CN102589582B

CN102589582B - Chemistry that temperature is unrelated and biosensor

Info

Publication number: CN102589582B
Application number: CN201110461799.0A
Authority: CN
Inventors: R·A·波泰雷洛; C·M·叙尔曼
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 2010-12-23
Filing date: 2011-12-22
Publication date: 2016-12-14
Anticipated expiration: 2031-12-22

Abstract

The present invention entitled " chemistry that temperature is unrelated and biosensor ".Method for selectivity fluid sensing and sensor are provided.A kind of sensor, including: resonant inductor capacitor resistor (LCR) circuit and be arranged on the sensing material on sensing area.Sensing area includes at least some of of LCR circuit.The temperature relevant response coefficient of the character of the inductance L of LCR circuit and sensing material, electric capacity C and resistance R differs at least about 5% each other.The difference of the temperature relevant response coefficient of the character of LCR circuit and sensing material enables the sensor to the most independently detect selectively from analyzed fluid mixture analyte fluid with temperature.

Description

Chemistry that temperature is unrelated and biosensor

Statement about federal funding research and development

The present invention is carried out with governmental support, and part is studied by Environmental hygienic science Being subsidized, license number is 1R01ES016569-01A1.Government has some power in the present invention Profit.

Technical field

Presently disclosed subject matter relates to chemistry and biosensor, and more particularly, relates to And the unrelated chemistry of high selectivity temperature and biosensor.

Background technology

Chemistry and biosensor are often used for the detection of many of steam and can be used for discriminating and have With many application of information.Such as, in monitoring biopharmaceutical products, the change of Foods or drinks In, monitoring industrial occupancy chemically or physically harm aspect and safety applications (such as, live Quarter monitoring, the national security on airport) in, in varying environment and clinical settings and wherein The detection of some harmful and/or noxious vapors can be passed through in other public place useful especially The existence meeting of steam is measured in the change of some environmental variable among classified sensor or around It is useful especially.

A kind of technology for sensing this kind of environmental change is to be coated with specific sensing by employing The sensor of material, such as RFID sensor.It addition, sensor can by be coated with one or The array of the independent transducer of multiple sensing material is arranged.Many sensor arraies include multiple Identical sensor.But, although use identical sensor to simplify the manufacture of sensor array, But this array can have for only sense single response (such as, resistance, electric current, electric capacity, Work function, quality, optical thickness, light intensity etc.) limited capability.In some applications, Multiple responses or the change of multiple character can occur.In this type of application, including such sensing The array of device can be favourable: wherein the different transducers in array use identical or different response (such as, resistance, electric current, electric capacity, work function, quality, optical thickness, light intensity etc.) And it is coated with different sensing material, enables to measure more than one character.Disadvantageous It is that manufacture has the sensor array of unique separated sensor made with sensing specific response to be made The manufacture of this array complicates.

Additionally, in many actual application, it is advantageous to use high selective chemical and biology pass Sensor.That is, it is often desired to situation about can exist at other steam and mixture is provided The lower multiple steam of sensing and the sensor array of vapour mixture.Steam that may be present and steam The quantity of mixture is the biggest, the most accurately senses and differentiates steam certain types of, to be sensed Or vapour mixture may be the most difficult.When one or more steam are with higher than other sense to be detected In the presence of the amplification level of interest steam, situation may the most so.Such as, high humility ring The ability of the steam of traditional sensors detection selection is often disturbed in border.Additionally, when sensor is used as Separated sensor or when arranging according to array, variations in temperature reduces chemistry and biological sensing Precision.

Various embodiments disclosed herein can solve the one or more of an above-mentioned difficult problem.

Summary of the invention

According to an embodiment, it is provided that a kind of sensor, including resonant inductor-electric capacity Device-resistor (LCR) circuit and be arranged on the sensing material on sensing area.Sensing area includes LCR circuit at least some of.The inductance L of LCR circuit and sensing material, electric capacity C and electricity The temperature relevant response coefficient of the character of resistance R differs at least about 5% each other.LCR circuit and sense The difference of temperature relevant response coefficient of character of material of measuring and monitoring the growth of standing timber enable the sensor to temperature substantially without Close ground from analyzed fluid mixture, detect analyte fluid selectively.

According to another embodiment, it is provided that a kind of chemistry detected in fluid or the side of biological species Method.The method includes the reality measuring the impedance spectrum of the resonant transducer antenna being coated with sensing material Portion and imaginary part.The temperature relevant response coefficient of the character of resonant transducer antenna and sensing material that These are different.The method is additionally included at multiple temperature and calculates the resonance sensor being coated with sensing material At least 6 spectrum parameters of device antenna.The method also includes using multivariate analysis to be subtracted by impedance spectrum Little to individual data point, with discriminatory analysis thing selectively.The method also includes using being stored Calibration parameter determines one or more ambient parameter from impedance spectrum.One or more ambient parameters Determination the most unrelated with temperature.

According to another embodiment, it is provided that a kind of method manufacturing sensor.The method includes group Dress includes the transducer of resonant inductor-capacitor-resistor (LCR) circuit.Transducer includes At least three temperature relevant response of the character of the inductance L of LCR circuit, electric capacity C and resistance R Coefficient.At least three temperature relevant response coefficient of the character of LCR circuit differs the biggest each other About 5%.Dielectric constant that the method also includes selecting to include sensing material and electrical resistance property are extremely The sensing material of few two temperature relevant response coefficients.At least two temperature of the character of sensing material Spend at least three temperature relevant response coefficient phase of relevant response coefficient and the character of LCR circuit Difference at least about 5%.The method also includes being arranged on sensing area sensing material.Sensing District includes at least some of of LCR circuit.

In one embodiment, LCR circuit includes substrate, coil, memory chip, collection Become circuit (IC) chip, transducer and sensing material film, wherein said substrate, coil, deposit The temperature of the character of memory chip, integrated circuit (IC) chip, transducer and sensing material film Relevant response coefficient is different from each other.

In another embodiment, LCR circuit includes supplementary sensor, wherein said supplementary The temperature relevant response coefficient of the character of sensor and sensing material is different from each other.

Accompanying drawing explanation

Read described in detail below by referring to accompanying drawing, it will be more fully understood that these of the present invention And further feature, aspect and advantage, in accompanying drawing, similarity sign represents similar the most in the whole text Parts, accompanying drawing includes:

Fig. 1 illustrates the sensing system according to embodiments of the invention；

Fig. 2 illustrates the RFID sensor according to embodiments of the invention；

Fig. 3 illustrates the RFID sensor of the alternative according to the present invention；

Fig. 4 illustrates the response of the measurement of the RFID sensor according to embodiments of the invention；

Fig. 5 is to illustrate according to embodiments of the invention, in the presence of variable temperature Analyze the flow chart of the process of steam；And

Fig. 6-11 illustrate test explanation according to embodiments of the invention, can be temperature independent The test data of the single sensor of difference humidity level.

Detailed description of the invention

Presently disclosed embodiment provides the temperature independent methodology for selectivity steam sensing And system, the most single sensor is provided and can detect and individually or each other exists In the case of multiple steam and/or the mixture of steam.At entitled " Highly Selective Chemical and Biological Sensors " U.S. patent application serial number 12/942,732 In describe for using single sensor to carry out the example of conventional method of steam sensing, pass through Quote and be incorporated into herein.Disclosed sensor even under high humidity environment or Wherein one or more steam have much higher concentration (example compared with other composition in mixture As, 10 times) in the environment of also be able to the detection different steam in the presence of variable temperature And mixture.Each sensor includes the resonant inductor-capacitor-resistance being coated with sensing material Device (LCR) sensor.The temperature relevant response coefficient of the character of LCR circuit and sensing material that These are different.The difference of the temperature relevant response coefficient of character affects the measurement of disclosed sensor.But It is about the knowledge of temperature relevant response coefficient of character and/or how to be subject to about sensor The knowledge of the difference impact of the temperature relevant response coefficient of character starves impedance together with the measurement of sensor Multivariate analysis be used together, in order to provide temperature unrelated selectivity steam sensing and improve Response stability.Such as, the lookup of the coefficient including sensor-based experiment test can be formed Table.During the use of sensor, the coefficient that experiment determines can be for examining in multivariate analysis The change of the temperature during worry sensing.Other embodiments disclosed herein provides for selectivity Chemistry and the temperature independent methodology of biological sensing and system, the most single sensor be provided and In the case of can detecting individually or there is (presense of one another) each other Chemistry or the liquid of biological species and/or mixture in multiple chemistry or biological species.

The non-limiting example of LCR sensor includes having integrated circuit (IC) memory chip RFID sensor, there is the RFID sensor of IC chip and there is no IC memory chip RFID sensor (chipless RFID sensor).LCR sensor can be wirelessly or non-wirelessly. In order to collect data, the resonant frequency range of narrower frequency range, such as LCR circuit is obtained Take impedance spectrum.This technology also includes from acquired spectrum to calculate multivariate signature, and manipulation should Data are to differentiate the existence of some steam and/or vapour mixture.The existence of steam is by following Step detects: by the change of resonant electrical character of observation circuit, measure dielectric, dimension, Change in electric charge transfer and other change of the character of employing material.By using mathematics mistake Journey, such as principal component analysis (PCA) etc., multiple steam and mixture can be in the feelings existed each other It is detected, as described further below under condition and in the presence of chaff interference.Herein The disclosed embodiments provide the temperature independent methodology for selectivity fluid sensing and system, its In single sensor be provided and can detect individually or each other in the presence of Multiple fluids and/or the mixture of fluid.Further embodiment is open for through the following steps The method manufacturing this kind of sensor: assemble the transducer including LCR circuit, and will sensing Material be arranged on transducer at least some of on, wherein transducer and the character of sensing material Temperature relevant response coefficient different from each other.In other embodiments, except for steam and stream Outside the chemical sensor of body, biosensor also can have temperature extraneous detection ability.

In order to become apparent from describing exactly the theme of claimed invention, it is provided that be described below With being defined below of the concrete term used in claims.

Term " fluid " includes gas, steam, liquid, particle, biomone, biology point Son and solid.

Term " numeral ID " includes all numbers stored in the memory chip of RFID sensor According to.The non-limiting example of these data is the manufacturer for sensor, electronics pedigree (pedigree) data, user data and calibration data.

Term " monitoring process " includes but not limited to measure the physical change occurred around sensor. Such as, monitoring process includes the physics of environment around monitoring and sensor, chemistry and/or life Bio-pharmaceuticals that the change of physical property matter is relevant, the change of Foods or drinks manufacture process.Monitored Journey may also include those industry of the change of monitoring physical change and the composition of composition or position Process.Non-limiting example include national security monitoring, residential quarter monitoring for protection, environmental monitoring, Clinic or bedside patient's monitoring, airport security monitoring, admission ticket checking and other public accident.Energy Reach when sensor signal has reached slightly steady-state response and/or sensor has dynamic response Shi Zhihang monitors.Steady state sensor response be determined by the time cycle from the sound of sensor Should, wherein respond and there is no change slightly in the measurement time.Therefore, steady state sensor response with The measurement of time produces similar value.Dynamic pickup response be measured ambient parameter (temperature, Pressure, chemical concentrations, biological concentration etc.) change time from the response of sensor.Therefore, Time significant change is being measured in dynamic pickup response, in order to produce measured one or many The dynamic signature of the response of individual ambient parameter.The non-limiting example of the dynamic signature of response includes The maximal positive slope of average response slope, average response amplitude, signal response, signal respond Maximum negative slope, the mean change of signal response, the maximum of signal response are just changing and signal The negative change of the maximum of response.The dynamic signature of the generation of response can be used in further enhancing at list The solely selectivity of the sensor in the kinetic measurement of steam and mixture thereof.Being produced of response is dynamic State signature can also be used to optimize sensing material and the combination of transducer geometry further, with Just strengthen in independent steam and the selection of the sensor dynamically and in steady state measurement of mixture thereof Property.

Term " ambient parameter " is for representing measuring among manufacture or monitoring system or around Environmental variable.Measure environment variables can include at least one in physics, chemistry and biological property, And include but not limited to temperature, pressure, material concentration, conductivity, dielectric property, sensing Near device or with the quantity of electrolyte, metal, chemistry or the biomone of sensor contacts, The dosage of ionizing irradiation and the measurement of light intensity.

Term " analyte " includes that ambient parameter is measured in any expection.

Term " disturbs " precision and accuracy including undesirably affecting the measurement of sensor Any undesirable ambient parameter.Term " chaff interference " expression can be produced by sensor potentially The fluid of raw disturbance response or ambient parameter (including but not limited to temperature, pressure, light etc.).

Term " multivariate analysis " represents for analyzing more than one variable from sensor response And provide the type with at least one ambient parameter from measured sensor spectra parameter to have The information closed and/or the water of at least one ambient parameter with next self-metering sensor spectra parameter The mathematical procedure of flat relevant quantitative information.Term " principal component analysis (PCA) " expression is used for Cube is reduced to more low-dimensional for the mathematical procedure analyzed.Principal component analysis is multivariate A part for the Eigenanalysis method of the statistical analysis of data, and can use covariance matrix or Correlation matrix performs.The non-limiting example of multivariate analysis tools includes relevant point of canonical Analysis, regression analysis, nonlinear regression analysis, principal component analysis, distinctive function analysis, multidimensional Calibration, linear discriminatant analysis, logarithm regression or analysis of neural network.

Term " spectrum parameter " is for representing the measurable variable that sensor responds.Sensor responds It it is the impedance spectrum of the resonance sensor circuit of LCR or RFID sensor.Z is taked except measuring Outside the impedance spectrum of parameter, S parameter and other parametric form, impedance spectrum (its real part and imaginary part Both) can use and analyze for the many kinds of parameters analyzed simultaneously, the maximum of the real part of such as impedance Frequency (the F of number_P), the amplitude (Z of the real part of impedance_P), the resonant frequency (F of the imaginary part of impedance₁) Anti-resonance frequency (F with the imaginary part of impedance₂), at the resonant frequency (F of imaginary part of impedance₁) letter Number amplitude (Z₁), at the anti-resonance frequency (F of imaginary part of impedance₂) signal amplitude (Z₂) and zero Reactance frequency (F_z, the imaginary part of impedance is the frequency of zero).Other spectrum parameter can use whole impedance The amplitude of spectrum, the factor of quality of such as resonance, phase angle and impedance is measured simultaneously.From impedance " spectrum parameter " that spectrum is calculated here is referred to as " feature " or " descriptor ".From can The all potential feature calculated by spectrum is to perform the suitable selection of feature.Entitled The U.S. of " Methods and systems for calibration of RFID sensors " State's patent application serial number 12/118, describes multivariate spectrum parameter, by quoting it in 950 It is incorporated herein in.

Term " resonance impedance " or " impedance " represent extracts sensor " spectrum parameter " from which Sensor resonance around measurement sensor frequency response.

Term " protection material " includes but not limited to protection sensing in LCR or RFID sensor Device performs anticipated measurement from non-anticipated machinery, physically or chemically effect, the most still allowance Material.Such as, it is contemplated that measuring and can include that solution conductivity rate is measured, wherein protecting film is by sensor Separate with liquid solution, but still allow for electromagnetic field and penetrate in solution.One example of protection material It is consequently exerted at above sensor to protect the sensor against the paper membrane of mechanical failure and abrasion.Protection Another non-limiting example of material is consequently exerted at above sensor and is putting with protection sensor Enter the polymeric film from corrosion when measuring in liquid.Protection material can also be consequently exerted at Time above sensor to prevent the antenna circuit of sensor from measuring in putting into conducting liquid The polymeric film of short circuit.The non-limiting example of protecting film is paper, polymerization and inoranic membrane, such as Polyester, polypropylene, polyethylene, polyethers, Merlon, polyethylene terephthalate, Zeolite, metallic organic framework and cryptand (cavitand).Protection material can be arranged on and change Can be between device and sensing film, in order to protection transducer.Protection material can be arranged on and itself be in Above sensing film above transducer, in order to protection sensing film and transducer.Itself is in transducing The protection material above sensing film above device can act as filtering material, in order to prevents from sensing film It is exposed to gas or ion interference.The non-limiting example of filtering material includes that zeolite, metal have Machine skeleton and cryptand.

