CN104458972B - Indium sesquioxide. modification integral post and preparation method thereof - Google Patents
Indium sesquioxide. modification integral post and preparation method thereof Download PDFInfo
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- CN104458972B CN104458972B CN201410470989.2A CN201410470989A CN104458972B CN 104458972 B CN104458972 B CN 104458972B CN 201410470989 A CN201410470989 A CN 201410470989A CN 104458972 B CN104458972 B CN 104458972B
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Abstract
The invention provides the modified polyalcohol integral pole of a kind of Indium sesquioxide. and preparation method, be made up of methacrylic acid, base glycidyl acrylate function monomer, cross-linking agent, dodecanol porogen, Hexalin porogen and initiator azodiisobutyronitrile, nano indium oxide；Adding nano indium oxide 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 nanoparticle and integral post simultaneously；Preparation method of the present invention is simple, reliable, and strong mechanical property, permeability are good, and the introducing of nano material significantly improves the separation efficiency of integral post.Use this composite integral post as separation and preconcentration medium, be suitable for the analysis of the coal-tar middle oil pigment content of food, have in organic separation and Solid-Phase Extraction field and apply potential greatly.
Description
Technical field
The invention provides the polyalcohol integral pole that a kind of Indium sesquioxide. is modified, the sample extraction for the detection of food coal-tar middle oil pigment purifies, and invention additionally discloses the preparation method of the polymer-modified integral post of Indium sesquioxide., belongs to analytical chemistry field of material technology.
Background technology
Tar colorant, also known as synthetic food color, makes with coal tar for raw material, and tar colorant has with low cost, stable in properties, easy to use, color and luster is bright gorgeous and the feature such as strong coloring force, is widely adopted in food processing industry.Tar colorant is many with chemical products such as benzene, toluene, naphthalenes as raw material, is bound up through a series of organic reactions such as sulfonation, nitrification, azos, and therefore, edible synthesized coloring matter mostly is containing R-N=
N-R ' key, phenyl ring or xanthene structural compounds, have possibly together with 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.The toxic action of human body may be had three aspects, i.e. general toxicity, diarrhea inducing and carcinogenecity, particularly carcinogenecity more concerned by edible synthesized coloring matter.Toxicologic study finds, some combination color have chronic toxicity or carcinogenecity, human body exists certain insecurity or produces illeffects.Therefore, each state the most strictly controls its range and usage amount.Many edible synthesized coloring matters are also possible to be mixed into arsenic and lead in process of production, are also possible to be mixed into some poisonous intermediate products in pigment.
China allows the edible synthesized coloring matter used to have amaranth, carmine, red scarlet, the reddest, lemon yellow, indigo, sunset yellow and light blue, the food variety used is allowed to have fruity water, fruity powder, color equipment on fruit syrup, soda pop, assembled alcoholic drinks, confection, cake, canned food etc..In order to prevent it from endangering, on using, all make strict restriction.
The detection method that tar colorant is conventional has thin layer chromatography, ultraviolet spectrophotometry, derivative spectrophotometry, oscilloscopic polarography, high performance capillary electrophoresis, high performance liquid chromatography and tablets by HPLC-MS, detection box method etc..During the detection of tar colorant, it is frequently subjected to that the coal-tar middle oil pigment content of actual sample is low and the impact of the reason such as matrix interference is complicated.Existing analytical tool is difficult to the direct analysis of the coal-tar middle oil pigment of complex sample.The reliability of sample pretreatment not only impact analysis result and accuracy, also determine analysis speed simultaneously, is step the most crucial during whole analysis.In the sample pretreating method of tar colorant, polyamide, as a kind of organic adsorbent, has obtained widest application.Generally polyamide is placed into pillar, but the polyamide amount that can load in pillar is limited, the most often makes pigment in solution penetrate, thus causes the stability of polycaprolactam separation method and repeatability relatively low.Therefore, developing a kind of novel Solid-Phase Extraction product is the main object of the present invention.
Summary of the invention
The present invention discloses the polyalcohol integral pole that a kind of Indium sesquioxide. is modified, it it is a kind of solid-phase microextraction post, select Indium sesquioxide. modification integral material as post internal adsorption agent, solve and be traditionally used for the poor stability of tar colorant Solid-Phase Extraction product, shortcoming that repeatability is low, add the accuracy of sample detection, susceptiveness, be applicable to the detection of most coal-tar middle oil pigment of food samples.
Present invention also offers the preparation method of Indium sesquioxide. modification integral post, it is adaptable to industrialized production.
Of the present inventionThe polyalcohol integral pole that a kind of Indium sesquioxide. is modified, it is characterised in that be made up according to mass ratio of following raw material:
Function monomer: methacrylic acid 30-50, glycidyl methacrylate 150-170；
Cross-linking agent 120-140；
Porogen: dodecanol 90-110, Hexalin porogen 800-1000；
Initiator: azodiisobutyronitrile 4-6；
Nano indium oxide 30-40.
The preparation method of the polyalcohol integral pole that Indium sesquioxide. of the present invention is modified, comprises the following steps:
1) quartz capillary silanization treatment:
By the quartz capillary (530 μm, i.d.) of 20 cm respectively with acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes, use N2Fluidized drying, is filled into 3 (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V) in the capillary tube after activation, is sealed at capillary tube two ends with silicone rubber, react 12 h under 50 C.Then solution control remaining in capillary tube is gone out, thoroughly clean capillary tube with methanol solution, finally use N2Capillary tube inner wall is dried up；
2) prepared by the polymer that Indium sesquioxide. is modified:
In proportion by function monomer, cross-linking agent, porogen, initiator, Indium sesquioxide. mixing and stirring, injecting in the quartz capillary of silanization, sealing, at a temperature of 60 C, thermal-initiated polymerization reaction 18h, fully rinses with methanol after completing, obtains integral post of the present invention.
The positive 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 nanoparticle and integral post simultaneously: nano indium oxide has bigger serface and various surface chemical property, 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.Use this composite integral post as separation and preconcentration medium, be suitable for the analysis of the coal-tar middle oil pigment content of food, 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 sesquioxide. material modification prepared by the present invention.
Fig. 2 is liquid chromatography-mass spectrography/mass spectrum that the detection of confection coal-tar middle oil pigment obtains.Wherein, A and C is confection actual sample liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype)；B and D is that confection actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype).Spiked levels: 20ng/mL.
Fig. 3 A ~ Fig. 3 D.Liquid chromatography-mass spectrography/the mass spectrum obtained for the detection of beverage coal-tar middle oil pigment.Wherein, A and C is beverage actual sample liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype)；B and D is that confection actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype).Spiked levels: 20ng/mL.
Fig. 4 A ~ Fig. 4 D.Liquid chromatography-mass spectrography/the mass spectrum obtained for the detection of grain milk coal-tar middle oil pigment.Wherein, A and C is grain milk actual sample liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype)；B and D is that confection actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype).Spiked levels: 20ng/mL.
Fig. 5 A ~ Fig. 5 D.Liquid chromatography-mass spectrography/the mass spectrum obtained for the detection of fruit jelly coal-tar middle oil pigment.Wherein, A and C is grain milk actual sample liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype)；B and D is that confection actual sample mark-on reclaims liquid chromatography-mass spectrography/mass spectrum (negative mode/holotype).Spiked levels: 20ng/mL.
Detailed description of the invention:
Below in conjunction with detailed description of the invention, the invention will be further described, but the present invention is not limited to following example.
Embodiment
1
1, by the quartz capillary (530 μm, i.d.) of 20 cm respectively with acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes, N is used2Fluidized drying, is filled into 3 (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V) in the capillary tube after activation, is sealed at capillary tube two ends with silicone rubber, react 12 h under 50 C.Then solution control remaining in capillary tube is gone out, thoroughly clean capillary tube with methanol solution, finally use N2Capillary tube inner wall is dried up；
2, by function monomer methacrylic acid 30g, glycidyl methacrylate 140g, cross-linking agent ethylene glycol dimethacrylate 130g, porogen dodecanol 100g and Hexalin 900g, initiator azodiisobutyronitrile 4g, nano indium oxide 30g mixing and stirring, inject in the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 18h at a temperature of 60 C, fully rinse with methanol after completing, prepare poly-(methacrylic acid-glycidyl methacrylate) integral post.
Embodiment
2
1) quartz capillary silanization treatment:
By the quartz capillary (530 μm, i.d.) of 20 cm respectively with acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes, use N2Fluidized drying, is filled into 3 (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V) in the capillary tube after activation, is sealed at capillary tube two ends with silicone rubber, react 12 h under 50 C.Then solution control remaining in capillary tube is gone out, thoroughly clean capillary tube with methanol solution, finally use N2Capillary tube inner wall is dried up；
2) prepared by the polymer that Indium sesquioxide. is modified:
By function monomer methacrylic acid 50g, glycidyl methacrylate 170g, cross-linking agent ethylene glycol dimethacrylate 140g, porogen dodecanol 110g and Hexalin 900g, initiator azodiisobutyronitrile 6g, nano indium oxide 40g mixing and stirring, inject in the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 24h at a temperature of 60 C, fully rinse with methanol after completing, prepare poly-(methacrylic acid-glycidyl methacrylate) integral post.
The integral post that the nano indium oxide of synthesis is modified being used for the detection of the coal-tar middle oil pigment of beverage actual sample, separates good, bioaccumulation efficiency is high, and without obvious matrix effect.Concrete LC-MS/MS separates situation and sees Fig. 3.
Embodiment
3
1) quartz capillary silanization treatment:
By the quartz capillary (530 μm, i.d.) of 20 cm respectively with acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes, use N2Fluidized drying, is filled into 3 (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V) in the capillary tube after activation, is sealed at capillary tube two ends with silicone rubber, react 12 h under 50 C.Then solution control remaining in capillary tube is gone out, thoroughly clean capillary tube with methanol solution, finally use N2Capillary tube inner wall is dried up；
2) prepared by the polymer that Indium sesquioxide. is modified:
By function monomer methacrylic acid 40g, glycidyl methacrylate 160g, cross-linking agent ethylene glycol dimethacrylate 140g, porogen dodecanol 110g and Hexalin 900g, initiator azodiisobutyronitrile 6g, nano indium oxide 30g mixing and stirring, inject in the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 20h at a temperature of 60 C, fully rinse with methanol after completing, prepare poly-(methacrylic acid-glycidyl methacrylate) integral post.
The integral post that the nano indium oxide of synthesis is modified being used for the detection of the coal-tar middle oil pigment of grain milk actual sample, separates good, bioaccumulation efficiency is high, and without obvious matrix effect.Concrete LC-MS/MS separates situation and sees Fig. 4.
Embodiment
4
1) quartz capillary silanization treatment:
By the quartz capillary (530 μm, i.d.) of 20 cm respectively with acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes, use N2Fluidized drying, is filled into 3 (triethoxy is silica-based) propyl methacrylate acetone soln (50% V/V) in the capillary tube after activation, is sealed at capillary tube two ends with silicone rubber, react 12 h under 50 C.Then solution control remaining in capillary tube is gone out, thoroughly clean capillary tube with methanol solution, finally use N2Capillary tube inner wall is dried up；
2) prepared by the polymer that Indium sesquioxide. is modified:
By function monomer methacrylic acid 30g, glycidyl methacrylate 150g, cross-linking agent ethylene glycol dimethacrylate 120g, porogen dodecanol 90g and Hexalin 800g, initiator azodiisobutyronitrile 5g, nano indium oxide 40g mixing and stirring, inject in the quartz capillary of silanization, sealing, thermal-initiated polymerization reaction 20h at a temperature of 60 C, fully rinse with methanol after completing, prepare poly-(methacrylic acid-glycidyl methacrylate) integral post.
The integral post that the nano indium oxide of synthesis is modified being used for the detection of the coal-tar middle oil pigment of fruit jelly actual sample, separates good, bioaccumulation efficiency is high, and without obvious matrix effect.Concrete LC-MS/MS separates situation and sees Fig. 4.
Test case
1
With unmodified polymer (methacrylic acid-glycidyl methacrylate) integral post of embodiment 1 preparation and poly-(methacrylic acid-glycidyl methacrylate) integral post of Indium sesquioxide. material modification, the tar colorant in confection actual sample is detected.
Liquid chromatography-mass spectrography/mass spectral analysis condition: analytical column is Agilent
Pursuit XRs 5 C18 post (100mm × 2.0mm, 3 μm) flowing is methanol mutually, and flow velocity 0.25mL/min, detector is mass detector, MRM pattern.
Preparation adds target blank solution sample, and Xylene Red 2G, Acid Orange II, quinoline yellow 6, azorubine, patent blue, acid green 50, erythrosine, temptation are red, sunset yellow, D C Yellow No. 10, eosin W or W S, rhodamine B, the spiked levels of chrysoidine are 20ng/mL.Sample is by after 0.22 μm microporous filter membrane, and the polyalcohol integral pole through the Indium sesquioxide. material modification of embodiment 1 preparation extracts, and then with 0.5% ammonia water-methanol solution desorbing, stripping liquid is carried out liquid chromatography-mass spectrography/mass spectral analysis, and result is shown in Fig. 2.
Test case
2
With unmodified polymer (methacrylic acid-glycidyl methacrylate) integral post of embodiment 2 preparation and poly-(methacrylic acid-glycidyl methacrylate) integral post of Indium sesquioxide. material modification, the tar colorant in beverage actual sample is detected.
Liquid chromatography-mass spectrography/mass spectral analysis condition, extraction conditions and spiked levels are shown in Fig. 3 A ~ Fig. 3 D with test case 1, concrete LC-MS/MS spectrogram.
Test case
3
With unmodified polymer (methacrylic acid-glycidyl methacrylate) integral post of embodiment 3 preparation and poly-(methacrylic acid-glycidyl methacrylate) integral post of Indium sesquioxide. material modification, the tar colorant in grain milk actual sample is detected.
Liquid chromatography-mass spectrography/mass spectral analysis condition, extraction conditions and spiked levels are shown in Fig. 4 A ~ Fig. 4 D with test case 1, concrete LC-MS/MS spectrogram.
Test case
4
With unmodified polymer (methacrylic acid-glycidyl methacrylate) integral post of embodiment 4 preparation and poly-(methacrylic acid-glycidyl methacrylate) integral post of Indium sesquioxide. material modification, the tar colorant in fruit jelly actual sample is detected.
Liquid chromatography-mass spectrography/mass spectral analysis condition, extraction conditions and spiked levels are shown in Fig. 5 A ~ Fig. 5 D with test case 1, concrete LC-MS/MS spectrogram.
Claims (1)
1. the polyalcohol integral pole that an Indium sesquioxide. is modified, it is characterised in that be made up according to mass ratio of following raw material:
Function monomer: methacrylic acid 40, base glycidyl acrylate 160；
Cross-linking agent: ethylene glycol dimethacrylate 133.3；
Porogen: dodecanol 100, Hexalin porogen 900；
Initiator: azodiisobutyronitrile 4；
Nano indium oxide 30；
The preparation method of the polyalcohol integral pole that described Indium sesquioxide. is modified comprises the following steps:
1) quartz capillary silanization treatment:
By 530 μm of 20 cm, i.d quartz capillary with acetone, 1 mol/L NaOH, 1 mol/L HCl, redistilled water and acetone rinsing 20 minutes, uses N respectively2Fluidized drying, is filled into 3 (triethoxy is silica-based) propyl methacrylate acetone soln of 50% V/V in the capillary tube after activation, is sealed at capillary tube two ends with silicone rubber, react 12 h under 50 C；Then solution control remaining in capillary tube is gone out, thoroughly clean capillary tube with methanol solution, finally use N2Capillary tube inner wall is dried up；
2) prepared by the polymer that Indium sesquioxide. is modified:
In proportion by function monomer, cross-linking agent, porogen, initiator, Indium sesquioxide. mixing and stirring, injecting in the quartz capillary of silanization, sealing, at a temperature of 60 C, thermal-initiated polymerization reaction, fully rinses with methanol after completing, obtains integral post of the present invention.
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