CN105699535A - Method for detecting TBHQ (tert-butylhydroquinone) in food - Google Patents
Method for detecting TBHQ (tert-butylhydroquinone) in food Download PDFInfo
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- CN105699535A CN105699535A CN201610175957.9A CN201610175957A CN105699535A CN 105699535 A CN105699535 A CN 105699535A CN 201610175957 A CN201610175957 A CN 201610175957A CN 105699535 A CN105699535 A CN 105699535A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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Abstract
The invention discloses a method for detecting TBHQ (tert-butylhydroquinone) in food. The detection method comprises the following steps of (1) separating the TBHQ in to-be-detected food by utilization of a high-performance liquid chromatography; (2) under a flow injection condition, mixing effluent of the step (1) with a chemilumincscence reagent to obtain a system, performing chemilumincscence reaction on the system, and obtaining the concentration of the TBHQ in the food according to a chemilumincscence intensity value of the system, wherein the chemilumincscence reagent is a mixed solution of a luminol-potassium permanganate system and an alkaline pH regulator. The detection method disclosed by the invention has the following advantages that (1) a detection limit of the TBHQ is 0.1 ng/mL, the sensitivity is increased by one order of magnitude in comparison with that of the prior method, and the linear range is wide; (2) the analysis time of the method is within 6 minutes; a detector is low in cost (smaller than 2000 dollars), the condition is mild, and the automated analysis operation is beneficially performed; the method is good in reproducibility by adoption of a flow injection manner.
Description
Technical field
The present invention relates to the detection method of a kind of Determination of Antioxidant Tbhq In Foods, belong to field of food detection。
Background technology
Antioxidant is generally commonly used by people in oils and fats and fried food, is a kind of stop or delay that Food Oxidation is rotten, improving food stability and extend the food additive of food storage phase。Antioxidant is by sources divided into the Natural antioxidant and synthetic antioxidant, and wherein tert-butylhydroquinone (TBHQ) is a kind of synthetized oxidation preventive agent conventional in oils and fats and fried food。But, studies have found that, the hepatomicrosome part using meeting damaged animal of excessive TBHQ, therefore there is certain limit standard in a lot of country that uses for them, and even some country does not still permit use TBHQ in food so far。So the mensuration to these Antioxidants In Foods is necessary。
At present, there is a lot of method measuring TBHQ, for instance spectrophotography, gas chromatography, liquid chromatography, Capillary Micellar Electrokinetic Chromatography, electrochemical methods etc.。Although said method all has its advantage, but there is also the shortcomings such as step numerous and diverse, expensive equipment, use toxic solvent。Therefore, set up a kind of simple, cost is low and environmentally friendly and the method for TBHQ simultaneously is extremely urgent。
Recently, chemiluminometry owing to having range of linearity width, highly sensitive, instrument is simple, and does not have the advantages such as bias light interference, and is extensively used by people。Luminol is also to be the most common reagent being applied in chemiluminescence the earliest, and luminol-potassium permanganate system is already used to detect a variety of material。But up to the present, there is not been reported for the correlational study of employing luminol-potassium permanganate system detection TBHQ。
Summary of the invention
It is an object of the invention to provide the detection method of a kind of Determination of Antioxidant Tbhq In Foods, overcome the shortcomings such as existing assay method step is numerous and diverse, expensive equipment, use toxic solvent, analysis cost high, sensitivity can not meet demand, the range of linearity is narrow, analysis minute length, based on the TBHQ inhibitory action to luminol-potassium permanganate system, it is provided that the method for the detection antioxidant of a kind of brand-new simple and sensitive。
