CN112461813A - Method for detecting TBHQ (tert-butyl-hydroquinone) by surface enhanced Raman spectroscopy - Google Patents
Method for detecting TBHQ (tert-butyl-hydroquinone) by surface enhanced Raman spectroscopy Download PDFInfo
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- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000004250 tert-Butylhydroquinone Substances 0.000 title claims abstract description 65
- 235000019281 tert-butylhydroquinone Nutrition 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 18
- 229910017489 Cu I Inorganic materials 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229920000333 poly(propyleneimine) Polymers 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010931 gold Substances 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000003223 protective agent Substances 0.000 claims abstract description 4
- 238000001514 detection method Methods 0.000 claims description 18
- 102000004190 Enzymes Human genes 0.000 claims description 16
- 108090000790 Enzymes Proteins 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000012086 standard solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- AURFVNDXGLQSNN-UHFFFAOYSA-K trisodium 2-hydroxypropane-1,2,3-tricarboxylic acid phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O AURFVNDXGLQSNN-UHFFFAOYSA-K 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229960004441 tyrosine Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000013599 spices Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 150000004053 quinones Chemical class 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 25
- 230000008901 benefit Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 235000006679 Mentha X verticillata Nutrition 0.000 description 3
- 235000002899 Mentha suaveolens Nutrition 0.000 description 3
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 244000290333 Vanilla fragrans Species 0.000 description 2
- 235000009499 Vanilla fragrans Nutrition 0.000 description 2
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
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- 239000008371 vanilla flavor Substances 0.000 description 2
- IDGSXMQBQUGSRF-UHFFFAOYSA-N 2,4-dibutyl-3-methylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1C IDGSXMQBQUGSRF-UHFFFAOYSA-N 0.000 description 1
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000705930 Broussonetia papyrifera Species 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a method for detecting TBHQ by surface enhanced Raman spectroscopy, which relates to the technical field of chemical analysis. According to the method, Cu-I/CDs are used as a reducing agent, polypropylene imine is used as a protective agent, chloroauric acid is reduced, a composite nanoenzyme system consisting of gold nanoparticles and Cu-I/CDs is obtained, TBHQ is selectively oxidized into red oxidized quinones due to the superior catalytic property, and a novel method for detecting TBHQ by using a high-sensitivity and strong-selectivity surface enhanced Raman spectrum is established based on the surface enhanced Raman property of a TBHQ oxidation product.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a method for detecting TBHQ by surface enhanced Raman spectroscopy.
Background
In the production process of the essence and flavor, some antioxidants of synthetic phenols are often added to prevent or delay the oxidative deterioration of the essence, improve the stability of the essence and prolong the storage period, and the oxidation speed of the essence and flavor can be delayed by adding the antioxidants. Tert-butyl hydroquinone (TBHQ) is a common antioxidant, and has stronger oxidation resistance compared with the traditional antioxidants such as butyl hydroxy anisole, 2, 6-dibutyl hydroxy toluene and the like; in addition, TBHQ is relatively stable to heat and does not have any off-flavors when added to the grease samples. However, TBHQ has certain toxicity to human bodies, TBHQ can be decomposed after long-term storage, and the metabolite tert-butyl-p-benzoquinone has high toxicity. GB 27602014 clearly states that the maximum addition amount of TBHQ in edible vegetable oil is 200 mg/kg. Common detection methods of TBHQ include a colorimetric method, a liquid chromatography, a gas chromatography-mass spectrometry method and the like, the colorimetric method is frequently adopted due to simple and rapid operation and no need of large-scale instruments and equipment, but the colorimetric method becomes a difficult problem to be solved in detection due to poor characteristics and serious detection interference.
The Surface Enhanced Raman Spectroscopy (SERS) is a very effective tool for detecting intermolecular interaction and characterizing surface molecular adsorption behavior and molecular structure, has the advantages of high detection sensitivity, simple sample pretreatment, high analysis speed, low detection cost, realization of real-time in-situ detection and the like, has been used for rapid detection of food additives, pesticide residues and the like in food and agricultural products, but has not been reported for the technology of TBHQ detection.
The nano enzyme is a mimic enzyme which not only has the unique performance of nano materials, but also has a catalytic function. Carbon Dots (CDs) are a novel carbon nanomaterial with a size less than 10nm, and are composed of sp2/sp3 hybridized carbon atoms, the surfaces of the carbon dots have different functional groups, and the carbon dots have fluorescence properties depending on the components of the carbon dots, so that researchers have great interest due to good photoinduced electron transfer and electron energy storage properties and excellent up-conversion photoluminescence behavior and two-photon absorption properties. Research on carbon dots serving as nanoenzymes has been reported, gold nanometer preparation by utilizing carbon dot reducibility has also been reported, but composite nanoenzymes formed by combining the carbon dots and the nanoenzymes and catalytic oxidation by taking TBHQ as a substrate have been reported, and more importantly, catalytic oxidation products also have surface enhanced Raman characteristics.
Disclosure of Invention
Therefore, the invention provides a method for detecting TBHQ by surface enhanced Raman spectroscopy, which aims to solve the problems of poor characteristics, serious detection interference and the like of the conventional common detection method for TBHQ.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to a first aspect of the present invention, a method for detecting TBHQ by surface enhanced raman spectroscopy, the method comprising the steps of:
adding 50-100 μ L of composite nanoenzyme and TBHQ standard solution into colorimetric tube with plug, diluting to 2mL with buffer solution, shaking, standing for 5-10min, detecting by surface enhanced Raman spectroscopy, and measuring to 430.9cm-1Taking the TBHQ concentration as a horizontal coordinate and the Raman signal intensity as a vertical coordinate, drawing a standard curve to obtain a regression equation;
sucking sample extractive solution, volatilizing in water bath, adding 50-100 μ L composite nanometer enzyme, diluting with buffer solution to 2mL, shaking, standing for 5-10min, performing surface enhanced Raman spectroscopy, and measuring to 430.9cm-1And substituting the intensity of the Raman signal into the regression equation to calculate the TBHQ content of the sample.
Further, the composite nano enzyme is prepared by mixing gold nanoparticles and Cu-I/CDs, and is prepared by reducing chloroauric acid by using Cu-I/CDs as a reducing agent and polypropylene imine as a protective agent.
Further, the preparation method of the composite nano enzyme comprises the following specific steps: and (2) adding 10-15 parts of ultrapure water into 1 part of polypropylene imine, adding 0.04-0.06 part of chloroauric acid under stirring, adding 0.1-0.2 part of Cu-I/CDs, and stirring for 30-40min until the solution turns into reddish brown to obtain the composite nano enzyme.
Further, the concentration of the polypropylene imine is 0.25 g/mL; the concentration of the chloroauric acid is 1%.
Further, the preparation method of the Cu-I/CDs comprises the following specific steps: weighing 1 part of CuCl2And 3-5 parts of 3-iodine-L-tyrosine, dissolving in 400-800 parts of ultrapure water, mixing and dissolving, adding 0.1-0.3 part of ethylenediamine, performing ultrasonic treatment for 10-20min, transferring to a polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 8-10h, naturally cooling, filtering with a filter membrane with the aperture of 0.22 mu m, and performing dialysis treatment for 24h with a dialysis bag with the molecular weight cutoff of 3000D to obtain the water-soluble Cu-I/CDs.
Further, the concentration of the TBHQ standard solution is 0.033-33.33 mg/kg.
Further, the buffer solution is a sodium citrate-disodium hydrogen phosphate buffer solution having a pH of 7.4.
Further, the conditions of the surface enhanced raman spectroscopy detection are as follows: the excitation wavelength is 785nm, the laser power is 500mW, and the scanning time is 10 s.
Further, the preparation method of the sample extracting solution comprises the following steps: accurately sucking 2.0-5.0mL of essence and spice sample, placing in a 25mL brown volumetric flask, adding methanol to dilute to scale, ultrasonically extracting for 30min, and filtering with qualitative filter paper to obtain sample extract.
Further, the water bath drying temperature is 70 ℃.
The invention has the following advantages:
1. the method for detecting TBHQ by using surface enhanced Raman spectroscopy utilizes Cu-I/CDs as a reducing agent and polypropylene imine as a protective agent to reduce chloroauric acid to obtain a composite nanoenzyme system consisting of gold nanoparticles and Cu-I/CDs.
2. The catalytic oxidation system established in the method for detecting TBHQ by using the surface enhanced Raman spectroscopy has specific oxidation on TBHQ, other synthetic phenolic antioxidants with similar structures and properties do not have the reaction, and Raman spectroscopy under detection wave number does not exist, so that the method has the characteristics of high sensitivity, good reproducibility and accuracy.
3. The Cu-I/CDs in the method for detecting TBHQ by surface enhanced Raman spectroscopy are used as reducing agents and nano-enzymes, and the Cu-I/CDs and the gold nano-particles have a synergistic catalytic effect, so that a reaction system is stable and rapid.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so that those skilled in the art can understand and read the present invention, and do not limit the conditions for implementing the present invention, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the functions and purposes of the present invention, should still fall within the scope of the present invention.
Fig. 1 is a SERS spectrum of TBHQ oxidized by the composite nanoenzyme provided in example 1 of the present invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The Cu-I/CDs in the invention refer to iodine and copper-doped carbon dots.
Example 1: determination of TBHQ in fructus Broussonetiae essence
Step S1, preparation of Cu-I/CDs: 0.1g of CuCl2And 0.4g of 3-iodine-L-tyrosine is dissolved in 40mL of purified water, mixed and dissolved, 100 mu L of ethylenediamine is added, ultrasonic treatment is carried out for 10min, the mixture is transferred to a polytetrafluoroethylene reaction kettle, the mixture is heated for 8h at 180 ℃, after natural cooling, the mixture is firstly filtered by a filter membrane with the aperture of 0.22 mu m, and then dialysis treatment is carried out for 24h by a dialysis bag with the molecular weight cutoff of 3000D, so as to obtain the water-soluble Cu-I/CDs.
Step S2, preparation of composite nano enzyme: 2mL of 0.25g/mL polypropylene imine, 20mL of ultrapure water, 80 μ L of 1% chloroauric acid under stirring, 200 μ L of Cu-I/CDs under stirring, and after stirring for 30min, the solution turns into reddish brown, so as to obtain the composite nano enzyme formed by mixing gold nanoparticles and Cu-I/CDs.
Step S3, determining the detection wave number of the TBHQ oxidation product SERS spectrum: adding 50-100 μ L of composite nano enzyme and 1mg/kg of TBHQ standard solution into a colorimetric tube with a plug, diluting to 2mL by using a sodium citrate-disodium hydrogen phosphate buffer solution with the pH value of 7.4, shaking uniformly, standing for 5-10min, and collecting Raman spectrum by using a portable Raman spectrometer under the conditions of 785nm exciting light, 500mW laser power and 10s scanning time. As shown in FIG. 1, 430.96, 878.5, 1039.9, 1081.9 and 1363.3cm were observed in the SERS spectrum of TBHQ oxidized product-1SERS peak at (c). The concentration of TBHQ is in the range of 0.033-33.33mg/kg and the concentration of TBHQ is 430cm-1The intensity of the Raman spectrum peak shows a good linear relationship, so 430cm is selected-1The wavenumber was detected as SERS spectrum of TBHQ.
Step S4, TBHQ working curve making: adding 50 μ L of composite nanometer enzyme into colorimetric tube with plug, 0.033-33.33mg/kg TBHQ standard solution, diluting with 7.4 pH sodium citrate-disodium hydrogen phosphate buffer solution to 2mL, shaking, standing for 5-10min, measuring 430cm under conditions of 785nm exciting light, 500mW laser power and 10s scanning time-1And (4) determining the intensity of the Raman signal, and drawing a standard curve by taking the TBHQ concentration as a horizontal coordinate and the Raman signal intensity as a vertical coordinate to obtain a regression equation. See table 1.
TABLE 1 TBHQ working curve table
Step S5, determination of TBHQ in fructus Broussonetiae essence
Step S51: accurately sucking a 2.0mL sample of the Broussonetia papyrifera essence, placing the sample in a 25mL brown volumetric flask, adding methanol to dilute to a scale, ultrasonically extracting for 30min, and filtering with qualitative filter paper to obtain a sample extracting solution. Sucking 1.00mL of sample extract, volatilizing at 70 deg.C in water bath, adding 50 μ L of composite nanoenzyme, diluting to 2mL with pH 7.4 sodium citrate-disodium hydrogen phosphate buffer solution, shaking, standing for 5-10min, measuring 430cm under conditions of 785nm excitation light, laser power of 500mW, and scanning time of 10s-1And substituting the intensity of the Raman signal into the regression equation of the step S4 to calculate that the TBHQ content of the sample is 24.11 mg/kg.
Step S52: recovery and precision experiments: and respectively adding 2 TBHQ standard solutions with different concentrations into the sample of the fructus broussonetiae essence. Each concentration was assayed 3 times in parallel, spiked recoveries were calculated, and relative standard deviations RSD were calculated, with the results shown in table 2. The recovery rate of TBHQ is measured to be 95.2-98.9%, the RSD is measured to be 0.20-1.3%, and the method has good accuracy and precision.
Table 2 sample recovery and RSD (n ═ 3)
Example 2: determination of TBHQ in mint essence
Step S1, preparation of Cu-I/CDs: the same as example 1;
step S2, preparation of composite nano enzyme: the same as example 1;
step S3, determining the detection wave number of the TBHQ oxidation product SERS spectrum: the same as example 1;
step S4, TBHQ working curve making: the same as example 1;
step S5, measuring TBHQ in the mint essence sample: the TBHQ content of the mint samples was 30.21mg/kg as in example 1.
Example 3: determination of TBHQ in vanilla essence
Step S1, preparation of Cu-I/CDs: the same as example 1;
step S2, preparation of composite nano enzyme: the same as example 1;
step S3, determining the detection wave number of the TBHQ oxidation product SERS spectrum: the same as example 1;
step S4, TBHQ working curve making: the same as example 1;
step S5, determination of TBHQ in the vanilla flavor sample: as in example 1, the TBHQ content of the vanilla flavour sample was 9.36 mg/kg.
Example 4: determination of TBHQ in tobacco sesame oil-soluble essence
Step S1, preparation of Cu-I/CDs: the same as example 1;
step S2, preparation of composite nano enzyme: the same as example 1;
step S3, determining the detection wave number of the TBHQ oxidation product SERS spectrum: the same as example 1;
step S4, TBHQ working curve making: the same as example 1;
step S5, determination of TBHQ in the vanilla tobacco sesame oil soluble essence: in the same manner as in example 1, the content of TBHQ in the tobacco flavor oil-soluble essence sample was 12.15 mg/kg.
The TBHQ measuring method established by the invention has the advantages of few processing steps, short used time, low processing cost, simple and convenient operation, no need of large instruments and equipment and strong advantage in actual detection.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for detecting TBHQ by surface enhanced raman spectroscopy, comprising the steps of:
adding 50-100 mu L of composite sodium into a colorimetric tube with a plugDiluting the standard solution of rice enzyme and TBHQ to 2mL with buffer solution, shaking, standing for 5-10min, detecting by surface enhanced Raman spectroscopy, and measuring to 430.9cm-1Taking the TBHQ concentration as a horizontal coordinate and the Raman signal intensity as a vertical coordinate, drawing a standard curve to obtain a regression equation;
sucking sample extractive solution, volatilizing in water bath, adding 50-100 μ L composite nanometer enzyme, diluting with buffer solution to 2mL, shaking, standing for 5-10min, performing surface enhanced Raman spectroscopy, and measuring to 430.9cm-1And substituting the intensity of the Raman signal into the regression equation to calculate the TBHQ content of the sample.
2. The method of claim 1, wherein the composite nanoenzyme is prepared by mixing gold nanoparticles and Cu-I/CDs, and reducing chloroauric acid by using Cu-I/CDs as a reducing agent and polypropyleneimine as a protective agent.
3. The method according to claim 1 or 2, wherein the preparation method of the composite nanoenzyme is as follows: and (2) adding 10-15 parts of ultrapure water into 1 part of polypropylene imine, adding 0.04-0.06 part of chloroauric acid under stirring, adding 0.1-0.2 part of Cu-I/CDs, and stirring for 30-40min until the solution turns into reddish brown to obtain the composite nano enzyme.
4. The method of claim 3, wherein the concentration of polypropyleneimine is 0.25 g/mL; the concentration of the chloroauric acid is 1%.
5. The method of claim 2, wherein the Cu-I/CDs is prepared by a method comprising: weighing 1 part of CuCl2And 3-5 parts of 3-iodine-L-tyrosine, dissolving in 400-800 parts of ultrapure water, mixing and dissolving, adding 0.1-0.3 part of ethylenediamine, performing ultrasonic treatment for 10-20min, transferring to a polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 8-10h, naturally cooling, filtering with a filter membrane with the aperture of 0.22 mu m, and performing dialysis treatment for 24h with a dialysis bag with the molecular weight cutoff of 3000D to obtain the water-soluble Cu-I/CDs.
6. The method of claim 1, wherein the concentration of the TBHQ standard solution is from 0.033 to 33.33 mg/kg.
7. The method of claim 1, wherein the buffer solution is a sodium citrate-disodium phosphate buffer solution having a pH of 7.4.
8. The method of claim 1, wherein the conditions for surface enhanced raman spectroscopy detection are: the excitation wavelength is 785nm, the laser power is 500mW, and the scanning time is 10 s.
9. The method of claim 1, wherein the sample extract is prepared by: accurately sucking 2.0-5.0mL of essence and spice sample, placing in a 25mL brown volumetric flask, adding methanol to dilute to scale, ultrasonically extracting for 30min, and filtering with qualitative filter paper to obtain sample extract.
10. The method of claim 1, wherein the water bath has a temperature of 70 ℃.
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