CN103344725A - Method for simultaneously and quantitatively detecting content of ethyl carbamate and phthalate in distilled white wine - Google Patents
Method for simultaneously and quantitatively detecting content of ethyl carbamate and phthalate in distilled white wine Download PDFInfo
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Abstract
The invention belongs to the field of white wine detection, particularly relates to a method for simultaneously and quantitatively detecting the content of ethyl carbamate and phthalate in the distilled white wine and aims to solve the problems the existing method for detecting is complex in operation and consumes long time. The method comprises the following steps of: (a) adding an internal standard substance I and an internal standard substance II into a white-wine sample, and (b) detecting by adopting a gas chromatograph mass spectrometer, monitoring and quantitating by using selected irons, and obtaining the content of the ethyl carbamate and the phthalate in the distilled white wine by adopting the internal standard method. The method provided by the invention has good reproducibility, is accurate and is low in detection cost, thereby being easy to popularize.
Description
Technical field
The invention belongs to the liquor detection range, be specifically related to detect simultaneously quantitatively the method for urethanes and phthalic acid ester content in the distilled spirit.
Technical background
Urethanes (ethyl carbamate is called for short EC) has another name called urethane, is the accessory substance of fermented food natural formation in fermentation and storage process.After deliberation, the urethanes in the distilled spirit is generated by carbamino compound and ethanol spontaneous reaction.1987, IARC (IARC) classified EC as group2B: possible carcinogen; 2004, the list of " material of having reason to expect to cause cancer " was listed EC in the NTP plan; IARC in 2007 EC that reappraises is listed in group2A with plumbous, mercury and acrylamide etc.At present, Chinese patent 201210441000.6 open " high performance liquid chromatography of urethanes-Mass Spectrometer Method method in the Spirit ", this method adopts decompression distillation to remove ethanol, use the distilled water constant volume, directly advance the LC-MS(liquid chromatography-mass spectrography), calculate the urethane ester content with external standard method then.Chinese patent 201110339615.3 open " method of urethane ester content in a kind of quick mensuration Spirit ", this method adopts the rotary evaporation removal of impurities, urethanes in head space-solid phase micro-extraction technique enrichment wine sample, GC-MS quantitatively detects, and adopts external standard method to calculate the content of urethanes then.
Phthalic ester is the widely used plastifier of a class, can increase the flexibility of material or make material liquefaction, be widely used in toy, packaging material for food, medical blood bag and sebific duct, vinyl flooring, detersive, lubricating oil, personal care articles (as, nail polish, shampoo) etc. in hundreds of products.This compounds has been confirmed to be environmental estrogens, and people's reproductive system is had infringement.Storage wine container, bottle that phthalic ester in the liquor is mainly derived from plastic products cover interior plastic washer, plastic conduit etc.Chinese patent 201210281033.9 open " a kind of method of colorimetric probe in detecting phthalic ester "; Chinese patent 201210504503.3 open " a kind of mensuration is reproduced the method for phthalate compound content in the cigarette "; Chinese patent 201110076663.8 open " a kind of liquid chromatography-mass spectrography is measured the method for phthalic acid ester content in the Chinese medicine ".
At present, have only a few countries such as Canada, Czech, France to stipulate the upper content limit of urethanes in the Spirit, most of country there is no concrete regulation to the content of urethanes.Therefore, less at the method for the urethane ester content in the special detection Spirit.China's import-export commodity inspection industry standard: urethanes residual quantity method of inspection SN0285-1993 in the outlet drinks, this method operation is comparatively loaded down with trivial details, the time long, it is bigger influenced by personnel operation, is applicable to that not too enterprise is to producing the self check in enormous quantities of product.
Detect the content of phthalic ester in the distilled spirit mainly according to standard GB/T21911-2008 " mensuration of Phthalic Acid Esters in Food ", this method adopts liquid-liquid extraction, external standard method quantitative, after being applied to the distilled spirit sample, the testing result deviation is big, reappearance is relatively poor.
More than two kinds of detection methods all need to sample carry out pre-treatment, operation is comparatively loaded down with trivial details, the time is longer, and can not realize that single injected sampling detects the content of urethanes and phthalic ester two class materials simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is that conventional detection complex operation, time are longer.
