CN103048414B - Method for detecting fatty acid content in rice fat - Google Patents
Method for detecting fatty acid content in rice fat Download PDFInfo
- Publication number
- CN103048414B CN103048414B CN201210525239.1A CN201210525239A CN103048414B CN 103048414 B CN103048414 B CN 103048414B CN 201210525239 A CN201210525239 A CN 201210525239A CN 103048414 B CN103048414 B CN 103048414B
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- charge ratio
- ion
- rice
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 66
- 235000009566 rice Nutrition 0.000 title claims abstract description 65
- 239000000194 fatty acid Substances 0.000 title claims abstract description 57
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 51
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 51
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 47
- 240000007594 Oryza sativa Species 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 65
- 241000209094 Oryza Species 0.000 claims abstract description 64
- 238000005886 esterification reaction Methods 0.000 claims abstract description 45
- 230000032050 esterification Effects 0.000 claims abstract description 39
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 25
- 238000001819 mass spectrum Methods 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005815 base catalysis Methods 0.000 claims abstract description 9
- 238000005070 sampling Methods 0.000 claims abstract 2
- 239000000523 sample Substances 0.000 claims description 52
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 27
- 238000002552 multiple reaction monitoring Methods 0.000 claims description 26
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 7
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 claims description 6
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 claims description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000012113 quantitative test Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 claims description 4
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 claims description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 230000009514 concussion Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012054 meals Nutrition 0.000 claims description 4
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 235000013339 cereals Nutrition 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 3
- 229960001947 tripalmitin Drugs 0.000 claims description 3
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 claims description 2
- DVWSXZIHSUZZKJ-UHFFFAOYSA-N 18:3n-3 Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OC DVWSXZIHSUZZKJ-UHFFFAOYSA-N 0.000 claims description 2
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 claims description 2
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 claims description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 2
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 claims description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 2
- 229940073769 methyl oleate Drugs 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 50
- 241000143437 Aciculosporium take Species 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000002860 competitive effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000010813 internal standard method Methods 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004885 tandem mass spectrometry Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000004519 grease Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 235000013405 beer Nutrition 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 235000021588 free fatty acids Nutrition 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 235000019581 fat taste sensations Nutrition 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 240000000950 Hippophae rhamnoides Species 0.000 description 1
- 235000003145 Hippophae rhamnoides Nutrition 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001319 headspace solid-phase micro-extraction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003387 muscular Effects 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000005314 unsaturated fatty acid group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for detecting fatty acid content in rice fat. The method comprises the following steps of: carrying out base-catalysis methyl esterification and solid phase microextraction synchronously on a rice sample in a headspace bottle by means of a multifunctional sample injector, and then detecting and performing quantitative analysis on the fatty acid content in the rice fat after the rice sample enters a gas chromatography-tandem mass spectrum (GC-MS-MS). According to the invention, the on-line methyl esterification, the solid-phase microextraction and the gas chromatography-tandem mass spectrum technology are adopted, the five steps of methyl esterification, extraction, enrichment, sampling and detection are completed at the same time during one process, the operation is simple, and the consumed time is short; moreover, water acts as a base body during the methyl esterification reaction, so that the competitive adsorption of an extracting head to methyl alcohol and volatile substances is lowered, and the extraction and pre-enrichment of fatty acid methyl ester by the solid phase microextraction are improved effectively; and the minimum detection limit of fatty acid is 0.001-0.049 micro g/L, and is obviously lower than the minimum detection limit, 4.0mg/L, of an internal standard method which is used for performing quantitative determination on oil fatty acid.
Description
Technical field
The present invention relates to a kind of analyzing detecting method of fatty acid, be specifically related to the detection method of fatty acid in a kind of rice fat.
Background technology
Fat is the important component of rice, and the principal ingredient of rice fat is unsaturated fatty acid.Unsaturated fatty acid has many benefits to human body, has functions such as alleviating cholesterol excessive in blood, enhancing cell leakage, prevention cardiac muscular tissue and artery sclerosis.Because fatty deterioration is very fast, hydrolysis easily occurs free fatty acid is increased, and oxidation easily occurs unsaturated fatty acid and cause the minimizing of unsaturated fatty acid, thereby often acidity increases the rice that causes ageing, fragrance scatters and disappears.Therefore, the content of the fatty acid of rice fat and composition can be used as the evaluation means of rice quality.As auxiliary material conventional in Beer Brewage, rice has the beer production cost of reduction, adjusts the meanings such as wheat juice component.The fatty acid especially impact of the fermenting property of unsaturated fatty acid on yeast and beer quality is very large; Therefore, measure rice fatty acid the beer of production high-quality is had to certain directive significance.
