WO2021035855A1 - 一种检测汞离子的荧光试纸及检测方法 - Google Patents

一种检测汞离子的荧光试纸及检测方法 Download PDF

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WO2021035855A1
WO2021035855A1 PCT/CN2019/107980 CN2019107980W WO2021035855A1 WO 2021035855 A1 WO2021035855 A1 WO 2021035855A1 CN 2019107980 W CN2019107980 W CN 2019107980W WO 2021035855 A1 WO2021035855 A1 WO 2021035855A1
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standard
test paper
fluorescent
area
color
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PCT/CN2019/107980
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English (en)
French (fr)
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石吉勇
李文亭
邹小波
李志华
黄晓玮
郭志明
胡雪桃
梁妮妮
史永强
石海军
崔雪平
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江苏大学
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Priority claimed from CN201910789122.6A external-priority patent/CN110596084B/zh
Application filed by 江苏大学 filed Critical 江苏大学
Priority to US17/053,070 priority Critical patent/US11378519B2/en
Priority to EP19929179.0A priority patent/EP3812746B1/en
Priority to JP2020565783A priority patent/JP7032831B2/ja
Publication of WO2021035855A1 publication Critical patent/WO2021035855A1/zh

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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
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • 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
    • G01N2021/7756—Sensor type
    • G01N2021/7759—Dipstick; Test strip
    • 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
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6489—Photoluminescence of semiconductors

Definitions

  • the invention belongs to the technical field of food safety detection, and specifically relates to a fluorescent test paper for detecting mercury ions and a detection method.
  • Mercury is a highly toxic heavy metal. It is transmitted through the food chain and metabolized slowly in the human body. It is easy to cause accumulation and poisoning and affect the function of brain cells.
  • mercury ion (Hg 2+ ) detection methods mainly include atomic absorption spectrometry (AAS), inductively coupled plasma mass spectrometry (ICP-MS), electrochemical methods, etc. These methods have high detection sensitivity and accurate results, but the detection process is cumbersome , The operation is complicated and the equipment price is high. It needs to be carried out under laboratory conditions, which is difficult to meet the needs of on-site rapid testing and daily testing. In view of the harm caused by mercury ions to the human body and the deficiencies of existing detection methods, it is of great practical significance to develop a fast and convenient method for detecting the content of mercury ions in food.
  • the existing mercury ion fluorescent probe detection methods have two deficiencies.
  • the hardware cost is high and the operation is complicated.
  • the present invention provides a copper nanocluster (CuNCs)-carbon quantum dots (CQDs)-based fluorescent test paper and detection method for mercury ions in foods, which can achieve low cost of mercury ions in foods ,Quick check.
  • CuNCs copper nanocluster
  • CQDs carbon quantum dots
  • the present invention first provides a fluorescent test paper for detecting mercury ions, the fluorescent test paper includes a fluorescent color developing area, the fluorescent color developing area includes a carbon quantum dot distribution area and a copper nanocluster distribution area; wherein the carbon quantum dot distribution area Carbon quantum dot fluorescent probes are impregnated for environmental verification; the copper nanocluster distribution area is impregnated with copper nanocluster fluorescent probes for detecting mercury ion concentration.
  • the area ratio of the carbon quantum dot distribution area and the copper nanocluster distribution area is 1:1.
  • the fluorescent test paper also includes a hand-held area of the test paper.
  • the hand-held area of the test paper, the distribution area of the carbon quantum dots and the distribution area of the copper nanoclusters are separated by a T-shaped dividing line.
  • the fluorescent test paper further includes a standard fluorescent colorimetric card
  • the standard fluorescent colorimetric card includes a reference channel area
  • the reference channel area includes a reference channel excitation wavelength printing area and a reference channel corresponding excitation color printing area.
  • the standard fluorescence colorimetric card further includes a standard mercury ion sample concentration area
  • the standard mercury ion sample concentration area includes a standard mercury ion sample concentration identification area, a standard mercury ion sample corresponding excitation color identification area and a standard mercury ion concentration unit identification area .
  • the standard mercury ion sample concentration marking area includes a plurality of standard mercury ion sample concentration printing units; the standard mercury ion sample corresponding to excitation color marking area includes a plurality of standard mercury ion samples corresponding to excitation color printing unit.
  • the fluorescent color developing area and the standard fluorescent colorimetric card are located on the same test paper or are set independently.
  • the fluorescent test paper includes a plurality of color-developing regions.
  • the present invention also provides a method for preparing a fluorescent test paper for detecting mercury ions.
  • the method includes the following steps:
  • a carbon quantum dot distribution area and a copper nanocluster distribution area are formed on a blank test paper, the carbon quantum dot distribution area is distributed with carbon quantum dot fluorescent probes for environmental verification, and the copper nanocluster distribution area Copper nanocluster fluorescent probes for detecting the concentration of mercury ions are distributed.
  • Standard color acquisition of response channel/reference channel prepare multiple Hg 2+ standard samples with different Hg 2+ concentrations; each Hg 2+ standard sample is immersed in fluorescent test paper for several minutes and then taken out to obtain multiple reaction samples Test paper; respectively collect the RGB image of the reacted test paper under the preset light source illumination condition; extract the corresponding color signal of the carbon quantum dot distribution area in the RGB image, and take the average value of the color signal and record it as the standard corresponding to the reference channel Color: Extract the corresponding color signals of the copper nanocluster distribution area in the RGB image to obtain the response channel standard colors corresponding to Hg 2+ standard samples with different Hg 2+ concentrations.
  • Print the standard fluorescence colorimetric card area set the preset light source lighting conditions, the standard color corresponding to the reference channel, multiple Hg 2+ concentrations corresponding to the Hg 2+ standard sample, standard mercury ion concentration units, and the corresponding Hg 2+ standard sample
  • the standard color of the response channel is printed in the area of the standard fluorescent colorimetric card.
  • the specific printing operation is:
  • W 1 is a specific excitation wavelength
  • W 1 is greater than 0 and is a positive integer; preferably, the W 1 nm is 365 nm.
  • the present invention also provides a method for detecting mercury ions.
  • the method includes the following steps:
  • Fluorescence test paper reaction immerse the fluorescent test paper in the solution to be tested for a few minutes and then take it out, place it on a clean glass plate and air dry naturally to obtain the reacted test paper PP corresponding to the solution to be tested.
  • Fluorescence detection environment verification place the reacted test paper PP under a light source with a wavelength of W 1 nm to observe the color C_ CQDs' corresponding to the carbon quantum dot distribution area (3), if C_ CQDs' corresponds to the reference channel of the standard colorimetric card If the color C_CQDs of the excitation color printing area (7) is different, check the luminous intensity of the light source and adjust the distance between the reacted test paper PP and the light source to make the color C_ CQDs' and C_ CQDs consistent; preferably, W 1 nm It is 365nm.
  • Colorimetric reading of mercury ion content Observe the corresponding color signal C_CuNCs' of the copper nanocluster distribution area of the reaction test paper PP (4) in the fluorescence detection environment after verification, and obtain the standard mercury ion from the standard fluorescence colorimetric card Find the standard mercury ion sample closest to the color signal C_CuNCs' in the excitation color identification area (10) corresponding to the sample corresponding to the excitation color printing unit (11), then the standard mercury ion sample corresponds to the standard mercury above the excitation color printing unit (11) The number in the ion sample concentration printing unit (9) is the concentration of Hg 2+.
  • the solution of the present invention uses the excitation color corresponding to the reference channel in the standard colorimetric card as a reference, and observes the color corresponding to the distribution area of the carbon quantum dots to verify the fluorescence detection environment during the detection of the fluorescence test paper, which can reduce the comparison of the mercury ion standard sample during the test of the fluorescence test paper Respond to the difference in fluorescence detection environment when detecting the standard color of the channel, thereby reducing the influence of the difference in fluorescence detection environment on the colorimetric detection of mercury ion fluorescent test paper.
  • the mercury ion detection method based on the ratio fluorescent probe has attracted much attention because of its high detection accuracy and strong ability to resist environmental interference.
  • the ratio fluorescent probe has dual emission fluorescence signal channels (response channel and reference channel), in which the signal intensity of the response channel is related to the concentration of the analyte, while the signal intensity of the reference channel has nothing to do with the concentration of the analyte.
  • Environmental factors that affect the intensity of the fluorescence signal of the analyte are related.
  • the correction function of the reference channel can effectively reduce the interference of environmental factors on the detection results, so as to obtain more accurate detection results than single-channel fluorescent probes (single emission fluorescent probes).
  • FIG. 1 is a schematic structural diagram of a preferred embodiment of a fluorescent test paper for detecting mercury ions according to the present invention
  • FIG. 2 is a schematic diagram of the structure of a standard fluorescent colorimetric card of the fluorescent test paper shown in FIG. 1;
  • Figure 3 is a standard fluorescent colorimetric card prepared in the Examples.
  • 1 is the test paper hand-held area
  • 2 is the T-shaped boundary line
  • 3 is the carbon quantum dot distribution area
  • 4 is the copper nanocluster distribution area
  • 5 is the colorimetric card hand-held area
  • 6 is the reference channel excitation wavelength printing area.
  • 7 is the excitation color printing area corresponding to the reference channel
  • 8 is the standard mercury ion sample concentration marking area
  • 9 is the standard mercury ion sample concentration printing unit
  • 10 is the standard mercury ion sample corresponding to the excitation color marking area
  • 11 is the standard mercury ion sample corresponding to the marking area Excite the color printing unit
  • 12 is the mark area of the standard mercury ion concentration unit.
  • Embodiment 1 A fluorescent test paper for detecting mercury ions and its preparation method
  • Fluorescence test paper preparation includes three steps: blank test paper preparation, fluorescent probe preparation and fluorescent probe dip dyeing;
  • Step 1.1 Preparation of blank test paper: Take a blank neutral filter paper (without fluorescence) with a size of 3 ⁇ 4cm, the fluorescence color area of the filter paper, the fluorescence color area includes the carbon quantum dot distribution area 3 and the copper nanocluster distribution area 4.
  • the carbon quantum dot distribution area 3 is impregnated with carbon quantum dot fluorescent probes for environmental verification;
  • the copper nanocluster distribution area 4 is impregnated with copper nanocluster fluorescent probes for detecting the concentration of mercury ions.
  • the test paper also includes a handheld area 1, a carbon quantum dot distribution area 3 and a copper nanocluster distribution area 4 separated by a T-shaped dividing line 2.
  • the area ratio between the carbon quantum dot distribution area and the copper nanocluster distribution area is 1:1
  • Step 1.2 Fluorescent probe preparation: including the preparation of carbon quantum dot s fluorescent probe and the preparation of copper nanocluster fluorescent probe.
  • the preparation method of the carbon quantum dot s fluorescent probe is: take 1 mL of 30% sucrose aqueous solution, 0.2 mL of 98% concentrated sulfuric acid and 6 mL of polyethylene glycol with a molecular weight of 200, mix and stir, and place in a microwave oven. After heating for 15 seconds, the carbon quantum dot solution was obtained and purified by dialysis in deionized water with a dialysis bag (1000D) for 24 hours to obtain a carbon quantum dot fluorescent probe with an excitation wavelength of 365 nm and an emission wavelength of 550 nm and no fluorescence response to mercury ions.
  • the preparation method of the copper nanocluster fluorescent probe is to add 32mg CuSO 4 to 20g water, add 2mL NaOH solution (0.5M) and 20mL ascorbic acid solution (0.1M), adjust the pH to 8.0 ⁇ 9.0 and the temperature at 50°C. After stirring in a water bath for 15 hours, the original copper nanocluster solution was obtained, which was purified by dialysis in deionized water with a dialysis bag (1000D) for 24 hours to obtain a copper nanocluster fluorescent probe with an excitation wavelength of 365nm and an emission wavelength of 445nm and a fluorescence response to mercury ions;
  • Step 1.3 Fluorescent probe dip staining: Immerse the carbon quantum dot distribution area 3 of the blank test paper prepared in step 1.1 into the carbon quantum dot fluorescent probe solution prepared in step 1.2 and keep it for 10 minutes before taking it out; remove the blank prepared in step 1.1 The copper nanocluster distribution area 4 of the test paper is immersed in the copper nanocluster fluorescent probe solution prepared in step 1.2 and kept for 10 minutes, then taken out; then the blank test paper impregnated with the fluorescent probe is placed on a clean glass plate and air-dried naturally to obtain a fluorescent test paper P.
  • Step 2 Preparation of standard fluorescent colorimetric card: including three processes of colorimetric card design, response channel/reference channel standard color acquisition, and standard fluorescent colorimetric card printing;
  • the colorimetric card includes a hand-held area 5 of the colorimetric card, a reference channel area and a standard mercury ion sample concentration area, and the reference channel area includes a reference channel excitation wavelength printing area 6 and a reference channel.
  • the ratio channel corresponds to the excitation color printing area 7;
  • the standard mercury ion sample concentration area includes the standard mercury ion sample concentration marking area 8, the standard mercury ion sample corresponding excitation color marking area 10 and the standard mercury ion concentration unit marking area 12, in which the standard mercury ion concentration unit
  • the ion sample concentration identification area 8 contains 10 standard mercury ion sample concentration printing units 9, and the standard mercury ion sample corresponds to the excitation color identification area 10 contains 10 standard mercury ion samples corresponding to the excitation color printing unit 11; the standard mercury ion sample corresponds to excitation color printing
  • the color in the unit 11 and the number in the printing unit 9 respectively correspond to the excitation color and mercury ion concentration of the same standard mercury ion sample.
  • Step 2.2 The method of obtaining the standard color of the response channel/reference channel is:
  • the fluorescent test paper prepared by the above includes a fluorescent color developing area, the fluorescent color developing area includes a carbon quantum dot distribution area 3 and a copper nanocluster distribution area 4; the fluorescent test paper also includes a test paper holding area 1.
  • the fluorescent test paper also includes a standard fluorescent colorimetric card; the fluorescent color developing area and the standard fluorescent colorimetric card are located on the same test paper, or the fluorescent color developing area is located on the fluorescent test paper, and the standard fluorescent colorimetric card is set independently.
  • the fluorescent test paper includes a plurality of color-developing regions.
  • the colorimetric detection of Hg 2+ in food includes three processes: fluorescence test paper reaction, fluorescence detection environment verification, and colorimetric reading of mercury ion content;
  • Step 3.1 Fluorescence test paper reaction: first take a crab sample (commercially available), wash off the dirt on the surface of the Chinese mitten crab body, dissected, take the hepatopancreas, gonads and muscles, grind and mix them thoroughly, and store in the refrigerator. Take 1.0g of the sample, put it into a polytetrafluoroethylene digestion tank, and add 4mL nitric acid, then add 2mL hydrogen peroxide, and let it stand overnight. Place the digestion tank in a microwave digestion apparatus to complete the digestion and acid removal procedures to obtain crab digestion Add different concentrations of Hg 2+ (respectively 0.3, 0.5, and 0.8 mg/kg) standard solutions to the pre-treated crab digestion solution to obtain the test solution.