The technical scheme that the present invention solves the problems of the technologies described above has provided a kind of while and has quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, may further comprise the steps:
A, add internal standard compound I and internal standard compound II in the wine sample;
B, use gas chromatograph-mass spectrometer (GCMS) detect, and use and select ion monitoring and quantitative, and the employing internal standard method obtains the content of urethanes and phthalic ester.
Wherein, in the method for urethanes and phthalic ester, the described internal standard compound I of step a is that deuterium is for urethanes in quantitative detection of the above-mentioned while distilled spirit.Described deuterium is for purity 〉=98% of urethanes.
Further, in the method for urethanes and phthalic ester, the volume ratio of internal standard compound I and wine sample is 3 ︰ 5000 in quantitative detection of the above-mentioned while distilled spirit.
Wherein, in the method for urethanes and phthalic ester, the described internal standard compound II of step a is di-iso-amyl phthalate in quantitative detection of the above-mentioned while distilled spirit.The purity of described di-iso-amyl phthalate 〉=98%.
Further, in the method for urethanes and phthalic ester, the volume ratio of internal standard compound II and wine sample is 3 ︰ 5000 in quantitative detection of the above-mentioned while distilled spirit.
Wherein, the above-mentioned while is quantitatively detected in the method for urethanes and phthalic ester in the distilled spirit, the described internal standard method of step b comprises: add internal standard compound in sample, obtain peak area through instrumental analysis then, again according to the typical curve result of calculation of having drawn.
Further, the condition of the described gas chromatography of step b is: adopt the ZB-WAXplus capillary chromatographic column to separate, 250 ℃ of injector temperatures, sample size 0.5 μ L, split sampling not, post flow 1mL/min; Heating schedule: 40 ℃ keep 2min, rise to 160 ℃ with 10 ℃/min, rise to 230 ℃ with 30 ℃/min again, keep 15.6min.
Further, the length of described ZB-WAXplus capillary chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μ m.
Further, the described mass spectral condition of step b is: electron ionization sources, ionization voltage 70eV; Scan mode is for selecting ion monitoring, 230 ℃ of ion source temperatures, 150 ℃ of level Four bar temperature, 240 ℃ of the auxiliary heating-up temperatures of GC-MS.
Further, described selection ion monitoring is: the monitoring ion m/z62 of urethanes, deuterium is for the monitoring ion m/z64 of urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
The inventive method adopts internal standard method to detect the content of phthalic ester first, and can detect the content of urethanes simultaneously, and the testing result reappearance is better, error is low.This method is easy and simple to handle, does not need sample is carried out pre-treatment, and it is low to detect cost, and analysis time is short, only needs just can obtain in more than 30 minute the content of urethanes and phthalic ester, saves instrument, is applicable to that enterprises carries out the batch samples self check.The instrument that the present invention uses is laboratory conventional analysis instrument, and inventive method is easy to promote, and it is low to detect cost.
Description of drawings
The chromatogram of Fig. 1 urethanes standard solution (containing the internal standard compound I).
The chromatogram of Fig. 2 phthalic ester standard solution (containing the internal standard compound II).
The chromatogram of urethanes and phthalic ester (containing internal standard compound I, II) in Fig. 3 wine sample.
Embodiment
The method of urethanes and phthalic ester in quantitative detection of the while distilled spirit may further comprise the steps:
A, add internal standard compound I and internal standard compound II in the wine sample;
B, use gas chromatograph-mass spectrometer (GCMS) detect, and use and select ion monitoring and quantitative, and the employing internal standard method obtains the content of urethanes and phthalic ester.
Wherein, in the method for urethanes and phthalic ester, the described internal standard compound I of step a is that deuterium is for urethanes in quantitative detection of the above-mentioned while distilled spirit.Described deuterium is for purity 〉=98% of urethanes.
Further, in the method for urethanes and phthalic ester, add 30 μ L internal standard compound I in every 50mL wine sample in quantitative detection of the above-mentioned while distilled spirit.
