CN106841163B - The quickly Surface enhanced Raman spectroscopy method of detection fluorescent whitening agent FWA199 - Google Patents
The quickly Surface enhanced Raman spectroscopy method of detection fluorescent whitening agent FWA199 Download PDFInfo
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- 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
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Abstract
The invention discloses the Surface enhanced Raman spectroscopy methods of quickly detection fluorescent whitening agent FWA199 a kind of.Polymer is precipitated with Weak solvent and is removed while being extracted object completely with strong solvent by this method；Then surface enhanced reagent is mixed with prepare liquid, is centrifuged, remove part supernatant, remainder oscillation or ultrasound mix after so that nano particle is uniformly dispersed again and carry out Surface enhanced Raman spectroscopy test again；When 633,1013,1172,1327,1537,1592cm‑1Place is there are when obvious characteristic Raman peaks, then there are FWA199 in sample；Then with 1172cm‑1Calibration curve equation is established as quantitative peak in the Characteristic Raman peak at place, to carry out rapid quantitative detection to the FWA199 in sample.The method of the present invention is simple, quick, accurate, sensitive, and surface enhanced reagent cost is low, and easy to carry, storage can be used for field quick detection.
Description
Technical field
The present invention relates to a kind of detection method, belong to fluorescent whitening agent FWA199 in food contact plastic material or product
A kind of detection field, and in particular to Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199.
Background technique
With flourishing for plastics industry, people to performance requirements of the plastic products including appearance property not
It is disconnected to improve, thus improved with fluorescent whitening agent the appearance properties of colored plastic articles more and more attention has been paid to.Fluorescent brightening
Agent (Fluorescent whitening agents, FWAs) is that the colourless fluorescent dye of one kind under the irradiation of ultraviolet light can
Inspire blue, purple light, it is complementary with the yellow light of basic substance and have the effect of brightening.So far, FWAs is in plastics package material
Using the whiteness and gorgeous degree that product can be improved in material, to improve the appearance property of plastic package material.Although limited grind
Study carefully show by human health and environment influence the risk assessment carried out show FWAs under current service condition risk compared with
It is small, but due to the universal compound containing aromatic amino structure and cinnamenyl structure of FWAs, have on toxicity potential
Carcinogenicity, therefore, Chinese (GB 9685-2016), European Union (2002/72/EC) and the U.S. (Code of Federal
Regulations 2006) etc. country all formulated be allowed for produce plastic-food contact material and product lists of additives
(positive list), while alsoing specify the relevant amount of limiting the use of and/or Special migration.4,4'- bis- [2- (adjacent benzonitrile base) ethylene
Base] benzene (FWA 199) is widely applied in food contact plastic products as one of important fluorescent whitening agent, however its excess
Addition and migration dissolution threaten (burnt gorgeous Na etc., chromatography, 2013,31 (1): 83-87) there is huge to human health.
Currently, both at home and abroad to the detection of FWA 199 mainly use liquid chromatography (Tang Juan etc., chromatography, 2014,32 (11):
1230-1235；Wu Zhongling etc., modern food science and technology, 2013,29 (11): 2757-2761), above-mentioned detection method operation is more multiple
Miscellaneous, time-consuming, instrument cost is expensive, and solvent for use, mobile phase have biggish toxicity and corrosivity.Meanwhile product quality is pacified
Complete and risk analysis shows that FWA199 is a kind of quick, former there is an urgent need to establish in current food contact plastic material or product
The in-situ check and test method of position.The present invention with strong solvent dissolution food contact plastic material or product, Weak solvent precipitate high polymer from
The heart establishes the quickly side of analysis the SERS of FWA199 content in the food contact plastic products of matrix complexity after filtering with microporous membrane
Method.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of quickly detection fluorescent whitening agent FWA199's
Surface enhanced Raman spectroscopy method.This method will be gathered while being extracted object completely with strong solvent with Weak solvent
Interference of the object precipitating removal to avoid polymer matrix in SERS test process is closed, surface-enhanced Raman light can be rapidly utilized
Compose FWA199 content in quantitative analysis food contact plastic products.This method is easy to operate, high sensitivity, favorable reproducibility, accurate
Rate is high.
