CN105268415A - Solid phase extraction packing and application of solid phase extraction packing in measuring sulfonamide residues in food - Google Patents
Solid phase extraction packing and application of solid phase extraction packing in measuring sulfonamide residues in food Download PDFInfo
- Publication number
- CN105268415A CN105268415A CN201510647489.6A CN201510647489A CN105268415A CN 105268415 A CN105268415 A CN 105268415A CN 201510647489 A CN201510647489 A CN 201510647489A CN 105268415 A CN105268415 A CN 105268415A
- Authority
- CN
- China
- Prior art keywords
- ferrocene
- solid phase
- phase extraction
- silica gel
- anhydrous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a solid phase extraction packing and its application in measuring sulfonamide residues in food. Firstly, porous silica gel and a hydrochloric acid solution react, and activated silica gel is obtained after processing; secondly, activated silica gel reacts with aminopropyl triethoxysilane and anhydrous toluene, and aminopropyl triethoxysilane bonded silica gel is obtained after processing; thirdly, aminopropyl triethoxysilane bonded silica gel reacts with ferrocene, anhydrous benzene and a methanol solution of mercury acetate, and an ethanol solution of lithium chloride is added to react, and mono-substituted mercuric chloride ferrocene is obtained after processing; fourthly, mono-substituted mercuric chloride ferrocene reacts with 4,6-dichloropyrimidine, sodium iodide and tetra(triphenylphosphine)palladium, and 4-chloro-6-pyrimidinylferrocene is obtained after processing; and finally, the product reacts with aminopropyl silica gel, anhydrous potassium carbonate and diisopropylethyeneamine, and a product of the invention is obtained after processing. The product of the invention is a novel functionalized ferrocene bonded silica gel solid phase extraction packing. The packing is used for carrying out sample pretreatment on a matrix and simultaneously detect sulfonamide drug residues in food by the combination of high performance liquid chromatography.
Description
one, technical field:
The invention belongs to technical field of chemical detection, be specifically related to a kind of novel solid phase extraction filler (4-chloro-6-pyrimidine radicals ferrocene bonded silica gel) and measuring the application that in food, sulfanilamide (SN) is residual.
two, background technology:
Along with the development of separation science, high performance liquid chromatography is with its high sensitivity, high selectivity, Gao Zhuxiao, the feature such as reproducible and easy and simple to handle, in oil, chemical industry, environmental protection, food, medicine, method inspection, clinical and Analysis of Natural Products, play very important role, become an important technology of separate complex sample.Except detection means, the key factor of another impact analysis testing result accuracy and reliability is exactly sample pre-treatments, the sample substrate especially low for content, composition is complicated, as: in food, the content of fat is high, interfering material is many; Complicated component in environment water, residual concentration is low, circumstance complication is changeable; The quality of sample treatment etc. all directly affect the result detected.When using high performance liquid chromatography, often adopting n-hexane degreasing to carry out purifying to sample, but because purifying step is too simple, making its clean-up effect when analyzing animal derived food complex matrices such as (particularly) internal organ not satisfactory.
SPE is the physical extraction process between a liquid-solid two-phase.In solid phase extraction procedure, because solid-phase adsorbent is larger than object solvability in a solvent to the active force of object, when sample solution is by solid-phase extraction column, object is at solid-phase adsorbent surface enrichment, and other composition goes down along solution stream, such adsorbed target thing and do not adsorb other composition, makes that the purity of object is higher, concentration is larger, is easy to analyze.
In the last few years, food security often can cause people's concern especially.The residual problem of medicine in animal derived food especially people pay close attention to focus.At present, the general multiplex solid phase extraction of pre-treatment of sulfonamides matter sample, the solid phase extraction filler adopted in prior art carries out pre-treatment to sample, and its effect is not satisfactory.
three, summary of the invention:
The technical problem to be solved in the present invention is: remain according to sulfanilamide (SN) in food the weak point that in existing detection technique, sample pre-treatments exists, and the invention provides a kind of solid phase extraction filler (4-chloro-6-pyrimidine radicals ferrocene bonded silica gel) and is measuring the application that in food, sulfanilamide (SN) is residual.Namely the present invention have studied a kind of novel functionalization ferrocene bonded silica gel solid phase extraction filler, utilizes this solid phase extraction filler to carry out sample pre-treatments to matrix, detects sulfa drug residue in food in conjunction with high performance liquid chromatography simultaneously.GC-MS of the present invention, in animal derived food sulfa drug residue detection in application, substantially increase the detection sensitivity that sulfonamides is residual, simplify experimental procedures, for remarkable effect is played in the detection of sulfa drug residue.