Wherein, in the method for urethanes and phthalic ester, the described internal standard compound II of step a is di-iso-amyl phthalate in quantitative detection of the above-mentioned while distilled spirit.The purity of described di-iso-amyl phthalate 〉=98%.
Further, in the method for urethanes and phthalic ester, add 30 μ L internal standard compound II in every 50mL wine sample in quantitative detection of the above-mentioned while distilled spirit.
Wherein, the above-mentioned while is quantitatively detected in the method for urethanes and phthalic ester in the distilled spirit, the described internal standard method of step b comprises: add internal standard compound in sample, obtain peak area through instrumental analysis then, again according to the typical curve result of calculation of having drawn.
Further, the condition of the described gas chromatography of step b is: adopt the ZB-WAXplus capillary chromatographic column to separate, 250 ℃ of injector temperatures, sample size 0.5 μ L, split sampling not, post flow 1mL/min; Heating schedule: 40 ℃ keep 2min, rise to 160 ℃ with 10 ℃/min, rise to 230 ℃ with 30 ℃/min again, keep 15.6min.
Further, the length of described ZB-WAXplus capillary chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μ m.
Further, the described mass spectral condition of step b is: electron ionization sources, ionization voltage 70eV; Scan mode is for selecting ion monitoring, 230 ℃ of ion source temperatures, 150 ℃ of level Four bar temperature, 240 ℃ of the auxiliary heating-up temperatures of GC-MS.
Further, described selection ion monitoring is: the monitoring ion m/z62 of urethanes, deuterium is for the monitoring ion m/z64 of urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
In experimentation, the inventor once attempted using external standard method to carry out quantitative test, but find that the quantitative result reappearance is relatively poor, and error is bigger, the assay of phthalic ester especially, and its result error is also bigger.So, select for use internal standard method to carry out quantitative test.For the selection of internal standard compound, following ask for something is arranged: can not contain this internal standard compound in the sample, not react with sample, with the test substance similar performance, retention time and response factor are approaching as far as possible.Before the selection of carrying out internal standard compound, inventor elder generation is to the distilled spirit of various odor types, as, Luzhou-flavor, delicate fragrance type, Maotai-flavor, carry out full scan and detect, find mainly to contain in the distilled spirit five kinds of phthalate compounds: the own ester of repefral, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and phthalic acid two (2-ethyl).According to the selection requirement of internal standard compound, a kind of phthalate material that needs to select not contain in the distilled spirit is as interior mark.In the process of selecting the internal standard compound II, the inventor once used dioctyl phthalate as interior mark II, the data that obtain show: mark is low to the quantitative result error of the own ester of phthalic acid two (2-ethyl) in this, reappearance is better, but the quantitative result error of its dimethyl terephthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate is big, reappearance is on the low side.So it is suitable that the inventor must seek in numerous phthalate compounds again.Through a large amount of contrast experiments, the inventor has selected di-iso-amyl phthalate as interior mark II at last.Experimental result shows: when using di-iso-amyl phthalate as interior mark II, the quantitative result of five kinds of phthalic esters all accurately, low, the favorable reproducibility of error.Can not only quantitatively detect five kinds of phthalic esters with di-iso-amyl phthalate well as interior mark II, and itself and internal standard compound I be used each other and can not produce interference, can quantitatively detect urethanes and several phthalic ester well simultaneously.
The inventor not only needs to determine the internal standard compound II through a large amount of screening experiments, also needs to select suitable chromatographic column by a large amount of experiments.In the process of selecting chromatographic column, the inventor once used Agilent DB-5MS capillary chromatographic column to carry out the separation of composition in the wine sample, though this chromatographic column can be good at isolating several phthalic esters, can not effectively isolate urethanes.After having experienced failure many times, the inventor attempted using Phenomenex ZB-WAXplus capillary chromatographic column afterwards, was surprised to find that, this chromatographic column can be isolated urethanes and several phthalic ester simultaneously well, and the peak type is better.
