CN104142371A - Method for detecting hypophosphite in flour and flour improvers - Google Patents
Method for detecting hypophosphite in flour and flour improvers Download PDFInfo
- Publication number
- CN104142371A CN104142371A CN201410324059.6A CN201410324059A CN104142371A CN 104142371 A CN104142371 A CN 104142371A CN 201410324059 A CN201410324059 A CN 201410324059A CN 104142371 A CN104142371 A CN 104142371A
- Authority
- CN
- China
- Prior art keywords
- flour
- hypophosphites
- liquid chromatography
- performance liquid
- tandem mass
- 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
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for detecting hypophosphite in flour and flour improvers. Super high performance liquid chromatography tandem mass spectrometric detection is adopted by the method. The method comprises the following steps: (1) preparing a standard solution of hypophosphite; (2) preparing a test solution; and (3) measuring, namely precisely sucking the standard solution, injecting the sucked standard solution into a super high performance liquid chromatography tandem mass spectrometer for measurement, drawing a standard curve according to the test result, precisely sucking the test solution and injecting the sucked test solution into the super high performance liquid chromatography tandem mass spectrometer for measurement, thereby obtaining the content of hypophosphite. Inorganic salt (namely hypophosphite) in flour and flour improvers is detected by the super high performance liquid chromatography tandem mass spectrum analyzer, and the detection method is simple in pretreatment and high in accuracy and is suitable for batch detection on hypophosphite in flour and flour improvers.
Description
Technical field
The present invention relates to technical field of analysis and detection, particularly relate to the detection method of hypophosphites in a kind of flour and flour improver.
Background technology
China is maximum in the world Wheat Production state, and the flour being formed by wheat processing is one of topmost food of the mankind, and flour is the most important raw material of Flour product processing, and the quality of its quality directly has influence on the quality of Flour product.Along with the raising with living standards of the people that develops rapidly of China's food industry, bakery etc. are had higher requirement to its basic material flour, and all-purpose flour can not meet people's living needs, and the occupation rate of tailored flour on market significantly rises.In flour, add suitable modifying agent plays an important role in the production run of modern wheat flour specially preparation and Flour product.Flour improver is some chemosynthesis or natural additive for foodstuff.Flour improver can improve the performance of curing of dough, makes the rheological properties of dough and enzymatic activity balance moderate.The present situation of flour improver is current, and China has started to apply the flour improver of many kinds, comprising flour gluten-strengthening agent, whitening agent, thickening agent, weak muscle agent and fermentation accelerant etc.
China has GB2760-2011 < < food security national standard food additives to use standard > > about the safety and sanitation standard of food additives.This standard has proposed can be used for the adjuvant of food production, and stipulates its Limited Doses.The hypophosphites such as sodium hypophosphite are not listed in this standard, and sodium hypophosphite is colourless monoclinic system crystal or white crystalline powder, soluble in water and ethanol.The hypophosphites Using Sodium Hypophosphite of selling on market and calcium hypophosphite are main.There is HG/T3253-2009 < < commercial hypophosphorous acid sodium > > in China about the standard of sodium hypophosphite, and standard provides the physical and chemical determination method of sodium hypophosphite.China does not also have the assay method of hypophosphites in food at present, in order to supervise Flour production and processing enterprise to produce in accordance with the law, guarantees that the people is healthy and safe, is badly in need of developing the assay method of the content of hypophosphites in flour and flour improver.
Summary of the invention
Based on this, the object of this invention is to provide the detection method of hypophosphites in a kind of flour and flour improver.
