CN103134870B - Method for measuring sorbic acid and benzoic acid in foodstuff - Google Patents
Method for measuring sorbic acid and benzoic acid in foodstuff Download PDFInfo
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- CN103134870B CN103134870B CN201310047161.1A CN201310047161A CN103134870B CN 103134870 B CN103134870 B CN 103134870B CN 201310047161 A CN201310047161 A CN 201310047161A CN 103134870 B CN103134870 B CN 103134870B
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 121
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 235000010199 sorbic acid Nutrition 0.000 title claims abstract description 71
- 239000004334 sorbic acid Substances 0.000 title claims abstract description 71
- 229940075582 sorbic acid Drugs 0.000 title claims abstract description 71
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 53
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000012510 hollow fiber Substances 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000004817 gas chromatography Methods 0.000 claims abstract description 16
- 238000004853 microextraction Methods 0.000 claims abstract description 16
- 239000012071 phase Substances 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- 238000012360 testing method Methods 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 33
- 238000000605 extraction Methods 0.000 claims description 23
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 235000013305 food Nutrition 0.000 claims description 10
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001212 derivatisation Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000001334 liquid-phase micro-extraction Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract 1
- 238000012864 cross contamination Methods 0.000 abstract 1
- 239000012086 standard solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 235000013361 beverage Nutrition 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 150000007530 organic bases Chemical class 0.000 description 6
- 235000013555 soy sauce Nutrition 0.000 description 6
- 240000008415 Lactuca sativa Species 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 235000012045 salad Nutrition 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 4
- 238000000622 liquid--liquid extraction Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012113 quantitative test Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-N sorbic acid group Chemical group C(\C=C\C=C\C)(=O)O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000013409 condiments Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000007983 food acid Nutrition 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a method for measuring sorbic acid and benzoic acid in foodstuff. The method is that a hollow fiber liquid-phase micro-extraction device is manufactured by using hollow fibers as a carrier, organic alkali as a receptor phase and organic solvents as an organic phase, afterwards, samples to be measured are extracted by using the hollow fiber liquid-phase micro-extraction device, the extracted receptor phase is subjected to gas chromatography detection, a gas chromatography spectrogram of the samples to be measured is obtained, and the content of the sorbic acid and/or the benzoic acid in the samples to be measured is calculated according to the gas chromatography spectrogram of the samples and the standard curve of the sorbic acid and/or the standard curve of the benzoic acid. According to the method for measuring the sorbic acid and the benzoic acid in the foodstuff, liquid-liquid-liquid three-phase microextraction and an on-line derivatization gas chromatographic method are used at the same time for measuring the benzoic acid and the sorbic acid in the foodstuff, the detection sensibility of the benzoic acid and the sorbic acid in the gas chromatography is greatly improved, and the method for measuring the sorbic acid and the benzoic acid in the foodstuff has the advantages of being simple in device, low in cost, little in consumption of the organic solvents, capable of avoiding cross contamination and the like.
Description
(1) technical field
The present invention relates to a kind of sorbic acid and benzoic method in food of measuring, by by hollow fiber liquid-phase micro extraction technique in conjunction with the sorbic acid adding in gas chromatography online derivatization method Fast Measurement beverage and condiment, benzoic content.
(2) background technology
Antiseptic Main Function is to suppress microbial growth and breeding, to extend the holding time of food, and inhibiting substances corruption.Sorbic acid and benzoic acid and sodium benzoate and sylvite are one of antiseptics being most widely used at present, and mould, yeast and bacterium are had to certain bacteriostasis, are usually used in the food such as fruit juice, vinegar, soy sauce, vegetables, beverage.Use excessive meeting harmful, China's food security standard limits the use amount of the antiseptic in food, and as content in soda can not exceed 0.2g/kg, in soy sauce, content can not exceed 1.0g/kg, and in salad, content can not exceed 1.0g/kg.
Benzoic acid and sorbic acid addition in actual sample is less.If adopt conventional gc analysis, often need to adopt complicated pretreatment process in sample, it carries out enrichment.In addition, benzoic acid and sorbic acid have certain polarity, adopt when gas chromatographic analysis, and corresponding chromatographic peak there will be hangover and responds lowly, is unfavorable for quantitative accurately.The present invention is the acceptor phase in hollow fiber liquid-phase micro-extraction using organic base, complete acidic materials as the extraction while of benzoic acid and sorbic acid, can also they be derived and change into corresponding methyl esters at gas chromatographic sample introduction mouth, further improve the sensitivity detecting.And the method for hollow fiber liquid-phase micro-extraction (HF-LPME), have that device is simple, with low cost, organic solvent consumption less, avoid the advantages such as cross pollution.Therefore apply Liquid-liquid-liquid microextraction-online derivative gas chromatography method and can well analyze sorbic acid and benzoic acid.
(3) summary of the invention
The object of the invention is to provide one and utilizes Liquid-liquid-liquid microextraction and online derivative gas chromatography method to detect sorbic acid and benzoic method simultaneously, the phase of accepting using organic base as extraction, in to sample, in the extraction of sorbic acid and benzoic acid, complete its derivatization process, and to the benzoic acid in numerous food and sorbic acid carry out simultaneously, qualitative and quantitative analysis fast and effectively.
The technical solution used in the present invention is:
The invention provides a kind of sorbic acid and benzoic method in food of measuring, particularly measure sorbic acid and benzoic method in fluid test sample, described method is: taking hollow fiber as carrier, taking organic base as acceptor phase, make hollow fiber micro-extraction device of liquid phase taking organic solvent as organic phase, then adopt hollow fiber micro-extraction device of liquid phase to extract testing sample, the acceptor of getting after extraction carries out gas chromatographic detection mutually, obtain the gas chromatography spectrogram of testing sample, respectively sorbic acid standard items and benzoic acid standard items are carried out to gas chromatographic analysis again, taking peak area separately as ordinate, make respectively sorbic acid typical curve and benzoic acid typical curve taking standard items concentration separately as horizontal ordinate, gas chromatography spectrogram per sample and sorbic acid typical curve and/or benzoic acid typical curve calculate sorbic acid and/or benzoic acid content in testing sample.
Further, described organic base is with 0.1～0.5g/ml organic base aqueous solution.
Further, described organic base is tetramethyl ammonium acetate (TMAAc).
Further, described organic solvent is n-octyl alcohol.
Further, described hollow fiber is polypropylene hollow fiber, and internal diameter is 600 μ m, wall thickness 200 μ m, and aperture is 0.2 μ m, most preferably (membrane aperture 0.2 μ is m) for film internal diameter 600 μ m, the thick 200 μ m of membranous wall for AccureL Q3/2 polypropylene hollow fiber.
Before employing hollow fiber micro-extraction device of liquid phase of the present invention extracts testing sample, first testing sample and sulfuric acid and anhydrous sodium sulfate are mixed and made into sample mix liquid, then adopt hollow fiber micro-extraction device of liquid phase to extract sample mix liquid; In described sample mix liquid, sulfuric acid and testing sample volume ratio are the preferred 2.75:100 of 2～3:100(), described sulfuric acid is mass concentration 98% concentrated sulphuric acid, the quality consumption of anhydrous sodium sulfate is counted 0.05～0.25g/mL with testing sample volume, preferably 0.05～0.20g/mL.
Further, described the extraction of sample mix liquid is carried out as follows: testing sample and sulfuric acid and anhydrous sodium sulfate are mixed and made into sample mix liquid, again by hollow fiber ultrasonic cleaning in absolute ethyl alcohol, naturally dry, then hollow fiber one end closure (is connected to fiber one end by bar-shaped interface, make microsyringe can insert fiber core bottom to inject or to remove receptor solution, be placed on by the other end on the syringe needle of micro-sampling pin), make pretreated hollow fiber; Then after pretreated hollow fiber fully being soaked in organic phase, by washed with de-ionized water, obtain the hollow fiber containing organic phase, then acceptor is injected mutually containing the hollow fiber chamber of organic phase and makes hollow fiber liquid-phase extraction device; Hollow fiber liquid-phase extraction device is placed in to sample mix liquid, under the effect of stirrer, extracts, under the stirring rate of 100～1200r/min, extract 20～120min; Described acceptor is tetramethyl ammonium acetate mutually, and described organic phase is n-octyl alcohol; In described sample mix liquid, in sample mix liquid, sulfuric acid and testing sample volume ratio are 2.75:100, and described sulfuric acid is mass concentration 98% concentrated sulphuric acid, and the quality consumption of anhydrous sodium sulfate is counted 0.2g/mL with testing sample volume; Described hollow fiber is polypropylene hollow fiber, and internal diameter is 600 μ m, wall thickness 200 μ m, and aperture is 0.2 μ m, described hollow fiber length is 2cm.
Further, described gas chromatographic detection condition of the present invention is: gas chromatograph is Varian CP-3800 gas chromatograph, adopts UA-5 metal capillary post, column temperature: 50 DEG C of initial temperature, be raised to 200 DEG C with 10 DEG C/min speed, and keep 5min; Injector temperature is 320 DEG C, and detector temperature is 250 DEG C, split ratio 30:1; Carrier gas is N
2; Post flow 1.0mL/min.
The making of sorbic acid typical curve: accurately take sorbic acid 0.0235g and be placed in 500mL volumetric flask, use deionized water constant volume, ultrasonic dissolution, be made into the standard solution that concentration is 50mg/L, again with deionized water be diluted to 50,20,10,5,1,0.5,0.1mg/L sorbic acid standard solution, be stored in the refrigerator of 4 DEG C.Measure respectively sorbic acid concn and be 0.1,0.5,1,5,10,20,50mg/L standard solution carries out gas chromatographic analysis, obtains peak area, then taking peak area as ordinate, concentration of standard solution is horizontal ordinate, draws sorbic acid typical curve.
The making of benzoic acid typical curve: accurately take benzoic acid 0.0241g and be placed in 500mL volumetric flask, use deionized water constant volume, ultrasonic dissolution, is made into the standard solution that concentration is 50mg/L, be diluted to respectively again 20,10,5,1,0.5,0.1mg/L standard solution, be stored in the refrigerator of 4 DEG C.Measure respectively concentration of benzoic acid and be 0.1,0.5,1,5,10,20, the peak area of 50mg/L standard solution, then taking peak area as ordinate, concentration of standard solution is horizontal ordinate, drawing standard curve.
GC conditions is: gas chromatograph is Varian CP-3800 gas chromatograph, adopts UA-5 metal capillary post (30m × 0.25mm i.d. × 0.25 μ m thickness, 50% methyl polysiloxane, Japan), column temperature: 50 DEG C of initial temperature, be raised to 200 DEG C with 10 DEG C/min speed, keep 5min.Injector temperature is 320 DEG C, and detector temperature is 250 DEG C, split ratio 30:1; Carrier gas is N
2; Post flow 1.0mL/min.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: the present invention's application Liquid-liquid-liquid microextraction-online derivative gas chromatography method is measured benzoic acid and sorbic acid in food simultaneously, their detection sensitivities in gas chromatography are not only greatly improved, and the method has that device is simple, with low cost, organic solvent consumption less, avoid the advantages such as cross pollution, therefore the method is more suitable for the analysis fast and accurately of benzoic acid and sorbic acid in actual sample.
(4) brief description of the drawings
Fig. 1 is sorbic acid, benzoic typical curve, and curve a is sorbic acid typical curve, and the standard equation of curve a is y=40593x+4719.0(R
2=0.9994); Curve b is benzoic acid typical curve, and the standard equation of curve b is y=133269x+22325(R
2=0.9934).
Fig. 2 is sorbic acid and benzoic content gas chromatogram in 4 kinds of testing samples in embodiment 4.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Tetramethyl ammonium acetate (TMAAc) solid is purchased from Aladdin; Tetramethylammonium hydroxide (TMAH) 25% aqueous solution is purchased from lark prestige; Sulfuric acid (analyzing pure) is purchased from Quzhou Ju Hua reagent company limited; N-octyl alcohol (analyzing pure) is purchased from 5-linked chemical plant; Anhydrous sodium sulfate (analyzing pure) is purchased from Shishewei Chemical Co., Ltd., Shanghai; Sorbic acid (>99.0%) is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Benzoic acid (>99.5%) is purchased from Shanghai Lai Ze chemical institute.
(membrane aperture 0.2 μ is m) purchased from Membrana (WuppertaL, Germany) for film internal diameter 600 μ m, the thick 200 μ m of membranous wall for AccureL Q3/2 polypropylene hollow fiber;
Mirinda, plum juice, salad, soy sauce and cough mixture, purchased from local supermarket and pharmacy.
FINNGAN Trace DSQ gas chromatograph-mass spectrometer (power & light company, the U.S.) comprises NIST02 spectrum storehouse.CP-3800 gas chromatograph (the Varian U.S.), configuration flame ionization ditector; C-MAG HS4 heating magnetic stirring apparatus (IKA Germany).
Embodiment 1: liquid-liquid-liquid three-phase hollow fiber micro-extraction is in conjunction with the accuracy rate of benzoic acid and/or sorbic acid in online derivatization method working sample
Sorbic acid and benzoic acid final concentration are the preparation of 20mg/L sample: accurately take respectively 2mg benzoic acid and 2mg sorbic acid with analytical balance, then transfer in 100mL volumetric flask, with deionized water dissolving, constant volume is to scale mark.Get again the 98wt% concentrated sulphuric acid (sulfuric acid final concentration is 0.2mol/L) and the 2g anhydrous sodium sulfate that 10mL dilution adds 275 μ L and make sample mix liquid, then get an end closure (one end is placed on the syringe needle of micro-sampling pin), long hollow fiber (AccureL Q3/2 polypropylene hollow fiber) soaking at room temperature 20s in n-octyl alcohol for 2cm, then remove residual n-octyl alcohol with deionized water rinsing.Then inject mutually hollow fiber chamber with the TMAAc aqueous solution 3 μ L that micro-sampling pin is got 0.25g/ml as acceptor and make hollow fiber liquid-phase extraction device.Hollow fiber liquid-phase extraction device is placed in to sample mix liquid, opens magnetic stirring apparatus, with the stirring rate extraction 40min of 500r/min, then acceptor after pumpback 1 μ L extraction carries out gas chromatographic analysis mutually, obtains the gas chromatogram of testing sample.Gas chromatograph is Varian CP-3800 gas chromatograph, adopts UA-5 metal capillary post (30m × 0.25mm i.d. × 0.25 μ m thickness, 50% methyl polysiloxane, Japan), column temperature: 50 DEG C of initial temperature, be raised to 200 DEG C with 10 DEG C/min speed, keep 5min.Injector temperature is 320 DEG C, and detector temperature is 250 DEG C, split ratio 30:1; Carrier gas is N
2; Post flow 1.0mL/min.
The making of sorbic acid typical curve: accurately take sorbic acid 0.0235g and be placed in 500mL volumetric flask, use deionized water constant volume, ultrasonic dissolution, be made into the standard solution that concentration is 50mg/L, again respectively with deionized water be diluted to 50,20,10,5,1,0.5,0.1mg/L standard solution, be stored in the refrigerator of 4 DEG C.Adopt that Varian CP-3800 gas chromatograph for determination sorbic acid concn is 0.1,0.5,1,5,10,20, the peak area of 50mg/L standard solution, then taking peak area as ordinate, concentration of standard solution is horizontal ordinate, and drawing standard curve, is shown in Fig. 1.
The making of benzoic acid typical curve: accurately take benzoic acid 0.0241g and be placed in 500mL volumetric flask, use deionized water constant volume, ultrasonic dissolution, be made into the standard solution that concentration is 50mg/L, again respectively with deionized water be diluted to 50,20,10,5,1,0.5,0.1mg/L standard solution, be stored in the refrigerator of 4 DEG C.Adopt that Varian CP-3800 gas chromatograph for determination concentration of benzoic acid is 0.1,0.5,1,5,10,20, the peak area of 50mg/L standard solution, then taking peak area as ordinate, concentration of standard solution is horizontal ordinate, and drawing standard curve, is shown in Fig. 1.
Obtain sorbic acid and benzoic concentration in testing sample according to known sample gas chromatography spectrogram and sorbic acid typical curve and benzoic acid typical curve: obtaining sorbic acid peak area by stratographic analysis software is 775986, benzoic acid peak area is 2621070, then according to sorbic acid and benzoic typical curve, calculating Determination of sorbic is 19.0mg/L, benzoic acid content is 19.5mg/L, compared with being 20mg/L with actual content, the accuracy rate of this method is 95%.
Embodiment 2: liquid-liquid-liquid three-phase hollow fiber micro-extraction is the mensuration to Mirinda Benzene in Beverages formic acid and sorbic acid in conjunction with online derivatization method
Liquid-liquid-liquid three-phase hollow fiber micro-extraction step: first by the ultrasonic processing of ultrasonic washing instrument 5min for 10ml testing sample (Mirinda beverage), then with 50 times of deionized water dilutions, get again the 98wt% concentrated sulphuric acid (sulfuric acid final concentration is 0.2mol/L) and the 2g anhydrous sodium sulfate that 10mL dilution adds 275 μ L and make sample mix liquid, then get an end closure (one end is placed on the syringe needle of micro-sampling pin), long hollow fiber (AccureL Q3/2 polypropylene hollow fiber) soaking at room temperature 20s in n-octyl alcohol for 2cm, remove residual n-octyl alcohol with deionized water rinsing again.Then inject mutually hollow fiber chamber with the TMAAc aqueous solution 3 μ L that micro-sampling pin is got 0.25g/ml as acceptor and make hollow fiber liquid-phase extraction device.Hollow fiber liquid-phase extraction device is placed in to sample mix liquid, opens magnetic stirring apparatus, with the stirring rate extraction 40min of 500r/min, then acceptor after pumpback 1 μ L extraction carries out gas chromatographic analysis mutually, obtains the gas chromatogram of testing sample.Gas chromatograph is Varian CP-3800 gas chromatograph, adopts UA-5 metal capillary post (30m × 0.25mm i.d. × 0.25 μ m thickness, 50% methyl polysiloxane, Japan), column temperature: 50 DEG C of initial temperature, be raised to 200 DEG C with 10 DEG C/min speed, keep 5min.Injector temperature is 320 DEG C, and detector temperature is 250 DEG C, split ratio 30:1; Carrier gas is N
2; Post flow 1.0mL/min.
According to sorbic acid and benzoic concentration in testing sample gas chromatography peak area and sorbic acid typical curve and benzoic acid typical curve acquisition testing sample, known benzoic peak area is 17110076mv, sorbic acid peak area is 2161831mv, the making of the standard items curve of benzoic acid and sorbic acid is with embodiment 1, known Determination of sorbic is 53.14mg/kg, benzoic acid content is 128.22mg/kg, liquid-liquid extraction traditional from the known effect of extracting of the present invention of data and comparative example is similar, but liquid-liquid-liquid three-phase hollow fiber micro-extraction is more easy at survey fixed cycle operator in conjunction with online derivatization method.Its enrichment times is far longer than classic method, therefore in the time measuring, by 50 times of Sample Dilutions.
Embodiment 3 liquid-liquid-liquid three-phase hollow fiber micro-extractions in conjunction with online derivatization method to Mirinda Benzene in Beverages formic acid and sorbic acid setting-out line scope, detection limit
Under optimal conditions, the range of linearity, the detection limit of this method are investigated: the sample liquid that configures respectively sorbic acid and benzoic acid final concentration and be 0.1～50mg/L, other operate with embodiment 1, the results are shown in Table 1, show that sorbic acid and benzoic acid have good linear relationship in the concentration range of 0.1～50mg/L, related coefficient is respectively 0.9994 and 0.9934.Be greater than 3 by signal to noise ratio (S/N ratio) (S/N) and determine each analyte detection limit, obtaining sorbic acid is 17.8 μ g/L, and benzoic acid is 2.1 μ g/L, can see the low of detection limit completely, so be specially adapted to the analysis of trace materials.
Table 1 range of linearity, detection limit
Liquid-liquid extraction Mirinda Benzene in Beverages formic acid and sorbic acid that comparative example 1 use is traditional
Tradition liquid-liquid extraction step: get after the ultrasonic processing of testing sample (Mirinda beverage) 20ml ultrasonic cleaning instrument 5min, with salt acid for adjusting pH be 1.6 left and right, add 5ml extracted with diethyl ether once, lower floor's solution extracts once with 5ml ether again, merge ether layer twice, in the water bath with thermostatic control of 50 DEG C, be evaporated to dry, with absolute methanol dissolve after be settled to 1ml.Draw 1 μ L and carry out gas chromatographic analysis, GC conditions and sorbic acid typical curve and benzoic acid typical curve are with embodiment 1.
It is 48.8mg/kg that traditional liquid-liquid extraction records Determination of sorbic, and benzoic acid content is 136.8mg/kg.
Embodiment 4: the quantitative test of liquid-liquid-liquid three-phase hollow fiber micro-extraction to benzoic acid in 4 kinds of testing samples (Mirinda, plum juice, salad, soy sauce) and sorbic acid
1. first by the ultrasonic processing of ultrasonic washing instrument 5min for Mirinda 10mL testing sample, then with 50 times of deionized water dilutions, get again 10mL dilution, then add the 98wt% concentrated sulphuric acid (sulfuric acid final concentration 0.2mol/L) and the 2g anhydrous sodium sulfate of 275 μ L to make sample mix liquid, then get hollow fiber (AccureL Q3/2 polypropylene hollow fiber) (one end is placed on the syringe needle of micro-sampling pin) soaking at room temperature 20s in n-octyl alcohol of an end closure, then remove residual n-octyl alcohol with deionized water rinsing.Then inject mutually hollow fiber chamber with the TMAAc aqueous solution 3 μ L that micro-sampling pin is got 0.25g/ml as acceptor, make hollow fiber liquid micro-extraction device.Hollow fiber liquid micro-extraction device is placed in to sample mix liquid, opens magnetic stirring apparatus, with the stirring rate extraction 40min of 500r/min.
The same Mirinda of extraction of plum juice, salad, soy sauce testing sample.
2. after extraction finishes, respectively by the acceptor phase (Mirinda, plum juice, salad, the each 1 μ L of soy sauce) after pin pumpback 1 μ L extraction, throw respectively gas chromatographic sample introduction mouth into, gas chromatograph is Varian CP-3800 gas chromatograph, adopts UA-5 metal capillary post (30m × 0.25mm i.d. × 0.25 μ m thickness, 50% methyl polysiloxane, Japan), column temperature: 50 DEG C of initial temperature, be raised to 200 DEG C with 10 DEG C/min speed, keep 5min.Injector temperature is 320 DEG C, and detector temperature is 250 DEG C, split ratio 30:1; Carrier gas is N
2; Post flow 1.0mL/min, obtains respectively the gas chromatogram of benzoic acid and sorbic acid, as shown in Figure 2.
3. benzoic acid in testing sample and sorbic acid are carried out to quantitative test: the making of the standard items curve of benzoic acid and sorbic acid is with embodiment 1.According to the peak area of the gas chromatography of testing sample, typical curve, the concentration of benzoic acid and/or sorbic acid in acquisition testing sample, in table 2.
The content of benzoic acid and sorbic acid in table 2 testing sample
ND is not for detecting.
Claims (3)
1. measure sorbic acid and benzoic method in food for one kind, it is characterized in that described method is: testing sample and sulfuric acid and anhydrous sodium sulfate are mixed and made into sample mix liquid, in described sample mix liquid, sulfuric acid and testing sample volume ratio are 2～3:100, described sulfuric acid is mass concentration 98% concentrated sulphuric acid, the quality consumption of anhydrous sodium sulfate is counted 0.05～0.25g/mL with testing sample volume, taking hollow fiber as carrier, taking 0.1～0.5g/ml tetramethyl ammonium acetate aqueous solution as acceptor phase, make hollow fiber micro-extraction device of liquid phase taking n-octyl alcohol as organic phase, then adopt hollow fiber micro-extraction device of liquid phase to extract testing sample, the acceptor of getting after extraction carries out gas chromatographic detection mutually, obtain the gas chromatography spectrogram of testing sample, respectively sorbic acid standard items and benzoic acid standard items are carried out to gas chromatographic analysis again, taking peak area separately as ordinate, make respectively sorbic acid typical curve and benzoic acid typical curve taking standard items concentration separately as horizontal ordinate, gas chromatography spectrogram per sample and sorbic acid typical curve and/or benzoic acid typical curve calculate sorbic acid and/or benzoic acid content in testing sample, described hollow fiber is polypropylene hollow fiber, and internal diameter is 600 μ m, wall thickness 200 μ m, and aperture is 0.2 μ m.
2. measure as claimed in claim 1 sorbic acid and benzoic method in food, it is characterized in that described the extraction of sample mix liquid being carried out as follows: testing sample and sulfuric acid and anhydrous sodium sulfate are mixed and made into sample mix liquid, again by hollow fiber ultrasonic cleaning in absolute ethyl alcohol, naturally dry, then by hollow fiber one end closure, make pretreated hollow fiber; Then after pretreated hollow fiber fully being soaked in organic phase, by washed with de-ionized water, obtain the hollow fiber containing organic phase, then acceptor is injected mutually containing the hollow fiber chamber of organic phase and makes hollow fiber liquid-phase extraction device; Hollow fiber liquid-phase extraction device is placed in to sample mix liquid, under the effect of stirrer, extracts, under the stirring rate of 100～1200r/min, extract 20～120min; Described acceptor phase tetramethyl ammonium acetate, described organic phase is n-octyl alcohol; In described sample mix liquid, sulfuric acid and testing sample volume ratio are 2.75:100, and described sulfuric acid is mass concentration 98% concentrated sulphuric acid, and the quality consumption of anhydrous sodium sulfate is counted 0.2g/mL with testing sample volume; Described hollow fiber is polypropylene hollow fiber, and internal diameter is 600 μ m, wall thickness 200 μ m, and aperture is 0.2 μ m, described hollow fiber length is 2cm.
3. measure as claimed in claim 1 sorbic acid and benzoic method in food, it is characterized in that described gas chromatographic detection condition is: gas chromatograph is Varian CP-3800 gas chromatograph, adopt UA-5 metal capillary post, column temperature: 50 DEG C of initial temperature, be raised to 200 DEG C with 10 DEG C/min speed, keep 5min; Injector temperature is 320 DEG C, and detector temperature is 250 DEG C, split ratio 30:1; Carrier gas is N
2; Post flow 1.0mL/min.
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| CN105116084B (en) * | 2015-07-31 | 2017-10-20 | 巨化集团技术中心 | The gas chromatography analysis method of 3,3,3 trifluoroacetic acids in a kind of process waste liquor |
| CN108872437B (en) * | 2018-07-25 | 2021-06-04 | 浙江工业大学 | Method for determining preservative by combining hollow fiber membrane microextraction with online derivatization-gas chromatography |
| CN110132955A (en) * | 2019-06-14 | 2019-08-16 | 酒泉市食品检验检测中心 | The method of perchlorate in dispersive liquid-liquid microextraction-smart phone colorimetric estimation food |
| CN110609100A (en) * | 2019-09-26 | 2019-12-24 | 上海美农生物科技股份有限公司 | Method for simultaneously detecting 6 organic acids in compound acidifier by gas chromatography |
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