CN104843778A

CN104843778A - Preparation method of hydrophilic meso-porous titanium dioxide aerogel material

Info

Publication number: CN104843778A
Application number: CN201510197967.8A
Authority: CN
Inventors: 张丽媛; 董佩佩; 张丽华; 邵淑娟; 赵艳艳; 迟鑫明; 胡军; 孙兵
Original assignee: Dalian Medical University
Current assignee: Dalian Medical University
Priority date: 2015-04-24
Filing date: 2015-04-24
Publication date: 2015-08-19

Abstract

The invention relates to a preparation method of a hydrophilic meso-porous titanium dioxide aerogel material. The method comprises the following steps: 1, dissolving an initial titanium source compound in water to obtain a uniform titanium source solution; 2, reacting the titanium source solution with ammonia water in water to prepare a titanium dioxide sol; 3, washing the titanium dioxide sol by using water to remove impurities; 4, carrying out solvent displacement on the titanium dioxide sol by using an anhydrous solvent; and 5, drying the titanium dioxide sol by using a supercritical drying technology to complete preparation of the hydrophilic meso-porous titanium dioxide aerogel material. The preparation method is easy and is easy to control, and the hydrophilic meso-porous titanium dioxide aerogel material obtained in the invention has the advantages of strong hydrophilic property, large specific surface area, low density and stability at room temperature.

Description

A kind of preparation method of hydrophilic mesoporous titania aerogel material

Technical field

The present invention relates to mesoporous materials field, in particular to a kind of preparation method of hydrophilic mesoporous titania aerogel material.

Background technology

Protein phosphorylation is a kind of important reversibility protein post-translational modification, plays the vital role such as intracellular signaling, Metabolism regulation, cell function regulation and control in vital process.But phosphorylated protein/usual abundance of peptide section is lower, in mass spectroscopy, be often subject to the interference of a large amount of non-phosphorylating albumen/peptide section.Therefore, the selective enrichment technology developed for phosphated peptide section is most important for carrying out the research of phosphorylated protein group in a deep going way.

Metal oxide affinity chromatography, particularly titanium dioxide affinity chromatography have become one of the most frequently used at present phosphorylation beneficiation technologies (Liang, S. S., J.Chromatogr. A, 2006,1116 because of the phosphorylated peptide selective enrichment effect of its excellence; Wolschin, F., Wienkoop, S., Weckwerth, W, Proteomics, 2005,5 (17): 4389-4397.).But titanic oxide material specific surface area conventional is at present little, also less to the loading capacity of phosphorylated peptide, the titanic oxide material therefore developing high-specific surface area is significant to the research of phosphorylated protein group.

Titanium dioxide (TiO ₂) aerogel is by TiO ₂the inside that particle assembles formation mutually presents the meter Sized Materials of porous network shape, has TiO concurrently ₂the characteristic such as high-specific surface area, high porosity of excellent catalytic performance, bioaffinity, nontoxicity, chemical stability and aerogel, thus has very important application prospect.

Current titania aerogel adopts the metal alkoxides such as n-propyl alcohol titanium and n-butyl titanium to be that raw material obtains through supercritical drying usually, this preparation technology's expensive starting materials, complex process, strong acid need be added or highly basic makees catalyzer, and need the content of water in strict control preparation process to avoid the violent hydrolysis of alkoxide, preparation process is difficult to control, poor reproducibility.In addition, this preparation method is owing to employing the stronger alkoxide of hydrophobicity as titanium source, the titania aerogel remained on surface prepared has hydrophobic organic compound group, cause it to retain hydrophobic non-phosphorylating peptide in the enrichment of phosphorylated peptide to strengthen, hydrophilic phosphorylated peptide is retained and weakens, reduce its enrichment specificity to phosphorylated peptide.

Therefore, development have high-hydrophilic, high-specific surface area titania aerogel significant for realizing phosphated peptide section isolation identification.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of hydrophilic titanium oxide aerogel, be difficult to control to solving the preparation process existed in conventional titania aerogel preparation method, poor reproducibility, and the wetting ability of gained titanium dioxide airsetting material is poor, to problems such as phosphorylated peptide poor selectivity.This hydrophilic titanium oxide aerogel material is mainly used in online or off-line selective enrichment phospho-peptide.

For achieving the above object, the technical solution used in the present invention is:

1) under room temperature, initial titanium source compound water-soluble homogeneous titanium source solution: join to obtain the homogeneous titanium source solution of 0.05-0.25 mol/L by water-soluble for any one or more in the soluble inorganic such as titanium sulfate, titanium tetrachloride titanium salt.

2) described titanium source solution and ammoniacal liquor react obtained TiO 2 sol in water: in the titanium source solution stirred, dropwise add the ammoniacal liquor that mass concentration is 5-15%, often drip 0.5-1.5 mL.

3) wash TiO 2 sol and remove impurity: if titanium source compound is that 0.1 mol/L Ba (NO then used by titanium sulfate ₃) ₂detect to SO in washings ₄ ^2-for feminine gender, can think that Impurity removal is thorough; If titanium source compound is that titanium tetrachloride then uses 0.1 mol/L AgNO ₃detect Cl in washings ^-for feminine gender, can think that Impurity removal is thorough.

4) anhydrous solvent is utilized to carry out solvent exchange to TiO 2 sol: any one utilizing in dehydrated alcohol, anhydrous methanol, anhydrous propanone carries out solvent exchange to TiO 2 sol, and this solvent can dissolve each other with arbitrary proportion with water.The anhydrous solvent added during each solvent exchange is 1-5 times of TiO 2 sol volume, every displacement in 2-5 hour once.

5) supercutical fluid is utilized to carry out drying to TiO 2 sol: to utilize any one supercutical fluid in carbonic acid gas, methyl alcohol, ethanol to carry out drying to TiO 2 sol, complete the preparation of mesoporous TiO 2 aerogel material.

Advantage of the present invention is: mesoporous TiO 2 aerogel material good hydrophilic property prepared by (1), has good selectivity and higher enrichment capacity to phosphated peptide section; (2) this preparation method is nontoxic; (3) this preparation method is easy, and step is few, favorable reproducibility.

Accompanying drawing explanation

Fig. 1 is hydrophilic titanium oxide aerogel scanning electron microscope (SEM) photograph (c) after the scanning electron microscope (SEM) photograph (a) of hydrophilic titanium oxide aerogel and transmission electron microscope picture (b) enriching phosphated peptide section.

Fig. 2 is nitrogen adsorption-desorption and the pore size distribution curve (illustration) of hydrophilic titanium oxide aerogel.

Phosphorylated protein (β-casein) mixes than 1:100 according to amount of substance with the trypsin digestion product of non-phosphorylating albumen (bovine serum albumin) by Fig. 3, mass spectrum comparison diagram (A, non-enrichment before and after the enrichment of gained mixture; B, after the enrichment of embodiment 1 gained wetting ability ZrO_2 aerogel) (phospho-peptide Yong ﹡ indicates, and the neutral phospho-peptide # lost occurs and indicates, be non-phosphopeptide without what indicate).

Embodiment

Prepare a kind of hydrophilic mesoporous titania aerogel material in accordance with the following steps.

Under room temperature, at the Ti (SO of 0.2 mol/L ₄) ₂dropwise drip ammoniacal liquor (10%, m/m) while stirring in solution, often drip 0.5 mL, by gained precipitation with purified water repetitive scrubbing to SO ₄ ^2-(with 0.1 mol/L Ba (NO when being detected as feminine gender ₃) ₂detect), obtain TiO ₂sol material.In above-mentioned sol material, add dehydrated alcohol start solvent exchange, add 2 times that dehydrated alcohol is sol volume at every turn, after replacing 6 times in 24 h, gained alcosol is put into supercritical extraction pond, carries out CO 2 supercritical drying.Drying conditions: Chi Wen 35 DEG C, pressure 8.0 MPa, flow rate pump is 1.5 mL/min, and slowly release fluids after dry 8 h, is cooled to room temperature and namely obtains hydrophilic mesoporous titania aerogel material.

application examples 1

With hydrophilic mesoporous titania aerogel material of the present invention for off-line phosphated peptide section material for trapping, to contain trifluoroacetic acid volume fraction for 5%, acetonitrile volume fraction be 50% the aqueous solution be loading buffer, can realize in 30 min phosphated peptide section in protein sample selectivity trapping.

Advantage of the present invention is: preparation method is easy, and step is few, and preparation process is nontoxic, the high and favorable reproducibility of security; Compared with the preparation method of other titania aerogel materials, present method gained titania aerogel material hydrophilic is strong, has very high specific enrichment ability, stable performance to phosphated peptide section.

Claims

1. a preparation method for hydrophilic mesoporous titania aerogel material, is characterized in that including following steps:

1) under room temperature, initial titanium source compound is water-soluble obtains homogeneous titanium source solution;

2) described titanium source solution and ammoniacal liquor react obtained TiO 2 sol in water;

3) wash TiO 2 sol and remove impurity;

4) anhydrous solvent is utilized to carry out solvent exchange to TiO 2 sol;

5) utilize supercutical fluid to carry out drying to TiO 2 sol, complete the preparation of mesoporous TiO 2 aerogel material.

2. according to preparation method according to claim 1, it is characterized in that, in (1) described step, initial titanium source compound is any one or more in the soluble inorganic such as titanium sulfate, titanium tetrachloride titanium salt; Described initial titanium source compound is water-soluble joins to obtain the homogeneous titanium source solution of 0.05-0.25 mol/L.

3. according to preparation method according to claim 1, it is characterized in that, in (2) described step, ammoniacal liquor mass concentration is 5-15%.

4. according to preparation method according to claim 1, it is characterized in that, in (2) described step, ammoniacal liquor dropwise need add in the titanium source solution stirred, and often drips 0.5-1.5 mL.

5. according to preparation method according to claim 1, it is characterized in that, need in (3) described step thoroughly to remove impurity with water repetitive scrubbing; If titanium source compound is that 0.1 mol/L Ba (NO then used by titanium sulfate ₃) ₂detect to SO in washings ₄ ^2-for feminine gender, can think that Impurity removal is thorough; If titanium source compound is that titanium tetrachloride then uses 0.1 mol/L AgNO ₃detect Cl in washings ^-for feminine gender, can think that Impurity removal is thorough.

6. according to preparation method according to claim 1, it is characterized in that, in (4) described step, anhydrous solvent is any one in dehydrated alcohol, anhydrous methanol, anhydrous propanone, and this solvent can dissolve each other with arbitrary proportion with water; The anhydrous solvent added during each solvent exchange is 1-5 times of TiO 2 sol volume, every displacement in 2-5 hour once.

7. according to preparation method according to claim 1, it is characterized in that, in (5) described step, supercutical fluid can be any one in carbonic acid gas, methyl alcohol, ethanol.

8. according to preparation method according to claim 1, it is characterized in that, described hydrophilic mesoporous titania aerogel material specific surface area is 200-500 m ²/ g, mean pore size is 10-20 nm.