In order to solve the problem, the technical scheme that the present invention takes is:
The invention provides a kind of novel solid phase extraction filler, described solid phase extraction filler is prepared from by the following method:
1) activation of silica gel: take in Bio-sil immersion hydrochloric acid solution and soak, soak time is 22 ~ 26h, agitating heating is carried out after immersion, be heated to back flow reaction 20 ~ 24h under 90 ~ 100 DEG C of conditions, reaction removing metal ion, gained reactant liquor filters, after filtering, cyclic washing is to neutral, products therefrom carries out drying and dehydrating, obtains activated silica gel after drying, is stored in drier for subsequent use;
2) preparation of aminopropyl triethoxysilane bonded silica gel: take aminopropyl triethoxysilane in reactor, and add dry toluene and stir, under agitation add step 1) gained activated silica gel, back flow reaction 20 ~ 24h at being heated to 110 ~ 120 DEG C under nitrogen protection, reaction terminates rear products therefrom and carries out suction filtration, then toluene, acetone and redistilled water is adopted to wash successively, after washing, products therefrom carries out vacuum drying, obtains aminopropyl triethoxysilane bonded silica gel;
The volume ratio that both described aminopropyl triethoxysilane and dry toluene add is 1:9 ~ 10, and the ratio of both described activated silica gel and aminopropyl triethoxysilane addition is 1g:1.3 ~ 1.6mL;
3) preparation of monosubstituted chlorination mercuri ferrocene: first take ferrocene and anhydrous benzene is placed in reactor, the ratio of both described ferrocene and anhydrous benzene addition is 1g:4 ~ 5mL, then mercuric acetate methanol solution is dropwise added, between described mercuric acetate methanol solution and ferrocene, the ratio of addition is 6 ~ 7mL:1g, after adding under nitrogen protection, be warming up to 65 ~ 80 DEG C reaction 10 ~ 12h, obtain reactant liquor after reaction;
Anhydrous Lithium chloride is dissolved in ethanol water, lithium chloride ethanolic solution is obtained after abundant dissolving, lithium chloride ethanolic solution is dropwise added in gained reactant liquor, between lithium chloride ethanolic solution and reactant liquor, the volume ratio of addition is 1:6.5 ~ 7, stir 2 ~ 3h at ambient temperature, then back flow reaction 1 ~ 1.5h at being heated to 65 ~ 80 DEG C, carries out after reaction cooling, filtering; Gained solid is placed in apparatus,Soxhlet's, first extracts unreacted ferrocene with benzinum, then extracts product monosubstituted chlorination mercuri ferrocene with carrene, steams solvent and obtain yellow solid, be monosubstituted chlorination mercuri ferrocene;
4) preparation of 4-chloro-6-pyrimidine radicals ferrocene: the ratio being first 1:1.1 ~ 1.2:2:0.05 according to mol ratio takes gained monosubstituted chlorination mercuri ferrocene, 4, take four kinds of raw materials are joined in the mixed liquor of anhydrous tetrahydro furan and anhydrous propanone by 6-dichloro pyrimidine, sodium iodide and four (triphenyl phosphorus) palladium; Described monosubstituted chlorination mercuri ferrocene, 4, the ratio of 6-dichloro pyrimidine, sodium iodide and four (triphenyl phosphorus) palladium four kinds of raw materials and mixed liquor addition is therebetween 1mol:1.1 ~ 1.2mol:2mol:0.05mol:30 ~ 35mL, add rear oil bath and be heated to 70 ~ 80 DEG C, react 6 ~ 7h under nitrogen protection;
Reaction terminates rear water cooling, and organic layer is separated, and water layer dichloromethane extraction, then merges organic layer, and gained organic layer adopts anhydrous magnesium sulfate drying, filtration, revolves and steam except desolventizing after filtration; Then cross silica gel column chromatography and collect Part II product, obtain 4-chloro-6-pyrimidine radicals ferrocene;
5) synthesis of 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler: take Aminopropyl silica gel, 4-chloro-6-pyrimidine radicals ferrocene, Anhydrous potassium carbonate and diisopropyl ethyl amine, addition ratio between four kinds of raw materials is 2 ~ 2.5g:1g:1.5g:12 ~ 13mL, then join in oxolane, ratio 2 ~ 2.5g:1.0g:1.5g:12 ~ the 13mL:100mL of four kinds of additions between raw material and oxolane, is heated to 65 ~ 70 DEG C of back flow reaction 48 ~ 50 hours under a nitrogen atmosphere; Reaction terminates to filter gained reactant afterwards, and products therefrom respectively washes three times with carrene, oxolane, acetone, water and acetone successively, and products obtained therefrom carries out vacuum drying, obtains product solid phase extraction filler after drying.
According to above-mentioned novel solid phase extraction filler, Bio-sil described in step 1) is provided by Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences, and the particle diameter of Bio-sil is 40 ~ 63 μm, and aperture is 60, and specific area is 500m
2/ g.
According to above-mentioned novel solid phase extraction filler, the ratio of both Bio-sil described in step 1) and hydrochloric acid solution addition is 1g:25 ~ 30mL; Described hydrochloric acid solution is by HCl and H
2o is that 1:3 is formulated according to volume ratio.
According to above-mentioned novel solid phase extraction filler, when reactant liquor filters described in step 1), adopt G5 sand core funnel; Redistilled water is adopted during described washing; Described drying and dehydrating is that dry 10h sloughs surface water at 160 DEG C.
According to above-mentioned novel solid phase extraction filler, step 2) in suction filtration time adopt G5 sand core funnel; Described vacuum drying be vacuum be 0.1MPa, dry 24h at 80 DEG C.
According to above-mentioned novel solid phase extraction filler, the methanol solution of mercuric acetate described in step 3) is formed according to the proportions of 1g:5 ~ 6mL by mercuric acetate and absolute methanol.
According to above-mentioned novel solid phase extraction filler, described in step 3), anhydrous Lithium chloride is dissolved in ethanol water, and the ratio of both its anhydrous Lithium chloride and ethanol water addition is 1g:6 ~ 8mL; Described ethanol water be by ethanol and water formulated according to the volume ratio of 1:1.
According to above-mentioned novel solid phase extraction filler, the mixed liquor of anhydrous tetrahydro furan described in step 4) and anhydrous propanone, during the two mixing, the mixed volume ratio of anhydrous tetrahydro furan and anhydrous propanone is 1.5 ~ 1.6:1; Described when crossing silica gel column chromatography, the eluant, eluent of employing is carrene and the benzinum mixed liquor according to volume ratio 2:1 mixing gained.
According to above-mentioned novel solid phase extraction filler, when gained reactant being filtered described in step 5), adopt G5 sand core funnel; Described vacuum drying be vacuum be 0.1MPa, dry 12h at 65 DEG C.
The chemical equation of the present invention's novel solid phase extraction filler 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel is as follows:
The structural formula of the solid phase extraction filler 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel stationary phase that the present invention prepares is:
In addition, the invention provides a kind of novel solid phase extraction filler and measure the application that in food, sulfanilamide (SN) is residual.
positive beneficial effect of the present invention:
The solid phase extraction filler 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel utilizing technical solution of the present invention to prepare has the following advantages:
1, the solid phase extraction column utilizing the solid phase extraction filler prepared by the present invention to dress up has the advantages such as powerful adsorption function, stronger specificity, preparation cost that the rate of recovery is high and lower.
2, the solid phase extraction column using solid phase extraction filler of the present invention to dress up carries out pre-treatment to chemical example, can realize efficient separating resulting, and elution reagent is pure water, meets the theory of environmental protection, meet the requirement of national environmental protection.
3, solid phase extraction filler preparation method of the present invention is simple, is widely used, favorable reproducibility, has good application prospect.
4, present invention achieves the Sync enrichment to sulfanilamide (SN) component, a pillar can complete purification object, break away from the length consuming time caused that different binding mode many pillars are used in conjunction, target components lost large defect, the target also achieve wash-out simultaneously, simultaneously detecting.
four, accompanying drawing illustrates:
Fig. 1 is the infrared spectrogram of intermediate product activated silica gel in embodiment 1.
Fig. 2 is the infrared spectrogram of intermediate product aminopropyl triethoxysilane bonded silica gel in embodiment 1.
Fig. 3 is the infrared spectrogram of products obtained therefrom 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel in embodiment 1.
High-efficient liquid phase chromatogram technique analysis schematic flow sheet in Fig. 4 application example;
The lower three kinds of sulfanilamide (SN) separate colors spectrograms of high-efficient liquid phase chromatogram condition in Fig. 5 application example;
In Fig. 5: display sulfamethazine (SM2), sulfamethoxazole (SMZ), sulphadimethoxine (SDM) achieve baseline separation within a short period of time, separating degree is good, peak shape is symmetrical, for the detection of sulfanilamide (SN) is provided convenience.
In Fig. 6 application example, SPE material usage optimizes schematic diagram;
In Fig. 7 application example, eluant, eluent kind optimizes schematic diagram;
In Fig. 8 application example, eluant, eluent volumetric usage optimizes schematic diagram;
Loading speed-optimization schematic diagram in Fig. 9 application example;
In Figure 10 application example, pork blank is crossed solid phase extraction column purification and is contrasted figure with not purifying;
In Figure 10: A is that the pork not through purification is blank; B is blank through the pork of purification.
Figure 11 solid phase extraction column of the present invention contrasts with existing solid phase extraction column clean-up effect schemes;
In Figure 11, A: solid phase extraction column purification enrichment design sketch of the present invention; B:NH2 column purification concentration effect figure; C:MCX column purification enrichment figure.
The analysis collection of illustrative plates that in Figure 12 application example pork, sulfa drug residue detects;
In Figure 12: tested by mark-on, determining sulfa drug residue contained in pork is sulfamethazine (SM2), sulfamethoxazole (SMZ), sulphadimethoxine (SDM); By the impurity peaks after SPE column purification of the present invention, its peak height step-down, is more conducive to the quantitative analysis of target components in detection.
In Figure 12: A is mark-on 10ppm, B be mark-on 5ppm, C be mark-on 0.5ppm, D is actual pork sample; 1 is sulfadimidine; 2 is sulfamethoxazole; 3 is sulphadimethoxine.
five, detailed description of the invention:
Set forth the present invention further below in conjunction with embodiment, but do not limit content of the present invention.
Embodiment 1:
Solid phase extraction filler 4-of the present invention chloro-6-pyrimidine radicals ferrocene bonded silica gel, be prepared from by the following method, detailed step is as follows:
1) activation of silica gel: (particle diameter of Bio-sil is 40 ~ 63 μm, aperture 60, specific area 500m to take 20g Bio-sil
2/ g, provides production by Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences) immerse in 500mL hydrochloric acid solution that (hydrochloric acid solution is according to HCl:H
2the volume ratio 1:3 of O is formulated) in soak 24h, then heat under magnetic agitation, be heated to back flow reaction 24h under 95 DEG C of conditions, removing metal ion; Gained reactant liquor adopts G5 sand core funnel to filter, after filtering, products therefrom redistilled water is washed till neutrality repeatedly, then surface water is sloughed to products therefrom dry 10h at 160 DEG C, obtain activated silica gel (its infrared spectrogram refers to accompanying drawing 1), be stored in drier for subsequent use;
2) preparation of aminopropyl triethoxysilane bonded silica gel: get 12mL aminopropyl triethoxysilane in 250mL there-necked flask, adds the new dry toluene 115mL steamed, adds 9g activated silica gel under stirring; Be heated to 115 DEG C of back flow reaction 24h under nitrogen protection; After reaction terminates, with G5 sand core funnel suction filtration, products therefrom respectively washs three times with toluene, acetone and redistilled water successively, after washing, products therefrom carries out vacuum drying (vacuum is 0.1MPa, baking temperature is 80 DEG C, drying time is 24h), obtain aminopropyl triethoxysilane bonded silica gel (its infrared spectrogram refers to accompanying drawing 2);
3) preparation of monosubstituted chlorination mercuri ferrocene: take 3.12gHg (CH
3cOO)
2be dissolved in 17mL absolute methanol, then dropwise join in the anhydrous benzene of 2.5g ferrocene and 10mL under agitation, be warming up to 70 DEG C of reaction 10h under nitrogen protection; Then the anhydrous Lithium chloride of 0.6g is dissolved in (ethanol water is formulated according to the volume ratio of 1:1 by second alcohol and water) in 4mL ethanol water, gained lithium chloride ethanolic solution dropwise adds in above-mentioned reaction system, at room temperature stir 2h when producing orange coloured suspension thing, be then heated to 80 DEG C of back flow reaction 1h; Reaction cools, gained reactant suction filtration after cooling, collect the solid of separating out, by this solid transfer to apparatus,Soxhlet's, first extract unreacted ferrocene with benzinum, then extract mono-substituted chlorination mercuri ferrocene with carrene, steam solvent and obtain yellow solid, be monosubstituted chlorination mercuri ferrocene;
4) preparation of 4-chloro-6-pyrimidine radicals ferrocene: take 1mmol monosubstituted chlorination mercuri ferrocene, 1.1mmol4,6-dichloro pyrimidine, 2mmol sodium iodide and 0.05mmol tetra-(triphenyl phosphorus) palladium joins in 18mL anhydrous tetrahydro furan and 12mL anhydrous propanone, be placed in oil bath and be heated to 80 DEG C, react 6h under nitrogen protection; Reaction terminates rear water cooling, and organic layer is sufficiently separated by, and water layer dichloromethane extraction, then merges organic layer, and which floor gained has with anhydrous magnesium sulfate drying, filtration, revolves and steams except desolventizing; Products therefrom is crossed silica gel column chromatography and is separated (eluant, eluent of employing is the mixed liquor that carrene and benzinum are prepared according to volume ratio 2:1), collects Part II product and is 4-chloro-6-pyrimidine radicals ferrocene;
5) synthesis of 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler: take 2.0g Aminopropyl silica gel, 1.0g4-chloro-6-pyrimidine radicals ferrocene, 1.5g Anhydrous potassium carbonate and 12mL diisopropyl ethyl amine (acid binding agent) join in 100mL oxolane, be heated to 65 DEG C of back flow reaction 48 hours under a nitrogen atmosphere, reaction terminates rear G5 sand core funnel and filters, products therefrom uses carrene successively, oxolane, acetone, water, acetone respectively washes three times, after washing, products obtained therefrom is at vacuum 0.1MPa, dry 12h at 65 DEG C, obtain product 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler (infrared spectrum map analysis refers to accompanying drawing 3).
By the elementary analysis of the aminopropyl triethoxysilane bonded silica gel shown in accompanying drawing 2,3 and the SPE of 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel, refer to table 1.
Can draw from table 1 and accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3 result: 4-chloro-6-pyrimidine radicals ferrocene is successfully bonded to Silica Surface, calculating bonded amount according to carbometer is 0.30mmolg
-1.
Embodiment 2:
Solid phase extraction filler 4-of the present invention chloro-6-pyrimidine radicals ferrocene bonded silica gel, be prepared from by the following method, detailed step is as follows:
1) activation of silica gel: (particle diameter of Bio-sil is 40 ~ 63 μm, aperture 60, specific area 500m to take 20g Bio-sil
2/ g, provides production by Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences) immerse in 500mL hydrochloric acid solution that (hydrochloric acid solution is according to HCl:H
2the volume ratio 1:3 of O is formulated) in soak 22h, then heat under magnetic agitation, be heated to back flow reaction 20h under 100 DEG C of conditions, removing metal ion; Gained reactant liquor adopts G5 sand core funnel to filter, and after filtering, products therefrom redistilled water is washed till neutrality repeatedly, then sloughs surface water to products therefrom dry 10h at 160 DEG C, obtains activated silica gel, be stored in drier for subsequent use;
2) preparation of aminopropyl triethoxysilane bonded silica gel: get 10mL aminopropyl triethoxysilane in 250mL there-necked flask, adds the new dry toluene 95mL steamed, adds 6g activated silica gel under stirring; Be heated to 120 DEG C of back flow reaction 20h under nitrogen protection; After reaction terminates, with G5 sand core funnel suction filtration, products therefrom respectively washs three times with toluene, acetone and redistilled water successively, after washing, products therefrom carries out vacuum drying (vacuum is 0.1MPa, baking temperature is 80 DEG C, drying time is 24h), obtain aminopropyl triethoxysilane bonded silica gel;
3) preparation of monosubstituted chlorination mercuri ferrocene: take 3.12gHg (CH
3cOO)
2be dissolved in 15.6mL absolute methanol, then dropwise join in the anhydrous benzene of 2.5g ferrocene and 12.5mL under agitation, be warming up to 68 DEG C of reaction 11h under nitrogen protection; Then the anhydrous Lithium chloride of 0.6g is dissolved in (ethanol water is formulated according to the volume ratio of 1:1 by second alcohol and water) in 4.5mL ethanol water, gained lithium chloride ethanolic solution dropwise adds in above-mentioned reaction system, at room temperature stir 2.5h when producing orange coloured suspension thing, be then heated to 75 DEG C of back flow reaction 1.2h; Reaction cools, gained reactant suction filtration after cooling, collect the solid of separating out, by this solid transfer to apparatus,Soxhlet's, first extract unreacted ferrocene with benzinum, then extract mono-substituted chlorination mercuri ferrocene with carrene, steam solvent and obtain yellow solid, be monosubstituted chlorination mercuri ferrocene;
4) preparation of 4-chloro-6-pyrimidine radicals ferrocene: take 1mmol monosubstituted chlorination mercuri ferrocene, 1.15mmol4,6-dichloro pyrimidine, 2mmol sodium iodide and 0.05mmol tetra-(triphenyl phosphorus) palladium joins in 18mL anhydrous tetrahydro furan and 14mL anhydrous propanone, be placed in oil bath and be heated to 75 DEG C, react 6.5h under nitrogen protection; Reaction terminates rear water cooling, and organic layer is sufficiently separated by, and water layer dichloromethane extraction, then merges organic layer, and which floor gained has with anhydrous magnesium sulfate drying, filtration, revolves and steams except desolventizing; Products therefrom is crossed silica gel column chromatography and is separated (eluant, eluent of employing is the mixed liquor that carrene and benzinum are prepared according to volume ratio 2:1), collects Part II product and is 4-chloro-6-pyrimidine radicals ferrocene;
5) synthesis of 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler: take 2.20g Aminopropyl silica gel, 1.0g4-chloro-6-pyrimidine radicals ferrocene, 1.5g Anhydrous potassium carbonate and 12.5mL diisopropyl ethyl amine (acid binding agent) join in 100mL oxolane, be heated to 70 DEG C of back flow reaction 49 hours under a nitrogen atmosphere, reaction terminates rear G5 sand core funnel and filters, products therefrom uses carrene successively, oxolane, acetone, water, acetone respectively washes three times, after washing, products obtained therefrom is at vacuum 0.1MPa, dry 12h at 65 DEG C, obtain product 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler.
Embodiment 3:
Solid phase extraction filler 4-of the present invention chloro-6-pyrimidine radicals ferrocene bonded silica gel, be prepared from by the following method, detailed step is as follows:
1) activation of silica gel: (particle diameter of Bio-sil is 40 ~ 63 μm, aperture 60, specific area 500m to take 20g Bio-sil
2/ g, provides production by Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences) immerse in 500mL hydrochloric acid solution that (hydrochloric acid solution is according to HCl:H
2the volume ratio 1:3 of O is formulated) in soak 26h, then heat under magnetic agitation, be heated to back flow reaction 22h under 90 DEG C of conditions, removing metal ion; Gained reactant liquor adopts G5 sand core funnel to filter, and after filtering, products therefrom redistilled water is washed till neutrality repeatedly, then sloughs surface water to products therefrom dry 10h at 160 DEG C, obtains activated silica gel, be stored in drier for subsequent use;
2) preparation of aminopropyl triethoxysilane bonded silica gel: get 10mL aminopropyl triethoxysilane in 250mL there-necked flask, adds the new dry toluene 90mL steamed, adds 7g activated silica gel under stirring; Be heated to 110 DEG C of back flow reaction 22h under nitrogen protection; After reaction terminates, with G5 sand core funnel suction filtration, products therefrom respectively washs three times with toluene, acetone and redistilled water successively, after washing, products therefrom carries out vacuum drying (vacuum is 0.1MPa, baking temperature is 80 DEG C, drying time is 24h), obtain aminopropyl triethoxysilane bonded silica gel;
3) preparation of monosubstituted chlorination mercuri ferrocene: take 3.12gHg (CH
3cOO)
2be dissolved in 16mL absolute methanol, then dropwise join in the anhydrous benzene of 2.5g ferrocene and 11mL under agitation, be warming up to 65 DEG C of reaction 12h under nitrogen protection; Then the anhydrous Lithium chloride of 0.6g is dissolved in (ethanol water is formulated according to the volume ratio of 1:1 by second alcohol and water) in 4.8mL ethanol water, gained lithium chloride ethanolic solution dropwise adds in above-mentioned reaction system, at room temperature stir 3h when producing orange coloured suspension thing, be then heated to 65 DEG C of back flow reaction 1.5h; Reaction cools, gained reactant suction filtration after cooling, collect the solid of separating out, by this solid transfer to apparatus,Soxhlet's, first extract unreacted ferrocene with benzinum, then extract mono-substituted chlorination mercuri ferrocene with carrene, steam solvent and obtain yellow solid, be monosubstituted chlorination mercuri ferrocene;
4) preparation of 4-chloro-6-pyrimidine radicals ferrocene: take 1mmol monosubstituted chlorination mercuri ferrocene, 1.2mmol4,6-dichloro pyrimidine, 2mmol sodium iodide and 0.05mmol tetra-(triphenyl phosphorus) palladium joins in 18mL anhydrous tetrahydro furan and 13mL anhydrous propanone, be placed in oil bath and be heated to 70 DEG C, react 7.0h under nitrogen protection; Reaction terminates rear water cooling, and organic layer is sufficiently separated by, and water layer dichloromethane extraction, then merges organic layer, and which floor gained has with anhydrous magnesium sulfate drying, filtration, revolves and steams except desolventizing; Products therefrom is crossed silica gel column chromatography and is separated (eluant, eluent of employing is the mixed liquor that carrene and benzinum are prepared according to volume ratio 2:1), collects Part II product and is 4-chloro-6-pyrimidine radicals ferrocene;
5) synthesis of 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler: take 2.50g Aminopropyl silica gel, 1.0g4-chloro-6-pyrimidine radicals ferrocene, 1.5g Anhydrous potassium carbonate and 13mL diisopropyl ethyl amine (acid binding agent) join in 100mL oxolane, be heated to 65 DEG C of back flow reaction 50 hours under a nitrogen atmosphere, reaction terminates rear G5 sand core funnel and filters, products therefrom uses carrene successively, oxolane, acetone, water, acetone respectively washes three times, after washing, products obtained therefrom is at vacuum 0.1MPa, dry 12h at 65 DEG C, obtain product 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler.
solid phase extraction filler of the present invention is measuring the application example that in food, sulfanilamide (SN) is residual:
Solid phase extraction filler of the present invention is detecting the application of sulfanilamide (SN) content in pork:
1), the filling of solid phase extraction column:
Commercially available polypropylene void column pipe (specification is that 100mg/3cc, Di Ma Science and Technology Ltd. produces) is first used water and washed with methanol; Bottom column jecket, insert polypropylene sieve plate, accurately take 100mg(and be accurate to 0.001g) the solid phase extraction filler 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel prepared of the present invention; Appropriateness jolt ramming, shake flat after, insert polypropylene sieve plate in filler upper end, appropriate compacting, obtain the solid phase extraction column filled, for subsequent use;
2) solid phase extraction procedure and liquid-phase condition:
The solid phase extraction column filled is hanged disposed upright on rack for test tube, with the activation of 4mL acetonitrile, 4mL water balance, then adds the sample of 1mL process with pipette; After loading, with the drip washing of 3mL acetonitrile, 6mL ultra-pure water wash-out; Be collected into by eluent in centrifuge tube, draw 1mL solution with syringe, cross 0.22mm filter membrane, gained filtrate is analyzed for HPLC, and analysis process schematic diagram refers to accompanying drawing 4.
High-efficient liquid phase chromatogram condition: C18 column liquid chromatographic post (VPODS, 5 μm, 4.6mm × 150mm), mobile phase is methyl alcohol-0.1% glacial acetic acid aqueous solution (30:70, v/v), and determined wavelength is 270nm, flow velocity 1mL/min, and column temperature is 30 DEG C; Under this liquid-phase condition, the separate colors spectrogram of three kinds of sulfanilamide (SN) refers to accompanying drawing 5.
3) optimization of SPE condition:
The key factor affecting the SPE rate of recovery comprises: SPE material usage, eluant, eluent kind, eluant, eluent volume and loading speed etc.Experiment, using the rate of recovery of three kinds of medicines as foundation, is optimized above-mentioned several influence factor respectively, obtains best SPE treatment conditions.Concrete optimizing process is as follows:
The selection of SPE material usage:
Adsorbent amount can affect SPE effect, therefore present invention discusses the rate of recovery of the lower three kinds of sulfa drugs of different adsorbent amount.4 polypropylene void column pipes are got in experiment, solid phase extraction column is made respectively with the solid phase extraction filler of the present invention that quality is 50mg, 100mg, 150mg, 200mg, loading 1mL after the activation of 4mL methyl alcohol, 4mL water balance, then uses the drip washing of 3mL acetonitrile, 4mL ultra-pure water wash-out, collects eluent; Eluent is analyzed through HPLC and is found, when solid phase extraction filler amount is 100mg, the rate of recovery of three kinds of sulfa drugs is the highest (rate of recovery situation analysis refers to accompanying drawing 6).Therefore, best SPE material usage is 100mg.
The selection of eluant, eluent kind:
Eluant, eluent kind is one of key factor affecting sample pre-treatments effect.According to the physicochemical property of three kinds of sulfa drugs, experiment employing three kinds of sulfa drugs titers are optimized eluant, eluent kind.Concrete operations are as follows: get the solid phase extraction column 5 prepared, and loading 1mL after the activation of 4mL methyl alcohol, 4mL water balance, then uses the drip washing of 3mL acetonitrile, finally use 4mL ethyl acetate, 4mL normal propyl alcohol, 4mL acetone, 4mL water and 4mL ethanol elution respectively.Then feed liquor chromatography detects, and result of study finds, except water and acetone, other reagent does not almost reclaim out sulfa drugs, and uses water the highest as the rate of recovery of three kinds of sulfa drugs during eluant, eluent.Therefore, select water as eluant, eluent (eluant, eluent is optimized schematic diagram and referred to accompanying drawing 7).
The selection of eluant, eluent volume:
Eluant, eluent volume is the another factor affecting the SPE rate of recovery.Experiment employing three kinds of sulfa drugs standard liquids, eluant, eluent volume is optimized, concrete operations are as follows: get the solid phase extraction column 5 prepared, loading 1mL after the activation of 4mL methyl alcohol, 4mL water balance, after the drip washing of 3mL acetonitrile, carry out wash-out with 2mL, 3mL, 5mL, 6mL and 8mL water respectively, collect eluent.Eluent feed liquor chromatography is detected.Result of study finds, within the scope of 1-6mL, along with the increase of eluant, eluent volume, the rate of recovery of three kinds of sulfa drugs raises gradually, after 6mL, the rate of recovery is without obvious increase, therefore selects 6mL as eluant, eluent volume (eluant, eluent volume is optimized schematic diagram and referred to accompanying drawing 8).
The selection of loading flow velocity:
Loading flow velocity also also exists obvious impact to the SPE rate of recovery.When flow velocity is excessive, the rate of recovery can be caused to reduce; And flow velocity too low time, analysis efficiency can be caused to reduce, expend larger labour.In order to obtain the best rate of recovery and minimum manpower financial capacity input, the present invention is also optimized SPE loading flow velocity.Adopt the flow velocity of 90s/mL, 60s/mL, 30s/mL, 20s/mL to carry out loading respectively, interpretation of result as shown in Figure 9.In the scope of 20s/mL ~ 30s/mL, the rate of recovery of three kinds of sulfa drugs all increases, and in the scope of 60s/mL ~ 90s/mL, the rate of recovery of three kinds of sulfa drugs obviously declines.Consider the residual rate of recovery of medicine and the double influence of operating time, final selected 30s/mL is as best loading flow velocity.
In sum, SPE condition is: product functionalization ferrocene bonded silica gel solid phase extraction adsorbents consumption of the present invention is 100mg, and eluant, eluent is 6mL water, and loading flow velocity is 30s/mL.
At optimum conditions the blank pork sample handled well is crossed respectively solid phase extraction column purification to contrast with only pillar; As shown in Figure 10, the pork sample impurity peaks through solid phase extraction column obviously weakens, and the analysis contributing to target components is in quantitatively.
Above-mentioned for the present invention solid phase extraction column prepared is contrasted with commercial solid phase extraction column, the pork actual sample of 6 parts of mark-on 5ppm is carried out purified treatment respectively through C18, HLB, NH2, MAX, MCX and solid-phase extraction column of the present invention, and the analysis of gained chromatograms refers to accompanying drawing 11.Can find out that the rate of recovery of solid-phase extraction column of the present invention is the highest by accompanying drawing 11, although process there is not NH2 post clean, do not affect the mensuration of subsequent target component, and solid-phase extraction column of the present invention be higher than the rate of recovery of NH2 post to SM2.Because C18, HLB and MAX post is not enriched to target components, do not show on figure.
) detection of sulfanilamide (SN) in pork:
The calibration curve of method:
0.1gSM2,0.1gSMZ, 0.1gSDM (are marked product and are dissolved in constant volume in 100mL methyl alcohol by stock solution respectively, gained solution for standby, sulfanilamide (SN) mark product are from bureau of animal husbandry of Henan Province) stepwise dilution drawing standard curve, by the standard working solution of preparation from low to high concentration enter liquid chromatograph.With the peak area of each standard substance (Y), linear regression analysis is carried out to corresponding concentration (X, ug/mL), obtain working curve regression equation and the correlation coefficient r (referring to table 2) of three kinds of sulfamido materials.The standard working solution of each material least concentration is repeated sample introduction 5 times, and calculate standard deviation, the detection limit being method with 3 times of signal to noise ratios, 10 times of signal to noise ratios are quantitative limit.Result is as shown in table 2, and in the linear dynamic range of 0.01 μ g/mL ~ 10 μ g/mL, the linearly dependent coefficient of component of mixture is better, shows that the method linear relationship is good.
In pork sulfa drug residue detection:
Pork sample, through sample pre-treatments, obtains the extract of three kinds of sulfa drug residues in matrix; Through SPE process (conventionally operating), extract, mark-on extract are purified and enrichment, obtains eluent; After finally eluent being carried out high performance liquid chromatography operation, the analysis collection of illustrative plates (referring to accompanying drawing 12) that in pork, sulfa drug residue detects can be obtained.
In pork sulfa drug residue the recovery of standard addition of detection and detection limit and quantitative line, refer to table 3.
In table 3 pork sulfa drug residue the recovery of standard addition of detection
As can be seen from Table 3, utilize solid-phase extraction column of the present invention to process, its rate of recovery is better, and relative standard deviation is less, and cost is low, has good application prospect.
The obtained solid phase extraction filler of the embodiment of the present invention 2,3 measure application example that in food, sulfanilamide (SN) is residual and embodiment 1 completely the same.
Claims (10)
1. a novel solid phase extraction filler, is characterized in that, described solid phase extraction filler is prepared from by the following method:
1) activation of silica gel: take in Bio-sil immersion hydrochloric acid solution and soak, soak time is 22 ~ 26h, agitating heating is carried out after immersion, be heated to back flow reaction 20 ~ 24h under 90 ~ 100 DEG C of conditions, reaction removing metal ion, gained reactant liquor filters, after filtering, cyclic washing is to neutral, products therefrom carries out drying and dehydrating, obtains activated silica gel after drying, is stored in drier for subsequent use;
2) preparation of aminopropyl triethoxysilane bonded silica gel: take aminopropyl triethoxysilane in reactor, and add dry toluene and stir, under agitation add step 1) gained activated silica gel, back flow reaction 20 ~ 24h at being heated to 110 ~ 120 DEG C under nitrogen protection, reaction terminates rear products therefrom and carries out suction filtration, then toluene, acetone and redistilled water is adopted to wash successively, after washing, products therefrom carries out vacuum drying, obtains aminopropyl triethoxysilane bonded silica gel;
The volume ratio that both described aminopropyl triethoxysilane and dry toluene add is 1:9 ~ 10, and the ratio of both described activated silica gel and aminopropyl triethoxysilane addition is 1g:1.3 ~ 1.6mL;
3) preparation of monosubstituted chlorination mercuri ferrocene: first take ferrocene and anhydrous benzene is placed in reactor, the ratio of both described ferrocene and anhydrous benzene addition is 1g:4 ~ 5mL, then mercuric acetate methanol solution is dropwise added, between described mercuric acetate methanol solution and ferrocene, the ratio of addition is 6 ~ 7mL:1g, after adding under nitrogen protection, be warming up to 65 ~ 80 DEG C reaction 10 ~ 12h, obtain reactant liquor after reaction;
Anhydrous Lithium chloride is dissolved in ethanol water, lithium chloride ethanolic solution is obtained after abundant dissolving, lithium chloride ethanolic solution is dropwise added in gained reactant liquor, between lithium chloride ethanolic solution and reactant liquor, the volume ratio of addition is 1:6.5 ~ 7, stir 2 ~ 3h at ambient temperature, then back flow reaction 1 ~ 1.5h at being heated to 65 ~ 80 DEG C, carries out after reaction cooling, filtering; Gained solid is placed in apparatus,Soxhlet's, first extracts unreacted ferrocene with benzinum, then extracts product monosubstituted chlorination mercuri ferrocene with carrene, steams solvent and obtain yellow solid, be monosubstituted chlorination mercuri ferrocene;
4) preparation of 4-chloro-6-pyrimidine radicals ferrocene: the ratio being first 1:1.1 ~ 1.2:2:0.05 according to mol ratio takes gained monosubstituted chlorination mercuri ferrocene, 4, take four kinds of raw materials are joined in the mixed liquor of anhydrous tetrahydro furan and anhydrous propanone by 6-dichloro pyrimidine, sodium iodide and four (triphenyl phosphorus) palladium; Described monosubstituted chlorination mercuri ferrocene, 4, the ratio of 6-dichloro pyrimidine, sodium iodide and four (triphenyl phosphorus) palladium four kinds of raw materials and mixed liquor addition is therebetween 1mol:1.1 ~ 1.2mol:2mol:0.05mol:30 ~ 35mL, add rear oil bath and be heated to 70 ~ 80 DEG C, react 6 ~ 7h under nitrogen protection;
Reaction terminates rear water cooling, and organic layer is separated, and water layer dichloromethane extraction, then merges organic layer, and gained organic layer adopts anhydrous magnesium sulfate drying, filtration, revolves and steam except desolventizing after filtration; Then cross silica gel column chromatography and collect Part II product, obtain 4-chloro-6-pyrimidine radicals ferrocene;
5) synthesis of 4-chloro-6-pyrimidine radicals ferrocene bonded silica gel solid phase extraction filler: take Aminopropyl silica gel, 4-chloro-6-pyrimidine radicals ferrocene, Anhydrous potassium carbonate and diisopropyl ethyl amine, addition ratio between four kinds of raw materials is 2 ~ 2.5g:1g:1.5g:12 ~ 13mL, then join in oxolane, ratio 2 ~ 2.5g:1.0g:1.5g:12 ~ the 13mL:100mL of four kinds of additions between raw material and oxolane, is heated to 65 ~ 70 DEG C of back flow reaction 48 ~ 50 hours under a nitrogen atmosphere; Reaction terminates to filter gained reactant afterwards, and products therefrom respectively washes three times with carrene, oxolane, acetone, water and acetone successively, and products obtained therefrom carries out vacuum drying, obtains product solid phase extraction filler after drying.
2. novel solid phase extraction filler according to claim 1, is characterized in that: Bio-sil described in step 1) is provided by Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences, and the particle diameter of Bio-sil is 40 ~ 63 μm, and aperture is 60, and specific area is 500m
2/ g.
3. novel solid phase extraction filler according to claim 1, is characterized in that: the ratio of both Bio-sil described in step 1) and hydrochloric acid solution addition is 1g:25 ~ 30mL; Described hydrochloric acid solution is by HCl and H
2o is that 1:3 is formulated according to volume ratio.
4. novel solid phase extraction filler according to claim 1, is characterized in that: adopt G5 sand core funnel when reactant liquor filters described in step 1); Redistilled water is adopted during described washing; Described drying and dehydrating is that dry 10h sloughs surface water at 160 DEG C.
5. novel solid phase extraction filler according to claim 1, is characterized in that: step 2) in suction filtration time adopt G5 sand core funnel; Described vacuum drying be vacuum be 0.1MPa, dry 24h at 80 DEG C.
6. novel solid phase extraction filler according to claim 1, is characterized in that: the methanol solution of mercuric acetate described in step 3) is formed according to the proportions of 1g:5 ~ 6mL by mercuric acetate and absolute methanol.
7. novel solid phase extraction filler according to claim 1, is characterized in that: described in step 3), anhydrous Lithium chloride is dissolved in ethanol water, and the ratio of both its anhydrous Lithium chloride and ethanol water addition is 1g:6 ~ 8mL; Described ethanol water be by ethanol and water formulated according to the volume ratio of 1:1.
8. novel solid phase extraction filler according to claim 1, is characterized in that: the mixed liquor of anhydrous tetrahydro furan described in step 4) and anhydrous propanone, and during the two mixing, the mixed volume ratio of anhydrous tetrahydro furan and anhydrous propanone is 1.5 ~ 1.6:1; Described when crossing silica gel column chromatography, the eluant, eluent of employing is carrene and the benzinum mixed liquor according to volume ratio 2:1 mixing gained.
9. novel solid phase extraction filler according to claim 1, is characterized in that: adopt G5 sand core funnel when filtering gained reactant described in step 5); Described vacuum drying be vacuum be 0.1MPa, dry 12h at 65 DEG C.
10. a solid phase extraction filler according to claim 1 is measuring the application that in food, sulfanilamide (SN) is residual.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510647489.6A CN105268415A (en) | 2015-10-09 | 2015-10-09 | Solid phase extraction packing and application of solid phase extraction packing in measuring sulfonamide residues in food |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510647489.6A CN105268415A (en) | 2015-10-09 | 2015-10-09 | Solid phase extraction packing and application of solid phase extraction packing in measuring sulfonamide residues in food |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105268415A true CN105268415A (en) | 2016-01-27 |
Family
ID=55138769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510647489.6A Pending CN105268415A (en) | 2015-10-09 | 2015-10-09 | Solid phase extraction packing and application of solid phase extraction packing in measuring sulfonamide residues in food |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105268415A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109908866A (en) * | 2019-03-28 | 2019-06-21 | 中国科学院兰州化学物理研究所 | The method and its application of two-dimensional magnetic porous carbon composite are prepared by calcining |
| CN110201714A (en) * | 2019-07-04 | 2019-09-06 | 蚌埠学院 | Dihydropyrimidinones synthetic method and catalyst |
| CN114057552A (en) * | 2021-11-22 | 2022-02-18 | 黑龙江冠卓检测科技有限公司 | Preparation method of cannabidiol standard substance for detection |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721690A (en) * | 2014-01-17 | 2014-04-16 | 郑州大学 | N-ferrocenyl (benzoyl)-phenylalanine methyl ester bonded silica gel stationary phase as well as preparation method and application thereof |
-
2015
- 2015-10-09 CN CN201510647489.6A patent/CN105268415A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721690A (en) * | 2014-01-17 | 2014-04-16 | 郑州大学 | N-ferrocenyl (benzoyl)-phenylalanine methyl ester bonded silica gel stationary phase as well as preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| AJUAN YU，ET AL: ""A new 4-ferrocenylbenzoyl chloride-bonded stationary phase for high performance liquid chromatography"", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| CHEN XU，ET AL: ""Design and synthesis of tetranuclear cluster monophosphinecyclopalladated ferrocenylpyrimidinone complexes from the palladium-catalyzed hydroxylation of chloropyrimidine"", 《CHEMICAL COMMUNICATIONS》 * |
| CHRISTOPHER IMRIE，ET AL: ""The use of a modified Suzuki reaction for the synthesis of monoarylferrocenes"", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1》 * |
| 乔丽君，等: ""4-氯-6-嘧啶基二茂铁键合硅胶固定相分离六种多环芳烃"", 《第二十届全国色谱学术报告会及仪器展览会论文集（第四分册）》 * |
| 曹爱娟，等: ""新型二茂铁固相萃取液相色谱法富集测定水中磺胺类物质"", 《第十届全国生物医药色谱及相关技术学术交流会论文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109908866A (en) * | 2019-03-28 | 2019-06-21 | 中国科学院兰州化学物理研究所 | The method and its application of two-dimensional magnetic porous carbon composite are prepared by calcining |
| CN109908866B (en) * | 2019-03-28 | 2021-12-31 | 中国科学院兰州化学物理研究所 | Method for preparing two-dimensional magnetic porous carbon composite material through calcination and application thereof |
| CN110201714A (en) * | 2019-07-04 | 2019-09-06 | 蚌埠学院 | Dihydropyrimidinones synthetic method and catalyst |
| CN110201714B (en) * | 2019-07-04 | 2022-07-29 | 蚌埠学院 | Synthesis method and catalyst of dihydropyrimidinone compound |
| CN114057552A (en) * | 2021-11-22 | 2022-02-18 | 黑龙江冠卓检测科技有限公司 | Preparation method of cannabidiol standard substance for detection |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ou et al. | Determination of DL-tetrahydropalmatine in Corydalis yanhusuo by L-tetrahydropalmatine imprinted monolithic column coupling with reversed-phase high performance liquid chromatography | |
| CN101768238B (en) | Citrinin molecular engram material and preparation method as well as application thereof | |
| CN109293938A (en) | Prepare the composite material of metallic framework compound binding molecule imprinted polymer | |
| CN102924645B (en) | Preparation method and application of molecularly imprinted polymer of penicillin antibiotics and intermediate of penicillin antibiotics | |
| CN101864021B (en) | Preparation method of nanometer silicon gel surface gastrodin molecular engram polymers | |
| CN104788612A (en) | Preparation method of magnetic microspheres-based levofloxacin surface imprinted material | |
| CN105268415A (en) | Solid phase extraction packing and application of solid phase extraction packing in measuring sulfonamide residues in food | |
| CN104083904B (en) | Functionalization porous zinc sulfide nano microballoon solid-phase extraction column and preparation method thereof | |
| CN104193875B (en) | The preparation method of stilboestrol magnetic molecularly imprinted polymer and application thereof | |
| CN108872447A (en) | The detection method of thyroid imhibitor based on hydrophily Solid Phase Extraction | |
| CN104174390B (en) | The preparation method and application of ethopabate molecular imprinted solid phase extraction cartridge | |
| CN103301820B (en) | Core-shell type Rhodamine B molecular imprinting solid-phase extraction magnetic material, and preparation method and application thereof | |
| Zhou et al. | Selective extraction and analysis of catecholamines in rat blood microdialysate by polymeric ionic liquid-diphenylboric acid-packed capillary column and fast separation in high-performance liquid chromatography-electrochemical detector | |
| CN105561958A (en) | Ionic liquid bonded silica gel used for enriching and purifying shellfish toxins and preparation method for ionic liquid bonded silica gel | |
| CN109847407B (en) | Purification method of valrubicin | |
| CN102527334B (en) | Solid phase extraction column with functionalized multi-walled carbon nanotube substrate, and preparation method thereof | |
| CN102343258A (en) | Triazolyl bonded cyclodextrin-silica gel chiral stationary phase and preparation method thereof | |
| CN106279488B (en) | The preparation for the molecularly imprinted polymer that three kinds of alkaloids of sandliving sophora seed extract at the same time and extracting process | |
| CN105223258A (en) | Amikacin and streptomysin double-template molecularly imprinted solid phase extraction column and using method | |
| CN105921116A (en) | Cation exchange solid-phase extraction material with mixing effect mode and preparation method and application thereof | |
| CN102866226A (en) | Method for using pyrazosulfuron-ethyl molecularly imprinted polymer for analyzing sulfonylurea herbicide and application thereof | |
| CN105536749A (en) | Imidazole calix [4] arene bonded silica stationary phase and preparation method and application thereof | |
| CN105289532A (en) | Molecularly-imprinted solid-phase extraction magnetic material for vitamin B12 and preparation method and application thereof | |
| CN102304164B (en) | Senegenin derivative, as well as preparation method and application thereof | |
| CN102746442B (en) | Terpene-based macroporous adsorption resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160127 |