CN104849389A - Method for detecting spices in rice by ionic liquid two-aqueous-phase extraction/high performance liquid chromatography (HPLC) - Google Patents
Method for detecting spices in rice by ionic liquid two-aqueous-phase extraction/high performance liquid chromatography (HPLC) Download PDFInfo
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Abstract
The invention belongs to the technical field of food safety detection, and particularly discloses a method for detecting spices in rice by ionic liquid two-aqueous-phase extraction/high performance liquid chromatography (HPLC). The method comprises the following steps of firstly, extracting by using a [Bmim]Cl/dipotassium phosphate two-aqueous-phase system; then analyzing by combining the HPLC, wherein the mass fractions of the [Bmim]Cl and the dipotassium phosphate in the [Bmim]Cl/dipotassium phosphate two-aqueous-phase system are respectively 10-25% and 30-50%. The method has the advantages of being simple in detection steps, easy to operate, low in limit of detection, environmentally friendly and the like, thus having wider application prospect in the food detection field.
Description
Technical field
The present invention relates to technical field of food safety detection, more specifically, relate to the method that a kind of ionic liquid aqueous two-phase extraction/HPLC detects spices in rice.
Background technology
The population of China more than 2/3rds take rice as staple food.Along with the raising of people's living standard, have higher requirement to the edible quality of rice, scented rice receives the welcome of consumer.But at present scented rice total amount also cannot meet consumer demand, cause people in rice production process, to use rice essence because interests are ordered about, to pretend to be scented rice.What is more, adds rice essence and pretend to be new rice to cheat consumer in old rice.Principal ingredient or the batching of related documents report rice essence have propylene glycol, 2-acetylpyridine, vanillic aldehyde, Ethyl vanillin and ethyl maltol etc.Vanillic aldehyde wherein and ethyl maltol and respective homolog Ethyl vanillin and maltol are broad spectrum type spices, and being widely used in the preparation of essence, is fragrance component conventional during rice essence is produced.But show that these spices of Excess free enthalpy can cause dizziness, Nausea and vomiting and expiratory dyspnea about studying, even affect liver and renal function.In the staple food of rice of people, with the addition of rice essence, virtually greatly can increase the exposure level of people and these adjuvants, in the past for a long time, grievous injury can be brought to health, especially child and teenager, they are also in growth period, and various functions organ is not also grown completely.Define in 27 kinds of food such as rice and must not add essence and flavoring agent in GB 2760-2011 " national food safety standard food additives use standard " simultaneously.Therefore the spices detected in rice has very important significance to ensuring food safety.
Spectrophotometric method, HPLC, GC, LC/MS etc. is mainly contained at present for detecting the method for spices in food.HPLC method because the accuracy detected is high, sensitivity good, can many kinds of substance be realized while detect and the advantage such as testing cost is low, become the main flow means that spices detects.The pre-treating method reported mainly contains the method such as solvent extraction, Solid-Phase Extraction.Solvent extraction method adopts a large amount of organic solvent, not only pollutes the environment, and the impurity extracted is more, the accuracy that impact detects.Although solid phase extraction can reduce the interference of impurity, will experience the series of steps such as the activation of pillar, adsorbed target thing, wash-out impurity, wash-out object in use procedure, complex operation is consuming time, is not suitable for the process of batch sample.Simultaneously because commercial solid phase extraction column price is higher, therefore also greatly testing cost can be increased.
Summary of the invention
The present invention, in order to overcome the above-mentioned deficiency of prior art, provides a kind of ionic liquid aqueous two-phase extraction/HPLC to detect the method for spices in rice.The present invention adopts the spices in ionic liquid double-aqueous phase system extraction rice, and adopts HPLC method to detect.Feature due to ionic liquid aqueous two-phase extraction is that homogeneous phase extraction out-phase is separated, therefore can realize extraction, purification synchronously completes, greatly reduce operation steps, amount simultaneously due to the ionic liquid that uses in this system and inorganic salts is less, therefore running cost also reduces greatly, can meet the check processing of batch sample.The method has simple to operate, that extraction and cleaning efficiency is high, detection speed is fast feature on the whole, can realize quick, the efficient detection of spices in rice.
To achieve these goals, the present invention is achieved by following scheme:
A kind of ionic liquid aqueous two-phase extraction/HPLC detects the method for spices in rice, comprises the following steps:
S1. extract: in rice, add [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system by the mass ratio of 1:5 ~ 20,20 ~ 50 DEG C of water-bath 10 ~ 40min after mixing, phase solution in taking-up;
Wherein, in [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system, the massfraction of [Bmim] Cl is 10 ~ 25%, and the massfraction of dipotassium hydrogen phosphate is 30 ~ 50%;
S2.HPLC detects: with mobile phase solution by upper phase solution dilution, carry out HPLC analysis, drawing standard curve and recovery of standard addition after filtering with microporous membrane.
