CN102353728B - Rapid detection method for production process quality control of yellow wine - Google Patents
Rapid detection method for production process quality control of yellow wine Download PDFInfo
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- CN102353728B CN102353728B CN 201110177702 CN201110177702A CN102353728B CN 102353728 B CN102353728 B CN 102353728B CN 201110177702 CN201110177702 CN 201110177702 CN 201110177702 A CN201110177702 A CN 201110177702A CN 102353728 B CN102353728 B CN 102353728B
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Abstract
The invention discloses a rapid detection method for production process quality control of yellow wine, belonging to the technical field of food analysis and food safety, comprising the following steps: (1) carrying out dilution and determining capacity on a yellow wine sample with absolute ethyl alcohol; (2) mixing the diluted yellow wine sample with a 9-hydroxy-xanthene solution in a hydrochloric acid solution and reacting for 60 min at room temperature; and (3) carrying out component separation on the derivative yellow wine sample with high performance liquid chromatography, and calculating the content of urea and ethyl carbamate (EC) in the sample with the external standard method. According to the invention, by setting different parameters at different time periods for a fluorescence detector, the technical difficulty of simultaneously detecting the content of EC and urea in yellow wine is solved, a HPLC-FLD method for simultaneously detecting EC and urea in yellow wine is established, thus a rapid, convenient, accurate and effective monitoring method for yellow wine safety production is provided.
Description
Technical field
The invention belongs to food analysis and food security technical field, relate to a kind of ethyl carbamate in yellow wine and precursor substance thereof measured simultaneously---high performance liquid chromatography (HPLC) method of urea.
Background technology
Urethanes (be called for short EC, claim again urea alkane) is a kind of material with gene carcinogenesis, can cause lung neoplasm, lymph cancer, liver cancer, cutaneum carcinoma etc.International cancer research institution of the World Health Organization (WHO) has been classified as EC 2A class carcinogenic substance.EC is the natural component of Tobacco Leaf and cigarette, also is the product of following of fermented food (such as bread, yoghurt, cheese etc.) and alcoholic beverage (such as grape wine, applejack, Chinese rice wine and sake etc.).The World Health Organization (WHO) (WHO) and food additives Professional Committee of FAO (Food and Agriculture Organization of the United Nation) (FAO) (JECFA) have carried out system evaluation in 2005 to EC, think that EC is to main the drinking from alcoholic beverage of people's harm.The suggestion various countries adopt an effective measure and control EC content in the alcohol product, and Protection of consumer is healthy.Research is thought, urea is one of main precursor substance that forms in the fermented wine EC, 90% EC generates by urea and ethanol synthesis in the yellow rice wine, the urea content level is directly connected to the contents level of EC in the yellow rice wine product in the yellow rice wine, and the content of urea is the key of control EC content in the control yellow rice wine.
Owing to complicated component in the yellow rice wine, increased the detection difficulty of EC and urea.Traditional organophosphorous pesticides/mass spectrometry (SPE-GC/MS) technology has become the standard detecting method of EC in U.S. analytical chemistry Shi Xiehui (AOAC), European Union and OIV (OIV) alcoholic drink, but this method sample pre-treatments is complicated, consuming time and cost is higher, is difficult to adapt to laboratory conventional sense requirement.In recent years, there is the scholar to develop to utilize the method for EC in the high-performance liquid chromatogram determination yellow rice wine.
At present, domestic assay method about urea generally has four kinds.The one, spectrophotometric method; The 2nd, chemical colorimetry; The 3rd, urease method; The 4th, infrared technique, but these method sensitivity are all lower and be subject to other compositions and disturb.Take spectrophotometric method as example, have and the direct quantitative result that affect of the citrulline meeting of urea similar structures; And urease method, ammonium ion content can directly have influence on the Accurate Determining of yellow rice wine urea content in the yellow rice wine.Therefore above-mentioned detection method is not suitable for the mensuration of urea in the drinks.The carbamide detection method that AOAC recommends is the dixanthylurea that generates by measuring the reaction of urea and xanthydrol, is dissolved in the absorbance of the yellow solution that forms behind 50% sulfuric acid solution, and then the content of definite urea.In addition, the people such as external P.Herbert has set up the manually derivative method of utilizing HPLC to measure urea content in the grape wine.The people such as Shona Clark have set up the method for urea content in the automatic derivatization HPLC mensuration grape wine on this basis.
