WO2023207168A1 - 一种同时检测减肥类保健品中西布曲明和芬氟拉明的方法 - Google Patents

一种同时检测减肥类保健品中西布曲明和芬氟拉明的方法 Download PDF

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WO2023207168A1
WO2023207168A1 PCT/CN2022/141667 CN2022141667W WO2023207168A1 WO 2023207168 A1 WO2023207168 A1 WO 2023207168A1 CN 2022141667 W CN2022141667 W CN 2022141667W WO 2023207168 A1 WO2023207168 A1 WO 2023207168A1
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zif
fenfluramine
sibutramine
solution
sample liquid
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PCT/CN2022/141667
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French (fr)
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谢云飞
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江南大学
南京福喆未来食品研究院有限公司
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Publication of WO2023207168A1 publication Critical patent/WO2023207168A1/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
    • G01N21/62—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
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons

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  • the invention relates to a method for simultaneously detecting sibutramine and fenfluramine in weight loss health products, and belongs to the field of food testing.
  • sibutramine is a drug that acts on the 5-hydroxytryptamine and norepinephrine pathways, which can enhance The body's sense of fullness; Fenfluramine is also a drug that acts on 5-hydroxytryptamine, which can reduce appetite and achieve weight loss.
  • Both of the above two drugs have strong side effects. Consumers who take weight-loss health products containing such drugs may suffer symptoms such as diarrhea, headache, hypotension, epilepsy, etc. Therefore, my country prohibits the addition of the above two kinds of drugs to weight-loss health products. substance.
  • the detection methods for prohibited added substances in health products are mainly TLC methods, chromatography, etc.
  • the above methods have problems such as cumbersome operation and long detection time, and are not suitable for large-scale on-site screening. Therefore, it is necessary to establish a rapid and accurate screening method. How to check for prohibited additives.
  • SERS Surface Enhanced Raman Scattering
  • Au@ZIF-8 is a kind of metal-organic frameworks (MOFs), a new type of nanoporous functional material, which is often used in the field of catalysis and has not yet been applied in surface-enhanced Raman technology.
  • MOFs metal-organic frameworks
  • the detection methods for prohibited added substances in health products are mainly TLC methods, chromatography, etc.
  • the above methods have problems such as cumbersome operation and long detection time, and are not suitable for large-scale on-site screening. Therefore, it is necessary to establish a fast and accurate method.
  • Methods to screen for prohibited additives SERS detection is fast and convenient, with high sensitivity and short detection time.
  • the traditional SERS method uses precious metal sol as an enhanced substrate, so the detection limit of the method is relatively higher than that of high-performance liquid chromatography tandem mass spectrometry. How to develop new substrates to reduce detection costs? Limitation is an issue worth exploring.
  • the present invention provides a method for simultaneous detection of sibutramine and fenfluramine using a surface-enhanced Raman method.
  • the method of the present invention is simple to operate, has a short detection time, and can ensure accuracy while ensuring effectively improve detection efficiency.
  • the first object of the present invention is to provide a method for qualitative detection of sibutramine and fenfluramine, which includes the following steps:
  • the sample liquid contains sibutramine; if the spectral information contains the following characteristic peaks: 753, 1361, 1446 and 1601cm -1 , then the sample liquid contains fenfluramine; if the spectral information contains the following characteristic peaks: 731, 1137 and 1361cm -1 , then the sample liquid contains both sibutramine and fenfluramine.
  • the presence of sibutramine and fenfluramine is determined based on the presence of the above qualitative peaks;
  • the preparation method of the surface-enhanced Raman substrate Au@ZIF-8 in step (1) uses polyvinylpyrrolidone as a bridging agent to wrap the surface of gold nanoparticles, and the gold nanoparticles modified with the bridging agent are Zinc nitrate solution and 2-methylimidazole solution were added to the nanoparticles in sequence, and Au@ZIF-8 was finally obtained.
  • the preparation method of surface-enhanced Raman substrate Au@ZIF-8 includes the following steps:
  • A. Preparation of gold sol Mix potassium chloroaurate solution and ultrapure water and heat, stir and heat until boiling, then add trisodium citrate solution and continue stirring to obtain a deep red gold sol solution;
  • Gold sol modification Mix the prepared gold sol solution with 2.5% polyvinylpyrrolidone aqueous solution and stir to obtain a polyvinylpyrrolidone-modified gold sol;
  • Au@ZIF-8 when using the new core-shell substrate Au@ZIF-8, Au@ZIF-8 is dispersed in methanol.
