CN103335995A - Method for detecting synthetic pigments in food by utilizing raman enhanced spectrum - Google Patents
Method for detecting synthetic pigments in food by utilizing raman enhanced spectrum Download PDFInfo
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Abstract
The invention relates to a method for detecting synthetic pigments in food by utilizing a raman spectrum method, and belongs to the field of food safety detecting. The method is characterized in that nano gold modified by mercaptoethylamine is used for synthesizing nano gold sol with positive charge, and the nano gold sol serves as a raman spectrum enhanced reagent to detect the synthetic pigments in the food. The enhanced reagent and a sample to-be-detected are uniformly mixed, and subjected to laser focusing, and raman spectrum detection during a detection process. Molecules of the synthetic pigments such as sunset yellow, acid orange, allura red, lemon yellow, brilliant blue, bright red, carmine and quinoline yellow carry negative charges, and are similar in structure; the raman spectrum enhanced reagent with the positive charge can absorb the molecules of the synthetic pigments on the surface of the nano gold due to electrostatic interaction; and the quick and sensitive detection is realized by a raman enhanced spectrum technology. Therefore, with the adoption of the method, the molecules of the synthetic pigments with the negative charges can be detected. The method for detecting the synthetic pigments in the food has quick and economical operation processes, and accurate results.
Description
Technical field
The present invention relates to the food safety detection field, be specifically related to a kind of nm of gold colloidal solution of anamorphic zone positive electricity of using as the synthetic dyestuff in the Raman enhancing reagent detection food.
Background technology
Along with the reach of science, a lot of organic pigments are synthesized in succession, these synthetic dyestuff lovely lusters, and stable in properties, and cheap, therefore, a lot of synthetic dyestuffs are applied in the food additives.Sunset yellow, luring red and lemon yellow etc. is that China allows the edible synthesized coloring matter that uses, these pigments can improve the color of food, and stable in properties, and are cheap, are subjected to the favor of a lot of businessmans.But these pigments have certain harm to human body, and chronic toxicity and carcinogenicity are arranged, and for this reason, its amount of adding in food is subjected to strict control.According to China's " food additives use hygienic standard " regulation, sunset yellow, lemon yellow maximum consumption in beverage are 0.1 g/kg, and luring red is 0.05 g/kg.Acid orange adds pigment for violating a ban.
Because a little less than children's the liver kidney function of detoxification, growth and development stage is the most responsive, after taking in for a long time that pigment is excessive and waiting the underproof food of food additives, may causes slow poisoning, even have influence on physiology and intelligence development.If the long-term or disposable a large amount of edible food that contains lemon yellow, sunset yellow and exceed standard of people may cause symptoms such as allergy, diarrhoea, when intake surpasses the liver detoxification ability, can accumulate in vivo, kidney, liver are produced certain injury.
Now, the method that detects synthetic dyestuff adopts high performance liquid chromatography, thin layer chromatography and spectrophotometric method mostly.These method detection sensitivity height need complicated exact instrument but exist, and are loaded down with trivial details relatively to the sample separation purifying step, and operative technique is required high deficiency.
Raman spectroscopy has need not specimen preparation, be not subjected to hydrone interference, can not have the wound fast detecting, characteristics such as checkout equipment is light.The Surface enhanced raman spectroscopy technology makes its detectability improve 4 to 10 orders of magnitude, even can reach ten part per trillion (10
-12G/g), not only aspect the material molecular structure analysis, and also more and more demonstrating great potential aspect the trace chemistry material fast detecting.
Among the present invention, the gold nano colloidal particle of anamorphic zone positive electricity, with this particle as Surface enhanced raman spectroscopy reagent, sunset yellow, acid orange, lure red, lemon yellow, light blue, red scarlet, carmine, synthetic dyestuff molecules such as quinoline yellow are electronegative, and structural similarity, and positively charged Raman spectrum strengthens reagent can make the synthetic dyestuff molecular adsorption on the nm of gold surface by electrostatic interaction, utilize Raman enhanced spectrum technology to obtain rapid sensitive and detect, realize fast detecting to synthetic dyestuff in the food with this.
Summary of the invention
The object of the invention is to provide the detection method of synthetic dyestuff in a kind of food.Preparation strengthens reagent with the mercaptoethylmaine gold nano-particles modified as Raman in this method, detects the synthetic dyestuff in the food.
Realize concrete grammar of the present invention:
A kind of method of utilizing the Raman enhanced spectrum to detect synthetic dyestuff in the food is characterized in that its concrete steps are:
1) Raman strengthens the synthetic of reagent: with gold chloride, sodium borohydride and mercaptoethylmaine are pressed (28 ~ 112): (0.05 ~ 0.2): the mixed in molar ratio reaction of (42.5 ~ 170), the nano gold sol of anamorphic zone positive charge;
2) actual sample pre-treatment obtains liquid to be measured; Concrete operations are: a) after the water extraction, measure by the water intaking extract after smashing to pieces for the solid food sample; B) liquid sample is if directly measure during no obvious solid matter; If obvious solid matter is arranged, get filtrate mensuration behind 0.22 micron the filter membrane of taking a sample;
3) Raman of synthetic dyestuff strengthens technology for detection in the food; Be specially after liquid to be measured and the Raman enhancing reagent mix, laser is assembled, and carries out Raman spectrum and detects; According to the contrast of the collection of illustrative plates of standard items, whether qualitative discrimination detects;
Described synthetic dyestuff is characterized in that it is that water-soluble back molecule is electronegative.
Concrete: the synthetic concrete operations that the described Raman of step 1) strengthens reagent mix stirring 10 ~ 60 minutes for getting 0.71-2.84 mmol/L chlorauric acid solution and 100-426 mmol/L mercaptoethylmaine solution in aqueous solution, the 1-50 mmol/L sodium borohydride solution lucifuge that adds new system again stirred the nano gold sol of anamorphic zone positive charge 20 ~ 60 minutes; Gold chloride wherein, the mol ratio of sodium borohydride and mercaptoethylmaine is (28 ~ 112): (0.05 ~ 0.2): (42.5 ~ 170).
Step 2) described actual sample pre-treatment is,
Solid sample: smash to pieces, in the ratio of sample: redistilled water=1g:2mL, in sample, add redistilled water, and regulate pH to 8-9, soaks filtration or centrifugal after 20-60 minute, get filtrate filtered or centrifugal after supernatant to be measured;
Liquid sample: when liquid sample does not have obvious solid matter, directly to be measured; If obvious solid matter is arranged, to get fluid sample and cross 0.22 micron filter membrane, filtrate is to be measured;
The described detection of step 3, the step 2 of learning from else's experience liquid to be measured and after Raman strengthens reagent and mixes with the volume ratio of 10:1 ~ 1:10, laser is assembled, and carries out Raman spectrum and detects; According to the contrast of the collection of illustrative plates of standard items, whether qualitative discrimination detects.
Above-described synthetic dyestuff comprises sunset yellow, acid orange, lure red, lemon yellow, light blue, red scarlet, famille rose, quinoline yellow.
It is simple that this method has the food samples pre-treatment, and operating process is fast economical, and the result is accurate.Detect and be limited to 1 ug/mL.
Description of drawings
The positively charged nm of gold of Fig. 1 strengthens the transmission electron microscope figure (TEM) of Raman particle
Fig. 2 sunset yellow standard model Raman spectrogram (1 μ g/mL-100 μ g/mL)
Fig. 3 orange beverage actual sample strengthens Raman spectrogram
Fig. 4 cotton candy actual sample strengthens Raman spectrogram
Raman strengthens the synthetic of reagent:
In 39 mL secondary water, add 950 μ L, 20 mg/mL gold chloride (HAuCl
4) solution, add 400 μ L, 0.213 mol/L mercaptoethylmaine solution again, stirred 20 minutes, then add 10 μ L, 10 mmol/L sodium borohydride (NaBH
4) solution, lucifuge stirred 15 minutes, stirred after color reddens 20 minutes again.The solution of gained is positioned in 4 ℃ of refrigerators and keeps in Dark Place.Fig. 1 is the transmission electron microscope figure (TEM) that positively charged nm of gold strengthens the Raman particle, and the scale among the figure is 200 nm, and as can be seen from the figure, the size of particle is 30-60 nm.
Embodiment2: the detection of sunset yellow standard model
The sunset yellow standard solution of preparation 1 mg/mL is diluted to this solution respectively 100 μ g/mL, 10 μ g/mL and 1 μ g/mL more earlier.As strengthening particle, the testing sample that strengthens reagent 20 μ L and 20 μ L mixes with the nano gold sol of positively charged, and both volume ratios are 1:1, gets 6-10 μ L in the carrying groove, and laser is assembled, and Raman spectrum detects.Be illustrated in figure 2 as among the 1 μ g/mL-100 μ g/mL sunset yellow sample Raman enhanced spectrum figure figure arrow mark part and be the characteristic peak of sunset yellow.When the characteristic peak of sunset yellow appearred in specimen, thinking had sunset yellow to exist, and sample detects and is limited to 1 ug/mL.
Embodiment3: the detection of sunset yellow in the fruit drink
Orange beverage (is measured by GB/T5009.35-2003 " mensuration of synthetic coloring matter in the food ", it contains the sunset yellow of 1.2ug/mL) as actual sample, getting 20 μ L orange beverages and isopyknic Raman enhancing reagent (being made by embodiment 1) mixes, get 10 μ L on aluminium flake, laser is assembled, and Raman spectrum detects.Fig. 3 is the Raman spectrogram of orange beverage actual sample, and square frame partly is the raman characteristic peak of sunset yellow in the orange beverage among the figure.Standard model comparison with sunset yellow has illustrated that sunset yellow detects.
Embodiment4: the red detection of temptation in the cotton candy
Get cotton candy (contain temptation red) as test sample, weighing 5 gram samples are smashed to pieces with glass rod, add 10 milliliters of redistilled waters, regulate pH to 8-9, soaked 20 minutes, and filtration, collection filtrate is liquid to be measured (perhaps 5000rpm, centrifugal 5 minutes, it was to be measured to get supernatant).It is even to get 20 uL liquid to be measured and 20 uL Ramans enhancing mix particles, gets 10uL in aluminium flake, and laser focuses on, and Raman spectrum detects.Fig. 4 is the Raman spectrogram of cotton candy actual sample, and square frame partly is the red raman characteristic peak of temptation in the cotton candy among the figure.
Claims (5)
1. method of utilizing the Raman enhanced spectrum to detect synthetic dyestuff in the food is characterized in that its concrete steps are:
Raman strengthens the synthetic of reagent: with gold chloride, sodium borohydride and mercaptoethylmaine are pressed (28 ~ 112): (0.05 ~ 0.2): the mixed in molar ratio reaction of (42.5 ~ 170), the nano gold sol of anamorphic zone positive charge;
The actual sample pre-treatment obtains liquid to be measured; Concrete operations are: a) after the water extraction, measure by the water intaking extract after smashing to pieces for the solid food sample; B) liquid sample is if directly measure during no obvious solid matter; If obvious solid matter is arranged, get filtrate mensuration behind 0.22 micron the filter membrane of taking a sample;
The Raman of synthetic dyestuff strengthens technology for detection in the food; Be specially after liquid to be measured and the Raman enhancing reagent mix, laser is assembled, and carries out Raman spectrum and detects; According to the contrast of the collection of illustrative plates of standard items, whether qualitative discrimination detects;
Described synthetic dyestuff is characterized in that it is that water-soluble back molecule is electronegative.
2. utilize the Raman enhanced spectrum to detect the method for synthetic dyestuff in the food according to claim 1, it is characterized in that: the synthetic concrete operations that the described Raman of step 1) strengthens reagent mix stirring 10 ~ 60 minutes for getting 0.71-2.84 mmol/L chlorauric acid solution and 100-426 mmol/L mercaptoethylmaine solution in aqueous solution, the 1-50 mmol/L sodium borohydride solution lucifuge that adds new system again stirred the nano gold sol of anamorphic zone positive charge 20 ~ 60 minutes; Gold chloride wherein, the mol ratio of sodium borohydride and mercaptoethylmaine is (28 ~ 112): (0.05 ~ 0.2): (42.5 ~ 170).
3. utilizing the Raman enhanced spectrum to detect the method for synthetic dyestuff in the food according to claim 1, it is characterized in that: step 2) described actual sample pre-treatment is,
Solid sample: smash to pieces, in the ratio of sample: redistilled water=1g:2mL, in sample, add redistilled water, and regulate pH to 8-9, soaks filtration or centrifugal after 20-60 minute, get filtrate filtered or centrifugal after supernatant to be measured;
Liquid sample: when liquid sample does not have obvious solid matter, directly to be measured; If obvious solid matter is arranged, to get fluid sample and cross 0.22 micron filter membrane, filtrate is to be measured.
4. utilize the Raman enhanced spectrum to detect the method for synthetic dyestuff in the food according to claim 1, it is characterized in that: the described detection of step 3, the step 2 of learning from else's experience liquid to be measured and after Raman strengthens reagent and mixes with the volume ratio of 10:1 ~ 1:10, laser is assembled, and carries out Raman spectrum and detects; According to the contrast of the collection of illustrative plates of standard items, whether qualitative discrimination detects.
5. utilize the Raman enhanced spectrum to detect the method for synthetic dyestuff in the food according to claim 1, it is characterized in that: described synthetic dyestuff comprises sunset yellow, acid orange, lure red, lemon yellow, light blue, red scarlet, famille rose, quinoline yellow.
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Cited By (14)
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| CN104237198A (en) * | 2014-07-31 | 2014-12-24 | 中国人民解放军第二军医大学 | Method for judging whether traditional Chinese medicines or traditional Chinese medicine decoction pieces are dyed or not |
| CN104374762A (en) * | 2014-12-08 | 2015-02-25 | 河北省食品检验研究院 | Laser Raman spectrum detection method for quickly analyzing content of basic flavine in soybean hull |
| CN104483303A (en) * | 2015-01-05 | 2015-04-01 | 贵州省流通环节食品安全检验中心 | Method for measuring citrus red II in citrus through surface-enhanced Raman spectroscopy |
| CN104792711A (en) * | 2015-05-05 | 2015-07-22 | 中国计量科学研究院 | Synthetic pigment detection method and synthetic pigment detection system |
| WO2016176823A1 (en) * | 2015-05-05 | 2016-11-10 | 中国计量科学研究院 | Synthetic pigment detection method and system |
| CN106770159A (en) * | 2016-12-02 | 2017-05-31 | 中国计量大学 | High sensitivity food color detection method |
| CN107121424A (en) * | 2017-06-16 | 2017-09-01 | 济南出入境检验检疫局检验检疫技术中心 | The quick determination method of rose red b in a kind of beverage |
| CN107192701A (en) * | 2017-08-07 | 2017-09-22 | 江苏师范大学 | A kind of surface enhanced Raman scattering substrate for detecting synthetic food color and its preparation method and application |
| CN107271424A (en) * | 2017-06-16 | 2017-10-20 | 济南出入境检验检疫局检验检疫技术中心 | The quick determination method of newly red in a kind of food |
| CN108181293A (en) * | 2017-12-15 | 2018-06-19 | 上海海洋大学 | The Surface enhanced Raman spectroscopy method of pigment in a kind of quick detection beverage |
| CN109406489A (en) * | 2018-11-08 | 2019-03-01 | 安徽中科赛飞尔科技有限公司 | A kind of surface enhanced Raman scattering substrate material and its preparation method and application |
| CN110125437A (en) * | 2019-05-29 | 2019-08-16 | 浙江工业大学 | Preparation method of positive charge modified gold nanoparticles with controllable particle size |
| CN112285092A (en) * | 2020-10-29 | 2021-01-29 | 浙江大学 | Safflower dyeing rapid detection method based on surface enhanced Raman spectroscopy |
| CN114184594A (en) * | 2021-11-24 | 2022-03-15 | 厦门大学 | Electronegative molecule SERS detection method based on electropositive SERS substrate |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104237198A (en) * | 2014-07-31 | 2014-12-24 | 中国人民解放军第二军医大学 | Method for judging whether traditional Chinese medicines or traditional Chinese medicine decoction pieces are dyed or not |
| CN104374762A (en) * | 2014-12-08 | 2015-02-25 | 河北省食品检验研究院 | Laser Raman spectrum detection method for quickly analyzing content of basic flavine in soybean hull |
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| CN104483303A (en) * | 2015-01-05 | 2015-04-01 | 贵州省流通环节食品安全检验中心 | Method for measuring citrus red II in citrus through surface-enhanced Raman spectroscopy |
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| CN106770159A (en) * | 2016-12-02 | 2017-05-31 | 中国计量大学 | High sensitivity food color detection method |
| CN107121424B (en) * | 2017-06-16 | 2019-09-27 | 济南海关技术中心 | The rapid detection method of rose red b in a kind of beverage |
| CN107271424A (en) * | 2017-06-16 | 2017-10-20 | 济南出入境检验检疫局检验检疫技术中心 | The quick determination method of newly red in a kind of food |
| CN107121424A (en) * | 2017-06-16 | 2017-09-01 | 济南出入境检验检疫局检验检疫技术中心 | The quick determination method of rose red b in a kind of beverage |
| CN107271424B (en) * | 2017-06-16 | 2019-09-27 | 济南海关技术中心 | The rapid detection method of newly red in a kind of food |
| CN107192701A (en) * | 2017-08-07 | 2017-09-22 | 江苏师范大学 | A kind of surface enhanced Raman scattering substrate for detecting synthetic food color and its preparation method and application |
| CN108181293A (en) * | 2017-12-15 | 2018-06-19 | 上海海洋大学 | The Surface enhanced Raman spectroscopy method of pigment in a kind of quick detection beverage |
| CN109406489A (en) * | 2018-11-08 | 2019-03-01 | 安徽中科赛飞尔科技有限公司 | A kind of surface enhanced Raman scattering substrate material and its preparation method and application |
| CN110125437A (en) * | 2019-05-29 | 2019-08-16 | 浙江工业大学 | Preparation method of positive charge modified gold nanoparticles with controllable particle size |
| CN112285092A (en) * | 2020-10-29 | 2021-01-29 | 浙江大学 | Safflower dyeing rapid detection method based on surface enhanced Raman spectroscopy |
| CN114184594A (en) * | 2021-11-24 | 2022-03-15 | 厦门大学 | Electronegative molecule SERS detection method based on electropositive SERS substrate |
| CN114184594B (en) * | 2021-11-24 | 2023-11-14 | 厦门大学 | Electronegative molecule SERS detection method based on electropositive SERS substrate |
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