The HPLC technology is faster a kind of food analysis of development in recent years and food safety detection method, uses more and more extensive in the Food Science field.Urea is as security control index in the rice wine production, and is very crucial to EC content in the control yellow rice wine.The content of EC and urea has become the important monitoring index that relates to food security in the rice wine production in the yellow rice wine.In yellow rice wine safety in production quality monitoring, EC and urea are two very important safety indexs, at present main HPLC or the GC/MS method of adopting measured respectively, but this is to manufacturing enterprise, is that input or testing staff's the input at checkout equipment all faces very large pressure.Therefore, set up a kind of can detect simultaneously EC and urea in the yellow rice wine fast, effectively and the method that is easy to promote very necessary.
Cited literature 2:
[1]FSANZ.Ethyl?Carbamate?in?Australian?foods.Survey?sampling?and?analysis?conducted?2007.
[2]EFSA.Ethyl?Carbamate?and?hydrocyanic?acid?in?food?and?beverages-Scientific?opinion?of?the?panel?on?contaminants，2008.
[3]Shona?Clark，Paul?S.Francis，Xavier?A.Conlan，Neil?W.Barnett，Determination?of?urea?using?high-performance?liquid?chromatography?with?fluorescence?detection?after?automated?derivatisation?with?xanthydrol，J.Chromatography?A，1161(2007)207-213.
[4] Xia Yanqiu, Zhu Qiang, Wang Zhijun. guard against the harm of ethyl carbamate in yellow wine. wine brewing, 2004,31 (3): 51-53.
[5] Wang Xiaojuan, Wang Deliang etc. reduce the progress of urea content in the fermented wine. brewing science and technology, 2009, (2): 93-95.
[6] Wang Xiaojuan, Fu Li etc. the content of urea in the high-performance liquid chromatogram determination yellow rice wine. food industry science and technology, 2009, (5): 317-319.
Summary of the invention
The present invention has developed a kind of yellow rice wine procedure quality control method for quick, the method utilizes column front derivation HPLC-FLD (high performance liquid chromatography-fluorescence method) can detect simultaneously EC and urea in the yellow rice wine, thereby provides a kind of facility, effective means for the yellow rice wine Safety control.This method has the characteristics such as sample pre-treatments is quick, simple, good reproducibility, precision is high, testing cost is low.
The invention provides a kind of rapid detection method for production process quality control of yellow wine, comprising:
(1) gets 200 μ L yellow rice wine samples and be settled to 1000 μ L with the absolute ethyl alcohol dilution, the yellow rice wine sample after obtaining to dilute;
(2) measure 400 μ L dilution wine sample, add 600 μ L xanthydrol solution (0.02mol/L) and 100 μ L hydrochloric acid solutions (1.5mol/L), obtain the derivatization sample behind the derivative certain hour of room temperature lucifuge;
(3) the yellow rice wine sample of high performance liquid chromatography after to the derivatization component of carrying out urea and urethanes is separated, and adopts external standard method to calculate the content of urea and urethanes:
Wine sample after derivative sample introduction behind filtering with microporous membrane is measured, and high performance liquid chromatograph adopts C18 post, 250mm * 4.6mm, particle diameter 5 μ m, 35 ℃ of detected temperatures; The fluorescence detector gain is 10; Sample size 10 μ L; The gradient elution program sees Table 1.
Table 1 gradient elution program
Annotate: A is sodium acetate solution; B is acetonitrile, and mobile phase ratio is percent by volume in the table;
Urea appearance time: 8min～10min; Urethanes appearance time: 19min～21min.
Wherein in step (1), described concentration of alcohol is absolute ethyl alcohol;
Wherein in step (2), the described derivative time is 60min.
Wherein in step (3), described sodium acetate solution concentration is 0.02mol/L.
Wherein in step (3), described fluorescence detector parameter is: 0～15min, λ ex=213nm, λ em=308nm; 15～30min, λ ex=233nm, λ em=600nm.
Wherein in step (3), described component is urea and urethanes.
Particularly, a kind of yellow rice wine safety in production procedure quality control method for quick provided by the present invention, performing step is as follows:
(1) the yellow rice wine Sample Dilution is processed: get 200 μ L yellow rice wine sample to be measured and be diluted to 1000 μ L with absolute ethyl alcohol, the yellow rice wine sample after obtaining to dilute.
