CN109765326A - The rapid detection method of tonyred in chilli products - Google Patents
The rapid detection method of tonyred in chilli products Download PDFInfo
- Publication number
- CN109765326A CN109765326A CN201910044610.4A CN201910044610A CN109765326A CN 109765326 A CN109765326 A CN 109765326A CN 201910044610 A CN201910044610 A CN 201910044610A CN 109765326 A CN109765326 A CN 109765326A
- Authority
- CN
- China
- Prior art keywords
- tonyred
- sample
- chilli
- detection method
- rapid detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention relates to the detection methods of tonyred, more particularly to the rapid detection method of tonyred in chilli products, rapidly extracting is carried out to chilli products with acetone, acetonitrile first and obtains extracting solution S, using liquid chromatogram-UV, visible light fiber spectrometer combination analysis extracting solution S, handles data and obtain the background spectra database N without tonyred；Then the ultraviolet-visible spectrum database V of series of concentrations tonyred standard items is acquired, finally analyze with vector-subspace angle criterion method the tonyred in chilli products: rapidly extracting chilli products to be measured obtains extracting solution c, the ultraviolet-visible light modal data for acquiring extracting solution c, calculates the content of tonyred in chilli products to be measured.Extracting method of the present invention is quick and effect is good, can carry out qualitative recognition and quantitative analysis to Sudan red, II, III, IV pure spectrum in mark-on sample mixed spectra respectively.
Description
Technical field
The present invention relates to the detection methods of tonyred, and in particular to the rapid detection method of tonyred in chilli products.
Background technique
In order to pursue broader food products market, some food additives are added in the product to obtain color in some businessmans
It is beautiful, the food of lover is sold, consumer is tried to please, to obtain good income.Tonyred is also illegally added in food.Soviet Union
Red red dye has carcinogenicity, is toxic organic compound in the intracorporal metabolite of people, if long-term intake, Jiu Hui
Cylinder accumulation and to human body cause damage or gene mutation and it is carcinogenic.Reinforce to the detection of additive tonyred illegal in food and
Supervision ensures that human health is of great significance to maintenance food safety.
Currently, mainly using high performance liquid chromatography, gas chromatography-mass spectrometry and liquid phase color to the detection of tonyred
Spectrum-Mass Spectrometry etc., but the above method is complicated for operation, and price is higher.
Summary of the invention
The purpose of the present invention is overcoming drawbacks described above, the rapid detection method of tonyred in chilli products is provided.
The present invention completes the fast qualitative of four kinds of tonyreds in chilli products with " vector-subspace angle " criterion algorithm
And quantitative analysis.
Technical solution of the present invention: the rapid detection method of tonyred in chilli products, comprising:
Step 1, pre-treatment is carried out to commercially available chilli products, obtains extracting solution S；
Step 2, using efficient liquid phase-ultraviolet-visual spectrometer combination acquisition extracting solution S after chromatographic column is kept completely separate
Spectroscopic data array, obtain the spectroscopic data array without tonyred, i.e. background spectra database N by data processing；
Step 3, Sudan red, II, III, IV standard items mother liquor is respectively configured, then standard mother liquor is successively diluted to difference
The standard solution of concentration acquires ultraviolet-visible spectrum, obtains standard spectral data library V through least square fitting；
Step 4, chilli products sample to be tested is taken, extracting solution DC is obtained by fast formulation, acquires the ultraviolet-visible spectrum of DC
Data c；
Step 5, standard items database V, background spectra database N and sample data c are imported into data processing software, used
Vector-subspace angle criterion method calculates the content of tonyred in chilli products.
Further, the chilli products includes capsicum oil sample and chilli powder sample.
Further, the pre-treating method of the capsicum oil sample are as follows: use acetone solution chilli oil, be centrifuged, take after constant volume
Clear liquid obtains extracting solution.
Further, the pre-treating method of the chilli powder sample are as follows: after weighing chilli powder, addition acetonitrile, ultrasonic wave extraction,
Extracting solution centrifugation, takes supernatant to obtain extracting solution.
Further, the sample spectral data acquisition instrument is ultraviolet-visible fiber spectrometer, and wave-length coverage is
200nm-1100nm。
Further, the vector-subspace angle criterion method includes:
(1) step number Δ is reduced according to quantitative accuracy setting；
(2) tonyred calibration curve equation is yi=aix+bi, wherein i is a certain wavelength, yiIt indicates under a certain wavelength i
Absorbance value, aiAnd biConstant is referred to, x indicates the different concentration of tonyred, v1As concentration is x1The multi-wavelength of lower tonyred is inhaled
Luminosity y1, V is matrix composed by the corresponding all y values of various concentration x different wave length i；
(3) tonyred standard items v is constantly deducted from the spectroscopic data c of capsicum sample to be measured1, v is deducted every time1/ Δ
Amount, the variable after deduction are dc, are denoted as M after background spectra database N is merged with the vector dc for deducting tonyred, calculating M and
v1Angle；
(4) when in sample to be tested tonyred deducted completely, when maximum value occurs in angle, by x and reducing step number
The content for calculating tonyred in sample is y1=x1×λmax/ Δ, y1Value is the content of tonyred in chilli products to be measured.
