CN101532995A - Method for determining antiseptic content rapidly in spice with grease - Google Patents
Method for determining antiseptic content rapidly in spice with grease Download PDFInfo
- Publication number
- CN101532995A CN101532995A CN200910136252A CN200910136252A CN101532995A CN 101532995 A CN101532995 A CN 101532995A CN 200910136252 A CN200910136252 A CN 200910136252A CN 200910136252 A CN200910136252 A CN 200910136252A CN 101532995 A CN101532995 A CN 101532995A
- Authority
- CN
- China
- Prior art keywords
- sample
- antiseptic
- assay method
- grease
- internal standard
- 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.)
- Granted
Links
Images
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for determining antiseptic content rapidly in spice with grease which includes steps as follows: a) weighing a spice sample; b) adding an internal standard substance solution in the sample, then processing pre-treatment for obtaining the sample solution without grease; c) adding an extractive agent to the sample solution; d) shaking up and taking an upper layer clear solution; e) processing chromatographic analysis to the upper layer clear solution and obtaining the chromatographic analysis data; f) comparing the chromatographic analysis data with a pre-set antiseptic standard data for obtaining the antiseptic content in the spice. The method provided by the invention can determine the antiseptic content in spice accurately and rapidly, and can determine multi-antiseptic content in the spice with grease one-time. The method has high efficiency and accurate result.
Description
Technical field
The present invention relates to the assay method that one-tenth is grouped in the flavouring, relate in particular to the assay method of antiseptic content in the spice with grease.
Background technology
The method of at present general detection antiseptic is " sorbic acid, a benzoic mensuration in the GB/T 5009.29-2003 food " and " mensuration of parabens in the GB/T 5009.31-2003 food ".These two kinds of detection side's ratio juris are identical, be all the sample acidifying after, with organic solvent extraction, concentrate, carry out separation determination with gas chromatograph again, adopt the external standard method quantitative test.This method is simple, stable, has been widely used in the middle of the detection of antiseptic.But, adopt this two kinds of methods, on average each sample is about 90 minutes at detection time of expending, and can not realize that multiple antiseptic detects simultaneously, and therefore, overall detection efficiency is lower.For production of condiments enterprise wide in variety, that output is big, so low detection efficiency causes that product antiseptic testing amount is big, task heavy, expend a large amount of detection resources, and the serious hysteresis of assay is unfavorable for the monitoring of production run.Therefore, how antiseptic content in the flavouring is carried out fast measuring, become an important research project.
At present, also less than research about multiple antiseptic rapid assay methods in the spice with grease.
Summary of the invention
Technical matters to be solved by this invention is, the assay method of antiseptic content in a kind of fast measuring spice with grease is provided, solve long, problems such as extraction ratio is low, the big molecule interference of introducing of pre-treatment time, realized the fast detecting of antiseptic in the spice with grease.
Basic design of the present invention is: adopt vapor-phase chromatography to measure, with inner mark method ration, internal standard method is a kind of analysis method accurately in the chromatogram ration analysis.When using internal standard method, add a certain amount of standard substance in sample, it can be separated by chromatographic column, is not subjected to the interference of other component peaks in the sample again, as long as measure the peak area and the relative response of internal standard compound and component to be measured, can obtain the percentage composition of component to be measured in sample.
In order to solve above technical matters, the invention provides following technical scheme:
The rapid assay methods of antiseptic content in a kind of flavouring, with gas chromatography determination, inner mark method ration comprises the steps:
A) take by weighing the spice with grease sample;
B) in sample, carry out pre-service after the adding internal standard substance solution, obtain not grease-contained sample solution;
C) in sample solution, add extraction agent;
D) shake up, get supernatant liquor;
E) supernatant liquor is carried out stratographic analysis, obtain chromatogram analysis data;
F), obtain the content of antiseptic in the flavouring with described chromatogram analysis data and the comparison of predetermined antiseptic normal data.In flavouring, the antiseptic that adds is generally: benzoic acid, sorbic acid, propylparaben, predetermined antiseptic normal data described in this step, can obtain in the following ways: the reference material solution that benzoic acid, sorbic acid, propylparaben is disposed a series of concentration known respectively as reference material, the internal standard substance solution that adds concentration known more respectively, the difference sample introduction, measure relevant chromatographic data, internal standard compound peak area data, peak height data, reference material peak area data, peak height data.