The technical scheme adopted by the invention is as follows: a kind of surface-enhanced Raman light of quickly detection fluorescent whitening agent FWA199
Spectral method, characterized in that the following steps are included:
(1) pre-treatment: the sample of the food contact plastic material or product that shred or shred is weighed, it is complete that strong solvent is added
After dissolution, Weak solvent is added and precipitates macromolecule matrix, filtering with microporous membrane is to be measured；
(2) preparation of surface enhanced reagent: being reacted using gold chloride (or its salt) solution with sodium citrate aqueous solution,
Prepare the aurosol that partial size is 11nm~49nm；
(3) test: by surface enhanced reagent, 2~6:1 is mixed by volume with prepare liquid, and centrifugation removes part supernatant,
Then remainder oscillation or ultrasound, which mix, makes nano particle be uniformly dispersed again, draws mixing liquid in progress surface increasing on carrier
Graceful spectrum test is haled, each sample random acquisition is multiple；
(5) qualitative: to be tested through Surface enhanced Raman spectroscopy, when 633,1013,1172,1327,1537,1592cm-1It deposits at place
In obvious characteristic Raman peaks, then there are fluorescent whitening agent FWA199 in sample；
(6) quantitative: with 1172cm-1The Characteristic Raman peak at place is as quantitative peak, according to the Raman of fluorescent whitening agent FWA199
The response intensity of spectral signal and the linear ratio relation of content obtain calibration curve equation, thus to the fluorescent brightening in sample
Agent FWA199 carries out rapid quantitative detection.
The material of of the invention food contact plastic material or product are as follows: polystyrene, polyvinyl chloride, polyethylene (including
High density polyethylene (HDPE), low density polyethylene (LDPE) etc.), polypropylene or polycarbonate.
The strong solvent of step (1) of the present invention be N,N-dimethylformamide (DMF), tetrahydrofuran (THF), ethyl acetate or
Methylene chloride, wherein the preferred strong solvent for polystyrene is ethyl acetate, and the preferred strong solvent for polyvinyl chloride is four
Hydrogen furans (THF).
The Weak solvent of step (1) of the present invention is methanol, acetonitrile or n-hexane, wherein for polystyrene or polyvinyl chloride
Preferred solvent is methanol.
Preferably, step (1) pre-treatment: weigh sample that 0.1-0.5g (being accurate to 0.001g) is shredded or shredded in
In 100mL stuffed conical flask, after addition 3-10mL strong solvent is completely dissolved, 15-40mL Weak solvent is added and precipitates macromolecule matrix,
Through 0.22 μm of filtering with microporous membrane, prepare liquid is obtained.
Preferably, the preparation of step (2) surface enhanced reagent: accurately weighing 1.0000-1.5000g gold chloride or its salt,
Gold chloride or its salting liquid are configured to 45-50mL water；0.1157-0.2314g sodium citrate accurately is weighed, is configured with 5mL water
At sodium citrate solution；It measures 1.0-3.0mL gold chloride or 110-130 DEG C of accurate temperature controlling, 800- is added in its salting liquid
In the 100g water of 1200r.p.m. constant speed stirring, after several minutes of temperature are stablized, 1.8-4.0mL citric acid is disposably rapidly joined
Sodium water solution continues to be stirred to react 40-60min, cooled to room temperature, the storage of the cool place place of being protected from light.
The accurate temperature controlling mode is oil bath or other heating methods.