  • step A the volume ratio of the gold sol and the 2.5% polyvinylpyrrolidone aqueous solution is 1:4.
  • the concentrations of the zinc nitrate solution and the 2-methylimidazole solution are both 20-30 mmol/L; both are preferably 25 mmol/L.
  • step A the volume ratio of the zinc nitrate solution and the 2-methylimidazole solution is 1:3.
  • step A the amount of zinc nitrate solution is 0.1 mL, and the amount of 2-methylimidazole solution is 0.3 mL.
  • step A the amount of zinc nitrate solution is 0.8 mL, and the amount of 2-methylimidazole solution is 2.4 mL.
  • step A the amount of zinc nitrate solution is 4 mL, and the amount of 2-methylimidazole solution is 12 mL.
  • the dosage volume ratio of the zinc nitrate solution and the modified gold sol is 0.1 to 4:20, and the preferred dosage volume ratio is 0.1:20.
  • the preparation method of Au@ZIF-8 in step A is as follows: mix 10 mL of prepared gold sol with 40 mL of 2.5% polyvinylpyrrolidone aqueous solution, and stir for 24 h to obtain polyvinylpyrrolidone. Modified gold sol; take 15 mL of modified gold sol, centrifuge (10000r, 10 min), discard the supernatant after centrifugation, add 5 mL of methanol, and mix to obtain a modified gold sol solution.
  • the preparation method of the gold sol in step A is specifically: mixing 3 mL of potassium chloroaurate solution with a concentration of 10 mg/mL and 47 mL of ultrapure water, heating, stirring and heating until boiling, and then adding Add 2 mL of trisodium citrate solution with a concentrated mass fraction of 1% and stir continuously for 20 minutes to obtain a deep red gold sol solution.
  • the sample liquid in the step (2) is obtained by mixing the sample to be tested and the extraction solvent evenly, ultrasonic, centrifuging and then taking the supernatant; to obtain the sample liquid.
  • the sample to be tested is a weight loss health product.
  • the sample to be tested is a pre-processed weight loss health product.
  • the weight loss health product is ground to obtain the ground weight loss health product.
  • the extraction solvent is methanol.
  • the dosage ratio of the extraction solvent and the sample to be tested is 10:1 in mL/g.
  • the preparation process of the sample liquid is: accurately weigh 1.000g of weight-loss health products, grind it into powder, put it into a centrifuge tube, add 10 mL of methanol, and shake thoroughly After ultrasonic for 10 minutes, centrifuge at 10000r/min.
  • the centrifugation is 10000r/min for 10min.
  • the uniform mixing is vortex mixing.
  • the conditions for Raman spectrum detection in step (2) are: scanning with a laser Raman spectrometer with an excitation light source of 785 nm, a scanning time of 3 s, and a scan number of 2 times.
  • step (2) Au@ZIF-8 is configured into a solution and mixed with the sample liquid; the solvent is methanol.
  • the conditions for configuring Au@ZIF-8 into a solution in step (2) are: for every 30 mg of gold nanoparticles prepared by potassium chloroaurate, 5 mL of solvent is used for dispersion.
  • the volume ratio of the sample liquid and Au@ZIF-8 in step (2) is 1:1-4, which is further optimized to 1:3.
  • Raman detection is performed within 2 minutes after the sample liquid and Au@ZIF-8 are evenly mixed in step (2).
  • the present invention also provides the application of the above method in the field of food testing.
  • the method of the present invention can simultaneously detect sibutramine and fenfluramine in weight loss health products.
  • the minimum detection concentration of sibutramine and fenfluramine in weight loss health products detected by the method of the present invention is 25 mg/kg.
  • This method can qualitatively analyze the prohibited addition of sibutramine and fenfluramine in weight loss health products.
  • the detection time of a single sample is controlled within 2 minutes.
  • Lamin Rapid Qualitative Screening provides a fast and convenient detection method.
  • Figure 1 shows the comparison between the enhanced Raman spectrum of sibutramine and the enhanced Raman spectrum; a is the solid Raman spectrum of sibutramine, and b is the enhanced Raman spectrum.