Concrete technical scheme is as follows:
A detection method for hypophosphites in flour and flour improver, adopts Ultra Performance Liquid Chromatography tandem mass spectrum to measure, and comprises the steps:
(1) preparation of hypophosphites standard solution
Precision takes hypophosphites standard items, is mixed with the standard solution of finite concentration gradient;
(2) preparation of need testing solution
Getting flour or flour improver sample, to add volumetric concentration be the ethanol water of 70-80%, and ultrasonic extraction is got supernatant after centrifugal, with after filtering with microporous membrane need testing solution;
(3) measure
The accurate standard solution injection Ultra Performance Liquid Chromatography tandem mass spectrometer of drawing is measured, according to test result drawing standard curve;
The accurate need testing solution injection Ultra Performance Liquid Chromatography tandem mass spectrometer of drawing is measured, and obtains;
Wherein chromatographic condition is: chromatographic column is SynergiMAX-RP; Column temperature is room temperature; Mobile phase is the acetonitrile of volume ratio 14-16:84-86: 10mmol/L ammonium acetate solution, and flow velocity is 0.5-1ml/min, carries out isocratic elution;
Mass spectrum condition is: ion gun is electric spray ion source; Scan mode is negative ion scanning; Capillary voltage is 0.4-0.5KV; Taper hole voltage is 28-32v; Ion source temperature is 148-152 ℃; Desolventizing temperature is 495-505 ℃; Desolventizing gas is the nitrogen of flow velocity 790-810L/h; Taper hole gas is the nitrogen of flow velocity 48-52L/h; Collision gas is the argon gas of flow velocity 0.18-0.22ml/min; Detecting pattern is many reaction detection pattern; Monitoring ion is m/z64.8/62.8.
In an embodiment, described mobile phase is the acetonitrile of volume ratio 15:85 therein: 10mmol/L ammonium acetate solution, flow velocity is 0.5ml/min, carries out isocratic elution.
In an embodiment, described mass spectrum condition is therein: ion gun is electric spray ion source; Scan mode is negative ion scanning; Capillary voltage is 0.5KV; Taper hole voltage is 30v; Ion source temperature is 150 ℃; Desolventizing temperature is 500 ℃; Desolventizing gas is the nitrogen of flow velocity 800L/h; Taper hole gas is the nitrogen of flow velocity 50L/h; Collision gas is the argon gas of flow velocity 0.2ml/min; Detecting pattern is many reaction detection pattern; Monitoring ion is m/z64.8/62.8.
In an embodiment, described flour improver is composite wheat flour Flour ingredient, compounded enzyme preparate or bread improver therein.
In an embodiment, in step (2), the time of ultrasonic extraction is 20-30min therein, and centrifugal rotating speed is 800-1200r/min, and the filter core of miillpore filter is of a size of 0.22 μ m.
Advantage of the present invention is as follows:
The present invention adopts Ultra Performance Liquid Chromatography Tandem Mass Spectrometry Analysis instrument to detect the inorganic salts (hypophosphites) in flour and flour improver, this detection method pre-treatment is simple, accuracy is high, is applicable to very much the batch detection of hypophosphites in flour and flour improver.Detection method of the present invention is 10mg/kg to the detectability of hypophosphites (S/N=3).For different flour and the different concentration of adding of flour improver, carry out 6 parallel laboratory tests, average recovery rate is between 82%～114%, and relative standard deviation is between 3.7%～10.3%.
Detection method of the present invention has been filled up the blank of hypophosphites detection method of content in flour and flour improver at present.For food quality, control, food safety monitoring provides important technology support.There is good economic and social profit.