In prior art, have multiple means to can be used for detecting the fatty acid in rice fat, methyl esterification of fatty acid can reduce vapourizing temperature, improves separating effect, is conducive to vapor-phase chromatography and separates and measure one by one its composition and content.What in the esterification of grease is analyzed, often adopt at present, has two kinds of means: (1) is resolved into fatty acid by grease and carried out esterification again; (2) directly grease and methyl alcohol are carried out to alcoholysis reaction and obtain esterification product.First method is generally in ethanol after saponification, then decomposes with mineral acid acidifying, and the free fatty acid finally decompositing by extracted by ether, then carries out esterification to fatty acid.What second method was conventional has boron trifluoride esterification method, alkaline process esterification method and acid system esterification method, and wherein boron trifluoride catalysis methyl esters rate is high, but its strong toxicity is difficult for preservation, and unfavorable operator uses; Acid catalysis esterification grease has that reaction is slow, methyl esters rate is low and require temperature high, is not suitable for solid phase micro-extraction technique.Therefore, most methods have all more or less adopted organic solvent, and complex steps.Hui Ruihua etc. utilize Soxhlet extracting or organic solvent to extract after fat, carry out again esterification sample introduction, adopt GC-MS or GC-FID to analyze the fatty acid (gas chromatography-mass spectrometry analysis of fatty acid in the rice grease of the different places of production of rice grease, mass spectrum journal, 2008,29 (6): 349 ~ 352).The method has not only adopted organic solvent, also must first fat be extracted from rice to be measured, and step is too loaded down with trivial details.In addition; there is researcher directly to add esterifying reagent esterification to rice; then add excessive NaCl, water and sherwood oil layering; after supernatant liquid is dewatered, under the protection of nitrogen, concentrate and obtain fatty acid methyl ester; last sample introduction GC-FID analyzing and testing (Chemical Composition and Fatty Acid Analysis of Saudi HassawiRice Oryza sativa L.; Pakistan Journal of Biological Sciences; 2002,5 (2): 212 ~ 214).The method has been avoided the extraction step of fatty acid, but still has adopted a large amount of organic solvents, but also will under the protection of nitrogen, concentrate, and step is still loaded down with trivial details, and the test sample time is long, can not meet a large amount of needs that detect in actual production.
Patent 201110462886.8 discloses " esterification-headspace solid-phase microextraction in bottle-gas chromatography combined with mass spectrometry is measured the detection method of beer free fatty acid ", and the method has adopted acid catalysis esterification method to carry out esterification in bottle to sample.But fat content is high in rice, free fatty acid is few, and the acid catalysis esterification method that therefore this method adopts is not suitable for the analysis of fatty acid in rice.Owing to thering is volatile feature as the methyl alcohol of methyl esterification reagent, therefore when esterification reaction of organic acid occurs in head space bottle, methyl alcohol enters head space part, cause fatty acid methyl ester rate to reduce, and affect effect of extracting, even can there is the competitive adsorption of extracting head to volatile matter and methyl alcohol, be unfavorable for the enrichment of fatty acid methyl ester.In addition, in prior art, seldom there is the report of quantitative detection fatty acid, the detection limit that wherein has article report to adopt inner mark method ration to measure oil fatty acid is only the fatty acid in 4.0mg/L(Sea-buckthorn Oil with Capillary Gas Chromatography by Using Internal Standard Method, China's grain and oil journal, 2008,23 (1): 198 ~ 202).
In the present invention, esterification reaction of organic acid is taking water as matrix, methanol aqueous solution reduces the adverse effect of methyl alcohol to extracting head greatly, base catalysis fat generates fatty acid methyl ester, enter afterwards head space part, solid-phase microextraction completes extraction and the preenrichment to fatty acid methyl ester by being coated on the polymeric coating layer on quartz fibre surface, after desorb, utilizes GC-MS-MS to separate detection.
Summary of the invention
The present invention is directed to the problems referred to above that prior art exists, a kind of fatty acid method that detects rice fat is provided, the method is used solvent few, and step is simple, and accuracy in detection is high, can effectively measure fast rice fatty acid.
Technical scheme of the present invention: a kind of method that detects content of fatty acid in rice fat, rice sample carries out by means of Multifunctional sample injection device base catalysis esterification and solid-phase microextraction in head space bottle simultaneously, enter afterwards that gas chromatography-tandem mass spectrum combined instrument (GC-MS-MS) detects and quantitative test rice fat in content of fatty acid.
