CN115290621A - Preparation method and application of bicolor fluorescence ratio probe - Google Patents
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Abstract
The invention discloses a preparation method and application of a bicolor fluorescence ratio probe, which comprises a preparation method for synthesizing and assembling a CDs-Fe-Zr-MOF bicolor fluorescence ratio probe and application based on a visual monitoring device, and is used for quantitative analysis and visual detection of spermine and histamine. The invention realizes the high-sensitivity detection and real-time detection of spermine and histamine in pork, fish and shrimp meat, and effectively solves the problems of low sensitivity, slow response, incapability of real-time detection and the like of a sensing system in the prior art.
Description
Technical Field
The invention belongs to the technical field of food detection, and particularly relates to a preparation method and application of a double-color fluorescence ratio probe.
Background
People take food as a topic which is unchangeable from ancient times, and in recent years, people pay more and more attention to food safety problems along with the improvement of living standard and the explosive growth of food problems. Among them, food spoilage is one of the most concerned problems for consumers and food industry, and not only does it cause huge economic losses, but it also causes serious damage to human health. According to the world health organization data, about 6 million people are ill each year by eating unsafe food and result in 42 tens of thousands of deaths. Biogenic Amines (BAs) are basic nitrogen compounds produced during food spoilage due to decarboxylation of amino acids during microbial activity or endogenous tissue metabolism, and histamine (His), putrescine (Pu), cadaverine (Ca), spermine (SP), tyramine (Tyr), and tryptamine (Typ) are typical BAs produced during food spoilage. Thus, BAs can be considered as an important indicator for monitoring food quality. Excessive intake of biogenic amines (especially, the intake of a plurality of biogenic amines simultaneously) can cause anaphylactic reactions such as headache, nausea, palpitation, blood pressure change, respiratory disturbance and the like, and can seriously threaten life. Among them, histamine is biogenic amine which is most harmful to human health, and spermine is the highest in meat content. Therefore, timely and effective detection of biogenic amines and monitoring freshness are at issue. Common methods for monitoring biogenic amines include liquid chromatography, electrochemical detection, detection of conductive polymer materials, ion mobility spectrometry, and optical sensing. The former methods are complicated to pre-treat samples and require large and expensive instruments. Optical sensing detection, especially fluorescence detection, is receiving attention due to its high sensitivity, rapid operation, response and good selectivity.
However, the conventional fluorescence detection of biogenic amines has the following problems:
the traditional method for detecting biogenic amine by fluorescence is based on the change of the fluorescence intensity of a single-emission fluorescence probe of a luminescent material, the measurement precision is easily influenced by the concentration of the fluorescent material, the state of an instrument, the temperature, the humidity and the like, and only the fluorescence color intensity changes, so that the traditional method is not very advantageous in detecting biogenic amine, and most of the existing double-color fluorescence probes for detecting biogenic amine have the fluorescence intensity which changes from one to the other.
In order to solve the problems, a preparation method and application of a bicolor fluorescence ratio probe are provided.
Disclosure of Invention
In order to solve the technical problems, the invention designs a preparation method and application of a bicolor fluorescence ratio probe, which is used for quantitative analysis and visual detection of spermine and histamine, realizes high-sensitivity detection and real-time detection of spermine and histamine in pork, fish and shrimp meat, and effectively solves the problems of low sensitivity, slow response, incapability of real-time detection and the like of a sensing system in the prior art.
In order to achieve the technical effects, the invention is realized by the following technical scheme: a preparation method of a bicolor fluorescence ratio probe is characterized by comprising the following steps:
s1, synthesis of CDs: weighing pyrocatechol, putting the pyrocatechol into a beaker, stirring and dissolving, adding ethylenediamine, stirring and mixing, heating in a water bath, filtering the obtained material through a filter membrane, and putting the solution into a refrigerator for refrigeration;
s2, synthesis of Fe-Zr-MOF: respectively dissolving Zr (NO 3) 4 & 5H2O, fe (NO 3) 3 & 9H2O and 2-amino terephthalic acid in DMF in advance; next, fully mixing the Zr (NO 3) 4 solution, the Fe (NO 3) 3 solution, the 1,4-BDC-NH2 solution, DMF and HAc, and then transferring the mixture to a hydrothermal reactor with a polytetrafluoroethylene lining for reaction; after cooling, the product is taken out and washed with acetone and ethanol for several times; after drying overnight, dissolving the material in a mixed acetic acid and aqueous solution, and refrigerating the solution in a refrigerator;
s3, assembling CD-Fe-Zr-MOF: and mixing the obtained CDs and Fe-Zr-MOF to obtain the bicolor sensing probe.
Further, the synthesis of CDs in step S1 specifically includes:
0.2202g of catechol was weighed into a beaker of water containing 20mL of the catechol, and after stirring and dissolution, 1mL of 1moL/L ethylenediamine was added thereto, and after stirring and mixing, the mixture was heated in a water bath at 50 ℃ for 2 hours, the resulting material was filtered through a filter membrane, and the solution was refrigerated in a refrigerator at 4 ℃.
Further, the synthesis of the Fe-Zr-MOF in the step S2 specifically comprises the following steps:
previously, 8mmol of Zr (NO 3) 4.5H 2O, 8mmol of Fe (NO 3) 3.9H 2O and 8mmol of 2-aminoterephthalic acid were dissolved in 30mL of DMF respectively; then, 5mL of Zr (NO 3) 4 solution, 5mL of LFe (NO 3) 3 solution, 10mL of 1,4-BDC-NH2 solution, 5mL of DMF and 5mL of HAc were thoroughly mixed, and then transferred to a 50mL polytetrafluoroethylene-lined hydrothermal reactor to react for 12 hours at 120 ℃; after cooling, the product is taken out and washed with acetone and ethanol for several times; after drying overnight at 40 ℃, 10mg of material was dissolved to 1:1 to 10mL of acetic acid and aqueous solution mixed, and the solution was refrigerated in a refrigerator at 4 ℃.
The response of the two-color ratiometric probes, spermine and histamine, was based on the electrostatic interaction principle and the luminophore C = N increase principle, respectively. The peak at 505nm of λ ex =365nm, cds increases with increasing spermine and histamine, and the peak at 450nm of Fe-Zr-MOF decreases with increasing spermine and histamine, thereby building a rise-fall response phenomenon that results in a change of the fluorescence color from blue to blue-green to green.
Further, use of a two-color ratiometric probe prepared as in any one of the above in a visual monitoring product.
Further, the application of the two-color fluorescence ratio probe in visual monitoring products is characterized in that: the visual monitoring product is a visual monitoring device and comprises an intelligent terminal and a cassette; the terminal can be used for receiving, storing and analyzing data; the cassette includes opaque box, and box one side is provided with the cell-phone standing groove, and is provided with the through-hole that supplies the camera to acquire the image on the box, and the box opposite side is provided with can dismantle many test tube support, and it has foretell double-colored fluorescence ratio probe to fill in the test tube on the many test tube support, and the inside top of box is provided with the ultraviolet lamp.
Further, the application of the bicolor fluorescence ratio probe in visual monitoring products is characterized in that: placing a bicolor fluorescence ratio probe into a test tube of a visual monitoring device, collecting a fluorescence image by using a camera in the visual monitoring device, and dividing the fluorescence image into a training set and a test set; marking all test tubes in a training set, and marking the training set with a VOC2007 format; predicting by using a YOLO v3 algorithm, and extracting RGB signal values of test tube positions and test tube colors in a training set labeled in a VOC2007 format; segmenting and extracting features of the predicted fluorescence image to finish the training of a YOLO v3 algorithm; extracting the RGB signal values of the test tube positions and the test tube colors in the test set by using a YOLO v3 algorithm, and generating a linear relation; the concentration of spermine and histamine was obtained from a linear relationship.
The beneficial effects of the invention are:
1. the two-color fluorescence ratio probe is a mixture of CDs and Fe-Zr-MOF, and can generate abundant color change. The increase of the content of spermine and histamine leads to the quenching of the fluorescence intensity of Fe-Zr-MOF based on electrostatic effect, CDs emit light due to the existence of C = N group, and after the spermine and histamine are added, schiff base reaction occurs, so that the C = N group is increased, the fluorescence is enhanced, and the visual monitoring of spermine and histamine is realized. The preparation is simple, and other complicated steps are not needed; it has excellent selectivity and ultra-high sensitivity to spermine and histamine contents based on a color change from blue to green observed by naked eyes; a portable optical device (cassette) combines deep learning techniques with a smartphone to capture RGB values for visual monitoring of spermine and histamine content.
2. The smartphone camera assisted deep learning function based on the YOLO v3 algorithm can capture a fluorescence colorimetric image, recognize and process a photo, and cut and read RGB values by using software to test the concentration of spermine and histamine in a real sample. And the end-to-end target detection method represented by the YOLO v3 model has the advantages of high identification speed, high identification precision, strong anti-interference capability of the model and the like, and has the potential of identifying the target in a complex environment. The sensing system can detect spermine and histamine of pork, fish and shrimp meat with high sensitivity. The multi-color proportion fluorescence portable sensing platform integrated with the smart phone provides a good application foundation for efficiently and portably detecting toxic and harmful substances.
3. The invention realizes the high-sensitivity detection of spermine and histamine in pork, fish and shrimp meat by preparing the bicolor fluorescence ratio probe for the quantitative analysis and visual detection of spermine and histamine, and effectively solves the problems of poor stability, low sensitivity, incapability of realizing field detection and the like of a sensing system in the prior art.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the detection range of spermine of the present invention is 0-937.5. Mu.M, LOD is 0.17. Mu.M, curve trend and fluorescence color change;
FIG. 2 shows the histamine detection range of the present invention is 0-937.5. Mu.M, LOD is 2.95. Mu.M, curve trend and fluorescence color change;
FIG. 3 is a schematic diagram of a fluorescence curve of a smart phone of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in FIGS. 1 to 3, the method for preparing a two-color fluorescence ratiometric probe of the present invention comprises the following steps:
s1, synthesis of CDs: weighing pyrocatechol, putting the pyrocatechol into a beaker, stirring and dissolving, adding ethylenediamine, stirring and mixing, heating in a water bath, filtering the obtained material through a filter membrane, and putting the solution into a refrigerator for refrigeration;
s2, synthesis of Fe-Zr-MOF: respectively dissolving Zr (NO 3) 4 & 5H2O, fe (NO 3) 3 & 9H2O and 2-amino terephthalic acid in DMF in advance; next, fully mixing the Zr (NO 3) 4 solution, the Fe (NO 3) 3 solution, the 1,4-BDC-NH2 solution, DMF and HAc, and then transferring the mixture to a hydrothermal reactor with a polytetrafluoroethylene lining for reaction; after cooling, the product is taken out and washed with acetone and ethanol for several times; after drying overnight, dissolving the material in a mixed acetic acid and aqueous solution, and refrigerating the solution in a refrigerator;
s3, assembling CD-Fe-Zr-MOF: and mixing the obtained CDs and Fe-Zr-MOF to obtain the bicolor sensing probe.
The synthesis of CDs in step S1 specifically comprises:
0.2202g of catechol was weighed into a beaker of water containing 20mL of the catechol, and after stirring and dissolution, 1mL of 1moL/L ethylenediamine was added thereto, and after stirring and mixing, the mixture was heated in a water bath at 50 ℃ for 2 hours, the resulting material was filtered through a filter membrane, and the solution was refrigerated in a refrigerator at 4 ℃.
The synthesis of the Fe-Zr-MOF in the step S2 specifically comprises the following steps:
previously, 8mmol of Zr (NO 3) 4.5H 2O, 8mmol of Fe (NO 3) 3.9H 2O and 8mmol of 2-aminoterephthalic acid were dissolved in 30mL of DMF, respectively; then, 5mL of Zr (NO 3) 4 solution, 5mL of LFe (NO 3) 3 solution, 10mL of 1,4-BDC-NH2 solution, 5mL of DMF and 5mL of HAc were thoroughly mixed, and then transferred to a 50mL polytetrafluoroethylene-lined hydrothermal reactor to react for 12 hours at 120 ℃; after cooling, the product is taken out and washed with acetone and ethanol for several times; after drying overnight at 40 ℃, 10mg of material was dissolved to 1:1 to 10mL of acetic acid and aqueous solution mixed, and the solution was refrigerated in a refrigerator at 4 ℃.
The response of the two-color ratiometric probes, spermine and histamine, was based on the electrostatic interaction principle and the luminophore C = N increase principle, respectively. The peak at 505nm of λ ex =365nm, cds increases with increasing spermine and histamine, and the peak at 450nm of Fe-Zr-MOF decreases with increasing spermine and histamine, thereby building a rise-fall response phenomenon that results in a change of the fluorescence color from blue to blue-green to green.
The preparation is simple, and other complicated steps are not needed; it has excellent selectivity and ultra-high sensitivity to spermine and histamine contents based on a color change from blue to green observed by naked eyes; a portable optical device (cassette) combines deep learning techniques with a smartphone to capture RGB values for visual monitoring of spermine and histamine content.
Use of a two-color fluorescence ratio probe prepared according to any of the above in a visual monitoring product.
The application of the bicolor fluorescence ratio probe in visual monitoring products is characterized in that: the visual monitoring product is a visual monitoring device and comprises an intelligent terminal and a cassette; the terminal can be used for receiving, storing and analyzing data; the cassette includes opaque box, and box one side is provided with the cell-phone standing groove, and is provided with the through-hole that supplies the camera to acquire the image on the box, and the box opposite side is provided with can dismantle many test tube support, and it has foretell double-colored fluorescence ratio probe to fill in the test tube on the many test tube support, and the inside top of box is provided with the ultraviolet lamp.
Further, the application of the bicolor fluorescence ratio probe in visual monitoring products is characterized in that: placing a bicolor fluorescence ratio probe into a test tube of a visual monitoring device, collecting a fluorescence image by using a camera in the visual monitoring device, and dividing the fluorescence image into a training set and a test set; marking all test tubes in a training set, and marking the training set with a VOC2007 format; predicting by using a YOLO v3 algorithm, and extracting RGB signal values of test tube positions and test tube colors in a training set labeled in a VOC2007 format; segmenting and extracting features of the predicted fluorescence image to finish the training of a YOLO v3 algorithm; extracting the RGB signal values of the test tube positions and the test tube colors in the test set by using a YOLO v3 algorithm, and generating a linear relation; the concentration of spermine and histamine was obtained from a linear relationship.
The smart phone camera assisted deep learning function based on the YOLO v3 algorithm can capture a fluorescent colorimetric image, recognize and process a photo, and cut and read RGB values by using software so as to test the concentration of spermine and histamine in a real sample. And the end-to-end target detection method represented by the YOLO v3 model has the advantages of high identification speed, high identification precision, strong anti-interference capability of the model and the like, and has the potential of identifying the target in a complex environment. The sensing system can detect spermine and histamine of pork, fish and shrimp meat with high sensitivity. The multi-color proportion fluorescence portable sensing platform integrated with the smart phone provides a good application foundation for efficiently and portably detecting toxic and harmful substances.
When the spermine is detected by using the bicolor probe, after the spermine is added, the blue fluorescence is quenched, and the green fluorescence is enhanced, so that the color of the fluorescence can be changed from blue to green, and the spermine is detected, and the aim of detecting freshness is fulfilled.
When the two-color probe is used for detecting histamine, after histamine is added, blue fluorescence is quenched, green fluorescence is enhanced, and further the color of fluorescence can be changed from blue to green, so that the histamine can be detected, and the aim of detecting freshness can be further achieved.
Example 2
As shown in fig. 1 to 3:
1. optimization of pH
Before optimization, aqueous solutions of spermine and histamine at certain concentrations were freshly prepared. CDs/Fe-Zr-MOF was added to PBS buffer at different pH values (pH =3, 4, 5, 6, 7, 8, 9, 10, 11) and diluted. The same volume of spermine and histamine solution with the same concentration are respectively added, then 8 sample tubes are reacted under the same temperature for the same time, the fluorescence intensity is tested at the position of 365nm of the excitation wavelength, and the absolute value of the difference value of the fluorescence intensity before and after the spermine and the histamine are added into the 8 sample tubes under different pH values is compared, so that the spermine with the pH =5 has the largest fluorescence change value, and the pH =4, 5 and 6 are several groups of pH values when the histamine has the largest fluorescence change value, and the pH =5 is the optimal condition of the pH test because the spermine and the histamine are measured to be a system.
2. Optimization of reaction time
The composite material is dispersed into PBS buffer solution with optimal pH =5, the fluorescence intensity of the composite material is tested after the composite material is incubated for 3min at the optimal reaction temperature, the fluorescence intensity is tested every 1min after spermine and histamine solution is added (Time =0-15 min), the reaction Time with the maximum change of the fluorescence intensity ratio is the optimal reaction Time, and it can be seen that the fluorescence intensity reaches the maximum in 30s, and then the fluorescence intensity is unchanged all the Time, so the fluorescence intensity is the optimal response Time in 30 s.
3. Composition of fluorescence linearity and smartphone fluorescence curve
Based on the optimal conditions of pH =5 and response time of 30s, ratiometric fluorescence was constructed to achieve quantitative detection of spermine and histamine. First, spermine and histamine solutions with different concentrations were added to a plurality of 5mL centrifuge tubes, and then the composite nanoprobe material diluted with PBS buffer was added to react under optimized conditions. And finally, transferring the sample into a quartz cuvette, measuring the fluorescence intensity at the excitation wavelength of 365nm, and establishing a standard curve by taking the concentration of spermine and histamine as the abscissa and the ratio of the fluorescence intensity as the ordinate.
4. Formation of smart hydrogel fluorescent labels
According to the modification of the literature, 3.8g of CMC-Na can be dissolved completely in 100mL of boiling water by continuous stirring. And cooling to 40 ℃, adding 4mLCDs/Fe-Zr-MOF aqueous solution, homogenizing, taking out, and freeze-drying to obtain the hydrogel label.
5. Determination of authentic samples
Fresh meat (pork duck chicken meat and shrimp) purchased from a local supermarket was selected as a real sample for fluorescence detection of freshness. First, the same mass of meat was put into sealed bags, respectively. One of the parts places the prepared fluorescent label in a sealed bag to avoid direct contact between the label and the sample. Thereafter, all containers were sealed and kept at different temperatures (-20 ℃,4 ℃ and 25 ℃) for 1-5 days. During the period, a dark box column attached to a camera of the mobile phone covers an intelligent packaging label for detecting spermine and histamine, a port of the mobile phone is connected with an ultraviolet lamp, the mobile phone is used for photographing and collecting a fluorescent image of the intelligent label in a dark environment in the dark box column, data are processed through a small mobile phone program, and the color of the fluorescent label is changed from blue to green. Blue is not rotten, while blue-green is slightly rotten, while green is severely rotten.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. A preparation method of a bicolor fluorescence ratio probe is characterized by comprising the following steps:
s1, synthesis of CDs: weighing pyrocatechol, putting the pyrocatechol into a beaker, stirring and dissolving, adding ethylenediamine, stirring and mixing, heating in a water bath, filtering the obtained material through a filter membrane, and putting the solution into a refrigerator for refrigeration;
s2, synthesis of Fe-Zr-MOF: respectively dissolving Zr (NO 3) 4 & 5H2O, fe (NO 3) 3 & 9H2O and 2-amino terephthalic acid in DMF in advance; next, fully mixing the Zr (NO 3) 4 solution, the Fe (NO 3) 3 solution, the 1,4-BDC-NH2 solution, DMF and HAc, and then transferring the mixture to a hydrothermal reactor with a polytetrafluoroethylene lining for reaction; after cooling, the product is taken out and washed with acetone and ethanol for several times; after drying overnight, dissolving the material in a mixed acetic acid and aqueous solution, and refrigerating the solution in a refrigerator;
s3, assembling CD-Fe-Zr-MOF: and mixing the obtained CDs and Fe-Zr-MOF to obtain the bicolor sensing probe.
2. The method for preparing a two-color ratiometric probe according to claim 1, wherein the synthesis of CDs in step S1 comprises:
0.2202g of catechol was weighed into a beaker of water containing 20mL of the catechol, and after stirring and dissolution, 1mL of 1moL/L ethylenediamine was added thereto, and after stirring and mixing, the mixture was heated in a water bath at 50 ℃ for 2 hours, the resulting material was filtered through a filter membrane, and the solution was refrigerated in a refrigerator at 4 ℃.
3. The method for preparing a two-color fluorescence ratio probe according to claim 1, wherein the synthesis of Fe-Zr-MOF in the step S2 specifically comprises:
previously, 8mmol of Zr (NO 3) 4.5H 2O, 8mmol of Fe (NO 3) 3.9H 2O and 8mmol of 2-aminoterephthalic acid were dissolved in 30mL of DMF, respectively; then 5mL of Zr (NO 3) 4 solution, 5mL of Fe (NO 3) 3 solution, 10mL of 1,4-BDC-NH2 solution, 5mL of DMF and 5mL of HAc are fully mixed, and then the mixture is transferred into a 50mL hydrothermal reactor with a polytetrafluoroethylene lining and is reacted for 12 hours at the temperature of 120 ℃; after cooling, the product is taken out and washed with acetone and ethanol for several times; after drying overnight at 40 ℃, 10mg of material was dissolved to 1:1 of 10mL of acetic acid and aqueous solution mixed together, and the solution was refrigerated in a refrigerator at 4 ℃.
4. Use of a bi-color fluorescence ratio probe prepared according to any of claims 1-3 in a visual monitoring product.
5. Use of a two-color fluorescence ratio probe according to claim 4 in a visual monitoring product, wherein: the visual monitoring product is a visual monitoring device.
6. Use of a two-color fluorescence ratio probe according to claim 5 in a visual monitoring product, wherein: placing a bicolor fluorescence ratio probe into a test tube of a visual monitoring device, collecting a fluorescence image by using a camera in the visual monitoring device, and dividing the fluorescence image into a training set and a test set; marking all test tubes in a training set, and marking the training set with a VOC2007 format; predicting by using a YOLO v3 algorithm, and extracting RGB signal values of test tube positions and test tube colors in a training set labeled in a VOC2007 format; segmenting and extracting features of the predicted fluorescence image to finish the training of a YOLO v3 algorithm; extracting the RGB signal values of the test tube positions and the test tube colors in the test set by using a YOLO v3 algorithm, and generating a linear relation; the concentration of spermine and histamine was obtained from a linear relationship.
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