CN104535755A - Reagent for hair water soy sauce detection and preparation method thereof - Google Patents
Reagent for hair water soy sauce detection and preparation method thereof Download PDFInfo
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Abstract
The invention provides a reagent for hair water soy sauce detection and a preparation method thereof. According to the method disclosed by the invention, firstly 1,3,5,7-tetramethyl-8-phenyl-(2-nitryl)-boron difluoride dipyrrylmethane (TMPB-o-N) is synthesized, then the 1,3,5,7-tetramethyl-8-phenyl-(2-amino)-boron difluoride dipyrrylmethane (TMPB-o-A) is synthesized, and finally the testing reagent disclosed by the invention is obtained. The testing reagent prepared by the method disclosed by the invention for the hair water soy sauce detection is added dropwise or put into to-be-tested soy sauce, then the content of cysteine in the into to-be-tested soy sauce can be determined by judgment of a fluorescence reaction, and thus a technicist can judge whether the to-be-tested soy sauce is hair water soy sauce or suspected hair water soy sauce by the judgment of the fluorescence reaction by eyes; the reagent is simple and convenient to use, obvious in effect and short in detection time. By using the testing reagent disclosed by the invention, a quality supervising officer can effectively supervise soy sauce markets and prevents introduction of the hair water soy sauce as far as possible, so a beneficial tool is provided for guaranteeing food safety.
Description
Technical field
The present invention relates to Product checking field, being specifically related to the preparation method of reagent thereof for detecting hair water soy sauce and corresponding reagent
Background technology
Food security is not only related to the healthy of the people and life security, and is related to the harmony of society and stablizes.In recent years, along with economic society constantly progress, food sanitation and safety becomes the hot issue received much concern.None does not affect the heart of the numerous common people, the pernicious food security accident occurred in rapid succession, and as " tonyred event ", " Sanlu milk powder case " etc., have caused people's showing great attention to food security.
Soy sauce refers to soybean or defatted soybean, wheat or wheat bran, salt, water for raw material, and through the liquid delicate flavour flavouring of one that microorganism is brewageed, this has clear stipulaties in national standard.Soy sauce has abundant nutritive value, containing multiple nutritional components.
China State Bureau of Quality and Technical Supervision 2000-09-01 has issued the national standard (GB18186-2000) made soy sauce.These standards with regard to soy sauce definition, classification done the explanation of specification.Soy sauce is divided into two classes, makes soy sauce and blended soy sauce.Make soy sauce be with soybean and/or defatted soybean, wheat and/or wheat bran for raw material, brewage.Blended soy sauce makes soy sauce as main body, and with acid hydrolyzed vegetable protein baste, food additives etc. are mixed with.And no matter make soy sauce or blended soy sauce, country all must not expressly provide add monosodium glutamate waste liquid, cystine waste liquid, with non-food raw material production aminoacids solution etc.
But because the soy sauce grade of country is determined according to the content of the amino-acid nitrogen of soy sauce, many illegal retailers start with from the nitrogen content with regard to soy sauce, improve amino acid whose composition in soy sauce with inferior raw material, wherein with hair water soy sauce the most people detested.
Hair water soy sauce refers to illegal retailer and uses the amino acid waste liquid of hair-hydrolyzation to blend making soy sauce, containing objectionable impuritiess such as a large amount of arsenic, lead, mercury, 4-methylimidazoles in this soy sauce inferior, larger toxic and side effect is had to the liver, kidney, hematological system, reproductive system etc. of human body, can be carcinogenic.Use the soy sauce that this seed amino acid waste liquid is prepared, not only do not need to ferment with raw materials such as soya beans, the content of nitrogen but can also reach amino acid whose national standard in soy sauce completely, and is difficult to distinguish hair water soy sauce according to the detection means of existing national standard.
Summary of the invention
For the problems referred to above, the present invention wishes that proposing one can be used in reagent detecting " hair water " soy sauce and preparation method thereof.
Applicant, through carefully studying hair water soy sauce and common soy sauce, have found the difference between hair water soy sauce and common soy sauce.Applicant finds the cystine often remaining rather high concentration in " hair water ", and with food plant albumen for raw material brewage pure make soy sauce in all do not detect cystine.This is because, " hair water " derives from the process of commercial production cystine usually, it is the waste liquid in cystine manufacture process.The hair of animal is rich in keratoprotein, is not easy digested absorption, under strongly acidic conditions, keratoprotein hydrolysis in hair, generate cystine and other amino acid, by the cystine in this mother liquor can be made near adjust ph to the isoelectric point of cystine to separate out, obtain cystine crude product.Be extracted most of cystine from mother liquor after, remaining waste liquid is rich in amino acid.This waste liquid can not use as food grade materials, is but bought by illegal retailer and be used for blending soy sauces in hair water soy sauce event.
Therefore, applicant finds, concerning indicating the soy sauce that plant material makes soy sauce, adding the amino acid whose suspicion of animal sources as detected that the cystine of abnormal concentrations then has wherein, may be hair water soy sauce.
And in fact, content that present inventor finds to want directly to measure cystine difficulty often.But present inventor finds that cystine and halfcystine can exist simultaneously and change in the solution.And halfcystine (Cys) is unique a kind of amino acid containing sulfydryl (-SH), disulfide bond can be formed between the sulfydryl of its different Cys residue, maintain the tertiary structure of protein.In addition, the sulfydryl in Cys residue is group the most active in all proteins amino acid residue, participates in anti-oxidant, the multiple important physiological reaction such as nitrosylation and the exchange of sulfydryl-two mercapto key in vivo.Therefore, the present invention can utilize cystine and halfcystine to exist in solution this characteristic simultaneously.In order to analyze soy sauce to be measured better, in preferred implementation, cystine all can be changed into halfcystine and analyzing as target group using sulfydryl.
Specifically, the invention provides a kind of preparation method of reagent thereof for detecting hair water soy sauce, it is characterized in that, described preparation method comprises the steps:
Step 1) o-nitrobenzaldehyde of scheduled volume is dissolved in CH
2cl
2in;
Step 2) in obtained solution, add 2,4-dimethyl pyrrole and instill trifluoroacetic acid sealing, the stirring schedule time;
Step 3) in gained solution, add triethylamine and boron trifluoride diethyl etherate;
Step 4) gained mixed liquor is concentrated, and obtained concentrate is washed;
Step 5) with anhydrous sodium sulfate, drying is carried out to gained concentrate, except desolventizing, and utilize silica gel column chromatography to purify, obtain the first dry solid matter;
Step 6) the first obtained solid matter is dissolved in CH
2cl
2with the mixed liquor of absolute ethyl alcohol;
Step 7) in mixed liquor, add Pd/C, under stirring condition, pass into hydrogen catalytic reduction, after reaction to be restored completes substantially, filtering Pd/C;
Step 8) solvent removed in filtrate obtains corresponding second solid matter;
Step 9) gained second solid matter is dissolved in glacial acetic acid, stir and add maleic anhydride, after stirring the schedule time, solvent is removed in decompression, and carries out silica gel column chromatography purification, obtains orange material;
Step 10) orange for gained material is dissolved in acetic anhydride, add sodium acetate, insulation predetermined hold-time, question response is completely by mixed liquor removal of solvent under reduced pressure, and remainder is poured into water, and stirs, separate out to solid, filter, silica gel column chromatography purification is carried out to gained solid product, obtain destination agent.
Further, in described method, the consumption of o-nitrobenzaldehyde is 1.06g, and the consumption of described 2,4-dimethyl pyrroles is 1.44mL; Described triethylamine consumption is 4.0mL, and boron trifluoride diethyl etherate consumption is 4.8mL, and the consumption of maleic anhydride is 0.27g, and each composition can increase in proportion.
Further, described first solid matter is 1,3,5,7-tetramethyl-8-phenyl-(2-nitro)-boron difluoride dipyrrylmethanes.
Further, described second solid matter is 1,3,5,7-tetramethyl-8-phenyl-(2-amido)-boron difluoride dipyrrylmethanes.
Further, described method also comprises the dimethyl sulfoxide solution or the methyl alcohol that the second obtained solid matter are dissolved in scheduled volume.
Further, in described step 4) described in washing comprise and utilize saturated NaHCO
3obtained concentrate is washed.
On the other hand, the invention provides a kind of reagent detected for hair water soy sauce, it is characterized in that, in described reagent, comprise 1,3,5,7-tetramethyl-8-phenyl-(2-maleimide)-boron difluoride dipyrrylmethanes.
On the other hand, present invention also offers described reagent and detect the application in hair water soy sauce.
As above, detection reagent of the present invention mainly judges hair water soy sauce based on to the detection of cystine.In the solution, cystine and halfcystine can exist simultaneously and change, therefore, when detection reagent of the present invention is joined in soy sauce to be measured, described detection reagent can with halfcystine generation fluorescence reaction, thus technician can judge the content of halfcystine in soy sauce to be measured qualitatively or quantitatively, and then infer the content cystine.Based on the content of cystine, technician just can judge soy sauce to be measured whether as hair water soy sauce.
Preferably, detection reagent can also comprise goes back original reagent, and this is gone back original reagent and can first join in soy sauce to be measured, for cystine can be converted into halfcystine.
Beneficial effect
The preparation method of detection reagent of the present invention is with low cost, can obtain quickly and in batch efficiently for detecting the reagent of hair water soy sauce.Detection reagent of the present invention only needs instillation or puts into soy sauce to be measured, just can by determining the content of cystine in soy sauce to be measured to the judgement of fluorescence, and then technician just can be judged by naked eyes, whether soy sauce to be measured is hair water soy sauce or doubtful hair water soy sauce, it is simple, convenient to use, successful, detection time is short.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of preparation method according to an embodiment of the invention;
Fig. 2 is the synthesis path schematic diagram carrying out tube-nursery according to one embodiment of the invention;
Fig. 3 is the molecular structure of detection reagent of the present invention;
Fig. 4 is the nuclear magnetic resoance spectrum of 1H in TMPAB-o-M.
Embodiment
Shown in Fig. 1 and 2, the building-up process of the reagent for the detection of hair water soy sauce of the present embodiment is described in detail.
In the present embodiment, by first synthesizing 1,3,5,7-tetramethyl-8-phenyl-(2-nitro)-boron difluoride dipyrrylmethanes (TMPB-o-N), then synthesize 1,3,5,7-tetramethyl-8-phenyl-(2-amido)-boron difluoride dipyrrylmethanes (TMPB-o-A), finally obtains test agent of the present invention.
Specifically, first, accurately take 1.06g (7.0mmol) o-nitrobenzaldehyde, be dissolved in the CH of 500mL drying
2cl
2.
Next, when utilizing nitrogen to protect, stir gained solution limit, limit slowly drips 1.44mL (14.0mmol) 2,4-dimethyl pyrrole.Afterwards, instill 1 trifluoroacetic acid, sealed by gained solution, at 25 DEG C, insulated and stirred is spent the night, and finds that the material point of o-nitrobenzaldehyde disappears until utilize thin-layer chromatography to detect.
Next add 4.0mL triethylamine, at 25 DEG C, 10min is stirred to gained solution, then add 4.8mL boron trifluoride diethyl etherate, stirred overnight at room temperature.Subsequently, gained mixed liquor is concentrated into about 150mL, utilizes saturated NaHCO
3solution washs (40mL × 3) concentrate.Organic phase anhydrous sodium sulfate drying, except desolventizing, silica gel column chromatography purification (eluent: cyclohexane: CH
2cl
2=30:70), obtain Orange red solid 0.91g (productive rate: 35.3%).
1H NMR(CDCl
3，300MHz)：1.36(s，6H)，2.56(s，6H)，5.99(s，2H)，7.47(d，1H)，7.69(t，1H)，7.78(t，1H),8.19(d，1H)。
Gained orange solids is 1,3,5,7-tetramethyl-8-phenyl-(2-nitro)-boron difluoride dipyrrylmethanes (TMPB-o-N), then TMPB-o-N is utilized to synthesize 1,3,5,7-tetramethyl-8-phenyl-(2-amido)-boron difluoride dipyrrylmethanes (TMPB-o-A).
Specifically, 0.91g (2.46mmol) TMPB-o-N of gained is dissolved in 20mL CH
2cl
2with 20mL absolute ethyl alcohol, add 0.1g 10%Pd/C, under stirring at room temperature, normal pressure passes into hydrogen catalytic reduction, utilizes thin-layer chromatography to monitor extent of reaction.Reacted after about 8h, rapid suction filtration removing Pd/C, filtrate rotary evaporation, except desolventizing, is drained, and (productive rate: 94.5%) is not done to purify further and characterize, directly used to obtain crude product TMPB-o-A 0.79g.
Next, the 0.79g TMPB-o-A of gained is dissolved in 100mL glacial acetic acid, under stirring, adds 0.27g (2.76mmol) maleic anhydride, stir 2h, removal of solvent under reduced pressure, silica gel column chromatography purification (eluent: CH
2cl
2: MeOH=19:1), obtain orange sterling 0.93g (productive rate: 91.3%).
1H NMR(CDCl
3，300MHz)：1.42(s，6H)，2.49(s，6H)，6.00(s，2H)，6.27(d，1H)，6.42(d，1H)，7.27(m，1H)，7.40(m，1H)，7.56(m，1H)，8.30(m，1H)，8.53(br，1H)。
Be dissolved in by products obtained therefrom in 150mL acetic anhydride, add sodium acetate 0.2g, 80 DEG C of incubated overnight, thin-layer chromatography monitoring reacts completely.The most of solvent of mixed liquor decompression removing, remainder is poured into water, and stirs, separates out to solid.Filter, gained solid crude product silica gel column chromatography purification (eluent: CH
2cl
2), (productive rate: 58.3%), its molecular structure is as shown in Figure 3 to obtain sterling TMPAB-o-M 0.52g.
1H NMR(CDCl
3，300MHz)：1.57(s，6H)，2.51(s，6H)，5.96(s，2H)，6.65(s，2H)，7.35-7.38(m，1H)，7.47-7.50(m，1H)，7.60-7.63(m，2H)。
By the way, just the test agent being used for carrying out fluorescence reaction with the halfcystine in hair water soy sauce is obtained.Although cystine and halfcystine are and deposit under normal circumstances, but in order to improve the checkability of testing reagent of the present invention, test agent of the present invention can also comprise reductive agent.This reductive agent can join in soy sauce to be measured in advance.
How the detection reagent introduced below prepared by the present invention uses to detect soy sample.
Under normal circumstances, obtained TMPAB-o-M solid can be configured to methyl alcohol or the dimethyl sulfoxide solution of predetermined concentration above, such as 1.0 × 10
-4m and 5.0 × 10
-4m.Then getting a certain amount of soy sample to be measured, in order to strengthen Detection results, pre-service can be carried out by soy sample.Pre-service can comprise utilize activated charcoal or other sorptive materials absorption soy sauce in large molecule or other impurity, can also comprise and soy sample is diluted, to be diluted to predetermined concentration.Then, in soy sample, add excessive reductive agent, make the cystine in soy sample, then all transform in halfcystine.Then, ready test agent is added dropwise in soy sample and goes, observe or measure fluorescence reaction situation.
In the present embodiment, have purchased precious pole board from supermarket: dark soy sauce special grade soy, light soy sauce special grade soy, one-level soy sauce, light color secondary soy sauce; Add board soy sauce: superfine product are fresh, gold mark one-level light soy sauce king, the extremely fresh special grade soy of extra large sky board taste, Li Jin remember that the multiple soy sauce such as the selected superfine light soy sauce of board are as sample, various soy sauce all purchased from hundred supermarkets.Further, inventor takes 0.0011g TMPAB-o-M solid and is dissolved in DMSO, is made into 2.0 × 10
-3m storing solution, for follow-up test.
Further, in order to regulate pH value, also prepared PBS buffer solution in the present embodiment, process for preparation is as follows: take 4.00g NaCl, 0.10g KCl, 0.10g KH
2pO
4, 1.39g Na
2hPO
412H
2o, is dissolved in 500mL intermediate water, on acidometer, be adjusted to required pH value with 1M HCl or NaOH.H
3cit-NaOH buffer solution is by 0.10M H
3cit solution and the mixing of 0.10M NaOH solution are adjusted to required pH value.This damping fluid is used for diluting reagent or sample.
During test, in 1.5mL plastics EP pipe, add 10 μ L 2.00 × 10 successively
-3mTMPAB-o-M storing solution and appropriate soy sample to be measured, be diluted to 300 μ L with the PBS buffer solution of pH=7.40, mixed liquor reacts 8min at 25 DEG C, with direct injection analysis after liquid chromatogram mobile phase dilution.The fluorescence reaction of direct observation sample, and quantitative test is carried out to fluorescence reaction.
In the present embodiment, multiple soy sample is tested.Specifically, the present invention gets soy sample above respectively, is diluted to finite concentration, is then divided into two parts, and portion mixes hair water, and another part does not then mix hair water.Then, respectively contrast test has been carried out to the soy sauce being mixed with hair water and the soy sauce that do not mix hair water.Applicant finds, the soy sauce not mixing hair water does not have fluorescence substantially, and what be mixed with the soy sauce of hair water then has very strong fluorescence.
Therefore, can prove based on above-mentioned experiment, the reagent prepared by method of the present invention can detect effectively to hair water soy sauce.Due to, detection reagent of the present invention uses simple, convenient, therefore, commercially can survey sample soy sauce anywhere or anytime, thus effectively supervise hair water soy sauce, avoid it to come into the market.
Although be described in detail principle of the present invention in conjunction with the preferred embodiments of the present invention, it should be appreciated by those skilled in the art that above-described embodiment is only the explanation to exemplary implementation of the present invention above, not the present invention is comprised to the restriction of scope.Details in embodiment does not form limitation of the scope of the invention; when not deviating from the spirit and scope of the present invention; the apparent changes such as any equivalent transformation based on technical solution of the present invention, simple replacement, all drop within scope.
Claims (7)
1. for detecting a preparation method of reagent thereof for hair water soy sauce, it is characterized in that, described preparation method comprises the steps:
Step 1) o-nitrobenzaldehyde of scheduled volume is dissolved in CH
2cl
2in;
Step 2) in obtained solution, add 2,4-dimethyl pyrrole and instill trifluoroacetic acid sealing, the stirring schedule time;
Step 3) in gained solution, add triethylamine and boron trifluoride diethyl etherate;
Step 4) gained mixed liquor is concentrated, and obtained concentrate is washed;
Step 5) with anhydrous sodium sulfate, drying is carried out to gained concentrate, except desolventizing, and utilize silica gel column chromatography to purify, obtain the first dry solid matter;
Step 6) the first obtained solid matter is dissolved in CH
2cl
2with the mixed liquor of absolute ethyl alcohol;
Step 7) in mixed liquor, add Pd/C, under stirring condition, pass into hydrogen catalytic reduction, after reaction to be restored completes substantially, filtering Pd/C;
Step 8) solvent removed in filtrate obtains corresponding second solid matter;
Step 9) gained second solid matter is dissolved in glacial acetic acid, stir and add maleic anhydride, after stirring the schedule time, solvent is removed in decompression, and carries out silica gel column chromatography purification, obtains orange material;
Step 10) orange for gained material is dissolved in acetic anhydride, add sodium acetate, insulation predetermined hold-time, question response is completely by mixed liquor removal of solvent under reduced pressure, and remainder is poured into water, and stirs, separate out to solid, filter, silica gel column chromatography purification is carried out to gained solid product, obtain destination agent.
2. preparation method according to claim 1, is characterized in that, the consumption of o-nitrobenzaldehyde is 1.06g, and the consumption of described 2,4-dimethyl pyrroles is 1.44mL; Described triethylamine consumption is 4.0mL, and boron trifluoride diethyl etherate consumption is 4.8mL, and the consumption of maleic anhydride is 0.27g, and each composition can increase in proportion.
3. preparation method according to claim 1, is characterized in that, described first solid matter is 1,3,5,7-tetramethyl-8-phenyl-(2-nitro)-boron difluoride dipyrrylmethanes.
4. preparation method according to claim 1, is characterized in that, described second solid matter is 1,3,5,7-tetramethyl-8-phenyl-(2-amido)-boron difluoride dipyrrylmethanes.
5. preparation method according to claim 1, is characterized in that, described method also comprises the dimethyl sulfoxide solution or the methyl alcohol that the second obtained solid matter are dissolved in scheduled volume.
6. preparation method according to claim 1, is characterized in that, in described step 4) described in washing comprise and utilize saturated NaHCO
3obtained concentrate is washed.
7., for the reagent that hair water soy sauce detects, it is characterized in that, in described reagent, comprise 1,3,5,7-tetramethyl-8-phenyl-(2-maleimide)-boron difluoride dipyrrylmethanes.
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|---|---|---|---|
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103163269A (en) * | 2013-03-21 | 2013-06-19 | 佛山市海天调味食品股份有限公司 | Method for fast identifying fermented soy sauce and blended soy sauce |
| CN103788076A (en) * | 2014-01-22 | 2014-05-14 | 山西大学 | Reagent and method for detecting cysteine |
-
2015
- 2015-01-20 CN CN201510026305.4A patent/CN104535755B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103163269A (en) * | 2013-03-21 | 2013-06-19 | 佛山市海天调味食品股份有限公司 | Method for fast identifying fermented soy sauce and blended soy sauce |
| CN103788076A (en) * | 2014-01-22 | 2014-05-14 | 山西大学 | Reagent and method for detecting cysteine |
Non-Patent Citations (2)
| Title |
|---|
| LUCAS C. D. DE REZENDE 等: "A Review of the Synthetic Strategies for the Development of BODIPY Dyes for Conjugation with Proteins", 《ORBITAL: THE ELECTRONIC JOURNAL OF CHEMISTRY》 * |
| 汪剑波: "基于分子内电荷转移的氟硼荧（BODIPY）等功能分子的合成及应用", 《中国博士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》 * |
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