CN102854183A - Method for detecting melamine through solid-state electrochemiluminescence - Google Patents

Method for detecting melamine through solid-state electrochemiluminescence Download PDF

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CN102854183A
CN102854183A CN201210324102XA CN201210324102A CN102854183A CN 102854183 A CN102854183 A CN 102854183A CN 201210324102X A CN201210324102X A CN 201210324102XA CN 201210324102 A CN201210324102 A CN 201210324102A CN 102854183 A CN102854183 A CN 102854183A
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melamine
ni
nanospheres
mesoporous
ruthenium
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CN201210324102XA
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贾能勤
曹宏梅
胡晓青
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上海师范大学
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Abstract

The invention relates to a method for detecting melamine based on mesoporous silica nanosphere/tris(bipyridyl) ruthenium solid-state electrochemiluminescence. The method is characterized by comprising the following steps: a, preparing mesoporous silica nanospheres; b, preparing a mesoporous silica nanosphere/tris(bipyridyl) ruthenium/Nafion modified electrode; c, detecting melamine by using the mesoporous silica nanosphere/tris(bipyridyl) ruthenium/Nafion modified electrode; and d, adopting an electroluminescence detection device to acquire optical signals produced by an electroluminescence detector, and carrying out a computer data processing to obtain the melamine content. According to the method of the present invention, the mesoporous silicon (mSiO2) material has a large surface area and a large pore volume, and the mesoporous silica nanosphere/tris(bipyridyl) ruthenium/Nafion modified electrode can be effectively used for melamine detection through electrochemiluminescence (ECL).

Description

一种固态电化学发光检测三聚氰胺的方法 A solid state electrochemical luminescence detection method of melamine

技术领域 FIELD

[0001] 本发明涉及一种检测三聚氰胺的方法,具体地说,是一种基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法。 [0001] The present invention relates to a method for detecting melamine, in particular, is based on mesoporous silica nanospheres / Ru terpyridine solid melamine electrochemiluminescent detection method.

背景技术 Background technique

[0002] 电化学发光(electrochemiluminescence, ECL)是通过电化学激发反应产生发光的现象。 [0002] ECL (electrochemiluminescence, ECL) is produced by electrochemical excitation luminescent reaction phenomenon. 近年来,它已经得到了广泛关注由于其线性范围宽,灵敏度高及可控性强等优点.在所有的电化学发光体系中,由于三联吡啶钌具有良好的化学和电化学稳定性,已成为目前应用范围最广和研究最为活跃的ECL体系之一,已被广泛用于检测草酸,烷基胺,NADH、胺和氨基等化合物。 In recent years, it has received wide attention because of its linear range, high sensitivity and controllability and other advantages. In all electrochemiluminescence, since terpyridine ruthenium has good chemical and electrochemical stability, has been one of the most widely used and best studied active ECL system, has been widely used to detect oxalate, alkyl amines, NADH, compounds such as amines and amino.

[0003]三聚氰胺(I, 3,4,6-triamine 5-triazine-2, C3H6N6MEL)是一种人工合成的化学物,主要用于生产氨基树脂、热固性塑料泡沫和化肥。 [0003] melamine (I, 3,4,6-triamine 5-triazine-2, C3H6N6MEL) is a synthetic chemical, mainly for the production of amino resins, thermosetting plastic foam and fertilizers. 近年来,由于其高氮含量出6%),三聚氰胺被非法添加到了食品和饲料中,在蛋白质浓度测试时以提高其蛋白质含量,因此,开发可靠、灵敏的三聚氰胺的检测方法在食品安全领域具有重要意义。 In recent years, due to its high nitrogen content of 6%), melamine illegally added to food and feed, protein concentration when tested to increase the protein content, therefore, to develop a reliable and sensitive method for the detection of melamine having a field of food safety Significance.

