CN103308620B - Method for rapidly measuring p-hydroxy-benzoate ester in cosmetics - Google Patents
Method for rapidly measuring p-hydroxy-benzoate ester in cosmetics Download PDFInfo
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- CN103308620B CN103308620B CN201310230203.5A CN201310230203A CN103308620B CN 103308620 B CN103308620 B CN 103308620B CN 201310230203 A CN201310230203 A CN 201310230203A CN 103308620 B CN103308620 B CN 103308620B
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Abstract
The invention discloses a method for rapidly measuring a p-hydroxy-benzoate ester in cosmetics and relates to a method for measuring components in the cosmetics. The method comprises the following steps: A, treating a sample to be measured; B, establishing a background spectral database, namely B1, acquiring spectral data of a cosmetic sample; B2, acquiring spectral data of components to be measured; B3, converting the data format; B4, acquiring spectral data of a background which does not contain the components to be measured; B5, reducing the dimensionality of a background database; C, acquiring a standard spectral database v of the p-hydroxy-benzoate ester; D, measuring a spectrum of the cosmetic sample to be measured; E, measuring the content of the p-hydroxy-benzoate ester in the cosmetic sample to be measured. The method is high in analysis efficiency, low in operating strength and low in analysis cost, the background database which does not contain the measured components is not required to be accumulated, the machine hour and the reagent loss can be reduced, the robustness is high, and the method is simple and suitable for rapidly analyzing and measuring the same type of large-scale samples.
Description
Technical field
The present invention relates to the assay method of ingredient components in a kind of cosmetics, especially a kind of rapid assay methods of Determination of Preservatives in Cosmetics p-hydroxybenzoate.
Background technology
P-hydroxybenzoate, nipagin esters, is antiseptic comparatively conventional in current cosmetics, its analytical approach is mainly chromatogram class methods, comprises thin layer chromatography, vapor-phase chromatography, high performance liquid chromatography (HPLC) and capillary electrophoresis etc.Vapor-phase chromatography, when containing hydroxyl and carboxyl isopolarity material for mensuration, generally need use gas chromatography qualitative after methyl-monosilane, derivatization again, quantitatively, therefore, in antiseptic detects, is subject to certain limitation; Thin-layered chromatography can be carried out the qualitative of various ingredients, does not need special instruments and equipment, easily promotes; High performance liquid chromatography is current most popular method, has the advantages such as easy and simple to handle, sensitivity is high.For example, but adopting the major limitation of chromatographic process is to need disengaging time, and the disengaging time of a sample of HPLC approaches 15-20 minute, the analysis efficiency of sample in enormous quantities is low, and manipulation strength is large.For the analysis operation of sample in enormous quantities, flow and equate that reagent loss is large, analysis cost is high.
Summary of the invention
The technical problem to be solved in the present invention is: provide the rapid assay methods of p-hydroxybenzoate in a kind of cosmetics, the weak point that analysis efficiency is low, manipulation strength is large and analysis cost is high existing to solve prior art.
The technical conceive solving the problems of the technologies described above: gather the multi-wavelength chromatogram data of known component to be measured, record the appearance time of component to be measured; The multi-wavelength chromatogram data of the polycomponent mixing sample that collection contains component to be measured; In deduction mixing sample chromatographic data, there are the data of identical retention time with component to be measured; The chromatographic data that merges the deduction component to be measured of a plurality of samples, obtains, not containing by the background data storehouse of component, calculating major component number; By svd in conjunction with major component number to background data storehouse dimensionality reduction, can obtain the background data storehouse that data volume is less.Use space angle criterion to calculate the content of test substance in polycomponent mixing sample, thus realize component to be measured in polycomponent mixed system quantitatively.
The technical scheme solving the problems of the technologies described above is: the rapid assay methods of p-hydroxybenzoate in a kind of cosmetics, comprises the following steps:
A. sample to be tested is processed:
Cosmetic samples to be measured is filtered with methanol extraction, make cosmetics filtrate;
B. the foundation of background spectra database:
B1. obtain the spectroscopic data of cosmetic samples:
The cosmetics filtrate that steps A is made, through efficient liquid phase chromatographic analysis, gathers the multi-wavelength spectrum data of a plurality of cosmetic samples;
B2. obtain the spectroscopic data of component to be measured:
Prepare the methanol solution of component p-hydroxybenzoate to be measured, filter by efficient liquid phase chromatographic analysis, gather the multi-wavelength spectrum data of component to be measured;
B3. conversion data form:
Step B1 is become to the absorbance under multi-wavelength under different time with the multi-wavelength spectrum data of cosmetic samples and the multi-wavelength spectrum data of component to be measured that gather gained in B2 by light intensity data format conversion, and the spectroscopic data of cosmetic samples obtains the multi-wavelength spectrum data of cosmetic samples after data transform; The spectroscopic data of component to be measured obtains the multi-wavelength spectrum data of p-hydroxybenzoate standard substance after data transform;
B4. obtain the spectroscopic data that does not contain the background of component to be measured:
The chromatogram of comparison cosmetic samples and p-hydroxybenzoate standard substance is deducted the spectroscopic data with p-hydroxybenzoate standard substance with identical retention time from the chromatogram of cosmetic samples, and remainder data deposits in background spectra database; The background spectra database that merges a plurality of samples forms background spectra database W;
B5. the dimensionality reduction in background data storehouse:
The background spectra database W of gained in step B4 is carried out to svd, according to system major component number, background spectra database W is dropped to suitable dimension, obtain background spectra database N;
C. obtain the standard spectrum database v of p-hydroxybenzoate;
D. cosmetic samples spectral measurement to be measured:
The cosmetics filtrate making after adopting fiber spectrometer to processing of step A is carried out spectral measurement after dilution, obtains cosmetic samples spectroscopic data a to be measured;
E. hydroxybenzoate assay in cosmetic samples to be measured:
Respectively the background spectra database N of step B, C, D gained, standard spectrum database v, cosmetic samples spectroscopic data a to be measured are imported to computing platform, application vector-subspace angle criterion algorithm is reduced the standard spectrum of p-hydroxybenzoate from cosmetic samples spectrum to be measured, draws the actual content of p-hydroxybenzoate in sample to be tested.
Further technical scheme of the present invention is: described steps A. the concrete steps that sample to be tested is processed are as follows:
Take 0.5～2.0 gram of cosmetic samples to be measured in tool plug test tube, add methyl alcohol 5.0～20.0mL vibration to disperseing, ultrasound wave extracts 10～15min, rotating speed 3500～4500rps, and centrifugal 5～20min, gets supernatant liquid filtering, obtains filtrate.
Further technical scheme of the present invention is: in the dimensionality reduction in step B5. background data storehouse, the described definite method of system major component number is:
In standardized sample, add the interference that the white noise of some strength covers inhomogeneous noise and non-linear factor, the break judgement independent variable number with second order difference value sequence, obtains system major component number q.
Further technical scheme of the present invention is: in the dimensionality reduction in step B5. background data storehouse, the described method that background spectra database W is dropped to suitable dimension is as follows:
Application [U, S, V]=svd (W) carries out svd dimensionality reduction to background spectra database W, obtains m rank row orthogonal matrix U, n rank row orthogonal matrix V and singular value matrix S after decomposition, gets the front q row of U, is the background data storehouse N after dimensionality reduction.
Further technical scheme of the present invention is: the standard spectrum database of described step C. p-hydroxybenzoate
vthe particular content obtaining is:
Quantitatively prepare the p-hydroxybenzoate-methanol solution of series concentration, record respectively concentration and the 190nm-650nm wavelength coverage spectrum of each solution, charge to standard spectrum database; Select 225nm-350nm wavelength coverage spectrum, and press serial p-hydroxybenzoate all with P-hydroxybenzoic acid content meter, carry out multivariate least square regression, obtain the standard spectrum database of p-hydroxybenzoate
v.
Further technical scheme more of the present invention is: described step e. in cosmetic samples to be measured, the concrete steps of hydroxybenzoate assay are as follows:
(1) according to quantitative accuracy, set and reduce step delta;
(2) at formula
in bring into larger
x 1 value, obtains
v 1 ;
Described
y i be illustrated in
ithe absorbance of p-hydroxybenzoate under wavelength,
a i , b i constant,
xthe concentration that represents P-hydroxybenzoic acid, v
1being illustrated in concentration is
x 1 time p-hydroxybenzoate multi-wavelength absorbance
y 1 , v
1for all
y i the matrix that value forms;
(3) from cosmetic samples spectroscopic data to be measured
amiddle deduction v
1/ Δ, the variable after deduction is designated as d
a; Background spectra database
nmerge postscript for contrast space M with variable da, calculate contrast space M with
v 1 angle;
(4) from cosmetic samples spectroscopic data to be measured
ain progressively deduction
v 1after, repeating step (3);
(5) p-hydroxybenzoate in cosmetic samples to be measured, completely by after deduction, is compared the spectrum vector v of space M and p-hydroxybenzoate
1space angle value there will be maximal value θ
max, record space angle maximal value θ
maxthe corresponding step number λ that reduces during appearance, by the concentration of P-hydroxybenzoic acid
x 1 with the content of reducing p-hydroxybenzoate in step number estimation cosmetic samples
y 1, calculating formula is
y 1=
x 1* λ/Δ, obtains
y 1be the content value of p-hydroxybenzoate in cosmetic sample to be measured.
In step (5), if
y 1value with
x 1 it is larger that value differs, bring into one with
y 1be close
x 2 recalculate.
Owing to adopting said structure, in the present invention's cosmetics, the rapid assay methods of p-hydroxybenzoate compared with prior art, has following beneficial effect:
1. analysis efficiency is high, manipulation strength is little:
Because the present invention adopts ultraviolet multi-wavelength, directly measure, direct quantitative p-hydroxybenzoate, does not need disengaging time, and sample is measured and is quantitatively less than 10 seconds computing time, its analysis efficiency is higher, and manipulation strength is less, and the express-analysis that is very suitable for similar sample in enormous quantities is measured.
2. analysis cost is low:
Because the present invention is accurate based on matrix-vector footmark between background spectra collection, spectrum to be measured and sample spectrum, by realizing quantitatively by the amount mode of reducing, can adopt the output data of modal single order spectral instrument, data dimension is not proposed to special requirement, therefore, the present invention is without special instruments and equipment, and reagent consumption significantly reduces, thereby reduced analysis cost.
3. without accumulation, do not contain the background data storehouse of tested component:
Because cosmetics are of a great variety, raw material is complicated, sets up complete background data storehouse workload large, thus the applicability of impact analysis precision and method.And the present invention proposes by high performance liquid chromatography-spectrum method for combined use, separation measures after each chromatogram of cosmetic samples one dimension spectrum constantly, classify, obtain not containing the background data of tested component, in conjunction with vector-subspace angle criterion algorithm, realize the analysis of tested component in sample.Therefore, the present invention, has not only reduced workload, and has improved analysis precision not containing the background data storehouse of tested component without accumulation, has expanded the applicability of method.
4. in the time of can reducing machine and reagent loss:
For the mensuration of similar sample, the present invention, after carrying out a chromatographic resolution, at the bottom of recycling coupling instrument cumulative volume, only can realize quantitatively by spectral measurement, thereby in the time of can reducing machine and reagent loss.
5. robustness is good:
The present invention compares with existing single wavelength, dual wavelength and several wavelength methods, and antijamming capability is strong, and can identification complexity high, robustness be good.
6. method is simple:
Analysis method comparison of the present invention is simple, without complex steps, is easy to apply.
Below, in conjunction with the accompanying drawings and embodiments the technical characterictic of the rapid assay methods of p-hydroxybenzoate in the present invention's cosmetics is further described.
Accompanying drawing explanation
Fig. 1: the cosmetic samples two dimension spectrogram in step B3 after data transform,
Horizontal ordinate in Fig. 1 is designated as time (unit: min), ordinate is wavelength (unit; Nm); Ordinate is absorbance;
Fig. 2: the liquid chromatogram of cosmetic samples reference substance;
Fig. 3: cosmetic samples is at the liquid chromatogram at 256nm place,
Horizontal ordinate in Fig. 3 is time (unit: min), ordinate is absorbance;
Fig. 4: space angle value and reduce the curve map between number of times.
Embodiment
Embodiment mono-:
A rapid assay methods for p-hydroxybenzoate in cosmetics, comprises the following steps:
A. sample to be tested is processed:
Cosmetic samples to be measured is filtered with methanol extraction, and its concrete operations are: take 1.00 grams of samples in tool plug test tube, add methyl alcohol 10.0mL vibration to disperseing, ultrasound wave extracts 15min; Rotating speed 4000rps, centrifugal 10min, gets supernatant liquid filtering, obtains cosmetics filtrate.
B. the foundation of background spectra database:
B1. obtain the spectroscopic data of cosmetic samples:
The cosmetics filtrate that steps A is made, through efficient liquid phase chromatographic analysis, gathers the multi-wavelength spectrum data of a plurality of cosmetic samples;
B2. obtain the spectroscopic data of component to be measured:
Methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, the propylparaben mixing methanol solution of preparation 10mg/L, for efficient liquid phase chromatographic analysis, obtain the multi-wavelength spectrum data of tested component p-hydroxybenzoate after filtration.
In step B1, B2, high-efficient liquid phase chromatogram condition is:
Chromatographic column: Pgrandsil-STC C
18chromatographic column (4.6mm * 150mm);
Gradient elution, mobile phase:
0～25min, acetonitrile: 0.02mol/L ammonium acetate solution=20:80～50:50(V/V)
25～35min, acetonitrile: water=5:95～15:85(V/V);
35～55min, acetonitrile: isopropyl alcohol=50:50～80:20(V/V);
55～65min, acetonitrile: water=5:95～15:85(V/V)
Flow velocity 1mL/min; Sample size: 20 μ L; Column temperature: 20 ℃; Ultraviolet detects wavelength: 190～380nm.
B3. conversion data form:
Step B1 is become to the absorbance under multi-wavelength under different time with the multi-wavelength spectrum data of cosmetic samples and the multi-wavelength spectrum data of component to be measured that gather gained in B2 by light intensity data format conversion, every a line of data after conversion represents a chromatographic data under wavelength, inscribes the spectroscopic data (referring to Fig. 1) that elutes material when each row represents one.The spectroscopic data of the cosmetic samples in B1 step obtains the spectroscopic data of cosmetic samples after data transform; The spectroscopic data of the component to be measured in B2 step obtains the spectroscopic data of p-hydroxybenzoate standard substance after data transform;
B4. obtain the spectroscopic data that does not contain the background of component to be measured:
Determine tested component, the tested component liquid phase chromatogram condition completely separated with background component.With this understanding sample is analyzed, obtained the liquid chromatogram of cosmetic samples to be measured and reference substance sample.Fig. 2 is the liquid chromatogram of reference substance.Wherein the appearance time of three kinds of esters is respectively methyl esters 3.9～4.8min, ethyl ester 6.0～7.3min, propyl ester 12.0～13.5min.Fig. 3 is a kind of liquid chromatogram of cosmetic samples wherein.Contrast by analysis, in Fig. 3, A is that methyl esters, B are that ethyl ester, C are propyl ester, other chromatographic peak is with respect to the background substance of p-hydroxybenzoate in cosmetic samples.From the chromatogram of cosmetic samples, deduct the spectroscopic data with p-hydroxybenzoate standard substance with identical retention time, remainder data deposits in background spectra database; The background spectra database that merges a plurality of cosmetic samples forms background spectra database W;
B5. the dimensionality reduction in background data storehouse:
The database W data volume that step B4 obtains is large, can cause calculated amount very large.The background spectra database W of gained in step B4 is carried out to svd, according to system major component number, background spectra database W is dropped to suitable dimension, obtain background spectra database N;
The described definite method of system major component number is:
In standardized sample, add the interference that the white noise of some strength covers inhomogeneous noise and non-linear factor, the break judgement independent variable number with second order difference value sequence, obtains system major component number q.
The described method that background spectra database W is dropped to suitable dimension is as follows:
Application [U, S, V]=svd (W) carries out svd dimensionality reduction to background spectra database W, obtains m rank row orthogonal matrix U, n rank row orthogonal matrix V and singular value matrix S after decomposition, gets the front q row of U, is the background data storehouse N after dimensionality reduction.
C. obtain the standard spectrum database v of p-hydroxybenzoate:
Preparing respectively a series of concentration is P-hydroxybenzoic acid first, the second of 0.2mg/L-12.0mg/L, the methanol solution of propyl ester, records respectively concentration and the 190nm-650nm wavelength coverage spectrum of each solution, charges to standard spectrum database.Select 225nm-350nm wavelength coverage spectrum, P-hydroxybenzoic acid first, second, propyl ester are pressed P-hydroxybenzoic acid content meter, obtain the standard spectrum database of p-hydroxybenzoate after multivariate least square regression
v.
D. cosmetic samples spectral measurement to be measured:
The range of linearity by the cosmetics filtrate making after processing of step A according to absorbance, quantitatively pipette filtrate, with methyl alcohol dilution, be settled in 5～20mL volumetric flask, adopt multi-wavelength ultraviolet-visible fiber spectrometer to carry out spectral measurement, obtain cosmetic samples spectroscopic data a to be measured;
E. hydroxybenzoate assay in cosmetic samples to be measured:
Respectively the background spectra database N of step B, C, D gained, standard spectrum database v, cosmetic samples spectroscopic data a to be measured are imported to computing platform, application vector-subspace angle criterion algorithm is reduced the standard spectrum of p-hydroxybenzoate from cosmetic samples spectrum to be measured, draw the actual content of p-hydroxybenzoate in sample to be tested.
The concrete steps of this step e are as follows:
(1) according to quantitative accuracy, set and reduce step delta (the present embodiment is 1000);
(2) at formula
in bring into larger
x 1 value, obtains
v 1 ,
Described
y i be illustrated in
ithe absorbance of p-hydroxybenzoate under wavelength,
a i , b i constant,
xthe concentration that represents P-hydroxybenzoic acid, v
1being illustrated in concentration is
x 1 time p-hydroxybenzoate multi-wavelength absorbance
y 1 , v
1for all
y i the matrix that value forms;
(3) from cosmetic samples spectroscopic data to be measured
amiddle deduction v
1(the present embodiment is deduction Δ v1=v to/Δ
1/ 1000), the variable after deduction is designated as d
a; Background spectra database
nmerge postscript for contrast space M with variable da, calculate contrast space M with
v 1 angle;
(4) from cosmetic samples spectroscopic data to be measured
ain progressively deduction
v 1after, repeating step (3);
(5) p-hydroxybenzoate in cosmetic samples to be measured is completely by the spectrum vector v of comparison space M and p-hydroxybenzoate after deduction
1space angle value there will be maximal value θ
max, record space angle maximal value θ
maxthe corresponding step number λ that reduces during appearance, (referring to Fig. 4, occurring that the step number of reducing that maximum angle is is 976), at this moment by the concentration of P-hydroxybenzoic acid
x 1 with the content of reducing p-hydroxybenzoate in step number cosmetic samples
y 1; Calculating formula is
y 1=
x 1* λ/Δ, obtains
y 1be the content value of p-hydroxybenzoate in cosmetic sample to be measured.If
y 1value with
x 1 it is larger that value differs, bring into one with
y 1be close
x 2 recalculate.
As a kind of conversion of the present embodiment, in described steps A, each parameter is also convertible, is generally:
Cosmetics to be measured are 0.5～2.0 gram, and the methyl alcohol adding is 5.0～20.0mL, and ultrasound wave extracts 10～15min, rotating speed 3500～4500rps, centrifugal 5～20min.
In order to verify that the present invention measures the accuracy of structure, selected the sample of six kinds of commercially available shampoo classes, by the coupling of high performance liquid chromatography-ultraviolet-visible fiber spectrometer, set up after local data base, by the rapid assay methods of p-hydroxybenzoate in the present invention's cosmetics, measure the content of p-hydroxybenzene acid in cosmetic samples, and and high performance liquid chromatography result comparison (referring to table 1).
Two kinds of methods of table 1 are measured the content of p-hydroxybenzoate in sample
The present invention has also carried out recovery experiment, and result is as shown in table 2.
The experiment of table 2 recovery
To parallel six experiments of B1, RSD value is 1.045%.
Claims (7)
1. a rapid assay methods for p-hydroxybenzoate in cosmetics, is characterized in that: comprise the following steps:
A. sample to be tested is processed:
Cosmetic samples to be measured is filtered with methanol extraction, make cosmetics filtrate;
B. the foundation of background spectra database:
B1. obtain the spectroscopic data of cosmetic samples:
The cosmetics filtrate that steps A is made, through efficient liquid phase chromatographic analysis, gathers the multi-wavelength spectrum data of a plurality of cosmetic samples;
B2. obtain the spectroscopic data of component to be measured:
Prepare the methanol solution of component p-hydroxybenzoate to be measured, filter by efficient liquid phase chromatographic analysis, gather the multi-wavelength spectrum data of component to be measured;
B3. conversion data form:
Step B1 is become to the absorbance under multi-wavelength under different time with the multi-wavelength spectrum data of cosmetic samples and the multi-wavelength spectrum data of component to be measured that gather gained in B2 by light intensity data format conversion, and the spectroscopic data of cosmetic samples obtains the multi-wavelength spectrum data of cosmetic samples after data transform; The spectroscopic data of component to be measured obtains the multi-wavelength spectrum data of p-hydroxybenzoate standard substance after data transform;
B4. obtain the spectroscopic data that does not contain the background of component to be measured:
The chromatogram of comparison cosmetic samples and p-hydroxybenzoate standard substance is deducted the spectroscopic data with p-hydroxybenzoate standard substance with identical retention time from the chromatogram of cosmetic samples, and remainder data deposits in background spectra database; The background spectra database that merges a plurality of samples forms background spectra database W;
B5. the dimensionality reduction in background data storehouse:
The background spectra database W of gained in step B4 is carried out to svd, according to system major component number, background spectra database W is dropped to suitable dimension, obtain background spectra database N;
C. obtain the standard spectrum database v of p-hydroxybenzoate;
D. cosmetic samples spectral measurement to be measured:
The cosmetics filtrate making after adopting fiber spectrometer to processing of step A is carried out spectral measurement after dilution, obtains cosmetic samples spectroscopic data a to be measured;
E. hydroxybenzoate assay in cosmetic samples to be measured:
Respectively the background spectra database N of step B, C, D gained, standard spectrum database v, cosmetic samples spectroscopic data a to be measured are imported to computing platform, application vector-subspace angle criterion algorithm is reduced the standard spectrum of p-hydroxybenzoate from cosmetic samples spectrum to be measured, draws the actual content of p-hydroxybenzoate in sample to be tested.
2. according to the rapid assay methods of p-hydroxybenzoate in cosmetics claimed in claim 1, it is characterized in that: described steps A. the concrete steps that sample to be tested is processed are as follows:
Take 0.5～2.0 gram of cosmetic samples to be measured in tool plug test tube, add methyl alcohol 5.0～20.0mL vibration to disperseing, ultrasound wave extracts 10～15min, rotating speed 3500～4500rps, and centrifugal 5～20min, gets supernatant liquid filtering, obtains filtrate.
3. the rapid assay methods of p-hydroxybenzoate in cosmetics according to claim 1, is characterized in that: in the dimensionality reduction in step B5. background data storehouse, the described definite method of system major component number is:
In standardized sample, add the interference that the white noise of some strength is sheltered inhomogeneous noise and non-linear factor, the break judgement independent variable number with second order difference value sequence, obtains system major component number q.
4. the rapid assay methods of p-hydroxybenzoate in cosmetics according to claim 1, is characterized in that: in the dimensionality reduction in step B5. background data storehouse, the described method that background spectra database W is dropped to suitable dimension is as follows:
Application [U, S, V]=svd (W) carries out svd dimensionality reduction to background spectra database W, obtains m rank row orthogonal matrix U, n rank row orthogonal matrix V and singular value matrix S after decomposition, gets the front q row of U, is the background data storehouse N after dimensionality reduction.
5. the rapid assay methods of p-hydroxybenzoate in cosmetics according to claim 1, is characterized in that: the particular content that the standard spectrum database v of described step C. p-hydroxybenzoate obtains is:
Quantitatively prepare the p-hydroxybenzoate-methanol solution of series concentration, record respectively concentration and the 190nm-650nm wavelength coverage spectrum of each solution, charge to standard spectrum database; Select 225nm-350nm wavelength coverage spectrum, and to series the p-hydroxybenzoate with P-hydroxybenzoic acid content meter, carry out multivariate least square regression, obtain the standard spectrum database v of p-hydroxybenzoate.
6. the rapid assay methods to p-hydroxybenzoate in the cosmetics described in the arbitrary claim of claim 5 according to claim 1, is characterized in that: described step e. in cosmetic samples to be measured, the concrete steps of hydroxybenzoate assay are as follows:
(1) according to quantitative accuracy, set and reduce step delta;
(2) at formula y
i=a
ix+b
iin bring larger x into
1value, obtains v
1;
Described y
ibe illustrated in the absorbance of p-hydroxybenzoate under i wavelength, a
i, b
ibe constant, x represents the concentration of P-hydroxybenzoic acid, v
1being illustrated in concentration is x
1time p-hydroxybenzoate multi-wavelength absorbance y
1, v
1for all y
ithe matrix that value forms;
(3) from cosmetic samples spectroscopic data a to be measured, deduct v
1/ Δ, the variable after deduction is designated as da; Background spectra database N and variable da are merged to postscript for contrast space M, calculate contrast space M and v
1angle;
(4) from cosmetic samples spectroscopic data a to be measured, progressively deduct v
1after, repeating step (3);
(5) p-hydroxybenzoate in cosmetic samples to be measured, completely by after deduction, is compared the spectrum vector v of space M and p-hydroxybenzoate
1space angle value there will be maximal value θ
max, record space angle maximal value θ
maxthe corresponding step number λ that reduces during appearance, by the concentration x of P-hydroxybenzoic acid
1with the content Y that reduces p-hydroxybenzoate in step number estimation cosmetic samples
1, calculating formula is Y
1=x
1* λ/Δ, the Y obtaining
1be the content value of p-hydroxybenzoate in cosmetic sample to be measured.
7. the rapid assay methods of p-hydroxybenzoate in cosmetics according to claim 6, is characterized in that: in step (5), if Y
1value and x
1it is larger that value differs, and brings one and Y into
1the x being close
2recalculate.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104297357B (en) * | 2013-12-10 | 2016-04-20 | 上海景峰制药股份有限公司 | The content assaying method of methyl p-hydroxybenzoate and Sodium Benzoate in a kind of solution |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262054A (en) * | 2011-07-06 | 2011-11-30 | 广西工学院 | Combined spectrum pattern recognition method based on subspace coincidence judgment |
| CN102306236A (en) * | 2011-07-06 | 2012-01-04 | 广西工学院 | Multivariable analysis method based on angle measurement |
| CN103018393A (en) * | 2012-12-07 | 2013-04-03 | 广西工学院 | Method for measuring content of components in mixed dye solution |
| CN103115884A (en) * | 2013-01-29 | 2013-05-22 | 广西工学院 | Method for measuring p-hydroxybenzoate in cosmetics |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3573883B2 (en) * | 1996-10-04 | 2004-10-06 | 株式会社ノエビア | Antibacterial hypoallergenic cosmetics |
-
2013
- 2013-06-09 CN CN201310230203.5A patent/CN103308620B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262054A (en) * | 2011-07-06 | 2011-11-30 | 广西工学院 | Combined spectrum pattern recognition method based on subspace coincidence judgment |
| CN102306236A (en) * | 2011-07-06 | 2012-01-04 | 广西工学院 | Multivariable analysis method based on angle measurement |
| CN103018393A (en) * | 2012-12-07 | 2013-04-03 | 广西工学院 | Method for measuring content of components in mixed dye solution |
| CN103115884A (en) * | 2013-01-29 | 2013-05-22 | 广西工学院 | Method for measuring p-hydroxybenzoate in cosmetics |
Non-Patent Citations (8)
| Title |
|---|
| JP特开平10-109923A 1998.04.28 |
| 分析化学计量学;吴海龙 等;《分析试验室》;19991130;第18卷(第6期);全文 * |
| 吴海龙 等.分析化学计量学.《分析试验室》.1999,第18卷(第6期),全文. |
| 多波长紫外可见光吸收光谱法用于中成药含量测定;黄莺 等;《中成药》;19981231;第20卷(第4期);全文 * |
| 姚志湘等.多变量统计分析中独立变量数目的判定方法.《华南理工大学学报(自然科学版)》.2007,第35卷(第1期),全文. * |
| 粟晖 等.紫外光谱法对维生素E油酸酯、维生素E与油酸的同时测定.《分析测试学报》.2009,第28卷(第11期),全文. |
| 紫外光谱法对维生素E油酸酯、维生素E与油酸的同时测定;粟晖 等;《分析测试学报》;20091130;第28卷(第11期);全文 * |
| 黄莺 等.多波长紫外可见光吸收光谱法用于中成药含量测定.《中成药》.1998,第20卷(第4期),全文. |
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