CN116242821A - Preparation method of colorimetric chip for detecting food spoilage marker gas - Google Patents

Preparation method of colorimetric chip for detecting food spoilage marker gas Download PDF

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CN116242821A
CN116242821A CN202310220204.5A CN202310220204A CN116242821A CN 116242821 A CN116242821 A CN 116242821A CN 202310220204 A CN202310220204 A CN 202310220204A CN 116242821 A CN116242821 A CN 116242821A
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chip
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food spoilage
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王铁
刘祥
李晓
刘加兴
包得字
李秀君
王鹏
李�荣
吴志龙
秦鹏飞
高意
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Tianjin University of Technology
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Abstract

The invention relates to the technical field of gas detection, and provides a preparation method of a colorimetric chip for detecting food spoilage marker gas, which comprises the steps of self-assembling polystyrene nanospheres, taking polystyrene nanospheres with uniform sizes, and obtaining a three-dimensional ordered polystyrene nanosphere integral template in a centrifugal self-assembling mode; the colorimetric chip has good stability, and the hierarchical porous structure of the colorimetric chip is beneficial to gas mass transfer, so that the colorimetric chip has lower detection limit. The detection chip does not need to be in direct contact with food in the sealed bag in the use process, but generates a signal through reaction with hydrogen sulfide generated by food spoilage, so that the detection chip has the advantages of non-contact and no damage, and the generated color signal is easy to identify.

Description

Preparation method of colorimetric chip for detecting food spoilage marker gas
Technical Field
The invention relates to the technical field of gas detection, in particular to a preparation method of a colorimetric chip for detecting food spoilage marker gas.
Background
The food safety problem is closely related to human health, and food is easily corroded by factors such as microorganisms, enzymes, temperature and the like in the transportation, storage and sales processes, so that the freshness of the food is reduced, and even substances which are toxic and harmful to human bodies are generated, so that the food safety problem has very important significance in detecting the freshness of the food. For the present time, evaluation of the degree of food spoilage or freshness is mainly dependent on organoleptic, physical, chemical assays. The sensory evaluation method has the advantages of being direct, simple, quick and the like, but is easily influenced by human subjective factors; the physical and chemical measurement methods have more reliable results, but require special experimental equipment and instruments, have complicated operation and high cost, and require special operators; therefore, it is necessary to provide a simple, portable and real-time method for food quality safety monitoring, which has important significance for normalizing food market order, maintaining food safety and protecting human health.
Hydrogen sulfide is a volatile gas produced by bacteria decomposing sulfur-containing amino acids (methionine and cysteine) during the spoilage process of foods, and thus, hydrogen sulfide can be used as a food spoilage marker gas. Although gas components can be precisely identified such as gas chromatography, gas chromatography-mass spectrometry, and selective ion flow tube mass spectrometry, they are difficult to lightweight applications and facilitate detection due to their high operating cost and slow processing rate, and in addition, semiconductor-based chemiresistors have been partially applied, but are difficult to apply in the field of food spoilage detection due to their poor chemiresistor selectivity and high operating temperature. Colorimetric sensors have attracted considerable attention because of their advantages of easy preparation, convenient use, visual observation, and the like. At present, reported lead acetate-based colorimetric sensors often have higher detection limits and lower sensitivity, and are difficult to meet food spoilage detection.
Disclosure of Invention
The invention provides a preparation method of a colorimetric chip for detecting food spoilage marker gas, aiming at solving the problems that the lead acetate-based colorimetric sensor in the prior art has higher detection limit but lower sensitivity and is difficult to meet the food spoilage detection.
In one aspect, the invention provides a method for preparing a colorimetric chip for detecting food spoilage marker gases, comprising the steps of,
s1, self-assembling polystyrene nanospheres, namely taking polystyrene nanospheres with uniform sizes, and obtaining a three-dimensional ordered polystyrene nanosphere integral template in a centrifugal self-assembly mode;
s2, filling precursor lead acetate, soaking the dried polystyrene nanosphere integral template in a lead acetate aqueous solution, and keeping the lead acetate molecules in ordered holes of the polystyrene nanosphere integral template for enough time;
s3, growing Pb-MOFs in situ, taking out the template filled with lead acetate molecules prepared in the step S2, soaking the template in an ethanol solution of 1,3, 5-trimesic acid, and enabling the Pb-MOFs to grow in situ in a template gap to obtain micropores and mesopores;
s4, preparing OM-Pb-MOFs, namely centrifuging the ethanol solution in which the 1,3, 5-trimesic acid with the template is soaked in the step S3, centrifuging at a rotating speed and for a time, removing supernatant, adding tetrahydrofuran, and repeating the step S4 for three times to completely remove the polystyrene integral template, so as to obtain an ordered macroporous structure, and obtaining the OM-Pb-MOFs;
s5, removing unreacted precursors, and sequentially washing the OM-Pb-MOFs obtained in the step S4 with ethanol and pure water for three times respectively to remove the unreacted precursors;
s6, preparing a colorimetric detection chip, dispersing the washed OM-Pb-MOFs in water, and dripping the water with the dispersed OM-Pb-MOFs on filter paper to serve as the colorimetric chip for detecting hydrogen sulfide gas molecules.
Further, the polystyrene nanospheres described in step S1 have a size of 200nm, 400nm, 600nm or 1000nm.
Further, the rotational speed of the centrifugal self-assembly in the step S1 is 3000r/min, and the centrifugal time is 8h.
Further, the drying mode in the step S2 is room temperature drying.
Further, the concentration of the lead acetate aqueous solution in the step S2 is 0.09M, and the soaking time is 24 hours.
Further, the concentration of the ethanol solution of the 1,3, 5-trimesic acid in the step S3 is 0.01M, and the soaking time is 8 hours.
Further, the rotational speed of the centrifugation in the step S4 is 8000r/min, and the time is 5min.
In another aspect, a colorimetric chip for detecting a food spoilage marker gas is provided, comprising a carrier and OM-Pb-MOFs attached to the carrier, wherein the carrier is a porous adsorption material.
Further, the OM-Pb-MOFs are hierarchical porous structures including micropores, mesopores and macropores.
Further, the micropore quantity is larger than the mesopore quantity, and the macropore quantity is larger than the mesopore quantity.
The invention has the advantages that:
the colorimetric chip has good stability, and in addition, the hierarchical porous structure of the detection chip is beneficial to gas mass transfer, so that the colorimetric chip has a lower detection limit. The detection chip does not need to be in direct contact with food in the sealed bag in the use process, but generates a signal through reaction with hydrogen sulfide generated by food spoilage, so that the detection chip has the advantages of non-contact and no damage, and the generated color signal is easy to identify.
Drawings
FIG. 1 is a schematic diagram of a colorimetric chip preparation flow for detecting a food spoilage marker gas according to the present invention;
FIG. 2 is a chart showing the distribution of OM-Pb-MOFs nitrogen adsorption and desorption-BET pore diameters in accordance with the present invention.
Detailed Description
The following description will explain the embodiments of the invention in conjunction with the embodiments of the invention. Unless otherwise indicated, the technical means used in the following examples and experimental examples are conventional means well known to those skilled in the art, and the materials, reagents and the like used are all commercially available.
Pb-MOFs are lead-based metal-organic framework materials.
A method for preparing a colorimetric chip for detecting food spoilage marker gas comprises the following steps,
s1, self-assembling polystyrene nanospheres, namely taking polystyrene nanospheres with uniform sizes, and obtaining a three-dimensional ordered polystyrene nanosphere integral template in a centrifugal self-assembly mode; the diameter of the polystyrene nanosphere is 200nm, 400nm, 600nm or 1000nm, the rotation speed of centrifugal self-assembly is 3000r/min, and the centrifugal time is 8h.
S2, filling precursor lead acetate, soaking the polystyrene nanosphere integral template dried at room temperature in a lead acetate aqueous solution, and keeping the lead acetate molecules in ordered holes of the polystyrene nanosphere integral template for a sufficient time; the concentration of the lead acetate aqueous solution is 0.09M, and the soaking time is 24 hours.
S3, growing Pb-MOFs in situ, taking out the template filled with lead acetate molecules prepared in the step S2, soaking the template in an ethanol solution of 1,3, 5-trimesic acid, and enabling the Pb-MOFs to grow in situ in gaps to obtain micropores and mesopores; the concentration of the ethanol solution of the 1,3, 5-trimesic acid is 0.01M, and the soaking time is 8h.
S4, preparing OM-Pb-MOFs, namely centrifuging the ethanol solution in which the 1,3, 5-trimesic acid with the template is soaked in the step S3, centrifuging at a rotating speed and for a time, removing supernatant, adding tetrahydrofuran, and repeating the step S4 for three times to completely remove the polystyrene integral template, so as to obtain an ordered macroporous structure, and obtaining the OM-Pb-MOFs; the rotational speed of the centrifugation is 8000r/min and the time is 5min.
S5, removing unreacted precursors, and washing the OM-Pb-MOFs obtained in the step S4 with pure water and ethanol for three times respectively to remove the unreacted precursors;
s6, preparing a colorimetric detection chip, dispersing the washed OM-Pb-MOFs in water, and dripping the water with the dispersed OM-Pb-MOFs on filter paper to serve as the colorimetric chip for detecting hydrogen sulfide gas molecules.
OM-Pb-MOFs are ordered hierarchical pore lead-based metal-organic framework materials.
Example 1
The colorimetric chip for detecting the food spoilage marker gas comprises a carrier and OM-Pb-MOFs, wherein the OM-Pb-MOFs are attached to the carrier, and the carrier is made of porous adsorption material, and filter paper is specifically selected.
The OM-Pb-MOFs are hierarchical porous structures, the hierarchical porous structures comprise micropores, mesopores and macropores, and the number of the micropores is larger than that of the mesopores and the number of the macropores.
76.4mg of 1,3, 5-trimesic acid and 138mg of lead acetate are accurately weighed, 4ml of ethanol is added to trimesic acid, 4ml of pure water is added to lead acetate, and ultrasonic treatment is carried out for 10 minutes to completely dissolve the materials.
Taking 1ml of polystyrene microsphere with the concentration of 5% and the diameter of 200nm, centrifuging for 8 hours at the rotating speed of 3000r/min, pouring out supernatant, drying at room temperature to obtain an assembled polystyrene microsphere template, soaking the template in lead acetate aqueous solution for 24 hours to enable lead acetate molecules to be filled in gaps among the polystyrene microsphere templates, then adding ethanol solution of 1,3, 5-trimesic acid to grow Pb-MOFs in situ, adding 8ml of tetrahydrofuran to etch the polystyrene microsphere, centrifuging for 5 minutes at the centrifuging speed of 8000r/min to obtain precipitate, washing with pure water and ethanol for three times respectively to remove unreacted precursor and other impurities, uniformly dispersing the obtained OM-Pb-MOFs in the pure water, and taking 10 mu l of the mixture to drop on filter paper to obtain the colorimetric type hydrogen sulfide sensor.
Example 2
The colorimetric chip for detecting the food spoilage marker gas comprises a carrier and OM-Pb-MOFs, wherein the OM-Pb-MOFs are attached to the carrier, and the carrier is made of porous adsorption material, and filter paper is specifically selected.
The OM-Pb-MOFs are hierarchical porous structures, the hierarchical porous structures comprise micropores, mesopores and macropores, and the number of the micropores is larger than that of the mesopores and the number of the macropores.
76.4mg of 1,3, 5-trimesic acid and 138mg of lead acetate are accurately weighed, 4ml of ethanol is added to trimesic acid, 4ml of pure water is added to lead acetate, and ultrasonic treatment is carried out for 10 minutes to completely dissolve the materials.
Taking 1ml of polystyrene microsphere with the concentration of 5% and the diameter of 400nm, centrifuging for 8 hours at the rotating speed of 3000r/min, pouring out supernatant, drying at room temperature to obtain an assembled polystyrene microsphere template, soaking the template in lead acetate aqueous solution for 24 hours to enable lead acetate molecules to be filled in gaps among the polystyrene microsphere templates, then adding ethanol solution of 1,3, 5-trimesic acid to grow Pb-MOFs in situ, adding 8ml of tetrahydrofuran to etch the polystyrene microsphere, centrifuging for 5 minutes at the centrifuging speed of 8000r/min to obtain precipitate, washing with pure water and ethanol for three times respectively to remove unreacted precursor and other impurities, uniformly dispersing the obtained OM-Pb-MOFs in the pure water, and taking 10 mu l of the mixture to drop on filter paper to obtain the colorimetric type hydrogen sulfide sensor.
Example 3
The colorimetric chip for detecting the food spoilage marker gas comprises a carrier and OM-Pb-MOFs, wherein the OM-Pb-MOFs are attached to the carrier, and the carrier is made of porous adsorption material, and filter paper is specifically selected.
The OM-Pb-MOFs are hierarchical porous structures, the hierarchical porous structures comprise micropores, mesopores and macropores, and the number of the micropores is larger than that of the mesopores and the number of the macropores.
76.4mg of 1,3, 5-trimesic acid and 138mg of lead acetate are accurately weighed, 4ml of ethanol is added to trimesic acid, 4ml of pure water is added to lead acetate, and ultrasonic treatment is carried out for 10 minutes to completely dissolve the materials.
Taking 1ml of polystyrene microsphere with the concentration of 5% and the diameter of 600nm, centrifuging for 8 hours at the rotating speed of 3000r/min, pouring out supernatant, drying at room temperature to obtain an assembled polystyrene microsphere template, soaking the template in lead acetate aqueous solution for 24 hours to enable lead acetate molecules to be filled in gaps among the polystyrene microsphere templates, then adding ethanol solution of 1,3, 5-trimesic acid to grow Pb-MOFs in situ, adding 8ml of tetrahydrofuran to etch the polystyrene microsphere, centrifuging for 5 minutes at the centrifuging speed of 8000r/min to obtain precipitate, washing with pure water and ethanol for three times respectively to remove unreacted precursor and other impurities, uniformly dispersing the obtained OM-Pb-MOFs in the pure water, and taking 10 mu l of the mixture to drop on filter paper to obtain the colorimetric type hydrogen sulfide sensor.
Example 4
The colorimetric chip for detecting the food spoilage marker gas comprises a carrier and OM-Pb-MOFs, wherein the OM-Pb-MOFs are attached to the carrier, and the carrier is made of porous adsorption material, and filter paper is specifically selected.
The OM-Pb-MOFs are hierarchical porous structures, the hierarchical porous structures comprise micropores, mesopores and macropores, and the number of the micropores is larger than that of the mesopores and the number of the macropores.
76.4mg of 1,3, 5-trimesic acid and 138mg of lead acetate are accurately weighed, 4ml of ethanol is added to trimesic acid, 4ml of pure water is added to lead acetate, and ultrasonic treatment is carried out for 10 minutes to completely dissolve the materials.
Taking 1ml of polystyrene microsphere with the concentration of 5% and the diameter of 1000nm, centrifuging for 8 hours at the rotating speed of 3000r/min, pouring out supernatant, drying at room temperature to obtain an assembled polystyrene microsphere template, soaking the template in lead acetate aqueous solution for 24 hours to enable lead acetate molecules to be filled in gaps among the polystyrene microsphere templates, then adding ethanol solution of 1,3, 5-trimesic acid to grow Pb-MOFs in situ, adding 8ml of tetrahydrofuran to etch the polystyrene microsphere, centrifuging for 5 minutes at the centrifuging speed of 8000r/min to obtain precipitate, washing with pure water and ethanol for three times respectively to remove unreacted precursor and other impurities, uniformly dispersing the obtained OM-Pb-MOFs in the pure water, and taking 10 mu l of the mixture to drop on filter paper to obtain the colorimetric type hydrogen sulfide sensor.
Example 5 sensitivity contrast experiment
The colorimetric chip for efficiently detecting the food spoilage marker hydrogen sulfide gas, which is prepared by the invention, changes the color of the colorimetric chip from white to yellow brown when reacting with hydrogen sulfide; the detection principle is that hydrogen sulfide is ionized into sulfide ions (HS-) and sulfur ions (S2-); when contacted with lead ions (pb2+), lead sulfide (PbS) reactions are generated.
The control experiment group is a commercial lead acetate test strip as a colorimetric chip, the blank experiment group is a colorimetric chip obtained by dripping 10 μl of pure water on filter paper, the experiment groups are 4 groups, the colorimetric chips prepared in examples 1-4 are respectively selected, and 3 replicates are arranged in each group.
Placing each group of colorimetric chips in a closed space to provide H with different concentrations 2 S reacts with the colorimetric chip in the closed space. Due to H 2 S concentration is different, color change of the colorimetric chip is different, the colorimetric chip after detection collects an image of the colorimetric detection chip by using a scanner, then RGB values of the image are read by using Matlab, and Euclidean distance delta E is introduced to establish a relation between delta E and hydrogen sulfide concentration.
Figure SMS_1
Subscripts 0 and i represent the RGB values for the colorimetric detection chip without detecting hydrogen sulfide and detecting hydrogen sulfide, respectively.
The experimental results are shown in table 1.
TABLE 1 color Change after reaction of colorimetric chips with Hydrogen sulfide at different concentrations
Figure SMS_2
Figure SMS_3
As can be seen from the table 1, the data of the present invention,experimental group for 50ppb concentration of H 2 S can be detected, the detection limit is obviously lower than that of a control group, the sensitivity of four experimental groups is better than that of the control group, and the four experimental groups find that the effect of the experimental group 2 is best (the larger Euclidean distance is, the larger the color change degree is). Thus, subsequent experiments were performed using the colorimetric chips prepared in example 2.
The detection limit is calculated by using a detection limit calculation formula lod=3δ/S, δ represents noise, and S represents sensitivity.
Example 6 food spoilage detection assay
Placing the colorimetric chip prepared in the embodiment 2 in a sealed bag, and placing equal amount of food in the sealed bag, wherein the food is pork or flower-shell; the colorimetric chip reacts with hydrogen sulfide generated in the food spoilage process to generate macroscopic color change so as to judge the freshness of the food.
25g of pork was placed in a disposable sealed bag, the colorimetric chip was also placed in the sealed bag without contact with pork, the sealed bag was sealed and refrigerated at 4 ℃.
About 20g of the turtleya is taken in a disposable sealing bag, a detection chip is also placed in the sealing bag but is not contacted with the turtleya, and the sealing bag is sealed and placed at 4 ℃ for refrigeration.
The color of the colorimetric chip gradually changes from white to black brown, so that the freshness of the food can be judged by visually observing the change of the color of the sensing chip.
Example 7 experiment of the indicating Effect of the colorimetric chip on food spoilage at different ambient temperatures
About 20g of the flower-nail was put in a disposable sealed bag, the colorimetric chip prepared in example 2 was also put in the sealed bag without contacting the flower-nail, 5 experimental groups were set up from the 1 st temperature group to the 5 th temperature group, and the sealed bags of the 5 experimental groups were sealed and placed in environments of 4 ℃, 20 ℃, 30 ℃, 38 ℃ and 60 ℃ respectively.
In the same time range, the color change of the colorimetric chip is more obvious along with the increase of the ambient temperature, which indicates that the food spoilage rate is accelerated along with the increase of the temperature, and the colorimetric chip prepared by the invention has good stability at 4-60 ℃ and does not influence the detection effect due to the increase of the ambient temperature.
EXAMPLE 8OM-Pb-MOFs Nitrogen adsorption-BET pore size distribution
Referring to fig. 2, the OM-Pb-MOFs prepared in example 2 is selected and subjected to isothermal adsorption and desorption with nitrogen to obtain a pore distribution map, specifically, as shown in fig. 2, the horizontal axis in fig. 2 represents pore diameter, and the vertical axis represents pore diameter distribution, and as shown in fig. 2, the number of micropores is greater than the number of mesopores.
The colorimetric detection chip has good stability, and the hierarchical porous structure of the detection chip is beneficial to gas mass transfer, so that the colorimetric detection chip has a lower detection limit. The detection chip does not need to be in direct contact with food in the sealed bag in the use process, but generates a signal through reaction with hydrogen sulfide generated by food spoilage, so that the detection chip has the advantages of non-contact and no damage, and the generated color signal is easy to identify.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof; the present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the invention, but any minor modifications, equivalents, and improvements made to the above embodiments according to the technical principles of the present invention should be included in the scope of the technical solutions of the present invention.

Claims (10)

1. A method for preparing a colorimetric chip for detecting food spoilage marker gas is characterized by comprising the following steps,
s1, self-assembling polystyrene nanospheres, namely taking polystyrene nanospheres with uniform sizes, and obtaining a three-dimensional ordered polystyrene nanosphere integral template in a centrifugal self-assembly mode;
s2, filling precursor lead acetate, soaking the dried polystyrene nanosphere integral template in a lead acetate aqueous solution, and keeping the lead acetate molecules in ordered holes of the polystyrene nanosphere integral template for enough time;
s3, growing Pb-MOFs in situ, taking out the template filled with lead acetate molecules prepared in the step S2, soaking the template in an ethanol solution of 1,3, 5-trimesic acid, and enabling the Pb-MOFs to grow in situ in a template gap to obtain micropores and mesopores;
s4, preparing OM-Pb-MOFs, namely centrifuging the ethanol solution in which the 1,3, 5-trimesic acid with the template is soaked in the step S3, centrifuging at a rotating speed and for a time, removing supernatant, adding tetrahydrofuran, and repeating the step S4 for three times to completely remove the polystyrene integral template, so as to obtain an ordered macroporous structure, and obtaining the OM-Pb-MOFs;
s5, removing unreacted precursors, and sequentially washing the OM-Pb-MOFs obtained in the step S4 with ethanol and pure water for three times respectively to remove the unreacted precursors;
s6, preparing a colorimetric detection chip, dispersing the washed OM-Pb-MOFs in water, and dripping the water with the dispersed OM-Pb-MOFs on filter paper to serve as the colorimetric chip for detecting hydrogen sulfide gas molecules.
2. The method of claim 1, wherein the polystyrene nanospheres in step S1 have a diameter of 200nm, 400nm, 600nm or 1000nm.
3. The method for preparing a colorimetric chip for detecting a food spoilage marker gas according to claim 1, wherein the rotational speed of the centrifugal self-assembly in step S1 is 3000r/min, and the centrifugation time is 8h.
4. The method of claim 1, wherein the drying in step S2 is performed at room temperature.
5. The method of claim 1, wherein the lead acetate aqueous solution in step S2 has a concentration of 0.09M and the soaking time is 24 hours.
6. The method for preparing a colorimetric chip for detecting a food spoilage marker gas according to claim 1, wherein the concentration of the ethanol solution of 1,3, 5-trimesic acid in step S3 is 0.01M and the soaking time is 8h.
7. The method of claim 1, wherein the centrifugation in step S4 is performed at a rotational speed of 8000r/min for 5min.
8. A colorimetric chip prepared by the method for preparing a colorimetric chip for detecting a food spoilage marker gas according to any one of claims 1 to 7, comprising a carrier and OM-Pb-MOFs, the OM-Pb-MOFs being attached to the carrier, the carrier being an adsorbent material having a porosity.
9. The colorimetric chip for detecting a food spoilage marker gas according to claim 8, wherein the OM-Pb-MOFs are of a hierarchical porous structure including micropores, mesopores and macropores.
10. The colorimetric chip for detecting a food spoilage marker gas according to claim 9, wherein the number of micropores is greater than the number of mesopores than the number of macropores.
CN202310220204.5A 2023-03-09 2023-03-09 Preparation method of colorimetric chip for detecting food spoilage marker gas Pending CN116242821A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116735883A (en) * 2023-08-14 2023-09-12 天津理工大学 Preparation method of portable colorimetric sensing chip for detecting breast cancer markers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116735883A (en) * 2023-08-14 2023-09-12 天津理工大学 Preparation method of portable colorimetric sensing chip for detecting breast cancer markers
CN116735883B (en) * 2023-08-14 2023-10-20 天津理工大学 Preparation method of portable colorimetric sensing chip for detecting breast cancer markers

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