CN109765211A - The rapid detection method of residual sulfur dioxide in a kind of natural plant extracts - Google Patents

The rapid detection method of residual sulfur dioxide in a kind of natural plant extracts Download PDF

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Publication number
CN109765211A
CN109765211A CN201910089625.2A CN201910089625A CN109765211A CN 109765211 A CN109765211 A CN 109765211A CN 201910089625 A CN201910089625 A CN 201910089625A CN 109765211 A CN109765211 A CN 109765211A
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solution
sulfur dioxide
plant extracts
natural plant
detection method
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张兰天
王红
李挥
史国华
刘�东
张斌
马宁
常化仿
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Oprah Winfrey Scientific Instruments (suzhou) Co Ltd
HEBEI FOOD INSPECTION AND RESEARCH INSTITUTE
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Oprah Winfrey Scientific Instruments (suzhou) Co Ltd
HEBEI FOOD INSPECTION AND RESEARCH INSTITUTE
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Abstract

The present invention relates to a kind of Fast Detection Technique of residual sulfur dioxide in natural plant extracts more particularly to a kind of detection method using Raman spectrum characteristic peak signal intensity, the residual sulfur dioxide detection method of natural plant extracts suitable for health food.Using Raman spectrum characteristic peak signal intensity, 618cm is selected‑1(±3cm‑1) it is used as Characteristic Raman peak, qualitative accurate, entire detection process is completed in 15 minutes, realizes fast qualitative, quantitative, convenient, inexpensive.

Description

The rapid detection method of residual sulfur dioxide in a kind of natural plant extracts
Technical field
The present invention relates to a kind of Fast Detection Techniques of residual sulfur dioxide in natural plant extracts, more particularly to one kind Using the detection method of Raman spectrum characteristic peak signal intensity, the residual dioxy of natural plant extracts suitable for health food Change sulphur detection method.
Background technique
Sulfur dioxide has Bleachability.Industrially commonly using sulfur dioxide comes bleached pulp, hair, silk, straw hat etc..Sulfur dioxide Blanching effect be since its (sulfurous acid) can generate unstable colourless substance with certain coloring matters.This colourless substance holds It easily decomposes and coloring matter is made to restore original color, therefore with the passing of time turned yellow again with the bleached plaited straw of sulfur dioxide. The blanching effect of sulfur dioxide and certain sulfur-containing compounds is also illegally used in processing health food naturally by some illegal manufacturers Plant extracts, so that natural plant extracts brighten.This kind of health food is eaten, is had seriously to liver, the kidney etc. of human body Damage, and have carcinogenic risk.
Currently, the detection method (GB 5009.34) of sulfur dioxide in food is the way of distillation: to sample in closed container It is acidified, distilled, distillation is absorbed with acetic acid lead solution.Solution after absorption is acidified with hydrochloric acid, iodine standard solution titrates, root The content of sulfur dioxide in sample is calculated according to consumed iodine standard solution meter.
Two are used in patent of invention " rapid detection method of sulfur dioxide in a kind of fructus lycii " (publication number 104198485A) The principle that sulfur oxide is easily oxidized is designed, and is first extracted using aqueous slkali to sulfur dioxide, then is acidified using acid solution, Cucurbit is heated simultaneously, is released from cucurbit conducive to sulfur dioxide, then the sulfur dioxide released is added to Redox reaction is carried out in starch solution containing titrating solution, is observed the variation of starch solution color, is judged titration end-point, root The amount of sulfur dioxide is calculated according to the titrating solution volume of consumption.
Raman light is utilized in patent of invention " a kind of detection method of sulfur dioxide in food " (publication number 106323944A) Spectrometer carry out screening sample in whether contain sulfur dioxide, concrete operation method will be added in the water of sample, be added carbonate with Acid produces carbon dioxide;Using sodium hydroxide solution collection retort gas and vapor, the sulfur dioxide prepare liquid waited until, and It is mixed by the way that metal nanometer sol and inorganic salts flocculant is added, is detected using Raman spectrometer.Realize the fast of batch samples Speed screening.
