydrogen that the feature of great solubleness is arranged in Metal Palladium, can absorb as Metal Palladium and hold 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, the 4-12 page, 1993 to 1994 versions).Because this cause, palladium metal are referred to as " trap of hydrogen " usually.Can not be subject to the restriction whether sorbing material conducts electricity because of the detection to analyte again, so the present invention has great dirigibility, can decide the ratio that contains the palladium particle in composite adsorbing material according to the variable concentrations of hydrogen in fluid, comprise the shape of particle.By having tackled the hydrogen that detects after hydrogen in fluid in fluid.
In addition, Metal Palladium is one of metal in the platinum group.The platinum group is comprised of ruthenium, Rhodium, palladium, osmium, iridium and platinum.They have the similar character (chemistry and physics handbook, the 24th edition, the 4-15 page is to the 4-12 page) that comprises the physics and chemistry of the solubleness of hydrogen.Like this, each metal in the platinum group is all suitable and can be applied among the present invention.
Gas Phase Adsorption chromatographic applications solid particle optionally adsorbs various gases 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 (the above-mentioned application of setting forth materials is seen everywhere, and comprises bohr and bohr: Poole, C.F.and Poole, S.K. such as the tetrafluoroethylene macromolecule material particle; Today chromatogram: Chromatography Today, 199 pages to 209 pages, Ai Er Seville Science Press: Elsevier ScientificPublisher, 1991 and the document wherein quoted).
For example molecular sieve is a kind of material that contains accurate dimension and even distribution micropore.Can control in molecular sieve making process and generate this kind micropore.Molecular sieve is by widely cognitive and be applied to adsorbed gas and liquid.Strong physical action is arranged between molecular sieve and absorbate.It can come separate analytes according to size, configuration, polarity and the unsaturation of analyte molecule.For example molecular sieve is easy to adsorb carbon monoxide and surpasses in the absorption helium, and can preferentially adsorb polar molecule or the asymmetric molecule that comprises aerobic, sulphur, chlorine and nitrogen element.Molecular sieve can adsorb and keep 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 each compound in a mixture is to carry out according to optionally being used between the vapor pressure of each compound and itself and the macromolecular material that is used as the fixedly phase in chromatographic column.In the 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 the capillary hollow post.
As will understand above-mentioned selectively acting on the degree of molecular action, this kind effect is that building is on each compound and the intermolecular effect between 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 helps 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 that is used for chromatographic column of polarity; And nonpolar compound trends towards nonpolar stationary phase material.
According to the above-mentioned principle that represents with metaphor, can use a kind of stationary phase material and reach the purpose of dividing selectively molten certain compounds.Fixedly the polarity of 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-three 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 derivatization reaction be well-known (bohr and bohr, today chromatogram, chapter 2, and the list of references of wherein quoting; West Buddhist: Hyver, volume is seized; The mulberry rank of nobility: Sandra, the author is invited; The high resolving power gas chromatograph: High ResolutionChromatography, 2-1 page be to the 2-16 page, the 3rd original text, and Xi Laite-Pan Kate company: Hewlett-Packard, 1989, and the list of references of wherein quoting).With regard to the similarity of polarity, changed the polymer siloxane macromolecule of polarity via specific derivatization reaction applicable to being permitted accordingly eurypalynous compound like this.
Be below all derivants of well-known siloxane polymer, it often is used to and optionally divides the classes of compounds that is dissolved in fluid.
1, contain 100% pair of methyl polymer siloxane, be used 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, be used for biphenyl that analysis of analytes comprises the hydrocarbon of pesticide, aromatic hydrocarbon, multiple chlorination, saturated oxygen compound, aminated compounds, aromatics oil, pharmaceutical compound, to the compound that comprises herbicide of 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, contain the polymer siloxane that 50% phenyl and 50% methyl or three are fluoridized the propyl group methyl, comprise the influential compound of environment, solvent, ketone compounds, drugs compounds, steroids and halogen-containing compound for detection of analyte.
5, contain the polymer siloxane of two methyl of two phenyl of 65% and 35%, include 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 comprise that with multiple the target compound of aminated compounds acts on mutually.And amine comprises that derivative aminated compounds is as confessed biochemical marker in patient's pathology sample comprises the oral cavity smell sample in numerous researchers' the research report for the diagnosis various diseases.The result of study of above-mentioned part has been listed in Lewis's 333 patents.For shortening length disclosed by the invention, now those results of study of enumerating all are incorporated in of the present invention disclosing.
Except above-mentioned siloxane high molecular polymer with and derivant, between the polymkeric substance of the phenylethanol polymkeric substance that connects of position, ester of phthalic acid, ester, such as the polymerization ethanol and the liquid organic salt that similarly are polymerization glycol and so on are all polymkeric substance commonly used in gas chromatography.It is used to the Compound Phase effect similar with its polarity.For example the polymerization glycol is the fixedly 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, usually is composed of by organic ammonium or organophosphorus positive ion and protophilic negative ion.This kind ion ratio is the 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; West Buddhist and the mulberry rank of nobility, high resolving power gas chromatograph, 2-9 page).
The high molecular polymer that comprises above-mentioned macromolecular material is to be painted on the outside surface that solid is supported particle when being used in the filled type chromatographic column, or is the inside surface that is painted on hollow pipe column when being used in hollow capillary chromatographic column.Yet, before implementing the coating step, solid is supported particle surface or is a common well-known step to the depolarization of hollow chromatographic column inside surface.Implement this step and be in order to keep or to strengthen the coated article surface to the wellability of macromolecular material, thus desirable uniform surface coating.
Generally speaking, depolarization is that silanol with solid surface changes into silicon ether through chemical reaction.This chemical reaction has been used the two chlorinated silane (DMCS) of two methyl, [dimethyl-(trimethyl silyl is amino) silicyl] methane (hexamethyldisilazane), trimethyl chlorinated silane (TMCS) or has been formed or also can use the 18 two methyl chlorinated silane (octadecyldimethylchlorosilane) of ring (Bohr and bohr, today chromatogram) by above-mentioned chemical agent combination.
In the making of gas chromatographic column, supporting particle surface to be connected modification and to form with being connected of high polymer material chemical key with the open hole capillary column inside surface to solid is also the means of commonly using.A kind of scheme relates to the surface of simple function group or multi-functional alkyl or cyclic silane reagent and elemental silicon or diatomaceous support particle, perhaps the chemical reaction of the hollow chromatographic column inside surface made of fused quartz.The connection of high molecular polymer may be connected chemical bond and produce being connected of firmly chemical bond that high molecular polymer and solid are supported the surface of particle or chromatographic column inside surface by being formed simultaneously the silane key with macromolecular polymerization reaction in reaction.
Another kind of scheme is that the surface of the support particle that is coated with macromolecular material or the inside surface of chromatographic column have been used 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 be used the siloxane of the vinyl that contains varying number, tolyl, octyl group and promote formed crosslinked polymkeric substance (bohr and bohr, today chromatogram, 122 pages to 127 pages, 132 pages to 152 pages).
The present invention's prior art that can use above-mentioned success is processed thick film or the thin-film electro pole plate surface of the corresponding single-sensor that is comprised of ceramic substrate or silicon matrix like this, perhaps be used in the surface of the solid support particle on space electrode, the coating of the macromolecule membrane of agreeing.
Use the technology of single-sensor and ac frequency scanning, the present invention not only can access the electrical properties with type feature of analyte, and can obtain the distinguished advantage that comprises undersized sensor and sensor storehouse in sensor design.And this undersized sensor and sensor storehouse make the present invention in fact in sensor production, particularly when making the palm type electronic nose instrument that is driven by battery power, can use the structure of dual sensor.
In the dual sensor organization plan, the present invention has used 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 that is 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 that is obtained by detecting sensor, ground unrest comprises that the impact of humidity just can be excluded.So just guaranteed can not to obtain to contain the information of analyte of the mistake of ground unrest.
One of application of dual sensor is particularly conducive to the medical diagnosis to patient's loss mode of operation, such as if in patient's ear and the diagnosis of mouth disease.In such diagnosis, the characteristic gas potpourri that is produced by the bacterium that causes disease, be namely the analyte of Electronic Nose instrument, covered by the humidity in the breathing gas sample of oral cavity, this be because the concentration of moisture that causes humidity normally significantly greater than the concentration of analyte.Use dual sensor structure of the present invention and just can remove humidity to the impact of analyte when detecting the oral cavity gas sample.
Use in detecting patient oral cavity gas sample and include 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 using 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 a plurality of biochemical objects.Use the dual sensor strategy when detecting biochemical object (group), available detecting sensor removes to detect the sample with the analyte in fluid of ground unrest.Remove to detect the analyte in fluid of being comprised in same ground unrest with reference sensor in addition, but do not contain this biochemistry object (group) in analyte this moment.This has utilized suitable sorbing material to come selectively before reference sensor, and the hurdle has cut and should cause (seeing Figure 11) by biochemistry object (group).This hurdle cut before reference sensor detects and completes.Then the electrical properties that detecting sensor is obtained deducts and obtain electrical properties on reference sensor, just can obtain the electrical properties of this biochemistry object (group).
Below enumerated the biochemical object corresponding with known organ disease that is used 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 in the researchist's of the University of Colorado in U.S.'s baud city (Boulder) result of study." 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﹠amp; The world, Pittsburg that Engineering News held in U.S. Pittsburg relevant 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: the people such as Narasimhan are published in NAS's journal: on PNAS, and 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﹠amp; Rectum, the 36th volume, No. 6,597 pages to 602 pages, in June, 1993.
(7) carbonyl sulfide relevant with lung qi bubble fiberization: cysticfibrosis.Visit branch school: UC by Europe, University of California, the press room newpapers and periodicals report of Irvine, on October 17th, 2005.This result of study also is reported in the online bulletin of NAS, in October, 2005.
(8) iso pentane two floride relevant with the 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 with comprise the aniline of contraposition toluidine.By O 'Neill: the people such as O ' Neil are reported in " medical clinic chemistry ": Clinical Chemistry, 34 phases,, the 1613rd page in 1988.
Simultaneously, have been reported 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 (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 has been used 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 the malabsorption that detects fat; Uracil is used for testing the activity of dihydro-pyrimidin deoxidation hydrogen enzyme; Conduct is caught as inner with urea: the test of H.Pylori inflammation (Li Si ratio and Suhl lattice).
Must be clear and definite be that biochemical object exists in urine, ight soil, serum, blood and saliva sample in sufferer 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 purpose of medical diagnosis.
The 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 that on February 28th, 2008 was reported recently; Du flutters inferior: Dobson, " the online mail " of Britain: Mail Online Internet enterprises, the result of the London's Imperial College that on June 5th, 2008 was reported).
Except being used to medical diagnosis, oral cavity breathing gas sample also is used to monitor the anesthetic content in patient's body in operation.This is 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 in the gaseous sample of oral cavity; Britain anesthesia institute periodical: British Journal of Anaesthesia, the 91st volume in 2003, No. 6,797 pages to 799 pages).
In the medical diagnosis field, the body odour that how to utilize the mankind is also a problem that receives much concern.Such as find afterwards after testing to have the compound Sai Qie Fo Ruiniya of family: Schizophrenia from the taste of one or two people's a kind of special epidermis (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).
In addition, the method and apparatus of collecting gaseous sample is also already by cognitive (special anti-people: the Gardiner of grade of loud, high-pitched sound, the disease in virgin child period: Archives of Disease in Childhood,, 56,125 pages to 127 pages in 1981).The present invention also just can be used to the researching human body body odour like this.Can use under study for action to detect at random, perhaps detect the sample of the patient's body odor that has been collected into.The sample that comprises the body odour that those foots from human body, oxter and thigh root are collected, this is to cause the generation of disease because bacterium is most likely at those positions assemblies.
In the structure of using dual sensor was come the impact of correcting background noise, except humidity, the present invention can also be used to compensate other ground unrest.Such as the aging effect of macromolecule membrane and the electrical properties fluctuation that is caused by temperature fluctuation.Accuracy and the accuracy of the electrical properties of analyte have so just been 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, the control program that comprises 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 temperature to the sensor storehouse that comprises sensor and analyte.The program also just in fact can application of temperature controlled of the present invention like this, the control program that comprises thermograde comes the sorption and desorption process in control analysis thing and sensor electrode mechanism.This temperature is controlled and is particularly conducive to that the present invention makes, the battery-powered portable Electronic Nose instrument of palm by using.After having used above-mentioned temperature controlled program, the present invention might come to show fully analyte the inherence chemical speciality and reach high-quality detection and discriminating to analyte.
Due to above-mentioned all characteristics being arranged, 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, when design Electronic Nose instrument, due to particularly because low sensor production cost, so single-sensor of the present invention is extremely to be suitable for making disposable sensor.
Example
Following discloses relate to example and the experiment situation of single-sensor that core technology of the present invention is namely used the principle of work of ac frequency scanning and vector analysis.It is only to be 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.Concentric cable with standard connects this electrode and an alternating current analytical instrument, such as Ai Jielun 4294 electrical impedance instrument: Agilent 4294A (Ai Jielun company: Agilent; California, USA Borrow Ao Erduo city: Palo Alto).Before specimen, first this electrode is carried out electricity and demarcate.Use the method for ac frequency scanning and vector analysis when test resistance is anti-, thereby on each frequency that is scanned, can have obtained simultaneously two kinds of electrical properties of electrical impedance and the various combinations such as phase place or reactance and resistance.
10 kilocycles have been used to the frequency sweeping in 500 kilocycle intervals in first experiment.Used 500 kilocycles to the frequency sweeping in 1 megacycle interval in second experiment.Five kinds of different compounds are used as corresponding analyte, comprise acetone, acetic acid, positive six carbon alkane, toluene and water, and indoor air is 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 when 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, at first the air in test cabinet is fluid, and records its electrical properties such as electrical impedance, reactance and resistance.And with them as reference numerical value.When specimen, open a sample plasma bottle that holds this sample, then this electrode is put in bottle until till the liquid level of electrode front end near this chemical example.Also clog cable and the space that bottleneck occurs simultaneously mutually with a cotton ball this moment, prevents the fluctuation of this chemical compound gas concentration in bottle.Before the electrical properties of specimen gas, again with the time of ten seconds as wait.Sample tested complete after, immediately this sample bottle is removed from electrode, and by capping upper bottle cover again.The sample of this tested mistake no longer is reused in experiment.
Before sample test next time, 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.
When data analysis, this sensor electrode can be by following formula to the change of a kind of electrical properties of each tested analyte.It has represented the electrical properties under this electricity frequency of this test compound.
The electrical properties of the electrical properties-air of the change=sample of electrical properties [7]
Collect the corresponding compound data that resulting electrical properties changes under different frequency, and construct thus the matrix of a raw data.And the frequency of these collections is at random to be taken from all frequencies that was scanned.
The data on every two adjacent perpendicular hurdles have represented at one and have selected the change of the compound resistance on frequency and the change of reactance (or change of the change of available electrical impedance and phase place) in matrix.The data that each in matrix is walked crosswise represent that this test compound is through once being selected the change of the corresponding electrical properties on frequency at all after test.And all walking crosswise represented the electrical properties data of the samples that is repeated to test all in experiment.Analyze data in this matrix by using 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 using 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 on each frequency of seven scanned frequencies 10 of taking out arbitrarily, 20,50,100,200,300 and 500 kilocycles and reactance are analyzed.After having used principal component analysis (PCA), the type of the electrical properties of many compounds has been distinguished, and according to the number axis of the quadrature of the two major component F1 that calculate and F2 and arrange.It must be noted that those data have first been passed through normalized before using principal component analysis (PCA) and analyzing reactance and resistance data in matrix.
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 a specific region that concentrates on the plane that major component F1 and F2 determine, and five kinds of different compounds are respectively disposed at F1 and F2 to determine corresponding zones of different on the plane.In other words, under the analysis of principal component analysis (PCA), five kinds of compounds have embodied them and have been distributed in the first and second major components and determine a kind of type feature on the plane.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 electrical properties comprised the sweep frequency interval 10 kilocycles between 500 kilocycles, obtain on each frequency 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 resistance of the correspondence that obtains on each frequency of the frequency 502,550,600,651,700,750,801,850,901 of being taken out arbitrarily, 949 and 1000 kilocycles 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.When the data of using principal component analysis (PCA) were processed, the raw data of the resistance of compound and reactance was done the analysis of type difference again after normalized in matrix.Experimental result has shown that electrical impedance and mutually responsive component thereof can be used to identify corresponding compound.This is feature is arranged to be distributed on by the first and second major components according to five kinds of different compounds to be determined that a type of different zones on the 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 the 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) use corresponding resistance and the reactance that obtains on each frequency of 7 frequencies 10,20,50,100,200,300 and 500 kilocycles.These frequencies are at random to be taken from interval 10 kilocycles of sweep frequency all frequencies that was scanned in 500 kilocycles.
By 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 on the plane that is 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 the organic compound of water, the alcohol take ethanol as Main Ingredients and Appearance and other many easy gasifications.Comprised too like this compound of these mixing in the gas on white wine liquid level top.The result of this experiment has proved that electrical properties can be used to distinguish the analyte that belongs to chemical mixture, because the zone of its distribution on F1 and F2 face is different from the zone that belongs to the correspondence that simplification compound acetone and toluene distributes.
Must be clear and definite be to use above-mentioned frequency just for the validity of the principle of the invention and purpose is described.Rather than attempt goes to limit the application in the present invention of other frequencies, and other frequencies refer to from published frequency in the present invention and different frequencies.
Again can be clear and definite be to be used for confirming just can setting up a model to an experiment of having stipulated by the step of using the resulting result of principal component analysis (PCA) according to well-known.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.
In case set up above-mentioned database, identification one unknown analyte, the result of the principal component analysis (PCA) that obtains according to the model regulation that can be by should the unknown analyte is compared with the result of the known analyte in database and is reached.Like this relatively can be according to well-known step, wherein also comprised the diagram intuitively of one of principal component analysis (PCA) feature 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 to differentiate to analyze with the type of above-mentioned principal component analysis (PCA) the result of electrical properties and the confirmation analysis of analyte in fluid.The present invention can use 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 analyte in fluid.Because can select an analytic approach after the different emphasis point of more various analytic approachs 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); Backbone network technology guidance and guideless cognitive-ability is arranged: Supervised and Unsupervised Learning Neural Network; With fuzzy backbone network technology: Fuzzy Neural Network (finish: Beebe, K.R. by skin; 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 generation publishing company thereafter: John Wiley﹠amp; Son, Ltd.).
From above-mentioned experimental result as can be known, except analyte in fluid was differentiated in the detection of applying frequency scanning, the present invention can also use 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 the numerous compound in this potpourri is separated in chromatographic column, and is 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 as if that the electrical properties that exchanges of different electrical impedance is arranged on this detected frequency because of the carrier of gaseous state and 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 a kind of in the above-mentioned electrical properties that detects on a frequency and come those separated compounds of alleged occurrence.
When application single-sensor of the present invention designed the detecting device of a gas chromatography, a preferred structure was that a space electrode of single-sensor can like the columniform axle sleeve of a hollow.The cylindrical electrode of this hollow is an 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 connected with the tail end of chromatographic column is coaxial 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, and are simple in structure and bring easy making by it, and characteristics cheaply.
In addition, to the above-mentioned detecting device that comes detection compound whether to exist with electrical impedance or voltage or electric current of using in chromatogram, the pumping signal that can use 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 application single-frequency test, the safety for mine is produced detects inflammable gas in well, is very important such as liking gas and so on.Detect this type of gas and can use single-sensor of the present invention equally.The pumping signal of added single-frequency can have the form that comprises square wave, triangular wave and sawtooth wave to detect a kind of electrical properties of this gas.
The ac-excited signal that produces single-frequency can be used well-known oscillator, include the 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 is from design: Electronic Devices, a design approach; Bi Yaxun, Pan Tesi room printing firm: Pearson, Prentice Hall, 2004).The integrated package AB-112 (Analog Devices Inc: Analog Devices, Massachusetts, United States: Massachusetts, USA) that uses Wien bridge oscillator is for example arranged on market.Like this electrical impedance of single-sensor can be used as this integrated package the 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 when 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.For example the first electrode of this sensor is the wall that is placed near a container, perhaps other structure.This wall or structure are made and be connected with the 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.When detecting, the detected analyte in fluid can be directed and pass through by the gap of the first electrode with this container wall or other structures.
Single-sensor of the present invention has been used the periodicity with frequency sweeping performance and has been comprised sinusoidal wave electric excitation signal and the method for vector analysis, thereby numerous advantages is arranged.It can just obtain two kinds of collection of illustrative plates of the alternating current character that the type law characteristic is arranged of record analysis thing in one-shot measurement.The little volume that sensor has only needs the sensor storehouse of small size and brief biography sensor storehouse temperature is controlled required low power consumption.These features make the structure that can adopt actually dual sensor, namely add when using a detecting sensor and use a reference sensor consistent with its structure.Use the dual sensor structure, can eliminate the impact of ground unrest, comprise the impact, macromolecule membrane aging effect of humidity in various degree and the variation of the electrical response that comprises sensor in test that causes because of temperature variation.
The principle of work of single-sensor of the present invention and method has been used 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 the type rule is arranged 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.But palm portable sensor apparatus of the present invention is like this advanced your practical application and is comprised that temperature control program fixing and that gradient is arranged optimizes detection and the discriminating to analyte in fluid.
In addition, use and periodically include sine-shaped alternating current driver signal, the present invention has just possessed the adsorption of application 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 have low manufacturing cost, compact volume, Portability and the convenient characteristics of using flexibly.
The above open core technology of the present invention of having introduced: the i.e. alternating current driver signal of the frequency sweeping that comprises 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 the analyte of discriminating in fluid; Determine the geographic position of analyte; And transmitting information wirelessly.The central information station has connected a local information receiving station by a network.This receiving station has comprised the structure of transmitting information wirelessly, can receive mutually and transmission information with sensor apparatus.This system just has the ability and the ability of determining relevant analyte geographic position of wireless telecommunications analyte information like this.On this framework, instrument system of the present invention can be provided to the full extent movably, detect at a distance and differentiate analyte in fluid.This kind performance has been worked in coordination with the performance that can determine the geographic position of relevant analyte simultaneously.In addition, if used numerous identical portable sensor apparatus, it is distributed in different regions accordingly numerous in a zone, and system of the present invention can set up the instantaneous distribution plan to this zone inner analysis thing.
The composition of sensor apparatus combine core technology of the present invention, at present known comprise for the so-called hardware technology of the electronic component of wirelessly transmitting data and comprise the so-called software engineering of calculation procedure and applied global positioning system after can obtain the technology of geo-localisation information.
What can feel glad favour is that the structure that contains the analytical instrument of microcomputer has just been known by people a long time ago, can be for example " chemical apparatuses: series ground elaboration " 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 generation publishing company thereafter: John Wiley﹠amp; Sons, lnc., cognitive this special topic over 1989.In a broad aspect, analytical instrument is to be analyzing and testing device mimic channel used part by one, has connected to include an analog quantity to the connecting portion of digital quantity converter.This connecting portion partly is connected with a digital circuit that contains a built-in microcomputer again.Specifically, this mimic channel is partly to be connected with the input and output numerical data transfering channel of microcomputer by converter.
had 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, the data address element, include calculating, the central microprocessor of logical block and register, the numerical data transfering channel of memory cell special use, 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.Obtaining this result is to have used single-sensor to have connected all as if the alternating current analytical equipment of Ai Jielun 4294 electrical impedance analysers is obtained after home computer with having used.Stored the application software that contains principal component analysis (PCA) that is used for analyzing the electrical properties data that obtain in computing machine.Like this, just drawn instrument into a combination if connect instrument Ai Jielun 4294 and home computer with the cascaded structure of digital transmission or parallel-connection structure.And this combination has just embodied the basic structure of sensor apparatus of the present invention.This alternating current analyser is as the analyzing and testing device of combined instrument in combined instrument, is used to measure the data that in the fluid sample of analyte obtains the sample electrical properties.Be equipped with and stored the hardware and software of suitable use for data transmission in this home computer, comprise drive software for the use of connections be used as combined instrument digital circuit partly.It is used to analyze data and discriminatory analysis thing.
Its this structure that the Electronic Nose instrument of narration is also arranged in the article that Na Geer delivers in addition.Its composition has three unit: a sample storer, a gas sensor group and a signal processing system.After connecting, these three units in series are used to detect gaseous sample odorous.
By Fig. 8 and shown in Figure 9, sensor instrument system including 16 of the present invention is comprised of following parts like this: the sensor apparatus 18, of an integration has central information station 90, one 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 comprised of the module of eight connections.Collect specimen module 20 comprising one, it includes a sample driver element 24, a sensor storehouse module 28, pastes the external heater 82, a detection module 40, a microcomputer module 50, a transmission of 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.Its equivalence is 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 as if at above-mentioned formula [5,6,7] change with respect to the electrical properties on each frequency of each analyte of discussing in, and and be established as a raw data matrix of the use of the follow-up data analysis of differentiating each analyte with it.Except using 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.
It is the required necessary element of self operation that module 50 has, and comprises a central microprocessor, remembers Yi component information transfering channel, comprises the note Yi element of 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, the positioning map of applied global positioning system that includes principal component analysis (PCA) at software, a software that is used for encrypting of interior numerous analytic approachs and include to determine the geographic position when 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 instruction into instrument work by operating corresponding button, thereby selects the work functions of required sensor apparatus.For example, the application software that shows this detection use.Except with button, the display screen 52 of module itself also has the function of input message.The 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 that obtains 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 satisfies the needs that comprise data wire transmission.
In a kind of preferred situation, the application software of this detection use is window type, and it has comprised numerous programs.These programs are to instruct each duty of analytical instrument 18, comprise detect analyte, collection is with storage data and connect other above-mentioned application software.For example its instruction that has operation to collect specimen module 20 and operation detection module 40 detects the analyte in fluid and puts down in writing data; The instruction of geographic position data is checked and approved in receiver module 72 work of indication location; Come the instruction of wirelessly transmitting data with indication the transmission of data module 68.This software can comprise following disclosed basic part.
First part is the identity of registering many analytes, comprises type and the title of analyte.If an analyte is to belong to the biological sample that gets from the 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 the patient, login this real sample type.In order to ensure authenticity, the date and time of analyte testing by the instrument onboard clock data and login.
The second part is the numerical value of logining as the alternating current that uses of test, for example comprises the amplitude of pumping signal and applies the type of frequency.The type of frequency has comprised to be used the single-frequency type of particular frequencies and has beginning and the type of the sweep frequency of termination frequency.In the type of sweep frequency, the multiple choices of how coming collection analysis thing electrical properties according to frequency have been comprised again.Some frequencies that are captured in arbitrarily in scanned frequency are wherein arranged, some particular frequencies that are chosen in arbitrarily in scanned frequency are perhaps arranged, perhaps collect the frequency of all numbers that in fact were scanned in the sweep frequency interval.In the second part, comprise that also selectable "Yes" and "No" determine whether to start location, global geographic position receiver module 72, also are included as the running parameter of determining the driving sample unit 24 in operation collection specimen module 20.
The 3rd part is to select to process the scheme of testing the analyte electrical properties data that arrive.Namely after being completed, the electrical properties data that obtain are to be processed by sensor apparatus, or by the central information station processing.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 with the local information receiving station of the data transmission to of analysis result.The data of the analyte result that these data have comprised the data of the original electrical properties of the analyte that detects, differentiated and the data in the geographic position that the display analysis thing is positioned.In this embodiment, as shown in Figure 8, in the locality, data wireless as above is transferred to a local information receiving station 96 by sensor apparatus 18, and then is transferred to a long way off central information station 90 by network 130.This central station be equipped with include memory function servocomputer at interior central computer 92.Also stored the identical global geographic position positioning map that includes at interior software in this computing machine.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, resulting according to sweep frequency in fluid the information data in the original electrical properties of analyte and analyte geographic position can be wirelessly transmitted to the central computer 92 at central information station.Because stored the application software used in the identical definite geographic position that comprises the global location map in this computing machine and included principal component analysis (PCA) in the application software of interior numerous analytic approachs, received like this electrical properties can be processed in the central information station.And the result that stores and show the analyte that is detected and identifies, comprise their residing geographic position.
If select the first embodiment, namely by sensor apparatus detection site come analyzing and testing to the electrical properties of analyte, after detection was complete, this testing software can show automatically 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 that detects of the result of the analyte that comprises discriminating.It has comprised the scheme of automatically result being exported after corresponding selected embodiment is completed, and keys in the manually operated output scheme of exporting again after the instruction that allows output according to the instrument user.
The application software that starts this detection use be positioned in the last mark " RUN " of software clicked after, so also make it be in duty with regard to having started simultaneously sensor apparatus 18.
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 complete instruction and the running parameter of cover, 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 using in gas chromatography and after the inspiration that obtains.
By Fig. 9 and shown in Figure 10, collect specimen module 20 and be the sensor storehouse 30 that physical construction ground has connected hollow in sensor storehouse module 28.
Collect the sample 10 that then collection carries the analyte in fluid that act as of specimen module 20.It is in the driving sample unit 24 in centre position by one and be connected to simultaneously the Sample introduction at its two ends and derive parts 22 and 26 form.Under a kind of preferred structure, this sample drive unit 24 is the small-sized or miniature pumps by the electric energy driving.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 comprised of corresponding pipeline, perhaps by one in multi-channel structure, perhaps any have the inner passage and form for the structure that is controlled at the fluid analyte flow.Under a kind of preferred structure, Sample introduction and derivation parts are comprised of the pipe of flexibility.Yet when sample when collecting the inner passage of specimen module, 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 the specimen module is front portion structures 32 that physical construction ground has connected the sensor storehouse 30 of hollow.Sensor storehouse 30 be by metal material such as if copper or metal alloy make, it also is connected with the ground zero potential and fetches radiation interference into the sensor mask electromagnetic field.
The sensor storehouse 30 conditional thickness of hollow (have comprised electrical connection) intermediate structure 34 by front portion structure 32 physical construction connections.This intermediate structure is machinery and be electrically connected to a tail structure 36 again.Tail structure physical construction has again connected a structure 38 such as the discharging that likes discharge tube.Under this structure, be in sample 10 near near the analyte in fluid of the outside Sample introduction parts 22 under the driving of pump 24, enter into Sample introduction parts 22, flow through pump 24 and derive parts 26 and enter into sensor storehouse 30, flow out by discharge structure 38 at last.
As shown in Figure 9, the front portion structure 32 in sensor storehouse has the shape of an isoceles triangle shape.The tip of front portion structure 32 and derived type structure 26 physical constructions ground are connected, 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, after sample 10 entered into 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 that increases 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 have flowed, and have also just facilitated the Laminar Flow of sample 10 in the sensor storehouse.And the Laminar Flow of sample has been dominated the even distribution of numerous sensor electrodes in the sample 10 pairs of storehouses.
By Fig. 9 and shown in Figure 10, the inside of sensor storehouse intermediate structure 34 is by the wall that makes progress 33 even partitions.The direction that this wall is disposed is parallel to the direction that sample 10 flows.The first and second identical sensors time storehouse 34a and 34b have just been formed like this in the storehouse.In each inferior storehouse, settling an identical sensor with two electrodes 1.The orientation of this electrode spread is consistent with the direction of sample flow.Yet can be clear and definite be that each sensor 1 with two electrodes can be positioned to any angles that become to comprise 90 degree with the sample flow direction.By 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 again.
As previously mentioned, two electrodes of sensor can be placed on the space and form space electrode, perhaps can be placed on pottery and silica substrate 86 and 88 and form corresponding thick film and membrane electrode.By Fig. 9 and shown in Figure 10, when using 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 intermediate structure in sensor storehouse.Under this structure, because pottery, silicon and metal are all the good conductors of heat, 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 words that the electronic circuit by heating module 80 heats by the control of heating schedule, just can and easily control the temperature of sensor storehouse module 28, the temperature that comprises the sensor with polytype electrode 1 of placing in sensor storehouse 30 and storehouse, and in interelectrode temperature with sample 10 of analyte in fluid.
Moreover because the little volume size of sensor, thereby only need undersized sensor time storehouse, and then determined sensor storehouse temperature is controlled required low power consumption.
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, but the also conductively-closed of electromagnetic field radiation that is caused by second sensor 1.Like this after having used the sensor storehouse, can prevent that the intersection that the possible electromagnetic field radiation effect by the first and second sensors causes from disturbing.
Yet must be clear and definite be, by the example that the above sensor that contains two maskable interference of electromagnetic field is connected with detection module, the disclosure has been narrated one of the present invention and has been implemented structure: use at least one sensor and detect and differentiate analyte in fluid.Fulfiling this enforcement structure is according to spirit of the present invention and purpose: the dimension of finding to be described in analyte feature in fluid.
Implement as shown in Figure 6, sorbing material 8 to be placed among the paired electrode of the sensor at least one sensor in structure at this.When using the analyte of this sensor in coming test fluid, after completing adsorption process this filling the sensor of sorbing material can record the electrical properties that exchanges that comprises resistance and reactance that a kind of compound of being adsorbed or several similar compound are compound group, as the information that is detected.
Obvious, when each analyte is a chemical mixture, from filling the relevant electrical properties that has comprised resistance and reactance that obtains of the sensor electrode of sorbing material reflected the sort of compound that is adsorbed potpourri or the feature of compound group, and the compound that is adsorbed (group) is this chemical mixture that has represented as analyte.This electrical properties that obtains is to be different from the resulting electrical properties that comprises resistance and reactance on the sensor of filling sorbing material never as can be known.They have represented the feature of an integral body of all compounds in the analyte, and namely they have comprised different intensions, describe this analyte from different dimensions.
In another case, when if each analyte is all a simple compound, compare with the electrical properties that obtains in the sensor electrode of filling sorbing material never, from filling the resulting electrical properties of sensor electrode of sorbing material have high signal to noise ratio (S/N ratio).The electrical properties of this kind high s/n ratio is to be conducive to be used to detect and the discriminatory analysis thing all the time.Like this according to spirit of the present invention and purpose: seek analyte feature can be measured dimension, the structure that the present invention can use at least one sensor when needed detects and differentiates analyte in fluid better.
By above-mentioned and analogize, filled different sorbing materials between the electrode that another enforceable structure of the present invention is each sensor at least one sensor.
Still be used for being described in spirit and the purpose of the different dimensions of analyte fluid from increase, of the present invention to also have an enforceable sensor construction be to select one or more known sensor of summing up in Na Geer article and Lewis's 333 patents to be used as one or more sensors in this structure, and then a plurality of or sensor of the present invention can serve as remaining sensor in this structure.This is because compare with the core technology of sensor of the present invention, and those known sensor technologies are the detected information of analyte that detects on different dimensions.
Figure 11 has set forth the another kind of structure of using dual sensor.A sensor that wherein is positioned in sensor time storehouse 34b is used as described detecting sensor 2, and another sensor that is 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.Yet 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.
From the foregoing as can be known, combine detect and reference sensor 2 and 3 in after the corresponding electrical properties that obtains, can only obtain those and comprise being the corresponding electrical properties of 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 that comprises 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 the medical diagnosis disease.
Except the embodiment in the dual sensor structure of this kind integration shown in Figure 11, also can use sensor as described in Fig. 4 A independent scheme separately.Under this scheme, detecting sensor 2 and reference sensor 3 can have special-purpose separately collection specimen module.
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.When design this kind alternative electrode, be when being placed in corresponding sensor time storehouse 34a and 34b as this electrode, 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 that the electrode of being connected with the film space, thick film also can connect corresponding metal connector in the way to insert, and the connector coated outside has suitable electrically insulating material.These are positioned in sensor time storehouse 34a and are connected with detection module 40 with corresponding connector in 34b.
According to such structure theory, for those veterans in sensor field, the detailed construction of this sensor of design is apparent thing.The present invention can use 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 once the direct synthetic core cell (DDS) of numeral but and a digital quantity form the ac-excited voltage that sweep frequency arranged to analog quantity converter.The AC signal that produces after this voltage is added on sensor is connected to a discrete type Fourier transform unit after the digital quantity converter through an analog quantity.Fourier's series of plural form can be from the analog quantity to the digital quantity converter and the synthetic core cell of Direct Digital obtain.After being stored in respectively in different registers, the real component resistance that is obtained by the Fourier transform unit and the reactance of imaginary part component can be read out.This integrated package can be come by calculation procedure initial frequency, frequency increment and the frequency number in scanning of gated sweep.
As according to Ai Jielun 4294 structures, have 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 that is applied on sensor.Transducer converts the electrical impedance that measures to two kinds of ac signal voltages.The vector ratio detector changes into numerical data with two kinds of ac signal voltages again.And digitized controller comprises the test result that the processing numerical data is exported sample.
This detection module 40 also can design from the electronic circuit according to 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, general prefecture method Du Lafushi breathes out in Britain: Fardoroagh, Hampshire, UK).
Above-mentioned technology has been used the principle of the alternating current driver signal of single sine wave.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 Ke Jiemubu and Cook strange company but: Zahner-Elektrik Gmbh﹠amp more can to use the Fourier frequency switch technology; CokG, Luo Nake coughs up in Germany: Kronach, Germany).
Can determine the structure of this detection module 40 like this.Its part by detecting that comprises can be made of in above-described detection principle, it such as similarly being after analog quantity is connected to digital quantity converter, then has connected a digital unit that contains the collection numerical data of 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 that contains the detection module 40 of 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 the 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 include only the Analogic Electronic Circuits that is used as detection of one of numerous detection principles according to above-mentioned, then is connected with comprising the connector of analog quantity to digital quantity converter.
In addition as previously mentioned, detect if only use 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, the transmission of data module 68 includes an antenna or antenna eliminator structure 70 and goes to connect one and receive and transmitter.This receiving-transmitting device is connected with a digital unit that contains small-sized central microprocessor again.The transmission of data module 68 is connected with microcomputer module 50, and module 68 can be carried in the information of the analyte that is encoded on a high-frequency electromagnetic wave and the numerical data of its geographic location information by antenna structure 70 transmission like this.Use 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 namely the electromagnetic field that the high-frequency electromagnetic wave signal by the transmission of data module 68 (perhaps should locality receiving station 96) transmission produces.Corresponding so local receiving station 96 (perhaps the transmission of data module 68) just can receive the signal that sends.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 areals 102 of disposing disposing with instrument 18.
By 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) that receives relevant for analyte in a fluid.Because be used for determining that the positioning map of the applied global positioning system in geographic position also is stored in the microcomputer module in interior application software, the on-site post-11.2 of the instrument that is detected like this can be displayed on instrument screen 52.Perhaps the data of this post-11.2 can be transferred in the central computer 92 of central station by the transmission of data module 68, then are displayed on this computer screen.
Heating module 80 includes external heater 82 and comprises the electronic circuit of digital circuit part.So heating module can be made by the commercial element of these existence.In the connection of instrument, the digital circuit in heating module has partly connected the microcomputer module.
But power module 76 by a switch 78, to each module in instrument 18 provide the recharge of electric energy dc-battery, be used for 79 rectifications of city's alternating current and the electronic circuit of output DC and other electronic circuit are formed.The effect of other electronic circuit is under the instruction of computer module 50, controls the DC voltage be used to other modules that comprise heating module 80 and collection specimen module 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 ".In case after instrument was in the state of " having power supply to supply with ", microcomputer module 50 had 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 that drives with battery power is very important.
Must be clear and definite be, above open in, it is very important being used for each suitable syndeton that each module connects the microcomputer module, it has guaranteed the normal operation of each module.
As mentioned above, the sensor storehouse 30 of metal can shield electromagnetic prevents that it is to the interference of sensor apparatus effect that at least one sensor is arranged.In addition, can also use the impact that additional electronic line structure is eliminated electromagnetic field.By shown in Figure 8, such as can use 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 that produces from detection module 40 can be in an orderly manner and periodically is added on each sensor of at least one sensor, constantly only has a sensor be energized and work thereby formed one.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 each the sensor defined at least one sensor in the time of detecting.
By 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 the transmission of this data by network 130, a kind of preferred embodiment is, when network was the form of internet, this digital information can the service by internet comprise that file is enjoyed mutually or the 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 is the identical local area 142a that disposes disposing with this instrument 18a, and this area is the medium 120a that belongs to local wireless telecommunications.
This instrument 18a also can interrelate with Global Positioning System (GPS) structure 110 and the geographic position 112a of instrument be detected in addition.This is because positioning system structure 110 has covered whole region 140.Under such structure, after this geographic position 112a and the electrical properties that detects can be transferred to 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 comes to 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 placed in with being moved numerous local area 142a, 142b in this region 140 ..., 142n can be in an orderly manner and central station 90 communications.
And this communication be by corresponding local wireless telecommunications medium (electromagnetic field) 120a, 120b ..., 120n comes with the corresponding 96a of local destination, 96b ..., 96n links.Again by 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 that detects in each department.Thereby can construct instantaneous, at the distribution plan of the analyte of this region.
Must be clear and definite be that the wireless data of above narration is propagated the restriction that is not subject to the zone on a celestial body.In fact, this type of propagation can occur between interspace.So 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, connect local destination 96 (96a, 96b ..., 96n) central station 90 be to settle on earth.
Though above disclosing certainly arranged, 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 that does not depart from above narration and purpose, they can be changed into multiple special form and relation.And the apparatus and method of above narration are only not show the change of all numerous forms that the present invention can show and operate in order to narrate and disclose a kind of or several exercisable specializing.

Claims (70)

  1. One for detection of with the sensor instrument system including of differentiating the analyte in fluid, it is characterized in that: a sensor apparatus is arranged, it is characterized in that:
    A) sensor that is used as detecting sensor is arranged, this detecting sensor has two electrodes of being isolated by an air space, measurable information when the sample that an analyte in a kind of fluid is arranged in this detecting sensor, this detecting sensor provide it to include this sample; With
    B) detection module has many multifrequency alternating current driver signals, this detection module electricity connects and applies this pumping signal measures described measurable information after this detecting sensor, this information is the numerous interchange electrical properties corresponding to this alternating current driver signal that applies, the feature of this electrical properties also is included in and two electrical properties detected on each frequency that applies, and is applied in some frequencies in these numerous frequencies that apply and the interchange electrical properties of the correspondence that detects is differentiated this analyte.
  2. One for detection of with the sensor instrument system including of differentiating the analyte in fluid, it is characterized in that: a sensor apparatus is arranged, it is characterized in that:
    a) sensor with dual sensor structure is arranged, it has a detecting sensor and to have reference sensor with this detecting sensor identical electrodes structure, this detecting sensor has two electrodes of being isolated by an air space, the sample that an analyte in a kind of fluid is arranged in this detecting sensor, measurable information when this detecting sensor provides it to include this sample, this reference sensor has two electrodes of being isolated by an air space, have a kind of with the fluid-phase homogeneous turbulence body in this detecting sensor in this reference sensor, measurable information when this reference sensor provides it to include this fluid, with
    b) detection module has many multifrequency alternating current driver signals, this detection module is connected with this detecting sensor electricity and applies this pumping signal measures described measurable information afterwards, this information is the numerous interchange electrical properties corresponding to this alternating current driver signal that applies, the feature of this electrical properties also is included in and two electrical properties detected on each frequency that applies, this detection module is connected with this reference sensor electricity and applies this pumping signal measures described measurable information afterwards, this information is the numerous interchange electrical properties corresponding to this alternating current driver signal that applies, the feature of this electrical properties also is included in and two electrical properties detected on each frequency that applies, be combined on this detecting sensor with obtain on this reference sensor numerous exchange electrical properties and obtain the interchange electrical properties of numerous combinations, the interchange electrical properties of the combination of the correspondence that is applied in some frequencies in these numerous frequencies that apply and obtains is differentiated this analyte.
  3. One for detection of with the sensor instrument system including of differentiating the analyte in fluid, it is characterized in that: have one to be in the central information station that local sensor apparatus and is in far-end; This sensor apparatus is characterised in that:
    A) sensor that is used as detecting sensor is arranged, this detecting sensor has two electrodes of being isolated by an air space, measurable information when the sample that an analyte in a kind of fluid is arranged in this detecting sensor, this detecting sensor provide it to include this sample;
    B) detection module has many multifrequency alternating current driver signals, this detection module electricity connects and applies this pumping signal measures described measurable information after this detecting sensor, this information is the numerous interchange electrical properties corresponding to this alternating current driver signal that applies, the feature of this electrical properties also is included in and two electrical properties detected on each frequency that applies, and is applied in some frequencies in these numerous frequencies that apply and the interchange electrical properties of the correspondence that detects is differentiated this analyte;
    C) location, a global geographic position receiver module, it is used to obtain the information in the geographic position at this sensor apparatus or this analyte place; With
    D) a transmission of data module, be used to wireless transmission after itself and this location, global geographic position receiver module contacts with this detection module electricity and comprise the measurable information that measures and the information of differentiating this analyte that arrives, and the information in the geographic position of obtaining.
  4. One for detection of with the sensor instrument system including of differentiating the analyte in fluid, it is characterized in that: have one to be in the central information station that local sensor apparatus and is in far-end; This sensor apparatus is characterised in that:
    a) sensor with dual sensor structure is arranged, it has a detecting sensor and to have reference sensor with this detecting sensor identical electrodes structure, this detecting sensor has two electrodes of being isolated by an air space, the sample that an analyte in a kind of fluid is arranged in this detecting sensor, measurable information when this detecting sensor provides it to include this sample, this reference sensor has two electrodes of being isolated by an air space, have a kind of with the fluid-phase homogeneous turbulence body in this detecting sensor in this reference sensor, measurable information when this reference sensor provides it to include this fluid, with
    b) detection module has many multifrequency alternating current driver signals, this detection module is connected with this detecting sensor electricity and applies this pumping signal measures described measurable information afterwards, this information is the numerous interchange electrical properties corresponding to this alternating current driver signal that applies, the feature of this electrical properties also is included in and two electrical properties detected on each frequency that applies, this detection module is connected with this reference sensor electricity and applies this pumping signal measures described measurable information afterwards, this information is the numerous interchange electrical properties corresponding to this alternating current driver signal that applies, the feature of this electrical properties also is included in and two electrical properties detected on each frequency that applies, be combined on this detecting sensor with obtain on this reference sensor numerous exchange electrical properties and obtain the interchange electrical properties of numerous combinations, the interchange electrical properties of the combination of the correspondence that is applied in some frequencies in these numerous frequencies that apply and obtains is differentiated this analyte,
    C) location, a global geographic position receiver module, it is used to obtain the information in the geographic position at this sensor apparatus or this analyte place; With
    D) a transmission of data module, after contacting with this detection module electricity, itself and this location, global geographic position receiver module is used to measurable information that wireless transmission comprises this detecting sensor that measures, measurable information of this reference sensor that measures, the information of this analyte that discriminating is arrived, and the information in the geographic position of obtaining.
  5. 5. according to claim 2 or 4 described sensor instrument system includings is characterized in that: the material of to be fillings before these two electrodes of described reference sensor be used for adsorbing or absorbing this analyte.
  6. 6. according to claim 1,2,3 or 4 described sensor instrument system includings, it is characterized in that: described two electrodes are a pair of space electrodes, or are placed on ceramic substrate or on silicon matrix and the corresponding thick membrane electrode or the membrane electrode that form.
  7. 7. sensor instrument system including according to claim 6 is characterized in that: the silicon matrix surface of the ceramic base plate surface of this thick membrane electrode or membrane electrode is depolarization.
  8. 8. sensor instrument system including according to claim 7 is characterized in that: this depolarization is to have used chemical substance to include the two chlorinated silane of two methyl or [dimethyl (trimethyl silyl is amino) silicyl] methane or trimethyl chlorinated silane or formed or the two methyl chlorinated silane of 18 rings by above-mentioned chemical agent combination.
  9. 9. sensor instrument system including according to claim 6, it is characterized in that: a described analyte in fluid comprises it being a compound or a chemical mixture.
  10. 10. sensor instrument system including according to claim 9, it is characterized in that: described analyte also includes known compound or known compound group.
  11. 11. sensor instrument system including according to claim 9 is characterized in that: described analyte is gaseous state, and described analyte comprises it being that tool is not odorous, or tool is odorous.
  12. 12. sensor instrument system including according to claim 9, it is characterized in that: described analyte contains violated thing, or relevant with environmental protection, or comprise that with medical care medical diagnosis is relevant, or comprise that with scientific research space research interest is relevant, or relevant with daily life, or be that safety is considered, or relevant with each industrial interest: as to comprise food industry, beverage industry, agro-industry, chemical industry, petroleum industry, plastics industry, building industry, medical industry, auto industry, biochemical industry, with transportation industry.
  13. 13. sensor instrument system including according to claim 12 is characterized in that: describedly comprise that with medical care the relevant analyte of medical diagnosis also includes the biochemical object relevant with organ disease or biochemical object group.
  14. 14. sensor instrument system including according to claim 13 is characterized in that: described biochemical object or biochemical object group comprise and existing in the sample of the urine of biosome or ight soil or serum or blood or saliva or body odour or oral cavity gas.
  15. 15. sensor instrument system including according to claim 14 is characterized in that: include anesthetic in the gaseous sample of described oral cavity.
  16. 16. sensor instrument system including according to claim 14 is characterized in that: the sample that described body odour sample comprises from the foot of human body or oxter or thigh root is collected.
  17. 17. sensor instrument system including according to claim 9 is characterized in that: described analyte be fixed with variable temperature controlled.
  18. 18. sensor instrument system including according to claim 9 is characterized in that: the sample of described analyte in fluid flows through this detecting sensor with the form of a laminar flow.
  19. 19. sensor instrument system including according to claim 9 is characterized in that: described sample contains identity information.
  20. 20. according to claim 1,2,3 or 4 described sensor instrument system includings, it is characterized in that: described alternating current driver signal has the multifrequency alternating current driver signal of single sine wave or many sinusoidal wave multifrequency alternating current driver signals is arranged.
  21. 21. sensor instrument system including according to claim 6 is characterized in that: described sensor is disposable.
  22. 22. sensor instrument system including according to claim 6 is characterized in that: described sensor be subject to comprising fixing and variable temperature controlled.
  23. 23. sensor instrument system including according to claim 6, it is characterized in that: described sensor apparatus has at least two detecting sensors, and each detecting sensor in these at least two detecting sensors is by electromagnetic screen, applied in an orderly manner, respectively many multifrequency alternating current driver signals again.
  24. 24. sensor instrument system including according to claim 23 is characterized in that: each detecting sensor in described at least two detecting sensors be subject to comprising fixing and variable temperature controlled.
  25. 25. sensor instrument system including according to claim 6 is characterized in that: this sensor apparatus contains the unitized construction of existing sensor and described detecting sensor.
  26. 26. sensor instrument system including according to claim 25 is characterized in that: in this structure, contain one or more existing sensors, and contain corresponding a plurality of or described detecting sensor and serve as remaining sensor in this structure.
  27. 27. sensor instrument system including according to claim 26 is characterized in that: described existing sensor comprises: metal-oxide film sensor, conducting polymer composite thin film sensor, by macromolecule membrane be coated in plane of crystal the weight induction sensor, by macromolecule material film be coated in plane of crystal saw sensor, by gate surface scribble the silicon field-effect transistor sensor of metal-oxide film, by the Fibre Optical Sensor of using many sound waves, by the corresponding sensor that forms according to gas chromatography, spectrum and mass spectrum principle.
  28. 28. sensor instrument system including according to claim 6 is characterized in that: described sensor is by electromagnetic screen.
  29. 29. sensor instrument system including according to claim 5 is characterized in that: described fluid flows through this sensor with the form of a laminar flow.
  30. 30. sensor instrument system including according to claim 5 is characterized in that: reduce ground unrest combine the measurable information that obtains and obtain in detecting sensor in reference sensor after.
  31. 31. sensor instrument system including according to claim 30 is characterized in that: this ground unrest has comprised the variation of measurable information of the detecting sensor that detects that is caused by humidity and caused by the temperature variation that is placed in the analyte between the detecting sensor electrode.
  32. 32. sensor instrument system including according to claim 30 is characterized in that: combine and detect and differentiate interest place thing in analyte in fluid after measurable information of obtaining and obtain in reference sensor in detecting sensor.
  33. 33. sensor instrument system including according to claim 32 is characterized in that: this interest place thing comprises known biochemical object or object group's known compound or compound group.
  34. 34. sensor instrument system including according to claim 33, it is characterized in that: reference sensor detects the fluid that does not contain interesting place thing in this detection and in differentiating, this fluid is that this material by the front end that is positioned in reference sensor adsorbs or is absorbed in after this interest place thing in sample resulting.
  35. 35. sensor instrument system including according to claim 34 is characterized in that: described material comprises organic and inorganic and metal adsorption or the absorbing material of all kinds.
  36. 36. sensor instrument system including according to claim 20, it is characterized in that: the multifrequency alternating current driver signal of described single sine wave comprises and obtaining with frequency sweeping, the alternating current driver signal of this frequency sweeping includes the beginning frequency and stops the sweep frequency interval of frequency, and the amplitude of pumping signal.
  37. 37. sensor instrument system including according to claim 20 is characterized in that: this electrical properties comprises voltage, electric current, electrical impedance, resistance, reactance and phase place.
  38. 38. according to claim 1,2,3 or 4 described sensor instrument system includings, it is characterized in that: this alternating current driver signal includes the square wave of single-frequency or the non-sinusoidal shape ripple of triangular wave or sawtooth wave, and is used to detect this analyte.
  39. 39. described sensor instrument system including according to claim 38, it is characterized in that: the alternating current driver signal of this single-frequency is applied on described sensor, detects corresponding to one of the alternating current driver signal of the frequency that applies and exchanges electrical properties.
  40. 40. described sensor instrument system including according to claim 39, it is characterized in that: this electrical properties comprises voltage, electric current and electrical impedance.
  41. 41. according to claim 1,2,3 or 4 described sensor instrument system includings, it is characterized in that: this alternating current driver signal includes the form of the sine wave of single-frequency, and is used to detect this analyte.
  42. 42. described sensor instrument system including according to claim 41, it is characterized in that: the alternating current driver signal of the sinusoidal wave form of this single-frequency is applied on described sensor, the interchange electrical properties corresponding to the alternating current driver signal of the frequency that applies detected.
  43. 43. described sensor instrument system including according to claim 42, it is characterized in that: this interchange electrical properties is included in two kinds of different electrical properties that obtain on this frequency.
  44. 44. described sensor instrument system including according to claim 43, it is characterized in that: this electrical properties comprises voltage, electric current, electrical impedance, resistance, reactance and phase place.
  45. 45. sensor instrument system including according to claim 20 is characterized in that: this detection module includes analog quantity to digital quantity converter.
  46. 46. described sensor instrument system including according to claim 45, it is characterized in that: this detection module includes a central microprocessor.
  47. 47. described sensor instrument system including, is characterized in that: the pretreated algorithm of the promising measurable information that detects of described sensor apparatus according to claim 45.
  48. 48. according to claim 1,2,3 or 4 described sensor instrument system includings, it is characterized in that: described sensor apparatus compares the discriminatory analysis thing with the information of the analyte that detects with the information of known analyte.
  49. 49. described sensor instrument system including according to claim 48 is characterized in that: described sensor apparatus compares the discriminatory analysis thing with the type of the analyte information that detects with the type of known analyte information.
  50. 50. described sensor instrument system including according to claim 49, it is characterized in that: the type of this analyte information obtains after the analysis of having used principal component analysis (PCA).
  51. 51. described sensor instrument system including according to claim 49 is characterized in that: the type of this analyte information obtains after the analysis of the analytic approach of analytic approach, Classical Least-Squares, principal component regression and the partial least square method of the analytic approach of having used the group who has comprised the similarity analysis method of classification of simulating separately conditionally, the most contiguous factor analysis, system, canonical discriminate analysis.
  52. 52. described sensor instrument system including according to claim 48 is characterized in that: using has backbone network technology guidance and guideless cognitive-ability, and fuzzy backbone network technology is come the discriminatory analysis thing.
  53. 53. 2,3 or 4 described sensor instrument system includings according to claim 1,, it is characterized in that: described sensor apparatus also includes one and drives sample unit, a sensor storehouse module, and a heating module, a microcomputer module and a power module of an external heater arranged.
  54. 54. 3 described sensor instrument system includings according to claim 5, it is characterized in that: this microcomputer module includes general order interface, serial interface and parallel interface and comes wire transmission to comprise data, the push-button unit that comprises the use of promising data and instruction input, include function with input message with can demonstrate the data that measure and comprised the display screen that shows the information of an instantaneous analyte that obtains according to scanned time or scanned frequency.
  55. 55. 3 described sensor instrument system includings according to claim 5 is characterized in that: this microcomputer module include one for detection of application software, a software that is used for encrypting during with secret formal output when numeral, the global geographic position arranged positioning map in interior application software with comprise the analytic approach software of the analytic approach that type is differentiated.
  56. 56. 5 described sensor instrument system includings according to claim 5, it is characterized in that: the analytic approach that this microcomputer module comprises has multivariate element analytic approach to include principal component analysis (PCA), simulates separately conditionally the similarity analysis method of classification, the group's of the most contiguous factor analysis, system analytic approach, analytic approach, Classical Least-Squares, principal component regression and the partial least square method of canonical discriminate analysis, backbone network technology guidance and guideless cognitive-ability is arranged, and fuzzy backbone network technology.
  57. 57. 3 described sensor instrument system includings according to claim 5, it is characterized in that: this microcomputer module includes a database, comprises the information of known analyte at this lane database, the model of the type of known analyte information and known analyte information.
  58. 58. according to claim 3 or 4 described sensor instrument system includings, it is characterized in that: described central information station by network connected numerous be in different regions in a region can wireless receiving and dispatching information local information stations, local information station and this sensor apparatus wireless messages that one of them and this sensor apparatus are in areal contact.
  59. 59. 8 described sensor instrument system includings according to claim 5, it is characterized in that: the central information station includes the central computer that is connected with a servocomputer, and the positioning map that this central computer includes the global geographic position is in interior application software with for the pretreated algorithm of measurable information of detecting with comprise the software of the analytic approach of the analytic approach that type is differentiated.
  60. 60. 9 described sensor instrument system includings according to claim 5, it is characterized in that: described analytic approach has multivariate element analytic approach to comprise the group's of the similarity analysis method of classification of simulating separately conditionally, the most contiguous factor analysis, system analytic approach, analytic approach, Classical Least-Squares, principal component regression and the partial least square method of canonical discriminate analysis, backbone network technology guidance and guideless cognitive-ability is arranged, and fuzzy backbone network technology.
  61. 61. 8 described sensor instrument system includings according to claim 5, it is characterized in that: this central computer includes a database, comprises the information of known analyte at this lane database, the model of the type of known analyte information and known analyte information.
  62. 62. 1 described sensor instrument system including according to claim 6 is characterized in that: central computer compares the discriminatory analysis thing with the information of the analyte that detects with the information of known analyte.
  63. 63. 1 described sensor instrument system including according to claim 6 is characterized in that: central computer compares the discriminatory analysis thing with the type of the analyte information that detects with the type of known analyte information.
  64. 64. 3 described sensor instrument system includings according to claim 6 is characterized in that: the type of this analyte information obtains after the analysis of having used the analytic approach that type differentiates.
  65. 65. 4 described sensor instrument system includings according to claim 6, it is characterized in that: the type of this analyte information obtains after the analysis of having used principal component analysis (PCA).
  66. 66. 8 described sensor instrument system includings according to claim 5, it is characterized in that: this network has comprised easy house network, network at an organization internal, network in a zone, with the internet network that is connected area, the whole world, described network comprises to be used up fibre, cable, metal cords or comprises the electromagnetic interior any mode that is wirelessly connected on.
  67. 67. sensor instrument system including according to claim 35 is characterized in that: described material comprises the compound substance of macromolecular material or macromolecular material and inorganic material or contains metal in the platinum group and compound substance or the solid mineral material of the packing material of organic or inorganic.
  68. 68. 7 described sensor instrument system includings according to claim 6, it is characterized in that: described solid mineral material comprises molecular sieve, silica gel, aluminium oxide, glass, cavernous carbon granule and calcium carbonate; Described macromolecular material comprises fluorinated carbon material or liquid organic salt material; The compound substance of described macromolecular material and inorganic material comprises that surface coverage has the solid mineral material particle of macromolecular material, and it comprises the alumina particle that is coated with macromolecular material, the glass particle that is coated with the silica gel particle of macromolecular material and is coated with macromolecular material.
  69. 69. according to claim 1,2,3 or 4 described sensor instrument system includings, it is characterized in that: this electrical properties comprises voltage, electric current, electrical impedance, resistance, reactance and phase place.
  70. 70. according to claim 1 or 3 described sensor instrument system includings is characterized in that: described fluid flows through this sensor with the form of a laminar flow.
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