CN102539565A - Method for quickly measuring methanal content in dried beancurd sticks - Google Patents
Method for quickly measuring methanal content in dried beancurd sticks Download PDFInfo
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- CN102539565A CN102539565A CN2011104473532A CN201110447353A CN102539565A CN 102539565 A CN102539565 A CN 102539565A CN 2011104473532 A CN2011104473532 A CN 2011104473532A CN 201110447353 A CN201110447353 A CN 201110447353A CN 102539565 A CN102539565 A CN 102539565A
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Abstract
The invention relates to a method for quickly measuring methanal content in dried beancurd sticks, which is characterized by adopting a combined using method of an efficient liquid phase chromatogram method and a viable wavelength detector (VWD) to qualitatively and quantitatively measure methanal content in dried beancurd stick products. The method comprises the steps of using Nash reagent to perform precolumn derivation and chromatographic analysis on derivation products, enabling the detection wavelength of the VWD to be 412nm, and performing gradient elution with a binary system of acetonitrile and water as flow phase. The flow speed is 0.8mL/min to 1mL/min, the judgment standard of the methanal content is that a linear range of the methanal content is 0.00 to 0.80mg/L, the linear equation is that Y is equal to 27.024X, the Y is the peak area of derivation reaction products, and the X is the methanal content. The method has the advantages that compared with GB/T21126-2007, the derivation reaction time is shortened from 40 minutes to 15minutes, products are not required to be extracted by organic solvent, loss of derivation products is reduced, labor intensity is reduced, and chemicals are saved. Methodology experimental results of the method meet analysis requirements of samples, thereby achieving the purpose of quick analysis.
Description
Technical field
The present invention relates to the food detection method field.Be particularly related to the method for content of formaldehyde in a kind of fast measuring bean curd stick.
Background technology
After bean curd stick was the infusion of soya bean soya-bean milk, contained fat and soybean protein conjunctiva were pulled out to dry and are obtained.Along with infusion time lengthening conjunctiva drags for fewer and fewer, remaining is that " browning reaction " can take place main material with the carbohydrates, even blackout.Add the extremely strong sodium formaldehyde sulfoxylate of reductibility, can play " bleaching " effect, both changed color and luster, also increased output.Sodium formaldehyde sulfoxylate is a kind of raw material of industry; When printing and dyeing industry, synthetic rubber, be used as reducing catalyst; Under acid condition, decompose and produce formaldehyde; The World Health Organization (WHO) confirms as carcinogenic, teratogen and generally acknowledged allergen with formaldehyde, and is therefore no matter external at home, all forbids sodium formaldehyde sulfoxylate or formaldehyde are used for the processed of food.
Issue bulletin on the Ministry of Public Health website in April, 2011, announced the non-edible material from soybeans list of the illegal interpolation of first possibility, has 17 kinds of non-edible material from soybeans on this part " blacklist ", and sodium formaldehyde sulfoxylate is listed in first position.The sodium formaldehyde sulfoxylate detection method of announcing simultaneously has rongalite Determination on content and the mensuration of defending prison (2001) No. 159 file formaldehyde in food sodium bisulphites in GB/T 21126-2007 wheat flour and rice meal and the goods thereof, on analytical approach, belongs to high performance liquid chromatography, the chromatography of ions and AAS.High performance liquid chromatography and AAS wherein relatively more commonly used exist not enough in practical application; The one, GB/T 21126-2007 method is with 2; The 4-dinitrophenylhydrazine is as derivative reagent; The derivatization reaction time is long, and derivative products needs the organic solvent n-hexane extraction, has the deficiency that experimental procedure is many, the time long, operation is loaded down with trivial details; The 2nd, defend the mensuration that prison is sent out (2001) No. 159 file formaldehyde in food sodium bisulphites; Sample is taked to distill the method for extracting formaldehyde, and concerning bean curd stick, still-process produces great amount of bubbles; Effluent is not clarified; Sometimes owing to have pigment in the sample, make effluent have color, influence the mensuration of absorbance; The 3rd, also be not directed against the comparatively detection method of outstanding sample of this problem of bean curd stick.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts high performance liquid chromatography to content of formaldehyde fast detecting in the bean curd stick; This method is measured content of formaldehyde in the bean curd stick sample as the derivative reagent column front derivation with Nash reagent; Reaction time is short; Product does not need organic solvent extraction, is suitable for the fast measuring of content of formaldehyde in the bean curd stick sample.
The technical scheme that the present invention adopted is:
Adopt high performance liquid chromatography (VWD detecting device) that the content of formaldehyde in the bean curd stick product is carried out qualitative, quantitative test; Wherein: carry out column front derivation with Nash reagent as derivative reagent, derivative products need not extract and directly carry out stratographic analysis, and it is 412 that UV-detector detects wavelength
Nm, as moving phase, volume ratio is 50:50 with acetonitrile and water; Flow velocity is 0.8
MLmin -1 The criterion of PARA FORMALDEHYDE PRILLS(91,95) content is: the content of formaldehyde range of linearity is 0.00～0.80
Mg/L,0.00～0.80
Mg/LIn the scope, linear equation: Y=27.024X, Y are the peak area of derivatization reaction product, and X is a content of formaldehyde.
Advantage of the present invention is: the analytical approach of having set up content of formaldehyde in the Nash reagent column front derivation high performance liquid chromatography fast measuring bean curd stick sample.Sample extracts, filters through concussion, high-performance liquid chromatogram determination behind the employing Nash reagent column front derivation, and this method is compared with GB/T 21126-2007, and the derivatization reaction time is by 40
MinShorten to 15
Min, product does not need organic solvent extraction, has reduced the loss of derivative products, has reduced labour intensity, has practiced thrift medicine, has shortened extraction in time, has left standstill 90 of step needs
MinThe methodology experimental result of this method meets the analysis requirement of sample, has reached the purpose of express-analysis.
Description of drawings
Fig. 1 DNPH and 2, the 4-dinitrophenylhydrazone chromatogram in water and normal hexane;
The chromatogram of Fig. 2 DDL in water and normal hexane;
Fig. 3 peak area and derivatization reaction temperature relation figure;
Fig. 4 peak area and derivatization reaction time chart;
Fig. 5 formaldehyde standard working curve figure;
Fig. 6 bean curd stick sample test chromatogram.
Embodiment
(1) preparation of reagent and standard solution: formaldehyde standard solution (Tianjin recovery fine chemistry industry research institute, formaldehyde titer C=1.000
Mg/mL); Anhydrous sodium sulfate, ammonium acetate, glacial acetic acid, diacetone are AR; Sample is commercially available bean curd stick.
40
Mg/LThe preparation of formaldehyde standard reserving solution: accurately draw formaldehyde titer (1.000
Mg/mL) 4.00
MLBe settled to 100 with deionized water
MLVolumetric flask.Refrigerator and cooled is hidden and is preserved.
2.0
Mg/LThe formaldehyde standard is used the preparation of liquid: accurately draw formaldehyde standard reserving solution 5.00
MLBe settled to 100 with deionized water
MLVolumetric flask.Use preparation on the same day.
The preparation of Nash reagent: 150
gAmmonium acetate, 3.00
MLGlacial acetic acid, 2 .0
MLDiacetone is settled to 1 with the deionized water dilution
L, lucifuge stores 12 in the brown bottle
hUse the back.
Metabisulfite solution: take by weighing 100
gAnhydrous sodium sulfate, dissolving back constant volume is in 500
MLVolumetric flask is subsequent use.
(2) instrument and chromatographiccondition: instrument is U.S. Agilent 1200 HPLC, is furnished with quaternary pump, the online degasser of vacuum, column oven and VWD detecting device; Agilent Zorbax Eclipse XDB-C18 (4.6 * 250
Mm, 5
μ m) chromatographic column; Moving phase adopts the binary system of chromatographic grade acetonitrile and deionized water, and the volume ratio of acetonitrile and water is 50:50; Adopt the isocratic elution mode, flow velocity is 0.8
MLmin -1 , temperature control not, sample size 10
μ L
(3) selection of derivative reagent: the detecting device that the formaldehyde high-efficiency liquid chromatography detecting method is used is UV-detector (VWD); UV-detector is applicable to that organic molecule has ultraviolet or visible absorption group; Because formaldehyde does not absorb in this light district; Need before the compartment analysis that carries out chromatographic column, carry out derivatization reaction, promptly column front derivation makes the derivative products that obtains have absorption to reach the purpose of qualitative, quantitative in ultraviolet or visible region.Using more general derivative reagent both at home and abroad at present is 2,4-dinitrophenylhydrazine (DNPH), and the derivative reagent that in national standard method, adopts also is 2; 4-dinitrophenylhydrazine (DNPH); 2,4-dinitrophenylhydrazone that it and formolite reaction generate extracts laggard circumstances in which people get things ready for a trip analysis of spectrum through organic solvent-normal hexane.But 2,4-dinitrophenylhydrazine also can be dissolved in the normal hexane solvent, and at test wavelength 355
NmThe ultraviolet range absorption is also arranged, sample determination is brought certain interference.
The present invention adopts Nash reagent to replace the derivative reagent of 2,4-dinitrophenylhydrazine as formaldehyde, and Nash reagent is the solution of diacetone and ammonium acetate preparation; This reaction principle is that diacetone and formaldehyde can react in the presence of ammonia, generates yellow complex 2,6-dimethyl-3; 5-diacyl-1,4-dihydropyridine (being called for short DDL), deriving of Nash reagent and formaldehyde has selectivity preferably; Not with other aldehyde ketone reactions; The chromatogram peak-to-peak type that forms is sharp-pointed, and symmetry is good, can satisfy the detection requirement of formaldehyde.
(4) dissolubility of derivative products relatively: 2,4-dinitrophenylhydrazine is different with the dissolving situation of product in water and organic phase of Nash reagent and formaldehyde generation derivatization reaction.
2,4-dinitrophenylhydrazine is as derivative reagent, at test wavelength 355
NmUnder the condition, first peak retention time 3.635
Min, be 2,4-dinitrophenylhydrazine, second peak retention time 4.790
Min, be 2,4-dinitrophenylhydrazone, 2,4-dinitrophenylhydrazone has obtained extracting and enriching in normal hexane, and 2,4-dinitrophenylhydrazine also has dissolving in normal hexane, when 2,4-dinitrophenylhydrazone content is low, can impact measuring the result.2,4-dinitrophenylhydrazine (DNPH) is seen Fig. 1 with the chromatogram of 2,4-dinitrophenylhydrazone in the WS and normal hexane.
Nash reagent is as derivative reagent, at test wavelength 412
NmUnder the condition, Nash reagent does not absorb, retention time 2.999
MinThe DDL peak occurs, measure the chromatogram that Nash reagent and DDL dissolve respectively in water and organic phase normal hexane, visible DDL is difficult to be dissolved in the normal hexane organic phase, and this is to adopt Nash reagent to do the foundation that derivative reagent does not need the organic phase extraction step.Nash reagent and formaldehyde reaction product (DDL) chromatogram in the WS and normal hexane is seen Fig. 2.
(5) derivatization reaction temperature: consider the influence of temperature, 25 to reaction rate and reaction product stability
℃-70
℃Carry out the derivatization reaction test under the different temperatures, product carries out stratographic analysis, is horizontal ordinate with the temperature of reaction, and the chromatographic peak area of product is an ordinate, draws and selects best derivatization reaction temperature
Be50 ℃.Peak area and derivatization reaction time relationship are seen Fig. 3.
(6) the derivatization reaction time: draw the formaldehyde standard and use liquid 2.0
ML, add Nash reagent 2.0
ML, add water constant volume to 10
ML, 50
℃Heat in the water-bath, the reaction time is respectively 10
Min, 20
Min, 30
Min, 40
Min, 50
Min, 60
Min, be cooled to room temperature with flowing water.With the derivatization reaction time be horizontal ordinate, be ordinate with the chromatographic peak area of derivatization reaction product, draw and select the best derivatization reaction time.The result is 10
Min-20
MinThe time internal reaction is complete, and it is maximum that peak area reaches, 20
MinBack peak area reduces to some extent, confirms that the best derivatization reaction time is 15
MinPeak area and derivatization reaction time relationship are seen Fig. 4.
(7) drafting of typical curve: at 10 10
MLAdd 2.0 in the color-comparison tube
Mg/LThe formaldehyde standard is used liquid 0.00
ML, 0.25
ML, 0.5
ML, 1.00
ML, 1.50
ML, 2.00
ML, 2.50
ML, 3.00
ML, 3.50
ML, 4.00
ML(containing formaldehyde is respectively 0.0
μ g, 0.5
μ g, 1.0
μ g, 2.0
μ g, 3.0
μ g, 4.0
μ g, 5.0
μ g, 6.0
μ g, 7.0
μ g, 8.0
μ g), each adds 2.00 respectively successively
MLNash reagent is mended and is added water to 10
ML, shake up, place 50
℃Carry out derivatization reaction in the water-bath, every interval 3
MinShake up reaction 15 1 time
MinThe back is cooled to room temperature with flowing water.Cross 0.45
μ mPut into sample hose behind the membrane filter and carry out stratographic analysis, with content of formaldehyde (
μ g) be horizontal ordinate, be ordinate with the peak area of derivatization reaction product, the drawing standard curve is seen Fig. 5.
(8) linear relationship, detection limit
Content of formaldehyde is 0.00～0.80
Mg/LIn the scope, linear equation: Y=27.024X, related coefficient is 0.9998, linear relationship is good.According to the computing method of detection limit, respectively with 3 times of signal to noise ratio (S/N ratio)s (
R SN=3) calculate, the detection limit that obtains this method is 0.013
Mg/Kg
(9) accuracy and accuracy
Take by weighing bean curd stick sample powder 10.0000 with analytical balance
gAccurately measure 100 with graduated cylinder
MLMetabisulfite solution puts into 250
MLIn the tool plug triangular flask, vibration extracts 40
MinCross and filter clear liquid; Measure 2.00
MLClear liquid is (10mL) in color-comparison tube, adds the formaldehyde standard and uses liquid (2.0
Mg/L) 0.00
ML, 0.50
ML, 1.50
ML, 2.50
ML(promptly content of formaldehyde is 5.0 in the sample of interpolation back
Mg/Kg, 15.0
Mg/Kg, 25.0
Mg/Kg), add 2.00mL Nash reagent, mend and add water to 10
ML, shake up; Place 50
℃Heat per 3 in the water-bath
MinShake up 15 1 time
MinThe back is cooled to room temperature with flowing water.Cross 0.45
μ mPut into sample hose behind the filter membrane and carry out stratographic analysis.Each concentration level is parallel to be done 5 times, on average adds the recovery and the precision result sees table 1.
The interpolation recovery of formaldehyde and precision (n=5) in table 1 bean curd stick
(10) mensuration of content of formaldehyde in the bean curd stick sample
Take by weighing bean curd stick sample powder 10.0000 with analytical balance
g, accurately measure 100
MLMetabisulfite solution puts into 250
MLIn the tool plug triangular flask, vibration extracts 40
MinCross and filter clear liquid (because of the bean curd stick sample swims in the solution, centrifugal effect is bad, changes filtration into); Accurately measure 2.00 respectively with calibrated pipet
MLSample preparation gained supernatant is in color comparison tube (10
ML), add 2.00
MLNash reagent is mended and is added water to 10
ML, shake up; Place 50
℃Heat per 3 in the water-bath
MinShake up 15 1 time
MinThe back is cooled to room temperature with flowing water.Cross 0.45
μ mPut into sample hose behind the membrane filter and carry out stratographic analysis.
Experimental procedure according to this can obtain following experimental formula:
Content of formaldehyde (
Mg/Kg)=Y/5.4048, Y are the peak area of sample, with content of formaldehyde 10 among the GB/T 21126-2007
Mg/KgThe standard that exceeds standard judge that promptly the sample peak area surpasses at 54.048 o'clock, can conclude the artificial antiseptic that adds formaldehydes.Bean curd stick sample test chromatogram is seen Fig. 6.
Claims (4)
1. the method for content of formaldehyde in the fast measuring bean curd stick is characterized in that: adopt high performance liquid chromatography that the content of formaldehyde in the bean curd stick product is carried out qualitative, quantitative test; Wherein: carry out column front derivation with Nash reagent as derivative reagent, derivative products is directly carried out stratographic analysis, it is 412 that UV-detector detects wavelength
Nm, the binary system with acetonitrile, water in the stratographic analysis is that moving phase is carried out isocratic elution, flow velocity: 0.8
MLmin -1 The criterion of PARA FORMALDEHYDE PRILLS(91,95) content is: the content of formaldehyde range of linearity is 0.00～0.80
Mg/L,0.00～0.80
Mg/LIn the scope, linear equation: Y=27.024X, Y are the peak area of derivatization reaction product, and X is a content of formaldehyde.
2. the method for content of formaldehyde in the fast measuring bean curd stick according to claim 1 is characterized in that: the derivatization reaction temperature of said Nash reagent column front derivation
Be50 ℃.
3. the method for content of formaldehyde in the fast measuring bean curd stick according to claim 1 is characterized in that: the derivatization reaction time of said Nash reagent column front derivation is 15
Min
4. the method for content of formaldehyde in the fast measuring bean curd stick according to claim 1 is characterized in that: the volume ratio=50:50 between said moving phase acetonitrile and the water.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103823003A (en) * | 2014-02-17 | 2014-05-28 | 浙江省林产品质量检测站 | High performance liquid chromatography (HPLC) determination method of total formaldehyde content in man-made board |
| CN105388232A (en) * | 2015-12-30 | 2016-03-09 | 田琳琳 | Method of detecting content of formaldehyde in bean curd sticks |
| CN105527360A (en) * | 2015-12-30 | 2016-04-27 | 田琳琳 | An improved rapid formaldehyde detecting method |
| CN108828133A (en) * | 2018-08-20 | 2018-11-16 | 上海添蓝生物科技有限公司 | A kind of measuring method for formaldehyde condensation products fungicide effective content |
| CN110749726A (en) * | 2019-10-30 | 2020-02-04 | 深圳天祥质量技术服务有限公司 | Method for detecting formaldehyde in textile |
| CN113418997A (en) * | 2021-05-18 | 2021-09-21 | 中华人民共和国梅州海关 | Method for determining formaldehyde content in tableware detergent by adopting high performance liquid chromatography |
-
2011
- 2011-12-28 CN CN2011104473532A patent/CN102539565A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 刘纯英: "乙酸丙酮法测定腐竹中甲醛", 《现代预防医学》 * |
| 王圣庆 等: "柱前衍生高效液相色谱法测定啤酒中微量甲醛", 《化学研究与应用》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103823003A (en) * | 2014-02-17 | 2014-05-28 | 浙江省林产品质量检测站 | High performance liquid chromatography (HPLC) determination method of total formaldehyde content in man-made board |
| CN103823003B (en) * | 2014-02-17 | 2015-12-02 | 浙江省林产品质量检测站 | The high performance liquid chromatography of total formaldehyde content in a kind of wood-based plate |
| CN105388232A (en) * | 2015-12-30 | 2016-03-09 | 田琳琳 | Method of detecting content of formaldehyde in bean curd sticks |
| CN105527360A (en) * | 2015-12-30 | 2016-04-27 | 田琳琳 | An improved rapid formaldehyde detecting method |
| WO2017114441A1 (en) * | 2015-12-30 | 2017-07-06 | 田琳琳 | Method for detecting content of formaldehyde in tofu skin |
| CN108828133A (en) * | 2018-08-20 | 2018-11-16 | 上海添蓝生物科技有限公司 | A kind of measuring method for formaldehyde condensation products fungicide effective content |
| CN110749726A (en) * | 2019-10-30 | 2020-02-04 | 深圳天祥质量技术服务有限公司 | Method for detecting formaldehyde in textile |
| CN113418997A (en) * | 2021-05-18 | 2021-09-21 | 中华人民共和国梅州海关 | Method for determining formaldehyde content in tableware detergent by adopting high performance liquid chromatography |
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Application publication date: 20120704 |