Further, the detection of the rapid detection method is limited to 10 μ g/kg.
Further, to background spectra database N, the dimension of the noise and redundancy in data is removed with principal component analytical method
Number carries out Data Dimensionality Reduction.
Further, number of principal components is determined using the method for system independent variable number.
The invention has the advantages that
1, chilli powder uses acetonitrile ultrasonic extraction, and chilli oil acetone solution simplifies the experimental implementation of sample pre-treatments,
Reduce the time, after sample rapidly extracting, each component and component to be measured it is Sudan red, II, III, IV on high performance liquid chromatography energy
It is enough kept completely separate, extraction effect is preferable.
2, it is based on vector-subspace angle criterion, quantitative result is more accurate.In the concentration range of 0.2~10 μ g/mL,
The standard working curve linear relationship of four kinds of tonyreds is good, linearly dependent coefficient r > 0.9990, commercial samples recovery of standard addition
Between 74%~136%, Precision Experiment relative standard deviation is less than 4%.
3, it is based on vector-subspace angle criterion, qualitative results are more accurate.False negative rate are as follows: 6.67%, false positive rate
Are as follows: 20.0%.
4, the calculating of Chemical Measurement can be carried out by only needing to measure the one-dimensional mixed spectra of sample using vector approach, with
" mathematical analysis " replacement " chemical analysis " greatly shortens the time of sample acquisition.Traditional high effective liquid chromatography for measuring Soviet Union
Red red content, a sample probably need 40min or so.The present invention improves the Fundamental database of chilli products, optimizes data mould
Shape parameter reduces false negative, positive rate, has great importance for the fast-field evaluation of Detection of Magdala in Food Through.
Detailed description of the invention
Fig. 1 is Sudan red, II, III, IV mixed standard solution high-efficient liquid phase chromatogram (478nm, 520nm)；
The high-efficient liquid phase chromatogram (478nm, 520nm) of Fig. 2 blank chilli oil (fast formulation)；
Fig. 3 is the high-efficient liquid phase chromatogram (520nm) that blank chilli oil adds the mixed mark (acetone solution) of tonyred；
Fig. 4 is the high-efficient liquid phase chromatogram (520nm) that blank chilli powder adds the mixed mark (acetonitrile extraction) of tonyred；
Fig. 5 is the high-efficient liquid phase chromatogram (520nm) of Different Extraction Method recovery rate effect；
Fig. 6 is Sudan red UV-visible spectrum；
Fig. 7 is the UV-visible spectrum of Sudan II；
Fig. 8 is the UV-visible spectrum of red Ⅲ；
Fig. 9 is the UV-visible spectrum of SudanⅣ；
Figure 10 is the ultraviolet spectrogram of 5 kinds of commercially available chilli oils (acetone solution)；
Figure 11 is the ultraviolet spectrogram of 5 kinds of commercially available chilli powders (acetonitrile extraction)；
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can various modifications may be made or change, such equivalent forms equally fall within the application the appended claims and limited to the present invention
Range.
1. experimental section
1.1 sample-pretreating methods determine
Sudan red, II, III, IV each 0.0010g of standard items is accurately weighed, is dissolved into 40.00mL blank chilli oil, is surpassed
Sound 10min obtains the mark-on sample of 25 μ g/mL after completely dissolution.
Mark-on chilli oil is divided into two parts, portion is handled according to national standard GBT19681-2005 method, and portion is pressed
Method processing is proposed fastly according to what the present invention designed.The high-efficient liquid phase chromatogram condition that tested component and background component are kept completely separate is investigated,
And the influence of National Standard Method and fast formulation to tonyred recovery rate in sample.
(1) National Standard Method is extracted
The pre-treatment of capsicum oil sample: accurately pipetting the mark-on oil sample 2.00mL of above-mentioned 25 μ g/mL in small beaker, is added big
About 10mL n-hexane dissolution can slightly carry out heating dissolution if sample indissoluble, merge hexane solution, and spin concentration will be concentrated
Liquid is slowly added in neutral alumina chromatographic column.To ensure that chromatographic effect is significant, when n-hexane liquid level maintains 2mm in chromatographic column
Left and right fashionable dress sample, and allow chromatographic column to keep moisture state in overall process, then repeatedly elute concentrate bottle on a small quantity with n-hexane, it will be dense
Contracting liquid is added in chromatographic column together.The colour band of control oxidation aluminum surface layer absorption is wide to be less than 0.5cm, after sample liquid flows completely out, depending on
In sample containing oil impurities number with 10mL-30mL n-hexane wash column, until efflux is colourless, discard whole n-hexanes elution
Liquid is eluted with the n-hexane 60mL containing 5% acetone, is collected, after concentration, is settled to 10mL with acetone, obtains theoretically respectively containing 5
The Sudan red of μ g/mL, II, III, IV mark-on sample extracting solution, it is to be measured after organic membrane filtration.
The pre-treatment of chilli powder sample: it accurately weighs 1-5g and (accurately to 0.001g) chilli powder sample in triangular flask, is added one
Quantitative tonyred mixed standard solution, is added 10mL-30mL n-hexane, ultrasonic 5min, and filtering washs residue with 10mL n-hexane
For several times, until eluate be it is colourless, merge n-hexane, be concentrated into 5mL with Rotary Evaporators hereinafter, being then slowly added into neutral alumina
In aluminium chromatographic column.To ensure that chromatographic effect is significant, when n-hexane liquid level maintains 2mm or so fashionable dress sample in chromatographic column, and
Overall process allows chromatographic column to keep moisture state, then repeatedly elutes concentrate bottle on a small quantity with n-hexane, and concentrate is added to chromatography together
In column.The colour band of control oxidation aluminum surface layer absorption is wide to be less than 0.5cm, after sample liquid flows completely out, depending on containing oil impurities in sample
Number with 10mL-30mL n-hexane wash column, until efflux is colourless, discard whole n-hexane leacheates, with containing 5% acetone just
Hexane 60mL elution collects, after concentration, is settled to 10mL with acetone, to be measured after organic membrane filtration.
(2) in sample tonyred rapid extracting method (hereinafter referred to as fast formulation)
The pre-treatment of capsicum oil sample: in the volumetric flask for accurately pipetting mark-on oil sample 2.00mL to the 10mL of above-mentioned 25 μ g/mL,
Directly with acetone solution, be settled to 10mL, obtain theoretically the respectively mark-on sample containing the Sudan red of 5 μ g/mL, II, III, IV
Extracting solution takes supernatant liquor to be measured after extracting solution centrifugation.
The pre-treatment of chilli powder sample: weighing the chilli products powder sample of 1-5g in the balance, and a certain amount of tonyred mixing mark is added
Extracting solution is centrifuged by quasi- solution through 10mL acetonitrile ultrasonic extraction, takes supernatant liquor to be measured.
The foundation of 1.2 background spectra database N
After carrying out quick pretreatment to sample, liquid phase-spectrum combination carries out principal component analysis and singular value decomposition dimensionality reduction,
Establish 5 kinds of chilli oil sample bottom spectra database D1 and 5 kinds of chilli powder sample bottom spectra database D2；
The background spectra database for merging chilli oil (powder) is N=[D1 D2].
Wherein: liquid phase chromatogram condition are as follows:
Chromatographic column: C18Chromatographic column (4.6mm × 250mm, 5 μm), column temperature: 25 DEG C；
Mobile phase: mobile phase A: the aqueous formic acid containing 0.1%: acetonitrile=85:15 (v/v)；
Mobile phase B: the acetonitrile containing 0.1% formic acid: acetone=80:20 (v/v)；
Flow velocity: 1mL/min；
Sample volume: 20 μ L；
Condition of gradient elution is as shown in table 1.
1 condition of gradient elution of table
Maximum absorption wavelength: Sudan red -474nm；Sudan II -488nm；Red Ⅲ -503nm；SudanⅣ-
510nm sample volume: 20 μ L.The chromatographic isolation effect of integrated survey sample and standard items, it is same as chilli oil (powder) using 520nm
When the wavelength that detects.
The foundation of 1.3 tonyred standard items library of spectra
It accurately weighs that 0.0100g is Sudan red, II, III, IV standard items powder respectively, with acetonitrile dissolution, constant volume, obtains 100
The Sudan red of μ g/mL, II, III, IV standard items mother liquor；Successively prepare obtain series of concentrations be 0.2,0.4,0.8,1.6,3.2,
5, Sudan red~IV acetonitrile solution of 8,10 μ g/mL, and acquire the ultraviolet-visible spectrum V of multi-wavelength.
The spectra collection of 1.4 chilli products analysis samples to be measured
500 μ L chilli oils or mark-on chilli oil are accurately measured with liquid-transfering gun in the drying capacity bottle of 5mL, it is molten with acetone
Solution, constant volume.Then the ultraviolet-visible spectrum for acquiring sample, is denoted as c.
Tonyred content in 1.5 measurement samples
By collected Sudan red, II, III, IV standard spectral data library, blank background spectra database and sample spectra
Data import data processing tools, are calculated using vector-subspace angle criterion, obtain the Soviet Union in chilli oil and chilli powder
Red red content, and be compared with high performance liquid chromatography measurement result.
1.6 methodologies are examined
According to the method for inspection of methodology, the precision of the method for inspection, recovery of standard addition, detection limit, yin and yang attribute, steady respectively
Qualitative five indexs.
1.6.1 Precision Experiment
In 100 μ L chilli oils, Sudan red, II, III, IV standard that concentration is respectively 10,15,15,15 μ g/mL is added
Each 70 μ L of solution is carried out ultrasonic vibration to the sample added after mixing mark and is sufficiently dissolved with acetone solution, constant volume to 2mL, parallel acquisition
5 ultraviolet-visible light modal datas calculate relative standard deviation using vector-subspace method.
1.6.2 the rate of recovery is tested
It takes 100 μ L blank chilli products oil samples in 2mL volumetric flask, it is molten to be separately added into a certain amount of tonyred standard
Liquid, 4 kinds of standard items are pressedTotally 15 kinds of combination mixing are added in chilli products oil sample, fixed with acetone solution
Hold to 2mL, sample introduction acquires ultraviolet-visible spectrum, calculates recovery of standard addition with vector subspace angle criterion and judges its yin-yang
Property.
1.6.3 detection limit is tested
Sudan red, II, III, IV each 0.0010g of standard items is accurately weighed, is dissolved into 40.00g blank capsicum oil sample, is surpassed
Sound 10min obtains the mark-on sample of 25000 μ g/kg after completely dissolution, and the 1.00mL mark-on oil sample is accurately pipetted with pipette
Into 50mL volumetric flask, with the dilution of blank capsicum oil sample, constant volume, obtains concentration and be the mark-on sample of 500 μ g/kg, then accurately pipette
For the mark-on sample of 1.00mL500 μ g/kg into the volumetric flask of 50mL, obtaining concentration with the dilution of blank capsicum oil sample, constant volume is 10 μ
The mark-on oil sample of g/kg accurately pipettes the mark-on oil sample of 10 μ g/kg of 0.50mL into 2mL volumetric flask, with acetone solution constant volume
It to scale, sufficiently after dissolution, centrifugation, acquires its ultraviolet-visible spectrum and is examined fastly, and carried out pair with high performance liquid chromatography
Than.
1.6.4 stability experiment
The tonyred standard items under various concentration are taken, acquire ultraviolet-visible spectrum at regular intervals, calculate content value simultaneously
It is compared with original standard items, sees whether to be overlapped.
1.6.5 interference is tested
The mark-on chilli oil for taking known concentration adds a certain amount of food-grade natural capsanthin pigment as interference, ultrasound
Concussion, acetone sufficiently dissolve.The ultraviolet-visible spectrum before and after interferon is added in acquisition respectively, is sentenced based on vector subspace angle
According to the standard items rate of recovery before and after interferon is added in calculating, investigates whether generate interference.
2 results and analysis
2.1 National Standard Methods and fast formulation compare
By chilli oil (powder) sample extracting solution of National Standard Method and the processing of fast formulation, through the laggard efficient liquid phase of filtering with microporous membrane
Chromatography.
Efficient liquid phase chromatographic analysis is carried out to Sudan red, II, III, IV mixed standard solution, using 478nm and
The double UV check of 520nm obtains the high-efficient liquid phase chromatogram of mixed standard solution as shown in Figure 1, when hybrid standard product appearance
Between be respectively as follows: it is Sudan red: 9.036min Sudan II: 14.576min red Ⅲ: 20.401min SudanⅣ:
27.436min；Sudan red, II optimal absorption wavelength is 478nm, and red Ⅲ, IV are better than 478nm in the absorption of 520nm.
It is compared by the dual wavelength chromatogram of Fig. 2 blank chilli oil and the chromatogram of Fig. 3 chilli oil mark-on sample it is found that capsicum
Oil is directly dissolved with acetone, added in sample it is Sudan red, II, III can be kept completely separate with other components of capsicum oil samples,
At 28min, there is an impurity peaks of a doubtful SudanⅣ, but impurity peaks are far below the absorption of 472nm in 520nm, can it is qualitative not
It is SudanⅣ, but other components of chilli powder sample, and mark-on rear impurity peak is basically separated with SudanⅣ, therefore in sample
It is Sudan red, II, III, IV while detect 520nm may be selected, eliminate interference of the sample impurity peaks to SudanⅣ.Mark-on capsicum
After powder sample is extracted using acetonitrile, chromatographic peak is sharply symmetrical, and response is high, and separating effect is preferable, as shown in Figure 4.
The high-efficient liquid phase chromatogram that mark-on capsicum oil samples are handled through fast formulation and National Standard Method is as shown in figure 5, the two
Comparison, can significantly find out, the chromatogram baseline of fast formulation is gentle, and each natural pigment peak can be good at separating.
National Standard Method extract capsicum oil samples after, natural pigment all removed not impact analysis as a result, but tonyred recovery rate it is obvious
Lower than fast formulation.
The results are shown in Table 2 for recovery rate of the fast formulation and National Standard Method to mark-on oil sample.
The fast formulation of watch 2 is compared with National Standard Method is to the recovery rate result of mark-on oil sample
The foundation of 2.2 liquid phases-spectrum combination background spectra database
Optimize the efficient liquid that component to be measured (tonyred) and other components (pigment) is kept completely separate by high performance liquid chromatography
Then high performance liquid chromatograph and ultraviolet spectrometer are combined by phase chromatographic condition, acquire chilli oil and chilli powder sample passes through color
The all-wave length ultraviolet spectrum data after column is kept completely separate is composed, the spectrum number of component tonyred to be measured is deducted in data processing platform (DPP)
According to (being not necessarily to deduct if without tonyred component), number of principal components is determined using the method for system independent variable number, takes chilli products
Oil sample number of principal components 18, chilli products powder number of principal components are 10, and through singular value decomposition, the 1-28 column after taking degradation, which are used as, to be calculated,
Obtain background spectra database D.
The foundation in 2.3 tonyred standard spectral data libraries
Tonyred (I, II, III, IV) is dissolved with acetonitrile and is configured to 0.2 μ g/mL, 0.4 μ g/mL, 0.8 μ g/mL, 1.6 μ
The standard solution of g/mL, 3.2 μ g/mL, 5 μ g/mL, 10 μ g/mL, acquire the ultraviolet spectra in 200nm~1100m multi-wavelength respectively
Data establish standard items spectra database, linear equation, the range of linearity and the phase relation of four kinds of standard items as shown in Fig. 6-Fig. 9
Number is shown in Table 3.
The standard working curve (200nm~1100m) of 3 tonyred of table
From the experimental results in the 0.2-10 μ g/mL range of linearity, it is Sudan red, II, III, IV have it is good linear
Curve, correlation coefficient r > 0.9990.
2.4 sample to be tested spectrum data gatherings
The chilli oil for selecting 5 kinds of different brands, according to method is proposed fastly, by chilli oil and acetone according to certain volume ratio
(1:20) mixed dissolution, acquires the ultraviolet spectra of 200nm-1100nm, as shown in Figure 10.
With electronic analytical balance precise 1.0000g 5 kinds of chilli products powder samples in the market, carried out fastly with 10mL acetonitrile
It mentions, ultrasonic dissolution is then centrifuged for, and takes supernatant liquor, and acquisition 200nm-1100nm spectrum is as shown in figure 11.Using vector-subspace
Angle criterion calculates sample size, as a result consistent with liquid phase result, is free of tonyred.
2.5 methodology inspection results
2.5.1 precision experiment result
100 μ L capsicum oil samples are added in 2mL volumetric flask and concentration is respectively the tonyred of 10,15,15,15 μ g/mL
I, II, III, IV each 70 μ L, with acetone constant volume, 5 ultraviolet-visible spectrums of parallel acquisition are calculated using vector-Subspace algorithm
The content of tonyred, the results are shown in Table 4.
4 tonyred Precision Experiment of table
The experimental results showed that the tonyred that fast formulation extracts in capsicum oil sample obtains relative standard deviation and is respectively less than 4%, it should
Method detects the tonyred in food, and accurate accuracy is good.
2.5.2 rate of recovery experimental result
Take certain blank chilli oil without tonyred that a certain amount of Sudan red, II, III, IV standard solution, 4 kinds of marks are added
Quasi- product are pressedTotally 15 kinds of combination mixing are added in capsicum oil sample, are settled to 2mL with acetone solution, sample introduction is adopted
Collect ultraviolet-visible spectrum, calculates its content with vector subspace angle criterion and recovery of standard addition obtains 8 result of table 5- table.
Table 5 adds a kind of tonyred standard items recovery test result in blank chilli oil
It can be seen from Table 5 thatCombination is that simple sample adds single mark, it can be seen that recovery of standard addition 98.0%~
Between 108%, show that the method for carrying out quantitative analysis to tonyred content in capsicum oil sample with vector-subspace angle criterion is quasi-
Really, false positive and negative rate is 0%, and single calibration property is accurate.
As shown in Table 6, it is added in the sample without component to be measuredTwo kinds of tonyred standard items of combination, the rate of recovery exist
82%-123%, when carrying out qualitative analysis, there is false positive and false negative in Sudan II, it is also necessary to for Sudan II
Computation model advanced optimizes.
Table 6 adds two kinds of tonyred standard items recovery test results in blank chilli oil
Three kinds of tonyred standard items recovery test results are added in 7 blank chilli oil of table
Four kinds of tonyred standard items recovery test results are added in 8 blank chilli oil of table
As shown in 7 result of table, added in the sample without component to be measuredCombined tonyred standard items, increase sample
The complexity of product, obtaining recovery of standard addition at this time is 74%-135%.When carrying out qualitative analysis, there is false sun in Sudan II
Property, it is also necessary to further progress repeats experiment to verify, and optimizes for the computation model parameter of Sudan II.
As shown in Table 8, tonyred standard items4 kinds of tonyred standard items are added in combination in the sample, due to 4 kinds of marks
Quasi- product can not investigate its yin and yang attribute in the case of all existing, and can only investigate the quantitative of them and whether have interference, tonyred to each other
The recovery of standard addition of standard items is between 97%-136%.
2.5.3 detection limit experimental result
Sudan red, II, III, IV each 0.0010g of standard items is accurately weighed, is dissolved into 40.00g blank capsicum oil sample, is surpassed
Sound 10min obtains the mark-on sample of 25000 μ g/kg, then dilute 2500 times with chilli oil, obtains 10 μ g/kg's after completely dissolution
Mark-on sample.Mark-on sample acetone solution is acquired ultraviolet-visible spectrum, is counted using vector-subspace angle criterion
It calculates, the results are shown in Table 9.
It is computed, the corresponding maximum of sample size that pitch-based sphere is 10 μ g/kg reduces step number greater than 20 and elder generation is presented
The phenomenon that successively decreasing after being incremented by, illustrates to remain to detected using vector-subspace angle criterion method, and detection is limited to 10 at this time
μ g/kg then has found that the corresponding step number of reducing of maximum angle is 1, shows to be lower than when diluting the sample of the 10 μ g/kg containing tonyred again
10 μ g/kg cannot detected.
9 linearity curve of table and detection limit (LOD) experimental result
2.5.4 stability experiment result
Spectral detection is carried out to four kind of 3.2 μ g/mL tonyred standard items by (3 days) at regular intervals, as a result such as table
Shown in 10.
The concentration table that 10 3.2 μ g/mL tonyred standard items different time of table measures
It is learnt by table 10, tonyred standard items are able to maintain good stability in longer period of time 13d, substantially not
It decomposes, for relative standard deviation less than 0.35%, precision is good.
2.5.5 interference experimental result
The individually ultraviolet-visible spectrum of acquisition natural capsicum red spectrum, is incorporated in chilli oil background library.It accurately pipettes again
100 μ L interferon --- in the mark-on chilli oil of natural capsanthin pigment (oily) to known concentration, with acetone ultrasonic dissolution, from
The heart, acquire it is ultraviolet-can spectrum, with vector subspace angle criterion calculate tonyred content.It is as shown in table 11 to obtain result.From
Table 11 is it can be seen that calculate chilli products oil sample tonyred content with good steady with vector subspace-angle criterion method
Strong property, not by the interference of natural capsanthin pigment.
Table 11 adds natural pigment interference experiment result
The present invention select in chilli products oil and chilli products powder Sudan red, II, III, IV content quick detection as
Research contents.Based on traditional detection method, there are sample pretreatment process complexity, the disadvantages of should not realizing quick detection, first with third
Ketone, acetonitrile etc. carry out rapidly extracting to chilli oil (powder), then carry out high performance liquid chromatograph-ultraviolet spectrometer combination, handle number
The background spectra database without component to be measured is obtained after；Then acquisition tonyred standard solution and commercially available chilli oil (powder) sample
The ultraviolet-visible light modal data of product；Finally tonyred in sample is calculated with vector-subspace angle criterion method to contain
Amount.After background spectra database is established in liquid phase-spectrum combination, only need to acquire sample spectra can be to the tonyred in mixed spectra
I, II, III, IV fast qualitative, quantitative analysis are carried out.
Claims (9)
1. the rapid detection method of tonyred in chilli products characterized by comprising
Step 1, pre-treatment is carried out to commercially available chilli products, obtains extracting solution S；
Step 2, it is combined using efficient liquid phase-ultraviolet-visual spectrometer, acquires light of the extracting solution S after chromatographic column is kept completely separate
Modal data array obtains the spectroscopic data array without tonyred, i.e. background spectra database N by data processing；
Step 3, Sudan red, II, III, IV standard items mother liquor is prepared respectively, then standard mother liquor is successively diluted to various concentration
Standard solution, acquire ultraviolet-visible spectrum, obtain standard items spectra database V through least square fitting；
Step 4, chilli products sample to be tested is taken, extracting solution DC is obtained by fast formulation, acquires the ultraviolet-visible light modal data of DC
c；
Step 5, by standard items database V, background spectra database N and sample data c import data processing software, using to
Amount-subspace angle criterion method calculates the content of tonyred in chilli products.
2. rapid detection method according to claim 1, it is characterised in that: the chilli products includes chilli products oil sample
With chilli products powder sample.
3. rapid detection method according to claim 1, which is characterized in that the pre-treating method of the capsicum oil sample are as follows:
Chilli oil acetone ultrasonic dissolution is centrifuged after constant volume, supernatant is taken to obtain extracting solution.
4. rapid detection method according to claim 1, which is characterized in that the pre-treating method of the chilli powder sample are as follows:
Chilli powder sample is weighed, acetonitrile, ultrasonic wave extraction is added, extracting solution centrifugation takes supernatant to obtain extracting solution.
5. rapid detection method according to claim 1, which is characterized in that the sample spectral data acquires instrument
For ultraviolet-visible fiber spectrometer, wave-length coverage 200nm-1100nm.
6. rapid detection method according to claim 1, which is characterized in that the vector-subspace angle criterion method
Include:
(1) step number Δ is reduced according to quantitative accuracy setting；
(2) tonyred calibration curve equation is yi=aix+bi, wherein i is a certain wavelength, yiIndicate the absorbance under a certain wavelength i
Value, aiAnd biConstant is referred to, x indicates the different concentration of tonyred, v1As concentration is x1The multi-wavelength absorbance y of lower tonyred1,
V is matrix composed by the corresponding all y values of various concentration x different wave length i；
(3) tonyred standard items v is constantly deducted from the spectroscopic data c of capsicum sample to be measured1, v is deducted every time1The amount of/Δ,
Variable after deduction is dc, and M is denoted as after background spectra database N is merged with the vector dc for deducting tonyred, calculates M and v1's
Angle；
(4) when in sample to be tested tonyred deducted completely, when maximum value occurs in angle, by x and reduce step number and can calculate
The content in sample is y out1=x1×λmax/ Δ, y1Value is the content of tonyred in chilli products to be measured.
7. rapid detection method according to claim 1, which is characterized in that the detection of the rapid detection method is limited to 10
μg/kg。
8. rapid detection method according to claim 1, which is characterized in that background spectra database N, with principal component point
Analysis method removes the dimension of noise and redundancy in data, carries out Data Dimensionality Reduction.
9. rapid detection method according to claim 8, which is characterized in that determined using the method for system independent variable number
Number of principal components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910044610.4A CN109765326A (en) | 2019-01-17 | 2019-01-17 | The rapid detection method of tonyred in chilli products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910044610.4A CN109765326A (en) | 2019-01-17 | 2019-01-17 | The rapid detection method of tonyred in chilli products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109765326A true CN109765326A (en) | 2019-05-17 |
Family
ID=66452492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910044610.4A Pending CN109765326A (en) | 2019-01-17 | 2019-01-17 | The rapid detection method of tonyred in chilli products |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109765326A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111999418A (en) * | 2020-09-04 | 2020-11-27 | 山东拜尔检测股份有限公司 | Method for detecting residual quantity of Sudan red in food |
| CN113848260A (en) * | 2021-08-17 | 2021-12-28 | 广西科技大学 | Method for detecting paraffin in rice based on space angle |
| CN115047103A (en) * | 2022-06-13 | 2022-09-13 | 四川敏恩检测技术有限公司 | Detection method for detecting content of Sudan red in capsanthin |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323405A (en) * | 2011-05-27 | 2012-01-18 | 无锡安迪生物工程有限公司 | Rhodamine B rapid detection card and detection method thereof |
| CN103308620A (en) * | 2013-06-09 | 2013-09-18 | 广西工学院 | Method for rapidly measuring p-hydroxy-benzoate ester in cosmetics |
| CN103592251A (en) * | 2013-11-14 | 2014-02-19 | 广西科技大学 | Method for directly measuring potassium sorbate in soybean sauce |
| CN103823004A (en) * | 2013-12-18 | 2014-05-28 | 广西科技大学 | Method for quickly measuring pigment and preservative in jelly |
| CN104101661A (en) * | 2014-07-03 | 2014-10-15 | 广西大学 | Quick detecting method for sudan red in food |
| CN104614471A (en) * | 2015-01-20 | 2015-05-13 | 宁波市疾病预防控制中心 | Fast extraction, purification and detection method for Sudan red dye residues in food |
| CN104730195A (en) * | 2013-12-24 | 2015-06-24 | 青岛休闲食品有限公司 | Rapid detection method for sudan colorant in dry powdered pepper products |
| CN104950060A (en) * | 2015-04-01 | 2015-09-30 | 广西科技大学 | Analysis method for content of paeonol based on chromatograph-spectrograph combination and sub-space included angle criteria |
| CN105158189A (en) * | 2015-08-28 | 2015-12-16 | 广西科技大学 | Method for analyzing content of antioxidants in vegetable oil on basis of criterion of space angle |
-
2019
- 2019-01-17 CN CN201910044610.4A patent/CN109765326A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323405A (en) * | 2011-05-27 | 2012-01-18 | 无锡安迪生物工程有限公司 | Rhodamine B rapid detection card and detection method thereof |
| CN103308620A (en) * | 2013-06-09 | 2013-09-18 | 广西工学院 | Method for rapidly measuring p-hydroxy-benzoate ester in cosmetics |
| CN103592251A (en) * | 2013-11-14 | 2014-02-19 | 广西科技大学 | Method for directly measuring potassium sorbate in soybean sauce |
| CN103823004A (en) * | 2013-12-18 | 2014-05-28 | 广西科技大学 | Method for quickly measuring pigment and preservative in jelly |
| CN104730195A (en) * | 2013-12-24 | 2015-06-24 | 青岛休闲食品有限公司 | Rapid detection method for sudan colorant in dry powdered pepper products |
| CN104101661A (en) * | 2014-07-03 | 2014-10-15 | 广西大学 | Quick detecting method for sudan red in food |
| CN104614471A (en) * | 2015-01-20 | 2015-05-13 | 宁波市疾病预防控制中心 | Fast extraction, purification and detection method for Sudan red dye residues in food |
| CN104950060A (en) * | 2015-04-01 | 2015-09-30 | 广西科技大学 | Analysis method for content of paeonol based on chromatograph-spectrograph combination and sub-space included angle criteria |
| CN105158189A (en) * | 2015-08-28 | 2015-12-16 | 广西科技大学 | Method for analyzing content of antioxidants in vegetable oil on basis of criterion of space angle |
Non-Patent Citations (3)
| Title |
|---|
| 孙卫明等: "调料粉中苏丹红等9种工业染料的液相色谱测定法", 《职业与健康》 * |
| 宋光均等: "液相-子空间夹角判据联用分析饮料中的柠檬黄和日落黄", 《湖北农业科学》 * |
| 王永姣等: "辣椒粉中非法添加苏丹红的测定方法研究", 《西北药学杂志》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111999418A (en) * | 2020-09-04 | 2020-11-27 | 山东拜尔检测股份有限公司 | Method for detecting residual quantity of Sudan red in food |
| CN113848260A (en) * | 2021-08-17 | 2021-12-28 | 广西科技大学 | Method for detecting paraffin in rice based on space angle |
| CN113848260B (en) * | 2021-08-17 | 2023-08-15 | 广西科技大学 | Method for detecting paraffin in rice based on space angle |
| CN115047103A (en) * | 2022-06-13 | 2022-09-13 | 四川敏恩检测技术有限公司 | Detection method for detecting content of Sudan red in capsanthin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dalzell et al. | A rapid method for the measurement of Leucaena spp proanthocyanidins by the proanthocyanidin (butanol/HCl) assay | |
| CN109765326A (en) | The rapid detection method of tonyred in chilli products | |
| CN105403630A (en) | Method for detecting concentration of nine compound coloring agents in auxiliary materials for reconstituted tobacco | |
| CN103675147B (en) | Method for rapidly determining caffeine in drink | |
| CN105738494A (en) | Isotope dilution high resolution chromaticness combination method for simultaneously detecting organic chlorine pesticides and polychlorinated biphenyl in biological sample, and application | |
| CN105675582A (en) | Method using Raman spectrum to detect beta-carotene content in fruit | |
| CN105181866A (en) | Method for rapid detection of benzalkonium chloride in eye drops | |
| CN111830141A (en) | Method for screening pesticide residues in medicine-food homology food by using pesticide residue mass spectrum database | |
| CN105158189A (en) | Method for analyzing content of antioxidants in vegetable oil on basis of criterion of space angle | |
| CN105486794A (en) | Method for detecting banned dye in printing ink | |
| CN108663337A (en) | A kind of method and its application measuring tanshinone component | |
| CN109765322A (en) | The characteristic spectrum construction method and quality determining method of schizonepeta | |
| CN107422053B (en) | Method for detecting trichloroacetic acid in cosmetics by liquid chromatography-mass spectrometry | |
| Es’haghi | Photodiode array detection in clinical applications; quantitative analyte assay advantages, limitations and disadvantages | |
| CN105158372B (en) | Method for determining urocanic acid and ethyl ester thereof in cosmetics | |
| CN106908527A (en) | A kind of method for differentiating the honey of lychee flowers place of production | |
| CN103823004B (en) | Method for quickly measuring pigment and preservative in jelly | |
| Yuan et al. | Determination of Sudan I in chilli powder from solvent components gradual change–visible spectra data using second order calibration algorithms | |
| CN109187830A (en) | The method of 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance | |
| CN112326853B (en) | Method for simultaneously detecting 25 triterpene compounds in ganoderma lucidum fruiting body | |
| CN109580803A (en) | A kind of Russia's color leaf extract and its quality determining method | |
| CN109030683B (en) | A method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid | |
| CN106706824B (en) | The detection method of juvenile hormone JH II in a kind of insect bodies of application of gas chromatorgraphy/mass | |
| Frenich et al. | Multicomponent determination of pesticides in vegetables by gas chromatography with mass spectrometric detection and multivariate calibration | |
| Hu et al. | Multi-way calibration coupling with fluorescence spectroscopy to determine magnolol and honokiol in herb and plasma samples |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190517 |