CN101762660A - Method for testing formaldehyde in food by means of derivation extraction - Google Patents
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Abstract
The invention relates to a method for testing the content of formaldehyde in food by means of liquid chromatography, in particular to a method for testing the formaldehyde in import and export aquatic products, vegetables (including mushroom), cereal products, dairy products and beers, etc. The method for testing the content of the formaldehyde in the food by means of liquid chromatography comprises the steps of: (1) extracting; (2) purifying; (3) preparing formaldehyde standard work solution; (4) testing; (5) blank testing; and (6) computing and expressing a result. The method adopts acetonitrile/ pH 5 ethylic acid buffer solution (1/1, v/v) of 2, 4-dinitrophenylhydrazine to directly derive and extract the formaldehyde in a sample and test by means of the liquid chromatography. The formaldehyde is extracted from the sample under water bath at the temperature of 60 DEG C and the derivatization reaction is performed. The 2, 4-dinitrophenylhydrazine and the group in protein compete for the formaldehyde in the reaction solution, thereby being capable of effectively preventing the formaldehyde from combining with the protein in the sample and having higher formaldehyde recovery ratio than that of by using an immersion method.
Description
Technical field
The present invention relates to a kind of assay method of liquid chromatography for measuring formaldehyde in food, relate in particular to the assay method of importing and exporting formaldehyde in aquatic products, vegetables (comprising mushroom), cereal product, dairy products, the beer etc.
Background technology
Formaldehyde is commonly called as formalin, is irritative gas colourless, that have overpowering odor, its aqueous solution of 35%～40% common name formalin.Formaldehyde is the magma poisonous substance, can and protein bound, suck high-concentration formaldehyde after, the serious stimulation of respiratory tract and oedema, eye shouting pain, headache can appear, also bronchial astehma can take place.Skin directly contacts formaldehyde, can cause dermatitis, color spot, necrosis.Often suck a small amount of formaldehyde, can cause slow poisoning, mucous hyperemia, skin irritatin disease, allergic dermatitis, nail angling and fragility, nail matrix finger tip pain appear, the long-term suction of pregnant woman may cause the ewborn infant deformity, even dead, the long-term suction of man can cause man's teratospermia, death, sexual disorder, serious caused fecundity disappearance, constitutional symptom have headache, weak, that stomach is received is poor, palpitaition, have a sleepless night, lose weight and vegetative nervous disorder etc.
Calendar year 2001 Japan concocts in the mushroom " formaldehyde incident ": Japan and foreign media propagate China's outlet mushroom in a large number and contain carcinogenic formaldehyde, and mushroom is carried out " import limit the quantity of " with " anti-dumpling investigation ".China's mushroom all stops outlet, causes the tremendous economic loss." formaldehyde exceed standard problem " in the goods such as squid has had a strong impact on the development and the outlet of squid goods of squid secondary industry in recent years.Zhoushan Zhejiang is as the main exit base, and is impaired serious.4 kinds of candies such as Philippine's detection White Rabbit creamy candy contained formaldehyde in 2007, and Philippine and market abroad Related product meet with and remove frame, and foodsafety is subjected to global query once more.
Because formaldehyde has high reaction activity and high, can with have-OH (hydroxyl) ,-SH (sulfydryl) ,-the molecule generation nucleophilic addition of NH2 (amino) group, in the cell of animal body, exist a large amount of above-mentioned groups in the enzyme system, can react immediately behind the contact formaldehyde, produce cytotoxicity, make protein denaturation.The superpower sterilizing ability of formaldehyde is former in just this reaction.When being rich in protein in the sample, the formaldehyde of interpolation easily combines with group in the protein, forms formaldehyde-protein complex.Therefore, endogenous formaldehyde mechanism of production in the food is studied, proposing a kind of method for determining formaldehyde highly sensitive, easy and simple to handle will contribute for China's food export breakthrough international " green barrier ".
The formaldehyde in food assay method is as follows in the prior art:
1, AOAC 931.08 (the 17th edition): the way of distillation, chromotropic acid is qualitative.
2, the mensuration of formaldehyde in the SCT 3025-2006 aquatic products: steam distillation, spectrophotometric method, HPLC method are measured.
3, the mensuration of content of formaldehyde in the NYT 1283-2007 mushroom: steam distillation, colorimetric method for determining.
4, the mensuration high performance liquid chromatography of DB33T 555-2005 plant source formaldehyde in food residual quantity: 60 ℃ of water-baths are extracted, and formaldehyde extracts with acetic acid zinc solution in the mushroom, and the HPLC method is measured.
5, the analytical approach of GBT 5009.49-2003 fermented wine hygienic standard: steam distillation, colorimetric method for determining.
6, content of formaldehyde is measured liquid phase chromatography in the SNT 1547-2005 import and export food: 40 ℃ of water-baths are extracted, and the HPLC method is measured.
For steam distillation: utilize formaldehyde volatile, under acid condition, retortable separation obtains the formaldehyde of free state and reversible combined state in the sample.But high temperature may cause the generation of endogenous formaldehyde, and steam distillation is high to the impermeability requirement of experimental provision, and complicated operation is unfavorable for the detection of sample in enormous quantities.