Detection method provided by the invention, antioxidant is easily separated by the high separating efficiency first with high performance liquid chromatography, then flow out after post, TBHQ is on chemiluminescent impact for recycling, set up a kind of HPLC-CL method of quick mensuration TBHQ simple, sensitive, the measuring principle of the inventive method is: when existing without TBHQ, and luminol-potassium permanganate system produces a very strong chemiluminescence signal；And when TBHQ exists, owing to it can react with the oxidant potassium permanganate in reaction system, thus causing that chemical signal reduces, thus realizing the mensuration to antioxidant。
The detection method of Determination of Antioxidant Tbhq In Foods provided by the present invention, comprises the steps:
(1) utilize high performance liquid chromatography that the tert-butylhydroquinone in food to be measured is easily separated；
(2) when flow injection, the effluent of step (1) and chemical illuminating reagent carry out being mixed to get a system, and carry out chemiluminescence reaction, and the relative chemical luminous intensity values according to described system, namely obtain the concentration of Determination of Antioxidant Tbhq In Foods；
Described chemical illuminating reagent is the mixed liquor of luminol-potassium permanganate system and alkaline pH adjusting agent:
Described luminol-potassium permanganate system is the aqueous solution of luminol and potassium permanganate。
In above-mentioned detection method, described food can be edible oil；
Described edible oil can be at least one in Oleum Gossypii semen, Oleum Arachidis hypogaeae semen and soybean oil。
In above-mentioned detection method, the concentration of tert-butylhydroquinone described in described food can be 5 × 10-9G/mL～1 × 10-5g/mL。
In above-mentioned detection method, in step (1), the testing conditions of described high performance liquid chromatography is as follows:
Mobile phase is the mixed liquor of methanol and water, and the volume ratio of described methanol and described water can be 70:30；
Flow velocity can be 0.5～1.0mL/min, concretely 1.0mL/min。
In above-mentioned detection method, in step (2), in described chemical illuminating reagent, described alkaline pH adjusting agent is sodium hydroxide or sodium carbonate-bicarbonate buffer；
In described chemical illuminating reagent, the concentration of described luminol can be 0.1～0.8mmol/L, concretely 0.8mL/min, the concentration of described potassium permanganate can be 0.01～0.2mmol/L, concretely 0.2mL/min, the concentration of described sodium hydroxide can be 0.05～0.5mmol/L, concretely 0.5mL/min；
The flow velocity of described chemical illuminating reagent can be 1.0～2.95mL/min。
In above-mentioned detection method, in step (2), realize the detection of the concentration to Determination of Antioxidant Tbhq In Foods as steps described below:
1) the preparation at least 3 kinds standard solution containing tert-butylhydroquinone；
2) respectively described food standard sample is processed according to step (1) and step (2), obtain corresponding chemiluminescence intensity value, in described standard sample, the concentration of tert-butylhydroquinone is for abscissa, with the relative chemical luminous intensity values of system corresponding with described standard sample for vertical coordinate, make standard curve；
3) according to the relative chemical luminous intensity values measured in step (2) and described standard curve, the concentration of tert-butylhydroquinone in food is namely obtained。
In above-mentioned detection method, the concentration of tert-butylhydroquinone described in described food standard sample can be 5 × 10-9～1 × 10-5g/mL。
Chemical illuminating reagent application in detection Determination of Antioxidant Tbhq In Foods falls within protection scope of the present invention；
Described chemical illuminating reagent is luminol-potassium permanganate system (i.e. the aqueous solution of luminol and potassium permanganate), and comprises alkaline pH adjusting agent such as sodium hydroxide, is used for adjusting acid-base value；
Described food is edible oil；
Described edible oil is at least one in Oleum Gossypii semen, Oleum Arachidis hypogaeae semen and soybean oil；
In described chemical illuminating reagent, the concentration of described luminol is 0.1～0.8mmol/L, and the concentration of described potassium permanganate is 0.01～0.2mmol/L, and the concentration of described sodium hydroxide is 0.05～0.5mmol/L。