Accompanying drawing explanation
Fig. 1 is that hypophosphites concentration is the Ultra Performance Liquid Chromatography tandem mass spectrum figure of the standard solution of 0.5mg/L;
Fig. 2 is hypophosphites concentration-peak area canonical plotting;
The Ultra Performance Liquid Chromatography tandem mass spectrum figure of the negative wheat flour sample of Fig. 3;
Fig. 4 is for adding the Ultra Performance Liquid Chromatography tandem mass spectrum figure of the negative wheat flour sample of hypophosphites concentration 10mg/kg;
The negative Strong flour sample of Fig. 5 Ultra Performance Liquid Chromatography tandem mass spectrum figure;
Fig. 6 is for adding the negative Strong flour sample Ultra Performance Liquid Chromatography tandem mass spectrum figure of hypophosphites concentration 10mg/kg;
The negative bread flour sample of Fig. 7 Ultra Performance Liquid Chromatography tandem mass spectrum figure;
Fig. 8 is for adding the negative bread flour sample Ultra Performance Liquid Chromatography tandem mass spectrum figure of hypophosphites concentration 10mg/kg;
The negative composite wheat flour Flour ingredient sample Ultra Performance Liquid Chromatography tandem mass spectrum figure of Fig. 9;
Figure 10 is for adding the composite wheat flour Flour ingredient sample Ultra Performance Liquid Chromatography tandem mass spectrum figure of hypophosphites concentration 10mg/kg;
Figure 11 is compounded enzyme preparate sample Ultra Performance Liquid Chromatography tandem mass spectrum figure;
Figure 12 is for adding the compounded enzyme preparate sample Ultra Performance Liquid Chromatography tandem mass spectrum figure of hypophosphites concentration 10mg/kg;
Figure 13 is bread improver sample Ultra Performance Liquid Chromatography tandem mass spectrum figure;
Figure 14 is for adding the bread improver sample Ultra Performance Liquid Chromatography tandem mass spectrum figure of hypophosphites concentration 10mg/kg.
Embodiment
Below in conjunction with drawings and the specific embodiments, detection method of the present invention is described in further detail.
The detection method of hypophosphites in a kind of flour of the present invention and flour improver, adopts Ultra Performance Liquid Chromatography tandem mass spectrum to measure, and comprises the steps:
(1) preparation of hypophosphites standard solution
Precision takes hypophosphites standard items, is mixed with the standard solution of finite concentration gradient;
(2) preparation of need testing solution
Getting flour or flour improver sample, to add volumetric concentration be the ethanol water of 70-80% (being preferably 75%), ultrasonic extraction (extracting 20-30min under normal temperature), after centrifugal (the centrifugal 3-5min of 800-1200r/min), get supernatant, after filtering with miillpore filter (filter core is of a size of 0.22 μ m), obtain need testing solution;
(3) measure
The accurate standard solution injection Ultra Performance Liquid Chromatography tandem mass spectrometer of drawing is measured, according to test result drawing standard curve;
The accurate need testing solution injection Ultra Performance Liquid Chromatography tandem mass spectrometer of drawing is measured, and obtains;
Wherein chromatographic condition is: chromatographic column is SynergiMAX-RP; Column temperature is room temperature; Mobile phase is the acetonitrile of volume ratio 14-16:84-86 (being preferably 15:85): 10mmol/L ammonium acetate solution, and flow velocity is 0.5-1ml/min, carries out isocratic elution;
Mass spectrum condition is: ion gun is electric spray ion source; Scan mode is negative ion scanning; Capillary voltage is 0.4-0.5 (preferably 0.5) KV; Taper hole voltage is 28-32 (being preferably 30) v; Ion source temperature is 148-152 (being preferably 150) ℃; Desolventizing temperature is 495-505 (being preferably 500) ℃; Desolventizing gas is the nitrogen of flow velocity 790-810 (being preferably 800) L/h; Taper hole gas is the nitrogen of flow velocity 48-52 (being preferably 50) L/h; Collision gas is the argon gas of flow velocity 0.18-0.22 (being preferably 0.2) ml/min; Detecting pattern is many reaction detection pattern; Monitoring ion is m/z64.8/62.8.
Detecting of detection method of the present invention is limited to 10mg/kg, and average recovery rate is 82-114%, and relative standard deviation is 3.7-10.3%.
Described flour improver is selected from but is not limited to composite wheat flour Flour ingredient, compounded enzyme preparate or bread improver.
Be below specific embodiment part:
The mensuration of embodiment 1 hypophosphorous acid root standard items
One, the preparation of hypophosphites standard solution: precision takes sodium hypophosphite standard items 100mg in 10mL volumetric flask, and water constant volume, to scale, shakes up, being mixed with concentration is 10.0mg/mL hypophosphites standard solution, 4 ℃ keep in Dark Place.
Two, chromatogram mass spectrum condition
1) chromatographic condition
Chromatographic column: SynergiMAX-RP4u250 * 4.6mm, or suitable person;
Column temperature: room temperature;
Mobile phase: acetonitrile: 10mmoL/L ammonium acetate solution=15:85 (V/V);
Flow velocity: 0.5mL/min, carries out isocratic elution;
2) mass spectrum condition
Ion gun: electric spray ion source (ESI);
Scan mode: negative ion scanning;
Capillary voltage: 0.5kV;
Taper hole voltage: 30V;
Ion source temperature: 150 ℃;
Desolventizing temperature: 500 ℃;
Desolventizing gas: nitrogen, 800L/h;
Taper hole gas: nitrogen, 50L/h;
Collision gas: argon gas, 0.2mL/min;
Detecting pattern: adopt multiple-reaction monitoring (MRM) pattern; Monitoring ion is m/z64.8/62.8.
Three, the foundation of hypophosphites standard items chromatogram
The accurate hypophosphites standard solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 1.
Four, drawing standard curve
Get the solution that hypophosphites standard solution compound concentration is respectively 0mg/mL, 0.1mg/mL, 0.2mg/mL, 0.5mg/mL, 1.0mg/mL, 2.0mg/mL, concentration is carried out the detection of Ultra Performance Liquid Chromatography tandem mass spectrum from low to high successively, the hypophosphites Ultra Performance Liquid Chromatography tandem mass spectrum peak area of take is horizontal ordinate, phosphate concn is ordinate in proper order, drawing standard curve, as shown in Figure 2.
Use Excel Software on Drawing typical curve, obtain R
2value.Hypophosphites concentration is within the scope of 0～2.0mg/mL, and the concentration peak area value corresponding with it is good linear relation, coefficient R
2=0.9997.The linear equation of gained is y=12830x-74.565.
The mensuration of hypophosphites content in the negative wheat flour of embodiment 2
One. the preparation of need testing solution
Get wheat flour sample 1g, add 20mL75% (V/V) ethanol water (ethanol: water=3:1), ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, get 1mL supernatant filtering with microporous membrane, filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition
With embodiment 1.
Three. drawing standard curve
Adopt the typical curve of embodiment 1.
Four. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 3.Because the signal of chromatographic peak/noise ratio is less than 3, in this wheat flour, hypophosphites do not detected.
Embodiment 3 adds the mensuration of the negative wheat flour content of hypophosphites concentration 10mg/kg
One. the preparation of need testing solution
Get the negative wheat flour sample 1.0g of embodiment 2, adding concentration is the sodium hypophosphite standard solution 100 μ L of 100mg/L, then adds 20mL75% (V/V) ethanol water (ethanol: water=3:1), vortex mixes.Ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, gets 1mL supernatant filtering with microporous membrane, and filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain hypophosphites chromatogram as shown in Figure 4.The chromatographic peak area of hypophosphites is 6250.625 millivolts * second, and the content that checks in hypophosphites test sample solution liquid from typical curve is 0.493mg/kg.Because 1mL test solution is equivalent to 0.050g sample, so the content of hypophosphites is 9.86mg/kg in this sample.
The mensuration of hypophosphites content in the negative Strong flour sample of embodiment 4
One. the preparation of need testing solution
With embodiment 2.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 5.Because the signal of chromatographic peak/noise ratio is less than 3, in this wheat flour, hypophosphites do not detected.