The present invention includes following steps:
1. the setting of instrument parameter:
A. Multifunctional sample injection device: temperature 60 C, time 60min, adopts 85 μ m PA extracting head;
B. gas chromatograph: DB-225MS capillary column, 30m × 0.25mm × 0.25 μ m; Carrier gas is high-purity helium, constant current mode, and injection port flow is 1.0ml/min, Splitless injecting samples; Column oven keeps 2min at 50 DEG C, is then warming up to 230 DEG C with 5 DEG C/min;
C. tandem mass spectrum: 250 DEG C of transmission line temperature, electron impact ion source (EI), electron energy is 70Ev, and ion source temperature is 200 DEG C, and collision gas (argon gas) pressure is 1.5mTorr, and detection mode adopts multiple-reaction monitoring (MRM);
The testing conditions of each fatty acid methyl ester under table 1 tandem mass spectrum multiple-reaction monitoring (MRM) pattern
2. production standard curve: take appropriate myristin, tripalmitin, glyceryl tristearate, olein, Trilinoleyl glyceride and three glyceryl linolenates, be mixed with the mixed mark solution of variable concentrations with toluene.Get 2mL sample solution in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL 11mmol/L, add the mixed mark of 10 μ L solution in head space bottle, making its concentration gradient is 0.5 μ g/L, 2.5 μ g/L, 12.5 μ g/L, 50 μ g/L and 100 μ g/L.Head space bottle screws in the insulation can that is transferred to 60 DEG C after bottle cap, inserts 85 μ m PA extracting head, completes after absorption, extracting head is inserted to gas chromatograph injection port, and desorb 2min ensures complete desorb at 250 DEG C; After adopting instrument to detect, not add mixed target sample as blank, measure respectively the peak area of each fatty acid methyl ester after mark-on, after deduction blank, taking the peak area added value of each component after mark-on as y, adding scalar is x, draw a typical curve, typical curve was forced initial point.
3. the detection of testing sample: rice is pulverized after three times through Cyclone mill, is dissolved in 25mg rice meal in 200mL water, fully stirs.Get 2mL sample diluting liquid in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL 11mmol/L, screw head space bottle cap.Solid-phase microextraction completes by means of Multifunctional sample injection device, and concrete operations are: automatic sampler moves to sample bottle in insulation can, inserts 85 μ m PA extracting head, makes it under 60 DEG C, 250r/min concussion condition, adsorb 1h.After having adsorbed, fiber head moves into gas chromatographic sample introduction mouth desorb 2min at 250 DEG C.Utilize typical curve to calculate the content of various triglyceride in rice to be measured, obtain content of fatty acid in rice fat by conversion.
Preferably, described step 1. collision gas (argon gas) pressure of tandem mass spectrum is 1.5mTorr, and tandem mass spectrum multiple-reaction monitoring parameter.
Preferably, described esterification reaction of organic acid is taking water as matrix, and through ultrapure water system, processing obtains water, and described ultrapure water system is Milli-Q ultrapure water system (Millipore).
Preferably, described step 3. middle rice is pulverized three times through Cyclone mill, and grain fineness can be passed through 120 mesh sieves, and described Cyclone mill is Cyclotec 1093 Cyclone mills.
Beneficial effect of the present invention is: the present invention adopts online esterification solid-phase microextraction and gas chromatography-tandem mass spectrum coupling technique, compared with conventional detection method, possesses following advantage:
(1) directly base catalysis esterification analysis rice fatty acid in head space bottle of fat in rice, in esterification reaction of organic acid taking water as matrix, compared with not adding water, reduce the competitive adsorption of extracting head to methyl alcohol and volatile matter, effectively improved extraction and the preenrichment of solid-phase microextraction to fatty acid methyl ester;
(2) the present invention has completed esterification, extraction, enrichment, sample introduction and detection five steps in a process simultaneously, not only simple to operate, robotization, consuming time short, and whole process only needs 2h, and it is few to expend solvent;
(3) tandem mass spectrum is according to the one-level mass spectrogram of object, select suitable parent ion, under multiple-reaction monitoring condition determine quota ion to qualitative ion pair, and optimize optimum collision energy, determine tandem mass spectrum detected parameters, realize from complicated matrix and chaff interference and identified target compound, ensured the reliability of qualitative, quantitative result;
(4) to have set up triglyceride be the method for fatty acid in external standard method quantitative measurement rice fat in the present invention, and fatty acid lowest detection is limited to 0.001 ~ 0.049 μ g/L, is starkly lower than and adopts inner mark method ration to measure the minimum detectability 4.0mg/L of oil fatty acid.
(5) applied widely, can be applicable to content and the composition of fatty acid in the solid samples such as rice, barley, Fructus Hordei Germinatus, hops.
Brief description of the drawings
Fig. 1 is methyl myristate multiple-reaction monitoring chromatogram;
Fig. 2 is methyl hexadecanoate multiple-reaction monitoring chromatogram;
Fig. 3 is methyl stearate multiple-reaction monitoring chromatogram;
Fig. 4 is methyl oleate multiple-reaction monitoring chromatogram;
Fig. 5 is methyl linoleate multiple-reaction monitoring chromatogram;
Fig. 6 is methyl linolenate multiple-reaction monitoring chromatogram;
Fig. 7 is the extraction efficiencies of different extracting head to each fatty acid methyl ester.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1:
A kind of method that detects content of fatty acid in rice, rice sample carries out by means of Multifunctional sample injection device base catalysis esterification and solid-phase microextraction in head space bottle simultaneously, enter afterwards content of fatty acid in gas chromatography-tandem mass spectrum combined instrument (GC-MS-MS) detection quantitative test rice fat, comprise the following steps:
1. the setting of instrument parameter:
A. Multifunctional sample injection device: temperature 60 C, time 60min, adopts 85 μ m PA extracting head;
B. gas chromatograph: DB-225MS capillary column, 30m × 0.25mm × 0.25 μ m; Carrier gas is high-purity helium, constant current mode, and injection port flow is 1.0ml/min, Splitless injecting samples; Column oven keeps 2min at 50 DEG C, is then warming up to 230 DEG C with 5 DEG C/min;
C. tandem mass spectrum: 250 DEG C of transmission line temperature, electron impact ion source (EI), electron energy is 70Ev, and ion source temperature is 200 DEG C, and collision gas (argon gas) pressure is 1.5mTorr, and detection mode adopts multiple-reaction monitoring (MRM);
The testing conditions of each fatty acid methyl ester under table 1 tandem mass spectrum multiple-reaction monitoring (MRM) pattern
2. Optimal Experimental:
A, based on GC-MS/MS parent ion and daughter ion multiple-reaction monitoring pattern one to one, analyzes multiple fatty acid methyl ester by setting multiple time periods and scan channel simultaneously.First by gas phase separation and single-stage full scan, determine that material goes out peak retention time and one-level fragmention, the high one-level fragmention of selection intensity is as parent ion, application multiple-reaction monitoring pattern ionizes bombardment under different collision energies to parent ion, find the stronger secondary fragmention of generation as daughter ion, now making final daughter ion of monitoring produce the loudest collision energy is final optimization pass collision energy.Multiple-reaction monitoring (MRM) condition of 6 kinds of fatty acid methyl esters is in table 1, and chromatogram is as shown in accompanying drawing 1 ~ 6.
B adds successively after 2mL sample diluting liquid, 0.5mL 0.4mol/L potassium hydroxide/methyl alcohol in head space bottle, be 55min at extraction time, extraction temperature be under 55 DEG C and the stir speed (S.S.) condition that is 250r/min relatively the extracting head of 85 μ m CAR/PDMS, 7 μ mPDMS, 65 μ mPDMS/DVB and tetra-kinds of different fibers of 85 μ mPA to fatty acid methyl ester adsorption efficiency.As shown in Figure 7, relative peak area is the ratio of each component response peak area and this component peak response peak area.Contrast is found by experiment, the response maximum of fatty acid methyl ester while using 85 μ m PA extracting head.When this method analytic sample, select 85 μ m PA extracting head.
C salt adding can reduce the solubleness of polar organic matter in water, i.e. salting out impels fatty acid methyl ester to enter head space and is extracted head absorption.In head space bottle, add after 2mL sample diluting liquid, 0.5mL 0.4mol/L potassium hydroxide/methyl alcohol, add respectively 0.0g, 0.5g, 1.0g and 1.5g NaCl, be 55min at extraction time, extraction temperature is 55 DEG C and extracts comparison fatty acid methyl ester adsorption efficiency under the condition that stir speed (S.S.) is 250r/min.Contrast is found by experiment, the response maximum of fatty acid methyl ester while adding 1.0g NaCl.Control methods is identical with b.When this method analytic sample, select to add 1.0gNaCl.
The reaction of d methyl esters is reversible reaction, and the amount of reaction substrate methyl alcohol and catalyzer potassium hydroxide has significant effect for reaction rate and the extent of reaction.In head space bottle, add after 2mL sample diluting liquid and 1.0g NaCl, optimize respectively the amount of hydro-oxidation potassium and methyl alcohol, be 55min at extraction time, extraction temperature is 55 DEG C and extracts the effect of extracting that compares esterification efficiency and extracting head under the condition that stir speed (S.S.) is 250r/min.In the time that methyl alcohol addition is constant, the response maximum of fatty acid methyl ester while adding 0.4mol/L potassium hydroxide/methyl alcohol of 20 μ L; In the time that 0.4mol/L potassium hydroxide/methyl alcohol addition is constant, the response maximum of fatty acid methyl ester while adding the methyl alcohol of 0.75mL.Control methods is identical with b.When this method analytic sample, select to add 0.75mL11mmol/L potassium hydroxide/methyl alcohol.
E is 55min at extraction time, under stir speed (S.S.) 250r/min condition, and the relatively effect of extracting of esterification efficiency and extracting head at 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C and 65 DEG C of different temperatures.Contrast is found by experiment, the response maximum of fatty acid methyl ester in the time of 60 DEG C.Control methods is identical with b.When this method analytic sample, slective extraction and esterification temperature are 60 DEG C.
The length that the extent of reaction of f fat esterification and methyl esters enter head space bottle and be extracted an absorption situation and determined analysis time.Under 60 DEG C of extractions, stir speed (S.S.) 250r/min condition, the effect of extracting of esterification efficiency and extracting head under more different extraction time 45min, 60min, 75min, 90min.Contrast is found by experiment, the response maximum of fatty acid methyl ester when be 60min analysis time.Control methods is identical with b.This method analytic sample time is 60min.
3. production standard curve:
Take appropriate myristin, tripalmitin, glyceryl tristearate, olein, Trilinoleyl glyceride and three glyceryl linolenates, be mixed with the mixed mark solution of variable concentrations with toluene.Get 2mL sample solution in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL 11mmol/L, add the mixed liquor of 10 μ L in head space bottle, making its concentration gradient is 0.5 μ g/L, 2.5 μ g/L, 12.5 μ g/L, 50 μ g/L and 100 μ g/L.Head space bottle screws in the insulation can that is transferred to 60 DEG C after bottle cap, inserts 85 μ m PA extracting head, completes after absorption, extracting head is inserted to gas chromatograph injection port, and desorb 2min ensures complete desorb at 250 DEG C; After adopting instrument to detect, not add mixed target sample as blank, measure respectively the peak area of each fatty acid methyl ester after mark-on, after deduction blank, taking the peak area added value of each component after mark-on as y, adding scalar is x, draw a typical curve, typical curve was forced initial point.Result shows that each triglyceride concentration is in the time of the range of linearity of 0.5 μ g/L ~ 100 μ g/L, and typical curve is linear good, R
2all be greater than 0.99, can meet accurate quantitative analysis and analyze requirement.The results are shown in Table 2.
Table 2 method regression equation, related coefficient, detection limit, sample recovery of standard addition (n=5)
4. method evaluation:
By calculating the precision of relative standard deviation investigation method of 5 Duplicate Samples, determine its detection limit by signal to noise ratio (S/N ratio) S/N >=3.Sample mark-on concentration is 12.5 μ g/L, through identical pre-treatment, and assay method recovery of standard addition.Result shows that the relative standard deviation of the method is 6.59% ~ 13.01%, and detection limit is at 0.001 μ g/L ~ 0.051 μ g/L, and recovery of standard addition is 86.61% ~ 128.29%, as shown in table 2.Triglyceride detection limit obtains fatty acid detection limit by reduction formula, and fatty acid detection limit scope is 0.001 μ g/L ~ 0.049 μ g/L, and reduction formula is as follows:
Wherein: D
i-fatty acid detection limit; D'
i-triglyceride detection limit; M
i-fatty acid molecule amount; M '
ithe molecular weight of-triglyceride.
Jiangsu long-grained nonglutinous rice is pulverized after three times through Cyclone mill, and 25mg rice meal is dissolved in 200mL water, fully stirs.Get 2mL sample diluting liquid in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL 11mmol/L, screw head space bottle cap.Solid-phase microextraction completes by means of Multifunctional sample injection device, and concrete operations are: automatic sampler moves to sample bottle in insulation can, inserts 85 μ m PA extracting head, makes it under 60 DEG C, 250r/min concussion condition, adsorb 1h.After having adsorbed, fiber head moves into gas chromatographic sample introduction mouth desorb 2min at 250 DEG C.Utilize typical curve to calculate the content of various triglyceride in rice to be measured, obtain content of fatty acid in rice fat by conversion, computing formula is as follows:
Wherein: m
i-content of fatty acid; A
i-fatty acid methyl ester peak area; Liquor capacity in V-head space bottle; k
i-triglyceride typical curve regression equation coefficient; m
0-rice sample quality.
In the long-grained nonglutinous rice sample of Jiangsu, fatty acid result is as shown in table 3.
Fatyy acids result in the long-grained nonglutinous rice sample of table 3 Jiangsu
Embodiment 2:
A kind of method that detects content of fatty acid in rice, rice sample carries out by means of Multifunctional sample injection device base catalysis esterification and solid-phase microextraction in head space bottle simultaneously, enter afterwards content of fatty acid in gas chromatography-tandem mass spectrum combined instrument (GC-MS-MS) detection quantitative test rice fat, comprise the following steps:
1. the setting of instrument parameter:
A. Multifunctional sample injection device: temperature 60 C, time 60min, adopts 85 μ m PA extracting head;
B. gas chromatograph: DB-225MS capillary column, 30m × 0.25mm × 0.25 μ m; Carrier gas is high-purity helium, constant current mode, and injection port flow is 1.0ml/min, Splitless injecting samples; Column oven keeps 2min at 50 DEG C, is then warming up to 230 DEG C with 5 DEG C/min;
C. tandem mass spectrum: 250 DEG C of transmission line temperature, electron impact ion source (EI), electron energy is 70Ev, and ion source temperature is 200 DEG C, and collision gas (argon gas) pressure is 1.5mTorr, and detection mode adopts multiple-reaction monitoring (MRM);
The testing conditions of each fatty acid methyl ester under table 1 tandem mass spectrum multiple-reaction monitoring (MRM) pattern
Northeast polished rice is pulverized after three times through Cyclone mill, and 25mg rice meal is dissolved in 200mL water, fully stirs.Get 2mL sample diluting liquid in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL 11mmol/L, screw head space bottle cap.Solid-phase microextraction completes by means of Multifunctional sample injection device, and concrete operations are: automatic sampler moves to sample bottle in insulation can, inserts 85 μ m PA extracting head, makes it under 60 DEG C, 250r/min concussion condition, adsorb 1h.After having adsorbed, fiber head moves into gas chromatographic sample introduction mouth desorb 2min at 250 DEG C.Utilize the typical curve obtaining in embodiment 1 to calculate the content of various triglyceride in rice to be measured, obtain content of fatty acid in rice fat by conversion, computing formula is as follows:
Wherein: m
i-content of fatty acid; A
i-fatty acid methyl ester peak area; Liquor capacity in V-head space bottle; k
i-triglyceride typical curve regression equation coefficient; m
0-rice sample quality.
In the polished rice sample of northeast, fatty acid result is as shown in table 4.
Fatyy acids result in the polished rice sample of table 4 northeast
Claims (4)
1. one kind is detected the method for content of fatty acid in rice fat, it is characterized in that: rice sample carries out by means of Multifunctional sample injection device base catalysis esterification and solid-phase microextraction in head space bottle simultaneously, enter afterwards gas chromatography-tandem mass spectrum combined instrument and detect, and content of fatty acid in quantitative test rice fat;
The described base catalysis esterification of simultaneously carrying out in head space bottle and solid-phase microextraction step comprise the following steps:
1. rice is pulverized after three times through Cyclone mill, and 25mg rice meal is dissolved in 200mL water, fully stirs;
2. get 2mL sample diluting liquid in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL11mmol/L, screw head space bottle cap;
3. automatic sampler moves to sample bottle in insulation can, inserts 85 μ m PA extracting head, makes it at 60 DEG C, the 250r/min concussion following esterification of condition limit extraction 1h;
The detecting step of described gas chromatography-tandem mass spectrum combined instrument is:
1. sampling condition: PA extracting head moves into the injection port of gas chromatography-tandem mass spectrum combined instrument, desorb 2min at 250 DEG C, Splitless injecting samples;
2. chromatographic condition: DB-225MS capillary column, 30m × 0.25mm × 0.25 μ m; Carrier gas is high-purity helium, constant current mode, and injection port flow is 1.0ml/min; Column oven keeps 2min at 50 DEG C, is then warming up to 230 DEG C with 5 DEG C/min;
3. tandem mass spectrum condition: 250 DEG C of transmission line temperature, electron impact ion source, electron energy is 70Ev, and ion source temperature is 200 DEG C, and collision atmospheric pressure is 1.5mTorr, and described collision gas is argon gas; Mensuration mode adopts multiple-reaction monitoring;
In described quantitative test rice fat, the step of content of fatty acid comprises:
1. drawing standard curve:
A. take appropriate myristin, tripalmitin, glyceryl tristearate, olein, Trilinoleyl glyceride and three glyceryl linolenates, be mixed with the mixed mark solution of variable concentrations with toluene;
B. get 2mL sample solution in head space bottle, add potassium hydroxide/methyl alcohol methyl esterification reagent of 1gNaCl and 0.75mL11mmol/L, add the mixed mark of 10 μ L solution in head space bottle, making its concentration gradient is 0.5 μ g/L, 2.5 μ g/L, 12.5 μ g/L, 50 μ g/L and 100 μ g/L;
C. head space bottle screws in the insulation can that is transferred to 60 DEG C after bottle cap, inserts 85 μ m PA extracting head, completes after absorption, extracting head is inserted to gas chromatograph injection port, and desorb 2min ensures complete desorb at 250 DEG C;
D., after adopting instrument to detect, not add mixed target sample as blank, measure respectively the peak area of each fatty acid methyl ester after mark-on, after deduction blank, taking the peak area added value of each component after mark-on as y, adding scalar is x, draw a typical curve, typical curve was forced initial point;
2. calculate the content of various triglyceride in rice by the testing result of typical curve and testing sample;
3. adopt formula (1) to convert and obtain the content of fatty acid in rice fat:
Wherein: m
i-content of fatty acid; M
i-fatty acid molecule amount; M'
ithe molecular weight of-triglyceride; A
i-fatty acid methyl ester peak area; Liquor capacity in V-head space bottle; k
i-triglyceride typical curve regression equation coefficient; m
0-rice sample quality.
2. a kind of method that detects content of fatty acid in rice fat according to claim 1, it is characterized in that: described base catalysis esterification reaction of organic acid is taking water as matrix, through ultrapure water system, processing obtains described water, and described ultrapure water system is Milli-Q ultrapure water system.
3. a kind of method that detects content of fatty acid in rice fat according to claim 1, is characterized in that: described rice is pulverized three times through Cyclone mill, and grain fineness can be passed through 120 mesh sieves, and described Cyclone mill is Cyclotec1093 Cyclone mill.
4. a kind of method that detects content of fatty acid in rice fat according to claim 1, is characterized in that: the condition of described multiple-reaction monitoring is:
1. methyl myristate, methyl hexadecanoate and methyl stearate, all selecting mass-to-charge ratio is that the ion pair of 74 (parent ions) and 43 (daughter ions) is as quota ion pair, mass-to-charge ratio is that the ion pair of 87 (parent ions) and 55 (daughter ions) is qualitative ion pair, described mass-to-charge ratio is that 43 daughter ion is that to adopt the collision energy of 5Ev to bombard described mass-to-charge ratio be that 74 parent ion obtains, and the daughter ion that described mass-to-charge ratio is 55 is that to adopt the collision energy of 10Ev to bombard described mass-to-charge ratio be that 87 parent ion obtains;
2. to select mass-to-charge ratio be that the ion pair of 74 (parent ions) and 43 (daughter ions) is as quota ion pair to methyl oleate, mass-to-charge ratio is that the ion pair of 69 (parent ions) and 41 (daughter ions) is qualitative ion pair, described mass-to-charge ratio is that 43 daughter ion is that to adopt the collision energy of 5Ev to bombard described mass-to-charge ratio be that 74 parent ion obtains, and the daughter ion that described mass-to-charge ratio is 41 is that to adopt the collision energy of 10Ev to bombard described mass-to-charge ratio be that 69 parent ion obtains;
3. to select mass-to-charge ratio be that the ion pair of 81 (parent ions) and 79 (daughter ions) is as quota ion pair to methyl linoleate, mass-to-charge ratio is that the ion pair of 67 (parent ions) and 41 (daughter ions) is qualitative ion pair, described mass-to-charge ratio is that 79 daughter ion is that to adopt the collision energy of 10Ev to bombard described mass-to-charge ratio be that 81 parent ion obtains, and the daughter ion that described mass-to-charge ratio is 41 is that to adopt the collision energy of 10Ev to bombard described mass-to-charge ratio be that 67 parent ion obtains;
4. to select mass-to-charge ratio be that the ion pair of 67 (parent ions) and 41 (daughter ions) is as quota ion pair to methyl linolenate, mass-to-charge ratio is that the ion pair of 67 (parent ions) and 39 (daughter ions) is qualitative ion pair, described mass-to-charge ratio is that 41 daughter ion is that to adopt the collision energy of 10Ev to bombard described mass-to-charge ratio be that 67 parent ion obtains, and the daughter ion that described mass-to-charge ratio is 39 is that to adopt the collision energy of 15Ev to bombard described mass-to-charge ratio be that 67 parent ion obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210525239.1A CN103048414B (en) | 2012-12-08 | 2012-12-08 | Method for detecting fatty acid content in rice fat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210525239.1A CN103048414B (en) | 2012-12-08 | 2012-12-08 | Method for detecting fatty acid content in rice fat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103048414A CN103048414A (en) | 2013-04-17 |
| CN103048414B true CN103048414B (en) | 2014-08-13 |
Family
ID=48061129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210525239.1A Active CN103048414B (en) | 2012-12-08 | 2012-12-08 | Method for detecting fatty acid content in rice fat |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103048414B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104297381B (en) * | 2014-11-05 | 2016-06-22 | 光明乳业股份有限公司 | A kind of assay method of free medium-chain fatty acid |
| CN104655774B (en) * | 2015-02-09 | 2016-05-18 | 广西壮族自治区中医药研究院 | The assay method of palmitic acid and oleic acid content in Polyhachis vicina Roger |
| CN104764834B (en) * | 2015-03-24 | 2017-10-27 | 石河子大学 | A kind of method for fast and effectively extracting grease in mesoderm growing early stage cottonseed |
| CN105334284B (en) * | 2015-12-04 | 2018-01-02 | 国家环境分析测试中心 | It is a kind of to identify and remove the method that carboxylic acids disturbs in perfluorobutyric acid detection |
| CN106568869B (en) * | 2016-11-16 | 2019-07-09 | 浙江方圆检测集团股份有限公司 | The synchronization detecting method of 10 kinds of fatty acid methyl ester mass contents in a kind of biodiesel |
| CN106404971B (en) * | 2016-11-29 | 2018-07-03 | 河南工业大学 | The method that gas chromatography identifies rice processing accuracy |
| CN109696500B (en) * | 2019-01-29 | 2021-07-09 | 中国药科大学 | Method for measuring target impurity correction factor by adopting high performance liquid chromatography and application |
| CN110736801B (en) * | 2019-12-02 | 2020-12-04 | 山东农业大学 | Method for measuring fatty acid in rice by using gas chromatography-mass spectrometry |
| CN111551663B (en) * | 2020-06-19 | 2023-03-17 | 南京林业大学 | Quantitative method for determining soil fatty acid methyl ester and application thereof |
| CN113030360A (en) * | 2021-02-23 | 2021-06-25 | 上海百趣生物医学科技有限公司 | Free fatty acid high-throughput target detection method and application |
| CN115015451A (en) * | 2022-06-02 | 2022-09-06 | 中国地质大学（北京） | Dehydration method before crude oil all-hydrocarbon gas chromatography |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102539609B (en) * | 2011-12-31 | 2014-07-16 | 青岛啤酒股份有限公司 | Detection method for measuring free fatty acid in beer through methyl esterification in bottle-headspace SPME (solid-phase micro-extraction)-gas chromatography and mass spectrum |
-
2012
- 2012-12-08 CN CN201210525239.1A patent/CN103048414B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103048414A (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103048414B (en) | Method for detecting fatty acid content in rice fat | |
| Monteleone et al. | A reliable and simple method for the assay of neuroendocrine tumor markers in human urine by solid-phase microextraction–gas chromatography-triple quadrupole mass spectrometry | |
| Zhao et al. | Simultaneous determination of isoflavones and resveratrols for adulteration detection of soybean and peanut oils by mixed-mode SPE LC–MS/MS | |
| CN104237447B (en) | A kind of method detecting glyceryl ester and free fatty acid content in biofuel | |
| áde Sa et al. | Analysis of biodiesel and biodiesel–petrodiesel blends by high performance thin layer chromatography combined with easy ambient sonic-spray ionization mass spectrometry | |
| CN101620206B (en) | Method for detecting ethyl carbamate in yellow wine | |
| Schmarr et al. | Two-dimensional gas chromatographic profiling as a tool for a rapid screening of the changes in volatile composition occurring due to microoxygenation of red wines | |
| CN104849390B (en) | A kind of method of applying component in the qualitative white wine of comprehensive two dimensional gas chromatography-flight time mass spectrum coupling | |
| Qiu et al. | Progress in pretreatment and analysis of organic Acids: An update since 2010 | |
| Luan et al. | Gas-phase postderivatization following solid-phase microextraction for rapid determination of trans-resveratrol in wine by gas chromatography-mass spectrometry | |
| Zhao et al. | Determination of ethyl carbamate in fermented liquids by ultra high performance liquid chromatography coupled with a Q Exactive hybrid quadrupole-orbitrap mass spectrometer | |
| Olivero et al. | A new method for the determination of short-chain fatty acids from the aliphatic series in wines by headspace solid-phase microextraction–gas chromatography–ion trap mass spectrometry | |
| CN102445505A (en) | Method for quickly determining ethyl carbamate (EC) in alcoholic drink | |
| Zhu et al. | Profiling free fatty acids in edible oils via magnetic dispersive extraction and comprehensive two-dimensional gas chromatography-mass spectrometry | |
| CN103869015B (en) | Method for quantitatively determining 14 types of trans-2-aldehydes and diolefine aldehydes compounds in white spirit | |
| Sun et al. | A chiral ligand exchange CE system for monitoring inhibitory effect of kojic acid on tyrosinase | |
| CN103364515A (en) | Method for detecting aldehydes in rice | |
| CN105067734B (en) | Method for determining content of natamycin in wine | |
| CN107315038A (en) | A kind of mass is to the quick method for measuring of urethanes in drinks sample | |
| Li et al. | Current analytical strategies for the determination of resveratrol in foods | |
| CN108845068B (en) | Detection method of pyrazine compounds in pan-fired green tea | |
| CN105259266B (en) | The method of the four kinds of wheats perfume class flavor substance in detection beer and wheat juice | |
| Meyers et al. | Analysis of gamma-hydroxybutyric acid (GHB) in spiked water and beverage samples using solid phase microextraction (SPME) on fiber derivatization/gas chromatography-mass spectrometry (GC/MS) | |
| CN108120791A (en) | A kind of method of three kinds of ochratoxin total amounts in Rapid Simultaneous Determination sample | |
| Fa et al. | Color and alcohol removal for the simultaneous detection of amino acids and sugars in wine by two-dimensional ion chromatography |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 266000 Shandong city of Qingdao Province North Dengzhou Road No. 56 Applicant after: Qingdao Beer Co., Ltd. Address before: Shinan District 266000 in Shandong province Qingdao City 54 square building in Tsingtao Applicant before: Qingdao Beer Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |