CN107389654A - Food additive detection method based on surface enhanced Raman spectroscopy - Google Patents
Food additive detection method based on surface enhanced Raman spectroscopy Download PDFInfo
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- CN107389654A CN107389654A CN201710588389.XA CN201710588389A CN107389654A CN 107389654 A CN107389654 A CN 107389654A CN 201710588389 A CN201710588389 A CN 201710588389A CN 107389654 A CN107389654 A CN 107389654A
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- 238000001514 detection method Methods 0.000 title claims abstract description 44
- 235000013373 food additive Nutrition 0.000 title claims abstract description 18
- 239000002778 food additive Substances 0.000 title claims abstract description 18
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 15
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 32
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 32
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- 235000013312 flour Nutrition 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000001509 sodium citrate Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 54
- 150000002148 esters Chemical class 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000020097 white wine Nutrition 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 235000019998 barley wine Nutrition 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 235000014101 wine Nutrition 0.000 abstract description 2
- -1 di (2-ethyl) hexyl phthalate Chemical compound 0.000 abstract 3
- 239000012086 standard solution Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000209072 Sorghum Species 0.000 description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ZAEOWXUVMZSOCH-UHFFFAOYSA-M silver sodium 3-carboxy-3,5-dihydroxy-5-oxopentanoate nitrate Chemical compound [N+](=O)([O-])[O-].[Ag+].C(CC(O)(C(=O)O)CC(=O)O)(=O)[O-].[Na+] ZAEOWXUVMZSOCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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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- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
A food additive detection method based on surface enhanced Raman spectroscopy relates to the technical field of analytical chemistry detection of food additives. The method comprises the steps of taking silver nano sol obtained by reducing silver nitrate with sodium citrate as an SERS substrate, and respectively carrying out SERS detection on pure azodicarbonamide and di (2-ethyl) hexyl phthalate standard solution to obtain a standard curve. And performing SERS detection on azodicarbonamide in the flour purchased in the market and di (2-ethyl) hexyl phthalate in the highland barley wine and the Erguotou wine, and performing comparison and identification with a standard peak spectrogram. The SERS technology based on the silver nanosol can meet the requirement for detecting food additives of azodicarbonamide and di (2-ethyl) hexyl phthalate, the detection limit of the SERS technology is smaller than the limited use range specified by the state, and the SERS technology can be used for semi-quantitative detection of the additives in actual food.
Description
Technical field
The present invention relates to the analytical chemistry detection technique field of food additives, is specifically related to one kind and is based on surface enhanced
The food additives detection method of Raman spectrum.
Background technology
According to China's food hygiene law, food additives are a kind of artificial synthesized materials or natural materials, are to change
The quality and the demand of anti-corrosion and processing technology of kind food and add in food.Research shows, in flour and its flour system
The azodicarbonamide (structural formula is as shown in Figure 1A) of addition in product can cause allergy with other substance reactions in food, roar
The symptoms such as asthma.In addition, the product semicarbazides of its cometabolism, can trigger cancer or gene mutation；Plasticiser phthalic acid
Two (2- ethyls) own esters (structural formula is as shown in Figure 1B) are a kind of colourless, tasteless liquid, and a kind of poisonous chemical industry
Plastics softening agent, it is more uniform that its addition can allow the Particle Distribution in beverage to obtain, and the beverage added with plasticiser can cause people
The hormonal disorder of body；Thus, quick, sensitive, efficient detection method is found, there is certain contain for ensuring food safety
Justice.
Surface Enhanced Raman Scattering Spectrum (SERS) technology overcomes the weakness of normal Raman muting sensitivity, gives structure
The stronger molecular level information of characteristic, it is widely used in analysis detection trace samplings.Meanwhile the detection method has sample pre-
Handle the advantages that quick, detection cost simple, simple to operate is low and reappearance is good.
The present invention prepares silver sol with reduction of sodium citrate method, and is added as substrate with SERS technology for detection food
Agent --- plasticiser O-phthalic common in common oxidant azodicarbonamide and barley wine, strong, colourless liquor distilled from sorghum white wine in flour
Sour two (2- ethyls) own esters.
The content of the invention
The technical problem to be solved in the present invention is offer a kind of simplicity, the sensitively food based on SERS
Additive detection method.
To achieve these goals, the technical solution adopted in the present invention is：It is a kind of based on SERS
Food additives detection method, for detecting the plasticizing often added in the oxidant azodicarbonamide often added in flour, white wine
Agent phthalic acid two (2- ethyls) own ester, step are as follows：
1) silver nanoparticle colloidal sol, is synthesized：
The silver nanoparticle colloidal sol that silver nitrate obtains is reduced using sodium citrate as reducing agent and is used as SERS substrates；
2), the preparation of standard liquid
Prepare the azodicarbonamide standard liquid or phthalic acid two (2- ethyls) own ester standard of a series of various concentrations
Solution；
3), standard SERS spectrograms detect
A series of azodicarbonamide standard liquid of various concentrations or phthalic acid two (2- ethyls) own ester standard is molten
Liquid mixes with silver nanoparticle colloidal sol prepared by step 1), its SERS spectrogram is detected, as standard spectrogram；
4), the detection of food additives
The flour of actual purchase is mixed with distilled water, ultrasound, centrifugation, the silver nanoparticle for taking supernatant liquor to be prepared with step 1)
Colloidal sol is mixed, and detects its SERS spectrogram, and the standard spectrogram obtained with step 3) contrasted, carries out pointing out and containing for characteristic peak
The detection of amount；
Or the silver nanoparticle colloidal sol for directly preparing the white wine of actual purchase with step 1) mixes, and detects its SERS spectrogram,
The standard spectrogram obtained with step 3) contrasted, carry out characteristic peak point out and the detection of content.
As the further preferred of the food additives detection method based on SERS of the invention：
Azodicarbonamide standard liquid is to be configured to 10 as solvent dilution using pure water in step 2)-3mol/L、10- 4mol/L、10-5mol/L、10-6mol/L、10-7Mol/L amounts to 5 various concentrations.Phthalic acid two (2- ethyls) own ester mark
Quasi- solution is to be configured to 10 as solvent dilution using ethanol-3mol/L、10-4mol/L、10-5mol/L、10-6mol/L、10- 7mol/L、10-8mol/L、10-9Mol/L amounts to 7 various concentrations.
The silver nanoparticle colloidal sol that the present invention is mainly obtained using reduction of sodium citrate silver nitrate is as SERS substrates, respectively to pure
Azodicarbonamide and the own ester standard liquid of phthalic acid two (2- ethyls) carry out SERS detections, obtain standard curve.It is right again
(the 2- second of phthalic acid two in two kinds of white wine of azodicarbonamide and barley wine and strong, colourless liquor distilled from sorghum in the flour of market purchase
Base) own ester carries out SERS detections, compare pointing out with base peak spectrogram.SERS technologies based on silver nanoparticle colloidal sol can meet
Requirement for detection food additives azodicarbonamide and phthalic acid two (2- ethyls) own ester, its detection limit are respectively less than state
Limitation use range as defined in family, and the half-quantitative detection for the additive that can be used in actual food product.
Relative to prior art, beneficial effects of the present invention performance is as follows：
1), material required for detection method of the invention is simple, it is not necessary to which complicated pretreatment, the operation cycle is short, cost
It is low, and very low Monitoring lower-cut can be reached.
2), SERS detection techniques of the invention are expected to be used for the relevant food such as food additives security fields, for detection
Food additives, ensure that human health is significant.
Brief description of the drawings
A kind of food additives based on SERS of the present invention are examined with accompanying drawing with reference to embodiments
Survey method, which is made, to be discussed further.
Fig. 1 is the chemical structural formula for the food additives that the present invention detects：A is azodicarbonamide
(Azodicarbonamide)；B is the own ester (DEHP) of phthalic acid two (2- ethyls)；
Fig. 2 is the standard SERS spectrograms of various concentrations azodicarbonamide；
Fig. 3 is contained azodicarbonamide SERS spectrograms from the flour of market purchase；
Fig. 4 is the standard SERS spectrograms of various concentrations phthalic acid two (2- ethyls) own ester；
Fig. 5 is two kinds of certain brand white wine (barley wine (highland barley wine) and the strong, colourless liquor distilled from sorghum from market purchase
(erguotou liquor)) in contained phthalic acid two (2- ethyls) own ester SERS spectrograms.
Embodiment
Embodiment 1
Step 1: synthesis silver nanoparticle colloidal sol
0.0395g silver nitrate is weighed with electronic analytical balance, places it in three of the deionized water three times containing 150ml
In mouth flask, boiling is quickly heated up to, 3ml, 1% sodium citrate solution is then added, solution is held in the state of boiling
Continuous heating 0.5h.The silver nanoparticle colloidal sol of celadon is finally obtained, washing, is centrifuged, 5 times of concentration is stand-by.
Step 2: the configuration of azodicarbonamide standard liquid
The azodicarbonamide that 0.0120g is weighed with electronic analytical balance is placed in beaker, adds a small amount of pure water dissolving, then will
It is poured into 100ml volumetric flask, continuously adds pure water, constant volume, you can obtain 10-3Mol/L azodicarbonamide.With pure water by
Step dilution obtains 10-4mol/L、10-5mol/L、10-6mol/L、10-7Mol/L azodicarbonamide solution.
Step 3: azodicarbonamide standard SERS spectrograms detect
Respectively with liquid-transfering gun draw 5 μ L silver sol and 5 μ L various concentrations azodicarbonamide standard liquid, will both in
Uniformly mixed in centrifuge tube, the mixed liquor for then drawing 2 μ L is dropped on chip, and SERS detections are carried out after naturally dry.Detection
As a result as shown in Fig. 2 the characteristic peak of the azodicarbonamide solution of various concentrations is obvious, and the intensity of characteristic peak is with the decline of concentration
And weaken, Monitoring lower-cut 10-7mol/L。
Step 4: the SERS detections of the azodicarbonamide in actual flour
Room temperature, appropriate flour is dissolved in pure water, with 1000r/min centrifugation 3min, draws supernatant liquor in dry
Testing sample is used as in net test tube；
Draw the upper strata of the flour after the μ L of silver nanoparticle colloidal sol 5 and 5 μ the L centrifugation of the synthesis of above-mentioned steps one respectively with liquid-transfering gun
Clear liquid is in centrifuge tube, and vibration makes it well mixed, then draws the 2 mixed solution of μ L and drops on chip, naturally dry,
Carry out SERS detections.(curve a represents concentration as 10 to testing result in Fig. 3 as shown in curve b in Fig. 3-5Azo formyl during mol/L
The standard SERS spectrograms of amine).
Contrast experiment：
1., the supernatant liquor of the silver sol of drawing with liquid-transfering gun 5 μ L respectively, flour after 5 μ L centrifugations and 5 μ L, 10- 4For mol/L azodicarbonamide standard liquids in centrifuge tube, vibration makes it well mixed, then draws the mixed solution drops of 2 μ L
On chip, naturally dry, SERS detections are carried out.Testing result is as shown in curve c in Fig. 3.
2., the supernatant liquor of the silver sol of drawing with liquid-transfering gun 5 μ L respectively, flour after 5 μ L centrifugations and 5 μ L, 10- 3For mol/L azodicarbonamide standard liquids in centrifuge tube, vibration makes it well mixed, then draws the mixed solution drops of 2 μ L
On chip, naturally dry, SERS detections are carried out.Testing result is as shown in curve d in Fig. 3.
Testing result is shown, flour sample is carried out after simply pre-processing, you can be detected using SERS technologies to it
It is qualitative, and the standard liquid spectrogram added in flour soln is contrasted, the azodicarbonamide that wherein flour sample directly detects
Feature peak intensity between contrast experiment 1. and 2. between, can be with the concentration of the azodicarbonamide contained of the actual flour of initial guess
Between 10-3mol/L-10-4Between mol/L.
Embodiment 2
Step 1: synthesis silver nanoparticle colloidal sol
With embodiment 1.
Step 2: the configuration of phthalic acid two (2- ethyls) own ester standard liquid
Because phthalic acid two (2- ethyls) own ester is not dissolved in water and be dissolved in ethanol, thus we with ethanol to neighbour
The own ester of phthalic acid two (2- ethyls) carries out gradient dilution.4ml phthalic acid two (2- ethyls) own ester is taken, it is dilute to add ethanol
Release to 10ml, you can obtain 10-3Mol/L phthalic acid two (2- ethyls) own ester, and progressively it is diluted to 10 with ethanol- 4mol/L、10-5mol/L、10-6mol/L、10-7mol/L、10-8mol/L、10-9Mol/L phthalic acid two (2- ethyls) oneself
Ester standard liquid.
Step 3: the own ester standard SERS spectrograms detection of phthalic acid two (2- ethyls)
5 μ L silver sol and phthalic acid two (2- ethyls) own ester mark of 5 μ L various concentrations are drawn with liquid-transfering gun respectively
Quasi- solution, both are uniformly mixed in centrifuge tube, the mixed liquor for then drawing 2 μ L is dropped on chip, and naturally dry is laggard
Row SERS is detected.Testing result is as shown in figure 4, the characteristic peak of phthalic acid two (2- ethyls) own ester solution of various concentrations is bright
It is aobvious, and the intensity of characteristic peak weakens with the decline of concentration, Monitoring lower-cut 10-9mol/L。
Step 4: the SERS detections of phthalic acid two (2- ethyls) own ester in actual white wine
The μ L of silver sol 5 and 5 μ L of the synthesis of above-mentioned steps one two kinds of white wine are drawn respectively with liquid-transfering gun in centrifuge tube, are shaken
Swinging makes it well mixed, and the mixed solution for then drawing 2 μ L is dropped on chip, naturally dry, carries out SERS detections.Inspection
It is as shown in Figure 5 to survey result.The SERS characteristic peaks of two kinds of Wine Samples of gained contrast with the standard liquid characteristic peak in step 3,
It can point out as phthalic acid two (2- ethyls) own ester molecule.In addition, (the 2- second of phthalic acid two present in every kind of white wine
Base) own ester content can use as described in Example 1 method be measured.
Above content is only to design example and explanation of the invention, affiliated those skilled in the art
Various modifications or supplement are made to described specific embodiment or is substituted using similar mode, without departing from invention
Design or surmount scope defined in the claims, protection scope of the present invention all should be belonged to.
Claims (3)
- A kind of 1. food additives detection method based on SERS, for detecting the oxidation often added in flour Plasticiser phthalic acid two (2- ethyls) own ester often added in agent azodicarbonamide, white wine, it is characterised in that step is such as Under：1) silver nanoparticle colloidal sol, is synthesized：The silver nanoparticle colloidal sol that silver nitrate obtains is reduced using sodium citrate as reducing agent and is used as SERS substrates；2), the preparation of standard liquidPrepare the azodicarbonamide standard liquid or phthalic acid two (2- ethyls) own ester standard liquid of a series of various concentrations；3), standard SERS spectrograms detectBy a series of azodicarbonamide standard liquid of various concentrations or phthalic acid two (2- ethyls) own ester standard liquid with Silver nanoparticle colloidal sol mixing prepared by step 1), detects its SERS spectrogram, as standard spectrogram；4), the detection of food additivesThe flour of actual purchase is mixed with distilled water, ultrasound, centrifugation, the silver nanoparticle colloidal sol for taking supernatant liquor to be prepared with step 1) Mixing, detects its SERS spectrogram, the standard spectrogram obtained with step 3) contrasted, carry out characteristic peak point out and content Detection；Or the silver nanoparticle colloidal sol for directly preparing the white wine of actual purchase with step 1) mixes, and its SERS spectrogram is detected, with step The rapid standard spectrogram 3) obtained contrasted, carry out characteristic peak point out and the detection of content.
- 2. detection method as claimed in claim 1, it is characterised in that azodicarbonamide standard liquid is using pure in step 2) Water is configured to 10 as solvent dilution-3mol/L、10-4mol/L、10-5mol/L、10-6mol/L、10-7Mol/L amounts to 5 differences Concentration.
- 3. detection method as claimed in claim 1, it is characterised in that phthalic acid two (2- ethyls) own ester mark in step 2) Quasi- solution is to be configured to 10 as solvent dilution using ethanol-3mol/L、10-4mol/L、10-5mol/L、10-6mol/L、10- 7mol/L、10-8mol/L、10-9Mol/L amounts to 7 various concentrations.
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| CN109557069A (en) * | 2018-05-30 | 2019-04-02 | 厦门市普识纳米科技有限公司 | A kind of Raman detection method of forbidding azo dyes |
| CN108844944A (en) * | 2018-06-28 | 2018-11-20 | 广西桂林锐德检测认证技术有限公司 | The Raman spectra detection process of phthalic ester plasticizer in vinegar |
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