  • Figure 2 shows the comparison between the enhanced Raman spectrum of fenfluramine and the enhanced Raman spectrum; a is the solid Raman spectrum of fenfluramine, and b is the enhanced Raman spectrum.
  • Figure 3 shows the Raman spectra of mixed solutions of sibutramine and fenfluramine at different concentrations; from a to g are the base, 20mg/L, 25mg/L, 50mg/L, 100mg/L, 250mg/L, 500mg respectively. /L solution.
  • Figure 4 is a comparison chart of the Raman spectra of the supplemented extracts of weight loss health products with different spike levels; a is the blank weight loss health product extract, b is 20 mg/kg, c is 25 mg/kg, and d is 50 mg/kg. kg, e is 100mg/kg, f is 250mg/kg, and g is 500mg/kg.
  • Figure 5 shows the comparison of Raman intensity after mixing different proportions of the test liquid and Au@ZIF-8, a is 1:1, b is 1:2, c is 1:3, and d is 1:4.
  • Figure 6 shows the comparison of Raman intensity at different mixing times, a is 1 min, b is 2 min, c is 3 min, and d is 4 min.
  • a method for qualitatively detecting sibutramine and fenfluramine in weight loss health products including the following steps:
  • 631cm -1 and 821cm -1 are attributed to the vibration of the para-disubstituted benzene ring
  • 731cm -1 is attributed to the in-plane swing of -CH 2 in cyclobutane
  • 1091cm -1 is attributed to the ring vibration of the para-disubstituted benzene ring. It is the ring vibration of the benzene ring.
  • the position at 1137cm -1 is attributed to the CH vibration within the benzene ring surface
  • the position at 1594cm -1 is the stretching vibration of the intracyclic olefin double bond.
  • 753cm -1 is the ring vibration of the benzene ring
  • 1341cm -1 is the CF stretching vibration
  • the characteristic peaks when both exist at the same time are 731, 1137 and 1361cm -1 .
  • the detection results are as follows: the gold sol and the liquid to be tested are mixed in different proportions. The results are shown in Figure 5. When the volume of the gold sol and the liquid to be tested is 1:2, the signal intensity is the highest.
