CN101513608B - Visualization detecting aquagel of melamine and preparing method thereof - Google Patents
Visualization detecting aquagel of melamine and preparing method thereof Download PDFInfo
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- CN101513608B CN101513608B CN2009100249668A CN200910024966A CN101513608B CN 101513608 B CN101513608 B CN 101513608B CN 2009100249668 A CN2009100249668 A CN 2009100249668A CN 200910024966 A CN200910024966 A CN 200910024966A CN 101513608 B CN101513608 B CN 101513608B
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Abstract
The invention discloses visualization detecting aquagel of melamine which is mutually folded double-layer aquagel. Sensitive aquagel and non-sensitive aquagel are bound together to compose the double-layer aquagel. In the preparing method, monomer, cross linker and evocating agent of the aquagel are dissolved in water to obtain non-sensitive aquagel polymer fluid, and then the non-sensitive aquagel polymer fluid is added in a mould to be polymerized into a non-sensitive aquagel film; the non-sensitive aquagel film is tiled on a piece of glass for the dehydration, and then the dehydrated non-sensitive aquagel film, the glass and a holding strip compose the mould; functional monomer, cross linker, melamine and evocating agent of print aquagel are dissolved in water to obtain print aquage polymer fluid which is then added in the mould to be polymerized into a sensitive print aquagel film, and a double-layer aquagel film is formed; the prepared double-layer aquagel film is cut into strips and is washed in acid solution to remove melamine molecules, wherein, the pH value of the acid solution is less than 3. Then, the prepared doube-layer aquagel is washed in pure water until the shape is unchanged.
Description
Technical field
The present invention relates to visual test material of a kind of melamine and preparation method thereof.By preparing a kind of molecule imprinting hydrogel, the melamine molecule in can response environment and produce deformation.Specifically, the present invention relates to utilize molecular imprinting, preparation forms two glue with responsive trace hydrogel and non-sensitive hydrogel again to the trace hydrogel of melamine sensitivity, promptly gets a kind of visualized aquogel.Again sample is carried out simple pre-service, just can come whether to exist in the judgement sample melamine by the deformation of this visualized aquogel.The invention belongs to the technical field of visual analyzing.
Background technology
Melamine (English name Melamine) is a kind of triazines nitrogen heterocyclic ring organic compound, important azacyclo-Organic Chemicals.Because the defective of food and feed industry protein content method of testing, melamine often are used as food additives by illegal businessman, with the protein content index in the lifting food inspection, so melamine also is " extract of protein " by person.
Existing melamine detection method all is based on the detection of chromatogram, high performance liquid chromatography especially, and cost is higher, is difficult to extend to the department of basic unit of quality inspection and Quality Control and producers and consumers individual's use.
(molecularly imprinted technique is the existing molecular specificity recognition reactions of organic sphere such as simulation enzyme-to-substrate, antibody and antigen MIT) to molecular imprinting, is the technology of the synthetic imprinted polymer of template with the target molecule.(molecularly imprintedpolymer MIP) has specific recognition ability to microsphere to He Cheng imprinted polymer in this way.At present, molecular imprinting has been applied to fractionation (chiral separation), Solid-Phase Extraction (the solid-phase extraction of chipal compounds, SPE), antibody simulation (antibody mimics), enzymatic simulation (enzyme mimics) and controlled release drug fields such as (controlled release drugs), also be applied to the analysis such as the sensor (US2008179191-A1 such as (biomimeticsensor) in fields such as environment, biology and medical science, US_20080179191_A1, WO_2008045596_A2).
The general step of molecularly imprinted polymer preparation is as follows: at first make between template molecule and the function monomer by covalent bond, non-covalent or other effects and combine formation host-guest coordination compound (Host-guest complex); Add cross-linking monomer (cross-linker) then, in initiating agent, heat or light-initiated following, at template molecule---produce polyreaction around the function monomer complex, polymkeric substance captures the complex of template molecule and monomer in the spatial structure of polymkeric substance; At last the template molecule wash-out (elution) in the polymkeric substance or dissociate (dissociation) are come out, but in polymkeric substance, just stayed " the trace hole " of recognition template molecule.
Hydrogel is the hydrophilic high molecular polymer of a class, apply to Template trace, organization restoration, applied researcies such as medicament slow release.Has certain biocompatibility, can respond the change of osmotic pressure and expand or shrink, also has memory function, have the character such as environment pattern before can replica polymerization, so hydrogel is applied to sensing Study of An, Asher SA etc. is fixed in colloidal crystal in the hydrogel, grafting specific recognition molecule on hydrogel again, be used for analyzing (US2002031841-A1, WO9841859-A, WO9819787-A).