Further, need the drawing standard curve.Wherein, sample is the y axle with the ratio of interior target peak area, and sample is the x axle with the ratio of interior target concentration.The step of drawing standard curve is:
1, draws the urethanes typical curve
The preparation of urethanes storing solution: accurately take by weighing the urethanes of 22.8mg in the 50mL beaker, add and be transferred in the 100mL volumetric flask after about 20mL ethanol dissolves fully, wash beaker 2-3 time with small amount of ethanol, washing fluid is transferred in the volumetric flask, is settled to scale with ethanol at last.
The preparation of internal standard compound I solution: the deuterium that accurately takes by weighing 41.6mg for urethanes in the 50mL beaker, add and be transferred in the 50mL volumetric flask after about 20mL ethanol dissolves fully, wash beaker 2-3 time with small amount of ethanol, washing fluid is transferred in the volumetric flask, is settled to scale with ethanol at last.
The preparation of series urethanes standard operation solution: pipette the urethanes storing solution of 50 μ L, 250 μ L, 500 μ L and 60 μ L internal standard compound I solution respectively in the 100mL volumetric flask, use 50%(v/v) ethanol is settled to scale.
Adopt gas chromatography-mass spectrum successively serial urethanes standard operation solution to be measured, the drawing standard curve obtains linear equation: y=ax, R
2=0.9999, a=1.058 wherein; The ratio of x=urethanes and the concentration of internal standard compound I; The ratio of y=urethanes and the peak area of internal standard compound I.
2, draw the phthalic ester typical curve
The preparation of phthalic ester storing solution: the DMP(repefral that accurately takes by weighing 20mg), the DEP(diethyl phthalate of 50mg), the DIBP(diisobutyl phthalate of 35mg), the DBP(dibutyl phthalate of 45mg) and the own ester of DEHP(phthalic acid two (2-ethyl) of 65mg) in the 50mL beaker, add and be transferred in the 100mL volumetric flask after about 30mL ethanol dissolves fully, wash beaker 3-5 time with small amount of ethanol, washing fluid is transferred in the volumetric flask, is settled to scale with ethanol at last.
The preparation of internal standard compound II solution: accurately take by weighing the di-iso-amyl phthalate of 100mg in the 50mL beaker, add and be transferred in the 100mL volumetric flask after about 30mL ethanol dissolves fully, wash beaker 3-5 time with small amount of ethanol, washing fluid is transferred in the volumetric flask, is settled to scale with ethanol at last.
The preparation of series phthalic ester standard operation solution: pipette the phthalic ester storing solution of 50 μ L, 75 μ L, 150 μ L and 60 μ L internal standard compound II solution in the 100mL volumetric flask, use 50%(v/v) ethanol is settled to scale.
Adopt gas chromatography-mass spectrum successively serial phthalic ester standard operation solution to be measured, the drawing standard curve, the linear equation that obtains every kind of phthalic ester is: y=ax
2+ bx; Wherein,
The linear equation of repefral is: y=0.2044x
2+ 0.6239x, R
2The ratio of=0.9999, x=repefral and the concentration of internal standard compound II; The ratio of y=repefral and the peak area of internal standard compound II;
The linear equation of diethyl phthalate is: y=0.07384x
2+ 0.5726x, R
2The ratio of=0.9999, x=diethyl phthalate and the concentration of internal standard compound II; The ratio of y=diethyl phthalate and the peak area of internal standard compound II;
The linear equation of diisobutyl phthalate is: y=0.1350x
2+ 0.8949x, R
2The ratio of=0.9999, x=diisobutyl phthalate and the concentration of internal standard compound II; The ratio of y=diisobutyl phthalate and the peak area of internal standard compound II;
The linear equation of dibutyl phthalate is: y=0.1284x
2+ 1.118x, R
2The ratio of=0.9999, x=dibutyl phthalate and the concentration of internal standard compound II; The ratio of y=dibutyl phthalate and the peak area of internal standard compound II;
The linear equation of the own ester of phthalic acid two (2-ethyl) is: y=0.06119x
2+ 0.8346x, R
2The ratio of the own ester of=0.9998, x=phthalic acid two (2-ethyl) and the concentration of internal standard compound II; The ratio of the own ester of y=phthalic acid two (2-ethyl) and the peak area of internal standard compound II.
Further, calculate the content of urethanes in the wine sample by following formula:
m=A/A
S×m
s/a
Wherein, the content of urethanes in m-wine sample, unit are mg/litre (mg/L);
The peak area of A-urethanes;
A
S-deuterium is for the peak area of urethanes;
m
sMark content in-wine sample the solution, unit is mg/litre (mg/L);
A-drawn by equation of linear regression.
Further, calculate the content of phthalic ester in the wine sample by following formula:
m=[-b+(4a×A/A
s+b
2)
1/2]×m
s/2a
Wherein, the content of every kind of phthalic ester in m-wine sample, unit are mg/litre (mg/L);
B-drawn by equation of linear regression;
A-drawn by equation of linear regression;
The peak area of A-every kind phthalic ester;
A
SThe peak area of-di-iso-amyl phthalate;
m
sMark content in-wine sample the solution, unit is mg/litre (mg/L).
Instrument and reagent that the embodiment of the invention is used:
The Agilent7890A of U.S. Agilent Technologies gas chromatograph, the Agilent5975C of U.S. Agilent Technologies mass spectrometer, the ZB-WAXplus capillary chromatographic column that Phenomenex company produces.
Ethanol is that top grade is pure; Urethanes standard items, deuterium are U.S. AccuStandard company and produce for purity 〉=98% of urethanes standard items and phthalic ester standard items.
Embodiment 1
Clean the 50mL volumetric flask 2-3 time with wine sample to be measured, the cleaning back that finishes adds wine sample to be measured about 10mL in the volumetric flask, adds 30 μ L internal standard compound I and 30 μ L internal standard compound II respectively to volumetric flask with liquid-transfering gun then, is settled to scale with wine sample to be measured at last, jog, mixing.The wine sample to be measured that is added with internal standard compound that mixing is good is poured in the Agilent sample bottle, carries out gas chromatography-mass spectrometry analysis and detects.
The condition of gas chromatography is: adopt the ZB-WAXplus capillary chromatographic column to separate, the length of chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μ m; 250 ℃ of injector temperatures, sample size 0.5 μ L, split sampling not, post flow 1mL/min; Heating schedule: 40 ℃ keep 2min, rise to 160 ℃ with 10 ℃/min, rise to 230 ℃ with 30 ℃/min again, keep 15.6min.
Mass spectral condition is: electron ionization sources, ionization voltage 70eV; Scan mode is for selecting ion monitoring, 230 ℃ of ion source temperatures, 150 ℃ of level Four bar temperature, 240 ℃ of the auxiliary heating-up temperatures of GC-MS.The selection ion monitoring is: the monitoring ion m/z62 of urethanes, deuterium is for the monitoring ion m/z64 of urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
By internal standard compound and the calculated by peak area urethanes of component to be measured and the content of phthalic ester that obtains.With the peak area that obtains, concentration and a in the linear equation and the b substitution formula of internal standard compound:
Calculate the content of urethanes in the wine sample by following formula:
m=A/A
S×m
s/a
Wherein: the content of urethanes in m-wine sample, unit are mg/litre (mg/L);
The peak area of A-urethanes;
A
S-deuterium is for the peak area of urethanes;
m
sMark content in-wine sample the solution, unit is mg/litre (mg/L);
A-drawn by equation of linear regression.
Linear equation: y=ax, R
2=0.9999, a=1.058 wherein;
Calculate the content of phthalic ester in the wine sample by following formula:
m=[-b+(4a×A/A
s+b
2)
1/2]×m
s/2a
Wherein: the content of every kind of phthalic ester in m-wine sample, unit are mg/litre (mg/L);
B-drawn by equation of linear regression;
A-drawn by equation of linear regression;
The peak area of A-every kind phthalic ester;
A
SThe peak area of-di-iso-amyl phthalate;
m
sMark content in-wine sample the solution, unit is mg/litre (mg/L).
The linear equation of repefral: y=ax
2+ bx, a=0.2044 wherein, b=0.6239;
The linear equation of diethyl phthalate: y=ax
2+ bx, a=0.07384 wherein, b=0.5726;
The linear equation of diisobutyl phthalate: y=ax
2+ bx, a=0.1350 wherein, b=0.8949;
The linear equation of dibutyl phthalate: y=ax
2+ bx, a=0.1284 wherein, b=1.118;
The linear equation of the own ester of phthalic acid two (2-ethyl): y=ax
2+ bx, a=0.06119 wherein, b=0.8346.
Be respectively 0.3295mg/L, 0.1044mg/L, 0.2946mg/L, 0.2906mg/L, 0.2926mg/L, 0.3476mg/L by the content that calculates the own ester of urethanes, repefral, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and phthalic acid two (2-ethyl) in this wine sample.
Precision and the sensitivity of embodiment 2 the inventive method
To certain wine sample replicate determination 5 times, the precision result who obtains sample is as shown in table 1 according to the method for embodiment 1:
The precision of table 1 the inventive method
| ? | 1# | 2# | 3# | 4# | 5# | RSD(%) |
| EC(mg/L) | 0.3322 | 0.3291 | 0.3312 | 0.3254 | 0.3260 | 0.925 |
| DMP(mg/L) | 0.0126 | 0.0126 | 0.0124 | 0.0124 | 0.0125 | 0.799 |
| DEP(mg/L) | 0.0360 | 0.0364 | 0.0360 | 0.0361 | 0.0361 | 0.482 |
| DIBP(mg/L) | 0.1209 | 0.1223 | 0.1222 | 0.1221 | 0.1222 | 0.468 |
| DBP(mg/L) | 0.0738 | 0.0736 | 0.0738 | 0.0738 | 0.0740 | 0.180 |
| DEHP(mg/L) | 0.0128 | 0.0125 | 0.0121 | 0.0120 | 0.0123 | 2.728 |
The result shows in the table 1, the RSD(relative standard deviation) less than 10%, show the content that can accurately measure urethanes and phthalic ester in the wine sample.
Quantitative limit and detectability are the sensitivity that embodies detection method, when only being starkly lower than maximum residue limit, can be used for measuring.Content during with signal to noise ratio (S/N ratio) S/N=3 is detectability; Content during with signal to noise ratio (S/N ratio) S/N=10 is quantitative limit.The result shows in the table 2, and the sensitivity of this method is higher.
The sensitivity of table 2 the inventive method
| ? | EC | DMP | DEP | DIBP | DBP | DEHP |
| Detectability (mg/L) | 0.0005 | 0.00005 | 0.00006 | 0.00002 | 0.00005 | 0.00002 |
| Quantitative limit (mg/L) | 0.023 | 0.0024 | 0.0025 | 0.0014 | 0.0021 | 0.0017 |
From above-mentioned experimental result as can be seen, method provided by the invention is simple to operate, and sensitivity is higher, accuracy height, favorable reproducibility.
Claims (9)
1. detect simultaneously quantitatively the method for urethanes and phthalic ester in the distilled spirit, may further comprise the steps:
A, add internal standard compound I and internal standard compound II in the wine sample;
B, use gas chromatograph-mass spectrometer (GCMS) detect, and use and select ion monitoring and quantitative, and the employing internal standard method obtains the content of urethanes and phthalic ester.
2. the while according to claim 1 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, and it is characterized in that: the described internal standard compound I of step a is that deuterium is for urethanes.
3. the while according to claim 2 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, and it is characterized in that: the volume ratio of internal standard compound I and wine sample is 3 ︰ 5000.
4. the while according to claim 1 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, and it is characterized in that: the described internal standard compound II of step a is di-iso-amyl phthalate.
5. the while according to claim 4 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, and it is characterized in that: the volume ratio of internal standard compound II and wine sample is 3 ︰ 5000.
6. the while according to claim 1 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, it is characterized in that: the condition of the described gas chromatography of step b is: adopt the ZB-WAXplus capillary chromatographic column to separate, 250 ℃ of injector temperatures, sample size 0.5 μ L, split sampling not, post flow 1mL/min; Heating schedule: 40 ℃ keep 2min, rise to 160 ℃ with 10 ℃/min, rise to 230 ℃ with 30 ℃/min again, keep 15.6min.
