CN113155814A - Portable colorimetric array image acquisition device based on optical fiber array and detection method - Google Patents

Portable colorimetric array image acquisition device based on optical fiber array and detection method Download PDF

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CN113155814A
CN113155814A CN202110169726.8A CN202110169726A CN113155814A CN 113155814 A CN113155814 A CN 113155814A CN 202110169726 A CN202110169726 A CN 202110169726A CN 113155814 A CN113155814 A CN 113155814A
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optical fiber
detected
array
colorimetric
darkroom
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潘宇祥
王镝
钱利滨
崔瑶轩
郑绪彬
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Zhejiang Lab
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems 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
    • G01N21/78Systems 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/251Colorimeters; Construction thereof
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/255Details, e.g. use of specially adapted sources, lighting or optical systems

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Abstract

The invention discloses a portable colorimetric array image acquisition device based on an optical fiber array and a detection method, wherein the device comprises: light source, light homogenizing sheet, darkroom, perforated plate, integrated optical fiber fixing table, polymer optical fiber, lens hood, smart phone, etc. The method comprises the steps of reacting a colorimetric array with a substance solution to be detected; acquiring a colorimetric array image through a smart phone, and generating a color fingerprint of a substance to be detected according to an RGB value; preparing different types of solutions of the objects to be detected, adding the solutions into the colorimetric array, generating respective color fingerprints, calculating Euclidean distances, and classifying the different objects to be detected; preparing solutions of the object to be detected with different concentrations, generating color fingerprints, calculating Euclidean distances, fitting out an optimal calibration curve of the object to be detected, substituting the Euclidean distances of the samples to be detected into the calibration curve, and calculating the concentration of the solution of the object to be detected. The invention realizes the rapid analysis, the material classification and the quantitative detection of the materials of the contrast color array, and has the advantages of simple operation, low cost, capability of meeting the requirement of rapid detection on site and the like.

Description

Portable colorimetric array image acquisition device based on optical fiber array and detection method
Technical Field
The invention relates to a portable colorimetric array image acquisition device and a detection method based on an optical fiber array, in particular to a device and a method for detecting water environment pollutants based on image analysis.
Background
The method has very important practical significance for the protection of the water environment and the detection of pollution. For water environment pollution detection, the current standard method depends on precise laboratory equipment analysis, and the instruments have large volume and high price and need special personnel to operate; existing on-site rapid detection methods rely on colorimetric reactions, where the colorimetric detection devices have low integration and functional integrity. In recent years, as the camera performance and hardware computing capability of smart phones are continuously improved, more and more research teams are dedicated to developing portable colorimetric analysis devices based on smart phones, so as to realize high-precision detection of samples in a laboratory on site. The portable colorimetric analysis device developed at present usually adopts a smart phone camera to directly shoot the porous plate, and due to the limitation of the focusing distance of a lens, the size of the optical structure is large, the portability of a prototype can be influenced, and the requirement of field detection cannot be perfectly met. Therefore, in the field of water environment pollution detection with special requirements on operation, cost and portability, a portable colorimetric array detection device and method with simple operation and low cost are urgently needed.
Disclosure of Invention
The invention aims to provide a portable colorimetric array image acquisition device and a detection method based on an optical fiber array aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a portable colorimetric array image capture device based on fiber optic arrays, the device comprising: the device comprises a current adjustable power adapter, a white light LED (light emitting diode) plane light source, a plane light source support, a light homogenizing sheet support, a darkroom, a perforated plate, an integrated optical fiber fixing table (divided into an objective table and an optical fiber beam converging end), polymer optical fibers, micropores, optical fiber end face protective glass, a light shield, a rectangular window, a smart phone and a smart phone clamping groove; the white light LED planar light source is buckled on a planar light source bracket and is fixed at the top end of the darkroom through screws, and a power line of the white light LED planar light source is connected with a current-adjustable power adapter outside the darkroom through an opening on the back surface of the darkroom; the light homogenizing sheet is fixed on the light homogenizing sheet bracket through universal glue; the porous plate is fixed on an object stage of the integrated optical fiber fixing table; 96 polymer optical fibers are fixed on the integrated optical fiber fixing table through universal glue, one end of each polymer optical fiber is connected to a micropore on the objective table to transmit a colorimetric array image of the porous plate, and the other end of each polymer optical fiber is fixed on a converging end of the optical fiber bundle to form a neat 96-channel optical fiber end face; the optical fiber end face protective glass is respectively fixed on two end faces of 96 polymer optical fibers through ultraviolet glue; the light shield is fixed on the outer side of the end face of the 96-channel optical fiber through universal glue; the integrated optical fiber fixing table is fixed at the bottom of the darkroom through screws; a clamping groove is formed in the top end of the darkroom, and the smart phone can be fixed to the outer side of the top end of the darkroom through the clamping groove; the top end of the darkroom is provided with a rectangular window of 24mm by 12mm, the window corresponds to the end face of the 96-channel optical fiber in the darkroom, and the camera of the smart phone shoots the end face of the 96-channel optical fiber through the window to realize image acquisition of the contrast color array.
A colorimetric array detection method based on image analysis using the above device, the method comprising the steps of:
(1) colorimetric array test experiments: and preparing colorimetric reaction reagents with different components, and sequentially adding the colorimetric reaction reagents into the multi-pore plate to form a colorimetric array. Adding a sample to be detected into a colorimetric array reaction hole, uniformly shaking to ensure complete reaction, placing a porous plate on an integrated optical fiber fixing table, irradiating by a white light LED (light-emitting diode) plane light source, allowing transmitted light to enter a polymer optical fiber through a micropore on the optical fiber fixing table, and transmitting the color change of the colorimetric array to the end face of a 96-channel optical fiber at the other end by the optical fiber;
(2) and (3) colorimetric array image processing: the smartphone placed at the top end of the darkroom shoots the end face of the 96-channel optical fiber in the darkroom through the rectangular window, and the collected image is processed. The processing process of the image comprises the following substeps:
(2.1) performing edge cutting on the original image, and segmenting a region where the colorimetric array is located, wherein the pixels of the region are 290-430 pixel points;
(2.2) extracting RGB values of 10 pixel points near the corresponding optical fiber center point in the area pixel according to the distribution of the optical fiber array, and respectively extracting R, G, B components of three color channels;
(2.3) carrying out mean value processing on the RGB components of 10 pixel points near the central point of the optical fiber extracted in the step (2.2); regenerating a 96-channel digital image according to the average pixel value, wherein the image is the color fingerprint of the current colorimetric array;
(3) distinguishing different types of substances to be detected: preparing different types of solutions to be detected, sequentially adding the solutions to be detected into a porous plate, repeating the step (2) to obtain color fingerprints of different substances, calculating to obtain Euclidean distances between different substances to be detected, and obtaining a tree classification chart between different substances to be detected through a hierarchical clustering analysis algorithm to realize the differentiation of different substances to be detected;
(4) determining the concentration of the substance to be tested:
(4.1) preparing solutions of substances to be detected with different concentrations, sequentially adding the solutions into a porous plate, repeating the step (2) to obtain color fingerprints of the solutions to be detected with different concentrations, calculating Euclidean distances of the substances to be detected with different concentrations, and fitting an optimal calibration curve of the solution to be detected by a least square method fitting curve algorithm;
and (4.2) adding the solution of the substance to be detected with unknown concentration into the multi-hole plate, repeating the step (2) to obtain the color fingerprint, calculating to obtain the Euclidean distance, and calculating the concentration of the solution of the unknown substance to be detected according to the determined optimal calibration curve of the solution of the substance to be detected in the step (4.1).
The invention has the beneficial effects that: the invention provides a portable colorimetric array image acquisition device based on an optical fiber array and a detection method based on image analysis, which can realize detection and analysis of a water environment pollutant colorimetric array reaction and can be expanded to be used for detection of other chemical substances based on the colorimetric reaction. Compared with the existing standard detecting instrument, namely a spectrophotometer and a liquid mass spectrometer, the portable spectrometer has the advantages of low cost, simplicity and convenience in operation, strong portability and the like. According to the advantages, the device and the method can be used for rapidly detecting and analyzing industrial wastewater, pesticides, heavy metals, petroleum and other common water environment pollutants on site.
Drawings
FIG. 1 is a block diagram of an embodiment of the present invention, illustrating an overall structure of a portable colorimetric array image capturing device based on an optical fiber array;
FIG. 2 is a block diagram of an integrated optical fiber fixing stage according to an embodiment of the present invention;
FIG. 3 is a graph of a substance color fingerprint determined by an embodiment of the present invention;
FIG. 4 is a graph of the results of substance classification determined by an embodiment of the present invention;
FIG. 5 is a graph showing the results of an optimal calibration curve for detecting heavy metals as determined by an embodiment of the present invention;
in the figure, a current adjustable power adapter 1, a light source lead 2, a white light LED planar light source 3, a planar light source support 4, a light homogenizing sheet 5, a light homogenizing sheet support 6, a darkroom 7, a perforated plate 8, an integrated optical fiber fixing table 9, an objective table 10, an optical fiber beam converging end 11, a polymer optical fiber 12, a micropore 13, optical fiber end face protective glass 14, a light shield 15, a rectangular window 16, a smart phone 17 and a smart phone clamping groove 18.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments, but without limiting the invention.
As shown in fig. 1 and 2, an embodiment of the present invention provides a portable colorimetric array image capture device based on an optical fiber array, including: the device comprises a current-adjustable power adapter 1, a light source lead 2, a white light LED planar light source 3, a planar light source support 4, a light homogenizing sheet 5, a light homogenizing sheet support 6, a darkroom 7, a perforated plate 8, an integrated optical fiber fixing table 9 (divided into an objective table 10 and an optical fiber beam converging end 11), a polymer optical fiber 12, micropores 13, optical fiber end face protective glass 14, a light shield 15, a rectangular window 16, a smart phone 17 and a smart phone clamping groove 18; the white light LED planar light source 3 is fixed on the planar light source support 4 through glue and then fixed at the top end of the darkroom 7 through screws, and the light source lead 2 is connected with the current-adjustable power adapter 1 outside the darkroom through an opening at the back of the darkroom; the light homogenizing sheet 5 is fixed on the light homogenizing sheet bracket 6 through glue; the porous plate 8 is fixed on an object stage 10 of the integrated optical fiber fixing table 9; 96 polymer optical fibers 12 are fixed on the integrated optical fiber fixing table 9 through glue, one end of each polymer optical fiber is connected to a micropore 13 on the objective table 10 to transmit a colorimetric array image of the porous plate 8, and the other end of each polymer optical fiber is fixed at the fiber bundle converging end 11 to form a neat 96-channel optical fiber end face table; the optical fiber end face protection glass 14 is respectively fixed on two end faces of the 96 polymer optical fibers 12 through ultraviolet glue; the light shield 15 is fixed on the outer side of the fiber bundle convergence end 11 through glue; the integrated optical fiber fixing table 9 is fixed at the bottom of the darkroom 7 through screws; a smart phone clamping groove 18 is formed in the top end of the darkroom 7, and a smart phone 17 can be fixed to the outer side of the top end of the darkroom through the clamping groove; a rectangular window 16 with the length of 24mm multiplied by 12mm is formed in the top end of the darkroom and corresponds to the optical fiber bundle converging end 11 in the darkroom, and a camera of the smart phone shoots the end face of the 96-channel optical fiber through the rectangular window 16 to achieve image acquisition of the contrast color array.
The embodiment of the invention also provides an image analysis method for detecting heavy metal ions by using the device, which comprises the following steps:
(1) colorimetric array test: different types of pH indicators, redox indicators, solvent-induced denaturation indicators and gold nanoparticles are sequentially added into the porous plate 8 to form a colorimetric array. Adding a heavy metal solution sample to be detected into the colorimetric array, shaking uniformly to enable the reaction to be complete, placing a porous plate 8 on an integrated optical fiber fixing table 9, irradiating by a white light LED plane light source 3, enabling transmitted light to enter a polymer optical fiber 12 through a micropore 13 on the optical fiber fixing table, and transmitting the color change of the colorimetric array to an optical fiber beam convergence end 11 at the other end by the optical fiber;
(2) and (3) colorimetric array image processing: the smartphone 17 placed at the top end of the darkroom 7 shoots the 96-channel optical fiber end face in the darkroom 7 through the rectangular window 16, and processes the collected image. The processing process of the image comprises the following substeps:
(2.1) performing edge cutting on the original image, and segmenting a region where the colorimetric array is located, wherein the pixels of the region are 290-430 pixel points;
(2.2) extracting RGB values of 10 pixel points near the corresponding optical fiber center point in pixels of the colorimetric array region according to the distribution of the optical fiber array, and respectively extracting R, G, B components of three color channels;
(2.3) carrying out mean value processing on the RGB components of 10 pixel points near the central point of the optical fiber extracted in the step (2.2); regenerating a digital image according to the average pixel value, wherein the image is the color fingerprint of the current heavy metal ions;
(3) distinguishing different heavy metal ions: preparing different types of solutions to be detected, sequentially adding the solutions to be detected into the porous plates 8, repeating the step (2) to obtain color fingerprints of different types of heavy metal ions, calculating Euclidean distances between different types of heavy metal ions, and obtaining a tree classification diagram among different types of heavy metal ions through a hierarchical clustering analysis algorithm to realize the differentiation among different types of heavy metal ions;
(4) determining the concentration of the heavy metal ions to be detected:
(4.1) preparing heavy metal ion solutions with different concentrations, sequentially adding the solutions into a porous plate, repeating the step (2) to obtain color fingerprints of the heavy metal ions with different concentrations, calculating Euclidean distances of the heavy metal ions with different concentrations, and fitting an optimal calibration curve of the heavy metal ions to be detected by a least square method fitting curve algorithm;
and (4.2) adding the heavy metal ion solution with unknown concentration into the porous plate, repeating the step (2) to obtain a color fingerprint, calculating to obtain a Euclidean distance, and calculating the concentration of the unknown heavy metal ions through the optimal calibration curve of the heavy metal ion solution determined in the step (4.1).
Fig. 3 is a color fingerprint diagram of heavy metal ions determined by the embodiment of the present invention, and it can be seen from the diagram that the color fingerprints of different types of heavy metal ions have detailed differences. FIG. 4 is a tree classification diagram for distinguishing different types of heavy metal ions according to the embodiment of the present invention, and it can be seen from the diagram that the method of the present invention can effectively distinguish different types of heavy metal ions. Fig. 5 is a graph showing the results of the lead ion optimum calibration curve determined in the example of the present invention. It can be seen from the figure that the optimum calibration curve obtained by the method of the present invention has the formula of-0.06829X +0.7774, where Y is the euclidean distance and X is the lead ion concentration. Experimental results prove that the method can accurately detect the concentration of the heavy metal ions to be detected.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. A portable colorimetric array image capture device based on fiber array, the device comprising: the device comprises a current adjustable power adapter, a white light LED (light emitting diode) plane light source, a plane light source support, a light homogenizing sheet support, a darkroom, a perforated plate, an integrated optical fiber fixing table, polymer optical fibers, optical fiber end face protective glass, a light shield, a rectangular window and a smart phone;
the white light LED planar light source is buckled on the planar light source bracket and is fixed at the top end of the darkroom, and a power line of the white light LED planar light source is connected with a current-adjustable power adapter outside the darkroom through an opening on the back surface of the darkroom; the light homogenizing sheet is fixed on the light homogenizing sheet bracket;
the integrated optical fiber fixing table is fixed at the bottom of a darkroom and is divided into an object stage and an optical fiber bundle converging end; the porous plate is fixed on an object stage of the integrated optical fiber fixing table; one end of each 96 polymer optical fiber is connected to the micro-hole on the objective table to transmit the colorimetric array image of the porous plate, and the other end of each polymer optical fiber is fixed on the converging end of the optical fiber bundle to form a regular 96-channel optical fiber end face; the optical fiber end face protective glass is respectively fixed on two end faces of 96 polymer optical fibers; the light shield is fixed on the outer side of the end face of the 96-channel optical fiber;
the top end of the darkroom is provided with a clamping groove, and the smart phone can be fixed on the outer side of the top end of the darkroom through the clamping groove; a rectangular window is formed in the top end of the darkroom and corresponds to the 96-channel optical fiber end face in the darkroom, and the smartphone camera shoots the 96-channel optical fiber end face through the window to achieve image acquisition of a contrast color array.
2. A colorimetric array detection method based on image analysis using the device of claim 1, comprising the steps of:
(1) colorimetric array test experiments: preparing colorimetric reaction reagents with different components, and sequentially adding the colorimetric reaction reagents into a multi-pore plate to form a colorimetric array; adding a sample to be detected into a colorimetric array reaction hole, uniformly shaking to ensure complete reaction, placing a porous plate on an integrated optical fiber fixing table, irradiating by a white light LED plane light source, allowing transmitted light to enter a polymer optical fiber through a micropore on the optical fiber fixing table, and transmitting the color change of the colorimetric array to the end face of a 96-channel optical fiber at the other end by the optical fiber;
(2) and (3) colorimetric array image processing: the intelligent mobile phone placed at the top end of the darkroom shoots the end face of a 96-channel optical fiber in the darkroom through a rectangular window, and the collected image is processed, wherein the image processing process comprises the following substeps:
(2.1) cutting the edge of the original image to segment the area where the colorimetric array is located;
(2.2) extracting RGB values of 10 pixel points near the corresponding optical fiber center point in the area pixel according to the distribution of the optical fiber array, and respectively extracting R, G, B components of three color channels;
(2.3) carrying out mean value processing on the RGB components of 10 pixel points near the central point of the optical fiber extracted in the step (2.2); regenerating a digital image according to the average pixel value, wherein the image is the color fingerprint of the current colorimetric array;
(3) distinguishing different types of substances to be detected: preparing different types of solutions to be detected, sequentially adding the solutions to be detected into a porous plate, repeating the step (2) to obtain color fingerprints of different substances, calculating to obtain Euclidean distances between different substances to be detected, and obtaining a tree classification chart between the different substances to be detected through a hierarchical clustering analysis algorithm to realize the differentiation of the different substances to be detected;
(4) determining the concentration of the substance to be tested:
(4.1) preparing solutions of substances to be detected with different concentrations, sequentially adding the solutions into a porous plate, repeating the step (2) to obtain color fingerprints of the solutions to be detected with different concentrations, calculating Euclidean distances of the substances to be detected with different concentrations, and fitting an optimal calibration curve of the solution to be detected by a least square method fitting curve algorithm;
and (4.2) adding the solution of the substance to be detected with unknown concentration into the multi-hole plate, repeating the step (2) to obtain the color fingerprint, calculating to obtain the Euclidean distance, and calculating the concentration of the solution of the unknown substance to be detected according to the optimal calibration curve of the solution of the substance to be detected determined by the step (4.1).
3. The colorimetric array detection method of claim 2 wherein the colorimetric reaction reagents comprise pH indicators, redox indicators, solvent-induced denaturation indicators, and gold nanoparticles.
4. The colorimetric array detection method according to claim 2, wherein the method is applied to the field rapid detection and analysis of industrial wastewater, pesticides, heavy metals, petroleum and other common water environment pollutants.
CN202110169726.8A 2021-02-07 2021-02-07 Portable colorimetric array image acquisition device based on optical fiber array and detection method Pending CN113155814A (en)

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CN114088706A (en) * 2021-10-28 2022-02-25 中央民族大学 Biochemical detection image acquisition system and image acquisition method
CN116051557A (en) * 2023-03-31 2023-05-02 至美时代生物智能科技(北京)有限公司 Image matching-based micro-fluidic chip reaction hole image recognition method and system
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