Adopt water seaoning to extract formaldehyde for SN/T 1547-2005: water fully extracts formaldehyde in the sample, again with extract and 2,4 dinitrophenyl hydrazine derivatization reaction, and direct liquid chromatogram measuring.Water seaoning can effectively be extracted the formaldehyde of free state in the sample, but sample (as aquatic products, dairy products etc.) is when being rich in protein, the formaldehyde that adds easily combines with group in the protein, forms formaldehyde-protein complex, and it is not good to make water seaoning measure the recovery that is rich in formaldehyde in the protein sample.SN/T 1547-2005 has adopted the correction work solution of formaldehyde, adds the formaldehyde of variable concentrations level in the low matrix of content of formaldehyde, presses sample and extracts operation back liquid chromatogram measuring, makes the formaldehyde recovery improve.But in the practical operation, all there is certain degree of difficulty in result's ratio equity between the making of blank choice of base, formaldehyde correction work curve, different experiments chamber.
Summary of the invention
For the technological deficiency that exists in the assay method that solves above-mentioned content of formaldehyde, the purpose of this invention is to provide a kind of means of derivation extraction and measure the method for formaldehyde in food, this method is directly extracted formaldehyde in the sample of deriving, change formaldehyde correction work solution into formaldehyde standard operation solution, improved the recovery that is rich in formaldehyde in the protein sample, measured lower bound and change into " in the liquid type sample
The mensuration lower bound of formaldehyde is 2.0mg/L, and the mensuration lower bound of formaldehyde is 5.0mg/kg in the solid kind sample ".
In order to realize above-mentioned purpose, the method that means of derivation extraction of the present invention is measured formaldehyde in food is made of following step:
(1) extracts
1. solid kind sample: take by weighing sample 2g, be accurate to 0.01g, place 50mL tool plug plastic centrifuge tube, accurately add the 20.0mL liquid of deriving; Screw stopper, mixing is placed in 60 ℃ of constant temperature oscillators, the 150r/min jolting, and 20min takes out mixing at interval, takes out cooling behind the jolting 1h; The above-mentioned liquid of deriving is the mixed solution that the buffer solution of 2,4 dinitrophenyl hydrazine acetonitrile solution and pH 5 constitutes, and the concentration of 2,4 dinitrophenyl hydrazine acetonitrile solution is 0.6g/L, acetonitrile in the liquid of deriving: the volume ratio of buffer solution is 1: 1;
2. liquid type sample: pipette sample 1mL, be accurate to 0.1mL, place the 10mL color-comparison tube, add 4.0mLpH
5 buffer solution is settled to 10mL with the 2,4 dinitrophenyl hydrazine acetonitrile solution, covers plug back mixing, and 60 ℃ of water-bath heating 1h take out cooling; The concentration of above-mentioned 2,4 dinitrophenyl hydrazine acetonitrile solution is 0.6g/L;
(2) purify
1. solid kind sample: with the above-mentioned solid kind sample extract that makes, to be not less than the centrifugal 5min of 4000r/min; For the clarification of centrifugal back solution, cross miillpore filter after, directly measure for HPLC; For centrifugal back solution muddiness, in extract, add 8g ammonium sulfate, mixing is to be not less than the centrifugal 5min of 4000r/min, pipette supernatant, 10mL acetonitrile re-extract 1 time of lower floor's solution, combining extraction liquid, be settled to 20mL with acetonitrile, cross miillpore filter behind the mixing, filtrate is measured for HPLC;
2. liquid type sample: the purification method of extract is identical with the solid kind sample, and the agents useful for same amount reduces by half;
(3) preparation of formaldehyde standard operation solution
Get the formaldehyde standard operation solution of 5 grades or above variable concentrations respectively, the preparation method of formaldehyde standard operation solution is as follows: pipette sample 1mL, be accurate to 0.1mL, place the 10mL color-comparison tube, add the buffer solution of 4.0mLpH 5, with 2,4-dinitrophenylhydrazine acetonitrile solution is settled to 10mL, cover plug back mixing, 60 ℃ of water-bath heating 1h take out cooling; Miillpore filter is crossed in the cooling back, and filtrate is measured for HPLC; The concentration of above-mentioned 2,4 dinitrophenyl hydrazine acetonitrile solution is 0.6g/L;
(4) measure
According to the selected close standard operation solution series of peak area of the situation of concentration of formaldehyde in the sample liquid, the response of formaldehyde derivatives all should be in the range of linearity of instrument detecting in standard operation solution and the sample liquid, standard operation solution and sample liquid equal-volume ginseng inject sample and measure, qualitative with retention time, external standard method is quantitative;
(5) blank test
Except that not adding the sample, all undertaken by above-mentioned (1)～(4) operation steps;
(6) result calculates and statement
Calculate the residual quantity of formaldehyde in the sample as follows or adopt the chromatographic data disposal system to calculate, result of calculation need be deducted blank value:
In the formula:
X---the residual quantity of formaldehyde in the sample, unit is mg/kg;
A---the peak area of formaldehyde derivatives in the sample liquid;
C---the concentration of formaldehyde derivatives in the standard solution, unit is mg/L;
V---the final constant volume of sample liquid, unit are mL;
A
s---the peak area of formaldehyde derivatives in the standard solution;
M---the sample mass of sample solution representative, unit are g.