[0004] 中国专利CN101975774B于2010年9月18日公开了一种电化学发光检测三聚氰胺的方法,其中将10_3mol/L的三联吡啶钌或104mol/L的钌吩噻嗪以及待测的三聚氰胺样品分别加入到PH值为10的0. IM硼酸盐缓冲溶液中,经扫描电位范围0〜I. 5V进行扫描,用光检测器采集电化学工作站扫描产生的光信号,再经计算机数据处理后得到三聚氰胺样品的含量。 [0004] Chinese Patent CN101975774B on September 18, 2010 discloses a method of electrochemiluminescent detection of melamine, which 10_3mol / L or Ru terpyridine 104mol / L ruthenium phenothiazine each sample to be tested and melamine 0. IM was added to a borate buffer solution of PH value of 10, the scanned potential range 0~I. 5V scanning photodetector collecting light signal generated by scanning electrochemical workstation, and then processing the data obtained by the computer melamine content of the sample. 但是通常在使用溶液相的三联吡啶钌电化学发光检测分析物时,需要不断地向反应体系加入三联吡啶钌,由于其价格昂贵使检测成本颇高,从而限制了三联吡啶钌在电化学发光领域的广泛应用。 However typically used terpyridine ruthenium electrochemiluminescent detection of the analyte solution phase and requires continuous terpyridine ruthenium added to the reaction system, which is expensive because high cost of the detector, thereby limiting the electrochemiluminescent ruthenium terpyridine art the wide range of applications.

[0005] 因此已知的电化学发光检测三聚氰胺的方法存在着上述种种不便和问题。 [0005] Thus electrochemiluminescent detection methods known melamine is present in said inconveniences and problems.

发明内容 SUMMARY

[0006] 本发明的目的,在于提出一种能循环使用三联吡啶钌,且在循环反应中不产生消耗的基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法。 [0006] The object of the present invention is to provide a terpyridine ruthenium can be recycled, and does not produce consumed in the reaction cycle mesoporous silica nanospheres electrochemiluminescent detection method of a solid melamine / terpyridine ruthenium based.

[0007] 为实现上述目的,本发明的技术解决方案是: [0007] To achieve the above object, the technical solution of the invention is:

[0008] 一种基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法,其特征在于包括以下步骤: [0008] A mesoporous silica nanospheres electrochemiluminescent detection method of a solid melamine / Ru terpyridine-based, comprising the steps of:

[0009] a、介孔二氧化硅纳米球的制备 Preparation of a, mesoporous silica nanospheres [0009]

[0010] 将乙醇、水、氨水和十六烷基溴化铵混合搅拌形成均匀的分散液,然后将正硅酸乙酯滴加到分散液中,反应10〜20小时,反应产物经过离心、洗涤、干燥后,将干燥产物在620〜670°C煅烧,即得到介孔二氧化硅纳米球,其粒径为400〜600nm -; [0010] The ethanol, water, ammonia and ammonium bromide, cetyl mixing to form a uniform dispersion, and then the TEOS was added dropwise to the dispersion, 10-20 hours the reaction, the reaction product was centrifuged, washed, dried, the dried product was calcined at 620~670 ° C, to obtain mesoporous silica nanospheres, a particle size of 400~600nm -;

[0011] 分散液pH值为9〜12,其中十六烷基溴化铵含量为0. 002〜0. 003g/ml,正硅酸乙酯与分散液的体积比为0. 002〜0. 003。 [0011] The dispersion pH of 9~12, wherein hexadecyltrimethylammonium bromide content of 0. 002~0. 003g / ml, the volume ratio of the positive dispersion and TEOS 0. 002~0. 003.

[0012] b、介孔二氧化娃纳米球/三联批唳钌/Nafion修饰电极的制备,包含以下步骤:[0013] (I)用2#和5#金相砂纸抛光打磨玻碳电极,再用0. 3和0. 05 i! m的Al2O3抛光粉抛光,冲洗去表面污物; Electrode preparation [0012] b, the mesoporous silica nanospheres baby / ruthenium triple batch Li / Nafion modified, comprising the steps of: [0013] (I) with # 2 and # 5 sandpaper metallographic polished glassy carbon electrodes, and then ! and 0.3 with 0. 05 i m of Al2O3 powder polishing, rinsing dirt to the surface;

[0014] (2)依次在体积比1:1的HNO3溶液、无水乙醇、二次蒸馏水中分别超声I〜2分钟,最后将处理好的电极用高纯N2吹干; [0014] (2) successively in a volume ratio of 1: HNO3 solution 1, absolute ethanol, sonicated in distilled water were I~2 minutes, and finally treated with high purity N2 good dry electrode;

[0015] (3)取6〜IOii L 2mgmL_1的介孔二氧化娃纳米球溶液滴到处理好的玻碳电极上,室温下自然干燥; [0015] (3) take 6~IOii L 2mgmL_1 baby mesoporous silica nanospheres treated solution was dropped on a glass carbon electrode good, natural drying at room temperature;

