CN101713713A - Sample pretreatment method for detecting harmful substances in dairy products - Google Patents
Sample pretreatment method for detecting harmful substances in dairy products Download PDFInfo
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- CN101713713A CN101713713A CN200810167719A CN200810167719A CN101713713A CN 101713713 A CN101713713 A CN 101713713A CN 200810167719 A CN200810167719 A CN 200810167719A CN 200810167719 A CN200810167719 A CN 200810167719A CN 101713713 A CN101713713 A CN 101713713A
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Abstract
The invention relates to a sample pretreatment method for detecting harmful substances in dairy products, which comprises the following steps: 1) precipitating protein: adding a reagent for precipitating protein into a pretreatment sample and mixing evenly; 2) removing saccharides and fibrous matters: then adding a reagent for removing saccharides and fibrous matters into the pretreatment sample and mixing evenly; 3) removing fats and other lipophilic matters: then adding a reagent for removing fats and other lipophilic matters into the pretreatment sample and mixing evenly; and 4) centrifuging: centrifuging the sample after finishing steps 1)-3) for separation, and taking supernatant liquid for further analysis and detection or for concentration and further analysis and detection. The method of the invention can be used for analyzing and detecting various chemical components in the dairy products, and has the advantages of high speed, strong universality and the like.
Description
Technical field
The present invention relates to the food hygiene detection field, especially relate to the sample pretreating method that is used for detecting the dairy produce objectionable impurities.
Background technology
Analyzing and testing for harmful chemical in food or the agricultural product, no matter use which kind of analyzing detecting method, usually all need analyzed microchemistry composition is separated preferably with sample main matrix (as protein, fat, starch and pigment etc.) and other impurity, to avoid the interference of matrix for detection accuracy.Normally used method comprises albumen precipitation, liquid-liquid extraction and Solid-Phase Extraction etc.Speed is slow, the defective of versatility difference but present detection method has.
Along with the Food Inspection growth of requirement, be necessary the further more simple and reliable method of exploitation.Dairy produce particularly, as the big series products of one in the food, the source disperses extensively, be necessary to develop a kind of fast, the detection dairy produce The pretreatment method of highly versatile.Be beneficial to analyzing and testing accurately.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of sample pretreating method that is used for detecting the dairy produce objectionable impurities.This sample pretreating method can be used for analyzing and detecting various chemical components in the dairy produce, be a kind of fast, the sample pretreating method of highly versatile.
For solving the problems of the technologies described above, the present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprises the steps:
1) protein precipitation; In pretreatment sample, add the reagent of protein precipitation, mix;
2) remove carbohydrate and fibrous matter; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix;
4) centrifugal, will finish above-mentioned all step 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Further improved technical scheme, described step 1)-3) any two steps or three steps can merge and carry out in a device simultaneously in; Albumen, carbohydrate and fibrous matter and fats and other lipophilic substance omit step 1) to 3 to the influence of analyzing and testing in also can be per sample) in one to two step.
As further improvement in the technical proposal, the reagent of described protein precipitation comprises: the potpourri of a kind of, two or more arbitrary proportion in trichloroacetic acid, lead acetate, sulfosalicylic acid, acetonitrile, hydrochloric acid or the NaOH.
As further improvement in the technical proposal, the described reagent of removing glucide comprises: phenylhydrazine, substituted phenylhydrazines, hole surface replace or polymeric resin, the surface of absorption phenylhydrazine or other hydrazine derivate is connected to or adsorb the potpourri of a kind of, two or more arbitrary proportion in the inorganic carrier of phenylhydrazine or other hydrazine derivate.
Described substituted phenylhydrazines comprises: 2,4 dinitrophenylhydrazines, 2,4 dichloro phenyl hydrazines, benzene sulfonyl hydrazide, to Methyl benzenesulfonyl hydrazine, benzoyl group hydrazine or to the methylbenzene acid hydrazide.
The polymeric resin that described surface is connected to phenylhydrazine or other hydrazine derivate comprises: the styrene-divinylbenzene copolymer carrier that contains phenylhydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains nitrophenyl hydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains benzene sulfonyl hydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene sulfohydrazide, the styrene-divinylbenzene copolymer carrier that contains phenylhydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene hydrazides.
The inorganic carrier that described surface is connected to phenylhydrazine or other hydrazine derivate comprises: contain the silica gel or the aluminium oxide of phenylhydrazine, the silica gel that contains dichloro phenyl hydrazine or aluminium oxide, the silica gel that contains the chloro phenylhydrazine or aluminium oxide, the silica gel that contains nitrophenyl hydrazine or aluminium oxide or contain the silica gel or the aluminium oxide of dinitrophenylhydrazine.
As further improvement in the technical proposal, the described reagent of removing glucide comprises: the potpourri of one or both arbitrary proportions in the calcium salt of sulfonated phenylethylene-divinylbenzene copolymer, the lead salt of sulfonated phenylethylene-divinylbenzene copolymer.
As further improvement in the technical proposal, the described reagent of removing glucide comprises the solid phase carrier that boric acid base group is modified; The solid phase carrier that described boric acid base group is modified comprises: the agarose that acid polyethylene fat carrier that the styrene-divinylbenzene copolymer carrier that boric acid base group is modified, boric acid base group are modified or boric acid base group are modified.
As further improvement in the technical proposal, the described reagent that removes degrease and other lipophilic substance comprises: the surface is connected to the potpourri of a kind of, two or more arbitrary proportion in the superpolymer solid phase carrier that the silica-gel carrier of lipophilic group, alumina support, lipophilicity superpolymer or lipophilicity that the surface is connected to lipophilic group replace; And the described reagent that removes degrease and other lipophilic substance can not dissolve in water, and particle size range is at 5 microns to 5 millimeters; Specific surface area is 10～800 square meter/grams.
The silica-gel carrier that described surface is connected to lipophilic group is the silica gel of silica gel, octyl bonding or coating of octadecyl bonding or coating or the silica gel of hexyl bonding or coating.
The alumina support that described surface is connected to lipophilic group is the aluminium oxide of aluminium oxide, octyl bonding or coating of octadecyl bonding or coating or hexane base key and or the aluminium oxide of coating.
Described lipophilicity superpolymer solid phase carrier is the styrene-divinylbenzene copolymer resin.
The superpolymer solid phase carrier that described lipophilicity replaces is the styrene-divinylbenzene copolymer resin of acid amides replacement, the styrene-divinylbenzene copolymer resin of carboxyl substituted, the amino styrene-divinylbenzene copolymer resin that replaces, ethene pyrrolidone and styrene, the divinylbenzene copolymer resin.
As further improvement in the technical proposal, a kind of energy removes degrease and other lipophilic substance, and can remove residual protein, polypeptide or amino acid whose mixed adsorbing material simultaneously, this mixed adsorbing material is the potpourri of lipophilic sorbing material and ion exchange material; Its part by weight is between 1: 9 to 9: 1.
Described lipophilicity sorbing material comprises: the silica gel of octadecyl bonding or coating, the aluminium oxide of octadecyl bonding or coating, the silica gel of octyl bonding or coating, the aluminium oxide of octyl bonding or coating, the silica gel of hexyl bonding or coating, the aluminium oxide of hexyl bonding or coating, the styrene-divinylbenzene copolymer resin, the high polymer material that has adsorptive power for lipoid material that still possesses lipophilic styrene-divinylbenzene copolymer resin and inertia after the replacement; The particle size range of described lipophilicity sorbing material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers.
Described ion exchange material comprises: the silica gel of the styrene-divinylbenzene copolymer of styrene-divinylbenzene copolymer quaternary ammonium resin, amination styrene-divinylbenzene copolymer, sulfonated phenylethylene-divinylbenzene copolymer, carboxyl substituted, benzene sulfonic acid class bonding, contain carboxyl bonded silica gel, contain the bonded silica gel of quaternary ammonium salt or contain amino bonded silica gel; The particle size range of described ion exchange material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers.
As further improvement in the technical proposal, the reagent that can remove protein, fat and other lipophilic substance simultaneously comprises: the sulfonic acid degree of substitution is that styrene-divinylbenzene copolymer sulfonate resin, the quaternary ammonium ion degree of substitution of 0.1～1 mM/gram is the styrene-divinylbenzene copolymer quaternary ammonium salt of 0.1～1 mM/gram.
When adding above-mentioned resin material, can add the aqueous solution that contains 3% to 80% polar organic solvent.Polar solvent commonly used has: methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, acetone etc.
As further improvement in the technical proposal, the mixed type reagent material that can remove protein, carbohydrate and lipophilic class matrix simultaneously is: lipophilicity sorbing material, ion exchange material and contain the potpourri of the carrier of phenylhydrazine class material can reach the effect that removes deproteinize, carbohydrate and grease simultaneously.In the 3 class mixtures of material, the weight percent of each class material is not less than 1%, is not higher than 80%.
Described lipophilicity sorbing material comprises: the silica gel of octadecyl bonding or coating, the aluminium oxide of octadecyl bonding or coating, the silica gel of octyl bonding or coating, the aluminium oxide of octyl bonding or coating, the hexane base key and or the coating silica gel, the hexane base key and or the coating aluminium oxide, the styrene-divinylbenzene copolymer resin, the high polymer material that has adsorptive power for lipoid material that still possesses lipophilic styrene-divinylbenzene copolymer resin and inertia after the replacement; The particle size range of described lipophilicity sorbing material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers.
Described ion exchange material comprises: the silica gel of the styrene-divinylbenzene copolymer of styrene-divinylbenzene copolymer quaternary ammonium resin, amination styrene-divinylbenzene copolymer, sulfonated phenylethylene-divinylbenzene copolymer, carboxyl substituted, benzene sulfonic acid class bonding, contain carboxyl bonded silica gel, contain the bonded silica gel of quaternary ammonium salt or contain amino bonded silica gel; The particle size range of described ion exchange material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers.
The described carrier that contains phenylhydrazine class material comprises: phenylhydrazine, substituted phenylhydrazines, hole surface replace or the polymeric resin, the hole surface that are adsorbed with phenylhydrazine or other hydrazine derivate is connected to or adsorbs the potpourri of a kind of, two or more arbitrary proportion in inorganic carrier, borax or the immobilized borax of phenylhydrazine or other hydrazine derivate; Described substituted phenylhydrazines comprises: 2,4 dinitrophenylhydrazines, 2,4 dichloro phenyl hydrazines, benzene sulfonyl hydrazide, to Methyl benzenesulfonyl hydrazine, benzoyl group hydrazine or to the methylbenzene acid hydrazide; Described hole surface replaces or the polymeric resin that is adsorbed with phenylhydrazine or other hydrazine derivate comprises: the styrene-divinylbenzene copolymer carrier that contains phenylhydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains nitrophenyl hydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains benzene sulfonyl hydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene sulfohydrazide, the styrene-divinylbenzene copolymer carrier that contains phenylhydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene hydrazides; The inorganic carrier that described hole surface was connected to or was adsorbed with phenylhydrazine or other hydrazine derivate comprises: contain the silica gel or the aluminium oxide of phenylhydrazine, the silica gel that contains dichloro phenyl hydrazine or aluminium oxide, the silica gel that contains the chloro phenylhydrazine or aluminium oxide, the silica gel that contains nitrophenyl hydrazine or aluminium oxide or contain the silica gel or the aluminium oxide of dinitrophenylhydrazine; Load content is at the every every gram of 4 mMs that restrains of 0.3 mM.
Styrene-divinylbenzene copolymer described in the present invention is meant: by the styrene polymeric resin that the arbitrary ratio copolymerization 1: 9 to 9: 1 forms to the divinylbenzene mol ratio.
Removing in the literary composition has explanation in addition, and the styrene-divinylbenzene copolymer of the replacement described in the present invention is meant that the degree of substitution of multipolymer through obtaining behind the functionalization is at the every functionalized resins that restrains between the every gram of 3.5 mMs of 0.3 mM thus.
The present invention can be used for milk, goat milk and other various liquid milk products; The present invention also can be used for milk powder or other similar dairy produce; Also can be used for ice cream, sour milk, ice cream, condensed milk and toffee etc. and the relevant goods of milk.
Adopt the sample of the resultant purification of the present invention further to use, carry out analyzing and testing but be not limited to following method: vapor-phase chromatography, gas chromatography-mass spectrography, liquid phase chromatography, liquid chromatograph mass spectrography, Capillary Electrophoresis, enzyme reagent immunodetection, various direct spectrum detection methods.
The chemical substance composition that is used for testing after purifying through method of the present invention comprises a class or a few class of following material: molecular weight is not higher than 2000 daltonian organic amines, nitrogenous organic heterocyclic compounds, amide-type, oxygen containing organic heterocyclic compounds, ether compound, phenol organic compound, organic acid or various alcohol compound.Concrete chemical substance composition example comprises: melamine, cyanuric acid, common pesticides and agrochemical.Also comprise each metal ion species through the chemical substance composition that is used to test after the method purification of the present invention, and the various inorganic or organic anion of pairing mutually.
The present invention can be used for analyzing and detecting various chemical components in the dairy produce, has fast, advantage such as highly versatile.
Embodiment
Complete sample purification process of the present invention mainly comprises following mode:
1) solid sample:
Sample dissolution is in water or acidic aqueous solution, the acetonitrile or the methyl alcohol that add albumen precipitation reagent and 1～15% carry out albumen precipitation, add and contain the lipophilicity resin, ion exchange resin and the mix reagent material that contains the carrier of phenylhydrazine class material, mix, placed 3～30 minutes down in room temperature or water-bath (15～100 degrees centigrade), centrifugal under 4000～20000 rev/mins of conditions then, get supernatant and carry out further derivatization or directly test.
2) fluid sample:
The acetonitrile or the methyl alcohol that add albumen precipitation reagent and 1～15% carry out albumen precipitation, add and contain the lipophilicity resin, ion exchange resin and the mix reagent material that contains the carrier of phenylhydrazine class material, mix, placed 1～30 minute down in room temperature or water-bath (15～100 degrees centigrade), centrifugal under 4000～20000 rev/mins of conditions then, get supernatant and carry out further derivatization or directly test.
3) can only add lipophilicity resin and ion exchange resin, to remove remaining albumen and lipophilic substance at albumen precipitation simultaneously or afterwards according to the test needs.
If it is more serious that carbohydrate disturbs, and albumen and fat disturb weak (such as in Raman spectrum detects), can only add the reagent material that removes sugar behind albumen precipitation.
Embodiment 1
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add trichloroacetic acid, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix; The described reagent of removing carbohydrate and fibrous matter is phenylhydrazine;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 550 microns, specific surface area are the octadecyl bonding of 20 square meter/grams or the silica gel of coating;
4) centrifugal, will finish above-mentioned all step 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 2
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add lead acetate, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is 2,4 dinitrophenylhydrazines;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 500 microns, specific surface area are the octyl bonding of 100 square meter/grams or the silica gel of coating;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 3
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add sulfosalicylic acid, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is 2,4 dichloro phenyl hydrazines;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 1000 microns, specific surface area are the hexyl bonding of 150 square meter/grams or the silica gel of coating;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 4
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add acetonitrile, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is benzene sulfonyl hydrazide;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 1500 microns, specific surface area are the octadecyl bonding of 200 square meter/grams or the aluminium oxide of coating;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 5
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add hydrochloric acid, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is to the Methyl benzenesulfonyl hydrazine;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 2000 microns, specific surface area are the octyl bonding of 250 square meter/grams or the aluminium oxide of coating;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 6
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add NaOH, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is the benzoyl group hydrazine;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 2500 microns, specific surface area are the hexyl bonding of 300 square meter/grams or the aluminium oxide of coating;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 7
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add the potpourri of trichloroacetic acid and lead acetate arbitrary proportion, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is the methylbenzene acid hydrazide;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 3000 microns, specific surface area are the styrene-divinylbenzene copolymer resin of 400 square meter/grams;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 8
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add the potpourri of trichloroacetic acid, lead acetate and acetonitrile arbitrary proportion, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that contains phenylhydrazine functional group;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 3500 microns, specific surface area are the styrene-divinylbenzene copolymer resin of the acid amides replacement of 450 square meter/grams;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 9
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add the potpourri of sulfosalicylic acid and acetonitrile arbitrary proportion, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that contains nitrophenyl hydrazine functional group;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 4000 microns, specific surface area are the styrene-divinylbenzene copolymer resin of the carboxyl substituted of 500 square meter/grams;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 10
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add trichloroacetic acid, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that contains benzene sulfonyl hydrazide;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 5000 microns, specific surface area are the styrene-divinylbenzene copolymer resin of the amino replacement of 800 square meter/grams;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 11
Be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) protein precipitation; In pretreatment sample, add the arbitrary proportion potpourri of lead acetate and acetonitrile, mix;
2) remove carbohydrate and fiber; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix, extract carbohydrate; The described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene sulfohydrazide;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix, extract fats and other lipophilic substance; The described reagent that removes degrease and other lipophilic substance be in water, can not dissolve, particle diameter is that 4500 microns, specific surface area are the aluminium oxide of silica gel, octyl bonding or coating of the octadecyl bonding of 700 square meter/grams or coating and the potpourri of polystyrene arbitrary proportion;
4) centrifugal, will finish all above-mentioned steps 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 12
Repeat embodiment 11, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that contains phenylhydrazide.
Embodiment 13
Repeat embodiment 10, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene hydrazides.
Embodiment 14
Repeat embodiment 1, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the silica gel that contains phenylhydrazine.
Embodiment 15
Repeat embodiment 1, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the aluminium oxide that contains phenylhydrazine.
Embodiment 16
Repeat embodiment 2, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the silica gel that contains dichloro phenyl hydrazine.
Embodiment 17
Repeat embodiment 3, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the aluminium oxide that contains dichloro phenyl hydrazine.
Embodiment 18
Repeat embodiment 3, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the silica gel that contains the chloro phenylhydrazine.
Embodiment 19
Repeat embodiment 4, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the aluminium oxide that contains the chloro phenylhydrazine.
Embodiment 20
Repeat embodiment 5, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the silica gel that contains nitrophenyl hydrazine.
Embodiment 21
Repeat embodiment 6, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the aluminium oxide that contains nitrophenyl hydrazine.
Embodiment 22
Repeat embodiment 7, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the silica gel that contains dinitrophenylhydrazine.
Embodiment 23
Repeat embodiment 8, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the aluminium oxide that contains dinitrophenylhydrazine.
Embodiment 24
Repeat embodiment 9, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the calcium salt of sulfonated phenylethylene-divinylbenzene copolymer.
Embodiment 25
Repeat embodiment 10, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the lead salt of sulfonated phenylethylene-divinylbenzene copolymer.
Embodiment 26
Repeat embodiment 11, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the styrene-divinylbenzene copolymer carrier that boric acid base group is modified.
Embodiment 27
Repeat embodiment 1, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the acid polyethylene fat carrier that boric acid base group is modified.
Embodiment 28
Repeat embodiment 1, its difference only is: the described reagent of removing carbohydrate and fibrous matter is the agarose that boric acid base group is modified.
Embodiment 29
Carbohydrate to the little situation of the interference of sample detection under, the present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprises the steps:
1) in pretreatment sample, adds acetonitrile, mix protein precipitation;
2) in pretreatment sample, add the reagent that to remove residual protein, polypeptide or amino acid and fat and other lipophilic substance again, mix; The described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance is the silica gel of octadecyl bonding or coating and the potpourri of styrene-divinylbenzene copolymer quaternary ammonium resin; Wherein wt number percent is the silica gel of octadecyl bonding or coating: styrene-divinylbenzene copolymer quaternary ammonium resin=1: 9;
The particle size range of the silica gel of described octadecyl bonding or coating is 1000 microns, and specific surface area is 100 square meter/grams, and average pore size is 10 nanometers;
The particle size range of described styrene-divinylbenzene copolymer quaternary ammonium resin is 1000 microns, and specific surface area is 100 square meter/grams, and average pore size is 10 nanometers;
3) centrifugal, will finish above-mentioned all step 1)-2) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
Embodiment 30
If carbohydrate has interference to the detection of sample, then repeat embodiment 29, its difference is to add before centrifugal again removes carbohydrate and fiber reagent, as the calcium salt of sulfonated phenylethylene-divinylbenzene copolymer.
Embodiment 31
Repeat embodiment 29, its difference only is: the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance is the aluminium oxide of octadecyl bonding or coating and the potpourri of amination styrene-divinylbenzene copolymer; Wherein wt number percent is the aluminium oxide of octadecyl bonding or coating: amination styrene-divinylbenzene copolymer=10: 9;
Embodiment 32
Repeat embodiment 29, its difference only is: the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance is the silica gel of octyl bonding or coating and the potpourri of sulfonated phenylethylene-divinylbenzene copolymer; Wherein wt number percent is the silica gel of octyl bonding or coating: sulfonated phenylethylene-divinylbenzene copolymer=20: 9.
Embodiment 33
Repeat embodiment 29, its difference only is: the potpourri of the aluminium oxide that the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance is octyl bonding or coating and the styrene-divinylbenzene copolymer of carboxyl substituted; Wherein wt number percent is the aluminium oxide of octyl bonding or coating: the styrene-divinylbenzene copolymer of carboxyl substituted=30: 9.
Embodiment 34
Repeat embodiment 29, its difference only is: the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance be the hexane base key and or the potpourri of the silica gel of the silica gel of coating and benzene sulfonic acid class bonding; Wherein wt number percent is, the hexane base key and or the silica gel of coating: the silica gel of benzene sulfonic acid class bonding=40: 9.
Embodiment 35
Repeat embodiment 29, its difference only is: the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance be the hexane base key and or the aluminium oxide of coating and contain the potpourri of the bonded silica gel of carboxyl; Wherein wt number percent is, the hexane base key and or the aluminium oxide of coating: contain the bonded silica gel of carboxyl=55: 9.
Embodiment 36
Repeat embodiment 29, its difference only is: the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance is styrene-divinylbenzene copolymer resin and the potpourri that contains the bonded silica gel of quaternary ammonium salt; Wherein wt number percent is, the styrene-divinylbenzene copolymer portions of resin contains the bonded silica gel of quaternary ammonium salt=65: 9.
Embodiment 37
Repeat embodiment 29, its difference only is: the described reagent that can remove residual protein, polypeptide or amino acid and fat and other lipophilic substance is the potpourri that still possesses lipophilic styrene-divinylbenzene copolymer resin after replacing and contain amino bonded silica gel; Wherein wt number percent is, the styrene-divinylbenzene copolymer portions of resin contains the bonded silica gel of quaternary ammonium salt=9: 1.
Embodiment 38
The present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprises the steps:
1) adding the sulfonic acid degree of substitution in pretreatment sample is the styrene-divinylbenzene copolymer sulfonate resin of 0.3 mM/gram, mixes, and can remove protein, fat and other lipophilic substance simultaneously;
2) centrifugal, the sample of finishing above-mentioned all step 1) is carried out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
If carbohydrate has interference to detection, in step 1), can also add and remove carbohydrate and fiber reagent, for example 2,4 dinitrophenylhydrazines.
Embodiment 39
Repeat embodiment 38, its difference only is: adding the quaternary ammonium ion degree of substitution in step 1) is the styrene-divinylbenzene copolymer quaternary ammonium salt of 0.3 mM/gram.
Embodiment 40
Repeat embodiment 38, its difference only is: the sulfonic acid degree of substitution is 3.5 mM/grams.
Embodiment 41
Repeat embodiment 39, its difference only is: the quaternary ammonium ion degree of substitution is 3.5 mM/grams.
Embodiment 42
Repeat embodiment 38, its difference only is: the sulfonic acid degree of substitution is 1 mM/gram.
Embodiment 43
Repeat embodiment 39, its difference only is: the quaternary ammonium ion degree of substitution is 1 mM/gram.
Embodiment 44
Repeat embodiment 38, its difference only is: the sulfonic acid degree of substitution is 2 mM/grams.
Embodiment 45
Repeat embodiment 39, its difference only is: the quaternary ammonium ion degree of substitution is 2 mM/grams.
Embodiment 46
The present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps: to take by weighing the milk powder that contains melamine and put into 20 milliliters of centrifuge tubes for 500 milligrams, add 8.5 milliliter of 0.1% trichloroacetic acid extract, mixing, add 0.5 milliliter of 1% lead acetate solution, ultrasonic 20 minutes, add surperficial styrene-divinylbenzene copolymer resin (the degree of substitution 1.8 mM/grams that are connected to benzene sulfonyl hydrazide of 1.0 grams, specific surface 400 square meter/grams, 50 microns of mean grain sizes) and 1 gram styrene-divinylbenzene copolymer resin (specific surface 400 square meter/grams, 50 microns of mean grain sizes) and 2 milliliters of acetonitriles, the water-bath heating is 10 minutes; 8000 rev/mins centrifugal 5 minutes, get 1 milliliter of supernatant, use for liquid chromatographic detection.
Embodiment 47
The present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprises the steps: to take by weighing 500 milligrams of milk powder that contain melamine, adds 8.5 milliliter of 0.1% trichloroacetic acid extract, and is evenly mixed; Join 0.5 milliliter of 1% lead acetate solution is housed, 1.0 the gram surface is connected to styrene-divinylbenzene copolymer resin (the degree of substitution 1.8 mM/grams of benzene sulfonyl hydrazide, specific surface 400 square meter/grams, 50 microns of mean grain sizes) and 1 gram styrene-divinylbenzene copolymer resin (specific surface 400 square meter/grams, 50 microns of mean grain sizes), in 20 milliliters of centrifuge tubes of 2 milliliters of acetonitriles, water-bath heating ultrasonic concussion simultaneously 10 minutes; 8000 rev/mins centrifugal 5 minutes, get 1 milliliter of supernatant, use for liquid chromatographic detection.
Embodiment 48
The present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps: to take by weighing 0.5g milk powder sample (being accurate to 0.001g), add the about 15mL of 0.1mol/L hydrochloric acid, the vortex mixing, add 60g/L sulfosalicylic acid 3～4mL behind the ultrasonic Extraction 30min, be settled to 25mL with 0.1mol/L hydrochloric acid, centrifugal behind the mixing, get supernatant.
Perhaps take by weighing 15g left and right sides fresh milk and sour milk sample (being accurate to 0.001g), add 60g/L sulfosalicylic acid 3mL～4mL, be settled to 25mL with 0.1mol/L HCl, centrifugal behind the mixing, get supernatant.
Get above-mentioned supernatant 10mL, add styrene-divinylbenzene copolymer quaternary ammonium resin 1g, the silica gel 1g of octadecyl bonding adds 5% acetonitrile, mixing, 8000 rev/mins centrifugal 5 minutes, get 1 milliliter of supernatant, use for liquid chromatographic detection.
Get 5 milliliters of supernatants in addition, add the agarose resin 1g that boric acid base group is modified, shook 5 minutes; 8000 rev/mins centrifugal 5 minutes, get 1 milliliter of supernatant, detect to use for Raman spectrum.
Embodiment 49
The present invention is used for detecting the sample pretreating method of dairy produce objectionable impurities, comprises the steps:
1) in pretreatment sample, adds and to remove albumen simultaneously, remove carbohydrate and fiber, remove the reagent of fats and other lipophilic substance;
2) centrifugal, will finish above-mentioned steps 1) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing;
The described mixed type reagent material that can remove protein, carbohydrate and lipophilic class matrix simultaneously is: lipophilicity sorbing material, ion exchange material and contain the potpourri of the carrier of phenylhydrazine class material; In the potpourri of 3 class reagent materials, the weight percent of each class reagent material is not less than 1%, is not higher than 80%.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be qualification to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (16)
1. be used for detecting the sample pretreating method of dairy produce objectionable impurities, it is characterized in that, comprise the steps:
1) protein precipitation; In pretreatment sample, add the reagent of protein precipitation, mix;
2) remove carbohydrate and fibrous matter; In pretreatment sample, add the reagent of removing carbohydrate and fibrous matter again, mix;
3) remove fats and other lipophilic substance; In pretreatment sample, add the reagent that removes degrease and other lipophilic substance again, mix;
4) centrifugal, will finish above-mentioned all step 1)-3) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
2. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 1 is characterized in that: can omit step 2) or step 3).
3. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 1 is characterized in that: the reagent of described protein precipitation comprises the potpourri of a kind of, two or more arbitrary proportion in trichloroacetic acid, lead acetate, sulfosalicylic acid, acetonitrile, hydrochloric acid or the NaOH.
4. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 1 is characterized in that: the described reagent of removing carbohydrate and fibrous matter comprises that phenylhydrazine, substituted phenylhydrazines, hole surface replace or the polymeric resin, the hole surface that are adsorbed with phenylhydrazine or other hydrazine derivate is connected to or adsorbs the potpourri of a kind of, two or more arbitrary proportion in the inorganic carrier of phenylhydrazine or other hydrazine derivate.
5. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 4, it is characterized in that: described substituted phenylhydrazines comprises 2,4 dinitrophenylhydrazines, 2,4 dichloro phenyl hydrazines, benzene sulfonyl hydrazide, to Methyl benzenesulfonyl hydrazine, benzoyl group hydrazine or to the methylbenzene acid hydrazide; Described hole surface replaces or the polymeric resin that is adsorbed with phenylhydrazine or other hydrazine derivate comprises: the styrene-divinylbenzene copolymer carrier that contains phenylhydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains nitrophenyl hydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains benzene sulfonyl hydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene sulfohydrazide, the styrene-divinylbenzene copolymer carrier that contains phenylhydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene hydrazides; Described hole surface is connected to or the inorganic carrier that adsorbs phenylhydrazine or other hydrazine derivate comprises: contain the silica gel or the aluminium oxide of phenylhydrazine, the silica gel that contains dichloro phenyl hydrazine or aluminium oxide, the silica gel that contains the chloro phenylhydrazine or aluminium oxide, the silica gel that contains nitrophenyl hydrazine or aluminium oxide or contain the silica gel or the aluminium oxide of dinitrophenylhydrazine;
6. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 1, it is characterized in that the described reagent of removing carbohydrate and fibrous matter comprises: the potpourri of one or both arbitrary proportions in the calcium salt of sulfonated phenylethylene-divinylbenzene copolymer, the lead salt of sulfonated phenylethylene-divinylbenzene copolymer.
7. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 1, it is characterized in that the described reagent of removing carbohydrate and fibrous matter comprises: the agarose that acid polyethylene fat carrier that the styrene-divinylbenzene copolymer carrier that boric acid base group is modified, boric acid base group are modified or boric acid base group are modified.
8. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 1, it is characterized in that the described reagent that removes degrease and other lipophilic substance comprises: the surface is connected to the potpourri of a kind of, two or more arbitrary proportion in the superpolymer solid phase carrier that the silica-gel carrier of lipophilic group, alumina support, lipophilicity superpolymer or lipophilicity that the surface is connected to lipophilic group replace; And the described reagent that removes degrease and other lipophilic substance can not dissolve in water, and particle size range is at 5 microns to 5 millimeters; Specific surface area is 20～800 square meter/grams.
9. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 8 is characterized in that: the silica-gel carrier that described surface is connected to lipophilic group is the silica gel of silica gel, octyl bonding or coating of octadecyl bonding or coating or the silica gel of hexyl bonding or coating; The alumina support that described surface is connected to lipophilic group be the aluminium oxide of aluminium oxide, octyl bonding or coating of octadecyl bonding or coating or hexane base key and or the aluminium oxide of coating; Described lipophilicity superpolymer solid phase carrier is the styrene-divinylbenzene copolymer resin; The superpolymer solid phase carrier that described lipophilicity replaces is styrene-divinylbenzene copolymer resin, the styrene-divinylbenzene copolymer resin of carboxyl substituted or the styrene-divinylbenzene copolymer resin of amino replacement that acid amides replaces.
10. be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) in pretreatment sample, adds protein precipitation reagent, mix;
2) in pretreatment sample, add the reagent that to remove residual protein, polypeptide or amino acid and fat and other lipophilic substance again, mix;
3) centrifugal, will finish above-mentioned all step 1)-2) sample carry out centrifuging, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
11. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 10, it is characterized in that the described reagent of removing residual protein, polypeptide or amino acid and fat and other lipophilic substance is: the potpourri that contains lipophilic sorbing material and ion exchange material; Its part by weight is between 1: 9 to 9: 1.
12. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 11, it is characterized in that described lipophilic sorbing material comprises the silica gel of octadecyl bonding or coating, the aluminium oxide of octadecyl bonding or coating, the silica gel of octyl bonding or coating, the aluminium oxide of octyl bonding or coating, the hexane base key and or the coating silica gel, the hexane base key and or the coating aluminium oxide, the styrene-divinylbenzene copolymer resin, the high polymer material that has adsorptive power for lipoid material that still possesses lipophilic styrene-divinylbenzene copolymer resin and inertia after the replacement; The particle size range of described lipophilicity sorbing material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers; Described ion exchange material comprises: the silica gel of the styrene-divinylbenzene copolymer of styrene-divinylbenzene copolymer quaternary ammonium resin, amination styrene-divinylbenzene copolymer, sulfonated phenylethylene-divinylbenzene copolymer, carboxyl substituted, benzene sulfonic acid class bonding, contain carboxyl bonded silica gel, contain the bonded silica gel of quaternary ammonium salt or contain amino bonded silica gel; The particle size range of described ion exchange material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers.
13. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 10, it is characterized in that the described reagent of removing residual protein, polypeptide or amino acid and fat and other lipophilic substance is: the sulfonic acid degree of substitution is that the styrene-divinylbenzene copolymer sulfonate resin or the quaternary ammonium ion degree of substitution of 0.3～3.5 mM/gram is the styrene-divinylbenzene copolymer quaternary ammonium salt of 0.3～3.5 mM/gram.
14. be used for detecting the sample pretreating method of dairy produce objectionable impurities, comprise the steps:
1) in pretreatment sample, adds the reagent that can remove deproteinize, carbohydrate, fiber and fat and other lipophilic substance, mix;
2) centrifugal, carry out centrifuging with finishing above-mentioned sample in steps, get supernatant and be used for further analyzing and testing or after concentrating, further carry out analyzing and testing.
15. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 14, it is characterized in that the reagent that described energy removes deproteinize, carbohydrate, fiber and fat and other lipophilic substance is lipophilicity sorbing material, ion exchange material and the potpourri that contains the carrier of phenylhydrazine class material; And in this three classes mixtures of material, the weight percent of each class material is not less than 10%, is not higher than 80%.
16. the sample pretreating method that is used for detecting the dairy produce objectionable impurities according to claim 15 is characterized in that:
Described lipophilicity sorbing material comprises: the silica gel of octadecyl bonding or coating, the aluminium oxide of octadecyl bonding or coating, the silica gel of octyl bonding or coating, the aluminium oxide of octyl bonding or coating, the hexane base key and or the coating silica gel, the hexane base key and or the coating aluminium oxide, the styrene-divinylbenzene copolymer resin, the high polymer material that has adsorptive power for lipoid material that still possesses lipophilic styrene-divinylbenzene copolymer resin and inertia after the replacement; The particle size range of described lipophilicity sorbing material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers;
Described ion exchange material comprises: the silica gel of the styrene-divinylbenzene copolymer of styrene-divinylbenzene copolymer quaternary ammonium resin, amination styrene-divinylbenzene copolymer, sulfonated phenylethylene-divinylbenzene copolymer, carboxyl substituted, benzene sulfonic acid class bonding, contain carboxyl bonded silica gel, contain the bonded silica gel of quaternary ammonium salt or contain amino bonded silica gel; The particle size range of described ion exchange material is 5 microns～5 millimeters, and specific surface area is 10～800 square meter/grams, and average pore size is 2～100 nanometers;
The described carrier that contains phenylhydrazine class material comprises: phenylhydrazine, substituted phenylhydrazines, hole surface replace or the polymeric resin, the hole surface that are adsorbed with phenylhydrazine or other hydrazine derivate is connected to or adsorbs the potpourri of a kind of, two or more arbitrary proportion in inorganic carrier, borax or the immobilized borax of phenylhydrazine or other hydrazine derivate; Described substituted phenylhydrazines comprises: 2,4 dinitrophenylhydrazines, 2,4 dichloro phenyl hydrazines, benzene sulfonyl hydrazide, to Methyl benzenesulfonyl hydrazine, benzoyl group hydrazine or to the methylbenzene acid hydrazide; Described hole surface replaces or the polymeric resin that is adsorbed with phenylhydrazine or other hydrazine derivate comprises: the styrene-divinylbenzene copolymer carrier that contains phenylhydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains nitrophenyl hydrazine functional group, the styrene-divinylbenzene copolymer carrier that contains benzene sulfonyl hydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene sulfohydrazide, the styrene-divinylbenzene copolymer carrier that contains phenylhydrazide, the styrene-divinylbenzene copolymer carrier that contains the nitrobenzene hydrazides; Described hole surface is connected to or the inorganic carrier that adsorbs phenylhydrazine or other hydrazine derivate comprises: contain the silica gel or the aluminium oxide of phenylhydrazine, the silica gel that contains dichloro phenyl hydrazine or aluminium oxide, the silica gel that contains the chloro phenylhydrazine or aluminium oxide, the silica gel that contains nitrophenyl hydrazine or aluminium oxide or contain the silica gel or the aluminium oxide of dinitrophenylhydrazine.
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| CN103645266A (en) * | 2013-12-27 | 2014-03-19 | 光明乳业股份有限公司 | Detection method of dissociated chiral amino acid in milk base material |
| CN105189774A (en) * | 2013-03-13 | 2015-12-23 | 贝克顿·迪金森公司 | A method for improving analysis of microorganisms in complex matrices |
| CN105518156A (en) * | 2013-09-05 | 2016-04-20 | 日本电气方案创新株式会社 | Method for producing sample and method for analyzing target |
| US9645057B2 (en) | 2012-04-05 | 2017-05-09 | Becton, Dickiinson and Company | Method for improving analysis of microorganisms in complex matrices |
| CN114410620A (en) * | 2021-12-20 | 2022-04-29 | 深圳市易瑞生物技术股份有限公司 | Nucleic acid extraction pretreatment of milk |
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| CN100507558C (en) * | 2007-03-02 | 2009-07-01 | 内蒙古伊利实业集团股份有限公司 | Method for checking organic phosphorus pesticide residue in animal milk |
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| US9645057B2 (en) | 2012-04-05 | 2017-05-09 | Becton, Dickiinson and Company | Method for improving analysis of microorganisms in complex matrices |
| CN105189774A (en) * | 2013-03-13 | 2015-12-23 | 贝克顿·迪金森公司 | A method for improving analysis of microorganisms in complex matrices |
| EP2971050A4 (en) * | 2013-03-13 | 2016-11-02 | Becton Dickinson Co | A method for improving analysis of microorganisms in complex matrices |
| CN105518156A (en) * | 2013-09-05 | 2016-04-20 | 日本电气方案创新株式会社 | Method for producing sample and method for analyzing target |
| CN103645266A (en) * | 2013-12-27 | 2014-03-19 | 光明乳业股份有限公司 | Detection method of dissociated chiral amino acid in milk base material |
| CN103645266B (en) * | 2013-12-27 | 2015-08-05 | 光明乳业股份有限公司 | The detection method of free state chiral amino acid in breast base-material |
| CN114410620A (en) * | 2021-12-20 | 2022-04-29 | 深圳市易瑞生物技术股份有限公司 | Nucleic acid extraction pretreatment of milk |
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