Owing to poor selectivity is the intrinsic shortcoming of chemiluminometry, be not suitable for being applied to the research of complex sample, the present invention is by combining chemiluminescence with high performance liquid chromatography separation means, thus well solving this problem, based on this, the present invention has been successfully set up with luminol-potassium permanganate system to measure the new analysis method of TBHQ, and separates with HPLC, measures the TBHQ in edible oil。
Detection method has the advantage that
(1) detection limit, TBHQ is 0.1ng/mL, and method sensitivity than before improves 1 order of magnitude, range of linearity width；
(2) analysis time of the method is within 6 minutes；
(3) detector cost low (< 2000 $), mild condition, be conducive to the analysis operation of automatization；
(4) mode of flow injection, method favorable reproducibility are adopted。
Accompanying drawing explanation
Fig. 1 is the schematic diagram of HPLC-CL analysis test method of the present invention。
Fig. 2 is the schematic diagram that in detection method, chemiluminescence intensity is affected by luminol concentration。
Fig. 3 is the schematic diagram that in detection method, chemiluminescence intensity is affected by potassium permanganate concentration。
Fig. 4 is the schematic diagram that in detection method, chemiluminescence intensity is affected by naoh concentration。
Fig. 5 is the standard curve between TBHQ concentration and the chemiluminescence intensity that the present invention sets up。
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method。
Material used in following embodiment, reagent etc., if no special instructions, all commercially obtain。
Key instrument equipment used by following embodiment and reagent:
IFFM-E Flow Injection Analysis/Chemiluminescence instrument machine corollary equipment (Xi'an Rui Mai Analytical Instrument Co., Ltd), high performance liquid chromatograph (Agilent 1100), F-4500 spectrofluorophotometer。
Luminol, potassium permanganate, sodium hydroxide and TBHQ all buy in Sigma Reagent Company (U.S.)。
The storing solution methanol of TBHQ dissolves and is settled to 1mgmL-1, dilute gradually with mobile phase during use。
0.01mol/L luminol storing solution: accurately weigh 0.1771g luminol, dissolves by the NaOH solution of 0.01mol/L and is settled in the volumetric flask of 1L；Methanol (chromatographically pure level, B&J company of the U.S.)。Agents useful for same is all analytical pure level, and water used in experimentation is all ultra-pure water。
The concentration of TBHQ in edible oil is detected by the flow chart shown in Fig. 1:
Embodiment 1, high-efficient liquid phase chromatogram condition optimization
Adopting methanol-water as mobile phase, the concentration of TBHQ in edible oil to be detected, it has been found that chemiluminescence baseline stability, therefore methanol-water is suitable as the mobile phase separating antioxidant TBHQ。
For chemiluminescence detection effective after better realizing performance liquid chromatographic column, it has been found that when the volume of methanol and water is 70:30, gained chemiluminescence intensity is relatively strong and retention time is suitable。
High-pressure pump flow velocity is too low, and the readily flowed phase of chemical luminous system forms significantly high background value, and peak shape width, disengaging time is long；But if high-pressure pump flow velocity is fast, then retention time is little, and isolated object is few, thus chemiluminescence intensity is low, additionally, the pressure of chromatographic column increases, can affect the life-span of pillar, so, high-pressure pump optimum flow rate is defined as 1.0mL/min。
Embodiment 2, chemiluminescence analysis condition optimization
Potassium permanganate is as the oxidant in this reaction system, and the change of its concentration is very big on chemiluminescence signal impact。The present invention has investigated potassium permanganate luminous signal in 0.005～0.3mmol/L concentration range, and experimental result is as it is shown on figure 3, Fig. 3 shows, when concentration is 0.2mmol/L, relative chemical luminous intensity is maximum, and higher than this concentration, chemiluminescence intensity reduces on the contrary。Accordingly, it is determined that 0.2mmol/L is the optimal concentration of potassium permanganate。
Luminol (luminol) is the most frequently used chemical illuminating reagent, its concentration is a key factor of chemiluminescence signal, fix other conditions constant, the present invention analyzes Luminol effect in 0.1～1mmol/L concentration range, result is as shown in Figure 2, can be seen that, when Luminol is in 0.1～0.8mmol/L concentration range, chemiluminescence intensity increases along with Luminol concentration and increases, but when Luminol concentration is more than 0.8mol/L, chemiluminescence intensity but reduces, so, 0.8mmol/L is defined as the optimum concentration of Luminol。
Owing to, in alkaline environment, Luminol is just stable, and potassium permanganate just can better play its Oxidation, and therefore NaOH is added in reaction system and improves its sensitivity。The present invention determines 0.001～0.1mol/LNaOH to chemiluminescent impact, and as shown in Figure 4, result shows result, when NaOH is 0.5mol/L, chemiluminescence intensity is maximum, higher or lower than this concentration, chemiluminescence intensity all reduces, therefore 0.5mol/L is defined as NaOH optimum concentration。
Considering to save the requirement of reagent and sensitivity, reaction reagent flow velocity the best is 2.95mL/min。
Embodiment 3, analytical performance
(1) the gradient standard solution of a series of TBHQ is prepared, concentration respectively 5.0 × 10-9g/mL、1.0×10-9g/mL、1.0×10-8g/mL、1.0×10-7g/mL、1.0×10-6G/mL and 1.0 × 10-5g/mL。
(2) TBHQ in standard sample is carried out high-efficient liquid and is separated by the optimal conditions obtained according to embodiment 1。
(3) when flow injection, the effluent of step (2) is carried out chemiluminescence analysis by the optimal conditions obtained according to embodiment 2, obtain the chemiluminescence intensity value of standard substance, and then obtain the standard curve between TBHQ concentration and its chemiluminescence intensity value, it appeared that, in Oleum Gossypii semen linear between its corresponding chemiluminescence intensity of TBHQ concentration, the range of linearity corresponding to this curve is: 5 × 10-9G/mL～1 × 10-5g/mL。
Linear relation corresponding to standard curve shown in Fig. 5 is Y=175.6+866.9X, R=0.9988 (wherein Y represents relative chemical luminous intensity, and X represents the concentration of TBHQ)。
Advise (3 σ) according to IUPAC, calculate the detection limit of above-mentioned detection method: TBHQ concentration is 0.1ng/mL。
It is 6 × 10 according to the inventive method to concentration-6The TBHQ standard sample (Oleum Gossypii semen) of g/mL repeats sample introduction 11 times, and the relative standard deviation of gained TBHQ concentration is 2.1%。
Embodiment 4, detection method reliability
The bought Oleum Gossypii semen in market, Oleum Arachidis hypogaeae semen, soybean oil sample 1.0g join 10mL tool plug conical flask, are subsequently adding 5mL methanol mixed；This mixture is centrifugal 10min at 3,000 rpm, and organic layer above is separated in 10mL volumetric flask；Whole process repeats three times, all methanol extraction thing methanol dilution to 10mL, then uses 0.45 μm of membrane filtration。
Mark-on method is adopted to investigate the reliability of detection method。
Measure the response rate obtained as shown in table 1, by the data in table 1 it can be seen that the response rate ranges for 97.9%～102.2%。
Additionally, the content of antioxidant TBHQ that detection method records is consistent with HPLC-UV。
The testing result (n=3) of antioxidant TBHQ in table 1 edible oil
Claims (10)
1. a detection method for Determination of Antioxidant Tbhq In Foods, comprises the steps:
(1) utilize high performance liquid chromatography that the tert-butylhydroquinone in food to be measured is easily separated；
(2) when flow injection, the effluent of step (1) and chemical illuminating reagent carry out being mixed to get a system, and carry out chemiluminescence reaction, and the chemiluminescence intensity value according to described system, namely obtain the concentration of Determination of Antioxidant Tbhq In Foods；
Described chemical illuminating reagent is the mixed liquor of luminol-potassium permanganate system and alkaline pH adjusting agent；
Described luminol-potassium permanganate system is the aqueous solution of luminol and potassium permanganate。
2. detection method according to claim 1, it is characterised in that: described food is edible oil；
Described edible oil is at least one in Oleum Gossypii semen, Oleum Arachidis hypogaeae semen and soybean oil。
3. detection method according to claim 1 and 2, it is characterised in that: the concentration of tert-butylhydroquinone described in described food is 5 × 10-9G/mL～1 × 10-5g/mL。
4. the detection method according to any one of claim 1-3, it is characterised in that: in step (1), the testing conditions of described high performance liquid chromatography is as follows:
Mobile phase is the mixed liquor of methanol and water, and the volume ratio of described methanol and described water is 70:30；
Flow velocity is 0.5～1.0mL/min。
5. the detection method according to any one of claim 1-4, it is characterised in that: in step (2), in described chemical illuminating reagent, described alkaline pH adjusting agent is sodium hydroxide or sodium carbonate-bicarbonate buffer；
The concentration of described luminol is 0.1～0.8mmol/L, and the concentration of described potassium permanganate is 0.01～0.2mmol/L, and the concentration of described alkaline pH adjusting agent is 0.05～0.5mmol/L；
The flow velocity of described chemical illuminating reagent is 1.0～2.95mL/min。
6. the detection method according to any one of claim 1-5, it is characterised in that: in step (2), realize the detection of the concentration to Determination of Antioxidant Tbhq In Foods as steps described below:
1) the preparation at least 3 kinds food standard sample containing tert-butylhydroquinone；
2) respectively described food standard sample is processed according to step (1) and step (2), obtain corresponding chemiluminescence intensity value, in described food standard sample, the concentration of tert-butylhydroquinone is for abscissa, with the relative chemical luminous intensity values of system corresponding with described standard sample for vertical coordinate, make standard curve；
3) according to the chemiluminescence intensity value measured in step (2) and described standard curve, the concentration of Determination of Antioxidant Tbhq In Foods is namely obtained。
7. method according to claim 6, it is characterised in that: described in described food standard sample, the concentration of tert-butylhydroquinone is 0～1 × 10-5g/mL。
8. chemical illuminating reagent application in detection Determination of Antioxidant Tbhq In Foods；
Described chemical illuminating reagent is the mixed liquor of luminol-potassium permanganate system and alkaline pH adjusting agent；
Described luminol-potassium permanganate system is the aqueous solution of luminol and potassium permanganate。
9. application according to claim 8, it is characterised in that: described food is edible oil；
Described edible oil is at least one in Oleum Gossypii semen, Oleum Arachidis hypogaeae semen and soybean oil。
10. application according to claim 8 or claim 9, it is characterized in that: in described chemical illuminating reagent, the concentration of described luminol is 0.1～0.8mmol/L, and the concentration of described potassium permanganate is 0.01～0.2mmol/L, and the concentration of described alkaline pH adjusting agent is 0.05～0.5mmol/L。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110887909A (en) * | 2019-12-10 | 2020-03-17 | 洽洽食品股份有限公司 | Detection method for TBHQ in compound additive of fried nut product |
| CN114062337A (en) * | 2021-11-23 | 2022-02-18 | 福州大学 | Method for detecting tert-butyl hydroquinone based on up-conversion nanoparticles of core-shell structure |
| CN115128062A (en) * | 2022-08-29 | 2022-09-30 | 中储粮成都储藏研究院有限公司 | Method for detecting freshness of grains and application |
| CN115452809A (en) * | 2022-08-16 | 2022-12-09 | 西南交通大学 | Based on H 2 O 2 -luminol chemiluminescence system and triphenyl phosphate detection method |
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2016
- 2016-03-24 CN CN201610175957.9A patent/CN105699535B/en not_active Expired - Fee Related
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110887909A (en) * | 2019-12-10 | 2020-03-17 | 洽洽食品股份有限公司 | Detection method for TBHQ in compound additive of fried nut product |
| CN114062337A (en) * | 2021-11-23 | 2022-02-18 | 福州大学 | Method for detecting tert-butyl hydroquinone based on up-conversion nanoparticles of core-shell structure |
| CN114062337B (en) * | 2021-11-23 | 2023-03-17 | 福州大学 | Method for detecting tert-butyl hydroquinone based on up-conversion nanoparticles of core-shell structure |
| CN115452809A (en) * | 2022-08-16 | 2022-12-09 | 西南交通大学 | Based on H 2 O 2 -luminol chemiluminescence system and triphenyl phosphate detection method |
| CN115128062A (en) * | 2022-08-29 | 2022-09-30 | 中储粮成都储藏研究院有限公司 | Method for detecting freshness of grains and application |
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