CN104495916A - Aminated nanometer titanium dioxide and its preparation method and use - Google Patents
Aminated nanometer titanium dioxide and its preparation method and use Download PDFInfo
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Abstract
The invention discloses aminated nanometer titanium dioxide and its preparation method and use. The preparation method comprises the following steps of a, mixing amino acids and an ethidene diamine solution to obtain an amino acid solution, and b, mixing tetrabutyl titanate and the amino acid solution to cause a contact reaction so that the aminated nanometer titanium dioxide is obtained by the reaction. Enzyme can be stably fixed to the surface of nanometer titanium dioxide so that the aminated nanometer titanium dioxide can be widely used in immobilized enzyme carriers. The preparation method of the aminated nanometer titanium dioxide has simple processes and adopts the easily available raw materials.
Description
Technical field
The present invention relates to nano titanium oxide, particularly, relate to a kind of amination nano titanium oxide and preparation method thereof, and this amination nano titanium oxide application in fixed enzyme vector.
Background technology
Function macromole is grafted on inorganic particulate surface, is the important channel of the functional composite particles of preparation at present.At inorganic (micron order and nano level) microparticle surfaces grafting functional macromole, make the macromolecular functional excellent mechanical properties with inorganic particles of function, heat combines with chemical stability, can give particle many new characteristics, as amphipathic, photosensitivity, biological activity, chemically reactive, dispersibility, absorption property and the chelating ability etc. to metal ion, chromatographic stationary phases can be widely used in, heterogeneous catalysis, enzyme immobilizatio, the separation of biomacromolecule, numerous scientific research and the practical application area such as the activeness and quietness of Novel adsorption parting material and plastics.
Nano-TiO
2a kind of research nano material comparatively early, because its specific surface area is large, surfactivity is higher, weathering resistance and the feature such as erosion resistance is good, uvioresistant ability is strong and be widely used in coating, makeup, catalyzer, sensitive materials, food product pack, environment-friendly engineering, medicine and other fields.In recent years, along with the development of nanotechnology, genetically engineered, proteomics, it is found that nano-TiO
2finishing be increase the basis of its applicability.At present, basis and Application Areas to nano-TiO
2do large quantity research, found because titanium dioxide surface contains a large amount of oh groups, make it be easy to, with other functional groups, association reaction occurs, thus the obtained functional nano TiO of surface containing several functions group
2particle, so just can carry out nano-TiO
2functionalization, fixing, and carry out the surface reaction etc. of other complexity, make it have applicability more widely.
Sintered glass, porous silicon ball, aluminum oxide and diatomite are current widely used inorganic carriers, but they are in the activation for needing during immobilized enzyme through strong acid or highly basic, in toluene, silanization is carried out in long-time backflow again, and the preparation process of carrier is loaded down with trivial details.Simultaneously nano titanium oxide is widely used in multiple enzyme immobilizatio due to its advantage such as good biocompatibility, larger specific surface area.But in most cases, enzyme is after being fixed to nano-carrier, and its catalysis activity all has reduction in various degree.
Summary of the invention
The object of this invention is to provide preparation method and this amination nano titanium oxide application in fixed enzyme vector of a kind of amination nano titanium oxide and this amination nano titanium oxide.The surface of this nano titanium oxide has abundant amino, thus makes this amination nano titanium oxide can widespread use in fixed enzyme vector; The step simultaneously preparing this amination nano titanium oxide is simple, and raw material is easy to get.
By research, the present inventor finds that the amino on inorganic carrier surface can not only play the effect in fixing site; the function simultaneously playing the enzyme that protection inorganic carrier adsorbs can avoid the destruction to enzyme molecule native conformation such as alkaline catalysts, high-speed stirring and high temperature to make enzyme, is conducive to the maintenance of the activity of enzyme.How empty the surface amino groups density of many empty glass, silicon ball and pure nano titanium oxide is all lower, therefore the present inventor carries out amido modified preparation amination nano titanium oxide on the surface of nano titanium oxide, abundant amino is just had to serve as fixing site to make amination nano titanium oxide surface, simultaneously in order to keep the activity of enzyme, thus this amination nano titanium oxide can be used as efficient fixed enzyme vector.
To achieve these goals, the invention provides a kind of preparation method of amination nano titanium oxide, described preparation method comprises:
A, Methionin and ethylenediamine solution are mixed with the operation of obtained lysine solution mutually;
B, tetrabutyl titanate mixed with described lysine solution and contact reacts with the operation of obtained amination nano titanium oxide.
Present invention provides a kind of amination nano titanium oxide, described amination nano titanium oxide is prepared from by above-mentioned preparation method.
Present invention also offers the above-mentioned application of amination nano titanium oxide in fixed enzyme vector.