  • the mixing time of the mixed solution and Au@ZIF-8 in Example 1 was adjusted to 1 min, 2 min, 3 min, and 4 min. The other conditions were kept consistent with Example 1 for detection.
  • the detection results are as follows: Au@ZIF-8 was mixed with the liquid to be tested at different times. The results are shown in Figure 6. The mixing time was 2 minutes and the signal intensity was the highest.

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Abstract

一种同时检测减肥类保健品中西布曲明和芬氟拉明的方法，包括：确定西布曲明和芬氟拉明同时存在的拉曼特征峰，对减肥类保健品样品进行预处理，采用提取溶剂进行提取，得到待测溶液；根据待测溶液的拉曼谱图，判断待测样品中是否存在西布曲明和芬氟拉明。最低检出浓度为25mg/kg，可以对减肥类保健品中西布曲明和芬氟拉明的存在进行定性分析，单个样本检测时间控制在2min内。

Description

一种同时检测减肥类保健品中西布曲明和芬氟拉明的方法 技术领域
本发明涉及一种同时检测减肥类保健品中西布曲明和芬氟拉明的方法，属于食品检测领域。
背景技术
近年来，随着生活水平的不断提高，肥胖问题日益严重，困扰着许多人。基于这种心理，多个商家推出了备受消费者青睐的减肥类保健品，然而，在利益的驱动下，某些商家经常在减肥类保健品中掺入国家规定禁止检出的物质，来获得更大的利益空间。目前不法商家在减肥类保健品中主要添加的物质有西布曲明和芬氟拉明两种，其中，西布曲明是一种作用于5-羟色胺和去甲肾上腺素通路的药物，可以增强人体的饱腹感；芬氟拉明同样也是作用于5-羟色胺的药物，可以减少食欲进而达到减肥目的。以上两种药物都具有强烈的副作用，消费者服用了含有此类药物的减肥类保健品，可能出现腹泻、头痛、低血压、癫痫等症状，因此我国禁止在减肥类保健品中添加上述两种物质。目前，对于保健品中违禁添加物质的检测方法主要是TLC法、色谱法等，以上方法存在操作繁琐、检测时间长等问题，不适合现场大规模筛查，因此有必要建立一种快速准确筛查违禁添加物的方法。
表面增强拉曼技术(Surface Enhanced Raman Scattering,SERS)是一种将纳米技术与普通拉曼光谱联用的技术，使用了纳米结构以增强分析物的拉曼散射并淬灭背景荧光，因此具有灵敏度高、筛查速度快等优势，近年来被广泛应用于食品中污染物的检测，然而受复杂食品基质以及增强基底的影响，SERS检测方法通常检出限较高，限制了它在食品检测领域的进一步应用。传统的SERS基底主要是贵金属溶胶，此类基底价格昂贵、稳定性较差，在某种程度上限制了SERS技术的进一步应用，因此亟待开发新型基底扩大应用范围。
Au@ZIF-8是一种金属-有机骨架材料(metal-organic frameworks,MOFs)是一类新型纳米多孔功能材料，常用于催化领域，尚未有在表面增强拉曼技术中的应用。
发明内容
[技术问题]
目目前，对于保健品中违禁添加物质的检测方法主要是TLC法、色谱法等，以上方法存在操作繁琐、检测时间长等问题，不适合现场大规模筛查，因此有必要建立一种快速准确筛查违禁添加物的方法。SERS检测快速便捷、灵敏度高、检测时间短，然而，传统SERS方法都是以贵金属溶胶作为增强基底，因此方法的检出限相对高于高效液相色谱串联质谱法，如何开发新型基底，降低检出限是一个值得探讨的问题。
[技术方案]
为了解决上述至少一个问题，本发明提供了一种利用表面增强拉曼方法对西布曲明和芬氟拉明进行同时检测的方法，本发明的方法操作简单、检测时间短，可以在保证准确度的情况下有效提高检测效率。
本发明的第一个目的是提供一种定性检测西布曲明和芬氟拉明的方法，包括如下步骤：
(1)制备表面增强拉曼基底Au@ZIF-8；
(2)将样品液与Au@ZIF-8混合，然后进行表面增强拉曼光谱检测，采集得到相应的光谱信息；
(3)若光谱信息含有如下特征峰：631、731、821、1091、1137和1594cm -1，则样品液中含有西布曲明；若光谱信息含有如下特征峰：753、1361、1446和1601cm -1，则样品液中含有芬氟拉明；若光谱信息含有如下特征峰：731、1137和1361cm -1，则样品液中同时含有西布曲明和芬氟拉明。
在本发明的一种实施方式中，根据上述定性谱峰的存在判定是否有西布曲明和芬氟拉明的存在；
在本发明的一种实施方式中，步骤(1)中表面增强拉曼基底Au@ZIF-8的制备方法以聚乙烯吡咯烷酮作为桥连剂包裹在金纳米粒子表面，在桥连剂修饰的金纳米粒子中依次加入硝酸锌溶液和2-甲基咪唑溶液，最终获得Au@ZIF-8。
在本发明的一种实施方式中表面增强拉曼基底Au@ZIF-8的制备方法包括如下步骤：
A、金溶胶制备：将氯金酸钾溶液与超纯水混合进行加热，搅拌加热至沸腾，之后加入柠檬酸三钠溶液，持续搅拌，即得到深红色的金溶胶溶液；
B、金溶胶改性：取配置好的金溶胶溶液与2.5％的聚乙烯吡咯烷酮水溶液混合，搅拌，获得聚乙烯吡咯烷酮改性的金溶胶；
C、得新型核壳基底：取改性后的金溶胶，离心，离心后弃去上清液，加入甲醇，混匀得到改性金溶胶溶液；取改性金溶胶溶液，加入硝酸锌溶液，搅拌，继续加入2-甲基咪唑溶液，搅拌后静置，待反应结束后离心，甲醇洗涤产物，将产物放入烘干，制得新型核壳基底Au@ZIF-8。
在本发明的一种实施方式中，使用新型核壳基底Au@ZIF-8时将Au@ZIF-8分散于甲醇中。
在本发明的一种实施方式中，步骤A中，所述金溶胶和2.5％的聚乙烯吡咯烷酮水溶液的用量体积比为1:4。
在本发明的一种实施方式中，步骤A中，所述硝酸锌溶液和2-甲基咪唑溶液的浓度均为20-30mmol/L；均优选25mmol/L。
在本发明的一种实施方式中，步骤A中，所述硝酸锌溶液和2-甲基咪唑溶液的用量体积比为1:3。
在本发明的一种实施方式中，步骤A中，所述硝酸锌溶液用量为0.1mL，2-甲基咪唑溶液用量为0.3mL。
在本发明的一种实施方式中，步骤A中，所述硝酸锌溶液用量为0.8mL，2-甲基咪唑溶液用量为2.4mL。
在本发明的一种实施方式中，步骤A中，所述硝酸锌溶液用量为4mL，2-甲基咪唑溶液用量为12mL。
在本发明的一种实施方式中，步骤A中，所述硝酸锌溶液和改性金溶胶的用量体积比为0.1～4:20，优选的用量体积比为0.1:20。
在本发明的一种实施方式中，步骤A中Au@ZIF-8的制备方法具体为：取10mL配置好的金溶胶与40mL2.5％的聚乙烯吡咯烷酮水溶液混合，搅拌24h，获得聚乙烯吡咯烷酮改性的金溶胶；取改性后的金溶胶15mL，离心(10000r，10min)，离心后弃去上清液，加入5mL甲醇，混匀得到改性金溶胶溶液。取改性金溶胶溶液，分别加入0.1mL 25mmol/L的硝酸锌溶液，搅拌5min，继续加入0.3mL 25mmol/L的2-甲基咪唑溶液，搅拌5min后静置15min，反应结束后离心(10000r，10min)，使用甲醇洗涤3次，将产物放入60℃烘箱过夜烘干，以此获得Au@ZIF-8材料。
在本发明的一种实施方式中，步骤A中金溶胶的制备方法具体为：将3mL浓度为10mg/mL的氯金酸钾溶液与47mL超纯水混合进行加热，搅拌加热至沸腾，之后加入2mL浓质量分数为1％的柠檬酸三钠溶液，持续搅拌20min，即得到深红色的金溶胶溶液。
在本发明的一种实施方式中，所述步骤(2)中样品液是将待测样品与提取溶剂混合均匀后超声、离心后取上清液；得到样品液。
在本发明的一种实施方式中，所述的待测样品是减肥类保健品。
在本发明的一种实施方式中，所述的待测样品是经过预处理的减肥类保健品，具体是将减肥类保健品研磨，得到研磨之后的减肥类保健品。
在本发明的一种实施方式中，所述的提取溶剂是甲醇。
在本发明的一种实施方式中，提取溶剂和待测样品的用量比例以mL/g计为10：1。
在本发明在本发明的一种实施方式中，所述样品液的制备过程为：准确称取1.000g减肥类保健品，将其研磨成粉末，放入离心管中，加入10mL甲醇，充分振荡后超声10min，在10000r/min条件下离心。
的一种实施方式中，离心是10000r/min离心10min。
在本发明的一种实施方式中，混合均匀是涡旋混匀。
在本发明的一种实施方式中，步骤(2)中拉曼光谱检测的条件是：用激发光源为785nm的激光拉曼光谱仪进行扫描，扫描时间为3s，扫描次数为2次。
在本发明的一种实施方式中，步骤(2)中Au@ZIF-8配置成溶液与样品液混合；溶剂为甲醇。
在本发明的一种实施方式中，步骤(2)中Au@ZIF-8配置成溶液的条件是：每30mg氯金酸钾制备的金纳米粒子，使用5mL溶剂进行分散。
在本发明的一种实施方式中，步骤(2)中样品液和Au@ZIF-8的体积比为1：1-4，进一步优化为1：3。
在本发明的一种实施方式中，步骤(2)中样品液和Au@ZIF-8混合均匀后2min内进行拉曼的检测。
本发明的第还提供上述方法在食品检测领域中的应用。
[有益效果]
(1)本发明的方法可以同时检测减肥类保健品中西布曲明和芬氟拉明。
(2)本发明的方法检测减肥类保健品中西布曲明和芬氟拉明的最低检出浓度为25mg/kg。
(3)本方法可以对减肥类保健品中西布曲明和芬氟拉明的违禁添加进行定性分析，单个样本检测时间控制在2min内，为减肥类保健品中违禁添加的西布曲明和芬氟拉明快速定性筛查提供了一种快速便捷的检测方法。
附图说明
图1为西布曲明增强拉曼光谱与增强拉曼光谱对比；其中a是西布曲明固体拉曼光谱，b增强拉曼光谱。
图2为芬氟拉明增强拉曼光谱与增强拉曼光谱对比；其中a是芬氟拉明固体拉曼光谱，b增强拉曼光谱。
图3为不同浓度的西布曲明和芬氟拉明混合溶液拉曼光谱；其中从a到g分别为基底，20mg/L，25mg/L，50mg/L，100mg/L，250mg/L，500mg/L溶液。
图4为不同加标水平的减肥类保健品加标提取液的拉曼光谱对比图；其中a为空白减肥类保健品提取液，b为20mg/kg，c为25mg/kg，d为50mg/kg，e为100mg/kg，f为250mg/kg，g为500mg/kg。
图5为不同比例的待测液与Au@ZIF-8混合后拉曼强度对比图，a为1:1，b为1:2，c为1:3，d为1:4。
图6为不同混匀时间拉曼强度对比图，a为1min，b为2min，c为3min，d为4min。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
实施例1
一种定性检测减肥类保健品中西布曲明和芬氟拉明的方法，包括如下步骤：
(1)拉曼增强基底的制备：
用王水浸泡所用到的玻璃器皿(圆底烧瓶)以及转子12h，取出用水冲至无味，再用超纯水冲洗三次，60℃烘箱烘干，备用；配制质量分数为1％柠檬酸三钠水溶液，10mg/mL氯金酸钾溶液，备用；将油浴锅升温至120℃并保持恒定；设置磁力搅拌器参数：565r/min；
①在圆底烧瓶中加入47mL超纯水与3mL氯金酸钾，充分混合；将圆底烧瓶放入120℃油浴锅内，同时用磁力搅拌器搅拌并保持温度恒定至溶液沸腾；加入2mL 1％柠檬酸三钠水溶液继续120℃恒温搅拌20min；冷却至常温，得到金溶胶，备用；
②取10mL配置好的金溶胶与40mL2.5％的聚乙烯吡咯烷酮水溶液混合，搅拌24h，获得聚乙烯吡咯烷酮改性的金溶胶。
③取改性后的金溶胶15mL，离心(10000r，10min)，离心后弃去上清液，加入5mL甲醇，混匀获得聚乙烯吡咯烷酮改性的金溶胶。取聚乙烯吡咯烷酮改性的金溶胶，加入25mmol/L的硝酸锌溶液0.1mL，搅拌5min，继续加入25mmol/L的2-甲基咪唑溶液0.3mL，搅拌5min后静置15min，反应结束后离心(10000r，10min)，使用甲醇洗涤3次，将产物放入60℃烘箱过夜烘干，以此获得不同厚度Au@ZIF-8材料。使用时将Au@ZIF-8分散于5mL甲醇中。
(2)标准品西布曲明和芬氟拉明的定性谱峰：
称取5mg西布曲明标准品，用甲醇在溶解后转移至5mL棕色容量瓶，得到1mg/mL的标准溶液，4℃保存备用；
称取5mg芬氟拉明标准品，用甲醇在溶解后转移至5mL棕色容量瓶，得到1mg/mL的标准溶液，4℃保存备用；
称取5mg西布曲明和芬氟拉明标准品，用甲醇在溶解后转移至5mL棕色容量瓶，得到1mg/mL的混合溶液，然后逐级稀释成浓度为500、250、100、50、25、20mg/L的混合溶液稀释成4℃保存备用；
取10μL西布曲明溶液与30μL Au@ZIF-8混合后滴加到锡纸包裹的玻璃片上，用激发光源为785nm的激光拉曼光谱仪进行扫描，扫描时间为3s，扫描次数为2次，得到西布曲明 标准溶液的的拉曼光谱(图1)；
从图1可以看出：西布曲明的特征峰631、731、821、1091、1137和1594cm -1。
在400～2000cm -1范围内，631cm -1和821cm -1处归属为对位双取代苯环环振动，731cm -1归属为环丁烷中-CH 2的面内摇摆，1091cm -1处归属为苯环环振动，1137cm -1处归属为苯环面内C-H振动，1594cm -1处为环内烯烃双键伸缩振动。
取10μL芬氟拉明溶液与30μL Au@ZIF-8混合后滴加到锡纸包裹的玻璃片上，用激发光源为785nm的激光拉曼光谱仪进行扫描，扫描时间为3s，扫描次数为2次，得到芬氟拉明标准溶液的的拉曼光谱(图2)；
从图2可以看出：芬氟拉明的特征峰753、1361、1446和1601cm -1。
在400～2000cm-1范围内，其中753cm -1处为苯环环振动，1341cm -1处为C-F伸缩振动，1446cm -1和1601cm -1处为苯环的C＝C伸缩振动。
取10μL混合溶液与30μL Au@ZIF-8混合后滴加到锡纸包裹的玻璃片上，用激发光源为785nm的激光拉曼光谱仪进行扫描，扫描时间为3s，扫描次数为2次，得到不同浓度混合溶液的的拉曼光谱(图3)；
在400～2000cm-1范围内，两者同时存在时的特征峰为731、1137和1361cm -1。
(3)实际样品检测
准确称取1.000g减肥类保健品，将其研磨成粉末，放入离心管中，加入10mL甲醇，充分振荡后超声10min，在10000rpm条件下离心，取上清液进行拉曼检测；
取10μL加标提取液与30μL Au@ZIF-8混合后滴加到锡纸包裹的玻璃片上，用激发光源为785nm的激光拉曼光谱仪进行扫描，扫描时间为3s，扫描次数为2次，得到拉曼光谱图，如图4所示，在25mg/kg的加标浓度下，西布曲明和芬氟拉明的特征峰还可以观察到，731、1137cm -1特征峰可以判断西布曲明的存在，1361cm -1特征峰可以判断芬氟拉明存在，因此检出限为25mg/kg。
实施例2
调整实施例1中混合溶液和Au@ZIF-8的体积比为1:1、1:2、1:3、1:4，其他和实施例1保持一致，进行检测。
检测结果为：按照不同比例将金溶胶与待测液混合，结果如图5所示，金溶胶与待测液体积为1：2时，信号强度最高。
实施例3
调整实施例1中混合溶液和Au@ZIF-8的混匀时间为1min、2min、3min、4min，其他和实施例1保持一致，进行检测。
检测结果为：按照不同时间将Au@ZIF-8与待测液混合，结果如图6所示，混匀时间2min，信号强度最高。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的技术和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (10)

  1. 一种定性检测西布曲明和芬氟拉明的方法，其特征在于，包括如下步骤：
    (1)制备表面增强拉曼基底Au@ZIF-8；
    (2)将样品液与Au@ZIF-8混合，然后进行表面增强拉曼光谱检测，采集得到相应的光谱信息；
    (3)若光谱信息含有如下特征峰：631、731、821、1091、1137和1594cm -1，则样品液中含有西布曲明；若光谱信息含有如下特征峰：753、1361、1446和1601cm -1，则样品液中含有芬氟拉明；若光谱信息含有如下特征峰：731、1137和1361cm -1，则样品液中同时含有西布曲明和芬氟拉明。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中表面增强拉曼基底Au@ZIF-8的制备方法以聚乙烯吡咯烷酮作为桥连剂包裹在金纳米粒子表面，在桥连剂修饰的金纳米粒子中依次加入硝酸锌溶液和2-甲基咪唑溶液，最终获得Au@ZIF-8。
  3. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中样品液是将待测样品与提取溶剂混合均匀后超声、离心后取上清液；得到样品液。
  4. 根据权利要求3所述的方法，其特征在于，所述的提取溶剂是甲醇。
  5. 根据权利要求3所述的方法，其特征在于，提取溶剂和待测样品的用量比例以mL/g计为10：1。
  6. 根据权利要求1所述的方法，其特征在于，步骤(2)中拉曼光谱检测的条件是：用激发光源为785nm的激光拉曼光谱仪进行扫描，扫描时间为3s，扫描次数为2次。
  7. 根据权利要求1所述的方法，其特征在于，步骤(2)中Au@ZIF-8配置成Au@ZIF-8溶液，然后与样品液混合；溶剂为甲醇。
  8. 根据权利要求7所述的方法，其特征在于，步骤(2)中样品液和Au@ZIF-8溶液的体积比为1：1-4。
  9. 根据权利要求1-8任一项所述的方法，其特征在于，步骤(2)中样品液和Au@ZIF-8混合均匀后2min内进行拉曼的检测。
  10. 权利要求1-9任一项所述方法在食品检测领域中的应用。
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