CN109342620A - The method of means of derivation extraction Rapid Determination of Formaldehyde in Food - Google Patents
The method of means of derivation extraction Rapid Determination of Formaldehyde in Food Download PDFInfo
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- G—PHYSICS
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- 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
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention provides a kind of method of means of derivation extraction Rapid Determination of Formaldehyde in Food, and this method is using the derivative liquid of pH2, and after room temperature column front derivation, solvent extraction blocks derivative reaction, avoids endogenous formaldehyde during derivatization from generating, lower limit of measurement 1.0mg/kg.
Description
Technical field
The present invention relates to a kind of measuring method of liquid chromatography for measuring formaldehyde in food more particularly to milk powder, inlet and outlet
The measuring method of formaldehyde in aquatic products (including squid), vegetables (including mushroom).
Background technique
Formaldehyde is commonly called as formalin, is irritative gas colourless, with overpowering odor, 35%~40% aqueous solution
It is generally called formalin.Formaldehyde is magma poisonous substance, can in conjunction with protein, suck high-concentration formaldehyde after, it may appear that respiratory tract it is tight
Sharp and oedema, eye shouting pain, headache are remised, bronchial asthma can also occur.Formaldehyde can be waited by diet, breathing or skin contact
Journey enters human body.The food after formaldehyde impregnates is taken in, stomachache, vomiting, breathing suffering can be caused, or even dead.Formaldehyde enters people
It can cause pulmonary edema, liver, the nephremia and blood vessel peripheral edema after body.Meanwhile formaldehyde can be changed into methanol in vivo, there is weak paralysis
Effect, and optic nerve is had some impact on.
Japan in 2001 processes in mushroom " formaldehyde event ": Japan and foreign media largely publicize China's export mushroom containing cause
Cancer formaldehyde carries out " import limitation " and " anti-dumpling investigation " to mushroom.The wholly off outlet of China's mushroom, causes tremendous economic to damage
It loses." formaldehyde problem " in the products such as squid in recent years, has seriously affected development and the sleeve-fish product of squid secondary industry
Outlet.Zhoushan Zhejiang is damaged serious as main exit base.4 kinds of candies such as Philippine's detection White Rabbit creamy candy in 2007
Containing formaldehyde, Philippine and overseas market Related product experience remove frame, and foodsafety is again by global query.
Due to formaldehyde reactivity with higher, can with-OH (hydroxyl) ,-SH (sulfydryl) ,-NH2 (ammonia
Base) nucleophilic addition occurs for the molecule of group, there is a large amount of above-mentioned group in the intracellular of animal body, enzyme system, connect
It can react immediately after touching formaldehyde, generate cytotoxicity, make protein denaturation.The superpower sterilizing ability of formaldehyde is exactly former from this
Kind reaction.When being rich in protein in sample, it is compound to form formaldehyde-protein easily in conjunction with group in protein for the formaldehyde of addition
Object.Therefore, by proposing that a kind of quick, easy, high sensitivity formaldehyde is surveyed to endogenous formaldehyde mechanism of production research in food
The method of determining is of great significance.Formaldehyde in food measuring method is as follows in the prior art:
1, AOAC 931.08 (the 17th edition): the way of distillation, chromotropic acid are qualitative.
2, SC/T 3025-2006 " measurement of formaldehyde in aquatic products ": steam distillation, spectrophotometry, HPLC method are surveyed
It is fixed.
3, NY/T 1283-2007 " measurement of methanal content in mushroom ": steam distillation, colorimetric method for determining.
4, DB33/T 555-2005 " the measurement high performance liquid chromatography of residual formaldehyde in plant derived foods ": 60 DEG C of water
Bath is extracted, and formaldehyde is extracted with acetic acid zinc solution in mushroom, the measurement of HPLC method.
5, GB/T 5009.49-2003 " analysis method of fermented wine sanitary standard ": steam distillation, colorimetric method are surveyed
It is fixed.
6, SN/T 1547-2011 " the measurement liquid chromatography of formaldehyde in import and export food ": 60 DEG C of water-baths are extracted, HPLC
Method measurement.