As further improved plan, above-mentioned liquid phase chromatogram condition is:
A) chromatographic column: C
18Post, 250mm * 4.6mm (internal diameter), 5 μ m, or suitable person;
B) moving phase: methanol-water (70+30, V+V),
C) flow velocity: 1.0mL/min;
D) detect wavelength: 365nm;
E) sample size: 20 μ L.
As further improved plan, higher for fat content in step (2) the solid kind sample, distribute grease removal to purify with the saturated normal hexane liquid of acetonitrile-liquid.
As further improved plan, the buffer solution of above-mentioned pH 5 adopts and takes by weighing the 2.64g sodium acetate, with the suitable quantity of water dissolving, adds the 1.0mL glacial acetic acid, and water is settled to 500mL and makes.
As preferably, above-mentioned sample is silverfish, mushroom, flour, milk powder, toffee, cream, milk beverage or beer.
The present invention adopt 2,4 dinitrophenyl hydrazine acetonitrile-acetate buffer solution (50+50 V+V), directly derives and extracts formaldehyde in the sample, after liquid-liquid extraction purifies, liquid chromatogram measuring.When formaldehyde is extracted in the samples in 60 ℃ of water-baths, carry out derivative reaction.Formaldehyde in 2,4 dinitrophenyl hydrazine and the protein in the group competitive reaction solution can effectively suppress protein bound in formaldehyde and the sample, thereby than water seaoning the higher formaldehyde recovery is arranged.This method is directly extracted formaldehyde in the sample of deriving, and changes formaldehyde correction work solution into formaldehyde standard operation solution, has improved the recovery that is rich in formaldehyde in the protein sample.This method can effectively be extracted formaldehyde in the mushroom, can block enzyme reaction in the mushroom again simultaneously, suppresses the release of endogenous formaldehyde, has improved the stability and the reappearance of detected value.This method combines extraction step and derivative reaction, has effectively improved detection efficiency.Measure lower bound and change " the mensuration lower bound of formaldehyde is 2.0mg/L in the liquid type sample, and the mensuration lower bound of formaldehyde is 5.0mg/kg in the solid kind sample " into.
Description of drawings
Fig. 1～Fig. 4 is the measurement result figure of formaldehyde in the different system mushrooms in the test example 3; Wherein:
Fig. 1 is a pure aquatic system, and Fig. 2 is acetonitrile/water (a 1/1) system, and Fig. 3 is acetonitrile/water (2/1) system and acetonitrile, and Fig. 4 is acetonitrile/water (1/1) system of deriving.
Fig. 5 is the chromatogram of concentration 0.2 μ g/mL formaldehyde standard derivative solution.
Sample chromatogram figure after Fig. 6～Figure 13 is respectively each blank sample and adds standard specimen; Wherein:
Fig. 6 (a) silverfish blank sample and Fig. 6 (b) add 5.0mg/kg formaldehyde sample chromatogram figure;
Fig. 7 (a) mushroom blank sample and Fig. 7 (b) add 5.0mg/kg formaldehyde sample chromatogram figure;
Fig. 8 (a) flour blank sample and Fig. 8 (b) add 5.0mg/kg formaldehyde sample chromatogram figure;
Fig. 9 (a) milk powder blank sample and Fig. 9 (b) add 5.0mg/kg formaldehyde sample chromatogram figure;
Figure 10 (a) toffee blank sample and Figure 10 (b) add 5.0mg/kg formaldehyde sample chromatogram figure;
Figure 11 (a) cream blank sample and Figure 11 (b) add 5.0mg/kg formaldehyde sample chromatogram figure;
Figure 12 (a) milk beverage blank sample and Figure 12 (b) add 2.0mg/L formaldehyde sample chromatogram figure;
Figure 13 (a) beer blank sample and Figure 13 (b) add 2.0mg/L formaldehyde sample chromatogram figure.
Embodiment
The following specific embodiments of the present invention is to make a detailed explanation.
1.1 method summary
Directly extract the formaldehyde in the sample of deriving.After liquid-liquid extraction purified, at 365nm wavelength place liquid chromatogram measuring, external standard method was quantitative.
1.2 reagent and material
Unless otherwise indicated, it is pure that agents useful for same is analysis.Institute's water is to boil the ultrapure water that cools off behind the 10min.
1.2.1 acetonitrile: chromatographically pure.
1.2.2 normal hexane: chromatographically pure.
1.2.3 ammonium sulfate.
1.2.4 sodium acetate.
1.2.5 glacial acetic acid
1.2.6 buffer solution (pH 5): take by weighing the 2.64g sodium acetate, with the suitable quantity of water dissolving, add the 1.0mL glacial acetic acid, water is settled to 500mL and makes.
1.2.7 2,4 dinitrophenyl hydrazine: purity 〉=99%.
1.2.8 2,4 dinitrophenyl hydrazine solution: take by weighing 2,4 dinitrophenyl hydrazine 300mg, be settled to 500mL with the acetonitrile dissolving.
The liquid 1.2.9 derive: get 100mL buffer solution (1.2.6) and 100mL 2,4 dinitrophenyl hydrazine solution (1.2.8), mixing.
1.2.10 formaldehyde standard solution (100 μ g/mL): GSB07-1179.
1.2.11 formaldehyde standard operation solution: pipette an amount of formaldehyde standard solution (1.2.7), (1.2.3) is diluted to debita spissitudo with buffer solution.
