CN115290635A - Three-color sensing probe and preparation method and application thereof - Google Patents

Three-color sensing probe and preparation method and application thereof Download PDF

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CN115290635A
CN115290635A CN202211003206.0A CN202211003206A CN115290635A CN 115290635 A CN115290635 A CN 115290635A CN 202211003206 A CN202211003206 A CN 202211003206A CN 115290635 A CN115290635 A CN 115290635A
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ultrapure water
quantum dots
sensing probe
room temperature
carbon quantum
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饶含兵
吴春
鲁志伟
常洪榕
王妍媖
刘涛
孙萌萌
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Sichuan Agricultural University
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    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material

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Abstract

The invention discloses a three-color sensing probe and a preparation method and application thereof, wherein the three-color sensing probe comprises the following steps: step 1, preparing blue emission carbon quantum dots: adding 1ml of ethylenediamine into 0.35-3g of dandelion powder and 20-40ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 4.5-8h, cooling to room temperature, and dialyzing and purifying for 20-32h to obtain blue emitting carbon quantum dots; step 2, preparing green emission quantum dots: dissolving 0.1-0.5g of m-phenylenediamine in 7-15ml of absolute ethanol, dripping 45-70 mu l of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 160-200 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-25 min, and eluting and purifying to obtain green emitted carbon quantum dots; step 3, preparation of RuMOF. The invention realizes the high-sensitivity detection of the freshness of the meat products in daily life, and effectively solves the problems of single color change, low sensitivity, complex manufacturing process, high operation professional requirement and the like in the prior art.

Description

Three-color sensing probe and preparation method and application thereof
Technical Field
The invention relates to the field of food detection, in particular to a three-color sensing probe and a preparation method and application thereof.
Background
Food quality and safety are closely related to public health, and have always attracted a great deal of attention. The world health organization (world health organization) estimates that ingesting unsafe food can cause over 200 diseases, ranging from diarrhea to cancer. Worse still, 6 million people suffer from illness each year, and 42 million die from ingesting contaminated food. Total volatile basic nitrogen (TVB-N) is a key indicator of freshness of protein-rich food products, since basic nitrogen-containing substances, including dimethylamine, trimethylamine, and ammonia, are released during spoilage of protein-rich food products. In addition, the release of basic nitrogen-containing substances can result in an increase in the pH of the food product during storage. Therefore, ammonia and pH generated during food storage become important indicators for determining food quality, and the problems of on-site real-time monitoring are followed.
At present, mature techniques and progress are made on the detection, qualitative and quantitative research of biogenic amine and ammonia. Common analytical methods for biogenic amines include thin layer chromatography, liquid chromatography, ion chromatography, gas chromatography, electrophoresis, raman spectroscopy, enzyme linked immunosorbent assay, molecular imprinting, sensor, fluorescence, and the like. Among the above methods, the fluorescence method is distinguished by its visualization, high sensitivity, and high selectivity. In addition, some simple fluorescence sensors are also a large detection tool that can achieve real-time monitoring without the need for complex equipment operations and professionals. Existing fluorescence sensors for detecting ammonia include Carbon Dots (CDs), metal Organic Frameworks (MOFs), metal clusters (M-NCs), perovskites, fluorescent organic molecules, and complex multi-emissive materials, among others. They, when used alone as sensors, tend to exhibit either an "on" or "off" response; they are also often used in pairs or triplets to form dual-emitting or triple-emitting ratio sensors.
Among them, the ratio sensor is favored by many researchers because of its higher sensitivity, small error, and multi-color change. For example, xiao-Yu Xu et al constructed dual emission rate probes to detect histamine using covalent modification of methyl red dye with EuMOF.
Ruonan Jia et al covalently immobilized Fluorescein Isothiocyanate (FITC) as an indicator and protoporphyrin IX (PpIX) on Cellulose Acetate (CA), respectively, by using reactive hydroxyl groups on the cellulose chain. Subsequently, a series of dual-emitting solid fluorescent materials were realized by simply mixing the green-emitting CA-FITC with different ratios of the red-emitting CA-PpIX. They exhibit a sensitive, rapid and linear response to ammonia in the 5.0ppm range and can be used to detect food freshness. However, the dual-emission probe has a complicated manufacturing process and a small color variation range, and therefore, the development of a multi-color fluorescence sensing system is urgently inevitable.
Disclosure of Invention
Objects of the invention
In view of this, the present invention aims to provide a three-color sensing probe, and a preparation method and an application thereof, so as to solve the problems of single color change, low sensitivity, complex manufacturing process, high operation professional requirements, and the like when food freshness is detected in the prior art.
(II) technical scheme
In order to achieve the above technical object, in one aspect, the present invention provides a method for preparing a three-color sensing probe, including the steps of:
step 1, preparing blue emission carbon quantum dots: adding 0.3-2.5ml of ethylenediamine into 0.35-3g of dandelion powder and 20-40ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 4.5-8h, cooling to room temperature, and dialyzing and purifying for 20-32h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.5g m-phenylenediamine in 7-15ml of absolute ethanol, dripping 45-70 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 160-200 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-25 min, and eluting and purifying to obtain a green emitted carbon quantum dot;
step 3, preparation of RuMOF: mixing 15-20mg [ Ru (dcbpy) ] 3 ] 2+ Dissolving 40-65mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1-2h, standing for 24h at room temperature, centrifuging at 8000rpm for 4-6 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
Further preferably, the method comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 0.4-2ml of ethylenediamine into 0.4-2.2g of dandelion powder and 22-36ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 5-7h, cooling to room temperature, dialyzing and purifying for 22-30h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.4g m-phenylenediamine in 8-12ml of absolute ethanol, dripping 50-65 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 180 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-22 min, and eluting and purifying to obtain a green emitted carbon quantum dot;
step 3, preparation of RuMOF: mixing 16-19mg [ Ru (dcbpy) ] 3 ] 2+ And 45-60mg of zinc nitrate hexahydrate are dissolved in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, ultrasonic treatment is carried out for 1h, standing is carried out for 24h at room temperature, centrifugation is carried out for 4-6 minutes at 8000rpm, washing is carried out for 3 times by using the ultrapure water, and the solution is re-dispersed in 2ml of the ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
Further preferably, the method comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 0.5-1.5ml of ethylenediamine into 0.5-2g of dandelion powder and 25-35ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 5-7h, cooling to room temperature, and dialyzing and purifying for 23-25h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.3g m-phenylenediamine in 10ml of absolute ethanol, dripping 50-65 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 180 ℃ for 1.5-2.5h, cooling to room temperature, centrifuging at 12000rpm for 12-20 min, and eluting and purifying to obtain a green emitting carbon quantum dot;
step 3, preparation of RuMOF: mixing 17-19mg [ Ru (dcbpy) ] 3 ] 2+ Dissolving 50-60mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1h, standing for 24h at room temperature, centrifuging at 8000rpm for 4-6 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
Further preferably, the method comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 1ml of ethylenediamine into 1g of dandelion powder and 30ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 6 hours, cooling to room temperature, dialyzing and purifying for 24 hours to obtain blue emitting carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1g m-phenylenediamine in 10ml of absolute ethanol, dripping 60 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating for 2h at 180 ℃, cooling to room temperature, centrifuging at 12000rpm for 15 min, and eluting and purifying to obtain a green-emitting carbon quantum dot;
step 3, preparation of RuMOF: mixing 18mg [ Ru (dcbpy) ] 3 ] 2+ Dissolving 54mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1h, standing at room temperature for 24h, centrifuging at 8000rpm for 5 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
Further preferably, the mixing ratio of the three materials in the step 4 is 1:100:3100.
further preferably, the dandelion powder is dried and crushed.
In one aspect, the present invention provides a three-color sensing probe, which is prepared by the above-mentioned method for preparing a three-color sensing probe.
In another aspect, the present invention provides an application of the three-color sensing probe, wherein the three-color sensing probe prepared by the preparation method of the three-color sensing probe is applied to quantitative analysis and field detection of ammonia.
Further preferably, when the three-color sensing probe is used for detection, the fluorescence color of the three-color sensing probe shows rich changes from lake green, yellow, orange to red when the pH is increased from 2.5 to 9.5.
According to the technical scheme, the method has the following beneficial effects:
1. the invention designs and constructs a three-color sensing probe for visual detection of ammonia and pH value, realizes high-sensitivity detection of meat products in daily life, and effectively solves the problems of single color change, low sensitivity, complex manufacturing process, high professional operation requirement and the like when the food freshness is detected in the prior art.
2. The three-color sensing probe is a mixture formed by three different fluorescent materials, and the color change is more abundant. The fluorescence color changed from yellow to orange with increasing ammonia concentration. When the pH value is increased from 2.5 to 9.5, the color of the solution changes from lake green, yellow, orange to red. Its advantages mainly include: (1) the preparation of each luminescent material is simple; (2) Abundant and wide color changes can be observed by naked eyes under the assistance of an ultraviolet lamp, and the environment with different pH values can be rapidly identified and detected; (4) Portable optical equipment (magazine) combines together degree of deep learning technique and smart mobile phone, realizes the on-the-spot monitoring of food corruption for it is effectual to detect the new freshness of food.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram showing the detection range of ammonia in the range of 0-20ppm, the detection limit of 0.4ppm, the curve trend and the fluorescence color change.
FIG. 2 is a view showing (F) provided by the present invention 420 +F 625 )/F 501 And NH 3 The concentrations are shown in a linear relationship between 0.4-9ppm and 9-30ppm, respectively.
Fig. 3 is a graph showing a change in a curve and a change in fluorescence color in an environment with pH = 2.5-9.5.
FIG. 4 is a view showing (F) provided by the present invention 420 +F 625 )/F 501 And the pH value is between 2.5 and 9.5.
FIG. 5 is a smart phone platform versus NH based on deep learning 3 The linear range of the quantitative analysis of (2) is 0-45 ppm.
Fig. 6 is a schematic diagram of pH value analysis by a smartphone platform based on deep learning, where a linear range is 2.5-10.
Detailed Description
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
Example one
A preparation method of a three-color sensing probe comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 0.3-2.5ml of ethylenediamine into 0.35-3g of dandelion powder (dried and smashed in advance) and 20-40ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 4.5-8h, cooling to room temperature, dialyzing and purifying for 20-32h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.5g m-phenylenediamine in 7-15ml of absolute ethanol, dripping 45-70 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 160-200 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-25 min, and eluting and purifying to obtain a green emitted carbon quantum dot;
step 3, preparation of RuMOF: 15-20mg [ 2 ] Ru (dcbpy) 3 ] 2+ Dissolving 40-65mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1-2h, standing for 24h at room temperature, centrifuging at 8000rpm for 4-6 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain a three-color sensing probe, wherein the ratio of the three materials is 1:100:3100.
example two
A preparation method of a three-color sensing probe comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 0.4-2ml of ethylenediamine into 0.4-2.2g of dandelion powder (dried and smashed in advance) and 22-36ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 5-7h, cooling to room temperature, dialyzing and purifying for 22-30h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.4g m-phenylenediamine in 8-12ml of absolute ethanol, dripping 50-65 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 180 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-22 min, and eluting and purifying to obtain a green emitted carbon quantum dot;
step 3, preparation of RuMOF: 16-19mg [ 2 ], [ Ru (dcbpy) ] 3 ] 2+ And 45-60mg of zinc nitrate hexahydrate are dissolved in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, ultrasonic treatment is carried out for 1h, standing is carried out for 24h at room temperature, centrifugation is carried out for 4-6 minutes at 8000rpm, washing is carried out for 3 times by using the ultrapure water, and the solution is re-dispersed in 2ml of the ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain a three-color sensing probe, wherein the ratio of the three materials is 1:100:3100.
EXAMPLE III
A preparation method of a three-color sensing probe comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 0.5-1.5ml of ethylenediamine into 0.5-2g of dandelion powder (dried and smashed in advance) and 25-35ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 5-7h, cooling to room temperature, dialyzing and purifying for 23-25h to obtain blue emitting carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.3g m-phenylenediamine in 10ml of absolute ethanol, dripping 50-65 mul of concentrated sulfuric acid (98%) under the condition of vigorous stirring, transferring the above-mentioned liquid into a high-pressure reaction kettle, heating at 180 deg.C for 1.5-2.5h, cooling to room temperature, centrifuging at 12000rpm for 12-20 min, eluting and purifying to obtain green-emitting carbon quantum dots;
step 3, preparation of RuMOF: mixing 17-19mg [ Ru (dcbpy) ] 3 ] 2+ Dissolving 50-60mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1h, standing for 24h at room temperature, centrifuging at 8000rpm for 4-6 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain a three-color sensing probe, wherein the ratio of the three materials is 1:100:3100.
example four
A preparation method of a three-color sensing probe comprises the following steps:
the method comprises the following steps:
step 1, preparing blue emission carbon quantum dots: adding 1ml of ethylenediamine into 1g of dandelion powder, pouring 30ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 6 hours, cooling to room temperature, dialyzing and purifying for 24 hours to obtain blue emitting carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1g m-phenylenediamine in 10ml of absolute ethanol, dripping 60 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating for 2h at 180 ℃, cooling to room temperature, centrifuging at 12000rpm for 15 min, and eluting and purifying to obtain a green-emitting carbon quantum dot;
step 3, preparation of RuMOF: 18mg [ 2 ], [ Ru (dcbpy) ] 3 ] 2+ Dissolving 54mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1h, standing at room temperature for 24h, centrifuging at 8000rpm for 5 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain a three-color sensing probe, wherein the ratio of the three materials is 1:100:3100.
EXAMPLE five
A three-color sensing probe, which is prepared by the method of one of the first to fourth embodiments. The three-color sensing probe consists of blue emission carbon quantum dots (D-CDs), green emission quantum dots (M-CDs) and red emission RuMOF. In this three-color sensing system, the fluorescence intensities of M-CDs and RuMOF showed quenching and fluorescence enhancement, respectively, with ammonia addition, while D-CDs served as an internal reference, since it did not respond to ammonia. These changes would be a change in the fluorescent color from initially yellow to orange. And as the pH is increased from 2.5 to 9.5, the fluorescence color of the three-color sensing probe shows abundant changes from lake green, yellow, orange to red, so that the sensitivity is better when the three-color sensing probe is used for detecting the freshness of food.
EXAMPLE six
The application of the three-color sensing probe obtained in the fifth embodiment is applied to quantitative analysis and field detection of ammonia.
It should be noted that, when the three-color sensing probe is used for detection, the fluorescence color of the three-color sensing probe shows rich changes from lake green, yellow, orange to red as the pH is increased from 2.5 to 9.5.
EXAMPLE seven
The invention provides a visual detection device based on deep learning, which comprises an intelligent terminal (a mobile phone) and a cassette. The smart phone is used for shooting, storing photos and reading related data of the photos.
The main body of the cassette is a frame with three covers, the top surface is provided with a black panel for shading light, the back surface is provided with a sample pool for containing 11 cuvettes, the front surface is provided with a clamping groove for shooting by a mobile phone, and a hole for a camera to shoot pictures is also designed at the corresponding position. These arrangements are removable and when they are all assembled as a single unit, the cassette is completely light tight. A portable lamp having UV channels of 254nm and 365nm is also provided as a UV source.
Example eight
The invention also provides a visual detection method based on deep learning, which comprises the following steps:
acquiring a large batch of fluorescence images by using a camera in the visual detection device based on deep learning, wherein the fluorescence images comprise a training set and a testing set;
in the training set, marking all cuvettes, and marking the training set as VOC2007 format;
predicting by using a YOLO v3 algorithm, and extracting RGB and HSV signal values of positions of cuvettes and colors of test tubes in a training set marked in a VOC2007 format;
segmenting and extracting features of the predicted fluorescence image to finish the training of a YOLO v3 algorithm;
and extracting RGB signal values of the positions and colors of the cuvettes in the test set by using a YOLO v3 algorithm, inputting corresponding concentrations, and generating a linear relation.
The smart phone camera assisted deep learning function based on the YOLO v3 algorithm can capture, recognize and analyze fluorescence images, and uses software to cut and read RGB values and HSV values so as to obtain linear relations between ammonia with different concentrations and fluorescence intensities under different pH values. The detection method based on deep learning has the advantages of high identification speed, increased generalization performance, improved network precision, reduced parameters, improved real-time identification precision, strong model anti-interference capability and the like, and has the potential of accurately identifying targets in a complex environment. The multi-color proportion fluorescence portable sensing platform integrated by the smart phone provides a good application basis for timely judging food spoilage.
The three-color sensing probe in the first to fourth embodiments is used in combination with the above-mentioned detection device to perform detection, and it is found that the detection effect of the fourth embodiment is the best, and the schematic diagrams of color change during detection are shown in fig. 1 and fig. 2.
Exemplary embodiments of the proposed solution of the present disclosure have been described in detail above with reference to preferred embodiments, however, it will be understood by those skilled in the art that many variations and modifications may be made to the specific embodiments described above, and that many combinations of the various technical features and structures presented in the present disclosure may be made without departing from the concept of the present disclosure, without departing from the scope of the present disclosure, which is defined by the appended claims.

Claims (9)

1. A preparation method of a three-color sensing probe is characterized by comprising the following steps:
step 1, preparing blue emission carbon quantum dots: adding 0.3-2.5ml of ethylenediamine into 0.35-3g of dandelion powder and 20-40ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 4.5-8h, cooling to room temperature, dialyzing and purifying for 20-32h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.5g m-phenylenediamine in 7-15ml of absolute ethanol, dripping 45-70 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 160-200 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-25 min, and eluting and purifying to obtain a green emitted carbon quantum dot;
step 3, preparation of RuMOF: 15-20mg [ 2 ] Ru (dcbpy) 3 ] 2+ Dissolving 40-65mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1-2h, standing for 24h at room temperature, centrifuging at 8000rpm for 4-6 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
2. The method of claim 1, comprising the steps of:
step 1, preparing blue emission carbon quantum dots: adding 0.4-2ml of ethylenediamine into 0.4-2.2g of dandelion powder and 22-36ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 5-7h, cooling to room temperature, dialyzing and purifying for 22-30h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.4g m-phenylenediamine in 8-12ml of absolute ethanol, dripping 50-65 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 180 ℃ for 1-3h, cooling to room temperature, centrifuging at 12000rpm for 10-22 min, and eluting and purifying to obtain a green emitted carbon quantum dot;
step 3, preparation of RuMOF: mixing 16-19mg [ Ru (dcbpy) ] 3 ] 2+ And 45-60mg of zinc nitrate hexahydrate are dissolved in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, ultrasonic treatment is carried out for 1h, standing is carried out for 24h at room temperature, centrifugation is carried out for 4-6 minutes at 8000rpm, washing is carried out for 3 times by using the ultrapure water, and the solution is re-dispersed in 2ml of the ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
3. The method of claim 2, comprising the steps of:
step 1, preparing blue emission carbon quantum dots: adding 0.5-1.5ml of ethylenediamine into 0.5-2g of dandelion powder and 25-35ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 5-7h, cooling to room temperature, and dialyzing and purifying for 23-25h to obtain blue emission carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1-0.3g m-phenylenediamine in 10ml of absolute ethanol, dripping 50-65 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating at 180 ℃ for 1.5-2.5h, cooling to room temperature, centrifuging at 12000rpm for 12-20 min, and eluting and purifying to obtain a green emitting carbon quantum dot;
step 3, preparation of RuMOF: will be provided with17-19mg[Ru(dcbpy) 3 ] 2+ Dissolving 50-60mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1h, standing for 24h at room temperature, centrifuging at 8000rpm for 4-6 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain the red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
4. The method of claim 3, comprising the steps of:
step 1, preparing blue emission carbon quantum dots: adding 1ml of ethylenediamine into 1g of dandelion powder and 30ml of ultrapure water, mixing, pouring into a high-pressure reaction kettle, heating at 200 ℃ for 6 hours, cooling to room temperature, dialyzing and purifying for 24 hours to obtain blue emitting carbon quantum dots;
step 2, preparing green emission quantum dots: dissolving 0.1g m-phenylenediamine in 10ml of absolute ethanol, dripping 60 mul of concentrated sulfuric acid (98%) under vigorous stirring, transferring the liquid into a high-pressure reaction kettle, heating for 2h at 180 ℃, cooling to room temperature, centrifuging at 12000rpm for 15 min, and eluting and purifying to obtain a green-emitting carbon quantum dot;
step 3, preparation of RuMOF: 18mg [ 2 ], [ Ru (dcbpy) ] 3 ] 2+ Dissolving 54mg of zinc nitrate hexahydrate in a mixed solution of 7.5ml of n-propanol and 2.5ml of ultrapure water, carrying out ultrasonic treatment for 1h, standing at room temperature for 24h, centrifuging at 8000rpm for 5 min, washing with ultrapure water for 3 times, and re-dispersing in 2ml of ultrapure water to obtain red-emitting MOF;
and 4, mixing the materials obtained in the three steps according to a certain ratio to obtain the three-color sensing probe.
5. The method for preparing a three-color sensing probe according to any one of claims 1 to 4, wherein the mixing ratio of the three materials in the step 4 is 1:100:3100.
6. the method of claim 5, wherein the dandelion powder is dried and crushed.
7. A three-color sensing probe prepared by the method of preparing a three-color sensing probe according to any one of claims 1 to 6.
8. Use of a three-color sensing probe prepared by the method of preparing a three-color sensing probe according to any one of claims 1 to 6 for quantitative analysis and in-situ detection of ammonia.
9. The use of the tricolor sensing probe according to claim 8, wherein the fluorescence color of the tricolor sensing probe shows a rich change from lake green, yellow, orange to red when the pH is increased from 2.5 to 9.5 during the detection.
CN202211003206.0A 2022-08-19 2022-08-19 Three-color sensing probe and preparation method and application thereof Pending CN115290635A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115678551A (en) * 2022-12-01 2023-02-03 南京工业大学 Preparation method of green fluorescence emission carbon quantum dots with high quantum yield

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115678551A (en) * 2022-12-01 2023-02-03 南京工业大学 Preparation method of green fluorescence emission carbon quantum dots with high quantum yield
CN115678551B (en) * 2022-12-01 2023-09-22 南京工业大学 Preparation method of green fluorescence emission carbon quantum dot with high quantum yield

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