CN108444991B - Manufacturing method of visual sensor suitable for polymorphic detection object - Google Patents
Manufacturing method of visual sensor suitable for polymorphic detection object Download PDFInfo
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- CN108444991B CN108444991B CN201810131474.8A CN201810131474A CN108444991B CN 108444991 B CN108444991 B CN 108444991B CN 201810131474 A CN201810131474 A CN 201810131474A CN 108444991 B CN108444991 B CN 108444991B
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- 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
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- 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
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- 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
- G01N2021/775—Indicator and selective membrane
Abstract
The invention discloses a method for manufacturing a visual sensor suitable for a polymorphic detection object, and belongs to the field of food and agricultural product detection sensors. The super-hydrophobic material is used as a substrate, and the surface of the super-hydrophobic material is modified by utilizing silane, so that the material has the capability of converting between hydrophilicity and hydrophobicity. The material is used for manufacturing a visual sensor, and the manufactured sensor array is wider in application range and can detect gas objects and liquid objects. The invention firstly manufactures the visual sensor with the hydrophobic and hydrophilic conversion functions. Compared with the existing visual sensor, the manufactured film can convert the hydrophobicity and the hydrophilicity, is suitable for detection objects in different forms, enlarges the application range of the visual sensor, and has popularization effect on the application of the visual sensor. The visual sensor can select the color-sensitive material according to a specific detection object, has high selectivity and short response time, and can be applied to detection of food and agricultural products.
Description
Technical Field
The invention relates to a method for manufacturing a visual sensor suitable for polymorphic detection objects, which is mainly used for manufacturing a visual sensor suitable for detection objects with different morphologies. Belongs to the field of food and agricultural product detection sensors.
Background
The visual sensor is a novel sensor for chip detection, and is characterized in that the difference of a sample is reflected according to the color change before and after the reaction of a sensor array and the sample. The color change of the sensor array is expressed in the form of an image, and the change of the olfactory information or the gustatory information is converted into the color change, so that the sensor array is more visual and vivid. The sensor is portable, low in labor cost and wide in potential application prospect.
In the existing stage, different substrates are required to be selected according to different forms of a detection object during manufacturing of the visual sensor, so that the manufactured sensor is very limited in use and the development of the visual sensor is limited. Generally, in the detection of gas, a silica gel plate, alumina or a hydrophobic film is often selected as a base material for the manufacture of a visual sensor; for liquid detection, a hydrophilic film, filter paper, or the like is selected as a substrate. To date, there is no universal visualization sensor. Through search, relevant patents are as follows: (1) TiO based on pigment sensitization2A method for preparing gas sensor of film is disclosed in patent ZL201210188675.4, which is prepared from TiO2The film being a sensorSubstrate, a sensor array suitable for the detection of gaseous objects is made, not suitable for the detection of liquid objects. (2) An array sensor for detecting heavy metal ions and a preparation method and application thereof are disclosed in patent No. ZL201410379653.5, wherein different indicators are fixed and printed on filter paper to construct a visual array, and the sensor array suitable for detecting heavy metal ion solution is manufactured but not suitable for detecting gas objects. The invention provides a method for manufacturing a visual sensor applicable to both gas-state and liquid-state detection objects. The super-hydrophobic material is adopted, namely the stable contact angle of the surface is more than 150 degrees, the rolling contact angle is less than 10 degrees, and after the surface of the super-hydrophobic material is modified, the material can be converted between hydrophilicity and hydrophobicity, so that the manufactured visual sensor can detect gas objects and liquid objects, and the requirement of multi-property detection objects is met. The method has important reference significance for manufacturing optimization, application range expansion and sensor popularization of the sensor.
Disclosure of Invention
In order to overcome the defects of the manufacturing method of the prior sensor technology, the invention provides a manufacturing method of a visual sensor suitable for a polymorphic detection object. The super-hydrophobic material is used as a substrate, and the surface of the super-hydrophobic material is modified by utilizing silane, so that the material has the capability of converting between hydrophilicity and hydrophobicity. The material is used for manufacturing a visual sensor, and the manufactured sensor array is wider in application range and can detect gas objects and liquid objects.
The technical scheme adopted by the invention for solving the technical problem comprises the following steps:
a method for manufacturing a visual sensor suitable for a polymorphic detection object comprises the following steps:
The bottom plate of the visual sensor needs to satisfy the following three conditions: (1) no reaction with color sensitive material; (2) the extraction of the characteristic value of the visual sensor is not influenced; (3) the property is stable.
The glass has stable property, does not react with the color-sensitive solution in the fixing process, has transparent color, is convenient for extracting the characteristics of the sensor, and is taken as the bottom plate of the visual sensor.
Firstly, a hydrophobic film is prepared, and 0.15mol/L TiCl is prepared by using a saturated sodium chloride aqueous solution3Solution, and erecting the pretreated glass sheet on TiCl3In the solution, the glass sheet is taken out and put in distilled water of 60 ℃ for immersion cleaning after reacting for 2 hours at 160 ℃ in a sealed reaction kettle with a polytetrafluoroethylene lining. A layer of compact titanium dioxide film is observed to be deposited on the glass substrate, and the film is dried at room temperature for standby; and modifying the surface of the titanium dioxide film by using octyl trimethoxy silane, adding 5ml of octyl trimethoxy silane into 95ml of ethanol, uniformly stirring for 30min to completely hydrolyze, putting the prepared film into an ethanol solution of octyl trimethoxy silane for reacting for 36-48 h, taking out, then soaking and washing by using absolute ethanol, and naturally airing at room temperature to enable the prepared film to have hydrophilic and hydrophobic conversion capacity.
Step 3, fixing the color sensitive material
Color sensitive materials such as porphyrin compounds and azo dyes used for food detection are respectively prepared into 2mg/ml solutions by using chloroform and a pH indicator and ethanol. Each color-sensitive solution is fixed on the prepared film by means of spotting or spraying.
Wherein the porphyrin compound specifically comprises tetraphenylporphyrin, ferriporphyrin, cobalt porphyrin and copper porphyrin; the pH indicator specifically comprises methyl orange, methyl red, bromocresol green, and phenol red; azo dyes include, in particular: 1- (2-pyridylazo) -2-naphthol and 4- (2-pyridylazo) -1, 3-benzenediol.
And (4) placing the manufactured visual sensor in a sealed bag, and storing in a dark environment. When the gas object detection device is used for detecting a gas object, the sensor is directly taken out for detection; when the intensity is used for detecting a liquid object, the intensity is 100 mu W/cm2Irradiating for 1h by ultraviolet light to convert the film into hydrophilic property for reuse.
The invention firstly manufactures the visual sensor with the hydrophobic and hydrophilic conversion functions. Compared with the existing visual sensor, the manufactured film can convert the hydrophobicity and the hydrophilicity, is suitable for detection objects in different forms, enlarges the application range of the visual sensor, and has popularization effect on the application of the visual sensor. The visual sensor can select the color-sensitive material according to a specific detection object, has high selectivity and short response time, and can be applied to detection of food and agricultural products.
Drawings
FIG. 1 is a diagram of a sensor array structure: the sensor array comprises a sensor array, a base plate, a hydrophobic and hydrophilic conversion coating and a color sensitive material, wherein 1 is a front view of the sensor array, 2 is a top view of the sensor array, 3 is the base plate, 4 is the hydrophobic and hydrophilic conversion coating, and 5 is the color sensitive material.
Detailed Description
The following describes the present invention in further detail by taking a method for manufacturing a visual sensor for detecting fish safety as an example, with reference to the accompanying drawings.
The invention has universality for the manufacture of the visual sensor. The method for manufacturing the visual sensor for detecting the safety of the fishes is taken as an implementation example, other sensor manufacturing methods refer to the method of the implementation example, corresponding color sensitive materials are screened according to indexes needing to be detected, and the corresponding visual sensor is manufactured, so that the measurement can be carried out.
Firstly, the structure of the visual sensor is briefly described, and the schematic diagram of the visual sensor is shown in fig. 1 and is composed of a bottom plate 3, a hydrophobic and hydrophilic conversion coating 4 and a color-sensitive material 5. Firstly, selecting glass as a bottom plate; then preparing a titanium dioxide super-hydrophobic film, and modifying the surface of the titanium dioxide super-hydrophobic film by utilizing silane to prepare a film capable of converting between hydrophilicity and hydrophobicity; selecting a color sensitive material for food detection, and fixing the color sensitive material on a film to prepare a visual sensor array. The manufactured visual sensor is placed in a dark vacuum environment for storage, and is taken out for use when a gas sample is detected; when the intensity of the sample is 100 muW/cm2Irradiating for 1h under ultraviolet light to generate photoproduction cavities on the surface of the film, wherein the photoproduction cavities and lattice oxygen act on the surface of the titanium dioxide to generate oxygen vacanciesSo as to generate coordination reaction with water molecules to convert the film into hydrophilicity for reuse.
The specific implementation steps are as follows:
(1) screening of color sensitive materials for fish safety detection
Volatile gas changes due to fish putrefaction in the storage process, porphyrin compounds and azo dyes are selected by combining the edible hazard factors of the fish body, and a pH indicator is used as a color sensitive material. The pH indicator detects the change of volatile gas in the fish sample, the azo dye detects heavy metal and fishery medicine in the fish sample, and the porphyrin compound detects toxic biogenic amine in the fish sample. Preparing the screened color sensitive materials into 20mg/ml solutions by using organic solvent ethanol respectively, filling the solutions into brown vials respectively, and storing the vials in a dark environment. Wherein the porphyrin compound specifically comprises tetraphenylporphyrin, ferriporphyrin, cobalt porphyrin and copper porphyrin; the pH indicator specifically comprises methyl orange, methyl red, bromocresol green, and phenol red; azo dyes include, in particular: 1- (2-pyridylazo) -2-naphthol and 4- (2-pyridylazo) -1, 3-benzenediol.
(2) Production of hydrophobic and hydrophilic conversion film
0.15mol/L TiCl is prepared with saturated aqueous sodium chloride solution3Solution of a glass sheet free of impurities on the surface standing on TiCl3In the solution, the glass sheet is taken out and put in distilled water of 60 ℃ for immersion cleaning after reacting for 2 hours at 160 ℃ in a sealed reaction kettle with a polytetrafluoroethylene lining. A dense titanium dioxide film is deposited on the glass substrate. And performing silane modification on the surface of the film, namely adding 5ml of octyl trimethoxy silane into 95ml of ethanol, uniformly stirring for 30min to completely hydrolyze the octyl trimethoxy silane, putting the prepared film into an ethanol solution of the octyl trimethoxy silane for reacting for 36-48 h, taking out the film, then soaking and washing the film with absolute ethanol, and naturally drying the film at room temperature. The membrane with hydrophilic and hydrophobic conversion capability is manufactured.
(3) And (3) manufacturing and packaging the sensor, namely fixing the color sensitive solution on the manufactured film in a spotting way to manufacture a sensor array, and placing the manufactured visual sensor in a sealing bag for storage in a black environment.
(4) And (5) detecting and verifying a fish sample. Firstly, a fish sample is placed in a reaction chamber, and the manufactured visual sensor is used for detecting volatile gas of the fish sample; extracting edible hazard factors of the fish sample, extracting biogenic amine in the fish by using perchloric acid, carrying out microwave digestion on the fish to extract heavy metals in the fish, and extracting the fish medicine in the fish by using a methanol-water (2:8) mixed solution; irradiating the visual sensor for 1h by using ultraviolet light with the intensity of 100 muW/cm 2, converting the film into hydrophilicity, and detecting the extracted solution; meanwhile, referring to a detection method of toxic biogenic amine in SNT 2209-; a quantitative prediction model is established by using partial least squares and a support vector machine and the color characteristic value of each color sensitive point of the sensor and the measured value of a chemical method, and the established model is perfected by adopting a large number of samples, so that the correct determination of the fish safety index is realized.
Claims (1)
1. A method for manufacturing a visual sensor suitable for a polymorphic detection object is characterized by comprising the following steps:
(1) screening of color sensitive materials for fish safety detection
Volatile gas changes due to the putrefaction of fishes in the storage process, porphyrin compounds and azo dyes are selected by combining the edible hazard factors of the fishes, and a pH indicator is used as a color sensitive material; wherein the pH indicator detects the change of volatile gas in the fish sample, the azo dye detects heavy metal and fishery medicine in the fish sample, and the porphyrin compound detects toxic biogenic amine in the fish sample; preparing the screened color sensitive materials into 20mg/ml solutions by using organic solvent ethanol respectively, placing the solutions into brown vials respectively, and storing the vials in a dark environment; wherein the porphyrin compound specifically comprises tetraphenylporphyrin, ferriporphyrin, cobalt porphyrin and copper porphyrin; the pH indicator specifically comprises methyl orange, methyl red, bromocresol green, and phenol red; azo dyes include, in particular: 1- (2-pyridylazo) -2-naphthol and 4- (2-pyridylazo) -1, 3-benzenediol;
(2) production of hydrophobic and hydrophilic conversion film
0.15mol/L TiCl is prepared with saturated aqueous sodium chloride solution3Solution of a glass sheet free of impurities on the surface standing on TiCl3In the solution, after reacting for 2 hours at 160 ℃ in a sealed reaction kettle with a polytetrafluoroethylene lining, taking out a glass sheet and putting the glass sheet into distilled water at 60 ℃ for immersion cleaning; a layer of compact titanium dioxide film is deposited on the glass substrate; performing silane modification on the surface of the film, firstly adding 5ml of octyl trimethoxy silane into 95ml of ethanol, uniformly stirring for 30min to completely hydrolyze the octyl trimethoxy silane, putting the prepared film into an ethanol solution of the octyl trimethoxy silane for reacting for 36-48 h, taking out the film, then soaking and washing the film with absolute ethanol, and naturally drying the film at room temperature; manufacturing a film with hydrophilic and hydrophobic conversion capability;
(3) manufacturing and packaging the sensor, namely fixing the color sensitive solution on the manufactured film in a spotting way to manufacture a sensor array, and placing the manufactured visual sensor in a sealing bag for storage in a black environment;
(4) detecting and verifying a fish sample; firstly, a fish sample is placed in a reaction chamber, and the manufactured visual sensor is used for detecting volatile gas of the fish sample; extracting edible hazard factors of the fish sample, extracting biogenic amine in the fish by using perchloric acid, carrying out microwave digestion on the fish to extract heavy metals in the fish, and extracting the fish medicine in the fish by using a mixed solution of methanol and water in a ratio of 2: 8; the intensity of the visual sensor is 100 mu W/cm2Irradiating for 1h by ultraviolet light, converting the film into hydrophilicity, and detecting the extracted solution; meanwhile, the method for detecting toxic biogenic amine in import and export aquatic products of SNT 2209-And the high performance liquid chromatography for detecting the fluoroquinolone drug residue in the animal food published by No. 1025 of agricultural department-14-2008, measuring the contents of biogenic amine, heavy metal and fishery drug in the fish meat, taking the measured value as an actual measurement value, taking the mackerel stored on the ninth day as an example, the content of biogenic amine is about 282mg/kg, the content of fishery drug is between 0 and 10 mug/kg, and the content of heavy metal is between 10 and 50 mug/kg; a quantitative prediction model is established by using partial least squares and a support vector machine and the color characteristic value of each color sensitive point of the sensor and the measured value of a chemical method, and the established model is perfected by adopting a large number of samples, so that the correct determination of the fish safety index is realized.
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