CN103285818A - Phenylboronic acid modified zirconium based material and its application - Google Patents
Phenylboronic acid modified zirconium based material and its application Download PDFInfo
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- CN103285818A CN103285818A CN2013100754305A CN201310075430A CN103285818A CN 103285818 A CN103285818 A CN 103285818A CN 2013100754305 A CN2013100754305 A CN 2013100754305A CN 201310075430 A CN201310075430 A CN 201310075430A CN 103285818 A CN103285818 A CN 103285818A
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- boric acid
- phenyl boric
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Abstract
The invention relates to a phenylboronic acid modified zirconium based material and its application in adsorption of carbohydrate compounds in biological samples. The preparation method of the material includes: dissolving m-aminophenylboronic acid in water, adding phosphorous acid and concentrated hydrochloric acid in order, stirring them evenly, then adding excessive formaldehyde dropwisely, conducting stirring reflux for 6h, and adding water to precipitate solids, thus obtaining (3-N, N-dimethylene phosphonic acid)-phenylboronic acid; adding a zirconia material into the (3-N, N-dimethylene phosphonic acid)-phenylboronic acid solution, and carrying out stirring reflux for 24h, thus obtaining the zirconium based material with a phenylboronic acid modified surface. The obtained zirconium based material with a phenylboronic acid modified surface shows adsorption performance on cis-polyhydroxy compound glucose. The method involved in the invention has the advantages of simple process and low operation cost, etc., and is of great significance in studying preparation of new zirconium based materials with selective adsorption performance and adsorption behaviors of polyhydroxy compounds on the zirconium based materials, developing novel analysis materials suitable for adsorption of cis-hydroxyl compounds in biological samples, and applying the analysis materials to pretreatment of biological samples.
Description
Technical field
The present invention relates to zirconio material that a kind of phenyl boric acid modifies and to the adsorption applications of saccharide compound in the biological sample.
Background technology
Carbohydrate is widespread in nature and plays a significant role in bio-identification, relates to one of three class large biological molecules of vital movement essence, plays important effect in the whole metabolic process of organism, is distributed widely in the organism.Carbohydrate almost relates to all life processes simultaneously as biological information molecule.Along with the interest to the carbohydrate analytical method day by day increases, " carbohydrate chemistry " becomes more and more important.
Phenyl boric acid and phenyl boric acid derivative have the unique biological recognition performance, under alkali condition, boric acid base group can with along the dihydroxy structure function, generate stable five-membered ring complex compound, complexing is opened under the acid condition, and this characteristic has been given boric acid class affinitive material enrichment and contained ability along the various biomolecule such as carbohydrate, glycoprotein, catecholamines and ucleosides of dihydroxy structure.The organic polymer matrix that boric acid is modified is easy to expand, and mechanical strength is not high; Silica gel material is widely used but can dissolves under the strong alkaline condition, and it can only be applied to pH 2-8.Zirconia becomes the more new material of research with its good ph stability, heat endurance and unique surface chemical property, by the Lewis acid-base function zirconium surface is carried out modification and prepares the zirconium base new material that glucose is had selective absorption.
The present invention is by the Lewis acid-base function, utilize the phenyl boric acid derivative that the zirconio material surface is modified, prepare the zirconium base new material that glucose is had selective absorption, research polyol absorption behavior thereon, understand the boric acid affinity ligand to the retention mechanism of polyol, exploitation is applicable to the novel analysis of material of cis hydroxyl groups compound in the absorption biological sample and applies it in the biological sample pre-treatment significant.
Summary of the invention
The zirconio material and the application process thereof that the object of the present invention is to provide a kind of phenyl boric acid to modify
The zirconio material of a kind of finishing phenyl boric acid of the present invention is characterized in that the preparation method of this zirconio material has following steps:
A. m-aminophenyl boric acid is water-soluble, add phosphorous acid and concentrated hydrochloric acid successively, dropwise add excess formaldehyde after stirring and evenly mixing, stirring and refluxing 6h adds elutriation and goes out solid, the sand core funnel decompress filter, use washed with de-ionized water, vacuum drying gets (3-N, N-dimethylene phosphonic acids) phenyl boric acid.
B. in (3-N, N-dimethylene phosphonic acids) phenyl boric acid solution, add zirconia material, it is 0.15: 2.0 that both mass ratios close, stirring and refluxing 24h;
C. the sand core funnel decompress filter is used deionized water successively, washed with methanol, and vacuum drying gets the zirconio material of finishing phenyl boric acid.
The application of the zirconio material of a kind of finishing phenyl boric acid of the present invention is that purposes is, the zirconio material of finishing phenyl boric acid is put in the aqueous media that contains cis polyol such as carbohydrate, under the condition that stirs, vibrates, control certain pH value and adsorption time, cis polyol such as glucose are adsorbed.
Description of drawings
Fig. 1 is that the zirconio material of finishing phenyl boric acid is to the ultraviolet-visible spectrogram of the adsorption effect of glucose in the urine sample.
Fig. 2 is that the zirconio material of finishing phenyl boric acid is to the ultraviolet-visible spectrogram of the adsorption effect of glucose in the serum.
The specific embodiment
The present invention is described in detail below in conjunction with embodiment.
Embodiment one
The concrete steps of present embodiment are as follows:
A. 3-aminobenzene boric acid 1.36 g and phosphorous acid 1.64 g, ultrasonic mixing, add 2 mL concentrated hydrochloric acids after, slowly drip 4mL formalin simultaneously 100 ℃ stir down, stir 6 h; Reactant liquor is separated out solid after adding water, and the G4 sand core funnel filters, the washing drying obtain (3-N, N-dimethylene phosphonic acids)-phenyl boric acid.
B. with above-mentioned preparation gained (3-N, N-dimethylene phosphonic acids)-phenyl boric acid 0.15 g is dissolved in 40 mL SASs, drop into 2.0 g zirconia materials, the control temperature is 100 ℃, stirring and refluxing 24 h, the sand core funnel decompress filter is used deionized water successively, washed with methanol, vacuum drying get the zirconio material of finishing phenyl boric acid.
C. the zirconio material of 150 mg finishing phenyl boric acids is put in the urine sample or serum that contains glucose, under the stirring at room condition, control mixing time 6 h and pH=7.5 carry out adsorption reaction to glucose.
D. get supernatant after the absorption, carry out ultraviolet-visible spectrum after the colour developing and measure.
Application of the present invention and adsorption reaction test example
Test example two:Present embodiment and embodiment one are basic identical, and difference is: when glucose in the urine sample was carried out adsorption reaction, the quality that feeds intake was 250 mg.
Test example three:Present embodiment and embodiment one are basic identical, and difference is: when glucose in the urine sample was carried out adsorption reaction, the quality that feeds intake was 350 mg.
Test example four:Present embodiment and embodiment one are basic identical, and difference is: when glucose in the urine sample was carried out adsorption reaction, the quality that feeds intake was 400 mg.
Test example five:Present embodiment and embodiment one are basic identical, and difference is: the zirconio material of 50 mg finishing phenyl boric acids is put in the serum that contains glucose, and under the stirring at room condition, control mixing time 6 h and pH=7.5 carry out adsorption reaction to glucose.
Test example six:Present embodiment and embodiment one are basic identical, and difference is: the zirconio material of 150 mg finishing phenyl boric acids is put in the serum that contains glucose, and under the stirring at room condition, control mixing time 6 h and pH=7.5 carry out adsorption reaction to glucose.
Test example seven:Present embodiment and embodiment one are basic identical, and difference is: the zirconio material of 250 mg finishing phenyl boric acids is put in the serum that contains glucose, and under the stirring at room condition, control mixing time 6 h and pH=7.5 carry out adsorption reaction to glucose.
Test example eight:Present embodiment and embodiment one are basic identical, and difference is: the zirconio material of 350 mg finishing phenyl boric acids is put in the serum that contains glucose, and under the stirring at room condition, control mixing time 6 h and pH=7.5 carry out adsorption reaction to glucose.
Referring to Fig. 1, Fig. 1 estimates the zirconio material of finishing phenyl boric acid to the ultraviolet-visible spectrogram of the adsorption effect of urine sample glucose for being used for.
Wherein: curve a: be the ultraviolet-visible spectrum curve of glucose solution in the urine sample before adsorbing;
Curve b: be the ultraviolet-visible spectrum curve through glucose solution in the urine sample after the zirconio material absorption of 150 mg finishing phenyl boric acids;
Curve c: be the ultraviolet-visible spectrum curve through glucose solution in the urine sample after the zirconio material absorption of 250 mg finishing phenyl boric acids;
Curve d: be the ultraviolet-visible spectrum curve through glucose solution in the urine sample after the zirconio material absorption of 350 mg finishing phenyl boric acids;
Curve e: be the ultraviolet-visible spectrum curve through glucose solution in the urine sample after the zirconio material absorption of 400 mg finishing phenyl boric acids;
Referring to Fig. 2, Fig. 2 estimates the zirconio material of finishing phenyl boric acid to the ultraviolet-visible spectrogram of the adsorption effect of serum glucose for being used for.
Wherein: curve a: be the ultraviolet-visible spectrum curve of glucose solution in the serum before adsorbing;
Curve b: be the ultraviolet-visible spectrum curve through glucose solution in the serum after the zirconio material absorption of 50 mg finishing phenyl boric acids;
Curve c: be the ultraviolet-visible spectrum curve through glucose solution in the serum after the zirconio material absorption of 150 mg finishing phenyl boric acids;
Curve d: be the ultraviolet-visible spectrum curve through glucose solution in the serum after the zirconio material absorption of 250 mg finishing phenyl boric acids;
Curve e: be the ultraviolet-visible spectrum curve through glucose solution in the serum after the zirconio material absorption of 350 mg finishing phenyl boric acids;
By to Fig. 1, in 2 the curve contrast as can be known, the zirconio material of resulting finishing phenyl boric acid has the good adsorption effect to glucose in the biological sample.
Claims (2)
1. the zirconio material of a finishing phenyl boric acid is characterized in that the preparation method of this zirconio material has following steps:
A. m-aminophenyl boric acid is water-soluble, add phosphorous acid and concentrated hydrochloric acid successively, dropwise add excess formaldehyde after stirring and evenly mixing, stirring and refluxing 6h adds elutriation and goes out solid, the sand core funnel decompress filter, use washed with de-ionized water, vacuum drying gets (3-N, N-dimethylene phosphonic acids) phenyl boric acid.
B. in (3-N, N-dimethylene phosphonic acids) phenyl boric acid solution, add zirconia material, it is 0.15: 2.0 that both mass ratios close, stirring and refluxing 24h;
C. the sand core funnel decompress filter is used deionized water successively, washed with methanol, and vacuum drying gets the zirconio material of finishing phenyl boric acid.
2. the application of the zirconio material of a finishing phenyl boric acid is that purposes is, the zirconio material of finishing phenyl boric acid is put in the aqueous media that contains cis polyol such as carbohydrate, under the condition that stirs, vibrates, control certain pH value and adsorption time, cis polyol such as glucose are adsorbed.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430289A (en) * | 2020-11-09 | 2021-03-02 | 南昌大学 | High-selectivity phenylboronic acid functionalized organic polymer and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3062859A (en) * | 1960-03-07 | 1962-11-06 | United States Borax Chem | Preparation of benzeneboronic esters |
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2013
- 2013-03-11 CN CN2013100754305A patent/CN103285818A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3062859A (en) * | 1960-03-07 | 1962-11-06 | United States Borax Chem | Preparation of benzeneboronic esters |
Non-Patent Citations (4)
| Title |
|---|
| E.HAGEMEIER ET AL.: "Synthesis and application of a boronic acid-substituted silica for high-performance liquid affinity chromatography", 《JOURNAL OF CHROMATOGRAPHY》 * |
| HAI-BO HE ET AL.: "Boronate affinity solid-phase extraction based on functionalized magnesia–zirconia composite for enrichment of nucleosides in human urine", 《ANALYTICAL METHODS》 * |
| J.J.KIRKLAND ET AL.: "High pH mobile phase effects on silica-based reversed-phase high-performance liquid chromatographic columns", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| MAGNUS GLAD ET AL.: "High-performance liquid affinity chromatography of nucleosides,nucleotides and carbohydrates with boronic acid-substituted microparticulate silica", 《JOURNAL OF CHROMATOGRAPHY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430289A (en) * | 2020-11-09 | 2021-03-02 | 南昌大学 | High-selectivity phenylboronic acid functionalized organic polymer and preparation method and application thereof |
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Application publication date: 20130911 |