To contrast by chromatogram analysis data one antiseptic and internal standard compound peak area, peak height data and the aforementioned respective standard data that step e) obtains in this step, can draw the concentration of antiseptic in the sample.
Wherein, in the step b), described pre-treatment step is: carry out degrease earlier and handle, carry out acidification again.
Wherein, described degrease is treated to: add alkali, organic solvent in sample, shake up, centrifugal, discard supernatant liquid.
Wherein, described organic solvent is one or more in normal hexane, sherwood oil, the cyclohexane.
Wherein, described acidification is: add hydrochloric acid in sample.Certainly, also can be other acid.
Wherein, in the step d), shake up after the step, get supernatant liquor and also carry out centrifugal treating before.
Wherein, in the step b), described internal standard substance solution, is made into as solvent with methyl alcohol or ethanol as internal standard compound by in C7～C11 organic acid any.
Wherein, in the step c), described extraction agent is the potpourri of ether and cyclohexane, and described ether is 1:4～1:1 with the mixed volume ratio of cyclohexane.
Wherein, in the step c), described extraction agent also can be ether and normal hexane potpourri, and the mixed volume of described ether and normal hexane is than being 1:4～1:1.
Wherein, in the said method, the heating mode of stratographic analysis process is: 80 ℃～100 ℃ of beginning temperature, after keeping 0.5min～1min, once heat up, be warming up to 180 ℃～220 ℃, carry out secondary temperature elevation again, be warming up to 250 ℃～300 ℃, keep 0.5min～3min; The described programming rate that once heats up is less than the programming rate of described secondary temperature elevation.
Wherein, the described programming rate that once heats up is 15 ℃/min～30 ℃/min, and the programming rate of described secondary temperature elevation is 40 ℃/min～60 ℃/min.
For whole assay method, in brief, at first take by weighing sample, sample is handled, extraction contains the solution of antiseptic and internal standard compound, and it is carried out stratographic analysis, by the chromatographic data of each antiseptic that records, in conjunction with the corresponding antiseptic normal data of making in advance, can calculate the content of each antiseptic in the flavouring, whole mensuration process required time is short, measures quick, accurate, and can measure the content of multiple antiseptic simultaneously, the efficient height.
More than the details in each step of the present invention is illustrated, wherein also narrated some and improved and preferred scheme.
The rapid assay methods of antiseptic content in the spice with grease of the present invention can accurately, promptly be measured the antiseptic content in the spice with grease, and once can measure the content of multiple antiseptic in the flavouring, so efficient height, result are accurate.
Description of drawings
Fig. 1 carries out stratographic analysis gained canonical plotting for antiseptic-sorbic acid with internal standard method.
Fig. 2 carries out stratographic analysis gained canonical plotting for antiseptic-benzoic acid with internal standard method.
Fig. 3 carries out stratographic analysis gained canonical plotting for antiseptic-propylparaben with internal standard method.
Fig. 4 is the mensuration process flow diagram of assay method preferred embodiment of the present invention.
Embodiment
For further understanding the present invention, above-mentioned technical scheme is further elaborated and illustrates below in conjunction with concrete embodiment.
In the assay method of the present invention, the chromatogram analysis method that is adopted is a vapor-phase chromatography, and GC conditions is as follows:
Detect with the gas chromatograph that has flame ionization ditector, carry out quantitatively with internal standard method.Instrument condition is: the carrier gas of gas chromatograph is a high pure nitrogen, nonpolar capillary chromatographic column, split ratio is 1:10, carrier gas flux is 1.17ml/min, injector temperature is 260 ℃, the detected temperatures of the flame ionization ditector that gas chromatograph has is 300 ℃, and hydrogen flowing quantity is 40ml/min, and air mass flow is 400ml/min.
In the assay method of the present invention, carry out antiseptic content at the flavouring sample and measure the following preparation of previous crops:
1, preparation reference material solution
Accurately take by weighing antiseptic (to call reference material in the following text) respectively: benzoic acid, sorbic acid, each 0.1000g of propylparaben, be settled to 100.00ml with ethanol, make reference material solution.
2, preparation internal standard substance solution
Accurately take by weighing caprylic acid 0.1000g as internal standard compound, be settled to 100.00ml, obtain the internal standard substance solution of preparation with ethanol.Also can select for use in other C7～C11 organic acid any as internal standard compound.
3, preparation extraction agent
Add 40 milliliters of cyclohexanes by 10 milliliters of ether and obtain extraction agent 1; Add 35 milliliters of cyclohexanes by 15 milliliters of ether and obtain extraction agent 2; Add 30 milliliters of cyclohexanes by 20 milliliters of ether and obtain extraction agent 3; Add 25 milliliters of cyclohexanes by 25 milliliters of ether and obtain extraction agent 4; Add 40 ml n-hexanes by 10 milliliters of ether and obtain extraction agent 5; Add 35 ml n-hexanes by 15 milliliters of ether and obtain extraction agent 6; Add 30 ml n-hexanes by 20 milliliters of ether and obtain extraction agent 7; Add 25 ml n-hexanes by 25 milliliters of ether and obtain extraction agent 8.
4, the making of typical curve
Dispose earlier the reference material solution of a series of concentration known respectively as reference material with antiseptics commonly used such as benzoic acid, sorbic acid, propylparabens, the internal standard substance solution that adds concentration known more respectively, the difference sample introduction, measure internal standard compound peak area and reference material peak area, with reference material and internal standard compound peak area concentration ratio when, make component typical curve to be measured, under the certain condition, reference material and internal standard compound peak area when concentration ratio are directly proportional.In the working sample during components contents to be measured, join in the sample with the internal standard compound of same concentrations, the sample introduction analysis contrasts the component to be measured that obtains and internal standard compound peak area ratio and aforesaid standards curve, can find component concentrations to be measured in the sample.Concrete manufacturing process is as follows:
Accurately draw reference material solution 2.00ml, 1.00ml, 0.50ml, 0.10ml, 0.01ml respectively, place the 10ml volumetric flask respectively, respectively add internal standard substance solution 1.00ml then, be settled to 10ml with ethanol again, difference sample introduction 1 μ l, can record variable concentrations reference material and internal standard compound peak area response, the concentration that records each reference material and internal standard compound by gas chromatography when chromatographic peak area ratio sees Table 1.
The concentration of each reference material concentration of table 1 and internal standard compound is the chromatographic peak area ratio when
| Reference material and internal standard compound concentration ratio | 0.010 | 0.100 | 0.500 | 1.000 | 2.000 |
| The ratio of sorbic acid and internal standard compound peak area | 0.0030341 | 0.0696183 | 0.3954925 | 0.7783516 | 1.546177 |
| The ratio of benzoic acid and internal standard compound peak area | 0.0032712 | 0.0548503 | 0.4184239 | 0.8804410 | 1.826348 |
| The ratio of propylparaben and internal standard compound peak area | 0.0072641 | 0.0811214 | 0.4321578 | 0.8712497 | 1.732574 |
According to table 1, as the x axle, be the y axle with the peak area ratio of each reference material and internal standard compound with the concentration ratio of reference material and internal standard compound, make the sorbic acid typical curve, see Fig. 1; Make the benzoic acid typical curve, see Fig. 2; Make the propylparaben typical curve, see Fig. 3.By Fig. 1, Fig. 2, Fig. 3 as can be seen, each reference material is directly proportional with concentration ratio with the peak area ratio of internal standard compound.