Term as used herein " sensing material and sensing film " includes but not limited to deposit to change Can device electronic module, as in LCR circuit assembly or RFID label tag in case perform with environment Time mutual measurable and reproducibly affect the material of the function that impedance transducer responds.Example As, the conducting polymer of such as polyaniline etc changes it when being exposed to the solution of different pH Conductivity.When this polyaniline film deposits on LCR or RFID sensor, impedance sensing Device response changes as the function of pH.Therefore, this LCR or RFID sensor conduct PH sensor is operated.When this polyaniline film deposits to supply on LCR or RFID sensor During detection in gas phase, impedance transducer response is being exposed to alkalescence (such as, NH₃) or acid Also change during (such as, HCl) gas.Alternatively, sensing film can be dielectric polymer. Sensor film includes but not limited to that environment based on they places changes its electric and/or dielectric The polymer of character, organic and inorganic, biological, synthesis and nanometer synthesis film.Sensor film Non-limiting additional examples can be such as Nafion (Nafion) etc The adhesive polymer of sulfonated polymer, such as silicone adhesive etc, such as sol gel film etc Inoranic membrane, the synthesis film of such as carbon black polyisobutylene sheet etc, such as CNT-high fluorine Change ion exchange resin membrane, golden nanometer particle polymeric film, metal nanoparticle polymeric film, Static Spinning polymer nanofiber, Static Spinning inorganic nano-fiber, Static Spinning synthesis nanofiber Etc nanometer synthesis film or doped with organic, metal is organic or the film of biologically-derived molecule / fiber and other sensing material any.In order to prevent the material in sensor film from leaching into liquid In body environment, use standard technique and this area of such as covalency joint, electrostatic joint etc Sensing material is attached to sensor surface by other standard technique known to the skilled person.It addition, Sensing material has the temperature associated change phase of the material dielectric constant with sensing material and resistance At least two temperature relevant response coefficient closed.

Term " transducer and sensor " for represent estimate for sensing electronic installation, as RFID device." transducer " is before being coated with sensing or protecting film or calibrated For the device before sensing application.Transducer includes the electric capacity C of LCR circuit, resistance R At least three temperature relevant response coefficient with the temperature associated change of inductance L." sensor " It is that typically in after being coated with sensing or protecting film and calibrated for sensing application After device.

Term as used herein " RFID label tag " represent electronic tag is used for mark and/or Following the tracks of RFID label tag can be with the mark of its attached product and reporting techniques.RFID label tag is usual Including at least two assembly, wherein the first assembly is for storing and process information and to radio frequency Integrated circuit (IC) memory chip that signal is modulated and demodulates.This memory chip is also Can be used in other dedicated functions, such as it can comprise capacitor.It can also comprise simulation At least one input of signal, such as resistance input, electric capacity input or inductance input.At centreless In the case of sheet RFID label tag, RFID label tag can not include IC memory chip.Not Need to identify particular RFID tag but the signal of the only existence of indicating label offer useful information In the application of (such as, product safety is applied), such RFID label tag can be useful. Second assembly of RFID label tag is the antenna for receiving and transmit radiofrequency signal.

Term " RFID sensor " is the RFID label tag of the sensing function with increase, its example As changed its impedance parameter also by the function as environmental change when the antenna of RFID label tag Perform sensing function.Use this kind of RFID sensor that accurately determining of environmental change is passed through Analyze resonance impedance to perform.Such as, can be by using sensing film coating RFID label tag, will RFID label tag is converted to RFID sensor.By using sensing film to apply RFID label tag, The electroresponse of film is converted to the impedance response to sensor antenna, and the impedance of sensor antenna rings Resonance peak position, spike width, peak height and the peak symmetry answered, the real part of impedance Amplitude, the resonant frequency of imaginary part of impedance, the anti-resonance frequency of imaginary part of impedance, zero reactance The amplitude of frequency, phase angle and impedance and in the definition of term sensor " spectrum parameter " Change while other parameter described." RFID sensor " can have and be attached to antenna Integrated circuit (IC) memory chip, or without IC memory chip.There is no IC The RFID sensor of memory chip is LCR sensor.LCR sensor is by forming LCR electricity Such as at least one inducer (L) on road, at least one capacitor (C) and at least one resistor Etc (R) known tip assemblies composition.

Term " disposable container " includes but not limited to be dropped after usage or can be through Cross and overhaul the manufacture or monitoring device and packaging Gong re-using.The non-returnable container bag of food service industry Include but be not limited to Food & Drink packaging and confection and tuck box.Disposable monitoring assembly bag Include but be not limited to disposable cartridges (cartridge), radiacmeter and catcher.Disposably manufacture appearance Device includes but not limited to disposable vessel, bag, case, pipeline, adapter and pillar.

Term " write device/reader " includes but not limited to write data into and read in memorizer The combination of the device of the memorizer of chip and the impedance of reading antenna." write device/reader " Another term be " interrogator ".

According to embodiment disclosed herein, describe and be used for sensing steam, vapour mixture, chemistry LCR or RFID sensor with biological species.As it was previously stated, RFID sensor includes coating There is the RFID mark of the sensing material of the temperature relevant response coefficient of the character different from LCR circuit Sign.In one embodiment, passive RFID tags can be used.Everybody can be appreciated that, RFID Label can include being connected the IC storage for communicating with write device/reader with aerial coil Device chip.Can be carried by the radio frequency (RF) sent via write device/reader and/or microwave Ripple signal irradiates label, reads IC memory chip.When RF and/or microwave field are through sky During line coil, coil produces AC voltage.To this voltage commutation in microchip, in order to Produce the D/C voltage for microchip operation.IC memory chip reaches predetermined electricity in D/C voltage Function at ordinary times.By detection from the backward scattered RF of microchip and/or microwave signal, The information of storage in microchip can be identified completely.RFID label tag/sensor and write device/reading Take distance between device by include operating frequency, RF and/or microwave power level, reader/ The receiving sensitivity of write device, antenna dimension, data rate, communication protocol and microchip power The design parameter required manages.There is no " RFID sensor " (nothing of IC memory chip Chip RFID sensor or LCR sensor or LCR transducer) and sensor reader between Distance is by including the reception spirit of operating frequency, RF or microwave power level, sensor reader The design parameter of sensitivity and antenna dimension manages.

In one embodiment, the passive RFID with and without IC memory chip can be used Label.Advantageously, passive RFID tags operates not against battery.But, write device/ Communication distance between reader and RFID label tag is typically limited within distance, because Passive label operates only with the several microwatt RF power from write device/reader.For It is operated in the passive label of 13.56MHz, reads distance typically not greater than several centimeters.13.56 The exemplary frequency range of the operation that MHz passive RFID tags carries out numeral ID write/reading is From 13.553 to 13.567MHz.13.56MHz passive RFID sensors sensing RFID passes The exemplary frequency range of the operation of the environmental change around sensor is to about from about 5MHz 20MHz, more preferably from 10 to 15MHz.The requirement of this frequency range is to adopt Label is identified, simultaneously RFID label tag with the write device/reader being operated in 13.56MHz Sensor section operates from 5 to 20MHz.

Deposit to sensing film on passive RFID tags, create RFID chemistry or biosensor. By measuring the impedance of the RFID sensor of the function as the environmental change around sensor Change, performs RFID sensing, as described further below.If the frequency of aerial coil Rate response is not above the frequency range of the operation of label, then microchip after deposition sensing film The information of middle storage can use conventional RFID writer/reader to identify.Impedance analyzer (sensor reader) can the impedance of reading antenna coil, in order to by emerging with sense for the change of impedance Interest chemistry is relevant with biological species, and corrects the temperature instability around sensor.

In operation, after using chemical-sensitive film coating RFID label tag, label can be measured The impedance of antenna and digital label ID.The digital ID measured provides and label itself, example Identification and character (the such as different condition of sensor such as this label and its attached object Calibration curve, Fabrication parameter, due date etc.) relevant information.Multicomponent is detected, Can determine that real part and many individual characteies of imaginary part of the measurement of impedance from single RFID sensor Matter, as described further below.

In a word, and according to embodiment as herein described, in order to realize changing existence in temperature In the case of the detection of analyte, sensor should present multiple characteristic.First, selected transducing Device should include that multivariate exports, in order to the independent detection varying environment parameter shadow to sensor Ring.Secondly, sensing material should have the response in large-scale variations in temperature to analyte The amplitude of preservation.Response to less analyte concentration should be incomplete by bigger variations in temperature Suppression.3rd, the temperature impact response of sensing material and transducer is to allow, but should In the multivariate of transducer exports the different directions of response.

In order to realize these characteristics, in one embodiment, sensing material has steam many Individual response mechanism, wherein, these response mechanisms and the dielectric constant of sensing material, resistance and swollen Swollen change is correlated with, and wherein these changes are not the most perfectly correlated, and is exposing Different mode is produced when independent steam and mixture thereof.Additionally, LCR transducer can have The multiple components responded from the LCR of LCR circuit, wherein these multiple components of LCR response Being derived from the different factors affecting converter circuitry, it includes material resistance as non-limiting example And contact resistance between electric capacity, transducer and sensing material and electric capacity and transducer substrate with Resistance between sensing material and electric capacity.Additionally, LCR transducer can have LCR circuit behaviour The multiple conditions made, wherein IC chip is a part for sensor circuit.

Therefore, a kind of method for controlling the response of temperature correction sensor relates to integrated circuit Chip power supply, in order to affect impedance spectrum section.Different impedance spectrum sections based on from different steam with And the temperature related sensor that changes alternately of chemistry and biological species responds.On resonant antenna IC chip or IC memory chip comprise rectifier diodes, and can be with different capacity level It is powered, in order to affect the impedance spectrum section of sensor.In the spectrum section of different capacity level Difference at F_P、F₁、F₂、F_Z、Z_P、Z₁、Z₂Different value and C and R calculating value in It is significant.In one embodiment, by suitably selecting IC chip or IC memory chip At least one power stage of operation realizes the unrelated sensor performance of temperature strengthened.At another In embodiment, by suitably selecting IC chip or at least two merit of IC memory chip operation Rate level, and analyze the combined impedance spectrum section of sensor under different capacity level, realize increasing The unrelated sensor performance of strong temperature.Perform between relatively low and higher-wattage according to over-over mode By at least two power stage to sensor power.In the dynamic change than measured ambient parameter Will soon at least 5 times time put on execution by least two power stage to sensor interleaved power. In all these embodiments, it is powered being in from-50dBm to+40 with different capacity level Within the scope of dBm, and provide the ability realizing the unrelated sensor performance of temperature.

By the operation power of change IC chip to strengthen temperature relevant response, provide The temperature unrelated LCR circuit operation improved.Specifically, with the IC chip of sensor At least two power stage of operation perform the pick up calibration of temperature independent operations.Sensor First being operated in lower slightly power, therefore IC chip disconnects that (power is in about substantially Between-50dBm to-10dBm), and determine in the case of analyte exists and be non-existent Transducer and the temperature correlation coefficient of sensing material.Subsequently, working sensor at slightly higher power, Therefore IC chip connects (power is between about-10dBm to+40dBm) substantially, And in the case of analyte exists and be non-existent, determine the temperature of transducer and sensing material Correlation coefficient.

Refer now to accompanying drawing, and with initial reference to Fig. 1, it is provided that sensing system 10, in order to illustrate utilization The temperature unrelated selectivity steaming that the RFID sensor 12 of sensing material 14 is carried out it is coated with on it The principle of vapour sensing.Sensing material 14 has at least two temperature of dielectric constant and electrical resistance property Degree relevant response coefficient.Referring briefly to Fig. 2, sensor 12 is to include being coated with sensing material The resonance circuit of the Inductor-Capacitor-resistor structure (LCR) of material 14.LCR structure includes At least three temperature relevant response of the character of the inductance L of LCR circuit, electric capacity C and resistance R Coefficient.At least three temperature relevant response coefficient of the character of LCR circuit differs the biggest each other About 5%.It addition, at least two temperature relevant response coefficient of the character of sensing material 14 and LCR At least three temperature relevant response coefficient difference at least about 5% of the character of circuit.Will sensing Material 14 is applied on the sensing area between electrode, and electrode forms sensor antenna 18, they Constitute resonance circuit.As will be described further below, by sensing material 14 is applied to On resonance circuit, the impedance response of circuit will be changed.Sensor 12 can be wired sensor Or wireless senser.Sensor 12 may also include the memory chip being coupled to resonant antenna 18 16, wherein resonant antenna 18 is coupled to substrate 20.Memory chip 16 can include depositing on it Manufaturing data, user data, calibration data and/or other data of storage.Memory chip 16 It is IC apparatus, and includes using complementary metal oxide semiconductors (CMOS) (CMOS) process institute The RF signal modulation circuit manufactured and nonvolatile memory.RF signal modulation circuit assembly Including diode rectifier, supply voltage control, manipulator, demodulator, clock generator and Other assembly.

Fig. 3 illustrates by an alternative of the sensor 12 represented by reference number 21, its Include that the supplementary sensor 23 of sensing material 14 is attached and stride across antenna 18 and integrated circuit (IC) Memory chip 16, in order to change sensor impedance response.(do not show in another embodiment Go out), supplementary sensor is attached across the antenna not having IC memory chip, and changes biography Sensor impedance response.The non-limiting example of supplementary sensor is sensor intersected with each other, resistance Sensor and capacitance sensor.At entitled " Methods and systems for Calibration of RFID sensors " U.S. patent application serial number 12/118,950 in Describe supplementary sensor, be incorporated into herein by quoting.

In one embodiment, 13.56MHz RFID label tag can be used.At sensing system 10 Operation during, impedance Z (f) and the memory chip 16 of sensor antenna 18 can be obtained The digital sensor calibration parameter of upper storage.Referring again to Fig. 1, the resonance impedance of antenna 18 The measurement of Z (f) and from memory chip 16 numerical data read/write via Mutual Inductance Coupling between the pick-up winding 22 of RFID sensor antenna 18 and reader 24 is held OK.As it can be seen, reader 24 can include RFID sensor impedance reader 26 and integrated Circuit memory chip reader 28.Friendship between RFID sensor 12 and pick-up winding 22 General mutual inductice coupled circuit model can be used mutually to describe.This model includes pick-up winding 22 Intrinsic impedance Z_CIntrinsic impedance Z with sensor 12_S.Mutual Inductance Coupling M and intrinsic impedance Z_C、 Z_SBy striding across the overall measurement impedance Z of the terminal of pick-up winding 22_TIt is correlated with, such as following formula institute table Show:

Z_T=Z_C+(ω²M²/Z_S) (1)

Wherein, ω is radian carrier frequency, and M is Mutual Inductance Coupling M coefficient.

Via monitoring by the sensing material 14 of the electromagnetism place detection generated in antenna 18 (Fig. 2) The change of character, perform sensing.RFID sensor is being read by pick-up winding 22 When 12, the electromagnetic field generated in sensor antenna 18 stretches out from the plane of sensor 12, And by the dielectric properties influence of surrounding, thus provide measure physical parameters, chemistry ginseng Number and the chance of biological parameter.

Via monitoring by the sensing of the electromagnetism place detection generated in supplementary sensor 23 (Fig. 3) The change of the character of material 14, performs sensing.RFID is being read by pick-up winding 22 During sensor 12, the electromagnetic field generated in supplementary sensor 23 is from supplementary sensor 23 Plane is stretched out, and by the dielectric properties influence of surrounding, thus measurement physics ginseng is provided Number, chemical parameters and the chance of biological parameter.

Fig. 4 illustrates the measured sound of the exemplary RFID sensor 12 according to embodiments of the invention The example answered, including full impedance spectrum and the spectrum parameter of some independent measurements of sensor. In order to use single RFID sensor, detect some selectively such as RFID sensor 12 Steam or fluid, from being coated with the sensor antenna 18 of sensing material to measure impedance spectrum Z (f)=Z_re(f)+jZ_imThe real part Z of (f)_re(f) and imaginary part Z_im(f), and from measured Z_re(f) And Z_imF () calculates at least four spectrum parameter, as shown in the curve 30 of Fig. 4.7 can be calculated Individual spectrum parameter, as shown in the curve 30 of Fig. 4.These parameters include Z_reThe frequency location of (f) F_PWith amplitude Z_P、Z_imResonant frequency F of (f)₁With anti-resonance frequency F₂, respectively at F₁And F₂Frequently Impedance magnitude Z of rate₁And Z₂And zero reactance frequency F_Z.Also can calculate such as the factor of quality it The additional parameter of class.From measured parameter, may further determine that the resonant antenna 18 of sensing film coating Resistance R, electric capacity C and other parameter.Multivariate analysis can be used for the dimension of impedance response From the measured real part Z of impedance spectrum_re(f) and imaginary part Z_im(f) or from calculated parameter F_P、Z_P、 F₁And F₂And the individual data point that other possible parameter is reduced in hyperspace, it is provided with choosing Quantify different steam or fluid with selecting, this it will be appreciated by persons skilled in the art that, and Will be further described below.

The generally acknowledged restriction bag of the impedance spectra in the real sensor of trace analysis analyte detection Include relatively muting sensitivity and big frequency range extremely grown the acquisition time.Embodiment as herein described By being put on the electrode of resonant LCR sensor circuit by material, strengthen measurement sensing material The ability of change of character.Similarly, the disclosed embodiments strengthen measurement resonance LCR biography The ability of the change of the character of the fluid near the electrode of sensor circuit.Experiment test examines and changes Become the effect with and without the dielectric constant on the sensing electrode of resonator.With conventional impedance light Spectrum is compared, and naked resonant LCR sensor provides the noise (SNR) that minimum is measured range delta ε At least 100 times of enhancings, wherein there is the corresponding improvement of the detectable limit that dielectric constant determines.

As used the performance of LCR sensor that multivariate analysis tools analyzed to provide individually The selective advantage of improvement of the individually process of response of sensor.Specifically, test result Show, and compared with the relation between the multivariable parameter presenting larger change, F_PWith Z_PBetween It is right that pass between the sensor resistance R and the sensor capacitance C of calculating of relation and calculating ties up to Between different steam or fluid, there is small selectivity, discussed in detail below.Additionally, LCR sensor description of test improves the independence of the overall selectivity of the multivariable response of LCR sensor Contact resistance and hand capacity response.This selectivity modification is derived from contact resistance and hand capacity Respond the individual contributions that the equivalent circuit to sensor responds.

Multiple group of the RFID sensor of all sensors 12 and 21 as Figure 1-3 etc Part respectively processes multiple physical property, such as but not limited to thermal conductivity, thermal expansion, modulus of elasticity, Resistance, impedance etc..This kind of character can be affected by variations in temperature.Therefore, the temperature of character Relevant response coefficient is defined as temperature and changes fixed amount, relatively becoming such as character when 1 degree Celsius Change.Such as, this character can change with linear or multinomial, logarithm or exponential manner with temperature. Properties can increase with temperature, and other character can reduce with temperature.Such as, impedance Temperature relevant response coefficient at another of sensing material 14 and RFID sensor 12 or 21 Assembly is (such as but not limited to memory chip 16, antenna 18, substrate 20, coil 22, collection Become circuit (IC) chip, transducer or film) between can be different.In other words, sensing material 14 Impedance can be with temperature in the way of being different from other assembly of RFID sensor 12 or 21 Change.Such as, for the variations in temperature of 1 degree Celsius, the impedance of sensing material 14 can increase 1 ohm.By contrast, for the identical variations in temperature of 1 degree Celsius, RFID sensor 12 Or the impedance of the antenna 18 of 21 can increase by 0.8 ohm.Therefore, two temperature of impedance are correlated with Percent difference between response coefficient is about 22%.In various embodiments, LCR circuit and The absolute value of the temperature relevant response coefficient of the character of sensing material 14 can about 0.5% to 500%, between 2% to 100% or 5% to 50%.Based on LCR circuit and the temperature of sensing material 14 Degree relevant response coefficient difference, RFID sensor 12 or 21 can with temperature the most independently from Analyzed fluid mixture detects analyte fluid selectively.

Fig. 5 is to illustrate to deposit in variable temperature for using RFID sensor 12 or 21 to analyze Flow process Figure 40 of the demonstration program of steam in case, wherein sensing material 14 and RFID The temperature relevant response coefficient of the impedance of other assembly of sensor 12 or 21 differs.Under In row step, the multivariate analysis of the impedance of the measurement of RFID sensor 12 or 21 is used for carrying Respond for temperature associated steam.At first step 42, RFID sensor 12 or 21 is via prison The change of the character surveying the sensing material 14 by the electromagnetism place detection generated in antenna 18 is held Row sensing, as described in detail above.At second step 44, the RFID antenna that makes a difference electricity The temperature fluctuation of the impedance of road and sensing material 14.But, RFID antenna circuit and sensing material The impedance of material 14 rings owing to RFID antenna circuit is relevant with the temperature of the impedance of sensing material 14 Answer the difference of coefficient rather than by equal impact.It addition, RFID antenna circuit and sensing material 14 The difference of temperature relevant response coefficient of impedance affect the impedance spectrum of measurement of resonant antenna.? Three steps 46, RFID sensor 12 or 21 senses the change of the concentration of steam to be quantified.Temperature Degree fluctuation can continue to occur at third step 46.In the 4th step 48, RFID sensor 12 Or 21 measure resonant antenna impedance spectrum.Can count from the real part of the measurement of impedance spectrum and imaginary part Calculate some spectrum parameters, as described in detail above.In the 5th step 50, perform full impedance spectrum Or the multivariate analysis of the spectrum parameter calculated, as described in detail later.

In the 6th step 52, obtain in the memory chip 16 of RFID sensor 12 or 21 The suitable multivariate calibration value of storage or calibration factor.Calibration factor in RFID sensor 12 or Determine during the experiment test of 21.Such as, RFID sensor 12 or 21 is in some temperature The vapour concentration that degree sensing changes.Then, PCA or other multivariable technique any or The combination of person's method can be used for producing each response curve of measured temperature.Determine best Corresponding to the optimum fit curve of each response curve, and determine such as polynomial function etc Function, in order to represent optimum fit curve with mathematical way.Each function includes characterizing this letter Some numeric factors of number.Then, these coefficients are used as calibration factor, and they such as can conduct Look-up table is stored in memory chip 16.During operation, by RFID sensor 12 or The concentration of 21 steam sensed and/or temperature be likely not to have corresponding to experimental concentration or temperature it One.But, the calibration factor using the experiment in look-up table to determine, can generate and be best represented by The interpolating function (that is, response curve) predicting behavior at the steam of sensed concentration and temperature.

In the 7th step 54, RFID sensor 12 or 21 is based on performed by the 5th step 50 Multivariate analysis and unrelated with variable temperature at response curve determined by the 6th step 52 Ground quantifies the concentration of steam.Specifically, by the result of many analysis on altered projects of the 5th step 50 Substitute at interpolating function determined by the 6th step 52, in order to calculate vapour concentration.Calculate Vapour concentration is accurately, because the previous steps in flow process Figure 40 has been contemplated that variable temperature Impact on RFID sensor 12 or 21.As shown in flow process Figure 40, it is not necessary to independent temperature Sensor, because individually RFID sensor 12 or 21 can be many based on measured resistance value Variable analysis provides the unrelated steam of temperature to respond.Therefore, RFID sensor 12 can make by ratio With other sensing system of individual temperature sensors is less, cost is lower, simpler and/or Relatively reliable.

Multiple sensing material is advantageously used on the sensing area of LCR resonant sensor, because The analyte sensing change of sensing material film is by material resistance and electric capacity, transducer and sensing material The resistance between contact resistance and electric capacity and transducer substrate and sensing material between material and Change in electric capacity affects the impedance of antenna LCR circuit.This kind of change provides independent RFID The multiformity of the response of sensor, and provide the single LCR of employing or RFID sensor to replace The chance of the whole array of conventional sensors.

The sensing film of disclosed LCR and RFID sensor can include multiple material, if environment Change is that the change by resonant LCR circuit parameter is detectable.It addition, the character of sensing film Temperature relevant response coefficient different from the temperature relevant response coefficient of the character of LCR circuit, as Described above in detail.The non-limiting example of possible sensing membrane material is the most poly-(2-first Base acrylic acid hydroxyl) etc hydrogel, such as Nafion etc sulfonation gather The adhesive polymer of compound, such as silicone adhesive etc, such as sol gel film etc inorganic Film, the containing of such as DNA, antibody, peptide or other biomolecule etc deposited as film Biomembrane, as inorganic or polymeric membrane, synthesis film, nanometer synthesis film, functionalization (functionalized) carbon nano-tube film or by functionalisation of surfaces golden nanometer particle, Static Spinning Polymerization, inorganic and synthesis nanofiber and there is a dielectric property and being combined in have another The part deposition of the film that the nanoparticle in the matrix of one dielectric property is formed is such as DNA, antibody, enzyme, peptide, polysaccharide, protein, fit or other biomolecule or virus, Spore, cell etc containing biomembrane.

Sensing material can be chosen to the different dielectric with the scope from about 2 to about 40 Constant.Non-limiting example include polyisobutylene (PIB, ε '_r=2.1), ethyl cellulose (EC, ε’_r=3.4), Polyglycol 166-450 (PECH, ε '_r=7.4), cyanogen hydroxypropyl methyl benzyl silicone (cyanopropyl methyl phenylmethyl silicone) (OV-275, ε '_r=33). Using of these materials provides the adaptation sensing response when being exposed to the steam of differing dielectric constant The ability of relative direction.Steam enters to the different partition coefficients in these or other sensing material The multiformity of one step modulated response and relative direction.

" synthetic " is to keep independent and different in finished product structure on a macro level by having The material that constituted of significantly different two or more composition materials physically or chemically.Example As, two or more composition materials can have the different temperatures of the character of such as impedance etc and be correlated with Response coefficient.The non-limiting example of synthetic includes having poly-(4-Vinyl phenol), poly-(benzene Ethylene propenyl altogether) (poly (styrene-co-allyl alcohol), poly-(vinyl chloride-be total to vinegar Vinyl acetate) and the carbon black synthetic of other material." nanocomposite " is by having Product structure keeps in nano-scale independent and different significantly different physically or chemically property The material that the two or more composition materials of matter are formed.The non-limiting example of nanocomposite Including: there is polymer (the most poly-(N-vinylpyrrolidone), Merlon, polystyrene Deng) carbon nanotube synthetic；There is polymer, metal oxide nano-wire and carbon receive The semiconductive nanocrystalline quantum dot nanocomposite of mitron；Use the gold of CNT functionalization Belong to nanoparticle or nano-cluster (nanocluster).

Sensing material presents analyte response, and this can pass through LCR or the three of RFID sensor The one or more of individual response mechanism describe, such as resistance variations, change in dielectric constant and swollen Swollen change.Can constitute to combine and respectively by dramatically different response mechanism, analyte be rung The synthesis sensing material of the independent sensing material of multiple differences answered.This kind of synthesis sensing material produces Multivariable response strengthens multiformity.This kind of synthesis sensing material can specific at LCR resonator Homogeneity or heterogeneous mixes or be partially formed pattern on part.

Such as, large-scale metal oxide semiconductor material (such as, ZnO, TiO₂、SrTiO₃、 LaFeO₃Deng) change of resistance is presented when being exposed to analyte gas, but some mixing gold Belong to oxide (such as CuO-BaTiO₃、ZnO-WO₃) change it when being exposed to analyte steam Dielectric constant/electric capacity.By these materials are combined into mixture or heavy by being spatially separating Amassing on same sensor, the individual contributions of the local environment around sensor is used for increasing by they The multiformity of the response mechanism of strong single analyte, thus strengthen selectivity.

As another example, part coating conduction (such as, metal) nanoparticle is due to them Because of analyte absorb the local that sensed in part shell expand the strong change of the resistance caused with And the follow-up change of the tunneling efficiency between adjacent conductive nanoparticle and these electrical-conductive nanometers The change in dielectric constant of the environment between particle and be used as steam sensing material.With dielectric polymer (non-limiting example includes silicone, poly-(ether urethane (etherurethane)), polyisobutylene silicon Ketone fluorinated alcohols etc.), conjugated polymer (polyaniline, polythiophene, poly-(ethylene ferrocene), poly-(fluorenes -diphenyl propane), poly-(3,4-rthylene dioxythiophene), polypyrrole, two pyrroles (bilypyrrole)) or carry out response analysis thing with the more prominent change of electric capacity or resistance to absorb Other material any (non-limiting example includes porphyrin, metalloporphyrin, metallophthalocyanine, carbon Nanotube, semiconductive nanocrystal, metal oxide nano-wire) combine, formation has wider The sensor of analyte response.

Additionally, in order to avoid disparate materials each other potentially harmful in synthesis sensing material Impact (such as, the conduction of high dielectric constant suppression conductive filling material), these materials become Component selections origin cause of formation hydrophilic/hydrophobic alternately or each other immiscibility and localized phase separation, thus allow Different mechanisms is active in each composition, in order to sensed by sensor.In another embodiment In, synthesis sensing material can be formed as the individual member deposited on single sensor adjacent one another are The sector of material.In another embodiment, synthesis sensing material can be formed as overlapping each other heavy Amass the layer of independent material on single sensor.

In certain embodiments, sensing material can be porphyrin, metalloporphyrin, metallophthalocyanine and Relevant macro ring.In these materials, gas sensing is by the layer that organises of gas to flat macro ring Pi accumulation or by the gas of metal center be coordinated and do not have cavity to comprise and realize.Gold Belong to porphyrin provide gas response some mechanism, including hydrogen engage, polarization, polarity mutual, golden Genus center is coordinated mutual and molecules align.Porphyrin, metalloporphyrin, metallophthalocyanine and relevant macro ring Molecule also be able to be assembled in nanostructured.

The material of type includes wherein aliging by multiple known method (dielectrophoresis pair further Together, material polymerization during alignment, because of space limit cause alignment, slow solvent evaporation during Alignment etc.) perform alignment nanostructured, self-assembled structures (such as, formed objects The colloidal crystal structure of particle, wherein different layers have the multilamellar glue of different size of assembling particle Body crystal film, wherein particle have the particle core with a dielectric property and another dielectric property Particle shell nucleocapsid structure nanoparticle assemble), bionical (bio inspired) material, Zero dimensional nanometer materials, monodimension nanometer material, two-dimension nano materials and three-dimensional nanometer material.

Self-assembled structures includes that the particle,colloid crystal structure of formed objects, wherein different layers have The multilayer colloid crystal film of different size of assembling particle, wherein particle have one dielectricity of band The nanoparticle subgroup of the nucleocapsid structure of the particle core of matter and the particle shell of another dielectric property Dress.The non-limiting example of the material of self-organized colloidal crystal structure includes polystyrene, poly-first Base acrylic acid methyl ester., polymethylstyrene, styrene/butadiene copolymers, styrene/toluene Ethylene copolymer and Silicon stone.The representative diameter of these colloidal particles depends on the type of material, and And scope can be from 50 nanometers to 25 micron.There is colloidal crystal structure non-limiting of multilamellar A kind of size of at least one of which that example includes being assembled in sensor substrate as colloid array Particle and be assembled at least one of which another kind size above preceding layer as colloid array Particle.The non-limiting example of biomimetic material includes super-hydrophobic or super-hydrophilic coating.

The non-limiting example of zero dimensional nanometer materials includes metal nanoparticle, dielectric nano grain Son, core-shell structure copolymer nanoparticle and semiconductive nanocrystal.The non-limiting of monodimension nanometer material is shown Example includes nanotube, nano wire, nanometer rods and nanofiber.Two-dimension nano materials unrestricted Property example includes Graphene.If the non-limiting example of three-dimensional nanometer material includes dried layer colloidal spheres The self-assembled film of body.

Have the core of the particle shell of particle core with a medium character and another dielectric property- The non-limiting example of the nanoparticle of shell structure includes: metal (gold, silver, their alloy Deng) core nanoparticle and organic shell (dodecyl mercaptans, decanethiol, 1-butyl mercaptan, 2- Ethyl hexyl mercaptan, hexyl mercaptan, tert-dodecyl mercaptan, 4-methoxyl group-toluenethiol, 2-sulfydryl benzene And oxazole, 11-sulfydryl-1-undecyl alcohol, 6-hydroxyl hexyl mercaptan)；Polymerization (polystyrene, poly- Methyl methacrylate) and inorganic shell (Silicon stone)；Isolation core (polystyrene, polymethylacrylic acid Methyl ester, Silicon stone) and semiconductive shell (CNT, TiO₂, ZnO, SnO2, WO3) and point It is embroidered with the carbon nanotube core of metal nanoparticle.Metal (gold, silver, their alloy etc.) core is received The nanoparticle of rice corpuscles and organic shell can use organic and polymerizable molecular to improve further. The non-limiting example of organic molecule includes porphyrin, metalloporphyrin, metallophthalocyanine and macro ring, cave Shape part, super molecular compound.The non-limiting example of polymerizable molecular includes having scope from 2 Polymerizable molecular to the differing dielectric constant of 40.Non-limiting example include polyisobutylene (PIB, ε’_r=2.1), ethyl cellulose (EC, ε '_r=3.4), Polyglycol 166-450 (PECH, ε '_r=7.4), Cyanogen hydroxypropyl methyl benzyl silicone (OV-225, ε '_r=11), double cyanogen pi-allyl silicone (OV-275, ε’_r=33).The non-limiting example manufacturing these sensing materials includes: (1) in a solvent Preparation has the metal core nanoparticle having casing, and this is formed and is polymerized by (2) in a solvent Or organic molecule another composition mixing, and (3) on LCR or RFID transducer by This combination mixture makes sensing film.These materials are used in combination with metal core nanoparticle The energy of the relative direction adapting to sensing response when being exposed to the steam of differing dielectric constant is provided Power.Steam is to the further modulated response of different partition coefficients in these or other sensing material Multiformity and relative direction.

Other sensing material includes semiconducting metal oxides, zeolite, cryptand, ionic liquid Body, liquid crystal, crown ether, enzyme, polysilsesquioxane, metallic organic framework (MOF).

Other sensing material includes having different polymer pendant groups degree of functionality and different polymer is joined The synthesis dielectric of side and conducting polymer；The biomolecule of gas phase sensing；There is leading intracavity join The total of steam that the cryptand of position and cryptand deposition are provided suppresses outside nonspecific chamber Absorb；Porphyrin and as independent molecule and be assembled in polymer and nanostructured relevant point Son.

In order to improve temperature correction response further, can perform to use the sense of auxiliary membrane filtration film Survey the coating of film.The non-limiting example of these filter membranes include zeolite, metallic organic framework and Cryptand filter.

The sensing area of LCR or RFID resonant transducer provides and shows as non-limiting example These the multiple sensing materials gone out, because material is passed through in the analyte sensing change of sensing material film Contact resistance between resistance and electric capacity, transducer and sensing material and electric capacity and transducer lining Resistance between the end and sensing material and the change of electric capacity affect the impedance of antenna LCR circuit. This kind of change provides the multiformity of the response of independent RFID sensor, and provides employing single LCR or RFID sensor replace the chance of the whole array of conventional sensors, as described below for Experimental data further illustrates.

Experimental data

All resonant antenna structure as previously discussed etc are used for proving disclosed technology.By often Rule paint painting, titration coating and spraying process, are applied on resonant antenna by multiple sensing material. The measurement of the impedance of RFID sensor for example with network analhyzer (model is E5062A, Agilent Technologies, Inc., Santa Clara, California), calculating Machine controls lower use Lab VIEW and performs.Network analhyzer is used for scanning range of interest (i.e., The resonant frequency range of LCR circuit) frequency, and collect the impedance from RFID sensor Response.By RFID sensor is put in environmental chamber, and with about 0.1 degree Celsius Accuracy and precision controlling temperature, produce variations in temperature.

For gas sensing, use the computer of internal build to control steam generating system and produce Different vapour concentrations.Collected impedance data use Excel (MicroSoft Inc., Seattle, the State of Washington) or KaleidaGraph (Synergy Software, inner fourth, Pennsylvania) and with Matlab (The Mathworks Inc., Nei Dike, Ma Sa Zhu Saizhou) compounding practice PLSToolbox (Eigenvector Research, Inc., graceful Gloomy, the State of Washington).

Example.Single sensor is used the most accurately to detect humidity level

As illustrated in figs. 6-11, test result is obtained, in order to prove to use single sensor (such as, The sensor 12) at some different temperatures, accurately detect water vapour.This kind of test result can For generating above in relation to the calibration factor described in Fig. 5.As shown in Fig. 6, Fig. 7 and Fig. 9, Sensor is exposed to the water vapor concentration of change under following temperature: 25 degrees Celsius, 30 Celsius Degree, 35 degrees Celsius and 40 degrees Celsius.Tested water vapor concentration be about 0ppm, 2807ppm, 4210ppm, 5614ppm, 7017ppm and 8421ppm.

Carefully select and provide for applying the sensing material of RFID label tag at four temperature Accurately detect the ability of water vapor concentration.In this experiment, selected sensing material is all Such as poly-(ether urethane) (PEUT) that the electrodeless solvent of dichloromethane etc dissolves.In experiment periods Between, RFID sensor four temperature each under be incrementally exposed to multiple water vapor concentration. Specifically, there is computer control temperature programmed environmental chamber by sensor is positioned at In, perform measurement.Use the steam generating system with computer control vapour concentration programming Perform the generation of different water vapor concentration.Test is carried out step by step, wherein, and water vapour dense Degree increases with each step.By monitor the change of some character and check to four temperature with And the multiple response of concentration level increased, data prove in above-mentioned experiment temperature independently The ability of accurate quantification water vapor concentration.

Fig. 6 and Fig. 7 illustrates when RFID sensor is for measuring steam (that is, in this example Water vapour) time example on the temperature impact of the individually response of RFID sensor.Chart 55 He 56 illustrate that the sensor being coated with film is being exposed to about 0,2807,4210,5614,7017 With the notable temperature that the electric capacity during water vapor concentration of 8421ppm responds C and electrical response R Relevant.In other words, electric capacity and electrical response change relative to temperature.In fig. 8, relatively In be coated with the sensor of film being exposed to about 0,2807,4210,5614,7017 and For the difference of about 25,30,35 and 40 degrees Celsius during the water vapor concentration of 8421ppm The electrical response R of temperature draws electric capacity response C.Each lines in Fig. 8 are corresponding in difference At a temperature of specific water vapor concentration sensor response.Such as, solid line circle is corresponding to four At individual temperature, the sensor to the water vapour of 8421ppm responds.The upper left quarter of lines corresponds to The response of 40 degrees Celsius, and the right lower quadrant of lines is corresponding to the response of 25 degrees Celsius.Fig. 8 shows Go out the relation between temperature appreciable impact electric capacity and electrical response.Accordingly, it is difficult to come based on Fig. 8 Distinguish temperature to affect with water vapor concentration.But as follows, rung by application sensor The multivariate analysis answered, obtains distinguishing temperature and significantly improving that vapour concentration affects.

A kind of convenient manner of the multiple response of analyte sensors is to use principal component analysis (PCA) Produce multivariate signature.Everybody it will be appreciated that PCA analyze be those skilled in the art The mathematical procedure analyzed for cube is reduced to more low-dimensional supply known.Such as, giving The multiple response of each steam determining concentration can be reduced to individual data point, and thus can differentiate can It is expressed as the single response of each steam of vector, as shown in Figure 9.Fig. 9 represents in aforementioned four The PCA curve 60 of the multiple response of six kinds of water vapor concentrations at temperature.Water vapor concentration edge The direction of arrow 62 increases.In other words, in the result of the highest water vapor concentration, i.e. 8421ppm Occur near the left side of curve 60, and occur in song in the result of the least concentration of 0ppm Near the right side of line 60, wherein the result at 0ppm overlaps onto individual data to four temperature Point.Everybody is it will be appreciated that FACTOR 1 (factor 1) represents the response with maximum change, And FACTOR 2 (factor 2) represents have time response of maximum change.Compared with Fig. 8, Fig. 9 The lines of the different vapour concentration of middle expression are more open, thus show to make district by multivariate analysis Other temperature is possible with the improvement of vapour concentration impact.As shown in Figure 9, although water vapour is dense Spend at 25 degrees Celsius of ratios 40 degrees Celsius of larger changes shown relative to FACTOR 1, but It is can be clearly distinguish between in the result of four temperature.Therefore, according to various embodiments Sensor can correct the impact of these temperature, in order to provides water vapor concentration information accurately.Tool For body, can be to each formation optimum fit curve of four temperature and respective function.These letters The coefficient of number then can be used as calibration factor described above in detail.Correspondingly, this test data carry For to can be temperature independent differentiate the support of sensor of water vapor concentration.

Use based at the function of the data collected by experimental temperature and calibration factor, can extrapolate or The impact on the sensor measurement at a temperature of other of the interpolation temperature.For example, it is possible to can extrapolate Water vapor concentration between 25 degrees Celsius and 30 degrees Celsius.This additional extrapolated data can also be used with Water vapor concentration at a temperature of detecting other selectively.Additionally, by selected by change Sensing material, utilizes single RFID sensor to have turned out in temperature in addition to the above Degree and concentration detect steam in addition to water selectively.

Other curve can be generated, in order to illustrate further collected by single RFID sensor How experimental data is for quantifying water vapor concentration temperature independently.Such as, from Fig. 9's Data are for generating the secondary mould formed compared with water vapor concentration shown in left side of Figure 10 The multivariable response curve 70 of the FACTOR 1 and FACTOR 2 of type.In other words, two are formed Secondary model is to represent the result of the PCA curve 60 shown in Fig. 9.Described above in detail many The predictive value of the water vapor concentration under the conditions of Zhong uses secondary model to calculate, and and Figure 10 Curve 72 in actual measured value compare.As shown in the curve 72 of Figure 10, point leans on The nearly lines corresponding with the slope of.Such as, the standard error of secondary model is about 212ppm Water vapour (that is, 0.7% relative humidity).Therefore, it was predicted that be worth closely related with actual value, from And prove the predictability of exemplary sensor and method.

Similarly, from the data of Fig. 9 for generating shown in the left side of Figure 11 and water vapour The multivariable response that concentration compares the FACTOR 1 and FACTOR 2 of formed three time model is bent Line 80.In other words, three models are formed to represent the result of the PCA curve 60 shown in Fig. 9. Described above in detail multiple under the conditions of water vapor concentration predictive value use three models Calculate, and compare with the actual measured value in the curve 82 of Figure 11.Such as Figure 11 Curve 82 shown in, point is near lines corresponding with the slope of.Such as, secondary model Standard error is about the water vapour (that is, 0.63% relative humidity) of 188ppm.Therefore, as Secondary model with Figure 10 is the same, it was predicted that is worth closely related with actual value, demonstrates again that demonstration Sensor and the predictability of method.In other embodiments, it is possible to use except secondary and three Other multinomial model outside secondary model.

Although the most only illustrate and describe some feature of the present invention, but those skilled in the art Will recognize that multiple modifications and changes.It is therefore to be understood that claims fall into this anticipated containing All such modifications and changes within the true spirit of invention.

Claims

1. a sensor, including:

Resonant inductor-capacitor-resistor LCR circuit；

It is arranged on the sensing material on sensing area, wherein, described sensing area includes at least some of of described LCR circuit, and wherein, the inductance L character of described LCR circuit, the at least three temperature relevant response coefficient of electric capacity C character and resistance R character differs at least 5% each other, and the temperature relevant response coefficient of the dielectric constant of described sensing material and electrical resistance property and the inductance L character of described LCR circuit, the described at least three temperature relevant response coefficient difference at least 5% of electric capacity C character and resistance R character, and sensor described in the official post of the described temperature relevant response coefficient of the described character of wherein said LCR circuit and described sensing material the most independently can detect analyte fluid from analyzed fluid mixture selectively with temperature.

2. sensor as claimed in claim 1, wherein, described sensor does not include individual temperature sensors.

3. sensor as claimed in claim 1, including memory chip, wherein said memory chip includes the calibration factor of the described difference of the described temperature relevant response coefficient of described character based on described LCR circuit and described sensing material.

4. sensor as claimed in claim 1, wherein, described sensor includes RFID sensor.

5. sensor as claimed in claim 1, wherein, LCR circuit includes substrate, coil, memory chip, integrated circuit (IC) chip, transducer or sensing material film.

6. sensor as claimed in claim 1, wherein, LCR circuit includes substrate, coil, memory chip, integrated circuit (IC) chip, transducer and sensing material film, and the temperature relevant response coefficient of the character of wherein said substrate, coil, memory chip, integrated circuit (IC) chip, transducer and sensing material film is different from each other.

7. sensor as claimed in claim 1; wherein, described sensing material includes synthesizing dielectric polymer, conjugated polymer, synthesis conducting polymer, polymer formulators, biomolecule, cryptand, single ply protective metal nanoparticle, having the metallic nanoparticle daughter nucleus of organic ligand shell, porphyrin, phthalocyanine, carbon black particle, CNT and combinations thereof.

8. sensor as claimed in claim 1, wherein, described LCR circuit includes antenna, and the temperature relevant response coefficient of the character of wherein said antenna and described sensing material is different from each other.

9. sensor as claimed in claim 1, wherein, described LCR circuit includes supplementary sensor, and the temperature relevant response coefficient of the character of wherein said supplementary sensor and described sensing material is different from each other.

10. sensor as claimed in claim 1, wherein, described sensing material is arranged between the electrode of described LCR circuit.

11. sensors as claimed in claim 1, wherein, described sensor configuration is disposable sensor.

12. 1 kinds of chemistry detected in fluid or the method for biological species, including:

Measuring real part and the imaginary part of the impedance spectrum of the resonant transducer antenna being coated with sensing material, the temperature relevant response coefficient of the character of wherein said resonant transducer antenna and described sensing material is different from each other；

Calculate at least 6 spectrum parameters of the described resonant transducer antenna being coated with described sensing material at multiple temperatures；

Multivariate analysis is used described impedance spectrum to be reduced to individual data point, with discriminatory analysis thing selectively；And

The calibration factor using storage determines one or more ambient parameter from described impedance spectrum, and wherein said one or more ambient parameters described determines the most unrelated with temperature.

13. methods as claimed in claim 12, wherein, the impact on described impedance spectrum of the calibration factor of described storage different temperatures based on described resonant transducer antenna and the described character of the described sensing material relevant response coefficient.

14. methods as claimed in claim 12, wherein, measure described impedance spectrum and calculating at least 6 spectrum parameters are included in the resonant frequency range of described resonant transducer antenna and measure.

15. methods as claimed in claim 12, wherein, calculate at least 6 spectrum parameters and include calculating the frequency location of described real part of described impedance spectrum and the amplitude of the described real part of described impedance spectrum.

16. methods as claimed in claim 12, wherein, calculate at least 6 spectrum parameters and include calculating the resonant frequency of described imaginary part of described impedance spectrum and the anti-resonance frequency of the described imaginary part of described impedance spectrum.

17. methods as claimed in claim 12, wherein, are reduced to described impedance spectrum individual data point and include calculating multivariate signature.

18. methods as claimed in claim 12, are included in multiple power levels IC chip so that resonant inductor-capacitor-resistor LCR circuit operates under numerous conditions.

19. methods as claimed in claim 18, wherein, the operations improvement of the described LCR circuit under the conditions of the plurality of temperature independent determination to the one or more ambient parameter.

20. 1 kinds of methods manufacturing sensor, including:

Assemble the transducer including resonant inductor-capacitor-resistor LCR circuit, wherein said transducer includes at least three temperature relevant response coefficient of the character of the inductance L of described LCR circuit, electric capacity C and resistance R, and the described at least three temperature correlation coefficient response of the described character of wherein said LCR circuit differs at least 5% each other；

Select sensing material, the at least two temperature relevant response coefficient of it dielectric constant including described sensing material and electrical resistance property, the described at least two temperature relevant response coefficient of the described character of wherein said sensing material differs at least 5% with the described at least three temperature relevant response coefficient of the described character of described LCR circuit；

Being arranged on sensing area by described sensing material, wherein said sensing area includes at least some of of described LCR circuit.

21. methods as claimed in claim 20, wherein, sensor described in the official post between described at least two temperature relevant response coefficient and the described at least three temperature relevant response coefficient of the described character of described LCR circuit of the described character of described sensing material provides the sensing the most unrelated with temperature.

22. methods as claimed in claim 20, wherein, described sensor configuration becomes to obtain impedance at multiple temperatures in the resonant frequency range of described transducer, and the impedance spectrum using the calibration factor of the storage of difference between the described at least two temperature relevant response coefficient of described character based on described sensing material and the described at least three temperature relevant response coefficient of the described character of described LCR circuit acquired from the plurality of temperature calculates multivariate signature.