CN103487455B - A kind of method of hydroxy-containing compounds in Quantitative detection olive oil - Google Patents
A kind of method of hydroxy-containing compounds in Quantitative detection olive oil Download PDFInfo
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- CN103487455B CN103487455B CN201310436221.9A CN201310436221A CN103487455B CN 103487455 B CN103487455 B CN 103487455B CN 201310436221 A CN201310436221 A CN 201310436221A CN 103487455 B CN103487455 B CN 103487455B
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- olive oil
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Abstract
The invention discloses the method for hydroxyl composition in a kind of Quantitative detection olive oil, belong to edible oil and fat detection field.The present invention is based on
19f? the method of NMR technological invention can the content of hydroxy-containing compounds in simple and quick quantitative detection olive oil, extensively can apply to the detection of other edible oil and fat.Fluorine derivatizing agent Fluorobenzoyl chloride and hydroxy-containing compounds generation substitution reaction, make hydroxy-containing compounds fluorine derivatization.Fourier NMR spectrometer with superconducting magnet is used to be done by the hydroxy-containing compounds of fluorine derivatization
19f? NMR collection of illustrative plates.Manual integration is carried out to collection of illustrative plates, accurately can calculate the content of hydroxy-containing compounds.Accurately and reliably, method simple possible, simple to operate easy to learn, the quality analysis that can be olive oil provides of great value reference to result, also can be used for the content of the hydroxy-containing compounds detecting other edible oils.
Description
Technical field
The invention belongs to edible oil and fat detection technique field, specifically detect the method for hydroxy-containing compounds in olive oil.
Background technology
Olive oil is the more rich one of conventional edible oil and fat Middle nutrition value ratio.Because olive oil contains abundant unsaturated fatty acid and microcomponent, make it have very high edibility and health-care efficacy." liquid golden ", " Mediterranean sweet dew " is described as in west.Hydroxy-containing compounds is the important component part of olive oil microcomponent, comprises the materials such as monoglyceride, diglyceride, straight chain fatty alcohols, sterols (cupreol, Δ-5-avenasterol, cholesterol), phenols (tocopherol, tyrosol, hydroxytyrosol, lignin etc.).
The fatty acid overwhelming majority in olive oil is all exist with the form of glycerate, wherein sweet three esters account for more than 90%, the content of monoglyceride is lower than 1%, DAG is mainly with 1, the form of 3-DAG exists, but due to the difference such as increase, refining, the place of production along with the storage time, 1 in olive oil, 3-DAG can turn to 1,2-DAG by isomery.Research shows that the ratio of 1,3-DAG and total DAG can as the important evidence of olive oil classification.
Clinical research shows, the plant sterol in diet can suppress small intestine to the absorption of cholesterol and the level reducing Blood Cholesterol.Modern study shows that plant sterol also has anti-inflammatory, antibacterial, antiulcer, anti-oxidant and antitumor activity.Free content of phytosterol in virgin oil is subject to the impact meeting esterification of storage time and condition of storage, and the free plant sterol in addition in refined olive oil also esterification can occur.The quality assessment of content to olive oil of the free plant sterol therefore detected in olive oil has important references and is worth, and is also detect the adulterated important indicator of olive oil.
Aldehydes matter in olive oil (
, hydroxytyrosol, olive bitter principle etc.) be natural antioxidant, olive oil is without the need to adding the antioxidant of other synthesis again, and aldehydes matter is also the main matter of giving olive oil particular tastes.Epidemiological study shows that aldehydes matter can be good at pre-anti-cancer and coronary heart disease, also has antidotal effect.Because the content of phenolic compounds in olive oil is low, complex structure, the detection method of traditional method is difficult to detect content fast and accurately.Aldehydes matter in refined olive oil is owing to declining through the process such as high temperature, deodorization content.
Acidity is used to the index of the ratio measured in each hectogram grease shared by free fatty acid, free fatty acid is free fatty acid again, is the fatty ingredient of " not behaving oneself " in grease, and acidity is too high easily causes oxidation, thus cause spoiled by rancid oil or fat, not edible.The standard display of International Olive Oil Council and European Union, the oleic acid content of Extra Virgin is lower than 0.8, and virgin oil is lower than 2.0, and refined olive oil is due to through chemical deacidification process, and acidity is lower than 0.3.The acidity detecting olive oil and other greases can judge easily to judge whether the ratio index of the free fatty acid of grease to become sour.Also aldehyde compound can be produced in Oxidation of Fat and Oils process, the content detecting aldehyde compound can judge the degree of oxidation of grease, virgin oil is not through high temperature, high pressure, so aldehyde compound content is all lower, the aldehyde group content of refined olive oil is more much higher than virgin oil, and this is one of important indicator judging olive oil grade.
Hydroxyl material in current detection olive oil mainly vapor-phase chromatography,
1hNMR method,
13cNMR method.Due to
1hNMR has overlap peak,
13the CNMR relaxation time is long insensitive, such spectrum analysis and quantitatively all have very large challenge.Gas chromatographic detection needs first by free sterol esterification, owing to inherently containing some esterification plant sterol in olive oil, so detect free plant sterol first will detect total plant sterol ability free plant sterol of detection further.This procedure very complicated and taking time and effort, to the operation of experiment and the control overflow of condition all higher.
The present invention is based on
19the method of FNMR technological invention can the content of hydroxy-containing compounds in simple and quick quantitative detection olive oil.
Summary of the invention
The present invention is based on
19the method kit of FNMR technological invention can the content of hydroxy-containing compounds in simple and quick quantitative detection olive oil, extensively can apply to the detection of other edible oil and fat.
The technical solution adopted in the present invention is: fluorine derivatizing agent 4-fluorobenzoyl chloride and hydroxy-containing compounds generation substitution reaction, make hydroxy-containing compounds fluorine derivatization.German BRUKERAVANCE/AV500MHz Fourier NMR spectrometer with superconducting magnet is used to be done by the hydroxy-containing compounds of fluorine derivatization
19fNMR collection of illustrative plates.
Use nuclear magnetic spectrum process software MestReNovaV6.1 to carry out manual integration to hydroxy-containing compounds image, calculate hydroxy-containing compounds content in sample.
A method for hydroxy-containing compounds in Quantitative detection olive oil,
it is characterized in that there is following process and step:
A. the selection of the fluorine derivatization reagent of hydroxyl compound: described fluorine derivatizing agent comprises 4-fluorobenzoyl chloride, 2,4,6-trifluorobenzoyl chlorides, 3,5-difluoro benzoyl chlorides.
B. the preparation of storing solution: described storing solution is deuterochloroform and pyridine volume ratio is the mixed liquor of 1.5:1 or 1.6:1, storage reagent dosage is 10.0ml, store reagent and contain 0.1mg phenyl-hexafluoride 20mg tert-butyl group Pyrogentisinic Acid, be placed on waterproof in molecular sieve and store.Phenyl-hexafluoride, tert-butyl group Pyrogentisinic Acid are interior mark.
C. the reaction treatment of olive oil sample: described olive oil sample injected volume 100mg to 150mg, to be placed in 5mm nuclear magnetic tube and to add the above-mentioned storage reagent of 0.5ml to 0.6ml and 30 μ L fluorine derivatizing agent, 30min is reacted under reaction mixture being placed room temperature, after complete reaction is complete, make of nuclear magnetic resonance spectrometer immediately
19fNMR collection of illustrative plates.
D. nuclear magnetic resonance spectrometer is utilized to do
19fNMR collection of illustrative plates: utilize nuclear magnetic resonance spectrometer to do
19fNMR collection of illustrative plates obtains in the operation of BRUKERAVANCE/AV500MHz Fourier NMR spectrometer with superconducting magnet; Probe temperature is 26 ± 1 ° of C; Typical spectrum parameter is as follows: 90 pulse width 19.3 μ s, sweep length 100kHz, relaxation delay 1s, memory size 64K.Each spectrum accumulated samples 64 times.All collection of illustrative plates, before carrying out Fourier transform, expand live width 0.3Hz tuning drift.
E. use nuclear magnetic resonance map process software MestReNovaV6.1 to carry out manual integration to hydroxy-containing compounds image, calculate the content of hydroxy-containing compounds in sample: computing formula is:
i dG with
i i be respectively the integration of diglyceride and 4-fluorobenzoyl chloride,
m dG for the molecular weight of diglyceride, m is the actual use amount of olive oil in experiment,
a for interior target mM amount.
The invention has the beneficial effects as follows: the content that simply quantitatively can detect hydroxy-containing compounds in olive oil fast.Accurately and reliably, method simple possible, simple to operate easy to learn, the quality analysis that can be olive oil provides of great value reference to result, also can be used for the content of the hydroxy-containing compounds detecting other edible oils.
Figure of description
Fig. 1, utilization
19fNMR detects the collection of illustrative plates of glycerine.
Fig. 2, utilization
19fNMR detects the collection of illustrative plates of hydroxytyrosol.
Fig. 3, utilization
19fNMR detects the collection of illustrative plates of palmityl alcohol.
Fig. 4, utilization
19fNMR detects
collection of illustrative plates.
Fig. 5, utilization
19fNMR detects the collection of illustrative plates of 1,2-diolein, 1,3-diolein.
Fig. 6, hydroxytyrosol,
, palmityl alcohol etc.
19fNMR collection of illustrative plates
Embodiment
below with reference to embodiment form, foregoing of the present invention is described further.
(1). store the preparation of reagent: preparation deuterochloroform and pyridine volume ratio are that 1.5:1 stores reagent 10.0ml, store reagent and contain 0.1mg phenyl-hexafluoride 20mg tert-butyl group Pyrogentisinic Acid, be placed on waterproof in molecular sieve and store.Phenyl-hexafluoride, tert-butyl group Pyrogentisinic Acid are interior mark.
(2). the preparation of nuclear-magnetism sample: accurately weigh olive oil 150mg and to be placed in 5mm nuclear magnetic tube and to add the above-mentioned storage reagent of 0.5ml and 30 μ L4-fluorobenzoyl chlorides, 30min is reacted under reaction mixture being placed room temperature, after complete reaction is complete, nuclear magnetic resonance spectrometer is used to do immediately
19fNMR collection of illustrative plates.
(3). magnetic resonance detection:
19fNMR collection of illustrative plates obtains in the operation of BRUKERAVANCE/AV500MHz Fourier NMR spectrometer with superconducting magnet.Probe temperature is 25 DEG C.In this research, typical spectrum parameter is as follows: 19.3 μ s of 90 pulse widths, sweep length 100kHz, relaxation delay 1s, memory size 64K.Each spectrum accumulated samples 64 times.All collection of illustrative plates, before carrying out Fourier transform, expand live width 0.3Hz tuning drift.
Model compound fluorine derivative
19under the chemical shift (ppm) of FNMR is shown in
table 1.
The fluorine derivative of table 1. model compound
19fNMR chemical shift (ppm)
| Compound 19The displacement of F nmr chemical |
1,2-diolein 107.94
1,3-diolein 107.84
Glycerine 107.89(alpha-position hydroxyl)
107.71(β-position hydroxyl)
Hydroxytyrosol 107.28(phenolic hydroxyl group)
108.54(alcoholic extract hydroxyl group)
107.62
Palmityl alcohol 108.95
Stearyl alcohol 108.95
Free fatty acid 103.90
Aldehyde radical 105.13
About the detection of olive oil sample
By Shanghai City Entry-Exit Inspection and Quarantine Bureau provide from five countries, 37 olive oil sample such as Spain, Italy, Greece, Tunisia, Turkey, wherein Spain's 12 samples, Italy's 13 samples, Greece's 5 samples, Turkey's 4 samples, 3, Tunisia sample.Sample 1 is Extra Virgin to sample 24, and sample 25 is mixed olive oil to sample 37.
The result statistics that detection computations obtains exists
table 2in.
Table 2.
19the content of the diglyceride that FNMR detects different regions, the olive oil of different brackets obtains.
。
Claims (1)
1. the method for hydroxy-containing compounds in Quantitative detection olive oil,
it is characterized in that there is following process and step:
A. the selection of the fluorine derivatizing agent of hydroxyl compound: described fluorine derivatizing agent is 4-fluorobenzoyl chloride, 2,4,6-trifluorobenzoyl chlorides or 3,5-difluoro benzoyl chloride;
B. the preparation of storing solution: described storing solution is deuterochloroform and pyridine volume ratio is the mixed liquor of 1.5:1 or 1.6:1, storing solution consumption is 10.0ml, storing solution contains 0.1mg phenyl-hexafluoride 20mg tert-butyl group Pyrogentisinic Acid, be placed on waterproof in molecular sieve to store, phenyl-hexafluoride, tert-butyl group Pyrogentisinic Acid are interior mark;
C. the reaction treatment of olive oil sample: described olive oil sample injected volume 100mg to 150mg, to be placed in 5mm nuclear magnetic tube and to add the above-mentioned storing solution of 0.5ml to 0.6ml and 30 μ L fluorine derivatizing agent, 30min is reacted under reaction mixture being placed room temperature, after complete reaction is complete, make of nuclear magnetic resonance spectrometer immediately
19fNMR collection of illustrative plates;
D. nuclear magnetic resonance spectrometer is utilized to do
19fNMR collection of illustrative plates: described in
19fNMR collection of illustrative plates operates and obtains on BRUKERAVANCE/AV500MHz Fourier NMR spectrometer with superconducting magnet; Probe temperature is 26 ± 1 ° of C; Spectrum parameter is as follows: 90 pulse width 19.3 μ s, sweep length 100kHz, relaxation delay 1s, memory size 64K, each spectrum accumulated samples 64 times; All collection of illustrative plates, before carrying out Fourier transform, expand live width 0.3Hz tuning drift.
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| WO2020186510A1 (en) * | 2019-03-21 | 2020-09-24 | Wacker Chemie Ag | A method for testing whether oil can penetrate into the hair and its penetrability |
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| JPH11142388A (en) * | 1997-11-11 | 1999-05-28 | Asahi Chem Ind Co Ltd | Method for analyzing terminal group of hydroxyl terminal group-containing polymer |
| WO1999031491A1 (en) * | 1997-12-17 | 1999-06-24 | Aventis Pharmaceuticals Products Inc. | Method and reagents for the quantification of solid-phase reactions using fluorine nmr |
| CN1898251A (en) * | 2003-11-28 | 2007-01-17 | 罗狄亚化学公司 | Reagent and method for preparing a fluorinated and silylated derivative |
| CN101095046A (en) * | 2004-12-30 | 2007-12-26 | 法国道达尔 | Method for measuring the acidity of hydrocarbons |
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| KR20050008788A (en) * | 2002-06-05 | 2005-01-21 | 파마시아 앤드 업존 캄파니 엘엘씨 | Use of fluorine nmr for high throughput screening |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11142388A (en) * | 1997-11-11 | 1999-05-28 | Asahi Chem Ind Co Ltd | Method for analyzing terminal group of hydroxyl terminal group-containing polymer |
| WO1999031491A1 (en) * | 1997-12-17 | 1999-06-24 | Aventis Pharmaceuticals Products Inc. | Method and reagents for the quantification of solid-phase reactions using fluorine nmr |
| CN1898251A (en) * | 2003-11-28 | 2007-01-17 | 罗狄亚化学公司 | Reagent and method for preparing a fluorinated and silylated derivative |
| CN101095046A (en) * | 2004-12-30 | 2007-12-26 | 法国道达尔 | Method for measuring the acidity of hydrocarbons |
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| 19F-NMR法测定聚醚多元醇中伯羟基的相对含量;吴美玉 等;《高分子学报》;19880430(第2期);149-151 * |
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| 五氟苯甲酰氯衍生色谱法分析水体中痕量羟基多溴联苯醚;赵茜 等;《环境化学》;20120531;第31卷(第5期);737-742 * |
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