(2) yellow rice wine sample and the xanthydrol after the dilution carries out derivative reaction in hydrochloric acid solution: get the wine sample after 400 μ L dilute, adding xanthydrol solution and the 100 μ L concentration that 600 μ L concentration are 0.02mol/L is the hydrochloric acid solution of 1.5mol/L, shake up, the room temperature lucifuge derives 60min.
Though EC and urea all without fluorescent characteristic, all can generate the derivative products with fluorescent characteristic with the xanthydrol reaction.
Because the derivative products of EC and xanthydrol can be launched the light of 600nm under the exciting of 233nm wavelength light; And the derivative products of urea and xanthydrol can be launched the light of 308nm under the exciting of 213nm wavelength light.In order to detect simultaneously two kinds of fluorescent component, urea and the EC when through HPLC effective separation after successively entering detecting device of the present invention in mobile phase is by to detecting device urea and EC catches, quantitative and qualitative analysis detects purpose in the method that different time sections is set different parameters reaches sample.
(3) the yellow rice wine sample of high performance liquid chromatography after to the derivatization component of carrying out urea and urethanes is separated, and determination data adopts external standard method to calculate the content of urea and EC:
Then wine sample after derivative adopts HPLC to measure through filtering with microporous membrane, and high performance liquid chromatograph adopts C18 post, 250mm * 4.6mm, particle diameter 5 μ m, 35 ℃ of detected temperatures; Fluorescence detector: 0～15min, λ ex (excitation wavelength)=213nm, λ em (emission wavelength)=308nm; 15～30min, λ ex=233nm, λ em=600nm, gain is 10; Sample size 10 μ L; The gradient elution program sees Table 1.
Urea appearance time: 8min～10min; Urethanes appearance time: 19min～21min.
The means that the inventive method adopts specific separation condition and fluoroscopic examination Parameter Subsection to arrange, effective separation and the assay of urea and EC have been realized, utilize external standard method gained typical curve when adopting this method quantitative, the peak area of urea and EC and the related coefficient between concentration are: R
2＞0.999.
Beneficial effect of the present invention: this method is the content that can detect simultaneously EC in the yellow rice wine sample and two kinds of compositions of prerequisite material urea thereof in the one-time detection process.Measure respectively with present two kinds of compositions and to compare, the time for sample pretreatment (pre-treatment is merged in twice pre-treatment carrying out respectively) that has reduced, (instrument measures separately that the time of urea and EC content was respectively 31 minutes and 30 minutes in the yellow rice wine, and the mensuration of finishing the two needs 61 minutes altogether to have reduced the Instrument measuring time; Only need now just can determine in 30 minutes the content of urea and EC in the yellow rice wine), whole detection efficiency and instrument utilization factor are more than doubled, reduced analytical test personnel working load, reduced the consumption of organic solution and derivative reagent, for implementing the effective control of EC in the production process of yellow rice wine, the monitoring means of more easy, quick, economic, practical and environmental protection are provided.
Description of drawings
The high-efficient liquid phase chromatogram of Fig. 1 urea and EC standard items
The high-efficient liquid phase chromatogram of Fig. 2 embodiment 1 sample
Fig. 3 urea chromatographic peak area and concentration correction typical curve
Fig. 4 urethanes chromatographic peak area and concentration correction typical curve
Embodiment
For a better understanding of the present invention, further set forth the present invention below in conjunction with example.
Adopt high performance liquid chromatograph and fluorescence detector: Waters2695 high performance liquid chromatograph, Waters 2475 fluorescence detectors (U.S. Waters company)
Chromatographic condition: C18 reversed-phase column, 250mm * 4.6mm, particle diameter 5 μ m, 35 ℃ of detected temperatures; Fluorescence detector: λ ex=213nm, λ em=308nm (0～15min), λ ex=233nm, (15～30min), gain is 10 to λ em=600nm; Sample size 10 μ L; The gradient elution program sees Table 1.
Urethanes (Sigma company, purity is greater than 99%), urea (Sigma company, purity is greater than 99%); Xanthydrol (Sigma company, purity is greater than 99%), acetonitrile (chromatographically pure), n-propanol (Fisher company); Sodium acetate (analyzing pure); Absolute ethyl alcohol (analyzing pure); Anhydrous acetic acid (analyzing pure); Hydrochloric acid (analyzing pure).
Solution preparation is as follows:
Urethanes standard stock solution: accurately weigh the 0.0100g urethanes, with anhydrous alcohol solution and be settled to 50mL, ultimate density is 200mg/L ,-4 ℃ of storages, the term of validity one month.
Urea standard stock solution: accurately weigh 0.0500g urea, with anhydrous alcohol solution and be settled to 50mL, ultimate density is 1000mg/L ,-4 ℃ of storages, the term of validity one month.
Xanthydrol solution: accurately weigh 0.1980g xanthydrol powder, with n-propanol dissolving and be settled to 50mL, ultimate density is 0.02mol/L, and lucifuge is placed ,-4 ℃ of storages, the term of validity one month.
Sodium acetate solution: the sodium acetate that accurately weighs 2.7216g is dissolved in the 1000mL water, and its PH is transferred to 7.2, ultimate density 0.02mol/L with 1% acetic acid solution.
Hydrochloric acid solution: measure the concentrated hydrochloric acid of about 6.2mL in the 50mL volumetric flask, use the distilled water constant volume, ultimate density is 1.5mol/L
Method validation:
Preparation EC and urea series hybrid standard working fluid, the peak face response y of tested component and the relation between the mass concentration x are measured in the sample introduction analysis, get urea equation of linear regression Y=2.85 * 10
5X+1.07 * 10
5, regression coefficient R
2Be 0.999, method detects and is limited to 24 μ g/L, quantitatively is limited to 80 μ g/L; EC equation of linear regression: Y=1.06 * 10
2X+2.34 * 10
2, regression coefficient R
2Be 0.999, detect and be limited to 5 μ g/L, quantitative limit 10 μ g/L.
Select a kind of yellow rice wine as the test sample of EC and determination of urea precision test, repeat 5 times and detect, urethanes RSD is 2.60%, and urea RSD is 1.50%.
Carry out the recovery of standard addition test according to 50%, 100%, 150% of 50%, 100%, 150% and urea content of EC content in the yellow rice wine.Test findings shows, the method recovery is good, and the average recovery of standard addition of EC is 93.2%.The average recovery of standard addition of urea is 99.7%.
Measure when EC and urea content in embodiment 1～2 yellow rice wine
The new yellow rice wine that sample 1 ferments for the firm end that domestic certain yellow rice wine factory provides, sample 2 are the finished product yellow rice wine of sample 1 storage after 12 months, and testing sample is got 200 μ L and is diluted to 1000 μ L with absolute ethyl alcohol; Get the wine sample after 400 μ L dilute, add xanthydrol solution and 100 μ L hydrochloric acid solutions that 600 μ L concentration are 0.02mol/L, shake up, the room temperature lucifuge derives 30min.
Yellow rice wine after utilizing high performance liquid chromatograph to derivatization carries out component to be separated, by the content of urethanes and urea in the external standard method calculation sample.
High performance liquid chromatograph adopts C18 post, 250mm * 4.6mm, particle diameter 5 μ m, 35 ℃ of detected temperatures; Fluorescence detector: λ ex=213nm, λ em=308nm (0～15min), λ ex=233nm, (15～30min), gain is 10 to λ em=600nm; Sample size 10 μ L; The gradient elution program sees Table 1.
Urea appearance time: 8min～10min; Urethanes appearance time: 19min～21min.
EC and urea content see Table 2:
EC and urea content in table 2 sample
Among the above embodiment, the peak area of urea and EC and the related coefficient between concentration are: R
2＞0.999, see Fig. 3, Fig. 4.
Same sample is repeatedly measured the method precision that obtains to be respectively: urea RSD＜1.5%; EC RSD＜5.0%
Table 3 urea and EC precision
The sample mark-on average recovery rate of method is respectively: urea 99.7%; EC 93.2%
Table 4 urea and EC recovery of standard addition (n=3)
As seen, method of the present invention has higher precision, the detection of urea and EC in the suitable yellow rice wine.
Claims (4)
1. rapid detection method for production process quality control of yellow wine is characterized in that:
(1) gets 200 μ L yellow rice wine samples and be settled to 1000 μ L with the absolute ethyl alcohol dilution, the yellow rice wine sample after obtaining to dilute;
(2) measure 400 μ L dilution wine sample, adding xanthydrol solution and the 100 μ L concentration that 600 μ L concentration are 0.02mol/L is the 1.5mol/L hydrochloric acid solution, obtains the derivatization sample behind the derivative certain hour of room temperature lucifuge;
(3) the yellow rice wine sample of high performance liquid chromatography after to the derivatization component of carrying out urea and urethanes is separated, and adopts external standard method to calculate the content of urea and urethanes:
Wine sample after derivative sample introduction behind filtering with microporous membrane is measured, and it is 250mm * 4.6mm that high performance liquid chromatograph adopts specification, the C18 post of particle diameter 5 μ m, and, 35 ℃ of detected temperatures; The fluorescence detector gain is 10; Sample size 10 μ L; Gradient elution program such as table 1:
Table 1 gradient elution program
Wherein: A is sodium acetate solution; B is acetonitrile, and mobile phase ratio is percent by volume in the table;
Urea appearance time: 8min～10min; Urethanes appearance time: 19min～21min.
2. the method for claim 1, it is characterized in that: in the step (2), the described derivative time is 60min.
3. the method for claim 1, it is characterized in that: in the step (3), described sodium acetate solution concentration is 0.02mol/L.
4. the method for claim 1, it is characterized in that: in the step (3), described fluorescence detector parameter is: 0～15min, λ ex=213nm, λ em=308nm; 15～30min, λ ex=233nm, λ em=600nm.
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| CN102735830A (en) * | 2012-07-04 | 2012-10-17 | 浙江农林大学 | Preparation method for ethyl urethane detection test paper and detection method of test paper |
| CN102809615B (en) * | 2012-08-16 | 2013-11-13 | 江苏中烟工业有限责任公司 | Method for detecting ethyl urethane content of cigarette sidestream smoke via LC-MS/MS combination |
| CN102778519B (en) * | 2012-08-16 | 2013-11-13 | 江苏中烟工业有限责任公司 | Method for detecting ethyl carbamate content of side stream smoke of cigarettes through combination utilization of gas chromatography-mass spectrometry (GC-MS) |
| CN102965263B (en) * | 2012-11-20 | 2014-08-13 | 中国食品发酵工业研究院 | Method for inhibiting ethyl carbamate from being generated in white wine storage process |
| CN103487529A (en) * | 2013-10-15 | 2014-01-01 | 谱尼测试科技(天津)有限公司 | Method for detecting residual amount of semi carbazide in flour and flour products by high performance liquid chromatography |
| CN103760266A (en) * | 2014-01-16 | 2014-04-30 | 深圳市华测检测技术股份有限公司 | Method for detecting content of urea in brewed wine by using high performance liquid chromatography |
| CN103954568A (en) * | 2014-04-22 | 2014-07-30 | 华南理工大学 | Chemical detection method for rapidly detecting content of ethyl carbamate |
| CN103954722A (en) * | 2014-05-21 | 2014-07-30 | 江南大学 | Detection method aiming at trace urea in white spirit |
| CN104764850B (en) * | 2015-04-28 | 2016-03-23 | 江南大学 | A kind of method utilizing urea in gas chromatography-mass spectrum fast quantification white wine |
| CN106468688B (en) * | 2015-08-21 | 2018-08-24 | 菏泽天鸿果蔬有限公司 | A kind of detection method of urethanes residual quantity |
| CN106317009B (en) * | 2016-08-16 | 2019-03-26 | 华南农业大学 | A kind of xanthene polyurethane haptens, artificial antigen and its application |
| CN108440689B (en) * | 2018-05-17 | 2019-08-20 | 华中农业大学 | Xanthenes alcohol modified resin and its preparation method and application |
| CN109164197A (en) * | 2018-09-20 | 2019-01-08 | 中国食品发酵工业研究院有限公司 | The liquid chromatography detecting method of sodium cyclohexylsulfamate in a kind of white wine |
| KR102526333B1 (en) * | 2020-03-19 | 2023-04-26 | 인더스트리얼 테크놀로지 리서치 인스티튜트 | Detection reagent, detection device, and method for detecting primary amide compound |
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| DE10063173A1 (en) * | 2000-12-18 | 2002-06-20 | Merck Patent Gmbh | Urea and urethane derivatives |
| CN101620206B (en) * | 2009-06-18 | 2011-09-21 | 浙江大学 | Method for detecting ethyl carbamate in yellow wine |
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