In patent of invention " a kind of rapid detection method of residual sulfur dioxide in food " (publication number 103698314A), hair Bright content are as follows: (1) extract: taking 1 parts by weight of sample in container, while the carbonate of 0.1-10 parts by weight, bicarbonate is added Or sodium borohydride etc. produces gas piece substance, then 0.05-10 parts by weight defoaming agent adds reaction reagent acid, the amount of addition is sample Product g/ reagent volume ratio ml=1:10-50;It distills in boiling, is collected caused by distillation using 2-10ml alkaline solution Sulfur dioxide gas;The amount of addition is sample g/ alkaline solution volume ratio ml=1:2-10;As collection liquid;(2) it detects: taking Collection liquid is stated in glass detection cell, metal nanometer sol is added later and inorganic salts flocculant mixes, is then placed on portable Raman It is detected spectrometer detection interior.The method of the present invention detection time is short, the quick screening of batch samples can be achieved.
Patent of invention " identification method of stove drying food or drug " (publication number 105806822A) is the following steps are included: (a) Sample to be tested is pre-processed to form sample to be tested extracting solution;(b) sample to be tested extracting solution is irradiated with exciting light and collect Raman diffused light from sample to be tested extracting solution;(c) sample to be tested extracting solution is obtained by collected Raman diffused light Raman spectrum curve;And it compares (d) by the Raman spectrum curve and with reference to Raman spectrum curve to determine sample to be tested In whether contain sulfur dioxide residue object.
But time-consuming, poor sensitivity for these method physico-chemical methods;Instrumental method pre-treatment and instrumentation process are complicated, take When (taking around 2-3 hours), expensive equipment.
Raman spectrum nineteen twenty-eight is found, and nineteen thirty obtains Nobel Prize in physics, it is prevalent in all molecules, The structural information of molecule can be reliably provided, do not influenced by various solvents, with the use of laser light source, LR laser raman light Spectrum has become the analysis means of important compound, is widely used in the fields such as criminal investigation identification, mineral analysis, and 1974 The Surface enhanced Raman scattering of FleischmannM discovery makes it possible that trace materials detects.Surface enhanced Raman spectroscopy technology (SERS) metal-sols such as Cu, Ag, Au and electrode surface are adsorbed in using trace molecules, raman spectral signal can enhance 104 ~106, overcome the low disadvantage of normal Raman spectroscopic methodology sensitivity.
Recently as surface enhancement techniques, the combination of Fourier's infrared technique and Surface enhanced Raman spectroscopy, start Applied to natural plant extracts safety detection.Surface enhanced Raman spectroscopy (SERS) has rapid sensitive, abundant information, selection The features such as property is high, but it is mainly used for qualitative detection.
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of based on Surface enhanced Raman spectroscopy test, surely It is fixed, quick, can be qualitative, quantitative detection natural plant extracts in residual sulfur dioxide method.
Summary of the invention
The present invention relates to a kind of rapidly extracting natural plant extracts, and in qualitative and quantitative analysis natural plant extracts The detection technique of sulfur dioxide selects 618cm using Raman spectrum characteristic peak signal intensity-1(±3cm-1) it is used as Characteristic Raman Peak, qualitative accurate, entire detection process is completed in 15 minutes, realizes fast qualitative, quantitative, convenient, inexpensive.
The present invention extracts residual sulfur dioxide in natural plant extracts using ultrasonic wave, and is swashed with surface enhanced Light Raman spectrum characteristic peak signal intensity is to sulfur dioxide fast qualitative in natural plant extracts material, quantitative, in which: including with Lower step:
(1) sulfur dioxide standard solution is prepared
A. two sodium solution of 1,2-diaminocyclohexane tetraacetic acid, c (CDTA-2Na)=0.05mol/L
The trans- 1,2-cyclohexanediaminetetraacetic acid of 1.82g (CDTA) is weighed, is added sodium hydroxide solution (1.5mol/L) 6.5mL is diluted with water to 100mL.
B. buffered formaldehyde absorbing liquid
Draw 36%~38% formalin 5.5mL, CDTA-2Na solution 20.00mL;Weigh 2.04g phthalic acid Hydrogen potassium is dissolved in a small amount of water;Three kinds of solution are merged, 100mL is being diluted with water to.100 times are diluted again, are faced with dilution.
C. sulfur dioxide standard solution
0.200g sodium sulfite is weighed, 200mL disodium ethylene diamine tetraacetate (EDTA-2Na) solution (0.05g/ is dissolved in In 100mL), slowly shakes up and make it dissolve.It is demarcated after placing 2~3h.Every milliliter of this solution is equivalent to 320~400 μ g titanium dioxides Sulphur.
Scaling method: the above-mentioned sulfur dioxide standard solution of three parts of 20.00mL is drawn, is respectively placed in 250mL iodine flask, adds Enter the water that 50mL is newly boiled but cooled down, 20.00mL iodine solution (0.05mol/L) and 1mL glacial acetic acid, Gai Sai shake up.In dark place After placing 5min, with sodium thiosulfate standard solution (0.05mol/L) titration solution to light yellow, addition 2mL starch solution (0.5g/100mL) continues to be titrated to solution blue and just take off for terminal.The body of record titration sodium thiosulfate standard solution Product V, mL.
Three parts of EDTA-2Na solution 20mL are drawn, carry out blank assay with same method.Record titration sodium thiosulfate standard is molten The volume V of liquid0, mL.
The difference that Duplicate Samples titrate consumed sodium thiosulfate standard solution volume should be not more than 0.04mL.Take its average value.
(2) sample pretreatment process
A. a certain amount of sample is weighed, is pulverized in centrifuge tube, appropriate pure water oscillation is added, is placed in ultrasonic extraction instrument Ultrasound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
The pure water and the mass ratio of sample to be tested of being added is 1-10:1;It is preferred that 1-5:1;More preferable 4:1.
(3) surface-enhanced laser Raman spectrum speed surveys analysis
A certain amount of prepare liquid is taken, surface enhanced reagent, inorganic salts flocculating agent are sequentially added, records 618cm-1(±3cm-1) The intensity at corresponding peak, finds corresponding content of sulfur dioxide from standard curve.
The surface enhanced reagent is any one in gold nano colloidal sol, silver nanoparticle colloidal sol or copper Nano sol, preferably Gold nano colloidal sol;
The inorganic salts flocculating agent is sodium-chloride water solution or potassium chloride solution;
The sodium-chloride water solution or potassium chloride solution concentration are the aqueous solution of 0.1%-10% mass fraction;
The volume ratio of the surface enhanced reagent and prepare liquid is 1:3-4;It is preferred that 1:3;
The volume ratio of the inorganic salts flocculating agent and prepare liquid is 1:1-10;It is preferred that 1:1-5.
The present invention is using dedicated and solidify the special-purpose software in Portable Raman spectrometer and a kind of plant to natural come what is realized Supper-fast, highly sensitive, inexpensive, the live discrimination method of sulfur dioxide in object extract.One sample detection time is less than 15 Minute, easy to operate, not needing operator has stronger specialty background, and reading is intuitive, can directly read from instrument interface Numerical value.
This research is for the first time by the quantitative detection of technical application sulfur dioxide into natural plant extracts, by dioxy Change the Raman spectrum specificity analysis of sulphur, detect content of sulfur dioxide situation in natural plant extracts, tests complete in 15min At detection limit reaches 10mg/kg, fully meets requirements of the national standard, has accurate, quick, lossless, inexpensive obvious spy Point is applicable in Emergent detection, enterprise self control detection and batch samples screening detection etc. on site, effectively distinguishes problem natural plants Extract protects consumers' rights and interests.
Advantages of the present invention:
1, simple and convenient, it is low in cost, it is conducive to execute-in-place, quickly provides testing result;
2, qualitative analysis and quantitative detection are realized simultaneously;
3, greatly reduce the usage amount of strong acid, reduce the harm to operator, while reducing dirt of the waste to environment Dye;
4, speed fast (in 15min), high sensitivity (10mg/kg), (each sample survey about needs 2 yuan of left sides of cost to low cost It is right), it is easy to operate.