[0016] (4)将3〜6 ii L0. 5%wtNafion滴加到经步骤(3)处理的玻碳电极表面,然后浸到 [0016] (4) 3~6 ii L0. 5% wtNafion dropwise added in step (3) treatment of the glassy carbon electrode surface, and then immersed

I. OX 10_3M六水合三联吡啶钌(Ru (bpy) 32+)溶液中制备成修饰电极; I. OX 10_3M hexahydrate terpyridine ruthenium (Ru (bpy) 32+) was prepared as a modified electrode;

[0017] C、用介孔二氧化娃纳米球/三联批唳钌/Nafion修饰电极对三聚氰胺的检测 [0017] C, with the mesoporous silica nanospheres baby / ruthenium triple batch Li / Nafion modified electrodes for detecting melamine

[0018] 在任意一种型号的电化学工作站上,根据三聚氰胺样品浓度,使用介孔二氧化硅·纳米球/三联吡啶钌/Nafion修饰电极进行定量检测三聚氰胺的含量,所述修饰电极在使用之前,使用二次蒸馏水冲洗,在pH值7〜12的0. IM的磷酸盐缓冲溶液进行循环伏安扫描,其中扫描电位范围所述修饰电极0〜+1. 25V. [0018] In any of the electrochemical workstation models, sample concentration according to the melamine using a mesoporous silica nanospheres · / Ru terpyridine / Nafion modified electrodes before the electrode used for the quantitative detection of the content of melamine, the modified , using a secondary distilled water, cyclic voltammetry at a pH value of 0. IM 7~12 phosphate buffer solution, wherein the scanning potential range of the modified electrode 0~ + 1. 25V.

[0019] d、用电致发光检测器采集电化学发光检测仪产生的光信号,再经计算机数据处理后得到三聚氰胺样品的含量。 [0019] d, electroluminescence luminescence detector collecting light signal generated by the electrochemiluminescent detection instrument, then the computer data processing to obtain the melamine content of the sample.

[0020] 本发明的基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法还可以采用以下的技术措施来进一步实现。 [0020] Based on mesoporous silica nanospheres / electrochemiluminescent detection method a solid melamine terpyridine ruthenium further following technical measures may be employed to further achieved the present invention.

[0021] 前述的方法,其中所述Nafion由Sigma-Aldrich化学公司生产。 [0021] The aforementioned method, wherein the Nafion manufactured by Sigma-Aldrich Chemical Company.

[0022] 前述的方法,其中所述三联卩比唳钌由Sigma-Aldrich化学公司生产。 [0022] The aforementioned method, wherein the production ratio of Li Jie ruthenium triple by the Sigma-Aldrich Chemical Company.

[0023] 前述的方法,其中所述方法适用于检测所有含有三聚氰胺的物质,检测可使用任意一款电化学发光检测仪。 [0023] The aforementioned method, wherein said method is suitable for detecting all melamine substances can be detected using any of a light emitting electrochemical detector.

[0024] 前述的方法,其中所述六水合三联吡啶钌的结构式如下: [0024] The aforementioned method, wherein structural formula of the ruthenium terpyridine hexahydrate follows:

[0025] [0025]

Figure CN102854183AD00041

[0026] 采用上述技术方案后,本发明的基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法具有以下优点: [0026] With the above technical solution, the present invention has the advantage that the mesoporous silica nanospheres / Ru terpyridine solid melamine based electrochemiluminescent detection:

[0027] I、介孔硅(mSi02)材料具有2〜50nm孔径,大比表面积和孔隙体积,以及可调孔径等优越性,有利于吸附更多的电活性物质三联吡啶钌。 [0027] I, mesoporous silicon (mSi02) 2~50nm material having a pore size, specific surface area and pore volume, and an adjustable aperture and other advantages, more in favor adsorption electroactive species terpyridine ruthenium.

[0028] 2、介孔二氧化娃纳米球(mSi02)/三联批唳钌(Ru(bpy)32+)/Nafion修饰电极能有效地用于电致化学发光(ECL)检测三聚氰胺,对三聚氰胺显示出高的灵敏度,宽的线性范围,长期稳定性; [0028] 2, the mesoporous silica nanospheres baby (mSi02) / Li triple batch ruthenium (Ru (bpy) 32 +) / Nafion modified electrodes can be effectively used in electro-chemiluminescence (ECL) detection of melamine, melamine display high sensitivity, wide linear range, long-term stability;

[0029] 3、能循环使用三联吡啶钌,且在循环反应中不产生消耗,降低检测成本,为生物样品及食品中三聚氰胺残留的检测提供了一种新方法。 [0029] 3, can be recycled Ru terpyridine, and consumed in the cycling reaction does not occur, reducing testing costs, there is provided a new method for biological samples and food residues in melamine.

附图说明 BRIEF DESCRIPTION

[0030] 图I为本发明实施例的mSi02 - Nafion - Ru (bpy) 32+修饰电极在0. IM缓冲溶液(pH 11)中含有不同浓度的三聚氰胺(a) 7. 81 X 1(T9M,(b) I. 562X 1(T8M,(c) I. 25X 1(T7M,(d) 5 X KT7M (e) 5 X KT6M的电化学发光图; mSi02 embodiment [0030] Figure I of the present invention - Nafion - Ru (bpy) 32+ modified melamine (a) an electrode containing different concentrations of 0. IM buffer solution (pH 11) in 7. 81 X 1 (T9M, (b) I. 562X 1 (T8M, (c) I. 25X 1 (T7M, (d) 5 X KT7M (e) electrochemiluminescence of FIG. 5 X KT6M;

[0031] 图2为本发明实施例的电化学发光强度变化值与三聚氰胺浓度的对数图; [0031] FIG 2 log FIG ECL intensity change and the concentration of melamine in the embodiment of the present invention;

[0032] 图3为本发明实施例的HiSiO2纳米球场发射扫描电镜图(ab)和透射电镜图(c. d)。 HiSiO2 nano stadium emission scanning electron micrographs (ab) [0032] FIG 3 embodiments of the present invention and FIG TEM (c. D).

具体实施方式 Detailed ways

[0033] 以下结合实施例及其附图对本发明作更进一步说明。 [0033] The following embodiments and the accompanying drawings in conjunction with embodiments of the present invention will be further described.

[0034] 实施例I [0034] Example I

[0035] 本发明的基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法,包括以下步骤: [0035] The method of the present invention mesoporous silica nanospheres / Ru terpyridine solid melamine based electrochemiluminescent detection, comprising the steps of:

[0036] a、介孔二氧化硅纳米球的制备 Preparation of a, mesoporous silica nanospheres [0036]

[0037] 图3为本发明实施例的mSi02纳米球场发射扫描电镜图(a、b)和透射电镜图(C、d)。 mSi02 nano stadium [0037] FIG. 3 is an embodiment of the emission scanning electron micrographs (a, b), and under TEM (C, d).

[0038] 将乙醇(60mL),蒸懼水(80mL),十六烧基溴化铵(0. 30g), 20wt%〜25wt%氨水(I. 2mL)混合到一起搅拌30分钟,形成均匀的分散液(pH=9〜12),然后将正硅酸乙酯(0. 3mL)逐渐滴加到所述分散液中,反应十二小时,反应产物经过离心、洗涤,干燥后,将干燥产物在650°C煅烧,即得到介孔二氧化硅纳米球;其粒径为400〜600nm ; [0038] Ethanol (60 mL), distilled water fear (80 mL), sixteen burning bromide (0. 30g), 20wt% ~25wt% aqueous ammonia (I. 2mL) was stirred for 30 minutes to mix to form a uniform dispersion (pH = 9~12), and then tetraethoxysilane (0. 3mL) was gradually added dropwise to the dispersion, twelve hours the reaction, the reaction product was centrifuged, washed, dried, the dried product calcined at 650 ° C, to obtain mesoporous silica nanosphere; a particle size of 400~600nm;

[0039] b、介孔二氧化娃纳米球/三联批唳钌/Nafion修饰电极的制备,包含以下步骤: Electrode preparation [0039] b, the mesoporous silica nanospheres baby / ruthenium triple batch Li / Nafion modified, comprising the steps of:

[0040] (I)用2#和5#金相砂纸抛光打磨玻碳电极,再用0. 3和0. 05 ii m的Al2O3抛光粉抛光,冲洗去表面污物; [0040] (I) with # 2 and # 5 sandpaper metallographic polished glassy carbon electrodes, and then the Al2O3 0. 3 0. 05 ii m polishing powder of polishing, rinsing dirt to the surface;

[0041] (2)依次在体积比为I: I的HNO3溶液、无水乙醇、二次蒸馏水中分别超声I〜2分钟,最后将处理好的电极用高纯N2吹干; [0041] (2) successively in a volume ratio of I: HNO3 solution I, absolute ethanol, sonicated in distilled water were I~2 minutes, and finally treated with high purity N2 good dry electrode;

[0042] (3)取8 L2mgmr1的介孔二氧化硅纳米球溶液滴到处理好的玻碳电极上,室温下自然干燥; [0042] (3) takes 8 L2mgmr1 mesoporous silica nanospheres treated solution was dropped on a glassy carbon electrode good, natural drying at room temperature;

[0043] (4)将4 U L0. 5wt%Nafion (由Sigma-Aldrich化学公司生产)滴加到经步骤(3)处理的玻碳电极表面,然后浸到I. OX 10_3M六水合三联吡啶钌(由Sigma-Aldrich化学公司生产)溶液中制备成修饰电极; [0043] (4) 4 U L0. 5wt% Nafion (manufactured by Sigma-Aldrich Chemical Co.) was added dropwise via step (3) treatment of the glassy carbon electrode surface, and then immersed I. OX 10_3M hexahydrate Ru terpyridine (manufactured by Sigma-Aldrich chemical Co.) was prepared as a modified electrode;

[0044] C、用介孔二氧化娃纳米球/三联批唳钌/Nafion修饰电极对三聚氰胺的检测 [0044] C, with the mesoporous silica nanospheres baby / ruthenium triple batch Li / Nafion modified electrodes for detecting melamine

[0045] 采用MPI-E型电致化学发光检测仪(由西安瑞迈分析仪器有限公司生产),称取 [0045] The MPI-E type electroluminescent chemiluminescence detector (manufactured by Xianruimai Analytical Instruments Ltd.), weighed

0. 5g商品奶粉,将其用5ml的无水乙醇溶解,加入已知浓度的三聚氰胺,超声散、离心后,取上清液,以待测试。 0. 5g milk product, which was treated with 5ml of absolute ethanol dissolved, a known concentration of melamine, ultrasonic dispersion, after centrifugation, the supernatant to be tested. 使用介孔二氧化硅纳米球/三联吡啶钌/Nafion修饰电极进行定量检测三聚氰胺的含量,所述修饰电极在使用之前,使用二次蒸馏水冲洗,在pH 11的0. IM的磷酸盐缓冲溶液进行循环伏安扫描,其中扫描电位范围所述修饰电极0〜+1. 25V ; Using mesoporous silica nanospheres / Ru terpyridine / Nafion modified electrodes quantitative content of melamine, the modified electrode before use, using double distilled water rinsed, and phosphate buffer solution pH 0. IM 11 cyclic voltammetry, the potential range where the scanning electrode modified 0~ + 1 25V.;

[0046] d、用电致发光检测器采集电化学发光检测仪产生的光信号,再经计算机数据处理后得到三聚氰胺样品的含量。 [0046] d, electroluminescence luminescence detector collecting light signal generated by the electrochemiluminescent detection instrument, then the computer data processing to obtain the melamine content of the sample.

[0047] 其中奶粉中三聚氰胺回收率的测定结果如下: [0047] wherein the measurement result of melamine powder recovery as follows:

[0048] 三聚氰胺加入量mo I • L—1,IX 10_7,检测结果mo I • L—1,三次分别为:0. 92 X 10_7, [0048] The addition amount of the melamine mo I • L-1, IX 10_7, the detection result of mo I • L-1, three times respectively:. 0 92 X 10_7,

0. 94X KT7和0. 93 X 10'平均值为0. 93 X 10'回收率是93%,标准偏差为I. 1%。 0. 94X KT7 and 0. 93 X 10 'average of 0. 93 X 10' recovery was 93%, the standard deviation of I. 1%.

[0049] 图I为本发明实施例的mSi02 - Nafion - Ru (bpy) 32+修饰电极在0. IM缓冲溶液(pH 11)中含有不同浓度的三聚氰胺(a) 7. 81 X 1(T9M,(b) I. 562X 1(T8M,(c) I. 25X 1(T7M,(d)5X10_7M(e)5X10_6M的电化学发光图,图2为本发明实施例的电化学发光强度变化值与三聚氰胺浓度的对数图。电化学发光强度的增加值(AECL)与三聚氰胺浓度(7. 81X IO-9M〜5X I(T6M)的对数内呈线性关系,线性相关系数为0. 9979,检测极限为 mSi02 embodiment [0049] Figure I of the present invention - Nafion - Ru (bpy) 32+ modified melamine (a) an electrode containing different concentrations of 0. IM buffer solution (pH 11) in 7. 81 X 1 (T9M, (b) I. 562X 1 (T8M, (c) I. 25X 1 (T7M, (d) 5X10_7M (e) electrochemiluminescence FIG 5X10_6M, FIG. 2 of the present ECL intensity variation value melamine embodiment of the present invention FIG logarithm of concentration. the added value of ECL intensity (the AECL) and the concentration of melamine (7. 81X IO-9M~5X I (T6M) to form the log-linear relationship, a correlation coefficient of 0.9979, the detection limit for

2. 6X1(T9M。 2. 6X1 (T9M.

[0050] 实施例2 [0050] Example 2

[0051] 其中奶粉中三聚氰胺回收率的测定结果如下: [0051] wherein the measurement result of melamine powder recovery as follows:

[0052] 三聚氰胺加入量mo I • L—1,IX 10_6,检测结果mo I • L—1,二次分别为:I • IX 10_6和 [0052] The addition amount of the melamine mo I • L-1, IX 10_6, the detection result of mo I • L-1, respectively, the second: I • IX 10_6 and

1. 05X 10_6,平均值为I. 056 X 10'回收率是106%,标准偏差为4. 4%。 1. 05X 10_6, an average value of I. 056 X 10 'recovery was 106%, a standard deviation of 4.4%.

[0053] 除获得以上测定结果外,其余同实施例I。 [0053] In addition to obtaining the above measurement result, the remaining in Example I.

[0054] 本发明的基于介孔二氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法将三联吡啶钌固定到电极表面,有效地用于电致化学发光(ECL)检测三聚氰胺,对三聚氰胺显示出高的灵敏度,宽的线性范围,长期稳定性等特点,且修饰电极对三聚氰胺表现出良好的电化学发光性质,并进一步应用于奶粉中三聚氰胺的检测,为生物样品及食品中三聚氰胺残留的检测提供了一种新方法。 [0054] The mesoporous silica nanospheres / Ru terpyridine solid electrochemiluminescent detection based on the melamine-terpyridine ruthenium present invention is fixed to the electrode surface, effective for electrochemiluminescence (ECL) detection of melamine, of melamine characteristics exhibited high sensitivity, wide linear range, long-term stability, and the melamine modified electrode showed good electrochemical light emitting property, and further applied to detection of melamine powder, a biological sample and food residues melamine the assay provides a new approach.

[0055] 以上实施例仅供说明本发明之用,而非对本发明的限制,有关技术领域的技术人员,在不脱离本发明的精神和范围的情况下,还可以作出各种变换或变化。 [0055] Example embodiments for illustrative purposes only with the present invention, not to limit the present invention, those skilled in the relevant art, without departing from the spirit and scope of the invention, also various modifications or variations may be made. 因此,所有等同的技术方案也应该属于本发明的范畴,应由各权利要求限定。 Therefore, all equivalent technical solutions should belong to the scope of the invention, the claims should be defined.

Claims (4)

1. 一种基于介孔ニ氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法,其特征在于包括以下步骤: a、介孔ニ氧化娃纳米球/三联卩比唳钌/Nafion修饰电极的制备,包含以下步骤: (1)用2#和5#金相砂纸抛光打磨玻碳电极,再用O. 3和O. 05 μ m的Al2O3抛光粉抛光,冲洗去表面污物; (2)依次在体积比为I: I的HNO3溶液、无水こ醇、二次蒸馏水中分别超声I〜2分钟,最后将处通好的电极用闻纯N2吹干; (3)取6〜10 μ L2mgmじ1的介孔ニ氧化娃纳米球溶液滴到处理好的玻碳电极上,室温下自然干燥; (4)将3〜6 μ L O. 5wt%的Nafion溶液滴加到经步骤(3)处理的玻碳电极表面,然后浸到I. OX IO-3M六水合三联吡啶钌溶液中制备成修饰电极; b、用介孔ニ氧化娃纳米球/三联卩比唳钌/Nafion修饰电极对三聚氰胺的检测在电化学发光检测仪上,使用介孔ニ氧化硅纳米球/三联吡啶钌/Nafi A Ni-based mesoporous silica nanospheres / electrochemiluminescent detection method of a solid melamine terpyridine ruthenium, comprising the steps of: a, mesoporous Ni oxide nanospheres baby / triad ratio Jie Li ruthenium / Nafion modified preparing an electrode, comprising the steps of: (1) # 2 and # 5 sandpaper metallographic polished glassy carbon electrode, Al2O3 powder polishing and then O. 3 of O. 05 μ m, the surface to flush dirt; ( 2) sequentially in a volume ratio of I: I HNO3 solution in anhydrous alcohol ko, double distilled water were sonicated I~2 minutes, and finally dried with the through electrode good smell pure N2; (3) take 6 ~ 10 μ L2mgm 1 ji ni mesoporous oxide nanospheres baby treated solution was dropped on a glassy carbon electrode good, natural drying at room temperature; (4) 3~6 μ L O. 5wt% Nafion solution was added dropwise via step glassy carbon electrode (3) processing, and then immersed I. OX IO-3M hexahydrate Ru terpyridine solution prepared modified electrode; B, Ni oxide nanospheres mesoporous baby / triad ratio Jie Li ruthenium / Nafion modified detection electrodes on melamine electrochemiluminescence detector, using mesoporous silica nanospheres Ni / Ru terpyridine / Nafi on修饰电极进行定量检测三聚氰胺的含量,所述修饰电极在使用之前,使用二次蒸馏水冲洗,在PH值7〜12的O. IM的磷酸盐缓冲溶液进行循环伏安扫描,所述修饰电极扫描电位范围O〜+1. 25V ; C、用电致发光检测器采集电化学发光检测仪产生的光信号,再经计算机数据处理后得到三聚氰胺样品的含量。 The content of the modified electrode on detection of melamine, the modified electrode before use, using a secondary distilled water, cyclic voltammetry in a phosphate buffer solution of PH value O. IM 7~12, wherein the modified electrode scanning potential range O~ + 1 25V;. C, electroluminescence luminescence detector collecting light signal generated by the electrochemiluminescent detection instrument, then the computer data processing to obtain the melamine content of the sample.
2.权利要求I所述基于介孔ニ氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法,其特征在于,所述介孔ニ氧化娃纳米球的粒径为400〜600nm。 2. The method of claim I electrochemiluminescent detection of melamine solid mesoporous silica nanospheres Ni / Ru terpyridine-based, characterized in that the particle size of the mesoporous Ni oxide nanospheres baby is 400~600nm.
3.权利要求I或2所述基于介孔ニ氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法,其特征在于,所述介孔ニ氧化硅纳米球的制备方法包括以下步骤: 将こ醇、水、氨水和十六烷基溴化铵混合搅拌形成均匀的分散液,然后将正硅酸こ酯滴加到分散液中,反应10〜20小吋,反应产物经过离心、洗涤、干燥后,将干燥产物在620〜670°C煅烧,即得到介孔ニ氧化硅纳米球; 分散液PH值为9〜12,其中十六烷基溴化铵含量为O. 002〜O. 003g/ml,正硅酸こ酯与分散液的体积比为O. 002〜O. 003。 I Ni based mesoporous silica nanospheres electrochemiluminescent detection method of a solid melamine or the 2 / Ru terpyridine as claimed in claim 3, characterized in that the method of preparing silica mesoporous Ni nanospheres comprising the steps of: the ko alcohol, water, ammonia and ammonium bromide, cetyl mixing to form a uniform dispersion, and the orthosilicate ester ko dropwise added to the dispersion, the reaction 10-20 inch small, the reaction product was centrifuged, washed after drying, the dried product was calcined at 620~670 ° C, to obtain the mesoporous silica nanospheres ni; dispersion PH value 9~12, wherein hexadecyltrimethylammonium bromide content of O. 002~O. 003g / ml, ko orthosilicate ester dispersion with a volume ratio of O. 002~O. 003.
4.如权利要求I所述的基于介孔ニ氧化硅纳米球/三联吡啶钌固态电化学发光检测三聚氰胺的方法,其特征在于,所述六水合三联吡啶钌的结构式如下: 4. The method of solid state terpyridine ruthenium electrochemiluminescent detection melamine ni silica based mesoporous nanospheres / I according to claim, characterized in that the hexahydrate of the formula Ru terpyridine follows:
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