1) accurately take by weighing the grease-contained seasoning bean sauce of 1.000g, place in the 15ml centrifuge tube, add 0.50ml internal standard substance solution, 5 concentration successively and be 10% NaOH solution, vibration a moment add the 1ml normal hexane, shake up, centrifugal, discard supernatant liquid;
2) add 10 hydrochloric acid, 5ml extraction agent 8 more successively, shake up, centrifugal, draw the supernatant liquor sample introduction.
3) according to aforesaid instrument condition, instrumentation column incubator temperature is risen to 100 ℃ initial temperature, behind the instrument stabilizer, the supernatant liquor sample introduction is analyzed.Instrument carries out temperature programme, that is: the beginning temperature is 100 ℃, keeps 0.5min, rises to 200 ℃ with 20 ℃/min, rises to 280 ℃ with 60 ℃/min again, keeps 3min, moves 9.83min altogether.
4) ratio and the typical curve of each that will obtain component peaks area to be measured and internal standard compound peak area compare, and calculate this and contain in the grease sauce, and benzoic acid content is 0.42g/kg, and sorbic acid and propylparaben all do not detect.
Embodiment 2
1) accurately take by weighing the grease-contained thick chilli sauce of 1.000g, place in the 15ml centrifuge tube, add 0.50ml internal standard substance solution, 5 concentration successively and be 10% NaOH solution, vibration a moment add the 1ml sherwood oil, shake up, centrifugal, discard supernatant liquid;
2) add 10 hydrochloric acid, 5ml extraction agent 5 more successively, shake up, centrifugal, draw the supernatant liquor sample introduction.
3) according to aforesaid instrument condition, instrumentation column incubator temperature is risen to 90 initial temperature, behind the instrument stabilizer, the supernatant liquor sample introduction is analyzed.Instrument carries out temperature programme, that is: the beginning temperature is 90 ℃, keeps 1min, rises to 220 ℃ with 25 ℃/min, rises to 250 ℃ with 40 ℃/min again, keeps 2min, moves 8.95min altogether.
4) ratio and the typical curve of each that will obtain component peaks area to be measured and internal standard compound peak area compare, and calculate this and contain in the grease sauce, and benzoic acid content is 0.44g/kg, and sorbic acid and propylparaben all do not detect.
Embodiment 3
1) accurately take by weighing the grease-contained fruit and vegetable jam of 1.000g, place in the 15ml centrifuge tube, add 0.50ml internal standard substance solution, 5 concentration successively and be 10% NaOH solution, vibration a moment add the 1ml cyclohexane, shake up, centrifugal, discard supernatant liquid;
2) add 10 hydrochloric acid, 5ml extraction agent 6 more successively, shake up, centrifugal, draw the supernatant liquor sample introduction.
3) according to aforesaid instrument condition, instrumentation column incubator temperature is risen to 110 initial temperature, behind the instrument stabilizer, the supernatant liquor sample introduction is analyzed.Instrument carries out temperature programme, that is: the beginning temperature is 110 ℃, keeps 1min, rises to 180 ℃ with 15 ℃/min, rises to 300 ℃ with 50 ℃/min again, keeps 1min, moves 9.07min altogether.
4) ratio and the typical curve of each that will obtain component peaks area to be measured and internal standard compound peak area compare, and calculate this and contain in the grease sauce, and benzoic acid content is 0.35g/kg, and sorbic acid and propylparaben all do not detect.
As can be seen from the above embodiments, utilizing the inventive method that sample is carried out antiseptic content measures, whole measuring process, detection time, by National Standard Method 90 minutes foreshortened to 15 minutes greatly, and once can determine the content of multiple antiseptic in the flavouring sample, improve detection efficiency greatly, helped production monitoring and goods turnaround speed; Detect cost and have only about 1/3 of National Standard Method, saved the inspection cost of enterprise, help popularizing of antiseptic detection; Detect and stablize, promptly relative standard deviation RSD is controlled at below 3%, and accuracy reaches more than 90%.