Detailed description of the invention
Sulfur dioxide Raman spectrogram in Fig. 1 natural plant extracts containing 10mg/kg
Specific embodiment
The present invention is described in further detail below with reference to embodiment.But the present invention is not limited with this.
One, sulfur dioxide standard solution is prepared, and is ready in advance.
A. two sodium solution of 1,2-diaminocyclohexane tetraacetic acid, c (CDTA-2Na)=0.05mol/L
The trans- 1,2-cyclohexanediaminetetraacetic acid of 1.82g (CDTA) is weighed, is added sodium hydroxide solution (1.5mol/L) 6.5mL is diluted with water to 100mL.
B. buffered formaldehyde absorbing liquid
Draw 36%~38% formalin 5.5mL, CDTA-2Na solution (6.1.1) 20.00mL;Weigh 2.04g neighbour Potassium hydrogen phthalate is dissolved in a small amount of water;Three kinds of solution are merged, 100mL is being diluted with water to.100 times are diluted again, are faced with dilute It releases.
C. sulfur dioxide standard solution
0.200g sodium sulfite is weighed, 200mL disodium ethylene diamine tetraacetate (EDTA-2Na) solution (0.05g/ is dissolved in In 100mL), slowly shakes up and make it dissolve.It is demarcated after placing 2~3h.Every milliliter of this solution is equivalent to 320~400 μ g titanium dioxides Sulphur.
Scaling method: the above-mentioned sulfur dioxide standard solution of three parts of 20.00mL is drawn, is respectively placed in 250mL iodine flask, adds Enter the water that 50mL is newly boiled but cooled down, 20.00mL iodine solution (0.05mol/L) and 1mL glacial acetic acid, Gai Sai shake up.In dark place After placing 5min, with sodium thiosulfate standard solution (0.05mol/L) titration solution to light yellow, addition 2mL starch solution (0.5g/100mL) continues to be titrated to solution blue and just take off for terminal.The body of record titration sodium thiosulfate standard solution Product V, mL.
Three parts of EDTA-2Na solution 20mL are drawn, carry out blank assay with same method.Record titration sodium thiosulfate standard is molten The volume V of liquid0, mL.
The difference that Duplicate Samples titrate consumed sodium thiosulfate standard solution volume should be not more than 0.04mL.Take its average value.Two Sulfur oxide concentration of standard solution is calculated as follows:
In formula:
The concentration of C--- sulfur dioxide standard solution, μ g/mL
The volume of the consumed sodium thiosulfate standard solution of V0--- blank titration, mL
V--- sulfur dioxide standard solution titrates the volume of consumed sodium thiosulfate standard solution, mL
--- the concentration of sodium thiosulfate standard solution, mol/L
32.02--- sulfur dioxide (1/2SO2) molal weight.
It is immediately 2.5 μ g/mL, 5.0 μ g/mL, 10.0 μ g/mL, 20.0 μ with diluted absorption solution after calibrating actual concentrations The standard solution of the sulfur dioxide of g/mL, 50.0 μ g/mL.
Two, sample preparation
A. 1 gram of sample is weighed, is pulverized in 10mL centrifuge tube, the oscillation of 4g pure water is added, is placed in ultrasonic extraction instrument and surpasses Sound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Three, qualitative determination
Instrument condition
A) laser power: 200mW.
B) time of integration: 10sec.
C) average time: 2.
D) smoothing parameter: 1.
A certain amount of prepare liquid is taken, surface enhanced reagent, inorganic salts flocculating agent is sequentially added, is detected after shaking up, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed: have, illustrate to contain sulfur dioxide in sample, such as without obvious special Raman peaks are levied, then illustrate that content of sulfur dioxide is below detection limit value in sample.