Polyacrylamide hydrophilic gel for example, under alkali condition, amide group is hydrolyzed into carboxyl group---can induced environment in pH be worth changing and the variation of volume take place, in hydrogel fixing on behind the microsphere, hydrogel can respond the environment that contains this specific molecular.But the volume change naked eyes of these responses are difficult to differentiate.
The present invention as the synthetic trace hydrogel of microsphere, produces visual double-deck hydrogel with melamine molecule.Can respond melamine visual deformation takes place, it is low to become a kind of cost, and speed is fast, the detection method that is easy to promote.
Summary of the invention
Technical matters: the purpose of this invention is to provide the visualization detecting aquagel and preparation method thereof that a kind of naked eyes can be distinguished the melamine of deformation, have the fast advantage of detection speed.
Technical scheme: the present invention adopts following technical scheme:
The visualization detecting aquagel of a kind of melamine of the present invention is the double-deck hydrogel that is superimposed, and described double-deck hydrogel is bonded together by the sensitive aquagel of one deck molecular imprinting preparation and the non-sensitive hydrogel of one deck and constitutes.
The preparation method of the visualization detecting aquagel of melamine of the present invention:
Step 1) is with the monomer of hydrogel, crosslinking chemical, initiating agent is 100～10: 100～0.1 in molar ratio: 10～0.1 ratio is soluble in water, obtain non-sensitive hydrogel polymer fluid, the monomer of hydrogel, the general assembly (TW) of crosslinking chemical and initiating agent is 2～25: 50 (W/V with the ratio of the volume of the non-sensitive hydrogel polymer fluid of gained, grams per milliliter), non-sensitive hydrogel polymer fluid being added to clamp bar thickness again and being in the mould of layer glass of 25～1000 μ m polymerization, to form thickness be the non-sensitive aquagel membrane of 25～1000 μ m
The monomer of described hydrogel is the molecule that contains mono alkenyl, as acrylamide, acrylic acid, methacrylic acid etc.;
Step 2) the non-sensitive aquagel membrane of above-mentioned preparation being tiled in the 10-80% of a dehydration on glass to non-sensitive aquagel membrane weight, is that the clamp bar of 50～2000 μ m is formed mould by the non-sensitive aquagel membrane after the dehydration, glass and thickness again;
Step 3) is with the function monomer of trace hydrogel, crosslinking chemical, melamine, initiating agent, be 100～10: 100～0.1 in molar ratio: 100～1: 1～0.1 ratio is soluble in water, obtain trace hydrogel polymer fluid, the function monomer of trace hydrogel, crosslinking chemical, the general assembly (TW) of melamine and initiating agent is 2～25: 50 (W/V with the ratio of the volume of gained trace hydrogel polymer fluid, grams per milliliter), again the trace hydrogel solution is added to by step 2) in the mould that obtains, polymerization forms the responsive trace aquagel membrane of melamine, simultaneously with mould in original non-sensitive aquagel membrane form double-deck aquagel membrane jointly
The function monomer of described trace hydrogel is the molecule that contains mono alkenyl, as acrylamide, acrylic acid, methacrylic acid etc.;
Step 4) cuts into strip with the prepared double-layer aquagel membrane, in the pH value less than 3 acid solution in washing remove melamine molecule, in pure water, wash to shape invariance, just can be used for the analysis of melamine,
Described crosslinking chemical is the molecule that contains the diene base: as methene acrylamide, 1, and 4-phenyl bisacrylamide etc., described initiating agent is azo-initiator, organic peroxide initiator or inorganic peroxy class initiating agent.
The visualized aquogel detection method, soon trace hydrogel and non-sensitive hydrogel are bonded together and form visual double-deck hydrogel, handle this double-deck hydrogel with testing sample again, promptly can determine the existence and the concentration of melamine by the degree whether this bilayer hydrogel deformation reaches deformation.
Use the visual detection melamine of the present invention method to be:
Prepared double-layer water-setting adhesive tape is added in the sample solution to be measured, and 15min is handled in concussion, if contain melamine molecule in the sample, will make the deformation that bends of double-deck water-setting adhesive tape.The degree that whether reaches deformation according to deformation can be determined the existence and the concentration range thereof of melamine.
Beneficial effect: compared with prior art, the present invention has following advantage:
1, the great advantage of visualized aquogel of the present invention is that the deformation that response produces to melamine is the variation that bends, and can observe intuitively by naked eyes, and is highly sensitive.Compare of the present invention with low costly, simple to operate with traditional detection method, be easy to promote.
2, intelligent crystal colloidal gel such as visualized aquogel of the present invention and Asher SA are compared, and polymerization single polymerization monomer can be neutral monomer, also can not be neutral monomer, and intelligent crystal colloidal gel can only be neutral polymerization single polymerization monomers.Responsive glue is more suitable for setting up the two glue preparations that detect the multiple molecule that comprises melamine with the engram technology preparation.
Description of drawings
Fig. 1 is the figure of melamine visualized aquogel in serial melamine aqueous solution.Concentration with melamine increases, and the flexibility of hydrogel increases, i.e. deformation increases, when concentration arrives 100ppm, and the hydrogel back-flexing.
Fig. 2 takes out after 15 minutes in fresh milk with visualized aquogel photo in the distilled water washing back, and wherein, a is that b is the photo that does not add melamine fresh milk to the photo of the fresh milk that adds the 2ppm melamine.
Embodiment
Embodiment 1
A kind of visualization detecting aquagel of melamine is the double-deck hydrogel that is superimposed, and described double-deck hydrogel is bonded together by the sensitive aquagel of one deck molecular imprinting preparation and the non-sensitive hydrogel of one deck and constitutes.
Embodiment 2
A kind of preparation method of visualization detecting aquagel of melamine, adopt following steps:
Step 1) is with the monomer of hydrogel, crosslinking chemical, initiating agent is 100～10: 100～0.1 in molar ratio: 10～0.1 ratio is soluble in water, obtain non-sensitive hydrogel polymer fluid, the monomer of hydrogel, the general assembly (TW) of crosslinking chemical and initiating agent is 2～25: 50 (W/V with the ratio of the volume of the non-sensitive hydrogel polymer fluid of gained, grams per milliliter), non-sensitive hydrogel solution being added to clamp bar thickness again and being in the mould of layer glass of 25～1000 μ m polymerization, to form thickness be the non-sensitive aquagel membrane of 25～1000 μ m
The monomer of described hydrogel is for containing the mono alkenyl molecule, as acrylamide, acrylic acid, methacrylic acid etc.;
Above-mentioned steps 1 at present embodiment) in, can select mol ratio is that monomer, crosslinking chemical, the initiating agent of hydrogel of 100: 100: 10,10: 0.1: 0.1 or 65: 12: 7 is soluble in water, and the general assembly (TW) of the monomer of hydrogel, crosslinking chemical and initiating agent is 2: 50,25: 50 or 17: 50 with the ratio of the volume of the non-sensitive hydrogel polymer fluid of gained; (W/V, grams per milliliter).
Step 2) the non-sensitive aquagel membrane with above-mentioned preparation is tiled in the 10-80% of a dehydration on glass to non-sensitive aquagel membrane weight, present embodiment can be selected non-sensitive hydrogel dehydration to 10%, 80% or 65% of non-sensitive aquagel membrane weight, is that the clamp bar of 50～2000 μ m is formed mould by the non-sensitive aquagel membrane after the dehydration, glass and thickness again;
Step 3) is with the function monomer of trace hydrogel, crosslinking chemical, melamine, initiating agent, be 100～10: 100～0.1 in molar ratio: 100～1: 1～0.1 ratio is soluble in water, obtain trace hydrogel polymer fluid, the function monomer of trace hydrogel, crosslinking chemical, the general assembly (TW) of melamine and initiating agent is 2～25: 50 (W/V with the ratio of the volume of gained trace hydrogel polymer fluid, grams per milliliter), again trace hydrogel polymer fluid is added to by step 2) in the mould that obtains, polymerization forms the responsive trace aquagel membrane of melamine, simultaneously with mould in original non-sensitive aquagel membrane form double-deck aquagel membrane jointly
The function monomer of described trace hydrogel is the molecule that contains mono alkenyl, as acrylamide, acrylic acid, methacrylic acid etc.;
Above-mentioned steps 3 at present embodiment) in, can select mol ratio is 100: 100: 100: 10,10: 0.1: 1: 0.1 or 65: 12: 33: the monomer of 7 hydrogel, crosslinking chemical, melamine and initiating agent are soluble in water, and, the ratio of the general assembly (TW) of the monomer of hydrogel, crosslinking chemical, melamine and initiating agent and the volume of the non-sensitive hydrogel polymer fluid of gained is 2: 50,25: 50 or 17: 50 (W/V, grams per milliliter);
Step 4) cuts into strip with the prepared double-layer aquagel membrane, in the pH value less than 3 acid solution in washing remove melamine molecule, in pure water, wash to shape invariance, just can be used for the analysis of melamine,
Described crosslinking chemical is the molecule that contains the diene base: as methene acrylamide, 1, and 4-phenyl bisacrylamide etc., described initiating agent is azo-initiator, organic peroxide initiator or inorganic peroxy class initiating agent.
In the present embodiment,
Containing the mono alkenyl molecule is acrylamide, acrylic or methacrylic acid.
Containing diene base molecule is methene acrylamide or 1,4-phenyl bisacrylamide.
Azo-initiator is azoisobutyronitrile or ABVN; Organic peroxide initiator is a dibenzoyl peroxide; Inorganic peroxy class initiating agent is a persulfate.
Form non-sensitive aquagel membrane polymerizing condition or form the difference of the responsive trace aquagel membrane polymerizing condition of melamine because of initiating agent, specifically,
Polymerizing condition when adopting azo-initiator is that wavelength is under illumination 20-80 minute of 365nm or the 60-80 ℃ of condition 20-80 minute;
Polymerizing condition when adopting organic peroxide initiator is that wavelength is under the illumination condition of 365nm 20-80 minute;
Polymerizing condition when adopting inorganic peroxy class initiating agent is under the 4-40 ℃ of condition 20-80 minute.
Embodiment 3
Get that (a copy of it adds the melamine of 2ppm in the market milk that double-deck hydrogel adhesive tape after the abundant washing is soaked in 2ml, portion does not add melamine), shook 15 minutes, the washing of taking-up distilled water, observe the variation of its shape, with reference to Fig. 2, contain double-deck hydrogel adhesive tape in the fresh milk of melamine and blank sample as can be known relatively, variation has taken place in shape.
Claims (3)
1. the preparation method of the visualization detecting aquagel of a melamine is characterized in that:
Step 1) is with the monomer of hydrogel, crosslinking chemical, initiating agent is 100～10: 100～0.1 in molar ratio: 10～0.1 ratio is soluble in water, obtain non-sensitive hydrogel polymer fluid, the monomer of hydrogel, the general assembly (TW) of crosslinking chemical and initiating agent is 2～25: 50 grams per milliliters with the ratio of the volume of the non-sensitive hydrogel polymer fluid of gained, non-sensitive hydrogel solution being added to clamp bar thickness again and being in the mould of layer glass of 25～1000 μ m polymerization, to form thickness be the non-sensitive aquagel membrane of 25～1000 μ m
The monomer of described hydrogel is the molecule that contains mono alkenyl;
Step 2) the non-sensitive aquagel membrane that will prepare is tiled in a dehydration on glass to the 10-80% of non-sensitive aquagel membrane weight, is that the clamp bar of 50～2000 μ m is formed mould by the non-sensitive aquagel membrane after the dehydration, glass and thickness again;
Step 3) is with the function monomer of trace hydrogel, crosslinking chemical, melamine, initiating agent, be 100～10: 100～0.1 in molar ratio: 100～1: 1～0.1 ratio is soluble in water, obtain trace hydrogel polymer fluid, the function monomer of trace hydrogel, crosslinking chemical, the general assembly (TW) of melamine and initiating agent is 2～25: 50 grams per milliliters with the ratio of the volume of gained trace hydrogel polymer fluid, again trace hydrogel polymer fluid is added to by step 2) in the mould that obtains, polymerization forms the responsive trace aquagel membrane of melamine, simultaneously with mould in original non-sensitive aquagel membrane form double-deck aquagel membrane jointly
The function monomer of described trace hydrogel is the molecule that contains mono alkenyl;
Step 4) cuts into strip with the prepared double-layer aquagel membrane, in the pH value less than 3 acid solution in washing remove melamine molecule, in pure water, wash to shape invariance, just can be used for the analysis of melamine,
Described crosslinking chemical is the molecule that contains the diene base, and described initiating agent is azo-initiator, organic peroxide initiator or inorganic peroxy class initiating agent, and the molecule that contains mono alkenyl is acrylamide, acrylic or methacrylic acid; The molecule that contains the diene base is methene acrylamide or 1,4-phenyl bisacrylamide.
2. the described preparation method of claim 1 is characterized in that azo-initiator is azoisobutyronitrile or ABVN; Organic peroxide initiator is a dibenzoyl peroxide; Inorganic peroxy class initiating agent is a persulfate.
3. the described preparation method of claim 1, the polymerizing condition when it is characterized in that adopting azo-initiator is that wavelength is under illumination 20-80 minute of 365nm or the 60-80 ℃ of condition 20-80 minute; Polymerizing condition when adopting organic peroxide initiator is that wavelength is under the illumination condition of 365nm 20-80 minute; Polymerizing condition when adopting inorganic peroxy class initiating agent is under the 4-40 ℃ of condition 20-80 minute.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1757431A (en) * | 2005-09-16 | 2006-04-12 | 东南大学 | Visualized aquogel, and its preparing method |
| CN101240076A (en) * | 2008-03-12 | 2008-08-13 | 天津大学 | Macromolecule and emulsion double-blotting alginate polymer micro-sphere and preparation method thereof |
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| CN1757431A (en) * | 2005-09-16 | 2006-04-12 | 东南大学 | Visualized aquogel, and its preparing method |
| CN101240076A (en) * | 2008-03-12 | 2008-08-13 | 天津大学 | Macromolecule and emulsion double-blotting alginate polymer micro-sphere and preparation method thereof |
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