1.2.12 miillpore filter: 0.45 μ m, organic phase.
1.3 instrument and equipment
1.3.1 high performance liquid chromatograph: be furnished with diode array detector or UV-detector.
1.3.2 bruiser.
1.3.3 constant temperature oscillator.
1.4 determination step
1.4.1 extract
1.4.1.1 solid kind sample
Take by weighing sample 2g (being accurate to 0.01g), place 50mL tool plug plastic centrifuge tube, accurately add the 20.0mL liquid (1.2.9) of deriving.Screw stopper, mixing is placed in 60 ℃ of constant temperature oscillators, the 150r/min jolting, and 20min takes out mixing at interval, takes out cooling behind the jolting 1h.
1.4.1.2 liquid type sample
Pipette sample 1mL (being accurate to 0.1mL), place the 10mL color-comparison tube, add 4.0mL buffer solution (1.2.6), (1.2.8) is settled to 10mL with 2,4 dinitrophenyl hydrazine solution, covers plug back mixing, and 60 ℃ of water-bath heating 1h take out cooling.
1.4.2 purify
1.4.2.1 solid kind sample
With the 1.4.1.1 extract, to be not less than the centrifugal 5min of 4000r/min.As the clarification of centrifugal back solution, cross miillpore filter (1.2.12) after, directly measure for HPLC.As centrifugal back solution muddiness, in extract, add 8g ammonium sulfate (1.2.3), mixing, to be not less than the centrifugal 5min of 4000r/min, pipette supernatant, 10mL acetonitrile re-extract 1 time of lower floor's solution, combining extraction liquid, be settled to 20mL with acetonitrile, cross miillpore filter (1.2.12) behind the mixing, filtrate is measured for HPLC.
Annotate:, can distribute grease removal to purify with the saturated normal hexane liquid of 10mL acetonitrile-liquid if fat content is higher in the sample.
1.4.2.2 liquid type sample
1.4.1.2 the purification of extract is referring to 1.4.2.1, the agents useful for same amount reduces by half.
1.4.3 the preparation of formaldehyde standard operation solution
Get the formaldehyde standard operation solution (1.2.11) of 5 grades or above variable concentrations respectively, press the 1.4.1.2 operation, miillpore filter (1.2.12) is crossed in the cooling back, and filtrate is measured for HPLC.
1.4.4 measure
1.4.4.1 liquid phase chromatogram condition
Liquid phase chromatogram condition is:
A) chromatographic column: C
18Post, 250mm * 4.6mm (internal diameter), 5 μ m, or suitable person;
B) moving phase: methanol-water (70+30, V+V);
C) flow velocity: 1.0mL/min;
D) detect wavelength: 365nm;
E) sample size: 20 μ L.
1.4.4.2 chromatographic determination
According to the selected close standard operation solution series of peak area of the situation of concentration of formaldehyde in the sample liquid.The response of formaldehyde derivatives all should be in the range of linearity of instrument detecting in standard operation solution and the sample liquid.Standard operation solution and sample liquid equal-volume ginseng inject sample and measure.Qualitative with retention time, external standard method is quantitative.The retention time of formaldehyde derivatives is about 6.5min under above-mentioned chromatographic condition.
1.4.5 blank test
Except that not adding the sample, all undertaken by the aforesaid operations step.
1.5 the result calculates and statement
Calculate the residual quantity of formaldehyde in the sample or adopt the chromatographic data disposal system to calculate by formula (1).Result of calculation need be deducted blank value.
In the formula:
X---the residual quantity of formaldehyde in the sample, unit is every kilogram (mg/kg) of milligram;
A---the peak area of formaldehyde derivatives in the sample liquid;
C---the concentration of formaldehyde derivatives in the standard solution, unit is every liter (mg/L) of milligram;
V---the final constant volume of sample liquid, unit is milliliter (mL);
A
s---the peak area of formaldehyde derivatives in the standard solution;
M---the sample mass of sample solution representative, unit is gram (g).；
The mensuration of formaldehyde in test example 1 animal-derived food
Formaldehyde has high reaction activity and high, can with have-OH (hydroxyl) ,-SH (sulfydryl) ,-the molecule generation nucleophilic addition of NH2 (amino) group, in the cell of animal body, exist a large amount of above-mentioned groups in the enzyme system, can react immediately behind the contact formaldehyde, produce cytotoxicity, make protein denaturation.The superpower sterilizing ability of formaldehyde is former in just this reaction.When being rich in protein in the sample, the formaldehyde of interpolation easily combines with group in the protein, forms formaldehyde-protein complex.
This method adopts embodiment 1 described technical scheme to measure formaldehyde: the acetonitrile/pH5 acetate buffer solution of usefulness 2,4 dinitrophenyl hydrazine (1/1, directly derive and extract formaldehyde in the sample, liquid chromatogram measuring by v/v) solution.When formaldehyde is extracted in the samples in 60 ℃ of water-baths, carry out derivative reaction.Formaldehyde in 2,4 dinitrophenyl hydrazine and the protein in the group competitive reaction solution can effectively suppress protein bound in formaldehyde and the sample, thereby than water seaoning the higher formaldehyde recovery is arranged.
Select silverfish, the blank matrix of milk powder, add the formaldehyde of 5mg/kg, 10mg/kg, 20mg/kg third gear concentration level, use water seaoning and means of derivation extraction operational processes respectively, the formaldehyde standard solution is as calibration curve, replicate determination is averaged for 3 times, and result's contrast sees Table 1.The blank determination value of means of derivation extraction and water seaoning is close, shows that means of derivation extraction does not cause containing the obvious generation of endogenous formaldehyde in the albumen sample; The formaldehyde recovery is 35～46% in the water seaoning silverfish, the formaldehyde recovery 70～74% in the means of derivation extraction silverfish; The formaldehyde recovery is 66～74% in the water seaoning milk powder, and the formaldehyde recovery 82～88% in the means of derivation extraction milk powder shows that means of derivation extraction can extract formaldehyde in the sample preferably.
Table 1 water seaoning and means of derivation extraction are measured and are contained formaldehyde contrast in the albumen sample
The mensuration of formaldehyde in the test example 2 plant source food (except that mushroom)
Adopt embodiment 1 described technical scheme to measure formaldehyde, select flour, the blank matrix of dehydration wild cabbage, add the formaldehyde of 5mg/kg, 10mg/kg, 20mg/kg third gear concentration level, use water seaoning and means of derivation extraction operational processes respectively, the formaldehyde standard solution is as calibration curve, replicate determination is averaged for 3 times, and result's contrast sees Table 2.The blank determination value of means of derivation extraction and water seaoning is close, shows that means of derivation extraction does not cause the obvious generation of endogenous formaldehyde in the plant-derived sample; The formaldehyde recovery of water seaoning is 75～88%, and the formaldehyde recovery 90～99% of means of derivation extraction shows that means of derivation extraction can extract formaldehyde in the sample preferably.
Table 2 water seaoning and means of derivation extraction are measured formaldehyde contrast in the plant-derived sample
The mensuration of formaldehyde in test example 3 mushrooms
Formaldehyde is proved to be mushroom fruiting body self metabolism generation in the mushroom.People such as Japan scholar Yasumotoc and Fujimoto isolate key enzyme and the precursor substance one mushroom essence thereof that participates in the metabolism of mushroom formaldehyde, think that formaldehyde is the accessory substance of mushroom characteristic flavor on basis material zymetology metabolism.Therefore, in the processes such as the transportation of mushroom, preservation, all may decompose release formaldehyde.
The extracting method of formaldehyde in the mushroom, adopt more fresh mushroom homogenate is arranged or pulverize after extract formaldehyde by distillation again, the continuous release formaldehyde and influence measurement result of organized enzyme in the mushroom in the still-process.The detection method of Japan official is explained and mentioned: the mushroom based food, because acid hydrolysis or enzymolysis can make the composition in the sample generate formaldehyde, this situation adopts cold water extraction sometimes, measures as testing liquid immediately.The improved method of domestic scholars has, and formaldehyde is simultaneously with the acetic acid zinc solution enzymatic activity of going out in 60 ℃ of water-baths extraction mushrooms, and the boiling water bath heat redistillation extraction etc. of going out behind the enzyme after the fresh mushroom homogenate is by the continuous release of enzymatic activity with formaldehyde in the blocking-up mushroom of going out.
The assay method of mushroom formaldehyde exists difference more, and measurement result is reappeared problems such as difference.How to extract and make the formaldehyde extraction efficiency the highest, can effectively block enzyme reaction in the mushroom simultaneously, we are dried with the higher mushroom of content of formaldehyde to be research object, has carried out series of studies.After pulverizing the mushroom dry-eye disease evenly, store, use in order to test with plastic bag sealing.Adopt embodiment 1 described technical scheme to measure formaldehyde:
1, extracts choice of Solvent
Take by weighing the 1.0g sample, use 20mLpH2 water, pH5 water, pH7 water, acetonitrile/pH2 water (1/1), acetonitrile/pH5 water (1/1), acetonitrile/pH7 water (1/1), acetonitrile/pH2 water (1/2), acetonitrile/pH5 water (1/2), acetonitrile/pH7 water (1/2) and acetonitrile as extraction agent respectively, under the room temperature condition, the centrifugal 5min of 4000rpm/min behind the homogeneous homogenate 30s, get 2mL filtrate, adopt " 1 formaldehyde and 2,4 dinitrophenyl hydrazine reaction conditions " to derive, wherein pH7 filtrate transfers to pH5 and derives.Behind above-mentioned 10 kinds of homogenate vortex mixings, place 60 ℃ of water-bath joltings and extract, respectively at 0.5h, 1h, 2h, 3h get 2mL filtrate and derive, the liquid liquid chromatogram measuring of deriving.
Measurement result is seen Fig. 1～3, derives immediately after the mushroom homogeneous extracts and measures when being t=0, and the enzymatic reaction release formaldehyde is less to measuring influence, can investigate the different effect of extracting that extract the reagent PARA FORMALDEHYDE PRILLS(91,95) this moment substantially; Relatively more different measurement results during with t=0 when extracting reagent t=0.5～3h can be investigated the influence of activity of enzyme reaction PARA FORMALDEHYDE PRILLS(91,95) mensuration in the leaching process.
As shown in Figure 1, derive immediately after the homogenate of mushroom homogeneous and measure when being t=0, pH2, pH5, pH7 aqueous extract content of formaldehyde are respectively 34.0,26.5,94.9mg/kg, and enzymatic activity pH5＜pH2＜pH7 in the mushroom aqueous solution tentatively is described.With the extraction time increase, pH7 extract content of formaldehyde is the highest, and the pH2 extract takes second place, and the pH5 extract is minimum, has further proved above-mentioned viewpoint.PH5 extract activity of enzyme reaction is lower, and content of formaldehyde increased and slowly increases with extraction time, extracts 3h and reaches mxm. 198mg/kg.PH2, pH7 extract activity of enzyme reaction are higher, and jolting 0.5h content of formaldehyde reaches mxm. 390,806mg/kg respectively, and extraction time increases to 1h～3h, and content of formaldehyde is more and more lower on the contrary.Infer the mushroom sample behind homogeneous, cell is fully broken, and higher activity of enzyme reaction makes jolting 0.5h formaldehyde fully discharge; Along with the extraction time increases, formaldehyde may participate in mushroom matrix metabolic response, makes content of formaldehyde reduce.
As shown in Figure 2, during t=0, acetonitrile/pH2 (1/1), acetonitrile/pH5 (1/1), acetonitrile/pH7 water (1/1) content of formaldehyde are respectively 27.3,22.6,28.0mg/kg, and to extract the formaldehyde result close with the pH5 water homogenisation.Illustrate that if ignore the influence of enzymatic reaction acetonitrile/water (1/1) system is suitable substantially with pure aquatic system to the effect of extracting of formaldehyde in the mushroom.With the extraction time increase, content of formaldehyde does not obviously increase, and illustrates that acetonitrile/water (1/1) system can suppress enzymatic activity in the mushroom preferably.3 curve shapes are similar among the figure, and very close, illustrate with respect to pH value of water solution, and acetonitrile plays a major role to the inhibition of mushroom enzymatic activity.
As shown in Figure 3, during t=0, in acetonitrile/pH2 water (1/2), acetonitrile/pH5 water (1/2), acetonitrile/pH7 water (1/2) and the acetonitrile content of formaldehyde be respectively 8.52,8.00,10.4,2.84mg/kg.Show the acetonitrile/water of comparing (1/1) system, acetonitrile/water (2/1) system is relatively poor to the effect of extracting of formaldehyde in the mushroom, and pure acetonitrile effect of extracting is the poorest.With the extraction time increase, content of formaldehyde has increase slightly, but is lower than the corresponding value of Fig. 2 acetonitrile/water (1/1) system.Infer the increase of extracting acetonitrile ratio in the solvent, can effectively suppress enzymatic activity in the mushroom, but be unfavorable for the release and the extraction of formaldehyde.
Take all factors into consideration, acetonitrile/water (1/1) system has suitable for pure aquatic system formaldehyde effect of extracting in the mushroom, the pure aquatic system of comparing simultaneously can effectively suppress activity of enzyme reaction in the mushroom, therefore selects acetonitrile/water (1/1) system to extract reagent as formaldehyde in the mushroom.In acetonitrile/water (1/1) the system leaching process, content of formaldehyde has up and down fluctuation, and stability and reappearance are not good, below further investigation acetonitrile/water (1/1) system as the derive extraction effect of liquid of the 2,4 dinitrophenyl hydrazine of solvent.
2, means of derivation extraction
Investigate acetonitrile/water (1/1) the derivating agent solution of different pH values, to the influence of formaldehyde extraction in the mushroom.Take by weighing the 1.0g sample, add acetonitrile/pH2 water (1/1), acetonitrile/pH5 water (1/1), the acetonitrile/pH7 water (1/1) solution of 20mL 2,4 dinitrophenyl hydrazine respectively, 2,4 dinitrophenyl hydrazine concentration is 0.3g/L.Behind the homogeneous homogenate 30s, 60 ℃ of water-bath joltings extraction of deriving, respectively at 0.5h, 1h, 2h, 3h, 4h get 1mL filtrate and carry out liquid chromatogram measuring.Ignore the influence of pH value to derivatization reaction, with the acetonitrile/pH5 water (1/1) of the formaldehyde liquid of deriving, 60 ℃ of water-bath jolting 1h back measured value of deriving is made calibration curve, and the formaldehyde determination of different extracts the results are shown in Figure 4.
As shown in Figure 4, the maximal value that acetonitrile/pH5 water (1/1) derivating agent extracts formaldehyde is 40mg/kg, than corresponding solvent extraction maximal value 27mg/kg among Fig. 2 increase is arranged slightly, show the adding of derivating agent, can impel the formaldehyde-derived molecular balance to carry out to the right, to reach at utmost formaldehyde in the extraction and determination mushroom.Acetonitrile/pH7 water (1/1) derivating agent extracts curve with acetonitrile/pH5 water (1/1) derivating agent is similar, but measurement result is lower, and analyzing reason may be that derivatization reaction sensitivity is lower under the pH7 condition.It is 77mg/kg that acetonitrile/pH2 water (1/1) derivating agent extracts the formaldehyde maximal value, than corresponding solvent extraction maximal value 39 among Fig. 2
Mg/kg increases by 1 times.Show under the pH2 condition that the release of endogenous formaldehyde in the mushroom has been induced in the adding of derivating agent.
In sum, acetonitrile/pH5 water (1/1) derivating agent has the derivatization reaction sensitivity higher with formaldehyde, can be at utmost to the extraction of deriving of formaldehyde in the mushroom, and not seeing the release that obviously causes endogenous formaldehyde in the mushroom, 1h～4h is more stable as a result in extraction.Water-bath 1h and the homogenate not 1h that directly derives that derives compares behind the homogeneous homogenate 30s, and experimental result is close.
Therefore, means of derivation extraction can effectively extract formaldehyde in the mushroom, can block enzyme reaction in the mushroom again simultaneously, and extraction step and derivative reaction are combined, and has effectively improved detection efficiency, and selecting it is extracting method.
The selection of test example 4 purification conditions
Acetonitrile/water (1/1) all has wellability preferably to water-soluble sample and fat-soluble sample, selects 10 times extraction quantity of solvent of sample size to carry out the extraction of formaldehyde.In the plant source food, contain compounds such as fiber, starch usually, after sample extracts dilution with derivating agent, as the centrifugal solution clarification, then needn't purified treatment, direct liquid chromatogram measuring, impurity disturbs less.But QQ candy etc. is rich in gelatin, mineral matter and carbohydrate etc., and the liquid of deriving is difficult for filtering membrane, needs purified treatment.In dairy products, the animal-derived food, contain rich in protein, fat, the liquid of deriving needs protein precipitation and grease removal to purify.
The precipitation agent of protein has lead acetate, trichloroacetic acid, salt, acetonitrile etc., and the background values of lead acetate and trichloroacetic acid is higher, and salting out method is precipitating proteins and water-solubility impurity preferably, and the acetonitrile/water ratio is 2～3 o'clock protein precipitations preferably.For the step that simplifies the operation, select the saturated normal hexane degreasing of acetonitrile, salt precipitation albumen and remove water-solubility impurity.In 20mL derives liquid, add the saturated normal hexane of 10mL acetonitrile, standing demix behind the vortex is removed upper solution, can remove most of fat.In 20mL derives liquid, add about 8g ammonium sulfate, salting out makes most of protein precipitation, and water-solubility impurity is separated out, and makes acetonitrile and water stratification simultaneously, and formaldehyde derivatives enters acetonitrile layer.After centrifugal, extract acetonitrile layer, use removing residue formaldehyde derivant in the 10mL acetonitrile extraction water solution again.Merge acetonitrile solution, be settled to 20mL, reach the purification purpose.Pure acetonitrile sample introduction, the chromatographic peak of derivant slightly broadens, but does not influence the quantitative of formaldehyde.With 10mL concentration is acetonitrile/water (1/1) solution of the formaldehyde standard derivant of 1.0 μ g/mL, carries out above-mentioned grease removal, protein precipitation respectively and handles the back and measure concentration and be respectively 0.96 μ g/mL and 0.99 μ g/mL.
Three index determinings of the method for embodiment 1
1, linear relationship and detectability
Under the experiment condition that this method is determined, formaldehyde has good linear relationship with response in 0.20～5.00mg/L scope, and linear equation is y=344.6x+7.222, and related coefficient is 0.99999.This method is 2.0mg/L to the mensuration lower bound of formaldehyde in the liquid type sample; Mensuration lower bound to formaldehyde in the solid kind sample is 5.0mg/kg.
2, the recovery and precision
The recovery test of this method is the test of adding the recovery.Select silverfish, mushroom, flour, milk powder, toffee, cream blank sample, adding concentration of formaldehyde respectively is 5.0mg/kg, 10.0mg/kg, 20.0mg/kg, replicate determination 6 times.Select milk beverage, beer blank sample, adding concentration of formaldehyde respectively is 2.0mg/L, 5.0mg/L, 10.0mg/L, replicate determination 6 times.Contain trace formaldehyde in the blank sample of selecting, reclaim measured value and need deduct the blank sample background values.The recovery and precision see Table 4～table 11.
The interpolation recovery test of formaldehyde in table 4 silverfish
The interpolation recovery test of formaldehyde in table 5 mushroom
The interpolation recovery test of formaldehyde in table 6 flour
The interpolation recovery test of formaldehyde in table 7 milk powder
The interpolation recovery test of formaldehyde in table 8 toffee
The interpolation recovery test of formaldehyde in table 9 cream
The interpolation recovery test of formaldehyde in table 10 milk beverage
The interpolation recovery test of formaldehyde in table 11 beer
3. method detection limit
This method is 2.0mg/L to the mensuration lower bound of formaldehyde in the liquid type sample, is 5.0mg/kg to the mensuration lower bound of formaldehyde in the solid kind sample.
In silverfish, mushroom, flour, milk powder, toffee, cream blank sample, add 5.0mg/kg formaldehyde standard items respectively, in milk beverage, beer blank sample, add 2.0mg/L formaldehyde standard items, press the experimental technique operation, liquid chromatogram measuring.Fig. 5 is the chromatogram of concentration 0.2 μ g/mL formaldehyde standard derivative solution, the sample chromatogram figure after Fig. 6～Figure 13 is respectively each blank sample and adds standard specimen.
4. method validation
Select silverfish, mushroom, flour, milk powder, toffee, cream, milk beverage, beer blank sample for use, divide and do not invite Shanghai Entry-Exit Inspection and Quarantine bureau, Hubei Entry-Exit Inspection and Quarantine Bureau, Ningbo inspection and quarantining for import/export, Hainan inspection and quarantining for import/export and Zhejiang Prov Industrial And Commercial University's food and five tame authoritative testing agencies of bioengineering institute to verify.Verification method adopts standard addition method, adds concentration and testing result and gathers and see Table 12.
Table 12 demonstration test is measured and is gathered
Claims (5)
1. means of derivation extraction is measured the method for formaldehyde in food, it is characterized in that this assay method is made of following step:
(1) extracts
1. solid kind sample: take by weighing sample 2g, be accurate to 0.01g, place 50mL tool plug plastic centrifuge tube, accurately add the 20.0 mL liquid of deriving; Screw stopper, mixing is placed in 60 ℃ of constant temperature oscillators, the 150r/min jolting, and 20min takes out mixing at interval, takes out cooling behind the jolting 1h; The above-mentioned liquid of deriving is the mixed solution that the buffer solution of 2,4 dinitrophenyl hydrazine acetonitrile solution and pH5 constitutes, and the concentration of 2,4 dinitrophenyl hydrazine acetonitrile solution is 0.6 g/L, acetonitrile in the liquid of deriving: the volume ratio of buffer solution is 1: 1;
2. liquid type sample: pipette sample 1mL, be accurate to 0.1mL, place the 10mL color-comparison tube, add the buffer solution of 4.0mLpH5, be settled to 10mL with the 2,4 dinitrophenyl hydrazine acetonitrile solution, cover plug back mixing, 60 ℃ of water-baths heating 1h take out and cool off; The concentration of above-mentioned 2,4 dinitrophenyl hydrazine acetonitrile solution is 0.6g/L;
(2) purify
1. solid kind sample: with the above-mentioned solid kind sample extract that makes, to be not less than the centrifugal 5min of 4000r/min; For the clarification of centrifugal back solution, cross miillpore filter after, directly measure for HPLC; For centrifugal back solution muddiness, in extract, add 8g ammonium sulfate, mixing is to be not less than the centrifugal 5min of 4000r/min, pipette supernatant, 10mL acetonitrile re-extract 1 time of lower floor's solution, combining extraction liquid, be settled to 20mL with acetonitrile, cross miillpore filter behind the mixing, filtrate is measured for HPLC;
2. liquid type sample: the purification method of extract is identical with the solid kind sample, and the agents useful for same amount reduces by half;
(3) preparation of formaldehyde standard operation solution
Get the formaldehyde standard operation solution of 5 grades or above variable concentrations respectively, the preparation method of formaldehyde standard operation solution is as follows:
Pipette sample 1mL, be accurate to 0.1mL, place the 10mL color-comparison tube, add the buffer solution of 4.0mLpH5, be settled to 10mL with the 2,4 dinitrophenyl hydrazine acetonitrile solution, cover plug back mixing, 60 ℃ of water-bath heating 1h take out cooling; Miillpore filter is crossed in the cooling back, and filtrate is measured for HPLC; The concentration of above-mentioned 2,4 dinitrophenyl hydrazine acetonitrile solution is 0.6g/L;
(4) measure
According to the selected close standard operation solution series of peak area of the situation of concentration of formaldehyde in the sample liquid, the response of formaldehyde derivatives all should be in the range of linearity of instrument detecting in standard operation solution and the sample liquid, standard operation solution and sample liquid equal-volume ginseng inject sample and measure, qualitative with retention time, external standard method is quantitative;
(5) blank test
Except that not adding the sample, all undertaken by above-mentioned (1)～(4) operation steps;
(6) result calculates and statement
Calculate the residual quantity of formaldehyde in the sample as follows or adopt the chromatographic data disposal system to calculate, result of calculation need be deducted blank value:
In the formula:
X---the residual quantity of formaldehyde in the sample, unit is mg/kg;
A---the peak area of formaldehyde derivatives in the sample liquid;
C---the concentration of formaldehyde derivatives in the standard solution, unit is mg/L;
V---the final constant volume of sample liquid, unit are mL;
A
s---the peak area of formaldehyde derivatives in the standard solution;
M---the sample mass of sample solution representative, unit are g.
2. means of derivation extraction according to claim 1 is measured the method for formaldehyde in food, it is characterized in that liquid phase chromatogram condition is:
A) chromatographic column: C
18Post, 250mm * 4.6mm (internal diameter), 5 μ m, or suitable person;
B) moving phase: methanol-water (70+30, V+V);
C) flow velocity: 1.0mL/min;
D) detect wavelength: 365nm;
E) sample size: 20 μ L.
3. means of derivation extraction according to claim 1 is measured the method for formaldehyde in food, it is characterized in that for fat content in step (2) the solid kind sample higherly, distributes grease removal to purify with the saturated normal hexane liquid of acetonitrile-liquid.
4. means of derivation extraction according to claim 1 is measured the method for formaldehyde in food, it is characterized in that the buffer solution employing of pH5 takes by weighing the 2.64g sodium acetate, with the suitable quantity of water dissolving, adds the 1.0mL glacial acetic acid, and water is settled to 500mL.
5. measure the method for formaldehyde in food according to the described means of derivation extraction of any claim of claim 1～4, it is characterized in that sample is silverfish, mushroom, flour, milk powder, toffee, cream, milk beverage or beer.
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