Four, it quantitative determines
Baseline adjustment and normalized are carried out to the raman spectrum of measurement, obtain sulfur dioxide standard curve, it is basic to grasp Make as follows:
(1) Raman spectrum data of measurement is subjected to baseline adjustment first;
(2) with 618cm-1(±3cm-1) at Characteristic Raman peak as quantitative reference peaks, to alkaline bright yellow Characteristic Raman peak It is normalized;
(3) standard curve that the Characteristic Raman peak intensity obtained after normalizing can be measured according to the same day is quantitatively evaluated, It is 10~200mg/kg that this analysis method, which is applicable in concentration range,.
It calculates
Standard curve is drawn, standard curve regression equation is obtained.
As a result it is calculated by formula (1):
In formula:
The content of sulfur dioxide in X-sample natural plant extracts, unit are mg/kg (mg/kg);
The content of sulfur dioxide that c-is obtained from standard curve, unit are mg/litre (mg/L);
V-sample constant volume, unit are milliliter (mL);
M-sample weighing quality, unit are gram (g).
Tolerance
The absolute difference of the measurement result independent twice obtained under the conditions of repeatability must not exceed arithmetic average 10%.
Residual sulfur dioxide qualitative and quantitative analysis in 1 Rhizoma Atractylodis Macrocephalae extract of embodiment
Sample: it is derived from commercially available Rhizoma Atractylodis Macrocephalae extract.
A. 1 gram of sample is weighed, is pulverized in 10mL centrifuge tube, the oscillation of 4mL pure water is added, is placed in ultrasonic extraction instrument and surpasses Sound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Qualitative analysis:
0.1mL prepare liquid is taken, the sodium chloride solution of 0.3mL gold nano colloidal sol, 0.1mL 1% is sequentially added, is examined after shaking up It surveys, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed:
The prepare liquid is in 618cm-1(±3cm-1) at have characteristic peak, then illustrate to contain sulfur dioxide in sample.
Quantitative analysis:
According to 618cm-1(±3cm-1) at Characteristic Raman peak as quantitative reference peaks, to alkaline bright yellow Characteristic Raman peak It is normalized;It is quantitatively evaluated according to the standard curve that the same day measures.
Calculate content X=(2.5*4)/1=10mg/kg of sulfur dioxide in sample.
Residual sulfur dioxide qualitative and quantitative analysis in 2 angelica extract of embodiment
Sample: it is derived from Angelica sinensis on Sale extract.
A. 5 grams of samples are weighed, are pulverized in 50mL centrifuge tube, the oscillation of 25mL pure water is added, is placed in ultrasonic extraction instrument Ultrasound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Qualitative analysis:
0.1mL prepare liquid is taken, the sodium chloride solution of 0.4mL gold nano colloidal sol, 0.5mL 1% is sequentially added, is examined after shaking up It surveys, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed:
The prepare liquid is in 618cm-1(±3cm-1) at there is no characteristic peak, in sample content of sulfur dioxide detection limit value with Under.Illustrate that sample may be without sulfur dioxide residue, if so, content is also in 10mg/kg hereinafter, well below requirements of the national standard Numerical value.
Residual sulfur dioxide qualitative and quantitative analysis in 3 angelica extract of embodiment
Sample: it is derived from Angelica sinensis on Sale extract.
A. 1 gram of sample is weighed, is pulverized in 10mL centrifuge tube, the oscillation of 6g pure water is added, is placed in ultrasonic extraction instrument and surpasses Sound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Qualitative analysis:
0.1mL prepare liquid is taken, the Klorvess Liquid of 0.3mL silver nanoparticle colloidal sol, 0.1mL 1% is sequentially added, is examined after shaking up It surveys, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed:
The prepare liquid is in 618cm-1(±3cm-1) at have characteristic peak, then illustrate to contain sulfur dioxide in sample.
Quantitative analysis:
According to 618cm-1(±3cm-1) at Characteristic Raman peak as quantitative reference peaks, to alkaline bright yellow Characteristic Raman peak It is normalized;It is quantitatively evaluated according to the standard curve that the same day measures.
Calculate content X=(20*6)/1=120mg/kg of sulfur dioxide in sample.
Residual sulfur dioxide qualitative and quantitative analysis in 4 RADIX PEUCEDANI extract of embodiment
Sample: it is derived from commercially available RADIX PEUCEDANI extract.
A. 10 grams of samples are weighed, are pulverized in 10mL centrifuge tube, the oscillation of 10g pure water is added, is placed in ultrasonic extraction instrument Ultrasound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Qualitative analysis:
0.1mL prepare liquid is taken, the Klorvess Liquid of 0.3mL silver nanoparticle colloidal sol, 0.1mL 1% is sequentially added, is examined after shaking up It surveys, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed:
The prepare liquid is in 618cm-1(±3cm-1) at have characteristic peak, then illustrate to contain sulfur dioxide in sample.
Quantitative analysis:
According to 618cm-1(±3cm-1) at Characteristic Raman peak as quantitative reference peaks, to alkaline bright yellow Characteristic Raman peak It is normalized;It is quantitatively evaluated according to the standard curve that the same day measures,
Calculate content X=(30.0*10)/10=30mg/kg of sulfur dioxide in sample.
Residual sulfur dioxide qualitative and quantitative analysis in 5 calendula extract of embodiment
Sample: it is derived from commercially available calendula extract.
A. 5 grams of samples are weighed, are pulverized in 10mL centrifuge tube, the oscillation of 10g pure water is added, is placed in ultrasonic extraction instrument and surpasses Sound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Qualitative analysis:
0.1mL prepare liquid is taken, the Klorvess Liquid of 0.4mL gold nano colloidal sol, 0.4mL 1% is sequentially added, is examined after shaking up It surveys, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed:
The prepare liquid is in 618cm-1(±3cm-1) at have characteristic peak, then illustrate to contain sulfur dioxide in sample.
Quantitative analysis:
According to 618cm-1(±3cm-1) at Characteristic Raman peak as quantitative reference peaks, to alkaline bright yellow Characteristic Raman peak It is normalized;It is quantitatively evaluated according to the standard curve that the same day measures.
Calculate content X=(5*10)/5=10mg/kg of sulfur dioxide in sample.
Residual sulfur dioxide qualitative and quantitative analysis in 6 licorice of embodiment
Sample: it is derived from commercially available licorice.
A. 1 gram of sample is weighed, is pulverized in 10mL centrifuge tube, the oscillation of 10g pure water is added, is placed in ultrasonic extraction instrument and surpasses Sound 10 minutes.
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR- B, vortex mixed 1 minute, in being centrifuged in centrifuge 2 minutes (10000 revs/min).
D. it takes 500 μ L supernatants in 2mL centrifuge tube, 50 μ L OTR-FB-SF is added, mix, acquired solution is as to be measured Liquid.
Qualitative analysis:
0.1mL prepare liquid is taken, the Klorvess Liquid of 0.4mL gold nano colloidal sol, 0.1mL 1% is sequentially added, is examined after shaking up It surveys, according to 618cm-1(±3cm-1) at whether there is or not Characteristic Raman peaks to be assessed:
The prepare liquid is in 618cm-1(±3cm-1) at have characteristic peak, then illustrate to contain sulfur dioxide in sample.
Quantitative analysis:
According to 618cm-1(±3cm-1) at Characteristic Raman peak as quantitative reference peaks, to alkaline bright yellow Characteristic Raman peak It is normalized;It is quantitatively evaluated according to the standard curve that the same day measures.
Calculate content X=(20*10)/1=200mg/kg of sulfur dioxide in sample.

Claims (7)

1. the rapid detection method of residual sulfur dioxide in a kind of natural plant extracts, in which: the following steps are included:
(1) sulfur dioxide standard solution is prepared
A. two sodium solution of 1,2-diaminocyclohexane tetraacetic acid, c (CDTA-2Na)=0.05mol/L
The trans- 1,2-cyclohexanediaminetetraacetic acid of 1.82g is weighed, the sodium hydroxide solution 6.5mL that concentration is 1.5mol/L is added, uses Water is diluted to 100mL;
B. buffered formaldehyde absorbing liquid
Draw 36%~38% formalin 5.5mL, CDTA-2Na solution 20.00mL;Weigh 2.04g hydrogen phthalate Potassium is dissolved in a small amount of water;Three kinds of solution are merged, 100mL is being diluted with water to.100 times are diluted again, are faced with dilution;
C. sulfur dioxide standard solution
0.200g sodium sulfite is weighed, being dissolved in 200mL concentration is in 0.05g/100mL disodium ethylene diamine tetra-acetic acid solution, slowly It shakes up and makes it dissolve;It is demarcated after placing 2~3h.Every milliliter of this solution is equivalent to 320~400 μ g sulfur dioxide;
(2) sample pretreatment process
A. a certain amount of sample is weighed, is pulverized in centrifuge tube, appropriate pure water oscillation is added, is placed in ultrasonic extraction instrument ultrasonic 10 minutes;
B. take 1.5mL extracting solution in 2mL centrifuge tube, in being centrifuged 2 minutes in centrifuge;
C. it takes 1mL supernatant in 2mL centrifuge tube, sequentially adds 200 μ L OTR-FB-PR-A and 200 μ L OTR-FB-PR-B, whirlpool Rotation mixing 1 minute, in being centrifuged 2 minutes in centrifuge;
D. take 500 μ L supernatants in 50 μ L OTR-FB-SF in 2mL centrifuge tube, are added, mixing, acquired solution is prepare liquid;
(3) surface-enhanced laser Raman spectrum speed surveys analysis
A certain amount of prepare liquid is taken, surface enhanced reagent, inorganic salts flocculating agent are sequentially added, records 618cm-1(±3cm-1) correspond to peak Intensity, corresponding content of sulfur dioxide is found from standard curve.
2. according to claim 1 in a kind of natural plant extracts residual sulfur dioxide rapid detection method, feature It is the scaling method of the sulfur dioxide standard solution are as follows: draw the above-mentioned sulfur dioxide standard solution of three parts of 20.00mL, respectively Be placed in 250mL iodine flask, be added the 50mL water that newly boils but cool down, 20.00mL concentration for 0.05mol/L iodine solution and 1mL glacial acetic acid, Gai Sai shake up.After 5min is placed in dark place, dripped with the sodium thiosulfate standard solution that concentration is 0.05mol/L Solution is determined to light yellow, and addition 2mL concentration is 0.5g/100mL starch solution, continues to be titrated to solution blue and just take off for end Point.The volume V, mL of record titration sodium thiosulfate standard solution.
Three parts of EDTA-2Na solution 20mL are drawn, carry out blank assay with same method.Record titration sodium thiosulfate standard solution Volume V0, mL.
The difference that Duplicate Samples titrate consumed sodium thiosulfate standard solution volume should be not more than 0.04mL.Take its average value.
3. according to claim 1 in a kind of natural plant extracts residual sulfur dioxide rapid detection method, feature It is in the sample pretreatment process, the mass ratio that pure water and sample to be tested is added is 1-10:1;It is preferred that 1-5:1;More preferably 4:1。
4. according to claim 1 in a kind of natural plant extracts residual sulfur dioxide rapid detection method, feature It is
The surface enhanced reagent is any one in gold nano colloidal sol, silver nanoparticle colloidal sol or copper Nano sol, preferably Jenner Rice colloidal sol.
5. the rapid detection method of residual sulfur dioxide, special according to claim 1 or in a kind of 4 natural plant extracts Sign is that the volume ratio of the surface enhanced reagent and prepare liquid is 1:3-4;It is preferred that 1:3.
6. according to claim 1 in a kind of natural plant extracts residual sulfur dioxide rapid detection method, feature It is that the inorganic salts flocculating agent is sodium-chloride water solution or potassium chloride solution.
7. according to claim 6 in a kind of natural plant extracts residual sulfur dioxide rapid detection method, feature It is the sodium-chloride water solution or potassium chloride solution concentration is the aqueous solution of 0.1%-10% mass fraction;The inorganic salts The volume ratio of flocculating agent and prepare liquid is 1:1-10;It is preferred that 1:1-5.
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