CN104458972A - Indium oxide modified monolithic column and preparation method thereof - Google Patents
Indium oxide modified monolithic column and preparation method thereof Download PDFInfo
- Publication number
- CN104458972A CN104458972A CN201410470989.2A CN201410470989A CN104458972A CN 104458972 A CN104458972 A CN 104458972A CN 201410470989 A CN201410470989 A CN 201410470989A CN 104458972 A CN104458972 A CN 104458972A
- Authority
- CN
- China
- Prior art keywords
- indium oxide
- monolithic column
- preparation
- kapillary
- nano
- 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.)
- Granted
Links
Abstract
The invention provides an indium oxide modified polymer monolithic column and a preparation method thereof. The indium oxide modified monolithic column is prepared by methacrylic acid, methacrylic acid glycidyl ester functional monomer, a cross-linking agent, a dodecyl alcohol pore-foaming agent, a cyclohexanol pore-forming agent as well as an initiator, namely azodiisobutyronitrile and nano indium oxide; nano indium oxide is added in the preparation process of the organic polymer monolithic column, and the prepared nano indium oxide material modified polymer monolithic column simultaneously has the unique natures of the nano particles and the monolithic column. The preparation method is simple and reliable, the material performance is stable, the permeability is good, and the separation efficiency of the monolithic column is remarkably improved by introducing the nano material. The composite material monolithic column is used as a separation preconcentration medium, the indium oxide modified monolithic column is suitable for analyzing the content of tar pigments in food, and the indium oxide modified polymer monolithic column has great application potential in the fields of separation and solid-phase extraction of organic matters.
Description
Technical field
The invention provides a kind of polyalcohol integral pole of indium oxide modification, for the sample extraction purification that tar colorant in food detects, the present invention also discloses the preparation method of the polymer-modified integral post of indium oxide, belongs to analytical chemistry field of material technology.
Background technology
Tar colorant, also known as synthetic food color, is that raw material is made with coal tar, and tar colorant has the features such as the bright gorgeous and strong coloring force of with low cost, stable in properties, easy to use, color and luster, is widely adopted in food processing industry.Tar colorant is raw material mainly with chemical products such as benzene, toluene, naphthalenes, form through a series of organic reaction chemical combination such as oversulfonate, nitrated, azos, therefore, edible synthesized coloring matter mostly is containing R-N=N-R ' key, phenyl ring or xanthene structural compounds, and what have also contains the carcinogen such as b-naphthylamines and alpha-amido naphthols.By chemical constitution, edible tar colorant is divided into azo, triarylmethane class, oxa anthracenes, fluorones, quinoline and indigoid dye.Edible synthesized coloring matter may have three aspects to the toxic action of human body, namely general toxicity, cause rushing down property and carcinogenicity, particularly carcinogenicity more people paid close attention to.Toxicologic study finds, some secondary colour have chronic toxicity or carcinogenicity, there is certain insecurity or produce illeffects to human body.Therefore, each state all strictly controls its usable range and use amount.Many edible synthesized coloring matters also may be mixed into arsenic and lead in process of production, also may be mixed into some poisonous intermediate products in pigment.
China allows the edible synthesized coloring matter used to have amaranth, famille rose, red scarlet, newly red, lemon yellow, indigo, sunset yellow and light blue, the food variety used is allowed to have fruity water, fruity powder, the color equipment on fruit syrup, carbonated drink, assembled alcoholic drinks, candy, cake, can etc.In order to prevent it from endangering, strict restriction is all done in use.
The detection method that tar colorant is conventional has thin-layered chromatography, ultraviolet spectrophotometry, derivative spectrophotometry, oscilloscopic polarography, capillary electrophoresis, high performance liquid chromatography and tablets by HPLC-MS, detection box method etc.In the testing process of tar colorant, be usually subject to the impact of the reasons such as the low and Matrix effects of tar colorant content in actual sample is complicated.Existing analytical instrument is difficult to the Direct Analysis realizing tar colorant in complex sample.The reliability of sample pretreatment not only impact analysis result and accuracy, also determine analysis speed simultaneously, is step very crucial in whole analytic process.In the sample pretreating method of tar colorant, polyamide, as a kind of organic adsorbent, obtains and applies the most widely.Usual polyamide is placed into pillar, but the polyamide amount that can load in pillar is limited, and pigment in solution often can be made in use to penetrate, thus cause the stability of polycaprolactam separation method and reappearance lower.Therefore, developing a kind of novel Solid-Phase Extraction product is fundamental purpose of the present invention.
Summary of the invention
The present invention discloses a kind of polyalcohol integral pole of indium oxide modification, it is a kind of solid-phase microextraction post, select indium oxide modification integral material as adsorbent in post, solve traditional poor stability for tar colorant Solid-Phase Extraction product, shortcoming that reappearance is low, add the accuracy of sample detection, sensitivity, be applicable to the detection of tar colorant in most food samples.
Present invention also offers the preparation method of indium oxide modification integral post, be applicable to suitability for industrialized production.
Of the present invention
a polyalcohol integral pole for indium oxide modification, it is characterized in that being made up according to mass ratio of following raw material:
Function monomer: methacrylic acid 30-50, glycidyl methacrylate 150-170;
Crosslinking chemical 120-140;
Pore-foaming agent: dodecanol 90-110, cyclohexanol pore-foaming agent 800-1000;
Initiating agent: azoisobutyronitrile 4-6;
Nano indium oxide 30-40.
the preparation method of the polyalcohol integral pole of indium oxide modification of the present invention, comprises the following steps:
1) quartz capillary silanization treatment:
The quartz capillary (530 μm, i.d.) of 20 cm is used acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes respectively, uses N
2fluidized drying, is filled in the kapillary after activation by 3 – (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V), is sealed at kapillary two ends, react 12 h under 50 C with silicon rubber.Then solution control remaining in kapillary is gone out, thoroughly clean kapillary with methanol solution, finally use N
2capillary tube inner wall is dried up;
2) the polymkeric substance preparation of indium oxide modification:
In proportion by function monomer, crosslinking chemical, pore-foaming agent, initiating agent, indium oxide mixing and stirring, inject the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 18h at 60oC temperature, fully rinse with methyl alcohol after completing, obtain integral post of the present invention.
good effect of the present invention is:
Nano indium oxide is added in the preparation process of Organic Polymer Monolithic Columns, the polyalcohol integral pole of the nano indium oxide material modification obtained has the peculiar property of both nano particle and integral post simultaneously: the surface chemical property that nano indium oxide has Large ratio surface sum various, contributes to the absorption of target pigment; Preparation method is simple, reliable, and strong mechanical property, permeability are good, and the introducing of nano material significantly improves the bioaccumulation efficiency of integral post.Adopt this composites post as separation and preconcentration medium, be suitable for tar colorant in food and, containing quantitative analysis, have in organic separation and Solid-Phase Extraction field and apply potential greatly.
accompanying drawing illustrates:
Fig. 1 is the polyalcohol integral pole cross-sectional scans Electronic Speculum figure of indium oxide material modification prepared by the present invention.
Fig. 2 is that in candy, tar colorant detects the liquid chromatography-mass spectrography/mass spectrogram obtained.Wherein, A and C is candy actual sample liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype); B and D is that candy actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype).Spiked levels: 20ng/mL.
Fig. 3 A ~ Fig. 3 D.For tar colorant in beverage detects the liquid chromatography-mass spectrography/mass spectrogram obtained.Wherein, A and C is beverage actual sample liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype); B and D is that candy actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype).Spiked levels: 20ng/mL.
Fig. 4 A ~ Fig. 4 D.For tar colorant in grain milk detects the liquid chromatography-mass spectrography/mass spectrogram obtained.Wherein, A and C is grain milk actual sample liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype); B and D is that candy actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype).Spiked levels: 20ng/mL.
Fig. 5 A ~ Fig. 5 D.For tar colorant in jelly detects the liquid chromatography-mass spectrography/mass spectrogram obtained.Wherein, A and C is grain milk actual sample liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype); B and D is that candy actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrogram (negative mode/holotype).Spiked levels: 20ng/mL.
embodiment:
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following examples.
embodiment 1
1, the quartz capillary (530 μm, i.d.) of 20 cm is used acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes respectively, use N
2fluidized drying, is filled in the kapillary after activation by 3 – (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V), is sealed at kapillary two ends, react 12 h under 50 C with silicon rubber.Then solution control remaining in kapillary is gone out, thoroughly clean kapillary with methanol solution, finally use N
2capillary tube inner wall is dried up;
2, by function monomer methacrylic acid 30g, glycidyl methacrylate 140g, crosslinking chemical ethylene glycol dimethacrylate 130g, pore-foaming agent dodecanol 100g and cyclohexanol 900g, initiating agent azoisobutyronitrile 4g, nano indium oxide 30g mixing and stirring, inject the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 18h at 60oC temperature, fully rinse with methyl alcohol after completing, obtained poly-(methacrylic acid-glycidyl methacrylate) integral post.
embodiment 2
1) quartz capillary silanization treatment:
The quartz capillary (530 μm, i.d.) of 20 cm is used acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes respectively, uses N
2fluidized drying, is filled in the kapillary after activation by 3 – (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V), is sealed at kapillary two ends, react 12 h under 50 C with silicon rubber.Then solution control remaining in kapillary is gone out, thoroughly clean kapillary with methanol solution, finally use N
2capillary tube inner wall is dried up;
2) the polymkeric substance preparation of indium oxide modification:
By function monomer methacrylic acid 50g, glycidyl methacrylate 170g, crosslinking chemical ethylene glycol dimethacrylate 140g, pore-foaming agent dodecanol 110g and cyclohexanol 900g, initiating agent azoisobutyronitrile 6g, nano indium oxide 40g mixing and stirring, inject the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 24h at 60oC temperature, fully rinse with methyl alcohol after completing, obtained poly-(methacrylic acid-glycidyl methacrylate) integral post.
The integral post of the nano indium oxide modification of synthesis is used for the detection of tar colorant in beverage actual sample, be separated good, bioaccumulation efficiency is high, and without obvious matrix effect.Concrete LC-MS/MS separation case is shown in Fig. 3.
embodiment 3
1) quartz capillary silanization treatment:
The quartz capillary (530 μm, i.d.) of 20 cm is used acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes respectively, uses N
2fluidized drying, is filled in the kapillary after activation by 3 – (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V), is sealed at kapillary two ends, react 12 h under 50 C with silicon rubber.Then solution control remaining in kapillary is gone out, thoroughly clean kapillary with methanol solution, finally use N
2capillary tube inner wall is dried up;
2) the polymkeric substance preparation of indium oxide modification:
By function monomer methacrylic acid 40g, glycidyl methacrylate 160g, crosslinking chemical ethylene glycol dimethacrylate 140g, pore-foaming agent dodecanol 110g and cyclohexanol 900g, initiating agent azoisobutyronitrile 6g, nano indium oxide 30g mixing and stirring, inject the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 20h at 60oC temperature, fully rinse with methyl alcohol after completing, obtained poly-(methacrylic acid-glycidyl methacrylate) integral post.
The integral post of the nano indium oxide modification of synthesis is used for the detection of tar colorant in grain milk actual sample, be separated good, bioaccumulation efficiency is high, and without obvious matrix effect.Concrete LC-MS/MS separation case is shown in Fig. 4.
embodiment 4
1) quartz capillary silanization treatment:
The quartz capillary (530 μm, i.d.) of 20 cm is used acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes respectively, uses N
2fluidized drying, is filled in the kapillary after activation by 3 – (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V), is sealed at kapillary two ends, react 12 h under 50 C with silicon rubber.Then solution control remaining in kapillary is gone out, thoroughly clean kapillary with methanol solution, finally use N
2capillary tube inner wall is dried up;
2) the polymkeric substance preparation of indium oxide modification:
By function monomer methacrylic acid 30g, glycidyl methacrylate 150g, crosslinking chemical ethylene glycol dimethacrylate 120g, pore-foaming agent dodecanol 90g and cyclohexanol 800g, initiating agent azoisobutyronitrile 5g, nano indium oxide 40g mixing and stirring, inject the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 20h at 60oC temperature, fully rinse with methyl alcohol after completing, obtained poly-(methacrylic acid-glycidyl methacrylate) integral post.
The integral post of the nano indium oxide modification of synthesis is used for the detection of tar colorant in jelly actual sample, be separated good, bioaccumulation efficiency is high, and without obvious matrix effect.Concrete LC-MS/MS separation case is shown in Fig. 4.
test case 1
Poly-(methacrylic acid-glycidyl methacrylate) integral post of unmodified polymkeric substance (methacrylic acid-glycidyl methacrylate) integral post prepared with embodiment 1 and indium oxide material modification detects the tar colorant in candy actual sample.
Liquid chromatography-mass spectrography/mass spectrophotometry condition: analytical column is Agilent Pursuit XRs 5 C18 post (100mm × 2.0mm, 3 μm) mobile phase is methyl alcohol, and flow velocity 0.25mL/min, detecting device is mass detector, MRM pattern.
Preparation adds target blank solution sample, acid red 2G, Acid Orange II, quinoline yellow 6, azorubine, patent blue, acid green 50, erythrosine, temptation are red, sunset yellow, quinoline yellow, eosin W or W S, rhodamine B, chrysoidine spiked levels be 20ng/mL.Sample is by after 0.22 μm of miillpore filter, and the polyalcohol integral pole through the indium oxide material modification of embodiment 1 preparation extracts, and then uses 0.5% ammoniacal liquor-methanol solution desorb, stripping liquid is carried out liquid chromatography-mass spectrography/mass spectrophotometry, the results are shown in Figure 2.
test case 2
Poly-(methacrylic acid-glycidyl methacrylate) integral post of unmodified polymkeric substance (methacrylic acid-glycidyl methacrylate) integral post prepared with embodiment 2 and indium oxide material modification detects the tar colorant in beverage actual sample.
Liquid chromatography-mass spectrography/mass spectrophotometry condition, extraction conditions and spiked levels is with test case 1, and concrete LC-MS/MS spectrogram is shown in Fig. 3 A ~ Fig. 3 D.
test case 3
Poly-(methacrylic acid-glycidyl methacrylate) integral post of unmodified polymkeric substance (methacrylic acid-glycidyl methacrylate) integral post prepared with embodiment 3 and indium oxide material modification detects the tar colorant in grain milk actual sample.
Liquid chromatography-mass spectrography/mass spectrophotometry condition, extraction conditions and spiked levels is with test case 1, and concrete LC-MS/MS spectrogram is shown in Fig. 4 A ~ Fig. 4 D.
test case 4
Poly-(methacrylic acid-glycidyl methacrylate) integral post of unmodified polymkeric substance (methacrylic acid-glycidyl methacrylate) integral post prepared with embodiment 4 and indium oxide material modification detects the tar colorant in jelly actual sample.
Liquid chromatography-mass spectrography/mass spectrophotometry condition, extraction conditions and spiked levels is with test case 1, and concrete LC-MS/MS spectrogram is shown in Fig. 5 A ~ Fig. 5 D.
Claims (2)
1. a polyalcohol integral pole for indium oxide modification, it is characterized in that being made up according to mass ratio of following raw material:
Function monomer: methacrylic acid 40, base glycidyl acrylate 160;
Crosslinking chemical 133.3;
Pore-foaming agent: dodecanol 100, cyclohexanol pore-foaming agent 900;
Initiating agent: azoisobutyronitrile 4;
Nano indium oxide 30.
2. the preparation method of the polyalcohol integral pole of indium oxide modification according to claim 1, comprises the following steps:
1) quartz capillary silanization treatment:
The quartz capillary (530 μm, i.d.) of 20 cm is used acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes respectively, uses N
2fluidized drying, is filled in the kapillary after activation by 3 – (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V), is sealed at kapillary two ends, react 12 h under 50 C with silicon rubber;
Then solution control remaining in kapillary is gone out, thoroughly clean kapillary with methanol solution, finally use N
2capillary tube inner wall is dried up;
2) the polymkeric substance preparation of indium oxide modification:
In proportion by function monomer, crosslinking chemical, pore-foaming agent, initiating agent, indium oxide mixing and stirring, inject the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 18h at 60oC temperature, fully rinse with methyl alcohol after completing, obtain integral post of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410470989.2A CN104458972B (en) | 2014-09-16 | 2014-09-16 | Indium sesquioxide. modification integral post and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410470989.2A CN104458972B (en) | 2014-09-16 | 2014-09-16 | Indium sesquioxide. modification integral post and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104458972A true CN104458972A (en) | 2015-03-25 |
| CN104458972B CN104458972B (en) | 2016-08-24 |
Family
ID=52905365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410470989.2A Expired - Fee Related CN104458972B (en) | 2014-09-16 | 2014-09-16 | Indium sesquioxide. modification integral post and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104458972B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106480436A (en) * | 2015-08-31 | 2017-03-08 | 中国科学院大连化学物理研究所 | A kind of preparation method of coating EFI pin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030134745A1 (en) * | 2001-12-18 | 2003-07-17 | Park Paul W. | Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems |
| CN101073714A (en) * | 2007-04-06 | 2007-11-21 | 武汉大学 | Method for producing solid-phase microextraction capillaries |
| CN103263900A (en) * | 2013-06-07 | 2013-08-28 | 吉林大学 | Method for preparing nano aluminum oxide material modified polymer integral column |
-
2014
- 2014-09-16 CN CN201410470989.2A patent/CN104458972B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030134745A1 (en) * | 2001-12-18 | 2003-07-17 | Park Paul W. | Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems |
| CN101073714A (en) * | 2007-04-06 | 2007-11-21 | 武汉大学 | Method for producing solid-phase microextraction capillaries |
| CN103263900A (en) * | 2013-06-07 | 2013-08-28 | 吉林大学 | Method for preparing nano aluminum oxide material modified polymer integral column |
Non-Patent Citations (3)
| Title |
|---|
| LI XU ET AL.: "Porous monoliths: sorbents for miniaturized extraction in biological analysis", 《ANAL BIOANAL CHEM》 * |
| YONGQIN LV ET AL.: "Preparation of porous polymer monoliths featuring enhanced surface coverage with gold nanoparticles", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| YUN LI ET AL.: "Preparation of polymeric monoliths by copolymerization of acrylate monomers with amine functionalities for anion-exchange capillary liquid chromatography of proteins", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106480436A (en) * | 2015-08-31 | 2017-03-08 | 中国科学院大连化学物理研究所 | A kind of preparation method of coating EFI pin |
| CN106480436B (en) * | 2015-08-31 | 2021-02-19 | 中国科学院大连化学物理研究所 | Preparation method of plating electric spray needle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104458972B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yan et al. | Molecularly imprinted matrix solid-phase dispersion combined with dispersive liquid–liquid microextraction for the determination of four Sudan dyes in egg yolk | |
| CN103335995B (en) | A kind of method utilizing Raman enhanced spectrum to detect synthetic dyestuff in food | |
| CN104391050B (en) | In cosmetics, 38 kinds limit the use of the method that coloring agent detects simultaneously | |
| CN109406474B (en) | Preparation method and application of aggregation-induced emission-molecular imprinting fluorescence sensor for detecting rhodamine B | |
| CN107121514B (en) | Method that is a kind of while detecting 24 kinds of synthetic food colors in cigarette packaging material | |
| CN101768238B (en) | Citrinin molecular engram material and preparation method as well as application thereof | |
| CN106810638A (en) | The preparation method and application of Sulfonamides hydrophilic magnetic molecular engram material | |
| CN104122359B (en) | Method for simultaneously detecting 12 types of forbidden coloring agents in cosmetics | |
| CN101513577B (en) | Melamine molecular imprinted solid phase extraction cartridge and a preparation method and application thereof | |
| CN110243980A (en) | The high-flux detection method of 94 kinds of disabling industrial dyes in a kind of food | |
| CN105675759B (en) | A kind of method for separating and detecting of bisphenol-A | |
| CN102636592A (en) | Method for simultaneous determination of a plurality of synthetic pigments in hot pot flavorings | |
| CN104193875B (en) | The preparation method of stilboestrol magnetic molecularly imprinted polymer and application thereof | |
| CN104927866A (en) | Preparation method and application of hollow porous silica sphere-coated quantum dot fluorescent sensor | |
| CN104818013B (en) | Diketopyrrolopyrrolederivative derivative is at Hg2+application in detection | |
| CN105921129A (en) | Preparation method of magnetic molecularly imprinted microspheres and application in separation and enrichment of cucurbitane triterpenoid | |
| CN102507808B (en) | Method for enriching and separating trace amount of polychlorinated biphenyls (PCBs) | |
| CN108579696A (en) | A kind of theophylline molecular engram material and its preparation method and application of silver nano-grain doping | |
| CN104458972A (en) | Indium oxide modified monolithic column and preparation method thereof | |
| CN104101661B (en) | A kind of method for quick of Detection of Magdala in Food Through | |
| CN103551125A (en) | Preparation method of Sudan red II molecular imprinting solid-phase extraction column filling material | |
| CN104458966A (en) | Detection method for forbidden azo dyes of textiles | |
| CN102507820B (en) | Method for detecting trichlorfon and monocrotophos | |
| CN107266627B (en) | A kind of the core-shell type molecularly imprinted polymer and preparation method of recognizable erythrosine | |
| CN108956843A (en) | A kind of quick multi information thin-layer identification method of banxia baizhu tianma decoction freeze-dried powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170527 Address after: 130000 Jilin province Changchun Puyang Street No. 1301 Co-patentee after: INSPECTION AND QUARANTINE TECHNOLOGY CENTER OF JILIN ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU Patentee after: China Certification & inspection group Jilin Co.,Ltd. Address before: 130021 Jilin province Changchun Puyang Street No. 45 Patentee before: INSPECTION AND QUARANTINE TECHNOLOGY CENTER OF JILIN ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20210916 |