7. the while according to claim 6 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, and it is characterized in that: the length of described ZB-WAXplus capillary chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μ m.
8. the while according to claim 1 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, and it is characterized in that: the described mass spectral condition of step b is: electron ionization sources, ionization voltage 70eV; Scan mode is for selecting ion monitoring, 230 ℃ of ion source temperatures, 150 ℃ of level Four bar temperature, 240 ℃ of the auxiliary heating-up temperatures of GC-MS.
9. the while according to claim 8 is quantitatively detected the method for urethanes and phthalic ester in the distilled spirit, it is characterized in that: described selection ion monitoring is: the monitoring ion m/z62 of urethanes, deuterium is for the monitoring ion m/z64 of urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
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| CN103822982A (en) * | 2014-02-25 | 2014-05-28 | 浙江大学宁波理工学院 | Method for enriching and detecting phthalate ester compound in wine sample by ionic liquid-dispersive liquid-liquid microextraction |
| CN103913525A (en) * | 2014-04-01 | 2014-07-09 | 山东省分析测试中心 | Method for detecting 17 plasticizers in white spirit by high performance liquid chromatography-tandem mass spectrometry |
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| CN104897865A (en) * | 2015-05-19 | 2015-09-09 | 中国食品发酵工业研究院 | A prediction method of the content of ethyl carbamate in a normal-temperature storage process of baijiu |
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| CN110007039A (en) * | 2019-05-13 | 2019-07-12 | 四川轻化工大学 | The qualitative determination method and its content assaying method of formic acid in edible wine |
| CN112980722A (en) * | 2019-09-29 | 2021-06-18 | 北京工商大学 | Burkholderia polyphylla culture method and application thereof in catalytic degradation of harmful esters of white spirit |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103822982A (en) * | 2014-02-25 | 2014-05-28 | 浙江大学宁波理工学院 | Method for enriching and detecting phthalate ester compound in wine sample by ionic liquid-dispersive liquid-liquid microextraction |
| CN103822982B (en) * | 2014-02-25 | 2015-12-09 | 浙江大学宁波理工学院 | A kind of ionic liquid-dispersive liquid-liquid microextraction method enrichment and the method detecting phthalate compound in wine sample |
| CN103913525A (en) * | 2014-04-01 | 2014-07-09 | 山东省分析测试中心 | Method for detecting 17 plasticizers in white spirit by high performance liquid chromatography-tandem mass spectrometry |
| CN103913525B (en) * | 2014-04-01 | 2015-04-22 | 山东省分析测试中心 | Method for detecting 17 plasticizers in white spirit by high performance liquid chromatography-tandem mass spectrometry |
| CN103954568A (en) * | 2014-04-22 | 2014-07-30 | 华南理工大学 | Chemical detection method for rapidly detecting content of ethyl carbamate |
| CN104897865A (en) * | 2015-05-19 | 2015-09-09 | 中国食品发酵工业研究院 | A prediction method of the content of ethyl carbamate in a normal-temperature storage process of baijiu |
| CN104897865B (en) * | 2015-05-19 | 2016-11-23 | 中国食品发酵工业研究院 | A kind of Chinese liquor is the Forecasting Methodology of ethyl carbamate content during storage at normal temperature |
| CN106468688A (en) * | 2015-08-21 | 2017-03-01 | 菏泽天鸿果蔬有限公司 | A kind of detection method of urethanes residual quantity |
| 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 |
| CN110007039A (en) * | 2019-05-13 | 2019-07-12 | 四川轻化工大学 | The qualitative determination method and its content assaying method of formic acid in edible wine |
| CN112980722A (en) * | 2019-09-29 | 2021-06-18 | 北京工商大学 | Burkholderia polyphylla culture method and application thereof in catalytic degradation of harmful esters of white spirit |
| CN112980722B (en) * | 2019-09-29 | 2022-10-14 | 北京工商大学 | Method for culturing Burkholderia polyphylla and application of Burkholderia polyphylla in catalytic degradation of harmful esters of white spirit |
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