WO2020087835A1 - 基于双发射量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法 - Google Patents

基于双发射量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法 Download PDF

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WO2020087835A1
WO2020087835A1 PCT/CN2019/078075 CN2019078075W WO2020087835A1 WO 2020087835 A1 WO2020087835 A1 WO 2020087835A1 CN 2019078075 W CN2019078075 W CN 2019078075W WO 2020087835 A1 WO2020087835 A1 WO 2020087835A1
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carbon quantum
quantum dots
silver nanoparticles
cymoxanil
solution
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French (fr)
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桂日军
姜晓文
金辉
孙玉娇
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青岛大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • 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"
    • G01N2021/6432—Quenching
    • 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 preparation of nanomaterials and fluorescent probes, and in particular relates to a preparation method of a fructocyanide ratio fluorescent probe based on a dual-emission quantum dot / silver nanoparticle composite, and the prepared probe can be used for frost urea Efficient detection of cyanide.
  • Cymoxanil is a highly effective, low-toxic fungicide, which is widely used in the preservation and storage of vegetables and fruits such as cucumbers, grapes, tomatoes, and litchi. Cream urea cyanide is usually mixed with other pesticides to enhance the efficacy of pesticides.
  • the human body ingests nutrients from vegetables and fruits every day to meet the needs of the body. Residual pesticides in fruits and vegetables can cause harm to human health. A small amount of residual pesticides will degrade itself and will not cause acute poisoning, but long-term consumption of agricultural products with residual pesticides that have not been cleaned will cause serious harm to human health. Cymoxanil is widely used in fruits and vegetables, and its residue is easily detected in the peel.
  • Pesticide residues can be dispersed in water bodies by means of volatilization, runoff, leaching, etc.
  • Xerocarbazide is also highly toxic to aquatic organisms and will have long-term adverse effects on the water environment.
  • the maximum amount of cream cyanuramide added is 0.05 mg / kg. Excessive intake of cream cyanuramide in the human body will cause a decline in the body's immunity, increase the burden on the liver, and cause gastrointestinal diseases. Cause cancer. Unreasonable addition of cymoxanil can cause a series of safety problems, therefore, quantitative detection of cymoxanil is of great significance.
  • Anne-Claire et al Used three chromatographic methods to detect Pesticide residues in raspberries and lettuce: Extension and comparision of three chromatographic methods: HPLC, HPTLC and GC, Anne-Claire Martel, Maurice Porthault, J. LIQ., CHROM . & REL.TECHNOL., 2000,23, 3043–3058); Matt J. et al. Used gas chromatography to detect the development of a Gas Chromatographic Method for Fungicide Cymoxanil Analysis in Dried Hops, Matt J. Hengel, Takayuki Shibamoto , J. Agric. Food Chem., 2001, 49, 570–573); Hulya Mercan et al.
  • Fluorescence analysis is an instrumental analysis method for substance identification and content determination based on the position and intensity of the fluorescence spectrum of a specific substance. This method has many advantages such as high sensitivity, high selectivity, and easy operation. In terms of pesticide detection, the fluorescence analysis method has the advantages of high analysis sensitivity, good selectivity, and easy operation. In the current report on fluorescence detection of pesticides, the interaction between fluorescent quantum dots and pesticides is mainly used to cause changes in quantum dot fluorescence intensity to detect pesticides. This method relies on a single fluorescent signal output mode. A single fluorescent signal detection method is susceptible to factors such as background fluorescence, reagents, system, and environmental conditions, resulting in unstable results.
  • the signal intensity ratio obtained by dual-signal ratio processing can have a self-calibration function, which effectively eliminates the interference between the self and the background signal, and improves the accuracy and reliability of the detection results.
  • the present invention has designed a novel ratio fluorescent probe method based on the dual-emission quantum dot / silver nanoparticle composite, which is used for the efficient detection of frost cyanide. Till now, there are no domestic and foreign literatures and patents that use the ratio fluorescent probe method to detect fruccarbamide, and the ratio fluorescent probe based on the dual emission quantum dot / silver nanoparticle composite to detect fruccarbamide.
  • the purpose of the present invention is to overcome the above-mentioned defects in the prior art, and to design a method for preparing a fluorocyanamide ratio fluorescent probe based on a dual-emission carbon quantum dot / silver nanoparticle composite with a simple method, low cost, and high sensitivity.