The mensuration of hypophosphites content in the Strong flour sample of embodiment 5 interpolation hypophosphites concentration 10mg/kg
One. the preparation of need testing solution
Get the negative Strong flour sample 1.0g of embodiment 4, adding concentration is the sodium hypophosphite standard solution 100 μ L of 100mg/L, then adds 20mL75% (V/V) ethanol water (ethanol: water=3:1), vortex mixes.Ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, gets 1mL supernatant filtering with microporous membrane, and filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain hypophosphites chromatogram as shown in Figure 6.The chromatographic peak area of hypophosphites is 5557.805 millivolts * second, and the content that checks in hypophosphites test sample solution liquid from typical curve is 0.439mg/kg.Because 1mL test solution is equivalent to 0.050g sample, so the content of hypophosphites is 8.77mg/kg in this sample.
The mensuration of the negative bread flour sample of embodiment 6 hypophosphites content
One. the preparation of need testing solution
Get bread flour sample 1g, add 20mL75% (V/V) ethanol water (ethanol: water=3:1), ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, get 1mL supernatant filtering with microporous membrane, filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrum tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 7.Because the signal of the chromatographic peak of hypophosphites do not detected, in this wheat flour, hypophosphites do not detected.
Embodiment 7 adds the mensuration of the negative bread flour sample hypophosphites content of hypophosphites concentration 10mg/kg
One. the preparation of need testing solution
Get the negative Strong flour sample 1.0g of embodiment 6, adding concentration is the sodium hypophosphite standard solution 100 μ L of 100mg/L, then adds 20mL75% (V/V) ethanol water (ethanol: water=3:1), vortex mixes.Ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, gets 1mL supernatant filtering with microporous membrane, and filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain hypophosphites chromatogram as shown in Figure 8.The chromatographic peak area of hypophosphites is 6122.325 millivolts * second, and the content that checks in hypophosphites test sample solution liquid from typical curve is 0.483mg/kg.Because 1mL test solution is equivalent to 0.050g sample, so the content of hypophosphites is 9.66mg/kg in this sample.
The mensuration of hypophosphites content in the negative composite wheat flour Flour ingredient of embodiment 8
One. the preparation of need testing solution
Take composite wheat flour Flour ingredient sample 1g, add 20mL75% (V/V) ethanol water (ethanol: water=3:1), ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, get 1mL supernatant filtering with microporous membrane, filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 9.Because the signal of hypophosphorous acid root do not detected, so hypophosphites do not detected in this composite wheat flour Flour ingredient.
The mensuration of hypophosphites content in the composite wheat flour Flour ingredient of feminine gender of embodiment 9 interpolation hypophosphites concentration 10mg/kg
One. the preparation of need testing solution
Take the composite wheat flour Flour ingredient of the feminine gender sample 1.0g of embodiment 8, adding concentration is the sodium hypophosphite standard solution 100 μ L of 100mg/L, then adds 20mL75% (V/V) ethanol water (ethanol: water=3:1), vortex mixes.Ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, gets 1mL supernatant filtering with microporous membrane, and filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain hypophosphites chromatogram as shown in Figure 10.The chromatographic peak area of hypophosphites is 5365.355 millivolts * second, and the content that checks in hypophosphites test sample solution liquid from typical curve is 0.424mg/kg.Because 1mL test solution is equivalent to 0.050g sample, so the content of hypophosphites is 8.47mg/kg in this sample.
The mensuration of hypophosphites content in the negative compounded enzyme preparate sample of embodiment 10
One. the preparation of need testing solution
Take composite compounded enzyme preparate sample 1g, add 20mL75% (V/V) ethanol water (ethanol: water=3:1), ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, get 1mL supernatant filtering with microporous membrane, filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 11.Because the signal of hypophosphorous acid root do not detected, so hypophosphites do not detected in this wheat flour.
The mensuration of hypophosphites content in the compounded enzyme preparate sample of embodiment 11 interpolation hypophosphites concentration 10mg/kg
One. the preparation of need testing solution
Take the negative compounded enzyme preparate sample 1.0g of embodiment 10, adding concentration is the sodium hypophosphite standard solution 100 μ L of 100mg/L, then adds 20mL75% (V/V) ethanol water (ethanol: water=3:1), vortex mixes.Ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, gets 1mL supernatant filtering with microporous membrane, and filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain hypophosphites chromatogram as shown in Figure 12.The chromatographic peak area of hypophosphites is 6545.715 millivolts * second, and the content that checks in hypophosphites test sample solution liquid from typical curve is 0.516mg/kg.Because 1mL test solution is equivalent to 0.050g sample, so the content of hypophosphites is 10.32mg/kg in this sample.
The mensuration of hypophosphites content in the negative bread improver sample of embodiment 12
One. the preparation of need testing solution
Take bread improver sample 1g, add 20mL75% (V/V) ethanol water (ethanol: water=3:1), ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, get 1mL supernatant filtering with microporous membrane, filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain Ultra Performance Liquid Chromatography tandem mass spectrum figure, as shown in Figure 13.Because the signal of hypophosphorous acid root do not detected, so hypophosphites do not detected in this bread improver.
Embodiment 13 adds the mensuration of the bread improver sample hypophosphites content of hypophosphites concentration 10mg/kg
One. the preparation of need testing solution
Take the negative bread improver sample 1.0g of embodiment 12, adding concentration is the sodium hypophosphite standard solution 100 μ L of 100mg/L, then adds 20mL75% (V/V) ethanol water (ethanol: water=3:1), vortex mixes.Ultrasonic extraction 20min at 20 ℃, centrifugal 3min under 1000r/min rotating speed, gets 1mL supernatant filtering with microporous membrane, and filtrate is for the test of Ultra Performance Liquid Chromatography tandem mass spectrometer.
Two. chromatographic condition, typical curve
With embodiment 1.
Three. measure
The accurate need testing solution 10 μ L injection liquid chromatographies of drawing, measure according to Ultra Performance Liquid Chromatography tandem mass spectrometry, obtain hypophosphites chromatogram as shown in Figure 14.The chromatographic peak area of hypophosphites is 7238.575 millivolts * second, and the content that checks in hypophosphites test sample solution liquid from typical curve is 0.570mg/kg.Because 1mL test solution is equivalent to 0.050g sample, so the content of hypophosphites is 11.4mg/kg in this sample.
Embodiment 14 recovery and precision test
According to the detectability of the inventive method, to embodiment 2 wheat flours, embodiment 4 Strong flours, embodiment 6 bread flours, embodiment 8 wheat flour Flour ingredients and embodiment 10 compounded enzyme preparates and embodiment 12 bread improvers, each adds the hypophosphites standard items that concentration is 10mg/kg and carries out 4 experiments.Result average recovery rate and precision result see table 1.
The average interpolation recovery and the relative standard deviation of table 1 hypophosphites in five kinds of food
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (6)
1. a detection method for hypophosphites in flour and flour improver, is characterized in that, adopts Ultra Performance Liquid Chromatography tandem mass spectrum to measure, and comprises the steps:
(1) preparation of hypophosphites standard solution
Precision takes hypophosphites standard items, is mixed with the standard solution that concentration gradient is 0-2.0mg/mL;
(2) preparation of need testing solution
Getting flour or flour improver sample, to add volumetric concentration be the ethanol water of 70-80%, and ultrasonic extraction is got supernatant after centrifugal, with after filtering with microporous membrane need testing solution;
(3) measure
The accurate standard solution injection Ultra Performance Liquid Chromatography tandem mass spectrometer of drawing is measured, according to test result drawing standard curve;
The accurate need testing solution injection Ultra Performance Liquid Chromatography tandem mass spectrometer of drawing is measured, and obtains;
Wherein chromatographic condition is: chromatographic column is SynergiMAX-RP; Column temperature is room temperature; Mobile phase is the acetonitrile of volume ratio 14-16:84-86: 10mmol/L ammonium acetate solution, and flow velocity is 0.5-1ml/min, carries out isocratic elution;
Mass spectrum condition is: ion gun is electric spray ion source; Scan mode is negative ion scanning; Capillary voltage is 0.4-0.5KV; Taper hole voltage is 28-32v; Ion source temperature is 148-152 ℃; Desolventizing temperature is 495-505 ℃; Desolventizing gas is the nitrogen of flow velocity 790-810L/h; Taper hole gas is the nitrogen of flow velocity 48-52L/h; Collision gas is the argon gas of flow velocity 0.18-0.22ml/min; Detecting pattern is many reaction detection pattern; Monitoring ion is m/z64.8/62.8.
2. the detection method of hypophosphites in flour according to claim 1 and flour improver, is characterized in that, described mobile phase is the acetonitrile of volume ratio 15:85: 10mmol/L ammonium acetate solution, flow velocity is 0.5ml/min, carries out isocratic elution.
3. the detection method of hypophosphites in flour according to claim 1 and flour improver, is characterized in that, described mass spectrum condition is: ion gun is electric spray ion source; Scan mode is negative ion scanning; Capillary voltage is 0.5KV; Taper hole voltage is 30v; Ion source temperature is 150 ℃; Desolventizing temperature is 500 ℃; Desolventizing gas is the nitrogen of flow velocity 800L/h; Taper hole gas is the nitrogen of flow velocity 50L/h; Collision gas is the argon gas of flow velocity 0.2ml/min; Detecting pattern is many reaction detection pattern; Monitoring ion is m/z64.8/62.8.
4. the detection method of hypophosphites in flour according to claim 1 and flour improver, is characterized in that, described flour improver is composite wheat flour Flour ingredient, compounded enzyme preparate or bread improver.
5. the detection method of hypophosphites in flour according to claim 1 and flour improver, is characterized in that, in step (2), the time of ultrasonic extraction is 20-30min, and centrifugal rotating speed is 800-1200r/min.
6. the detection method of hypophosphites in flour according to claim 1 and flour improver, is characterized in that, in step (2), the filter core of miillpore filter is of a size of 0.22 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410324059.6A CN104142371B (en) | 2014-07-08 | 2014-07-08 | The detection method of hypophosphites in flour and flour improver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410324059.6A CN104142371B (en) | 2014-07-08 | 2014-07-08 | The detection method of hypophosphites in flour and flour improver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104142371A true CN104142371A (en) | 2014-11-12 |
| CN104142371B CN104142371B (en) | 2015-09-30 |
Family
ID=51851605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410324059.6A Active CN104142371B (en) | 2014-07-08 | 2014-07-08 | The detection method of hypophosphites in flour and flour improver |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104142371B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104542800A (en) * | 2014-12-31 | 2015-04-29 | 南通双和食品有限公司 | Food flour treatment agent and preparation method thereof |
| CN109900835A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | The device of inorganic constituents and application in a kind of highly sensitive on-line checking cigarette ash |
| CN110455939A (en) * | 2019-07-05 | 2019-11-15 | 广州质量监督检测研究院 | The detection method of stearyl lactylic acid salt in flour or flour improver |
| CN117147711A (en) * | 2023-07-28 | 2023-12-01 | 山东省食品药品检验研究院 | Method for detecting hypophosphite, orthophosphate, bromate and bromide ions in wheat flour by on-line absorption and release technology |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102520098A (en) * | 2011-10-24 | 2012-06-27 | 南京大学 | Method for determining trace low-valent phosphate in natural water |
-
2014
- 2014-07-08 CN CN201410324059.6A patent/CN104142371B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102520098A (en) * | 2011-10-24 | 2012-06-27 | 南京大学 | Method for determining trace low-valent phosphate in natural water |
Non-Patent Citations (3)
| Title |
|---|
| MONICA M. MCDOWELL ET AL.: "Detection of hypophosphite, phosphite, and orthophosphate in natural geothermal water by ion chromatography", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 吕伟 等: "化学镀液中次磷酸根和亚磷酸根的离子色谱测定", 《分析化学》 * |
| 钟新林: "离子色谱电导法测定次磷酸、亚磷酸与磷酸", 《第十一届全国离子色谱学术报告会议文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104542800A (en) * | 2014-12-31 | 2015-04-29 | 南通双和食品有限公司 | Food flour treatment agent and preparation method thereof |
| CN109900835A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | The device of inorganic constituents and application in a kind of highly sensitive on-line checking cigarette ash |
| CN110455939A (en) * | 2019-07-05 | 2019-11-15 | 广州质量监督检测研究院 | The detection method of stearyl lactylic acid salt in flour or flour improver |
| CN117147711A (en) * | 2023-07-28 | 2023-12-01 | 山东省食品药品检验研究院 | Method for detecting hypophosphite, orthophosphate, bromate and bromide ions in wheat flour by on-line absorption and release technology |
| CN117147711B (en) * | 2023-07-28 | 2024-03-15 | 山东省食品药品检验研究院 | Method for detecting hypophosphite, orthophosphate, bromate and bromide ions in wheat flour by on-line absorption and release technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104142371B (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104142371B (en) | The detection method of hypophosphites in flour and flour improver | |
| CN108459096B (en) | Heishanyin tablet extract and ginseng radix aconiti lateralis preparata injection prepared by real-time release method in automatic extraction process of Heishanyin tablet | |
| CN104698114A (en) | Method for detecting 205 kinds of pesticide residues in rice | |
| CN103823006B (en) | High performance liquid chromatography tandem mass spectrum detecting method for fructo-oligosaccharides in milk powder | |
| CN109839458B (en) | Method for detecting sodium picosulfate in food | |
| CN106645483B (en) | A kind of method of quantitative detection sea cucumber polysaccharide | |
| CN110426476A (en) | The measuring method of Argireline content in a kind of cosmetics | |
| CN106770871B (en) | A kind of method of quantitative detection acid polysaccharide containing alditol | |
| CN110243952A (en) | A method of using each component content of AGEs in HPLC-MS/MS standard measure measurement milk powder | |
| CN104297359A (en) | Method for simultaneously determining seven compositions in edible flavoring essence and spices | |
| CN105911081B (en) | A kind of method for differentiating mannatide | |
| CN104181313A (en) | Preparation method of blood coagulation factor IX quality control product | |
| CN102749301B (en) | Method for determining melamine content by using ultraviolet spectroscopy | |
| CN107421975A (en) | The detection method of glycerol content in a kind of injection | |
| CN108426965B (en) | Method for detecting isomaltose, isomaltotriose, maltose and panose in yellow wine | |
| CN105954311A (en) | Method for constructing <1>H-NMR fingerprint spectra of Periplaneta americana and extract of Periplaneta americana | |
| CN103245658A (en) | Fast detection method of bromate in bread | |
| Takeda et al. | Additivity in split Cotton effect amplitudes of p-phenylbenzyl ethers and p-phenylbenzoates | |
| CN102375040A (en) | Method for determining content of simimtecan and chimmitecan in human or animal whole blood | |
| CN114524887B (en) | Method for separating and characterizing ginseng polysaccharide with pharmaceutical activity function | |
| CN104515823A (en) | Method for rapid determination of Flavobacterium farinofermentans toxin A in food poisoning sample | |
| CN102680606B (en) | Method for measuring sodium formaldehyde sulfoxylate in food | |
| CN108169374A (en) | The detection method of synthetic coloring matter in a kind of Grain and its product | |
| CN106770780A (en) | The detection method of active material in precious Rogor raw material or the product containing precious Rogor | |
| CN109870519A (en) | A kind of detection method characterizing sucrose doped level in tealeaves using sucrose and fructose conversion content |
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 |