  • the fluorescent test paper prepared in Example 2 is immersed in the solution to be tested for 10 minutes and then taken out, placed on a clean glass plate and air-dried naturally to obtain the reacted test paper PP corresponding to the solution to be tested;
  • Step 3.2 Fluorescence detection environment verification: place the reacted test paper PP under a light source with a wavelength of 365nm to observe the color C_CQDs' corresponding to the carbon quantum dot distribution area 3. If C_CQDs' is compared with the reference of the standard colorimetric card The color of the channel corresponding to the excitation color printing area 7 is different, then by verifying the luminous intensity of the light source and adjusting the distance between the reacted test paper PP and the light source, the color C_CQDs' is consistent with the excitation color corresponding to the reference channel of the standard colorimetric card ;
  • Step 3.3 Colorimetric reading of mercury ion content: Observe the copper nanocluster distribution area 4 of the reaction test paper PP with the eyes. After the verification in step 3.2, the corresponding color signal C_CuNCs' in the fluorescence detection environment, and from the standard colorimetric card The standard mercury ion sample corresponding to the excitation color marking area 10 searches for the standard mercury ion sample with the closest color signal C_CuNCs' corresponding to the excitation color printing unit 11, then the standard mercury ion sample corresponds to the excitation color printing unit 11 and the standard mercury ion sample concentration is printed above the printing unit 11. The number in cell 9 is the concentration of mercury ions in the crab.
  • the results of the detection of crab mercury ions by the national standard method inductively coupled plasma-mass spectrometry (ICP-MS), dual-channel fluorescence test paper method, and single-channel fluorescence test paper method are shown in Table 1. It can be seen from Table 1 that, compared with the detection result corresponding to the single-channel fluorescent test paper, the detection result corresponding to the dual-channel fluorescent test paper is closer to the detection result of the national standard method.
  • the above detection results show that the reference channel of the test paper in the present invention can effectively verify the environmental parameters of fluorescence detection and improve the detection accuracy of mercury ions.

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Abstract

食品安全检测技术领域的一种检测汞离子的荧光试纸及检测方法；首先制备了一种检测汞离子的荧光试纸，荧光试纸包括荧光显色区域和标准荧光比色卡，以标准比色卡中参比通道对应激发颜色为参照，同时观察荧光试纸碳量子点分布区域（3）对应的颜色来校验荧光试纸检测时的荧光检测环境。汞离子含量比色检测时，从标准比色卡内与荧光试纸铜纳米簇分布区域（4）颜色信号最接近的标准汞离子样品对应激发颜色来检测Hg2+的浓度。试纸和检测方法可以缩小荧光试纸测试时与汞离子标准样品响应通道标准颜色检测时的荧光检测环境差异，从而减少荧光检测环境差异对汞离子比色检测的影响。

Description

一种检测汞离子的荧光试纸及检测方法 技术领域
本发明属于食品安全检测技术领域，具体涉及一种检测汞离子的荧光试纸及检测方法。
背景技术
汞是一种剧毒重金属，通过食物链传递，在人体内代谢缓慢，易引起蓄积中毒，影响脑细胞的功能。目前，汞离子(Hg 2+)检测方法主要有原子吸收光谱法(AAS)、电感耦合等离子质谱法(ICP-MS)、电化学法等，这些方法检测灵敏度高，结果准确，但是检测过程繁琐、操作复杂且仪器设备价格高，需要在实验室条件下进行，难以满足现场快速检测和日常检测的需求。鉴于汞离子对人体造成的危害，以及现有检测方法的不足，开发一种快速便捷检测食品中汞离子含量的方法具有很重要的现实意义。
近年来，现有的汞离子荧光探针检测方法具有两方面的不足，一是采用的纳米材料比较昂贵，合成过程繁琐；二是需要专门的仪器来获取响应通道和参比通道的荧光信号，硬件成本高，操作复杂。
发明内容
为了克服现有方法的不足之一，本发明提供了一种基于铜纳米簇(CuNCs)-碳量子点(CQDs)的食品中汞离子荧光试纸及检测方法，可实现食品中汞离子的低成本、快速检测。
为实现上述发明目的，本发明采用的技术方案如下：
本发明首先提供一种检测汞离子的荧光试纸，所述荧光试纸包括荧光显色区域，所述荧光显色区域包括碳量子点分布区域和铜纳米簇分布区域；其中所述碳量子点分布区域浸渍有碳量子点荧光探针，用于环境校验；所述铜纳米簇分布区域浸渍有铜纳米簇荧光探针，用于检测汞离子浓度。
所述碳量子点分布区域和铜纳米簇分布区域的面积比为1:1。
所述荧光试纸还包括试纸手持区域。
所述试纸手持区域、碳量子点分布区域和铜纳米簇分布区域由T型分界线分隔开。
进一步的，所述荧光试纸还包括标准荧光比色卡，所述标准荧光比色卡包括参比通道区域，所述参比通道区域包括参比通道激发波长打印区域和参比通道对应激发颜色打印区域。所述标准荧光比色卡还包括标准汞离子样品浓度区域，所述标准汞离子样品浓度区域包括标准汞离子样品浓度标识区域、标准汞离子样品对应激发颜色标识区域和标准汞离子浓度单位标识区域。
其中，所述标准汞离子样品浓度标识区域包含多个标准汞离子样品浓度打印 单元；所述标准汞离子样品对应激发颜色标识区域包含多个标准汞离子样品对应激发颜色打印单元。
所述荧光显色区域和标准荧光比色卡位于同一试纸上或分别独立设置。
所述荧光试纸包括多个显色区域。
本发明还提供的一种检测汞离子的荧光试纸制备方法，所述方法包括如下步骤：
荧光试纸的制备：在空白试纸上形成碳量子点分布区域和铜纳米簇分布区域，所述碳量子点分布区域分布有用于环境校验的碳量子点荧光探针，所述铜纳米簇分布区域分布有用于检测汞离子浓度的铜纳米簇荧光探针。
响应通道/参比通道标准颜色获取：配制多份不同Hg 2+浓度的Hg 2+标准样品；在每份Hg 2+标准样品中分别浸入荧光试纸保持数分钟后取出，得到多个反应后的试纸；分别采集反应后的试纸在预设光源光照条件下的RGB图像；提取碳量子点分布区域在RGB图像中的对应颜色信号，并将所述颜色信号取均值后记为参比通道对应的标准颜色；提取铜纳米簇分布区域在RGB图像中的对应颜色信号，得到不同Hg 2+浓度的Hg 2+标准样品对应的响应通道标准颜色。
打印标准荧光比色卡区域：将预设光源光照条件、参比通道对应的标准颜色、Hg 2+标准样品对应的多个Hg 2+浓度、标准汞离子浓度单位、Hg 2+标准样品对应的响应通道标准颜色打印在标准荧光比色卡区域内。
具体的，所述打印具体操作为：
将预设光源光照条件“激发波长W 1nm”打印在参比通道激发波长打印区域内，将参比通道对应的标准颜色C_ CQDs打印在参比通道对应激发颜色打印区域内；将n个Hg 2+标准样品S 1,S 2,……,S n-1，S n对应的Hg 2+浓度依次打印在标准汞离子样品浓度标识区域内对应的标准汞离子样品浓度打印单元内，将标准汞离子浓度单位打印在标准汞离子浓度单位标识区域内；将n个Hg 2+标准样品S 1,S 2,……,S n-1,S n对应的响应通道标准颜色C_ CuNCs_ 1,C_ CuNCs_ 2,……,C_ CuNCs_ n-1,C_ CuNCs_ n依次打印在标准汞离子样品对应激发颜色标识区域内对应的标准汞离子样品对应激发颜色打印单元内。
其中，n＞0且为正整数，W 1为特定激发波长，W 1大于0且为正整数；优选的，所述W 1nm为365nm。
本发明还提供一种汞离子的检测方法，所述方法包括如下步骤：
荧光试纸反应：将荧光试纸浸入待测溶液保持数分钟后取出，放置在干净玻璃板上自然风干，得到待测溶液对应的已反应试纸PP。
荧光检测环境校验：将已反应试纸PP置于波长为W 1nm的光源下观察碳量 子点分布区域(3)对应的颜色C_ CQDs’，若C_ CQDs’与标准比色卡参比通道对应激发颜色打印区域(7)的颜色C_ CQDs有差异，则通过校验光源的发光强度及调节已反应试纸PP与光源之间的距离使得颜色C_ CQDs’与C_ CQDs一致；优选的，W 1nm为365nm。
汞离子含量比色读取：观察反应试纸PP的铜纳米簇分布区域(4)在经过校验后的荧光检测环境下对应的颜色信号C_ CuNCs’，并从标准荧光比色卡的标准汞离子样品对应激发颜色标识区域(10)内寻找与颜色信号C_ CuNCs’最接近的标准汞离子样品对应激发颜色打印单元(11)，则该标准汞离子样品对应激发颜色打印单元(11)上方标准汞离子样品浓度打印单元(9)内的数字为Hg 2+的浓度。
本发明的有益效果：
本发明方案利用标准比色卡中参比通道对应激发颜色为参照，观察碳量子点分布区域对应的颜色来校验荧光试纸检测时的荧光检测环境，可以缩小荧光试纸测试时与汞离子标准样品响应通道标准颜色检测时的荧光检测环境差异，从而减少荧光检测环境差异对汞离子荧光试纸比色检测的影响。
基于比率型荧光探针的汞离子检测法因其检测精度高、抗环境干扰能力强等优点而备受关注。比率型荧光探针具有双发射荧光信号通道(响应通道和参比通道)，其中响应通道的信号强度与待测物的浓度相关，而参比通道的信号强度与待测物浓度无关，仅与影响待测物荧光信号强度的环境因素有关。参比通道的校正功能可有效降低因环境因素对检测结果的干扰，从而获得比单通道荧光探针(单发射荧光探针)更精确的检测结果。
附图说明
图1为本发明检测汞离子的荧光试纸一较佳实施例的结构示意图；
图2为图1所示荧光试纸的标准荧光比色卡的结构示意图；
图3为实施例中制备的标准荧光比色卡。
图中，1为试纸手持区域，2为T型分界线，3为碳量子点分布区域，4为铜纳米簇分布区域；5为比色卡手持区域，6为参比通道激发波长打印区域，7为参比通道对应激发颜色打印区域，8为标准汞离子样品浓度标识区域，9为标准汞离子样品浓度打印单元，10为标准汞离子样品对应激发颜色标识区域，11为标准汞离子样品对应激发颜色打印单元，12为标准汞离子浓度单位标识区域。
具体实施方案
以下通过各实施方式对本发明进行详细描述。但这些实施例仅用于说明本发明而不用于限制本发明的范围。此外，在阅读本发明所述的内容之后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1：一种检测汞离子的荧光试纸及制备方法
步骤一、荧光试纸制备包括空白试纸制备、荧光探针制备以及荧光探针浸染三个步骤；
步骤1.1空白试纸制备:取空白的中性滤纸(不含荧光)大小为3×4cm，所述滤纸荧光显色区域，所述荧光显色区域包括碳量子点分布区域3和铜纳米簇分布区域4。所述碳量子点分布区域3浸渍有碳量子点荧光探针，用于环境校验；所述铜纳米簇分布区域4浸渍有铜纳米簇荧光探针，用于检测汞离子浓度。
所述试纸还包括手持区域1、碳量子点分布区域3和铜纳米簇分布区域4由T型分界线2分隔开。其中碳量子点分布区域和铜纳米簇分布区域的面积比为1:1
步骤1.2.荧光探针制备：包括碳量子点s荧光探针的制备和铜纳米簇荧光探针的制备。
碳量子点s荧光探针的制备方法为：取1mL质量分数为30％的蔗糖水溶液、0.2mL质量分数为98％的浓硫酸和6mL分子量为200的聚乙二醇，混合搅拌后置于微波炉中加热15s后，得到碳量子点溶液，并用透析袋(1000D)在去离子水中透析24h纯化，得到激发波长为365nm发射波长为550nm且对汞离子无荧光响应的碳量子点荧光探针。
铜纳米簇荧光探针的制备方法为取32mg CuSO 4加入到20g水中，加入2mL的NaOH溶液(0.5M)以及20mL抗坏血酸溶液(0.1M)，在pH调节至8.0～9.0、温度为50℃条件下水浴搅拌15h后得到铜纳米簇溶液原液，用透析袋(1000D)在去离子水中透析24h纯化，得到激发波长为365nm发射波长为445nm且对汞离子有荧光响应的铜纳米簇荧光探针；
步骤1.3.荧光探针浸染：将步骤1.1所制备的空白试纸的碳量子点分布区域3浸入步骤1.2所制备的碳量子点荧光探针溶液并保持10分钟后取出；将步骤1.1所制备的空白试纸的铜纳米簇分布区域4浸入步骤1.2所制备的铜纳米簇荧光探针溶液并保持10分钟后取出；随后将经过荧光探针浸染的空白试纸放置在干净玻璃板上自然风干，得到荧光试纸P。
步骤二、标准荧光比色卡制备：包括比色卡设计、响应通道/参比通道标准颜色获取、以及标准荧光比色卡打印三个过程；
步骤2.1.比色卡设计：所述比色卡包括比色卡手持区域5、参比通道区域和标准汞离子样品浓度区域，所述参比通道区域包括参比通道激发波长打印区域6和参比通道对应激发颜色打印区域7；所述标准汞离子样品浓度区域包括标准汞离子样品浓度标识区域8、标准汞离子样品对应激发颜色标识区域10和标准汞离子浓度单位标识区域12，其中标准汞离子样品浓度标识区域8包含10个标准汞离子样品浓度打印单元9，标准汞离子样品对应激发颜色标识区域10包含10个标准汞离子样品对应激发颜色打印单元11；标准汞离子样品对应激发颜色打印单元11内的颜色及其标准汞离子样品浓度打印单元9内的数字分别对应同一标准汞离子样品的激发颜色和汞离子浓度。
步骤2.2.响应通道/参比通道标准颜色获取方法为：
(1)配置10个浓度梯度Q 1,Q 2,……,Q 9,Q 10分别为0,0.1,0.2,0.3,0.4,0.5,0.7,0.9,1.1和1.3mg/kg的Hg 2+标准溶液S 1,S 2,……,S 9,S 10；
(2)将10片步骤一制备得到的荧光试纸P 1,P 2,……,P 9,P 10分别浸入Hg 2+标准溶液S 1,S 2,……,S 9,S 10并保持10分钟后取出，放置在干净玻璃板上自然风干，得到10张与Hg 2+标准溶液反应后的试纸P’ 1,P’ 2,……,P’ 9,P’ 10；
(3)利用相机采集10张已反应试纸P’ 1,P’ 2,……,P’ 9,P’ 10在365nm光源光照条件下的RGB图像I 1,I 2,……,I 9,I 10；
(4)提取碳量子点分布区域3在10张已反应试纸图像I 1,I 2,……,I 9,I 10对应的RGB信号[235 242 20]，[229 238 18]，[236 236 14]，[230 245 15]，[233 240 18]，[232 235 20]，[238 234 16]，[237 238 15]，[239 243 19]，[230 239 16]，将上述颜色值，取均值后记为参比通道对应的标准颜色[234 239 17]；提取铜纳米簇分布区域4在10张已反应试纸图像I 1,I 2,……,I 9,I 10对应的RGB信号，得到10个Hg 2+标准溶液浓度0,0.1,0.2,0.3,0.4,0.5,0.7,0.9,1.1和1.3mg/kg对应的响应通道标准颜色[21 87 242]，[123 160 255]，[76 158 235]，[55 176 228]，[85 197 226]，[111 201 236]，[129 226 214]，[113 220 185]，[109 209 134]，[211 218 73]；
步骤2.3.标准荧光比色卡制备和打印为：利用彩色打印机将“激发波长365nm”字样打印在参比通道激发波长打印区域6，将参比通道对应的标准颜色RGB＝[234 239 17]打印在参比通道对应激发颜色打印区域7，将10个Hg 2+标准样品S 1,S 2,……,S n-1,S n对应的Hg 2+浓度0,0.1,0.2,0.3,0.4,0.5,0.7,0.9,1.1和1.3mg/kg从左至右依次打印在标准汞离子样品浓度标识区域8内的10个标准汞离子样品浓度打印单元9内，将标准汞离子浓度单位“汞离子浓度mg/kg”打印在标准汞离子浓度单位标识区域12内；将10个Hg 2+标准样品S 1,S 2,……,S n-1,S n对应的响应通道标准颜色RGB＝[21 87 242]，[123 160 255]，[76 158 235]，[55 176 228]，[85 197 226]，[111 201 236]，[129 226 214]，[113 220 185]，[109 209 134]，[211 218 73]从左至右依次打印在标准汞离子样品对应激发颜色标识区域10内的10个标准Hg 2+样品对应激发颜色打印单元11内。
由以上制备得到的荧光试纸，包括荧光显色区域，所述荧光显色区域包括碳量子点分布区域3和铜纳米簇分布区域4；所述荧光试纸还包括试纸手持区域1。
所述荧光试纸还包括标准荧光比色卡；所述荧光显色区域和标准荧光比色卡位于同一试纸上，或所述荧光显色区域位于荧光试纸上，标准荧光比色卡独立设置。
所述荧光试纸包括多个显色区域。
实施例2：汞离子的检测
食品中Hg 2+比色检测包括荧光试纸反应、荧光检测环境校验、以及汞离子含量比色读取三个过程；
步骤3.1.荧光试纸反应：首先取螃蟹样本(市售)，洗去中华绒鳌蟹体表面污垢，解剖，取肝胰腺、性腺和肌肉，均充分研磨混匀，于冰箱中冷冻保存。取样品1.0g，放入聚四氟乙烯消解罐，并加入4mL硝酸，然后加入2mL过氧化氢，静置过夜，将消解罐置于微波消解仪中，完成消解及赶酸程序，得到螃蟹消化液，将不同浓度的Hg 2+(分别为0.3、0.5和0.8mg/kg)标准溶液，分别加入到预处理后的螃蟹消化液中，得到待测溶液。将实施例2制备得到的荧光试纸浸入待测溶液保持10分钟后取出，放置在干净玻璃板上自然风干，得到待测溶液对应的已反应试纸PP；
步骤3.2.荧光检测环境校验：将已反应试纸PP置于波长为365nm的光源下眼睛观察碳量子点分布区域3对应的颜色C_ CQDs’，若C_ CQDs’与标准比色卡参的参比通道对应激发颜色打印区域7的颜色有差异，则通过校验光源的发光强度及调节已反应试纸PP与光源之间的距离使得颜色C_ CQDs’与标准比色卡参比通道对应的激发颜色一致；
步骤3.3.汞离子含量比色读取：用眼睛观察反应试纸PP的铜纳米簇分布区域4在经过步骤3.2校验后荧光检测环境下对应的颜色信号C_ CuNCs’，并从标准比色卡的标准汞离子样品对应激发颜色标识区域10内寻找颜色信号C_ CuNCs’最接近的标准汞离子样品对应激发颜色打印单元11，则该标准汞离子样品对应激发颜色打印单元11上方标准汞离子样品浓度打印单元9内的数字为螃蟹中汞离子浓度。国标法电感耦合等离子体-质谱法(ICP-MS)、双通道荧光试纸法以及单通道荧光试纸法对螃蟹汞离子的检测结果如表1所示。由表1可以看出，与单通道荧光试纸对应的检测结果相比，双通道荧光试纸对应的检测结果与国标法检测结果更为接近。上述检测结果表明，本发明中试纸的参比通道可以有效校验荧光检测环境参数，提高对汞离子的检测精度。
表1.不同检测方法对应的螃蟹中Hg2+测定结果比较(mg/kg)
样品编号 ICP-MS检测结果 双通道荧光试纸* 单通道荧光试纸**
1 0.34 0.3 0.4
2 0.52 0.5 0.5
3 0.83 0.8 0.9
*本发明所述的基于铜纳米簇-碳量子点的汞离子荧光试纸
**仅包含铜纳米簇的汞离子荧光试纸

Claims (14)

  1. 一种检测汞离子的荧光试纸，其特征在于，所述荧光试纸包括荧光显色区域，所述荧光显色区域包括碳量子点分布区域(3)和铜纳米簇分布区域(4)；其中所述碳量子点分布区域(3)分布有碳量子点荧光探针，用于环境校验；所述铜纳米簇分布区域(4)分布有铜纳米簇荧光探针，用于检测汞离子浓度。
  2. 根据权利要求1所述的一种检测汞离子的荧光试纸，其特征在于，所述荧光试纸还包括试纸手持区域。
  3. 根据权利要求2所述的一种检测汞离子的荧光试纸，其特征在于，所述试纸手持区域、碳量子点分布区域和铜纳米簇分布区域由T型分界线分隔开。
  4. 根据权利要求1所述的一种检测汞离子的荧光试纸，其特征在于，所述碳量子点分布区域(3)和铜纳米簇分布区域(4)的面积比为1:1。
  5. 根据权利要求1所述的一种检测汞离子的荧光试纸，其特征在于，还包括标准荧光比色卡，所述标准荧光比色卡包括参比通道区域，所述参比通道区域包括参比通道激发波长打印区域(6)和参比通道对应激发颜色打印区域(7)。
  6. 根据权利要求5所述的一种检测汞离子的荧光试纸，其特征在于，还包括标准汞离子样品浓度区域，所述标准汞离子样品浓度区域包括标准汞离子样品浓度标识区域(8)、标准汞离子样品对应激发颜色标识区域(10)和标准汞离子浓度单位标识区域(12)。
  7. 根据权利要求6所述的一种检测汞离子的荧光试纸，其特征在于，所述标准汞离子样品浓度标识区域(8)包含多个标准汞离子样品浓度打印单元(9)。
  8. 根据权利要求6所述的一种检测汞离子的荧光试纸，其特征在于，所述标准汞离子样品对应激发颜色标识区域(10)包含多个标准汞离子样品对应激发颜色打印单元(11)。
  9. 根据权利要求5所述的一种检测汞离子的荧光试纸，其特征在于，所述荧光显色区域和标准荧光比色卡位于同一试纸上或分别独立设置。
  10. 根据权利要求1所述的一种检测汞离子的荧光试纸，其特征在于，所述荧光试纸包括多个显色区域。
  11. 一种如权利要求1至10任一所述荧光试纸的制备方法，其特征在于，包括：在空白试纸上形成碳量子点分布区域和铜纳米簇分布区域，所述碳量子点分布区域分布有用于环境校验的碳量子点荧光探针，所述铜纳米簇分布区域分布有用于检测汞离子浓度的铜纳米簇荧光探针。
  12. 根据权利要求11所述的制备方法，其特征在于，还包括获取响应通道/参比通道标准颜色，具体包括：
    配制多份不同Hg 2+浓度的Hg 2+标准样品；
    在每份Hg 2+标准样品中分别浸入荧光试纸保持数分钟后取出，得到多个反应后的试纸；
    分别采集反应后的试纸在预设光源光照条件下的RGB图像；
    提取碳量子点分布区域在RGB图像中的对应颜色信号，并将所述颜色信号取均值后记为参比通道对应的标准颜色；
    提取铜纳米簇分布区域在RGB图像中的对应颜色信号，得到不同Hg 2+浓度的Hg 2+标准样品对应的响应通道标准颜色。
  13. 根据权利要求11所述的制备方法，其特征在于，还包括在所述打印标准荧光比色卡区域，具体包括：
    将预设光源光照条件、参比通道对应的标准颜色、Hg 2+标准样品对应的多个Hg 2+浓度、标准汞离子浓度单位、Hg 2+标准样品对应的响应通道标准颜色打印在标准荧光比色卡区域内。
  14. 一种应用权利要求1至10任一所述荧光试纸检测汞离子的方法，其特征在于，所述方法包括如下步骤：
    荧光试纸反应：将荧光试纸浸入待测溶液保持数分钟后取出，放置在干净玻璃板上自然风干，得到待测溶液对应的已反应试纸PP；
    荧光检测环境校验：将已反应试纸PP置于预设光源下观察碳量子点分布区域(3)对应的颜色C_ CQDs’，环境校验使得C_ CQDs’与标准比色卡参比通道对应激发颜色打印区域(7)的颜色C_ CQDs一致；
    汞离子含量比色读取：观察反应试纸PP的铜纳米簇分布区域(4)在经过校验后的荧光检测环境下的颜色信号C_ CuNCs’，对应标准比色卡的标准汞离子样品对应激发颜色标识区域(10)内与颜色信号C_ CuNCs’最接近的标准汞离子样品对应激发颜色打印单元(11)，则该标准汞离子样品对应激发颜色打印单元(11)上方标准汞离子样品浓度打印单元(9)内的数字为Hg 2+的浓度。
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