Ionic liquid double-aqueous phase system is formed by a kind of organic salt, a kind of inorganic salts and water usually, and conventional organic salt is [Bmim] Cl, [Hmim] Cl, [Omim] Cl, [Dmim] Cl, [Bmmim] Cl, [BPy] Cl, [TBA] Cl, [TBP] Cl, [Bmim] Br, [TBA] Br, [Bmim] BF4, [BPy] BF4, [Bmim] NO
3; Conventional inorganic salts are potassium phosphate, sodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, ammonium sulfate, sal tartari, sodium carbonate, potassium hydroxide, NaOH; The performance of the double-aqueous phase system that different organic salt and inorganic salts collocation are formed is different.The present invention, according to the design feature of spices especially maltol, ethyl maltol, vanillic aldehyde, Ethyl vanillin, develops a kind of [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system of applicable extraction spices.
Preferably, in system, the massfraction of [Bmim] Cl is 15%, and the massfraction of dipotassium hydrogen phosphate is 35%.
Preferably, the mass ratio of rice and [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system is 1:10.
Preferably, HPLC described in S2 detects is adopt Atlantis C
18chromatographic column (150 mm × 4.6 mm, 5 μm), mobile phase is acetonitrile-0.5% formic acid solution, and flow velocity is 1.0 mL/min, and determined wavelength is 276 nm, column temperature 30 DEG C, sample size 10 μ L.
Preferably, with mobile phase solution by upper phase solution dilution 2 ~ 5 times.
The drawing process of described typical curve is: get blank rice sample, carries out pre-treatment according to step S1, obtains blank sample extract.Using the dilution of blank sample extract as spices standard items, prepare a series of standard working solution: 0.5,1.0,2.0,5.0,10.0,25.0 μ g/mL, above-mentioned standard working solution is crossed sample introduction analysis after 0.22 μm of membrane filtration, each concentration replicate determination 2 ~ 4 times, qualitative with retention time, quantitative with sample peak area and peak area ratio, with peak area A concentration C (μ g/mL) returned and obtain standard regression curve.
The determination step of described recovery of standard addition is: get blank rice sample, add a certain amount of spices mixed standard solution, make the content of spices in rice be respectively 1.0,2.0,10.0 mg/kg, get 0.2 g after mixing and add target sample, according to step S1 process.On the same day, each spiked levels carries out 4 ~ 6 times and repeats, METHOD FOR CONTINUOUS DETERMINATION 5 ~ 6 days, the recovery of assay method and withinday precision and day to day precision.
Compared with prior art, the present invention has following beneficial effect:
Using the sample-pretreating method that ionic liquid aqueous two phase extraction technique detects as spices in rice, using HPLC as detection means, by optimizing chromatographic resolution parameter and extraction conditions as mobile phase kind, type of elution, ionic liquid and Inorganic Salts and consumption, bath temperature, water bath time etc., set up that a kind of extraction and cleaning synchronously completes, detection method easy and simple to handle.The present invention has accurately and reliably, highly sensitive, advantages of environment protection, is applicable to the detection of spices in rice.
Accompanying drawing explanation
Fig. 1 is four kinds of spices standard items chromatograms; 1: maltol; 2: ethyl maltol; 3: vanillic aldehyde; 4: Ethyl vanillin.
Fig. 2 is blank rice sample chromatogram.
Fig. 3 is mark-on rice sample chromatogram; 1: maltol; 2: ethyl maltol; 3: vanillic aldehyde; 4: Ethyl vanillin.
Embodiment
To make the present invention below in conjunction with Figure of description and specific embodiment and elaborating further, described embodiment, only for explaining the present invention, is not intended to limit scope of the present invention.The test method used in following embodiment if no special instructions, is conventional method; The material used, reagent etc. if no special instructions, are the reagent that can obtain from commercial channels and material.
embodiment 1
The screening of ionic liquid double-aqueous phase system:
In preliminary experiment process, do the ionic liquid double-aqueous phase system of following several types altogether: [Bmim] Cl/ ammonium sulfate, [Bmim] Cl/ sodium sulphate, [Bmim] Cl/ sodium carbonate, [Bmim] Cl/ sodium chloride, [Bmim] Cl/ dipotassium hydrogen phosphate, [Omim] Cl/ammonium sulfate, [Omim] Cl/sodium sulphate, [Omim] Cl/sodium carbonate, [Omim] Cl/sodium chloride, [Omim] Cl/dipotassium hydrogen phosphate, [Bmim] BF
4/ ammonium sulfate, [Bmim] BF
4/ sodium sulphate, [Bmim] BF
4/ sodium carbonate, [Bmim] BF
4/ sodium chloride, [Bmim] BF
4/ dipotassium hydrogen phosphate, but find [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system only having following composition: and the massfraction of [Bmim] Cl is 10 ~ 25%, and the massfraction of dipotassium hydrogen phosphate is 30 ~ 50%; Be suitable for the extraction of spices.
embodiment 2
The rice of the present embodiment is general rice, and a kind of ionic liquid aqueous two-phase extraction/HPLC detects the method for spices in rice, and its concrete steps are:
1, the preparation of four kinds of spices (maltol, ethyl maltol, vanillic aldehyde, Ethyl vanillin) standard reserving solutions: accurately take 0.0100 g(be accurate to 0.0001 g) each standard substance sterling in small beaker, with 15%(V/V) acetonitrile solution dissolves and is settled in 10 mL volumetric flasks, being placed in 4 DEG C of refrigerators and laying in stand-by.
2, sample pre-treatments: first prepare the ionic liquid double-aqueous phase system that gross mass is 2 g, the quality of this system intermediate ion liquid ([Bmim]) is 0.3 g(15%, w/w), the quality of dipotassium hydrogen phosphate is 0.7g(35%, w/w) quality of water is 1.0 g(50%, w/w).Add rice articles for use 0.2 g after system configurations is good, after rocking mixing, be placed on water-bath 15min in the water-bath of 40 DEG C.Take out upper phase solution, i.e. ionic liquid phase afterwards, with mobile phase solution (acetonitrile-0.5% formic acid solution) constant volume to 2 mL, then get part solution and cross 0.22 μm of laggard HPLC of miillpore filter and analyze.
3, chromatographic condition
Chromatographic column: Atlantis C
18(150 mm × 4.6 mm, 5 μm); Mobile phase: acetonitrile-0.5% formic acid solution; Gradient elution: program is in table 1; Flow velocity: 1 mL/min; Column temperature: 30 DEG C; Determined wavelength: 276 nm; Sample size: 10 μ L.
Table 1 gradient elution program
4, Specification Curve of Increasing
Get blank rice sample, carry out pre-treatment according to step 2, obtain blank sample extract.Using the dilution of blank sample extract as spices standard items, prepare a series of standard working solution: 0.5,1.0,2.0,5.0,10.0,25.0 μ g/mL, above-mentioned standard working solution is crossed sample introduction analysis after 0.22 μm of membrane filtration, each concentration replicate determination 3 times, qualitative with retention time, quantitative with sample peak area and peak area ratio, with peak area A concentration C (μ g/mL) returned and obtain standard regression curve.
5, recovery of standard addition
Get blank rice sample, add a certain amount of spices mixed standard solution, make the content of spices in rice be respectively 1.0,2.0,10.0 mg/kg, get 0.2 g after mixing and add target sample, process according to step 2.On the same day, each spiked levels carries out 5 times and repeats, METHOD FOR CONTINUOUS DETERMINATION 5 days, the recovery of assay method and withinday precision and day to day precision.
Below by experimental data, testing result is analyzed.
1, chromatogram
The ionic liquid that the present invention chooses is [Bmim] Cl, and become phase salt to be dipotassium hydrogen phosphate, both can become phase in wider concentration range, are conducive to fast rapid-result phase.When the massfraction of ionic liquid in double-aqueous phase system is less than 15%, the recovery of object is lower, meets and analyzes requirement.When the massfraction of ionic liquid in double-aqueous phase system is greater than 15%, along with the increase of ionic liquid massfraction, the recovery has the trend of increase, but increases not obvious, and the massfraction therefore selecting double-aqueous phase system intermediate ion liquid is 15%.Fig. 1 to Fig. 3 is respectively the standard solution chromatogram of acetontrile, blank rice sample chromatogram and rice mark-on sample chromatogram figure, contrast as can be seen from figure, when ionic liquid aqueous two-phase does pre-treating method, impurity in extracting in sample liquid is little, and ionic liquid cognition went out peak before object is by wash-out, therefore can not affect the mensuration of object.Wherein the retention time of maltol is: 3.79, and the retention time of ethyl maltol is 7.20, and the retention time of vanillic aldehyde is 8.08, and the retention time of Ethyl vanillin is 10.80.
2, the range of linearity of method, sample recovery of standard addition, withinday precision and day to day precision
The range of linearity of four kinds of spices and respective regression equation are in table 2, and sample recovery of standard addition is respectively in table 3 and table 4.The range of linearity of four kinds of materials is 1.0 ~ 50.0 μ g/mL as shown in Table 2, and linear relationship is good, and related coefficient is all greater than 0.999.From table 3 and table 4, under different spiked levels, the recovery of standard addition of sample is between 95.34 ~ 104.85%, and relative standard deviation is between 2.47 ~ 4.71%.Method in the daytime RSD is less than 4.47%, and RSD is less than 4.79% in the daytime.
The range of linearity, regression equation, the related coefficient of table 2 four kinds of spices
Table 3 sample recovery of standard addition
Table 4 method in a few days with day to day precision
The present invention have studied method and the chromatographic condition that a kind of ionic liquid aqueous two-phase extraction/HPLC measures spices in rice.[Bmim] Cl-dipotassium hydrogen phosphate ionic liquid double-aqueous phase system has good extraction ability to the spices in rice, in conjunction with high performance liquid chromatography as detection means, can realize the detection accurately and rapidly of spices in rice.
The experiment condition obtained optimized is: [Bmim] Cl concentration 15%(w/w in system), dipotassium hydrogen phosphate concentration 35%(w/w), bath temperature 40 DEG C, water bath time 15 min.Adopt Atlantics C
18chromatographic column (150 mm × 4.6 mm, 5 μm), mobile phase is acetonitrile-0.5% formic acid solution, adopt gradient elution program, flow velocity is 1 mL/min, and determined wavelength is 276 nm, and under this condition, the range of linearity of material is 1 ~ 50 μ g/mL, recovery of standard addition is greater than 95.34%, and relative standard deviation is lower than between 4.71%.The in a few days RSD of method is less than 4.47%, and RSD is less than 4.79% in the daytime.
This method have easy and simple to handle, accuracy good, highly sensitive, advantages of environment protection, is applicable to the detection of spices in rice.
Claims (5)
1. ionic liquid aqueous two-phase extraction/HPLC detects a method for spices in rice, it is characterized in that, comprises the following steps:
S1. extract: in rice to be measured, add [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system by the mass ratio of 1:5 ~ 20,20 ~ 50 DEG C of water-bath 10 ~ 40min after mixing, phase solution in taking-up;
Wherein, in [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system, the massfraction of [Bmim] Cl is 10 ~ 25%, and the massfraction of dipotassium hydrogen phosphate is 30 ~ 50%;
S2.HPLC detects: with mobile phase solution by upper phase solution dilution, carry out HPLC analysis, drawing standard curve and recovery of standard addition after filtering with microporous membrane.
2. method according to claim 1, is characterized in that, in system, the massfraction of [Bmim] Cl is 15%, and the massfraction of dipotassium hydrogen phosphate is 35%.
3. method according to claim 1, is characterized in that, the mass ratio of rice to be measured and [Bmim] Cl/ dipotassium hydrogen phosphate double-aqueous phase system is 1:10.
4. method according to claim 1, is characterized in that, HPLC detects and adopts Atlantis C
18chromatographic column, mobile phase is acetonitrile-0.5% formic acid solution, and flow velocity is 1.0 mL/min, and determined wavelength is 276 nm, column temperature 30 DEG C, sample size 10 μ L.
5. method according to claim 1, is characterized in that, with mobile phase solution by upper phase solution dilution 2 ~ 5 times.
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Cited By (2)
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| CN105445081A (en) * | 2015-11-24 | 2016-03-30 | 长安大学 | Aqueous bi-phase system and application thereof to extraction of vitamin B6 from watermelon pulp |
| CN114858939A (en) * | 2022-04-27 | 2022-08-05 | 国家烟草质量监督检验中心 | Method for simultaneously determining eugenol, maltol, ethyl maltol, vanillin and ethyl vanillin in novel atomized product |
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Patent Citations (3)
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Cited By (3)
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| CN105445081A (en) * | 2015-11-24 | 2016-03-30 | 长安大学 | Aqueous bi-phase system and application thereof to extraction of vitamin B6 from watermelon pulp |
| CN105445081B (en) * | 2015-11-24 | 2018-06-08 | 长安大学 | The application of vitamin B6 in a kind of double-aqueous phase system and its separation watermelon flesh |
| CN114858939A (en) * | 2022-04-27 | 2022-08-05 | 国家烟草质量监督检验中心 | Method for simultaneously determining eugenol, maltol, ethyl maltol, vanillin and ethyl vanillin in novel atomized product |
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