  • the present invention relates to a preparation process of a fructocyanide ratio fluorescent probe based on a dual-emission carbon quantum dot / silver nanoparticle composite including the following steps:
  • a method for preparing a fluorescent probe based on a double-emission carbon quantum dot / silver nanoparticles composite frost cyanide ratio characterized in that the method specifically includes the following steps:
  • step (1) The silver nanoparticles prepared in step (1) are formulated into an aqueous solution and reacted at room temperature with slow magnetic stirring for 10 minutes to form a homogeneous solution of silver nanoparticles;
  • step (4) To the aqueous solution of carbon quantum dots containing silver nanoparticles prepared in step (4), add fructocyanide, react under magnetic stirring for 20 minutes to form a homogenous solution, and measure the homogenous solution under different molar concentrations of fructocyanide
  • the fluorescence emission spectrum of medium-carbon quantum dots was fitted to the linear relationship between the intensity ratio of the two fluorescence emission peaks of carbon quantum dots and the molar concentration of fenvalin cyanide, and a ratio fluorescence probe for the detection of fenvalin cyanide was constructed.
  • the size of the silver nanoparticles in the step (1) involved in the present invention is 5-20 nanometers, the volume of silver nitrate is 100-500 microliters, and the volume of trisodium citrate is 100-500 microliters; step (2)
  • the size of the carbon quantum dots described in is 1-10 nm;
  • the mass concentration of the silver nanoparticles described in step (3) is 0.1-1.0 ⁇ g / ml;
  • the carbon quantum dots described in step (4) are formulated into aqueous solutions
  • the mass concentration is 0.1-1.0 ⁇ g / ml, the silver nanoparticles concentration is 0.01-0.2 ⁇ g / ml, and the mass concentration ratio of carbon quantum dots to silver nanoparticles is 1: 5-5: 1; described in step (5)
  • the mass concentration ratio of the carbon quantum dot solution containing silver nanoparticles to cymoxanil is 1: 5 ⁇ 5: 1, the linear detection range of the molar concentration of cymoxan
  • the present invention adopts an internal filtering effect between the dual-emission carbon quantum dots and the dispersed silver nanoparticles, which causes the blue fluorescence of the carbon quantum dots to quench, and the frost cyanide and silver nanoparticles are specific
  • the combination results in the aggregation of silver nanoparticles, and an internal filtering effect occurs between the dual-emission carbon quantum dots and the dispersed silver nanoparticles, causing the green fluorescence of the carbon quantum dots to quench.
  • FIG. 1 is a schematic diagram of the principle of preparation of a fructocyanide ratio fluorescent probe based on a dual-emission carbon quantum dot / silver nanoparticle composite and detection of the fructocyanide ratio fluorescent probe;
  • Fig. 2 is the response of the fluorescent probe of cymoxanil ratio according to the present invention to the two fluorescent emission peak intensity signals of the double-emission carbon quantum dots as the molar concentration of cymoxanil increases, and the ratio of the intensity ratio of the fluorescence peak to the molar concentration of cymoxanil Linear relationship.
  • the invention relates to the preparation of a creamy cyanurate ratio fluorescent probe based on a dual-emission carbon quantum dot / silver nanoparticle composite and the detection of a creamy cyanide ratio fluorescent signal.
  • the preparation process and principle schematic diagram are shown in FIG. 1, The specific process steps are:
  • Preparation of silver nanoparticles prepare 100 mmol / L silver nitrate, 250 mmol / L trisodium citrate and 5 mmol / L sodium borohydride, add the prepared silver nitrate and trisodium citrate to In 100 ml of double-distilled water, add 1 ml of sodium borohydride solution under magnetic stirring. After stirring and reacting for 30 minutes, a yellow solution is obtained. This solution is centrifuged, washed with ethanol and vacuum-dried at low temperature to obtain silver nanoparticles and prepared silver. The nanoparticles are stored at 4 ° C protected from light for subsequent experiments.
  • Preparation of carbon quantum dots Add 54.5 mg of 3-aminophenol and 32.0 mg of oxalic acid to 50 ml of double-distilled water, mix evenly under magnetic stirring, and then react under heating in a water bath to obtain a transparent homogeneous mixed solution. Transfer to a high-pressure reaction kettle and heat at 180 ° C for 12 hours. After the reaction is completed, cool the product solution to room temperature, and use a 0.22 ⁇ m filter to remove large particles of impurities. Then, freeze-drying treatment is carried out until all the water is distilled off, and the prepared carbon quantum dot powder is stored at room temperature for further use.
  • the prepared silver nanoparticles with an average size of 5 nanometers were formulated into an aqueous solution, and reacted at room temperature with slow magnetic stirring for 10 minutes to form a homogeneous solution of silver nanoparticles.
  • the prepared carbon quantum dots with an average size of 2 nanometers were prepared To form an aqueous solution, add silver nanoparticle solution under slow magnetic stirring at room temperature, configure carbon quantum dot solutions containing different silver nanoparticle concentrations, react under magnetic stirring for 20 minutes to form a homogeneous solution, and determine the concentration of different silver nanoparticles.
  • the fluorescence emission spectrum of carbon quantum dots fits the linear relationship between the intensity ratio of the two fluorescence emission peaks of carbon quantum dots and the concentration of silver nanoparticles, where the mass concentrations of silver nanoparticles and carbon quantum dots are 0.1 to 0.5 micrograms / Ml and 0.01 ⁇ 0.1 ⁇ g / ml.
  • fructocyanide To the prepared aqueous solution of silver nanoparticles containing carbon quantum dots, add fructocyanide, react under magnetic stirring for 20 minutes to form a homogeneous solution, and measure the fluorescence emission of carbon quantum dots in the homogeneous solution under different molar concentrations of fructocyanide.
  • Example 2 the specific process steps for preparing silver nanoparticles and carbon quantum dots are the same as in Example 1.
  • the volume and amount of added silver nitrate and trisodium citrate are increased compared with Example 1.
  • the average size of the prepared particles is 10 nm.
  • the silver nanoparticles were formulated into an aqueous solution and reacted at room temperature with slow magnetic stirring for 10 minutes to form a homogeneous solution of silver nanoparticles.
  • the prepared carbon quantum dots with an average size of 5 nm were formulated into an aqueous solution and stirred slowly at room temperature with slow magnetic force Next, add silver nanoparticle solution, configure carbon quantum dot solutions containing different silver nanoparticle concentrations, react under magnetic stirring for 20 minutes to form a homogeneous solution, and measure the fluorescence emission spectrum of carbon quantum dots under different silver nanoparticle concentrations.
  • the fluorescence emission spectrum of carbon quantum dots in a homogeneous solution is fitted to the linear relationship between the intensity ratio of the two fluorescence emission peaks of carbon quantum dots and the molar concentration of cymoxanil to construct a ratio fluorescence for the detection of cymoxanil Probe, to measure the fluorescence emission spectrum of carbon quantum dots at different molar concentrations of cymoxanil, fitting the linear relationship between the intensity ratio of two fluorescence emission peaks I 425 / I 525 and the concentration of cymethrin C CYM
  • the concentration range is 0.02 to 0.5 micromole / liter, and the detection limit of cymoxanil is 0.01 micromole / liter.
  • Example 2 the specific process steps for preparing silver nanoparticles and carbon quantum dots are the same as in Example 1.
  • the volume and amount of added silver nitrate and trisodium citrate are increased compared with Example 1.
  • the average size of the prepared particles is 15 nm.
  • the silver nanoparticles were formulated into an aqueous solution and reacted at room temperature with slow magnetic stirring for 10 minutes to form a homogeneous solution of silver nanoparticles.
  • the prepared carbon quantum dots with an average size of 8 nanometers were formulated into an aqueous solution and stirred slowly at room temperature with slow magnetic force Next, add silver nanoparticle solution, configure carbon quantum dot solutions containing different silver nanoparticle concentrations, react under magnetic stirring for 20 minutes to form a homogeneous solution, and measure the fluorescence emission spectrum of carbon quantum dots under different silver nanoparticle concentrations.
  • the fluorescence emission spectrum of carbon quantum dots in a homogeneous solution is fitted to the linear relationship between the intensity ratio of the two fluorescence emission peaks of carbon quantum dots and the molar concentration of cymoxanil to construct a ratio fluorescence for the detection of cymoxanil Probe, to measure the fluorescence emission spectrum of carbon quantum dots at different molar concentrations of cymoxanil, fitting the linear relationship between the intensity ratio of two fluorescence emission peaks I 425 / I 525 and the concentration of cymethrin C CYM
  • the concentration range is from 0.05 to 1.0 micromole / liter, and the detection limit of cymoxanil is 0.05 micromole / liter.

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Abstract

本发明属于纳米材料和荧光探针的制备技术领域，具体涉及一种基于双发射量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法。制备出双发射碳量子点和银纳米粒，采用双发射碳量子点和分散的银纳米粒之间发生内滤效应，引起碳量子点的蓝色荧光淬灭，而霜脲氰与银纳米粒发生特异性结合，导致银纳米粒聚集，双发射碳量子点和分散的银纳米粒之间发生内滤效应，引起碳量子点的绿色荧光淬灭。基于此，建立了碳量子点两个荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针。该探针制备工艺简单，制备成本低，产品灵敏度高，可发展成为一种新颖的霜脲氰比率荧光探针，用于农药中霜脲氰的高效检测。

Description

基于双发射量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法 技术领域：
本发明属于纳米材料和荧光探针的制备技术领域，具体涉及一种基于双发射量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法，其制备的探针可用于霜脲氰的高效检测。
背景技术：
霜脲氰是一种高效，低毒的杀菌剂，广泛用于黄瓜、葡萄、蕃茄、荔枝等蔬菜与水果的保鲜和储存中。霜脲氰通常与其它农药混合使用，以加强农药的药效。人体每天从蔬菜水果中摄取营养来满足身体需要，瓜果蔬菜中的残留农药会对人类健康造成危害。少量残留的农药人体自身会降解，不会引起急性中毒，但长期食用没有清洗干净带有残留农药的农产品，会对人体健康带来严重危害。霜脲氰广泛用于水果与蔬菜中，在果皮中极易检测出它的残留。农药残留可通过挥发、径流、淋溶等方式分散在水体中，霜脲氰对水生生物也具有极高的毒性，会对水体环境产生长期的不良影响。在欧盟农残限量标准中，霜脲氰最大加入量为0.05毫克/千克，人体过量摄入霜脲氰会导致身体免疫力下降，加重肝脏负担，导致胃肠道疾病，在严重情况下甚至会导致癌症。不合理添加霜脲氰可引发了一系列的安全问题，因此，对霜脲氰进行定量检测具有重要的意义。
Anne-Claire等采用三种色谱法检测了霜脲氰(Pesticide residues in raspberries and lettuce:Extrection and comparision of three chromatographic methods:HPLC,HPTLC and GC,Anne-Claire Martel,Maurice Porthault,J.LIQ.,CHROM.&REL.TECHNOL.,2000,23, 3043–3058)；Matt J.等利用气相色谱法检测了霜脲氰(Development of a Gas Chromatographic Method for Fungicide Cymoxanil Analysis in Dried Hops,Matt J.Hengel,Takayuki Shibamoto,J.Agric.Food Chem.,2001,49,570–573)；Hulya Mercan等利用溶出伏安法检测了农药中霜脲氰含量(Determination of Cymoxanil Fungicide in Commercial Formulation and Natural Water by Square-wave Stripping Voltammetry,Hulya Mercan,Recai
Figure PCTCN2019078075-appb-000001
Clean-Soil,Air,Water 2010,38,558–564)。在当前检测霜脲氰的方法中，主要使用色谱分析法，如高液相色谱法(HPLC),高效液相色谱-质谱联用法(HPLC-MS)和气相色谱法(GC),其它方法包括超声辅助提取法，微波辅助提取法，红外光谱法(FTIR)等。使用色谱法时存在检测限较差，许多样品的谱线可能会重叠，无法特异性识别。其它方法也存在一些缺陷，如仪器昂贵，成本高，样品预处理复杂，操作要求高等。
荧光分析法是一种依据特定物质的荧光谱线的位置及其强度来进行物质鉴定和含量测定的仪器分析方法。该方法具有高灵敏性，高选择性，操作简便等诸多优点。在农药检测方面，荧光分析法具备分析灵敏度高，选择性好，操作简便等优点。在当前的荧光检测农药报道中，主要利用荧光量子点与农药的相互作用，引起量子点荧光强度变化来检测农药，这种方法依赖于单一荧光信号输出模式。单一荧光信号检测方法，易受到背景荧光、试剂、系统和环境条件等因素的影响，从而导致测定结果的不稳定性。相比而言，采用双信号比值处理获得信号的强度比率，可具备自校准功能，有效消除了自体和背景信号的干扰，提高了检测结果的准确性和可靠性。基于此，本发明设计了一种基于双发射量子点/银纳米粒复合物的新型比率荧光探针方法，用于霜脲氰的高效检测。截 止目前，尚未有采用比率荧光探针方法检测霜脲氰，以及基于双发射量子点/银纳米粒复合物的比率荧光探针来检测霜脲氰的国内外文献和专利的报道。
发明内容：
本发明的目的在于克服上述现有技术存在的缺陷，设计一种方法简单、成本低廉、灵敏度高的基于双发射碳量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法。
为了实现上述目的，本发明涉及的一种基于双发射碳量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备工艺包括以下步骤：
1.一种基于双发射碳量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法，其特征在于，该方法具体包括以下步骤：
(1)银纳米粒的制备：配制100毫摩尔/升的硝酸银，250毫摩尔/升的柠檬酸三钠和5毫摩尔/升的硼氢化钠，将配制好的硝酸银和柠檬酸三钠加入到100毫升二次蒸馏水中，在磁力搅拌下，加入1毫升硼氢化钠溶液，搅拌反应30分钟后得到黄色溶液，将此溶液离心，乙醇洗涤和低温真空干燥处理，得到银纳米粒，制备的银纳米粒在4℃下避光保存，以供后续实验使用；
(2)碳量子点的制备：将54.5毫克3-氨基苯酚和32.0毫克草酸加入到50毫升二次蒸馏水中，在磁力搅拌下混合均匀，然后在水浴加热下反应，得到透明均质混合溶液，将此溶液转移到高压反应釜中，在180℃加热12小时，反应结束后，将产物溶液冷却至室温，用0.22μm滤膜过滤去除大颗粒杂质，滤液经过旋蒸除水，丙酮和乙醇交替洗涤两次，再进行冷冻干燥处理，直至水份全部蒸出，制备的碳量子点粉末在 室温下保存，以供进一步使用；
(3)将步骤(1)制得的银纳米粒配制成水溶液，在室温和缓慢磁力搅拌下反应10分钟，形成银纳米粒均质溶液；
(4)将步骤(2)制得的碳量子点配制成水溶液，在室温和缓慢磁力搅拌下，加入银纳米粒溶液，配置含不同银纳米粒浓度的碳量子点溶液，在磁力搅拌下反应20分钟形成均质溶液，测定不同银纳米粒浓度下，碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与银纳米粒浓度之间的线性关系；
(5)向步骤(4)制得的含银纳米粒的碳量子点水溶液中加入霜脲氰，磁力搅拌下反应20分钟形成均质溶液，测定不同的霜脲氰摩尔浓度下，均质溶液中碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针。
本发明涉及的步骤(1)中所述的银纳米粒尺寸为5～20纳米，硝酸银体积用量为100～500微升，柠檬酸三钠体积用量为100～500微升；步骤(2)中所述的碳量子点尺寸为1～10纳米；步骤(3)中所述的银纳米粒质量浓度为0.1～1.0微克/毫升；步骤(4)中所述的碳量子点配制成水溶液的质量浓度为0.1～1.0微克/毫升，银纳米粒质量浓度为0.01～0.2微克/毫升，碳量子点与银纳米粒的质量浓度比为1:5～5:1；步骤(5)中所述的含有银纳米粒的碳量子点溶液与霜脲氰的质量浓度比为1:5～5:1，霜脲氰摩尔浓度的线性检测范围为0.01～1.0微摩尔/升，霜脲氰摩尔浓度的检测极限为0.01～0.5微摩尔/升。
本发明与现有技术相比，采用双发射碳量子点和分散的银纳米粒之间发生内滤效应，引起碳量子点的蓝色荧光淬灭，而霜脲氰与银纳米粒 发生特异性结合，导致银纳米粒聚集，双发射碳量子点和分散的银纳米粒之间发生内滤效应，引起碳量子点的绿色荧光淬灭。基于此，建立了碳量子点两个荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针；其制备工艺简单，制备成本低，产品灵敏度高，能够发展成为一种新颖的霜脲氰比率荧光探针，用于农药中霜脲氰的高效检测。
附图说明：
图1为本发明涉及的一种基于双发射碳量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备与霜脲氰比率荧光探针检测的原理示意图；
图2为本发明涉及的霜脲氰比率荧光探针随霜脲氰摩尔浓度增大对双发射碳量子点两个荧光发射峰强度信号的响应，以及荧光峰强度比率与霜脲氰摩尔浓度之间的线性关系。
具体实施方式：
下面结合附图并通过具体实施例对本发明进行详细说明。
实施例1：
为本发明涉及的一种基于双发射碳量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备与霜脲氰比率荧光信号检测，其制备工艺与原理示意图如图1所示，其具体工艺步骤为：
银纳米粒的制备：配制100毫摩尔/升的硝酸银，250毫摩尔/升的柠檬酸三钠和5毫摩尔/升的硼氢化钠，将配制好的硝酸银和柠檬酸三钠加入到100毫升二次蒸馏水中，在磁力搅拌下，加入1毫升硼氢化钠溶液，搅拌反应30分钟后得到黄色溶液，将此溶液离心，乙醇洗涤和低温真空干燥处理，得到银纳米粒，制备的银纳米粒在4℃下避光保存， 以供后续实验使用。
碳量子点的制备：将54.5毫克3-氨基苯酚和32.0毫克草酸加入到50毫升二次蒸馏水中，在磁力搅拌下混合均匀，然后在水浴加热下反应，得到透明均质混合溶液，将此溶液转移到高压反应釜中，在180℃加热12小时，反应结束后，将产物溶液冷却至室温，用0.22μm滤膜过滤去除大颗粒杂质，滤液经过旋蒸除水，丙酮和乙醇交替洗涤两次，再进行冷冻干燥处理，直至水份全部蒸出，制备的碳量子点粉末在室温下保存，以供进一步使用。
将制得的平均尺寸为5纳米的银纳米粒配制成水溶液，在室温和缓慢磁力搅拌下反应10分钟，形成银纳米粒均质溶液，将制得的平均尺寸为2纳米的碳量子点配制成水溶液，在室温和缓慢磁力搅拌下，加入银纳米粒溶液，配置含不同银纳米粒浓度的碳量子点溶液，在磁力搅拌下反应20分钟形成均质溶液，测定不同银纳米粒浓度下，碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与银纳米粒浓度之间的线性关系，其中，银纳米粒和碳量子点的质量浓度分别为0.1～0.5微克/毫升和0.01～0.1微克/毫升。
向制得的含银纳米粒的碳量子点水溶液中加入霜脲氰，磁力搅拌下反应20分钟形成均质溶液，测定不同的霜脲氰摩尔浓度下，均质溶液中碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针，在不同霜脲氰摩尔浓度下测定碳量子点荧光发射光谱，拟合两个荧光发射峰强度比率I 425/I 525与霜脲氰浓度C CYM之间的线性关系(参见图2)即I 425/I 525＝0.7180+1.7922C CYM(R 2＝0.9920)，其中霜脲氰浓度范围为0.05～0.50微摩尔/升，霜脲氰检测极限为0.02微摩尔/升。
实施例2：
本实施例中银纳米粒与碳量子点制备的具体工艺步骤同实施例1，其中加入的硝酸银和柠檬酸三钠的体积用量较实施例1有所增加，将制得的平均尺寸为10纳米的银纳米粒配制成水溶液，在室温和缓慢磁力搅拌下反应10分钟，形成银纳米粒均质溶液，将制得的平均尺寸为5纳米的碳量子点配制成水溶液，在室温和缓慢磁力搅拌下，加入银纳米粒溶液，配置含不同银纳米粒浓度的碳量子点溶液，在磁力搅拌下反应20分钟形成均质溶液，测定不同银纳米粒浓度下，碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与银纳米粒浓度之间的线性关系，其中，银纳米粒和碳量子点的质量浓度分别为0.2～0.8微克/毫升和0.02～0.2微克/毫升，向制得的含银纳米粒的碳量子点水溶液中加入霜脲氰，磁力搅拌下反应20分钟形成均质溶液，测定不同的霜脲氰摩尔浓度下，均质溶液中碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针，在不同霜脲氰摩尔浓度下测定碳量子点荧光发射光谱，拟合两个荧光发射峰强度比率I 425/I 525与霜脲氰浓度C CYM之间的线性关系，其中霜脲氰浓度范围为0.02～0.5微摩尔/升，霜脲氰检测极限为0.01微摩尔/升。
实施例3：
本实施例中银纳米粒与碳量子点制备的具体工艺步骤同实施例1，其中加入的硝酸银和柠檬酸三钠的体积用量较实施例1有所增加，将制得的平均尺寸为15纳米的银纳米粒配制成水溶液，在室温和缓慢磁力搅拌下反应10分钟，形成银纳米粒均质溶液，将制得的平均尺寸为8纳米的碳量子点配制成水溶液，在室温和缓慢磁力搅拌下，加入银纳米粒溶 液，配置含不同银纳米粒浓度的碳量子点溶液，在磁力搅拌下反应20分钟形成均质溶液，测定不同银纳米粒浓度下，碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与银纳米粒浓度之间的线性关系，其中，银纳米粒和碳量子点的质量浓度分别为0.5～1.0微克/毫升和0.05～0.2微克/毫升，向制得的含银纳米粒的碳量子点水溶液中加入霜脲氰，磁力搅拌下反应20分钟形成均质溶液，测定不同的霜脲氰摩尔浓度下，均质溶液中碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针，在不同霜脲氰摩尔浓度下测定碳量子点荧光发射光谱，拟合两个荧光发射峰强度比率I 425/I 525与霜脲氰浓度C CYM之间的线性关系，其中霜脲氰浓度范围为0.05～1.0微摩尔/升，霜脲氰检测极限为0.05微摩尔/升。

Claims (6)

  1. 一种基于双发射碳量子点/银纳米粒复合物的霜脲氰比率荧光探针的制备方法，其特征在于，该方法具体包括以下步骤：
    (1)银纳米粒的制备：配制100毫摩尔/升的硝酸银，250毫摩尔/升的柠檬酸三钠和5毫摩尔/升的硼氢化钠，将配制好的硝酸银和柠檬酸三钠加入到100毫升二次蒸馏水中，在磁力搅拌下，加入1毫升硼氢化钠溶液，搅拌反应30分钟后得到黄色溶液，将此溶液离心，乙醇洗涤和低温真空干燥处理，得到银纳米粒，制备的银纳米粒在4℃下避光保存，以供后续实验使用；
    (2)碳量子点的制备：将54.5毫克3-氨基苯酚和32.0毫克草酸加入到50毫升二次蒸馏水中，在磁力搅拌下混合均匀，然后在水浴加热下反应，得到透明均质混合溶液，将此溶液转移到高压反应釜中，在180℃加热12小时，反应结束后，将产物溶液冷却至室温，用0.22μm滤膜过滤去除大颗粒杂质，滤液经过旋蒸除水，丙酮和乙醇交替洗涤两次，再进行冷冻干燥处理，直至水份全部蒸出，制备的碳量子点粉末在室温下保存，以供进一步使用；
    (3)将步骤(1)制得的银纳米粒配制成水溶液，在室温和缓慢磁力搅拌下反应10分钟，形成银纳米粒均质溶液；
    (4)将步骤(2)制得的碳量子点配制成水溶液，在室温和缓慢磁力搅拌下，加入银纳米粒溶液，配置含不同银纳米粒浓度的碳量子点溶液，在磁力搅拌下反应20分钟形成均质溶液，测定不同银纳米粒浓度下，碳量子点的荧光发射光谱，拟合碳量子点两个荧光发射峰强度比率与银纳米粒浓度之间的线性关系；
    (5)向步骤(4)制得的含银纳米粒的碳量子点水溶液中加入霜脲氰，磁力搅拌下反应20分钟形成均质溶液，测定不同的霜脲氰摩尔浓度下，均质溶液中碳量子点的荧光发射光谱，拟合碳量子点两个 荧光发射峰强度比率与霜脲氰摩尔浓度之间的线性关系，构建出用于霜脲氰检测的比率荧光探针。
  2. 如权利要求1所述的方法，其特征是，所述步骤(1)中的银纳米粒尺寸为5～20纳米，硝酸银体积用量为100～500微升，柠檬酸三钠体积用量为100～500微升。
  3. 如权利要求1所述的方法，其特征是，所述步骤(2)中的碳量子点尺寸为1～10纳米。
  4. 如权利要求1所述的方法，其特征是，所述步骤(3)中的银纳米粒质量浓度为0.1～1.0微克/毫升。
  5. 如权利要求1所述的方法，其特征是，所述步骤(4)中的碳量子点配制成水溶液的质量浓度为0.1～1.0微克/毫升，银纳米粒质量浓度为0.01～0.2微克/毫升，碳量子点与银纳米粒的质量浓度比为1:5～5:1。
  6. 如权利要求1所述的方法，其特征是，所述步骤(5)中的含有银纳米粒的碳量子点溶液与霜脲氰的质量浓度比为1:5～5:1，霜脲氰摩尔浓度的线性检测范围为0.01～1.0微摩尔/升，霜脲氰摩尔浓度的检测极限为0.01～0.5微摩尔/升。
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