More than technical scheme provided by the present invention is described in detail.Used specific embodiment in this instructions principle of the present invention and embodiment have been set forth, for one of ordinary skill in the art, according to the thought of the present invention part that may in implementation process, can change in specific embodiments and applications.Therefore, the content of this instructions record should not be construed as limitation of the present invention.
Claims (11)
1, the rapid assay methods of antiseptic content in a kind of spice with grease, with gas chromatography determination, inner mark method ration is characterized in that, comprises the steps:
A) take by weighing the spice with grease sample;
B) in sample, carry out pre-service after the adding internal standard substance solution, obtain not grease-contained sample solution;
C) in sample solution, add extraction agent;
D) shake up, get supernatant liquor;
E) supernatant liquor is carried out stratographic analysis, obtain chromatogram analysis data;
F), obtain the content of antiseptic in the flavouring with described chromatogram analysis data and the comparison of predetermined antiseptic normal data.
2, assay method according to claim 1 is characterized in that, in the step b), described pre-treatment step is: carry out degrease earlier and handle, carry out acidification again.
3, assay method according to claim 2 is characterized in that, described degrease is treated to: add alkali, organic solvent in sample, shake up, centrifugal, discard supernatant liquid.
4, assay method according to claim 3 is characterized in that, described organic solvent is one or more in normal hexane, sherwood oil, the cyclohexane.
5, assay method according to claim 2 is characterized in that, described acidification is: add hydrochloric acid in sample.
6, assay method according to claim 1 is characterized in that, in the step d), shakes up after the step, gets supernatant liquor and also carries out centrifugal treating before.
According to each described assay method of claim 1-6, it is characterized in that 7, in the step b), described internal standard substance solution, is made into as solvent with methyl alcohol or ethanol as internal standard compound by in C7～C11 organic acid any.
According to each described assay method of claim 1-6, it is characterized in that 8, in the step c), described extraction agent is the potpourri of ether and cyclohexane, described ether is 1:4～1:1 with the mixed volume ratio of cyclohexane.
According to each described assay method of claim 1-6, it is characterized in that 9, in the step c), described extraction agent is ether and normal hexane potpourri, the mixed volume of described ether and normal hexane is than being 1:4～1:1.
10, according to each described assay method of claim 1-6, it is characterized in that, the stratographic analysis process heating mode be: 80 ℃～110 ℃ of temperature of beginning, after keeping 0.5min～1min, once heat up, be warming up to 180 ℃～220 ℃, carry out secondary temperature elevation again, be warming up to 250 ℃～300 ℃, keep 0.5min～3min; The described programming rate that once heats up is less than the programming rate of described secondary temperature elevation.