For steam distillation: it is volatile using formaldehyde, in acid condition, dissociate in retortable isolated sample
The formaldehyde of state and Reversible binding state；But high temperature may cause the generation of endogenous formaldehyde, and steam distillation fills experiment
The air-tightness requirement set is high, and complicated for operation, the rate of recovery is low, is unfavorable for the detection of high-volume sample.Water-bath extraction method can extract trip
Amorph formaldehyde cannot extract Reversible binding state formaldehyde, and mushroom enzyme digestion reaction can be promoted to generate endogenous formaldehyde.
For SN/T 1547-2011: using the derivative liquid of pH5,60 DEG C of water-bath 1h extract formaldehyde in sample, can extract sample
The formaldehyde of middle free state and Reversible binding state, while inhibiting the generation of endogenous formaldehyde；But when 60 DEG C of extractions, in milk powder sample
Formaldehyde has a small amount of increasing trend, fails the generation for blocking endogenous formaldehyde completely.
Summary of the invention
In order to solve technological deficiency present in the measuring method of above-mentioned formaldehyde, the object of the present invention is to provide a kind of derivatives
The method of extraction method Rapid Determination of Formaldehyde in Food, this method is using the derivative liquid of pH2, after room temperature column front derivation, solvent extraction resistance
Disconnected derivative reaction avoids endogenous formaldehyde during derivatization from generating, lower limit of measurement 1.0mg/kg.
In order to achieve the above purpose, the method for means of derivation extraction Rapid Determination of Formaldehyde in Food of the invention is by following step
It is rapid to constitute:
(1) extract
Sample 2.00g is weighed, is placed in 50mL tool plug plastic centrifuge tube or 10mL graduated centrifuge tube, it is derivative that 10mL is added
Liquid；Plug is screwed, is vortexed and mixes 1min, stands 2min；4g ammonium sulfate is added, mixes, to be centrifuged not less than 4000r/min
5min pipettes supernatant, and lower layer's solution repeats extraction 1 time with 5mL acetonitrile, and combining extraction liquid is settled to 10.0mL with acetonitrile, mixes
Miillpore filter is crossed after even, filtrate measures for HPLC；Above-mentioned derivative liquid is the buffering of 2,4-dinitrophenylhydrazine acetonitrile solution and pH2
The mixed solution that solution is constituted, the concentration of 2,4-dinitrophenylhydrazine acetonitrile solution are 2.0g/L, acetonitrile in derivative liquid: buffer solution
Volume ratio be 1:1；
(2) the preparation of formaldehyde derivatives standard working solution
The formaldehyde standard working solution of 5 grades or more various concentrations, the system of formaldehyde derivatives standard working solution are taken respectively
Preparation Method is as follows: pipetting formaldehyde standard working solution 1mL, is accurate to 0.1mL, be placed in 10mL color-comparison tube, 4.0mL is added
The buffer solution of pH 2 is settled to 10mL with 2,4-dinitrophenylhydrazine acetonitrile solution, mixes 1min after covering plug, stands 2min；
Miillpore filter is crossed, filtrate measures for HPLC；The concentration of above-mentioned 2,4-dinitrophenylhydrazine acetonitrile solution is 2.0g/L；
(3) measure
According to selecting the case where formaldehyde derivatives concentration in sample liquid, standard working solution similar in peak area is serial, standard work
The response for making formaldehyde derivatives in solution and sample liquid should all be in the range of linearity that instrument detects, standard working solution and sample liquid
Isometric ginseng injects sample measurement, quantified by external standard method qualitative with retention time；
(4) blank test
In addition to sample is not added, carried out by above-mentioned (1) and (3) operating procedure；
(5) result is calculated and is stated
The residual quantity of formaldehyde in sample is calculated as follows or is calculated using Chromatographic data system, and calculated result needs
It deducts empty
White value:
In formula:
X --- the residual quantity of formaldehyde in sample, unit mg/kg；
A --- the peak area of formaldehyde derivatives in sample liquid；
C --- the concentration of formaldehyde derivatives in standard solution, unit mg/L；
V --- the final constant volume of sample liquid, unit mL；
As--- the peak area of formaldehyde derivatives in standard solution；
Sample mass representated by m --- sample solution, unit g.
As further improved scheme, above-mentioned liquid phase chromatogram condition are as follows:
A) chromatographic column: C18Column, 250mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: acetonitrile-water (60+40, V+V)；
C) flow velocity: 1.0mL/min；
D) Detection wavelength: 355nm；
E) sample volume: 10 μ L.
N-hexane higher for fat content in step (1) sample as further improved scheme, being saturated with acetonitrile
Liquid-liquid distributes grease removal purification.
As further improved scheme, the buffer solution of above-mentioned pH 2 is using preparation 0.1mol/L sodium dihydrogen phosphate water
Solution, with phosphorus acid for adjusting pH to 2.0.
Preferably, above-mentioned sample is milk powder, mushroom, squid, bighead, broccoli.
The present invention uses acetonitrile-phosphate buffer (50+50, V+V) of 2,4-dinitrophenylhydrazine, and column front derivation extracts examination
Formaldehyde in sample, after liquid-liquid extraction blocking reaction, liquid chromatography for measuring.This method is under pH2 derivatization conditions, 2,4- dinitrobenzenes
Formaldehyde in hydrazine and protein in group competitive reaction solution, effectively can inhibit formaldehyde in conjunction with protein in sample, extract trip
The formaldehyde of amorph and Reversible binding state；This method use is stored at room temperature 2min and quickly derives, and solvent extraction blocks derivative reaction,
The release that the samples endogenous formaldehyde such as milk powder, mushroom, squid can effectively be blocked improves the stability and reproduction of detected value
Property.Lower limit of measurement is 1.0mg/kg.
Detailed description of the invention
FIG. 1 to FIG. 3 is the peak area of formaldehyde derivatives with the variation diagram of derivative time；Wherein:
Fig. 1 is the peak area of formaldehyde derivatives under different pH derivatization conditions with the variation diagram of 25 DEG C of derivative time.
Fig. 2 is the peak area of formaldehyde derivatives under different pH derivatization conditions with the variation diagram of 60 DEG C of derivative time.
Fig. 3 is the peak area of various concentration formaldehyde derivatives under pH2 derivatization conditions with the variation diagram of 25 DEG C of derivative time.
Fig. 4 is the chromatogram of concentration 1.0mg/L formaldehyde standard derivative solution.
Fig. 5 is milk powder blank sample chromatogram.
Fig. 6 is the sample chromatogram figure that milk powder blank sample adds formaldehyde standard specimen.
Specific embodiment
Embodiment 1
The following specific embodiments of the present invention is to make a detailed explanation.
1.1 method summaries
Derivative liquid extracts formaldehyde in sample, after liquid-liquid extraction purification, the liquid chromatogram measuring at 355nm wavelength, and external standard method
It is quantitative.
1.2 reagents and material
Unless otherwise stated, agents useful for same is that analysis is pure.Water used is ultrapure water.
1.2.1 acetonitrile: chromatographically pure.
1.2.2 n-hexane: chromatographically pure.
1.2.3 sodium dihydrogen phosphate.
1.2.4 ammonium sulfate.
1.2.5 phosphoric acid.
1.2.6 buffer solution (pH 2): 0.1mol/L biphosphate sodium water solution is prepared, with phosphorus acid for adjusting pH to 2.0.
1.2.7 2,4-dinitrophenylhydrazine: purity >=99%.
1.2.8 2,4-dinitrophenylhydrazine solution: weighing 2,4-dinitrophenylhydrazine 1g, is settled to 500mL with acetonitrile dissolution.
1.2.9 derive liquid: taking 100mL buffer solution (1.2.6) and 100mL 2,4-dinitrophenylhydrazine solution (1.2.8),
It mixes.
1.2.10 formaldehyde standard solution (100 μ g/mL).
1.2.11 formaldehyde standard working solution: pipetting appropriate formaldehyde standard solution (1.2.10), is diluted with water to appropriate dense
Degree.
1.2.12 miillpore filter: 0.45 μm, organic phase.
1.3 instrument and equipment
1.3.1 high performance liquid chromatograph: it be furnished with diode array detector or UV detector.
1.3.2 homogenizer.
1.3.3 vortex instrument
1.3.4 supercentrifuge.
1.4 determination step
1.4.1 extracting
Sample 2g (being accurate to 0.01g) is weighed, is placed in 50mL tool plug plastic centrifuge tube or 10mL graduated centrifuge tube, accurately
It is derivative liquid (1.2.9) that 10mL is added.Plug is screwed, is vortexed and mixes 1min, stands 2min；4g ammonium sulfate is added, mixes, with not low
It is centrifuged 5min in 4000r/min, pipettes supernatant, lower layer's solution repeats extraction 1 time with 5mL acetonitrile, and combining extraction liquid uses acetonitrile
It is settled to 10.0mL, crosses miillpore filter (1.2.12) after mixing, filtrate measures for HPLC.
Note: if fat content is higher in sample, the n-hexane liquid-liquid distribution grease removal purification that 10mL acetonitrile is saturated can be used；
The dry samples such as dried thin mushroom, need to first plus water redissolves.
1.4.2 the preparation of formaldehyde derivatives standard working solution
The formaldehyde standard working solution (1.2.11) for taking 5 grades or more various concentrations respectively, is placed in 10mL color-comparison tube
In, buffer solution (1.2.6) is added to 5.0mL, is settled to 10.0mL with 2,4-dinitrophenylhydrazine solution (1.2.8), is covered plug
After mix, be vortexed mix 1min, stand 2min, cross miillpore filter, filtrate for HPLC measure.
1.4.3 measurement
1.4.3.1 liquid phase chromatogram condition
Liquid phase chromatogram condition are as follows:
A) chromatographic column: C18Column, 250mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: acetonitrile-water (60+40, V+V)；
C) flow velocity: 1.0mL/min；
D) Detection wavelength: 355nm；
E) sample volume: 10 μ L.
1.4.3.2 chromatographic determination
According to selecting the case where formaldehyde derivatives concentration in sample liquid, standard working solution similar in peak area is serial.Standard work
The response for making formaldehyde derivatives in solution and sample liquid should all be in the range of linearity that instrument detects.Standard working solution and sample liquid
Isometric ginseng injects sample measurement.It is qualitative with retention time, quantified by external standard method.The reservation of formaldehyde derivatives under above-mentioned chromatographic condition
Time is about 5.5min.
1.4.4 blank test
In addition to sample is not added, carried out by above-mentioned 1.4.1 and 1.4.3 operating procedure.
1.5 results calculate and statement
The residual quantity of formaldehyde in sample is calculated by formula (1) or Chromatographic data system is used to calculate.Calculated result deducts
Blank value.
In formula:
X --- the residual quantity of formaldehyde in sample, unit are milligrams per kilogram (mg/kg) or milligrams per liter (mg/L)；
A --- the peak area of formaldehyde derivatives in sample liquid；
C --- the concentration of formaldehyde derivatives in standard solution, unit are milligrams per liter (mg/L)；
V --- the final constant volume of sample liquid, unit are milliliter (mL)；
As--- the peak area of formaldehyde derivatives in standard solution；
Sample mass representated by m --- sample solution, unit are gram (g).
The selection of 2.1 derivatization reaction conditions
Respectively with acetonitrile-pH2 phosphate buffer (volume ratio 1:1), acetonitrile-pH5 phosphate buffer (volume ratio 1:
1), acetonitrile-pH7 water (volume ratio 1:1) compound concentration is the derivative solution of 1g/L 2,4-dinitrophenylhydrazine, each to prepare 1mg/L first
Aldehyde derivatives standard specimen, respectively in 25 DEG C and 60 DEG C of derivatives, formaldehyde derivatives peak area-time graph is shown in Fig. 1 and Fig. 2 respectively.It adopts
With the derivative liquid of pH2,25 DEG C, 60 DEG C of standing 5min are derivative complete；Using the derivative liquid of pH5,25 DEG C of derivative 20min, 60 DEG C of derivatives
10min is derivative complete；Using the derivative liquid of pH7,25 DEG C of derivative 120min, 60 DEG C of derivative 30min are derivative complete.Selection pH2 spreads out
Raw liquid, prepares 1,10,20,40mg/L formaldehyde derivatives standard working solution, 25 DEG C of derivatives, formaldehyde derivatives peak area-respectively
Time graph is shown in Fig. 3 respectively.Therefore, when concentration of formaldehyde≤20mg/L, using the derivative liquid of pH2,25 DEG C of vortex 1min stand 2min
It can derive completely.
The blocking of 2.2 purification conditions and derivatization reaction
By the derivatization conditions test of formaldehyde standard specimen it is found that reaction efficiency when ethane nitrile content is 50% in reaction system is high,
Reaction efficiency is low when ethane nitrile content is 100%.Salting out method can preferable precipitating proteins and water-solubility impurity, acetonitrile/water ratio
Example can preferable protein precipitation when being 2~3.Test selection acetonitrile saturation n-hexane degreasing, ammonium sulfate precipitation protein precipitation and
Except water-solubility impurity.When being extracted using derivative liquid, increase of the samples such as milk powder, mushroom, squid with extraction time, endogenous formaldehyde
Release is incremented by；Derivatization reaction can be effectively blocked using organic solvent extraction derivative products.
2.3 methods compare
Derivative liquid extraction method, water-bath extraction method, steam distillation is respectively adopted, investigate different detection methods to milk powder,
The influence that endogenous formaldehyde generates in dried thin mushroom and squid loop, the results are shown in Table 1.Taking milk powder sample is blank, adds concentration of formaldehyde
The rate of recovery for 5mg/kg, the derivative liquid extraction method rate of recovery 90%, immersion method is 70%, and the rate of recovery of steam distillation is
65%.
Derivative liquid extraction method, with being incremented by for derivative time and temperature, formaldehyde has obvious increasing trend in three kinds of matrix.
25 DEG C of derivative 2min, the formaldehyde of milk powder, dried thin mushroom and squid loop is respectively 0.4mg/kg, 0.6mg/kg and 4.5mg/kg.60℃
Derivative 120min, the formaldehyde of milk powder, dried thin mushroom and squid loop is respectively 2.8mg/kg, 13.1mg/kg and 35.0mg/kg.It excludes
Exogenous formaldehyde adds, and endogenous formaldehyde desired result should be to be not detected in milk powder, dried thin mushroom and squid loop.Formaldehyde standard specimen is
It can derive completely, can utmostly inhibit the release of endogenous formaldehyde；
Water-bath extraction method, with being incremented by for extraction time and temperature, bacterium acid enzymatic hydrolysis release formaldehyde is obvious in dried thin mushroom, squid
Formaldehyde increasing trend is slightly slow in circle.When 25 DEG C of extraction 2min, content of formaldehyde is respectively 0.5mg/ in milk powder, dried thin mushroom and squid loop
Kg, 11mg/kg and 3.6mg/kg；40 DEG C of derivative 120min, in dried thin mushroom and squid loop content of formaldehyde be respectively 455mg/kg and
17.4mg/kg。
Steam distillation avoids conventional equipment distillation (1~2h) for a long time using automatic distilling apparatus 6min.Milk
Content of formaldehyde is respectively 0.5mg/kg, 10.5mg/kg and 29.3mg/kg in powder, dried thin mushroom and squid loop.Distillation process, squid
It is obvious to enclose high temperature decomposition approach generation endogenous formaldehyde.
In conclusion adding the formaldehyde rate of recovery with higher using derivative liquid extraction method in milk powder, free state can be extracted
With Reversible binding state formaldehyde；It is minimum to measure content of formaldehyde in three kinds of matrix, can utmostly inhibit milk powder, dried thin mushroom and squid loop
The release of middle endogenous formaldehyde.
The different detection methods of table 1 measure formaldehyde result
Three index determinings of the method for embodiment 1
1, linear relationship and detection limit
Under the experiment condition that this method determines, formaldehyde has good line within the scope of 0.20~5.00mg/L with response
Sexual intercourse, linear equation y=344.6x+7.222, related coefficient 0.9999.This method is low to the measurement of formaldehyde in sample
It is limited to 1.0mg/kg.
2, the rate of recovery and precision
The recovery test of this method is the test of TIANZHU XINGNAO Capsul.Milk powder, bighead, broccoli blank sample are selected, point
Not Tian Jia concentration of formaldehyde be 1.0mg/kg, 2.0mg/kg, 5.0mg/kg, be measured in parallel 6 times.Containing micro- in the blank sample of selection
Formaldehyde is measured, recycling measured value subtracts blank sample background values.The rate of recovery and precision are shown in Table 2~table 4.
The TIANZHU XINGNAO Capsul test of formaldehyde in 2 milk powder of table
The TIANZHU XINGNAO Capsul test of formaldehyde in 3 bighead of table
The TIANZHU XINGNAO Capsul test of formaldehyde in 4 broccoli of table
3. method detection limit
This method is 1.0mg/kg to the lower limit of measurement of formaldehyde in sample.Fig. 4 is that concentration 1.0mg/L formaldehyde standard derivative is molten
The chromatogram of liquid, Fig. 5, Fig. 6 are respectively milk powder blank sample and the sample chromatogram figure for adding formaldehyde standard specimen.
Claims (5)
1. the method for means of derivation extraction Rapid Determination of Formaldehyde in Food, which is characterized in that the measuring method is by following step structure
At:
(1) extract
Sample 2g is weighed, 0.01g is accurate to, is placed in 50mL tool plug plastic centrifuge tube, the derivative liquid of 10mL is added；Plug is screwed,
It is vortexed and mixes 1min, stand 2min；4g ammonium sulfate is added, mixes, to be centrifuged 5min not less than 4000r/min, pipettes supernatant,
Lower layer's solution repeats extraction 1 time with 5mL acetonitrile, and combining extraction liquid is settled to 10.0mL with acetonitrile, and miillpore filter is crossed after mixing,
Filtrate measures for HPLC；Above-mentioned derivative liquid is the mixing of 2,4-dinitrophenylhydrazine acetonitrile solution and the buffer solution composition of pH2
Solution, the concentration of 2,4-dinitrophenylhydrazine acetonitrile solution are 2.0g/L, acetonitrile in derivative liquid: the volume ratio of buffer solution is 1:1；
(2) the preparation of formaldehyde derivatives standard working solution
The formaldehyde standard working solution of 5 grades or more various concentrations, the preparation side of formaldehyde derivatives standard working solution are taken respectively
Method is as follows: pipetting formaldehyde standard working solution 1mL, is accurate to 0.1mL, be placed in 10mL color-comparison tube, 4.0mL pH is added
2 buffer solution is settled to 10mL with 2,4-dinitrophenylhydrazine acetonitrile solution, mixes 1min after covering plug, stands 2min；It crosses micro-
Hole filter membrane, filtrate measure for HPLC；The concentration of above-mentioned 2,4-dinitrophenylhydrazine acetonitrile solution is 2.0g/L；
(3) measure
According to the series of standard working solution similar in peak area is selected in sample liquid the case where formaldehyde derivatives concentration, standard work is molten
The response of formaldehyde derivatives should all be in the range of linearity that instrument detects in liquid and sample liquid, the bodies such as standard working solution and sample liquid
Product ginseng injects sample measurement, quantified by external standard method qualitative with retention time；
(4) blank test
In addition to sample is not added, carried out by above-mentioned (1) and (3) operating procedure；
(5) result is calculated and is stated
The residual quantity of formaldehyde in sample is calculated as follows or is calculated using Chromatographic data system, and calculated result needs to deduct
Blank value:
In formula:
X --- the residual quantity of formaldehyde in sample, unit mg/kg；
A --- the peak area of formaldehyde derivatives in sample liquid；
C --- the concentration of formaldehyde derivatives in standard solution, unit mg/L；
V --- the final constant volume of sample liquid, unit mL；
As--- the peak area of formaldehyde derivatives in standard solution；
Sample mass representated by m --- sample solution, unit g.
2. the method for means of derivation extraction Rapid Determination of Formaldehyde in Food according to claim 1, which is characterized in that liquid phase color
Spectral condition are as follows:
A) chromatographic column: C18Column, 250mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: acetonitrile-water (60+40, V+V)；
C) flow velocity: 1.0mL/min；
D) Detection wavelength: 355nm；
E) sample volume: 10 μ L.
3. the method for means of derivation extraction Rapid Determination of Formaldehyde in Food according to claim 1, which is characterized in that for step
Suddenly fat content is higher in (1) sample, the n-hexane liquid-liquid distribution grease removal purification being saturated with acetonitrile.
4. the method for means of derivation extraction Rapid Determination of Formaldehyde in Food according to claim 1, which is characterized in that pH's 2
Buffer solution is using 0.1mol/L biphosphate sodium water solution is prepared, with phosphorus acid for adjusting pH to 2.0.
5. the side of means of derivation extraction Rapid Determination of Formaldehyde in Food described in any one claim according to claim 1~4
Method, which is characterized in that sample is milk powder, mushroom, squid, bighead or broccoli.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115128199A (en) * | 2022-07-22 | 2022-09-30 | 郑州大学第一附属医院 | Method for detecting furfural compounds in suction head type microextraction injection and oral liquid |
| CN115248257A (en) * | 2021-04-26 | 2022-10-28 | 湖南中烟工业有限责任公司 | Preparation and detection method of sample to be detected of formaldehyde in packaging material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101762660A (en) * | 2010-01-08 | 2010-06-30 | 浙江出入境检验检疫局检验检疫技术中心 | Method for testing formaldehyde in food by means of derivation extraction |
| CN102798675A (en) * | 2012-08-13 | 2012-11-28 | 舟山市疾病预防控制中心 | Method for detecting free formaldehyde in instant seafood |
| CN104634889A (en) * | 2014-12-10 | 2015-05-20 | 浙江出入境检验检疫局检验检疫技术中心 | Method for measuring formaldehyde in cosmetics by using online derivatization |
| CN108469472A (en) * | 2017-12-19 | 2018-08-31 | 江苏康达检测技术股份有限公司 | The assay method of concentration of formaldehyde in solid waste |
-
2018
- 2018-11-22 CN CN201811399066.7A patent/CN109342620A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101762660A (en) * | 2010-01-08 | 2010-06-30 | 浙江出入境检验检疫局检验检疫技术中心 | Method for testing formaldehyde in food by means of derivation extraction |
| CN102798675A (en) * | 2012-08-13 | 2012-11-28 | 舟山市疾病预防控制中心 | Method for detecting free formaldehyde in instant seafood |
| CN104634889A (en) * | 2014-12-10 | 2015-05-20 | 浙江出入境检验检疫局检验检疫技术中心 | Method for measuring formaldehyde in cosmetics by using online derivatization |
| CN108469472A (en) * | 2017-12-19 | 2018-08-31 | 江苏康达检测技术股份有限公司 | The assay method of concentration of formaldehyde in solid waste |
Non-Patent Citations (2)
| Title |
|---|
| 吕春华 等: ""柱前衍生-萃取阻断反应-高效液相色谱法测定化妆品中游离甲醛"", 《色谱》 * |
| 吕春华 等: ""衍生液提取-高效液相色谱法测定食品中甲醛"", 《理化检验-化学分册》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115248257A (en) * | 2021-04-26 | 2022-10-28 | 湖南中烟工业有限责任公司 | Preparation and detection method of sample to be detected of formaldehyde in packaging material |
| CN115128199A (en) * | 2022-07-22 | 2022-09-30 | 郑州大学第一附属医院 | Method for detecting furfural compounds in suction head type microextraction injection and oral liquid |
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