Preferably, step (3) is tested: by surface enhanced reagent and prepare liquid, 2~6:1 is mixed and is made total volume by volume
1mL removes 400-800 μ L supernatant with 8000-12000r.p.m. centrifugation 8-12 minutes, then remainder ultrasound or concussion
So that nano particle is uniformly dispersed again, draws 200-400 μ L mixing liquid in carrying out Surface enhanced Raman spectroscopy test on carrier, often
A sample random acquisition is multiple.
The carrier is sheet glass, titanium sheet or plastic culture base.
The instrument parameter condition is as follows: it is 785nm that Raman spectrometer, which emits optical maser wavelength, and fixed laser power is
100-200mW, 3500~200cm of scanning range-1, time of integration 2-10s is averaged for each spot scan 5 times.
Beneficial effects of the present invention:
(1) Surface enhanced Raman spectroscopy rapid detection method of the present invention to FWA199 content in food contact plastic products
It is studied, plastic sample is dissolved through strong solvent, Weak solvent precipitates macromolecule matrix, is extracted quickly, completely by object
While out, by organic high molecular polymer precipitating removal to avoid the interference tested Raman；
(2) surface enhanced reagent is mixed with prepare liquid, is centrifuged, make hydrophobic object is close, be adsorbed on nanometer enhancing
While particle surface, mixture is concentrated to obtain optimization, stable surface-enhanced Raman signals；
(3) theoretical calculation auxiliary criteria sample Raman tests the standard Raman spectroscopy data that more means obtain FWA199, with
Accurate qualitative and quantitative analysis is carried out to object in actual sample.The method of the present invention is simple, quick, accurate, surface enhanced examination
Agent is at low cost, and easy to carry, storage can be used for field quick detection.
Detailed description of the invention
Fig. 1 is different mol ratio (sodium citrate/Au3+) gained aurosol UV-vis spectrum；
Fig. 2 is different mol ratio (sodium citrate/Au3+) gained aurosol HR-TEM and grain size distribution；A figure is HR-
TEM figure, partial size are followed successively by 11,15,27 and 49nm；B figure is grain size distribution；
The molecular structure that Fig. 3 is FWA199 optimizes figure；
Theoretical calculation Raman spectrum and solid etalon product that Fig. 4 is FWA199 test the comparison of Raman spectrum；
Fig. 5 is that (concentration is respectively as follows: 1.0 μM, 0.5 μM, 0.1 μM, 0.07 μM, 0.05 μM, 0.03 to various concentration from top to down
μM, 0.01 μM, 0.007 μM, 0.005 μM, 0.003 μM, solvent DMF/methanol) FWA199 standard solution SERS map；
Fig. 6 is SERS 1172cm-1The adsorption curve (3.0-1000nM) of FWA199 is monitored at characteristic peak；
Fig. 7 is SERS 1172cm-1The calibration curve (3.0-70nM) of characteristic peak；
Fig. 8 is the SERS map of FWA199 in polystyrene plastics sample；
Fig. 9 is the SERS map of FWA199 in igelite sample.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples, and embodiment is not construed as limiting the scope of the present invention.
1 instrument and reagent
Raman spectrometer: Ocean Optics QE65Pro Raman spectrometer；Sensibility reciprocal is the assay balance of 1mg, 0.1mg
(Mei Tele company, Switzerland)；Milli-Q water purifior (Millipore company, the U.S.)；TGL-16C centrifuge (Town in Shanghai pavilion science
Instrument plant)；TU-1901 dual-beam ultraviolet-uisible spectrophotometer (Beijing Puxi General Instrument Co., Ltd)；ZNCL-S
Intelligent electromagnetic stirring heater (Yu Hua Instrument Ltd., Gongyi City)；JEM-2100 high resolution transmission electron microscopy (Japan
Electronics Co., Ltd).
FWA199 standard items: 99.0%, German CNW；Methanol: chromatographically pure (Merk company)；Ethyl acetate: chromatographically pure
(Merk company)；DMF: chromatographically pure (Merk company)；Four hydration gold chlorides, citrate dihydrate trisodium: the pure (Chinese medicines group of analysis
Learn reagent Co., Ltd).
The preparation of standard solution: preparing the FWA199 Standard Stock solutions of 1 000mg/L with DMF, again with methanol when use
It dilutes step by step.
2 instrument conditions
Laser Raman spectrometer determination condition: optical maser wavelength 785nm, laser maximum intensity 200mW, scanning range 1800~
400cm-1, time of integration 5s, integral 10 times.Each sample at least scans 5 times, to obtain accurate Raman spectrogram.
3 sample pre-treatments
Polystyrene plastics sample that 0.25g (being accurate to 0.001g) is shredded or shredded is weighed in 100mL stuffed conical flask
In, after addition 5mL ethyl acetate is completely dissolved, add 15mL methanol extraction, stands 5 minutes, supernatant is transferred to 50mL volumetric flask
In, precipitating uses the supersound washing of 5mL methanol three times respectively again, merges cleaning solution and is also transferred in above-mentioned volumetric flask, is then settled to
50mL crosses 0.22 μm of filtering with microporous membrane, to be measured.
The preparation of 4 surface enhanced reagents
1.000g gold chloride powder is accurately weighed, a small amount of deionized water is added and is dissolved, then is settled to deionized water
The chlorauric acid solution that gold concentration is 1% is made in 47.820g.The sodium citrate solid of 0.1157-0.2314g is accurately weighed, then is used
Deionized water is settled to 5mL, and the sodium citrate solution of various concentration is made, and sodium citrate solution needs matching while using.It measures
The 100g ultrapure water of 110-130 DEG C of accurate temperature controlling, the stirring of 800-1200r.p.m. constant speed is added in 1.0-3.0mL chlorauric acid solution
In, after several minutes of temperature are stablized, 1.8-4.0mL sodium citrate aqueous solution is disposably rapidly joined, continues to be stirred to react 40-
60min, cooled to room temperature, the storage of the cool place place of being protected from light.The method of gold nano particle colloidal sols for configuring different-grain diameter size is
The particle size of gold nano particle colloidal sols is adjusted by controlling amount and the temperature of the trisodium citrate being added during the reaction.
5 uv-visible absorption spectras (Uv) characterization
The optical characteristics of nanogold particle colloidal sol obtained is carried out using quartz colorimetric utensil in ultraviolet-visible spectrophotometer
Characterization, wavelength scanning range 400-800nm.
6 high resolution transmission electron microscopies (HRTEM) characterization image
Example of transmission electron microscope preparation: a droplet colloidal sol is added drop-wise on the copper mesh for being covered with synovial membrane, is not being got dirty
Give free rein to drying in the environment of dye, is then characterized using transmission electron microscope, acceleration voltage 80kV, signal enhancing multiplying power
30000X to 150000X.The particle size, shape and distribution situation of metal nanoparticle are intuitively observed.
7 tests
After surface enhanced reagent is mixed (800 μ L of aurosol, 200 μ L of prepare liquid) by 4:1 volume ratio with prepare liquid,
It is centrifuged 10min under 10000r.p.m., removes 600 μ L supernatants, remainder is placed in Ultrasound Instrument ultrasonic in centrifuge tube, is made molten
Liquid is uniformly mixed again, from the homogeneous solution after above-mentioned centrifugation ultrasound, about 350 μ L is taken to carry out in biological plastics culture medium
SERS test, each sample random acquisition 5 times.
8 FWA199 Raman spectrum datas
Successive optimization is carried out to FWA199 with Gaussian W03 program and carries out the theory of raman frequency to optimum structure
It calculates, obtains theory characteristic spectrogram；FWA199 solid etalon product are scanned using Raman spectrometer, it is special to obtain solid mark product
Levy spectrogram.
9 results and discussion
The selection of 9.1 Pretreatments
The extraction of poisonous and harmful substance generallys use the side such as Soxhlet extraction, ultrasound, concussion in food contact material and product
Formula, if extraction time is inadequate, substance to be detected is extracted not exclusively, and it is relatively low to will lead to testing result.Due to the target of this research
It is to measure the content rather than the amount of dissolution of FWA199 in (foaming) polystyrene plastics, therefore dissolution-precipitation method is used to carry out sample
Pre-treatment goes polymer precipitating divided by protecting detecting instrument not contaminated while extracting object completely.
Inspection information, n,N-Dimethylformamide (DMF), tetrahydrofuran (THF), ethyl acetate, methylene chloride can be molten
Plastic material is solved, and methanol is very poor to high molecular solvability.It is positive that the above solvent dissolved polystyrene plastics are respectively adopted
Sample, again with methanol precipitate dissolved sample solution.For (foaming) polystyrene sample, this patent research discovery
Select the extraction of ethyl acetate/methanol target system object the most complete.
The characterization of 9.2 aurosols
As shown in Fig. 2, HRTEM image is highly uniform, particle is clearly demarcated, and partial size is 11-49nm (Fig. 2).It is molten that gold is carried out simultaneously
The absorption spectrum of glue detects, and maximum absorption band is located at 522-532nm (Fig. 1).According to document it is found that size is in 20nm~80nm
Between gold particle can obtain preferable SERS activity, therefore 24nm colloidal sol prepared by this experiment can achieve best increasing
Potent fruit.
9.3 theoretical Raman spectrums calculate and the ownership of vibration mode
Successive optimization is carried out with 03 program of Gaussian to FWA199 molecule and carries out the reason of raman frequency to optimum structure
By calculating, molecular structure optimum results as shown in figure 3, calculated result file and molecular configuration by the observation of Gaussview 5 and
It analyzes, high matching degree is presented with solid etalon product experiment Raman spectrum after the theoretical Raman spectrum calculating calibration of the output results of molecular structure
(Fig. 4, table 1).
The vibration of theoretical Raman spectrum (DFT) and solid etalon product experiment Raman spectrum (NRS) main peaks of table 1FWA199
Mode ownership
The foundation of 9.4 qualitative-and-quantitative methods and actual sample detection
9.4.1 qualitative detection
Its characteristic peak may be selected as standard of perfection to the qualitative detection of FWA199,633,1013,1172,1327,
1537,1592cm-1It is higher to locate peak intensity, so selected above six peaks are qualitative peak.
9.4.2 quantitative detection
Using 24nm aurosol respectively to a certain concentration gradient (1.0 μM, 0.5 μM, 0.1 μM, 0.07 μM, 0.05 μM, 0.03
μM, 0.01 μM, 0.007 μM, 0.005 μM, 0.003 μM) FWA199 solution carried out according to detection method determined by this experiment
SERS detection, obtains the serial solution SERS map of Fig. 5.By result as it can be seen that when the concentration of FWA199 solution is down to 3.0nM
1013,1172,1537cm-1Equal peaks remain to the presence for being seen that there is SERS enhancing peak, quantitative limit of this concentration as method.It takes
1172cm-1Place a series of peaks SERS come do peak intensity and FWA199 concentration adsorption saturation curve (Fig. 6) and linear relationship song
Line (Fig. 7), available standard curve (y=12918.61448x+10.37903), R2It is 0.9713, range of linearity 3.0-
70nM。
9.4.3 the comparison of actual sample SERS detection and HPLC-MS/MS method
Polystyrene plastics product is chosen as representative sample, is detected after carrying out pre-treatment using SERS method,
As a result curve as shown in Figure 8,633,1013,1172,1327,1537,1592cm-1The peak SERS and FWA199 powder reference substance at place
The Raman peaks of matter are substantially coincident, can be confirmed that SERS of the invention detects the signal of FWA199 in polystyrene plastics.
In order to verify the accuracy of the above method, to the positive plastic products of self-control (FWA199 additive amount is respectively 1mg/kg and 4mg/kg)
Pre-treatment is carried out by the method for the present invention, wherein FWA199 is detected using Liquid Chromatography-Tandem Mass Spectrometry, and comparison result is shown in
Table 2.
The testing result of 2 polystyrene plastics sample of table
It can be seen from comparing result SERS detection method can under the premise of guaranteeing accuracy, save detection time,
It is easy to operate, the pollution of organic phase flow is avoided compared to liquid chromatography-tandem mass, saves testing cost, SERS
Contrast agent can low cost self-control and field quick detection easy to carry, suitable for batch sample.
10. the SERS of FWA199 is quickly detected in polyvinyl chloride plastic material products
Poly- polyvinyl chloride plastic material products, the same 1-8 of remaining processing step are dissolved using tetrahydrofuran.
Test result shows: it has been investigated that selecting extraction of the tetrahydrofuran/methanol system to igelite material
The most completely.It is detected simultaneously through Raman spectrum, as shown in figure 9,633,1013,1172,1327,1537,1592cm-1Place, which exists, draws
Graceful characteristic peak, wherein the peak SERS of solvent does not interfere with measurement, the Characteristic Raman peak of FWA199 and the Raman of solid etalon product powder
Spectrum is consistent.Illustrate that using FWA199 in detection method detection pvc material of the invention or product be also feasible.Into
And infer, method of the invention can be used for detecting polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene or poly- carbon
FWA199 in acid esters material.
Embodiment 1:
The SERS of FWA199 is quickly detected in polystyrene own product
(1) sample pre-treatments
Sample that 0.25g (being accurate to 0.001g) is shredded or shredded is weighed in 100mL stuffed conical flask, 5mL second is added
After acetoacetic ester is completely dissolved, add 15mL methanol extraction, stand 5 minutes, supernatant is transferred in 50mL volumetric flask, and precipitating is distinguished again
Three times with the supersound washing of 5mL methanol, merge cleaning solution to be also transferred in above-mentioned volumetric flask, be then settled to 50mL, it is micro- through 0.22 μm
Hole membrane filtration, it is to be measured.
(2) preparation of surface enhanced reagent
1.000g gold chloride powder is accurately weighed, a small amount of deionized water is added and is dissolved, then is settled to deionized water
The chlorauric acid solution that gold concentration is 1% is made in 47.820g.The sodium citrate solid of 0.1157g is accurately weighed, then uses deionization
Water is settled to 5mL, and sodium citrate solution is made, and sodium citrate solution needs matching while using.2.0mL chlorauric acid solution is measured to be added
In the ultrapure water that 130 DEG C of accurate temperature controlling, 1000r.p.m. constant speed stir, after several minutes of temperature are stablized, disposably rapidly join
3.0mL sodium citrate aqueous solution continues to be stirred to react 50min, cooled to room temperature, the storage of the cool place place of being protected from light.Partial size is made
For the aurosol Contrast agent of 24nm.
(3) it tests
After surface enhanced reagent is mixed (800 μ L of aurosol, 200 μ L of prepare liquid) by 4:1 volume ratio with prepare liquid,
It is centrifuged 10min under 10000r.p.m., removes 600 μ L supernatants, remainder is placed on oscillating ultrasonic in Ultrasound Instrument in centrifuge tube,
Be uniformly mixed solution again, from the homogeneous solution after above-mentioned centrifugation ultrasound, take about 350 μ L in biological plastics culture medium into
Row SERS test, each sample random acquisition 5 times.
Polystyrene sample SERS enhancing map is shown in Fig. 8, and the rate of recovery and precision experiment result are shown in Table 2 sample 1.
Embodiment 2:
The SERS of FWA199 is quickly detected in polystyrene own product
(1) sample pre-treatments
Sample that 0.25g (being accurate to 0.001g) is shredded or shredded is weighed in 100mL stuffed conical flask, 5mL second is added
After acetoacetic ester is completely dissolved, add 15mL methanol extraction, stand 6 minutes, supernatant is transferred in 50mL volumetric flask, and precipitating is distinguished again
Three times with the supersound washing of 5mL methanol, merge cleaning solution to be also transferred in above-mentioned volumetric flask, be then settled to 50mL, cross 0.22 μm of filter
Film, it is to be measured.
(2) preparation of surface enhanced reagent
1.000g gold chloride powder is accurately weighed, a small amount of deionized water is added and is dissolved, then is settled to deionized water
The chlorauric acid solution that gold concentration is 1% is made in 47.820g.The sodium citrate solid of 0.2341g is accurately weighed, then uses deionization
Water is settled to 5mL, and sodium citrate solution is made, and sodium citrate solution needs matching while using.2.0mL chlorauric acid solution is measured to be added
In the ultrapure water that 110 DEG C of accurate temperature controlling, 1000r.p.m. constant speed stir, after several minutes of temperature are stablized, disposably rapidly join
4.45mL sodium citrate aqueous solution continues to be stirred to react 40min, cooled to room temperature, the storage of the cool place place of being protected from light.Partial size is made
For the aurosol Contrast agent of 15nm.
(3) it tests
Surface enhanced reagent is mixed into (820 μ L of aurosol, 180 μ L of prepare liquid) by 4.1:0.9 volume ratio with prepare liquid
Afterwards, it is centrifuged 8min at 12000r.p.m., removes 500 μ L supernatants, remainder is placed on to vibrate in Ultrasound Instrument and surpass in centrifuge tube
Sound is uniformly mixed solution again, from the homogeneous solution after above-mentioned centrifugation ultrasound, takes about 300 μ L in biological plastics culture medium
Middle progress SERS test, each sample random acquisition 5 times.As the result is shown: 633,1013,1172,1327,1537,1592cm-1
The peak SERS at place and the Raman peaks of FWA199 powder standard substance are substantially coincident, and the rate of recovery and precision experiment result are shown in Table
2 sample 2.
Claims (9)
1. a kind of Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199, characterized in that including following step
It is rapid:
(1) pre-treatment: the sample of the food contact plastic material or product that shred or shred is weighed, strong solvent is added and is completely dissolved
Afterwards, Weak solvent is added and precipitates macromolecule matrix, filtering with microporous membrane obtains prepare liquid；
(2) preparation of surface enhanced reagent: accurate temperature controlling 110-130 is added in the solution for measuring 1.0-3.0mL gold chloride or its salt
DEG C, 800-1200r.p.m. constant speed stirring 100g water in, after temperature stablize after, disposably rapidly join 1.8-4.0mL lemon
Acid sodium aqueous solution continues to be stirred to react 40-60min, and cooled to room temperature prepares the aurosol that partial size is 11nm~49nm,
As surface enhanced reagent；
(3) test: by surface enhanced reagent, 2~6:1 is mixed by volume with prepare liquid, and 8000-12000r.p.m. centrifugation is gone
Except part supernatant, then remainder oscillation or ultrasound, which mix, makes nano particle be uniformly dispersed again, draws mixing liquid in load
Surface enhanced Raman spectroscopy test is carried out on body；
(5) qualitative: to be tested through Surface enhanced Raman spectroscopy, work as 633cm-1, 1013cm-1, 1172cm-1, 1327cm-1, 1537cm-1
And 1592cm-1Place is there are when obvious characteristic Raman peaks, then there are fluorescent whitening agent FWA199 in sample；
(6) quantitative: with 1172cm-1The Characteristic Raman peak at place is as quantitative peak, according to the Raman spectrum of fluorescent whitening agent FWA199
The response intensity of signal and the linear ratio relation of content obtain calibration curve equation, to the fluorescent whitening agent FWA199 in sample
Carry out rapid quantitative detection.
2. the Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199 as described in claim 1, feature
It is the material of the food contact plastic material or product are as follows: polystyrene, polyvinyl chloride, polyethylene, polypropylene or poly- carbon
Acid esters.
3. the Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199 as claimed in claim 2, feature
It is that the strong solvent of the step (1) is n,N-Dimethylformamide, tetrahydrofuran, ethyl acetate or methylene chloride；It is described weak molten
Agent is methanol, acetonitrile or n-hexane.
4. the Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199 as claimed in claim 3, feature
It is that when the material of the food contact plastic material or product is polystyrene, strong solvent is ethyl acetate, and Weak solvent is first
Alcohol.
5. the Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199 as claimed in claim 3, feature
It is that when the material of the food contact plastic material or product is polyvinyl chloride, strong solvent is tetrahydrofuran, and Weak solvent is first
Alcohol.
6. the Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199 as claimed in claim 3, feature
It is the pre-treatment of the step (1) are as follows: weigh the sample that 0.1-0.5g is shredded or shredded, it is completely molten that 3-10mL strong solvent is added
Xie Hou is added 15-40mL Weak solvent precipitating macromolecule matrix through 0.22 μm of filtering with microporous membrane and obtains prepare liquid.
7. the Surface enhanced Raman spectroscopy method of quickly detection fluorescent whitening agent FWA199 as described in claim 1, feature
It is the test of the step (3) are as follows: by surface enhanced reagent and prepare liquid, 2~6:1 is mixed and is made total volume 1mL by volume,
With 8000-12000r.p.m. centrifugation 8-12 minutes, 400-800 μ L supernatant is removed, then remainder ultrasound or concussion make to receive
Rice grain is uniformly dispersed again, draws 200-400 μ L mixing liquid in progress Surface enhanced Raman spectroscopy test on carrier.
8. the Surface enhanced Raman spectroscopy method of quick detection fluorescent whitening agent FWA199 as claimed in claim 1 or 7, special
Sign is that the carrier of the step (3) is sheet glass, titanium sheet or plastic culture base.
9. the Surface enhanced Raman spectroscopy of the quick detection fluorescent whitening agent FWA199 as described in any one of claim 1-7
Method, characterized in that the surface-enhanced Raman spectroscopy device Parameter Conditions are as follows: Raman spectrometer emits optical maser wavelength and is
785nm, fixed laser power are 100-200mW, 3500~200cm of scanning range-1, time of integration 2-10s, each spot scan
It is averaged for 5 times.
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| CN101995400A (en) * | 2010-09-29 | 2011-03-30 | 江南大学 | Surface enhanced Raman spectroscopy detection method of bisphenol A |
| CN102095715A (en) * | 2010-12-03 | 2011-06-15 | 江南大学 | Surface enhanced Raman spectrum detection method for antioxidant BHT (Butylated Hydroxytoluene) |
| CN102095717A (en) * | 2010-12-09 | 2011-06-15 | 江南大学 | Method for detecting BHA (butylated hydroxyanisole) in edible oil and plastic packages by laser nanometer Raman spectroscopy |
| CN102230888A (en) * | 2011-06-16 | 2011-11-02 | 浙江大学 | Method for detecting content of plasticizing agent |
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| CN101995400A (en) * | 2010-09-29 | 2011-03-30 | 江南大学 | Surface enhanced Raman spectroscopy detection method of bisphenol A |
| CN102095715A (en) * | 2010-12-03 | 2011-06-15 | 江南大学 | Surface enhanced Raman spectrum detection method for antioxidant BHT (Butylated Hydroxytoluene) |
| CN102095717A (en) * | 2010-12-09 | 2011-06-15 | 江南大学 | Method for detecting BHA (butylated hydroxyanisole) in edible oil and plastic packages by laser nanometer Raman spectroscopy |
| CN102230888A (en) * | 2011-06-16 | 2011-11-02 | 浙江大学 | Method for detecting content of plasticizing agent |
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