11, assay method according to claim 10 is characterized in that, the described programming rate that once heats up is 15 ℃/min～30 ℃/min, and the programming rate of described secondary temperature elevation is 40 ℃/min～60 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101362526A CN101532995B (en) | 2009-05-04 | 2009-05-04 | Method for rapidly determining content of preservative in oil-containing seasoning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101362526A CN101532995B (en) | 2009-05-04 | 2009-05-04 | Method for rapidly determining content of preservative in oil-containing seasoning |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101532995A true CN101532995A (en) | 2009-09-16 |
| CN101532995B CN101532995B (en) | 2012-05-16 |
Family
ID=41103725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101362526A Active CN101532995B (en) | 2009-05-04 | 2009-05-04 | Method for rapidly determining content of preservative in oil-containing seasoning |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101532995B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102662009A (en) * | 2012-04-25 | 2012-09-12 | 辽宁省食品药品检验所 | Method for quickly determining content of additive of plurality of types in food |
| CN103076407A (en) * | 2012-12-26 | 2013-05-01 | 通标标准技术服务有限公司 | Fast detection method for food preservative agent and antioxidant |
| CN108845052A (en) * | 2018-07-04 | 2018-11-20 | 肇庆市创业帮信息技术有限公司 | Determination of Preservatives detection method of content in a kind of solid food |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308124A (en) * | 2008-06-17 | 2008-11-19 | 江南大学 | D-type and / or L-type phenyl-lactic acid rapid checking method |
-
2009
- 2009-05-04 CN CN2009101362526A patent/CN101532995B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102662009A (en) * | 2012-04-25 | 2012-09-12 | 辽宁省食品药品检验所 | Method for quickly determining content of additive of plurality of types in food |
| CN102662009B (en) * | 2012-04-25 | 2014-02-26 | 辽宁省食品药品检验所 | Method for quickly determining content of additive of plurality of types in food |
| CN103076407A (en) * | 2012-12-26 | 2013-05-01 | 通标标准技术服务有限公司 | Fast detection method for food preservative agent and antioxidant |
| CN103076407B (en) * | 2012-12-26 | 2014-07-09 | 通标标准技术服务有限公司 | Fast detection method for food preservative agent and antioxidant |
| CN108845052A (en) * | 2018-07-04 | 2018-11-20 | 肇庆市创业帮信息技术有限公司 | Determination of Preservatives detection method of content in a kind of solid food |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101532995B (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101526509B (en) | Method for rapidly determining content of preservatives in condiment | |
| CN102353742B (en) | Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum | |
| Pedersen et al. | Establishing and performing targeted multi-residue analysis for lipid mediators and fatty acids in small clinical plasma samples | |
| Rodinkov et al. | Static headspace analysis and its current status | |
| CN102520082B (en) | Method for determining volatile components in polyvinyl alcohol in full-evaporation headspace gas chromatography | |
| CN104655767A (en) | Method for simultaneously determining vanillin, ethyl vanillin and coumarin in electronic cigarette solution | |
| CN101532995B (en) | Method for rapidly determining content of preservative in oil-containing seasoning | |
| CN102608246B (en) | Method for measuring moisture content in glyceryl triacetate | |
| CN102323364A (en) | Method for determining content of benzene and benzene series in hot melt adhesive | |
| CN104198605B (en) | A kind of assay method of cigarette hot melt adhesive phenol antioxidant content | |
| CN111413451B (en) | Method for detecting cyanoacetamide by reversed-phase high performance liquid chromatography | |
| CN112326847B (en) | Method for detecting impurities in isophthalonitrile | |
| CN103134863A (en) | Method of determining content of methanol, isobutanol, isoamylol of alcohol | |
| Zhou et al. | A gas chromatography-flame ionization detection method for direct and rapid determination of small molecule volatile organic compounds in aqueous phase | |
| CN102507773A (en) | Method for selectively determining residual vinyl acetate in white latex for cigarette through static headspace gas and chromatography mass spectrometry | |
| CN102338779B (en) | Method for detecting sorbic acid content in cheese | |
| CN103399111B (en) | Method for selectively measuring ethylene glycol monoethyl ether acetate in dry food packaging paper based on headspace-gas chromatography/mass spectrometry | |
| CN102854279A (en) | Method for determining contents of benzene and benzene-series substances in tobacco-use triacetin | |
| CN106596740A (en) | Method for adopting gas chromatography method to determine residual quantity of pendimethalin in garlic | |
| CN105158348A (en) | Method for determining five effective components in zedoary oil by using gas chromatography | |
| CN103091196A (en) | Method for measuring 2-amino-5-nitropyridine saturated vapor pressure | |
| Xie et al. | Method for improving accuracy in full evaporation headspace analysis | |
| CN114487247A (en) | Glufosinate-ammonium and metabolite determination kit, and preparation method and determination method thereof | |
| CN104597188B (en) | A kind of method detecting dieldrite residual quantity in dairy products | |
| CN102288699A (en) | Method for measuring acetic anhydride and pyridine in reaction liquid with gas phase chromatography internal standard method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |