WO2023019606A1 - 一种仿生贴片传感器及其制备方法和检测方法 - Google Patents

一种仿生贴片传感器及其制备方法和检测方法 Download PDF

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WO2023019606A1
WO2023019606A1 PCT/CN2021/114200 CN2021114200W WO2023019606A1 WO 2023019606 A1 WO2023019606 A1 WO 2023019606A1 CN 2021114200 W CN2021114200 W CN 2021114200W WO 2023019606 A1 WO2023019606 A1 WO 2023019606A1
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bionic
bragg grating
fiber bragg
film
photoelectric conversion
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French (fr)
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张文
陈芷羽
石吉勇
苏小雨
袁磊
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Jiangsu University
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    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
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    • G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
    • G01D5/26—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light
    • G01D5/32—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light
    • G01D5/34—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells
    • G01D5/353—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre
    • G01D5/35306—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre using an interferometer arrangement
    • G01D5/35309—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre using an interferometer arrangement using multiple waves interferometer
    • G01D5/35316—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light with attenuation or whole or partial obturation of beams of light the beams of light being detected by photocells influencing the transmission properties of an optical fibre using an interferometer arrangement using multiple waves interferometer using a Bragg gratings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0218—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using optical fibers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/0286—Constructional arrangements for compensating for fluctuations caused by temperature, humidity or pressure, or using cooling or temperature stabilization of parts of the device; Controlling the atmosphere inside a spectrometer, e.g. vacuum
    • G—PHYSICS
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    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/12—Generating the spectrum; Monochromators
    • G01J3/18—Generating the spectrum; Monochromators using diffraction elements, e.g. grating
    • G01J3/1895—Generating the spectrum; Monochromators using diffraction elements, e.g. grating using fiber Bragg gratings or gratings integrated in a waveguide
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/02—Constructional details
    • G01J5/06—Arrangements for eliminating effects of disturbing radiation; Arrangements for compensating changes in sensitivity
    • G01J5/064—Ambient temperature sensor; Housing temperature sensor; Constructional details thereof
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
    • G01L1/242—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet the material being an optical fibre
    • G01L1/246—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet the material being an optical fibre using integrated gratings, e.g. Bragg gratings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/255—Details, e.g. use of specially adapted sources, lighting or optical systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80—Indicating pH value
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02—Food
    • G01N33/12—Meat; Fish
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
    • G01J2003/425—Reflectance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0054—Ammonia

Definitions

  • the invention belongs to the field of biological sample spectrum sensor detection, and relates to a bionic patch sensor, a preparation method and a detection method thereof.
  • Volatile basic nitrogen refers to the decomposition of protein in animal food under the action of enzymes and bacteria during the spoilage process to produce ammonia and amines, basic nitrogen-containing toxic substances.
  • TVB-N is volatile, and the higher the content of this substance in the food, the more the amino acid is destroyed, and the nutritional value of the food is also significantly reduced. Therefore, TVB-N is regarded as an important index to evaluate the freshness of animal food.
  • the traditional TVB-N detection often adopts the semi-micro Kjeldahl method in the national standard. This method has the advantages of high accuracy and strong stability, but the sample pretreatment is cumbersome and the detection process takes a long time. It is difficult to meet the increasing Growing market demand for rapid testing of large batches of samples and non-destructive testing.
  • the beef freshness disclosed in the patent "a new type of beef freshness rapid non-destructive detection device and method" CN104374702A and “beef freshness detection device and its detection method” CN104374705A The degree detection device and detection method can realize the non-destructive detection of the freshness of beef products on the market, but the detection device designed has high requirements for mechanical assembly and complex equipment composition, and it is still difficult to realize large-scale and real-time on-site detection of beef products .
  • the present invention provides a bionic patch sensor and its preparation method and detection method.
  • the present invention combines pressure-variable Bragg gratings and photoelectric conversion semiconductors to detect the freshness of meat, and solves the existing nondestructive
  • the mechanical device for detecting the freshness of beef has problems such as high equipment cost, incapability of real-time on-site detection, and incapability of large-scale detection.
  • the preparation of the bionic patch sensor includes a sensitive bionic skin prepared by electrospinning technology, a pH-sensitive material AG-AN film (agar-rose anthocyanin film) coated on the skin, the production of a tunable fiber Bragg grating and Packaging, fabrication of photoelectric conversion semiconductors, and construction of chip sensors. Since the AG-AN film on the surface of the biomimetic patch sensor can sensitively respond to pH changes, the pH change on the meat surface caused by the volatile TVB-N gas leads to a color change from red to yellow on the AG-AN film.
  • AG-AN film agar-rose anthocyanin film
  • the strain generated by applying voltage to the piezoelectric device can regulate the central characteristic wavelength of the fiber Bragg grating, and then obtain the spectral information of a specific band by wavelength domain scanning.
  • the strain information on the pH-sensitive AG-AN film is obtained by measuring the change and offset of the central characteristic wavelength signal, and then the semiconductor is used to realize photoelectric conversion and transmit the detection signal in real time to realize the monitoring of the freshness of the meat sample.
  • the bionic patch sensor designed by the present invention has realized the detection of the freshness of meat samples, and has the advantages of non-destructive detection, sensitivity, lightness, ease of use, and low preparation cost, and can solve the problem of traditional non-destructive detection of meat freshness. Existing problems.
  • a bionic patch sensor including a sensitive bionic skin, a pressure-variable fiber Bragg grating, an optical fiber and a photoelectric conversion semiconductor;
  • the surface of the sensitive bionic skin is prepared with an AG-AN film; the pressure-variable fiber Bragg grating is connected to the input end of the photoelectric conversion semiconductor through an optical fiber, and the output end of the photoelectric conversion semiconductor is connected to the terminal device; the sensitive bionic skin is used to communicate with The surface contact of the sample to be tested changes the spectral information.
  • the pressure-variable fiber Bragg grating is used to collect the wavelength-domain optical signal that passes through the sensitive bionic skin, and transmits it to the photoelectric conversion semiconductor through the optical fiber.
  • the photoelectric conversion semiconductor is used to convert the wavelength-domain light The signal is converted into a current signal and passed on to the terminal equipment.
  • the sensitive bionic skin is used to contact the surface of the sample to be tested, the surface of the sample to be tested has volatile TVB-N gas, and the TVB-N gas causes the pH change of the AG-AN film surface of the sensitive bionic skin , causing the AG-AN film to produce a color change from red to yellow, resulting in a change in the absorbance ratio of the AG-AN film.
  • the pressure-variable fiber Bragg grating includes a fiber Bragg grating and a ring-shaped micro piezoelectric unit; the ring-shaped micro piezoelectric unit is coaxially sleeved outside the fiber Bragg grating.
  • the photoelectric conversion semiconductor includes a lens coupling device, a photodiode array and a refrigerator module;
  • the wavelength-domain optical signal collected by the pressure-variable fiber Bragg grating enters the photodiode module array through the lens coupling device, and the photodiode array and the refrigeration module are connected after thermal coupling, and the photodiode array outputs the processed wavelength-domain signal to the terminal device .
  • the refrigeration module includes a refrigerator, a thermistor, a temperature compensation network, a first high-power operational amplifier and a second high-power operational amplifier;
  • the thermistor is connected to the refrigerator through the temperature compensation network, the first high-power operational amplifier and the second high-power operational amplifier.
  • the thermistor is used for heating, and the temperature is adjusted by the temperature compensation network. , and then amplified by the first high-power operational amplifier and the second high-power operational amplifier, and transmitted to the refrigerator for adjusting the working temperature of the photodiode array.
  • the photodiode array includes a constant current diode, a differential field effect transistor, a source resistor and a source resistor, a differential photocurrent signal amplifier and a signal output port; the source resistor and the source resistor are connected to a positive power supply , the constant current diode is connected to the negative power supply, and connected to the differential field effect tube to form a closed circuit; the current signal output by the photodiode array passes through the differential field effect tube to complete the primary amplification of the current, and then completes the secondary amplification through the differential photocurrent signal amplifier, The amplified signal is output from the output port.
  • a manufacturing method according to the bionic patch sensor comprising the following steps:
  • the preparation of the sensitive bionic skin polycaprolactone is used as a polymer carrier, N,N-dimethylformamide is used as a solvent, and after mixing and stirring, a polycaprolactone spinning solution is obtained, and a film is prepared by electrospinning technology As a sensitive bionic skin, configure AG-AN solution, and prepare an AG-AN film on the surface of the sensitive bionic skin;
  • the production of the pressure variable fiber Bragg grating prepare the fiber Bragg grating by interference method, deposit a gold layer on the outer surface of the fiber Bragg grating by magnetron sputtering, and cut the gold layer on the upper and lower surfaces of the piezoelectric ceramic sheet by magnetron sputtering , the obtained circular sheet forms a ring-shaped micro piezoelectric unit after laser machining the central hole, and the ring-shaped micro piezoelectric unit and the fiber Bragg grating are coaxially packaged;
  • the production of the photoelectric conversion semiconductor the wavelength-domain optical signal collected by the pressure-variable fiber Bragg grating enters the photodiode module array through the lens coupling device, the photodiode array and the refrigeration module are connected after thermal coupling, and the photodiode array will be processed
  • the wavelength domain signal is output to the terminal equipment; the photodiode module array is used as a detector, and each photodiode module in the photodiode module array works in different frequency bands to obtain the target wavelength domain, and the thermal noise is reduced through the cooler, and the differential field effect tube is used to complete
  • the photocurrent primary amplification uses a differential photocurrent signal amplifier to complete the secondary amplification, and the amplified signal is output from the signal output port and transmitted to the terminal device.
  • the spinning speed is set to 1.5mL/h
  • the voltage is set to 10-30kV
  • the receiving distance is set to 10-20cm
  • the concentration of the AG solution is 15-25g/L, and the AN content in the AG-AN solution is 75-85mg/L.
  • a detection method utilizing the bionic patch sensor comprising the following steps:
  • Establish the T/V cycle curve of the photocurrent establish the T/V cycle curve of the photocurrent, and obtain the voltage applied to the fiber Bragg grating by the annular micro piezoelectric unit at different times, corresponding to the spectral information in different wavelength domains;
  • the AG-AN film of the sensitive bionic skin is in direct contact with the sample to be tested, and the volatile TVB-N gas of the sample to be tested causes a change in the surface pH of the AG-AN film, and the AG -The color change from red to yellow on the AN film causes the absorbance ratio of the film to change accordingly, so that the current curve output by the photoelectric conversion semiconductor changes equivalently, thus establishing the absorbance-current ratio/TVB-N concentration curve for detection.
  • the beneficial effect of the present invention is: the present invention reacts with the volatile TVB-N on the surface of the sample through the AG-AN film coated on the sensitive bionic skin, and combines the photoelectric effect to output the detection result to measure TVB -N concentration, realizes the portable and sensitive design of the freshness detection sensor, and provides the possibility for online real-time monitoring of the freshness of perishable meat products.
  • the invention makes up for the shortcomings of traditional meat product freshness detection equipment and sensor detection process, such as complex sample processing, high equipment maintenance cost, and long detection time, and can realize in-situ detection of TVB-N concentration on the sample surface.
  • the invention can be applied to Real-time detection of freshness of meat products in the market.
  • Fig. 1 The structure of the bionic patch sensor of the present invention
  • Figure 2 Preparation process of sensitive biomimetic skin coated with AG-AN film
  • Figure 3 Fabrication and packaging of pressure-variable fiber Bragg gratings
  • FIG. 4 Circuit setup of photoelectric conversion semiconductors
  • Figure 7 Comparison chart of the TVB-N concentration of the sample detected by the invented method and the standard method.
  • the bionic patch sensor includes a sensitive bionic skin 1, a pressure-variable fiber Bragg grating 2, an optical fiber 3 and a photoelectric conversion semiconductor 4;
  • AG-AN film is prepared on the surface of the sensitive bionic skin 1; the pressure-variable fiber Bragg grating 2 is connected to the input end of the photoelectric conversion semiconductor 4 through the optical fiber 3, and the output end of the photoelectric conversion semiconductor 4 is connected to the terminal equipment; the sensitive The bionic skin 1 is used to contact the surface of the sample to be tested to change the spectral information, and the pressure-variable fiber Bragg grating 2 is used to collect the wavelength-domain optical signal transmitted through the sensitive bionic skin 1, and transmit it to the photoelectric conversion semiconductor 4 through the optical fiber 3 , the photoelectric conversion semiconductor 4 is used to convert the wavelength-domain optical signal into a current signal, and transmit it to the terminal device.
  • the sensitive bionic skin 1 is used to contact the surface of the sample to be tested, the surface of the sample to be tested has volatile TVB-N gas, and the TVB-N gas causes the AG-
  • the change of pH on the surface of the AN film makes the color change from red to yellow on the AG-AN film, resulting in a change in the absorbance ratio of the AG-AN film.
  • the pressure-variable fiber Bragg grating 2 includes a fiber Bragg grating 6 and an annular micro piezoelectric unit 8 ; the annular micro piezoelectric unit 8 is coaxially sleeved outside the fiber Bragg grating 6 .
  • the photoelectric conversion semiconductor 4 includes a lens coupling device 9, a photodiode array 10 and a refrigerator module; the wavelength domain optical signal collected by the pressure-variable fiber Bragg grating 2 enters the photoelectric
  • the diode module array 10, the photodiode array 10 and the cooling module are thermally coupled and connected, and the photodiode array 10 outputs the processed wavelength domain signal to the terminal device.
  • the refrigeration module includes a refrigerator 11, a thermistor 12, a temperature compensation network 13, a first high-power operational amplifier 14 and a second high-power operational amplifier 15; the thermistor 12 is The temperature compensation network 13, the first high-power operational amplifier 14 and the second high-power operational amplifier 15 are connected to the refrigerator 11.
  • the thermistor 12 is used for heating, and the temperature is adjusted through the temperature compensation network 13. After that, it is amplified by the first high-power operational amplifier 14 and the second high-power operational amplifier 15 , and then transmitted to the refrigerator 11 for adjusting the working temperature of the photodiode array 10 .
  • the photodiode array 10 includes a constant current diode 19, a differential field effect transistor 18, a first source resistor 16 and a second source resistor 17, a differential photocurrent signal amplifier 20 and a signal output port 21; the first source resistor 16 and the second source resistor 17 are connected to the positive power supply, the constant current diode 19 is connected to the negative power supply, and connected to the differential field effect transistor 18 to form a closed circuit; the output through the photodiode array 10 The current signal passes through the differential field effect transistor 18 to complete the primary amplification of the current, and then completes the secondary amplification through the differential photocurrent signal amplifier 20 , and the amplified signal is output through the output port 21 .
  • the model of the first high-power operational amplifier 14 and the second high-power operational amplifier 15 is OPA541AP, American TI company; the model of the differential photocurrent signal amplifier 20 is OPA627AP, American TI company.
  • the synchronous trigger signal of the differential photocurrent signal amplifier 20 is a grating tuning signal. Since the wavelength of the narrowband optical signal is known at any time, the complete spectral information can be restored by scanning in the wavelength domain, and then the status of the beef sample can be determined. for analysis.
  • the external white light source After the external white light source is incident through the optical fiber 3, it passes through the sensitive bionic skin 1 coated with AG-AN film, and then through the PDMS-packaged pressure-variable fiber Bragg grating 2 to obtain the spectral information after the sensitive response by scanning in the wavelength domain, and then through the optical fiber 3 It is transmitted to the photoelectric conversion semiconductor 4, and finally the spectral signal is converted into a current signal in real time and collected and outputted.
  • the bionic patch sensor is a sensitive device designed based on the internally packaged pressure-variable Bragg grating 2 and the photoelectric effect inside the semiconductor.
  • the patch sensor uses an electrospun flexible solid-phase sensitive layer as a biomimetic Raman-sensitive skin, and a pH-sensitive material agar-anthocyanin film (AG-AN film) that can sensitively respond to TVB-N gas is coated on the surface.
  • AG-AN film a pH-sensitive material agar-anthocyanin film
  • a visual bionic skin micro-touch detection method is established to quickly measure the freshness index TVB-N in meat on the market, and realize online monitoring of meat quality.
  • the preparation of sensitive bionic skin 1 coated with AG-AN film polycaprolactone was used as the polymer carrier, N,N-dimethylformamide was used as the solvent, and polycaprolactone was obtained after mixing and stirring for 24 hours.
  • Ester spinning solution a flexible solid-phase biomimetic skin film was prepared by electrospinning technology. Specifically, during the preparation process of the electrospinning film, a No. 20 needle is selected as the electrospinning exit terminal, the spinning speed is set to 1.5mL/h, the voltage is set to 10-30kV, and the receiving distance is set to 10-20cm. The selected setup conditions ensure the successful preparation of electrospun fiber structures with good spinnability.
  • the manufacture and packaging of the pressure-variable fiber Bragg grating 2 firstly, the fiber Bragg grating 6 is prepared by ultraviolet interference method. Specifically, the germanium-doped optical fiber 5 is placed in 2.5 ⁇ 10 5 Pa hydrogen gas and sensitized at -20° C. for 72 hours. The sensitized optical fiber is irradiated with coherent ultraviolet light with a central wavelength ⁇ 0 of 193nm or 244nm to obtain a fiber Bragg grating 6; a 100nm gold layer is obtained on the outer surface of the grating by magnetron sputtering, and placed in a dry environment at 120°C for annealing 8 hours to spare.
  • the ring-shaped micro piezoelectric unit 8 is prepared, and a 100nm gold layer is formed on the upper and lower surfaces of the piezoelectric ceramic sheet 7 by magnetron sputtering.
  • the piezoelectric ceramic sheet has a thickness of 1mm.
  • it is cut into circular slices, preferably, the diameter of the circular slices is 1-2.5 mm to ensure that the optical fiber can be inserted, and a ring-shaped micro piezoelectric unit 8 is formed after laser machining a central hole with a diameter of 150 ⁇ m. Coating low-temperature lead-tin solder on the electrode end of the piezoelectric unit 8, stacking 5-20 layers, welding and forming in an environment of 220°C, and coaxially packaging the fiber Bragg grating 6 under the same welding conditions.
  • the wavelength-domain optical signal obtained through the pressure-variable fiber Bragg grating 2 enters the avalanche-type InGaAs photodiode module array 10 as a detector through the lens coupling device 9 .
  • Each photodiode module in the array works in different frequency bands and jointly covers the target wavelength domain.
  • the photodiode array 10 is connected to the refrigerator 11 after being thermally coupled, and the photodiode array 10 outputs the processed wavelength domain signal to the terminal device.
  • the refrigeration module includes a thermistor 12, a temperature compensation network 13, two identical first high-power operational amplifiers 14 and second high-power operational amplifiers 15 to form a closed loop.
  • the thermistor 12 is connected to the refrigerator 11 through the temperature compensation network 13, the first high-power operational amplifier 14 and the second high-power operational amplifier 15.
  • the thermistor 12 is used for heating.
  • After the temperature is adjusted by the temperature compensation network 13 it is amplified by the first high-power operational amplifier 14 and the second high-power operational amplifier 15 , and then transmitted to the refrigerator 11 for adjusting the working temperature of the photodiode array 10 .
  • the high-power operational amplifier constitutes a bridge circuit to drive the refrigerator 11, which can reduce thermal noise and ensure that the photodiode module works at a low temperature of -18°C.
  • the photodiode array 10 includes a constant current diode 19 , a differential field effect transistor 18 , a first source resistor 16 and a second source resistor 17 , a differential photocurrent signal amplifier 20 and a signal output port 21 .
  • the first source resistor 16 and the second source resistor 17 are connected to the positive power supply, the constant current diode 19 is connected to the negative power supply, and connected to the differential field effect transistor 18 to form a closed circuit; the current signal output by the photodiode array 10
  • the primary amplification of the current is completed through the differential field effect transistor 18, and the secondary amplification is completed through the differential photocurrent signal amplifier 20.
  • the amplified signal is output by the output port 21, and finally read by computers and distributed terminals such as smart phones and tablet computers. Analyze and save.
  • the response of the array formed by the photodiode module 10 to incident light of different wavelengths may fluctuate, and a tunable narrowband light source and a fiber optic spectrometer are used to calibrate the response of the array in the wavelength domain.
  • the AG solution used in the preparation process of the sensitive biomimetic skin 1 coated with the AG-AN film is 20 g/L, and the AN content in the AG-AN solution prepared by mixing is 80 mg/L.
  • the fiber Bragg grating is manufactured by irradiating the sensitizing optical fiber with coherent ultraviolet light having six central wavelengths ⁇ 0 of 193 nm and 244 nm.
  • the thickness of the piezoelectric ceramic sheet 7 selected for the preparation of the micro piezoelectric device 8 is 1 mm.
  • each photodiode module in the array works in different frequency bands, covering the target wavelength range of 450-800nm together.
  • a kind of detection method that utilizes the bionic patch sensor described in embodiment 1, preferably according to the present embodiment, selects beef as the sample to be tested, comprises the following steps:
  • T/V cycle curve of photocurrent In one cycle, the voltage applied by the micro piezoelectric device to the fiber Bragg grating increases with time, and the fiber Bragg grating that is strained accordingly can collect different wavelength domain sets to obtain specific wavebands Spectral information is converted into current signal output in real time by photoelectric conversion semiconductor.
  • Establish the T/V cycle curve of the photocurrent to obtain the voltage applied by the micro piezoelectric device to the fiber Bragg grating at different times, corresponding to the spectrum acquisition in different wavelength domains;
  • the absorbance-current ratio/TVB-N concentration curve the AG-AN film on the sensitive surface of the bionic patch sensor is directly in contact with the sample to be tested. Due to the change of the surface pH of the AG-AN film caused by the volatile TVB-N gas, the color of the AG-AN film changes immediately. The absorbance ratio of the film at 595nm and 540nm (A 595 /A 540 ) changes accordingly, and similarly, the equivalent value of the current curve output by the photoelectric conversion semiconductor changes. Thus, the absorbance-current ratio/TVB-N concentration curve is established;
  • the freshness of the beef sample to be tested was measured according to the established absorbance-current ratio/TVB-N concentration curve: the worse the freshness of the beef sample, the greater the concentration of volatile gas TVB-N contained on the beef surface.
  • TVB-N combines with the moisture in the AG-AN film on the sensitive surface of the bionic patch sensor, causing the pH of the AG-AN film to change, causing the AG-AN film to change from red to yellow in color.
  • This color change causes the absorbance ratio of the film at 595nm and 540nm (A 595 /A 540 ) to increase, and the spectral information at 450-800nm is collected and output by the pressure-variable fiber Bragg grating and photoelectric conversion semiconductor, and the final current ratio is obtained, etc.
  • the bionic patch sensor of the present invention is compact in structure, easy to operate, and can be well used for on-site detection and analysis.
  • the present invention uses the bionic patch sensor to detect the freshness of beef.
  • a sensor that combines the photoelectric conversion effect to realize fast on-site detection is a feature that other sensors do not have, and the bionic patch sensor of the present invention is the first It is applied to practice with the structure of a portable patch.
  • the data measured by the method of the present invention and the standard method are shown in Figure 7.
  • the relative error of the detection result of the method of the present invention is less than 3.5%, which is suitable for the detection of actual samples. It is verified that the bionic patch sensor based on piezoelectric fiber Bragg grating and photoelectric conversion of the present invention has good sensitivity to TVB-N concentration, can effectively detect the freshness of beef in real time, and has fast detection response and accurate detection results. It has the characteristics of simple operation, wide measurable range, and portability, and can realize on-site detection of beef freshness and be applied to microanalysis.

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Abstract

一种仿生贴片传感器及其制备方法和检测方法，包括敏感仿生表皮、压变光纤布拉格光栅、光纤和光电转换半导体；敏感仿生表皮的表面制备AG-AN膜；压变光纤布拉格光栅通过光纤和光电转换半导体的输入端连接，光电转换半导体的输出端与终端设备连接；敏感仿生表皮用于与待测样品的表面接触，使光谱信息产生变化，压变光纤布拉格光栅用于采集透过敏感仿生表皮的波长域光信号，并通过光纤传递给光电转换半导体，光电转换半导体用于将波长域光信号转换成电流信号。上述方法结合压变布拉格光栅和光电转换半导体的联用对肉类新鲜度进行检测，解决现有无损检测牛肉新鲜度的机械装置存在设备成本高、无法实时现场检测、无法大批量检测等问题。

Description

一种仿生贴片传感器及其制备方法和检测方法 技术领域
本发明属于生物样品光谱学传感器检测领域，涉及一种仿生贴片传感器及其制备方法和检测方法。
背景技术
近年来，随着国民经济得到快速发展以及人民生活物质水平的提升，我国对肉类制品的需求量逐年攀升。面对大量增加的肉类食品消费需求，设计出快速、灵敏且准确的检测方法对肉类新鲜度进行监控已成为热点话题。挥发性盐基氮(TVB-N)是指动物性食品在酶和细菌的作用下，在腐败过程中，蛋白质分解产生氨及胺类碱性含氮有毒物质。TVB-N具有可挥发性，食品中该物质含量越高表明氨基酸被破坏的越多，食品营养价值也显著下降。因此，TVB-N被视作评价动物性食品新鲜程度的重要指标。传统TVB-N检测常采用国标中的半微量凯氏定氮法，这种方法具有准确性高，稳定性强的优点，但样品前处理操作繁琐，检测过程耗时较长，很难满足日益增长的大批量样品快速检测以及非破坏性检测的市场需求。
现有的应用于肉制品新鲜度检测的光学传感器中，专利“一种新型牛肉新鲜度快速无损检测装置及方法”CN104374702A以及“牛肉新鲜度检测装置及其检测方法”CN104374705A中所公开的牛肉新鲜度检测装置以及检测方法可以实现对市场上牛肉制品的新鲜度进行无损检测，但所设计的检测装置对机械组装要求高，设备组成复杂，仍然很难实现对牛肉制品的大批量、实时现场检测。
发明内容
针对现有技术的问题，本发明提供一种仿生贴片传感器及其制备方法和检测方法，本发明结合压变布拉格光栅和光电转换半导体的联用对肉类新鲜度进行检测，解决现有无损检测牛肉新鲜度的机械装置存在设备成本高、无法实时现场检测、无法大批量检测等问题。
所述仿生贴片传感器的制备包括以静电纺丝技术制备的敏感仿生表皮，表皮涂覆的pH敏感材料AG-AN膜(琼脂-玫瑰花青素膜)，可调谐的光纤布拉格光栅的制作与封装，光电转换半导体的制作，以及贴片传感器的构造。由于仿生贴片传感器表面的AG-AN膜可以敏感响应pH变化，可挥发的TVB-N气体所引起的肉类表面pH变化导致AG-AN膜上由红到黄的颜色变化。在仿生贴片传感器的主动调谐过程中，对压电器件施加电压产生的应变可对光纤布拉格光栅中心特征波长进行调控，继而以波长域扫描方式获取特定波段光谱信息。通 过测量中心特征波长信号的变化及偏移获取pH敏感AG-AN膜上的应变信息，再以半导体实现光电转换实时传输检测信号，实现对肉类样品新鲜度的监控。本发明根据这个原理设计出的的仿生贴片传感器已经实现对肉类样品新鲜度的检测，同时具有无损检测、灵敏轻便易使用、制备成本低等优点，可以解决传统无损检测肉类新鲜度时存在的问题。
本发明解决其技术问题所采用的技术方案是：一种仿生贴片传感器，包括敏感仿生表皮、压变光纤布拉格光栅、光纤和光电转换半导体；
所述敏感仿生表皮的表面制备AG-AN膜；所述压变光纤布拉格光栅通过光纤和光电转换半导体的输入端连接，光电转换半导体的输出端与终端设备连接；所述敏感仿生表皮用于与待测样品的表面接触，使光谱信息产生变化，压变光纤布拉格光栅用于采集透过敏感仿生表皮的波长域光信号，并通过光纤传递给光电转换半导体，光电转换半导体用于将波长域光信号转换成电流信号，并传递给终端设备。
上述方案中，所述敏感仿生表皮用于与待测样品的表面接触，待测样品的表面具有可挥发的TVB-N气体，TVB-N气体引起敏感仿生表皮的AG-AN膜表面pH的变化，使得AG-AN膜上产生由红到黄的颜色变化，导致AG-AN膜吸光度比值随之变化。
上述方案中，所述压变光纤布拉格光栅包括光纤布拉格光栅和环状微型压电单元；所述环状微型压电单元同轴套在在光纤布拉格光栅外。
上述方案中，所述光电转换半导体包括透镜耦合装置、光电二极管阵列和制冷器模块；
所述压变光纤布拉格光栅采集到的波长域光信号通过透镜耦合装置进入光电二极管模块阵列，光电二极管阵列与制冷模块经热耦合后连接，光电二极管阵列将处理后的波长域信号输出到终端设备。
进一步的，所述制冷模块包括制冷器、热敏电阻、温度补偿网络、第一大功率运算放大器和第二大功率运算放大器；
所述热敏电阻经温度补偿网络、第一大功率运算放大器和第二大功率运算放大器与制冷器相连，在光电二极管阵列工作时，热敏电阻用于制热，经温度补偿网络调节温度后，再经第一大功率运算放大器和第二大功率运算放大器放大，传输到制冷器，用于调节光电二极管阵列的工作温度。
上述方案中，所述光电二极管阵列包括恒流二极管、差分场效应管、源极电阻和源极电阻、差分光电流信号放大器和信号输出端口；所述源极电阻和源极电阻与正电源相连，恒流二极管与负电源相连，并与差分场效应管连接构成闭合电路；经光电二极管阵列输出的电流信号经过差分场效应管完成电流初级放大，再经差分光电流信号放大器完成次级放大，放大后信号由输出端口输出。
一种根据所述仿生贴片传感器的制作方法，包括以下步骤：
所述敏感仿生表皮的制备：以聚己内酯作为聚合物载体，N,N-二甲基甲酰胺为溶剂，混合搅拌后得到聚己内酯纺丝溶液，通过静电纺丝技术制得薄膜作为敏感仿生表皮，配置AG-AN溶液，在敏感仿生表皮表面制备AG-AN膜；
所述压变光纤布拉格光栅的制作：通过干涉法制备光纤布拉格光栅，通过磁控溅射在光纤布拉格光栅外表面沉积金层，在压电陶瓷片上下表面通过磁控溅射生成金层后切割，所得圆形薄片经激光加工中心孔后形成环状微型压电单元，将环状微型压电单元和光纤布拉格光栅同轴封装；
所述光电转换半导体的制作：所述压变光纤布拉格光栅采集到的波长域光信号通过透镜耦合装置进入光电二极管模块阵列，光电二极管阵列与制冷模块经热耦合后连接，光电二极管阵列将处理后的波长域信号输出到终端设备；通过光电二极管模块阵列作为探测器，光电二极管模块阵列中各光电二极管模块工作于不同频段，获取目标波长域，通过制冷器降低热噪声，使用差分场效应管完成光电流初级放大，使用差分光电流信号放大器完成次级放大，放大后信号由信号输出端口输出，并传递给终端设备。
上述方案中，所述静电纺丝过程中，纺丝速度设为1.5mL/h，电压设置为10-30kV，接收距离设置为10-20cm；
所述AG-AN溶液的制备过程中，AG溶液浓度为15-25g/L，AG-AN溶液中AN含量为75-85mg/L。
一种利用所述仿生贴片传感器的检测方法，包括以下步骤：
建立光电流的T/V周期曲线：建立光电流的T/V周期曲线，得到不同时间下环状微型压电单元对光纤布拉格光栅施加的电压，对应于不同波长域的光谱信息；
建立吸光度-电流比值/TVB-N浓度曲线：所述敏感仿生表皮的AG-AN膜与待测样品直接接触，待测样品可挥发的TVB-N气体引起AG-AN膜表面pH的变化，AG-AN膜上由红到黄的颜色变化，导致膜吸光度比值随之变化，使光电转换半导体输出的电流曲线等值变化，由此建立吸光度-电流比值/TVB-N浓度曲线，用于检测待测样品的新鲜度；
根据建立吸光度电流比值/TVB-N浓度曲线测出待测样品新鲜度：待测样品新鲜程度越差，表面含有的可挥发性气体TVB-N浓度越大，TVB-N与所述敏感仿生表皮的AG-AN膜中的水分结合，导致AG-AN膜的pH改变，引起AG-AN膜上由红到黄的颜色变化，引起膜吸光度比值增大，450-800nm的光谱信息经压变光纤布拉格光栅和光电转换半导体采集并输出，最终得到的电流比值等值变化，由于得到了建立在吸光度-电流比值和TVB-N浓度上的标准曲线，通过测得的吸光度比值，就可测出TVB-N浓度。
上述方案中，所述吸光度-电流比值/TVB-N浓度的标准曲线为：Y＝0.007x+0.825,R 2＝0.99，检测范围为0.03-16.2mg/100g。
与现有技术相比，本发明的有益效果是：本发明通过涂覆在敏感仿生表皮上的AG-AN膜与样品表面可挥发的TVB-N反应，结合光电效应将检测结果输出测得TVB-N浓度，实现了新鲜度检测传感器的便携灵敏式设计，为容易腐败的肉制品的新鲜度在线实时监控提供了可能性。本发明弥补了传统肉制品新鲜度检测器械及传感器检测过程中样品处理复杂、设备维护成本高、检测时间长的缺点，可实现对样品表面TVB-N浓度的原位检测，本发明能够应用到市场上肉制品新鲜度的实时检测。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1：本发明的仿生贴片传感器的构造；
图2：涂覆AG-AN膜的敏感仿生表皮的制备过程；
图3：压变光纤布拉格光栅的制作和封装；
图4：光电转换半导体的电路设置；
图5：光电流的T/V周期曲线；
图6：吸光度电流比值/TVB-N浓度标准曲线；
图7：发明方法检测样本TVB-N浓度与标准方法检测对比图。
图中，1、涂覆AG-AN膜的敏感仿生表皮；2、压变光纤布拉格光栅；3、光纤；4、光电转换半导体；5、掺锗光纤；6、光纤布拉格光栅；7、压电陶瓷片；8、环状微型压电单元；9、透镜耦合装置；10、光电二极管阵列；11、制冷器；12、热敏电阻；13、温度补偿网络；14、第一大功率运算放大器；15、第二大功率运算放大器；16、第一源极电阻；17、第二源极电阻；18、差分场效应管；19、恒流二极管；20、差分光电流信号放大器；21、光电流信号输出端口。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含 义。
实施例1
如图1所示为本发明所述仿生贴片传感器的一种较佳实施方式，所述仿生贴片传感器，包括敏感仿生表皮1、压变光纤布拉格光栅2、光纤3和光电转换半导体4；
所述敏感仿生表皮1的表面制备AG-AN膜；所述压变光纤布拉格光栅2通过光纤3和光电转换半导体4的输入端连接，光电转换半导体4的输出端与终端设备连接；所述敏感仿生表皮1用于与待测样品的表面接触，使光谱信息产生变化，压变光纤布拉格光栅2用于采集透过敏感仿生表皮1的波长域光信号，并通过光纤3传递给光电转换半导体4，光电转换半导体4用于将波长域光信号转换成电流信号，并传递给终端设备。
根据本实施例，优选的，所述敏感仿生表皮1用于与待测样品的表面接触，待测样品的表面具有可挥发的TVB-N气体，TVB-N气体引起敏感仿生表皮1的AG-AN膜表面pH的变化，使得AG-AN膜上由红到黄的颜色变化，导致AG-AN膜吸光度比值随之变化。
根据本实施例，优选的，所述压变光纤布拉格光栅2包括光纤布拉格光栅6和环状微型压电单元8；所述环状微型压电单元8同轴套在在光纤布拉格光栅6外。
根据本实施例优选的，所述光电转换半导体4包括透镜耦合装置9、光电二极管阵列10和制冷器模块；所述压变光纤布拉格光栅2采集到的波长域光信号通过透镜耦合装置9进入光电二极管模块阵列10，光电二极管阵列10与制冷模块经热耦合后连接，光电二极管阵列10将处理后的波长域信号输出到终端设备。
根据本实施例，优选的，所述制冷模块包括制冷器11、热敏电阻12、温度补偿网络13、第一大功率运算放大器14和第二大功率运算放大器15；所述热敏电阻12经温度补偿网络13、第一大功率运算放大器14和第二大功率运算放大器15与制冷器11相连，在光电二极管阵列10工作时，热敏电阻12用于制热，经温度补偿网络13调节温度后，再经第一大功率运算放大器14和第二大功率运算放大器15放大，传输到制冷器11，用于调节光电二极管阵列10的工作温度。
根据本实施例，优选的，所述光电二极管阵列10包括恒流二极管19、差分场效应管18、第一源极电阻16和第二源极电阻17、差分光电流信号放大器20和信号输出端口21；所述第一源极电阻16和第二源极电阻17与正电源相连，恒流二极管19与负电源相连，并与差分场效应管18连接构成闭合电路；经光电二极管阵列10输出的电流信号经过差分场效应管18完成电流初级放大，再经差分光电流信号放大器20完成次级放大，放大后信号由输出端口21输出。
根据本实施例，优选的，所述第一大功率运算放大器14和第二大功率运算放大器15型 号为OPA541AP，美国TI公司；所述差分光电流信号放大器20型号为OPA627AP，美国TI公司。
根据本实施例，优选的，所述差分光电流信号放大器20同步触发信号为光栅调谐信号，因任意时刻窄带光信号波长已知，可以通过波长域扫描还原完整的光谱信息，进而对牛肉样品状态进行分析。
外部白光光源经光纤3入射后，通过涂覆AG-AN膜的敏感仿生表皮1，再经由PDMS封装的压变光纤布拉格光栅2以波长域扫描方式获取敏感响应后的光谱信息，再由光纤3传输至光电转换半导体4，最终将光谱信号实时转换为电流信号并采集输出。
所述仿生贴片传感器是基于内部封装的压变布拉格光栅2及半导体内光电效应设计的一种敏感器件。贴片传感器以静电纺丝柔性固相敏感层作为仿生拉曼敏感表皮，并在表面涂覆一层可以敏感响应TVB-N气体的pH敏感材料琼脂-花青素膜(AG-AN膜)。同时以可调谐光纤布拉格光栅作为视觉神经元基础单位，建立一种可视化仿生皮肤微触检测方法，对市场上肉类中新鲜度指标TVB-N进行快速测定，实现对肉类品质的在线监控。
实施例2
一种制作实施例1所述仿生贴片传感器的方法，包括以下步骤：
如图2所示，涂覆AG-AN膜的敏感仿生表皮1的制备：以聚己内酯作为聚合物载体，N,N-二甲基甲酰胺为溶剂，混合搅拌24h后得到聚己内酯纺丝溶液，通过静电纺丝技术制得柔性固相仿生表皮薄膜。具体的，所述静电纺丝膜的制备过程中，选用20号针头作为静电纺丝出射端子，纺丝速度设为1.5mL/h，电压设置为10-30kV，接收距离设置为10-20cm，所选设置条件确保静电纺丝纤维结构的成功制备，可纺性好。同时，将琼脂(AG)溶解后在98℃下搅拌2h至澄清，得到浓度为15-25g/L的AG溶液。冷却至45℃后在AG溶液中加入玫瑰花青素提取粉末(AN)，并搅拌均匀，此时AG-AN混合溶液中AN含量为75-85mg/L，该浓度配比下制得的敏感层稳定性好，灵敏度高。利用超声仪对混合AG-AN溶液进行超声脱气处理后，将制得的静电纺丝薄膜完全浸入并置于水平台上的塑料培养皿中。冷却至室温后，AG-AN水凝膜形成，制得涂覆AG-AN膜的敏感仿生表皮。
如图3所示，压变光纤布拉格光栅2的制作和封装：首先使用紫外干涉法制备光纤布拉格光栅6。具体的，将掺锗光纤5置于2.5×10 5Pa氢气、-20℃环境增敏72小时。经中心波长λ 0为193nm或244nm的相干紫外光对增敏后光纤进行照射，制得光纤布拉格光栅6；通过磁控溅射在光栅外表面获得100nm金层，置于120℃干燥环境中退火8小时以备用。同时制备环状微型压电单元8，在压电陶瓷片7上下表面通过磁控溅射生成100nm金层。优选的， 所述压电陶瓷片厚度为1mm。然后将其切割成圆形薄片，优选的，所述圆形薄片的直径范围为1-2.5mm，保证光纤可以插入，经激光加工直径150μm中心孔后形成环状微型压电单元8。在压电单元8电极端面涂覆低温铅锡焊料，堆叠5-20层后在220℃环境下焊接成型，并以相同焊接条件对光纤布拉格光栅6进行同轴封装。
如图4所示，外部光电转换半导体4的制作：经由压变光纤布拉格光栅2得到的波长域光信号通过透镜耦合装置9进入作为探测器的雪崩型铟砷化镓光电二极管模块阵列10。阵列中各光电二极管模块工作于不同频段，共同覆盖目标波长域。同时光电二极管阵列10与制冷器11经热耦合后连接，光电二极管阵列10将处理后的波长域信号输出到终端设备。
所述制冷模块包括热敏电阻12、温度补偿网络13、两个相同的第一大功率运算放大器14和第二大功率运算放大器15构成闭合回路。所述热敏电阻12经温度补偿网络13、第一大功率运算放大器14和第二大功率运算放大器15与制冷器11相连，在光电二极管阵列10工作时，热敏电阻12用于制热，经温度补偿网络13调节温度后，再经第一大功率运算放大器14和第二大功率运算放大器15放大，传输到制冷器11，用于调节光电二极管阵列10的工作温度。大功率运算放大器构成桥式电路驱动制冷器11，可降低热噪声，保证光电二极管模块在低温状态下-18℃工作。
所述光电二极管阵列10包括恒流二极管19、差分场效应管18、第一源极电阻16和第二源极电阻17、差分光电流信号放大器20和信号输出端口21。所述第一源极电阻16和第二源极电阻17与正电源相连，恒流二极管19与负电源相连，并与差分场效应管18连接构成闭合电路；经光电二极管阵列10输出的电流信号经过差分场效应管18完成电流初级放大，再经差分光电流信号放大器20完成次级放大，放大后信号由输出端口21输出，最终通过计算机和分布式终端如智能手机、平板电脑等读取、分析和保存。
根据本实施例，优选的，所述光电二极管模块10形成的阵列对不同波长入射光响应可能存在波动，使用可调谐窄带光源、光纤光谱仪对阵列响应在波长域进行校准。
根据本实施例，优选的，所述涂覆AG-AN膜的敏感仿生表皮1在制备过程中使用的AG溶液为20g/L，混合制备的AG-AN溶液中AN含量为80mg/L。
根据本实施例，优选的，所述光纤布拉格光栅经6中心波长λ 0为193nm和244nm的相干紫外光对增敏光纤进行照射后制得。同时，制备微型压电器件8所选用的压电陶瓷片7厚度为1mm。
根据本实施例，优选的，所述作为探测器的雪崩型铟砷化镓光电二极管模块阵列10，阵列中各光电二极管模块工作于不同频段，共同覆盖目标波长域450-800nm。
实施例3
如图5所示，一种利用实施例1所述的仿生贴片传感器的检测方法，根据本实施例优选的，选用牛肉为待测样品，包括以下步骤：
建立光电流的T/V周期曲线：在一个周期内，微型压电器件对光纤布拉格光栅施加的电压随时间增大而增大，随之应变的光纤布拉格光栅可以采集不同波长域集合获取特定波段光谱信息，经光电转换半导体实时转换为电流信号输出。建立光电流的T/V周期曲线，得到不同时间下微型压电器件对光纤布拉格光栅施加的电压，对应于不同波长域的光谱采集；
建立吸光度-电流比值/TVB-N浓度曲线：的仿生贴片传感器敏感面的AG-AN膜直接与待测样品接触。由于可挥发的TVB-N气体所引起AG-AN膜表面pH的变化，AG-AN膜随即产生颜色变化。膜在595nm与540nm(A 595/A 540)处的吸光度比值随之变化，同样地，光电转换半导体输出的电流曲线等值变化。由此建立吸光度-电流比值/TVB-N浓度曲线；
根据建立吸光度电流比值/TVB-N浓度曲线测出待测牛肉样品新鲜度：牛肉样品新鲜程度越差，牛肉表面含有的可挥发性气体TVB-N浓度越大。TVB-N与的仿生贴片传感器敏感面的AG-AN膜中的水分结合，导致AG-AN膜的pH改变，引起AG-AN膜产生由红到黄的颜色变化。这种颜色变化引起膜在595nm与540nm(A 595/A 540)处的吸光度比值增大，450-800nm的光谱信息经压变光纤布拉格光栅和光电转换半导体采集并输出，最终得到的电流比值等值变化。由终端设备进行分析，得到TVB-N浓度：由于得到了建立在吸光度-电流比值和TVB-N浓度上的标准曲线，通过测得的吸光度比值，测出TVB-N浓度。可以看出本发明所述的仿生贴片传感器结构精巧，操作方便，能够很好用于现场检测分析。
根据本实施例，优选的，所述吸光度-电流比值/TVB-N浓度的标准曲线为：Y＝0.007x+0.825,R 2＝0.99。
本发明利用所述的仿生贴片传感器实现牛肉新鲜度的检测，这样一种结合光电转换效应实现快速现场检测的传感器是其他传感器所没有的特点，并且本发明所述的仿生贴片传感器是首次以便携式贴片的结构应用到实际当中。
测量范围：在TVB-N浓度在0.03-16.2mg/100g范围内，吸光度-电流比值与TVB-N浓度之间存在良好的线性关系，定义为Y＝0.007x+0.825，R 2＝0.99。当TVB-N浓度超过16.2mg/100g时，由于pH敏感AG-AN膜响应的饱和，所述的仿生贴片传感器开始失去灵敏度。根据预先确定的TVB-N浓度和传感器的读数，得到校准图，如图6所示。
样品分析：以2020年12月购自江苏省镇江市沃尔玛超市的生鲜牛肉作为实际检测样品，将购回的整块生鲜牛肉的表面切除，从中间部位切取大小尺寸一致(45mm×45mm×20mm)的小块，平行制成42个样，随机分为3组实验组和3组验证组，放入4℃恒温恒湿箱中分别贮藏 7天，每天分别测定实验组和验证组内的6个平行样。验证组中TVB-N含量参考GB 5009.228—2016《食品中挥发性盐基氮的测定》中的半微量定氮法进行测定。本发明所述方法和标准方法对样本测得数据如图7所示，与标准方法相比，本发明所述方法检测结果的相对误差小于3.5％，适用于实际样品的检测。验证了本发明基于压电光纤布拉格光栅和光电转换的仿生贴片传感器对TVB-N浓度具有良好的敏感性，可以实时有效地实现牛肉新鲜度的检测，且具有检测响应快，检测结果准确，操作简单、可测范围广、方便携带等特点，可以实现牛肉新鲜度的现场检测以及应用于微分析等。
应当理解，虽然本说明书是按照各个实施例描述的，但并非每个实施例仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施例的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施例或变更均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种仿生贴片传感器，其特征在于，包括敏感仿生表皮(1)、压变光纤布拉格光栅(2)、光纤(3)和光电转换半导体(4)；
    所述敏感仿生表皮(1)的表面制备AG-AN膜；所述压变光纤布拉格光栅(2)通过光纤(3)和光电转换半导体(4)的输入端连接，光电转换半导体(4)的输出端与终端设备连接；所述敏感仿生表皮(1)用于与待测样品的表面接触，使光谱信息产生变化，压变光纤布拉格光栅(2)用于采集透过敏感仿生表皮(1)的波长域光信号，并通过光纤(3)传递给光电转换半导体(4)，光电转换半导体(4)用于将波长域光信号转换成电流信号，并传递给终端设备。
  2. 根据权利要求1所述的仿生贴片传感器，其特征在于，所述敏感仿生表皮(1)用于与待测样品的表面接触，待测样品的表面具有可挥发的TVB-N气体，TVB-N气体引起敏感仿生表皮(1)的AG-AN膜表面pH的变化，使得AG-AN膜上由红到黄的颜色变化，导致AG-AN膜吸光度比值随之变化。
  3. 根据权利要求1所述的仿生贴片传感器，其特征在于，所述压变光纤布拉格光栅(2)包括光纤布拉格光栅(6)和环状微型压电单元(8)；所述环状微型压电单元(8)同轴套在在光纤布拉格光栅(6)外。
  4. 根据权利要求1所述的仿生贴片传感器，其特征在于，所述光电转换半导体(4)包括透镜耦合装置(9)、光电二极管阵列(10)和制冷器模块；
    所述压变光纤布拉格光栅(2)采集到的波长域光信号通过透镜耦合装置(9)进入光电二极管模块阵列(10)，光电二极管阵列(10)与制冷模块经热耦合后连接，光电二极管阵列(10)将处理后的波长域信号输出到终端设备。
  5. 根据权利要求4所述的仿生贴片传感器，其特征在于，所述制冷模块包括制冷器(11)、热敏电阻(12)、温度补偿网络(13)、第一大功率运算放大器(14)和第二大功率运算放大器(15)；
    所述热敏电阻(12)经温度补偿网络(13)、第一大功率运算放大器(14)和第二大功率运算放大器(15)与制冷器(11)相连，在光电二极管阵列(10)工作时，热敏电阻(12)用于制热，经温度补偿网络(13)调节温度后，再经第一大功率运算放大器(14)和第二大功率运算放大器(15)放大，传输到制冷器(11)，用于调节光电二极管阵列(10)的工作温度。
  6. 根据权利要求1所述的仿生贴片传感器，其特征在于，所述光电二极管阵列(10)包括恒流二极管(19)、差分场效应管(18)、第一源极电阻(16)和第二源极电阻(17)、差分光电流信号放大器(20)和信号输出端口(21)；所述第一源极电阻(16)和第二源极电阻(17) 与正电源相连，恒流二极管(19)与负电源相连，并与差分场效应管(18)连接构成闭合电路；经光电二极管阵列(10)输出的电流信号经过差分场效应管(18)完成电流初级放大，再经差分光电流信号放大器(20)完成次级放大，放大后信号由输出端口(21)输出。
  7. 一种根据权利要求1-6任意一项所述仿生贴片传感器的制作方法，其特征在于，包括以下步骤：
    所述敏感仿生表皮(1)的制备：以聚己内酯作为聚合物载体，N,N-二甲基甲酰胺为溶剂，混合搅拌后得到聚己内酯纺丝溶液，通过静电纺丝技术制得薄膜作为敏感仿生表皮(1)，配置AG-AN溶液，在敏感仿生表皮(1)表面制备AG-AN膜；
    所述压变光纤布拉格光栅(2)的制作：通过干涉法制备光纤布拉格光栅(6)，通过磁控溅射在光纤布拉格光栅(6)外表面沉积金层，在压电陶瓷片(7)上下表面通过磁控溅射生成金层后切割，所得圆形薄片经激光加工中心孔后形成环状微型压电单元(8)，将环状微型压电单元(8)和光纤布拉格光栅(6)同轴封装；
    所述光电转换半导体(4)的制作：所述压变光纤布拉格光栅(2)采集到的波长域光信号通过透镜耦合装置(9)进入光电二极管模块阵列(10)，光电二极管阵列(10)与制冷模块经热耦合后连接，光电二极管阵列(10)将处理后的波长域信号输出到终端设备；通过光电二极管模块阵列(10)作为探测器，光电二极管模块阵列(10)中各光电二极管模块工作于不同频段，获取目标波长域，通过制冷器(11)降低热噪声，使用差分场效应管(18)完成光电流初级放大，使用差分光电流信号放大器(20)完成次级放大，放大后信号由信号输出端口(21)输出，并传递给终端设备。
  8. 根据权利要求7所述的仿生贴片传感器的制作方法，其特征在于，所述静电纺丝过程中，纺丝速度设为1.5mL/h，电压设置为10-30kV，接收距离设置为10-20cm；
    所述AG-AN溶液的制备过程中，AG溶液浓度为15-25g/L，AG-AN溶液中AN含量为75-85mg/L。
  9. 一种利用权利要求1-6任意一项所述仿生贴片传感器的检测方法，其特征在于，包括以下步骤：
    建立光电流的T/V周期曲线：建立光电流的T/V周期曲线，得到不同时间下环状微型压电单元(8)对光纤布拉格光栅(6)施加的电压，对应于不同波长域的光谱信息；
    建立吸光度-电流比值/TVB-N浓度曲线：所述敏感仿生表皮(1)的AG-AN膜与待测样品直接接触，待测样品可挥发的TVB-N气体引起AG-AN膜表面pH的变化，AG-AN膜上由红到黄的颜色变化，导致膜吸光度比值随之变化，使光电转换半导体(4)输出的电流曲线等值变化，由此建立吸光度-电流比值/TVB-N浓度曲线，用于检测待测样品的新鲜度；
    根据建立吸光度电流比值/TVB-N浓度曲线测出待测样品新鲜度：待测样品新鲜程度越差，表面含有的可挥发性气体TVB-N浓度越大，TVB-N与所述敏感仿生表皮(1)的AG-AN膜中的水分结合，导致AG-AN膜的pH改变，引起AG-AN膜上由红到黄的颜色变化，引起膜吸光度比值增大，450-800nm的光谱信息经压变光纤布拉格光栅(2)和光电转换半导体(4)采集并输出，最终得到的电流比值等值变化，由于得到了建立在吸光度-电流比值和TVB-N浓度上的标准曲线，通过测得的吸光度比值，就可测出TVB-N浓度。
  10. 根据权利要求9所述的仿生贴片传感器的检测方法，其特征在于，所述吸光度-电流比值/TVB-N浓度的标准曲线为：Y＝0.007x+0.825,R 2＝0.99，检测范围为0.03-16.2mg/100g。
PCT/CN2021/114200 2021-08-19 2021-08-24 一种仿生贴片传感器及其制备方法和检测方法 Ceased WO2023019606A1 (zh)

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