By technique scheme, the present invention by water heat transfer nano titanium oxide, and directly carries out amination and modifies and obtain amination nano titanium oxide on the surface of nano titanium oxide.The amino density on the surface of this amination nano titanium oxide can up to 3mmolg
-1, thus this amination nano titanium oxide can be used as fixed enzyme vector completely.The preparation method of this nano titanium oxide is one step hydro thermal method simultaneously, and step is simple, and only needs solvent wash simply just can purify.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the result statistical graph of the amino content on each nano titanium oxide surface in test example 1;
Fig. 2 is the FT-IR collection of illustrative plates of amination nano titanium oxide A1 and nano titanium oxide B1 in test example 2;
Fig. 3 is the SEM figure of nano titanium oxide B1 under amplification 30,000 times in test example 3;
Fig. 4 is the SEM figure of nano titanium oxide B1 under amplification 100,000 times in test example 3;
Fig. 5 is the SEM figure of amination nano titanium oxide A1 under amplification 30,000 times in test example 3;
Fig. 6 is the SEM figure of amination nano titanium oxide A1 under amplification 100,000 times in test example 3;
Fig. 7 is the Tg figure of amination nano titanium oxide A1 and nano titanium oxide B1 in test example 3.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of amination nano titanium oxide, described preparation method comprises:
A, Methionin and ethylenediamine solution are mixed with the operation of obtained lysine solution mutually;
B, tetrabutyl titanate mixed with described lysine solution and contact reacts with the operation of obtained amination nano titanium oxide.
Methionin, quadrol and tetrabutyl titanate, in ethylenediamine solution, are directly carried out contact reacts by one pot of hydrothermal method by aforesaid method, and obtained surface is formed with a large amount of amino nano titanium oxide.The amino on this amination nano titanium oxide surface can as the fixing site of immobilized enzyme, thus make this amination nano titanium oxide stably can play effect of immobilized enzyme, namely this amination nano titanium oxide can use as efficient fixed enzyme vector completely.
In the present invention, the consumption of each reactant can change in wide scope, and the consumption of the quadrol namely in tetrabutyl titanate, Methionin and ethylenediamine solution can be selected in wide scope.In order to make the density on the surface of described nano titanium oxide larger, preferably, relative to the tetrabutyl titanate of 100 weight parts, the consumption of described Methionin is 2-20 weight part, and the consumption of the quadrol in described ethylenediamine solution is 20-300 weight part.More preferably, relative to the tetrabutyl titanate of 100 weight parts, the consumption of described Methionin is 5-15 weight part, and the consumption of the quadrol in described ethylenediamine solution is 80-210 weight part.
In step a, ethylenediamine solution used can be now with the current, also can be commercially available ethylenediamine solution.Consider quadrol can with water vapour volatilization and easily from air absorbing carbon dioxide generate nonvolatile carbonate, preferably, ethylenediamine solution used is now with the current, and namely before step a, described preparation method also comprises quadrol and solvent with the operation of obtained ethylenediamine solution.
In the embodiment that ethylenediamine solution used is now with the current, the solvent in described ethylenediamine solution is water, and relative to the tetrabutyl titanate of 100 weight parts, the consumption of described solvent is 700-1000 weight part.
In addition, in order to improve the productive rate of amination nano titanium oxide, preferably, described catalytic temperature of reaction is 100-120 DEG C, and the described catalytic reaction times is 10-12h.
Meanwhile, present invention provides a kind of amination nano titanium oxide, described amination nano titanium oxide is prepared from by above-mentioned preparation method.
In addition, present invention also offers the above-mentioned application of amination nano titanium oxide in fixed enzyme vector.From the above, the amino density on surface can up to 3mmolg
-1nano titanium oxide can serve as completely fixed enzyme vector use.
Below will be described the present invention by embodiment.In following examples, the detection method of amino density parameter is: get W
0g nano-TiO
2at V
1mLN
1more than the standard HCl solution soaking 3h of mol/L, then rinses the nano-TiO after bubble with water
2and collect washing lotion, and use N
2mol/L standard NaOH solution carries out back titration, spends standard NaOH solution V
2mL, calculates amino content (A, mmol/g) with following formula: A=(N
1v
1-N
2v
2)/W
0; Fourier transform infrared spectroscopy parameter (FT-IR) is recorded by the IRPrestige-21 FTIR technique instrument of Japanese Shimadzu; Scanning electron microscope (SEM) spectrogram is recorded by the S-4800 scanning electronic microscope instrument of FDAC; Thermogravimetry parameter (Tg figure) is recorded by the DSC6200 Thermal Synthetic Analysis instrument of NSK Electronics Co., Ltd..
Methionin is the Hui Xing biochemical reagents company limited trade mark is the commercially available product of 62016734, tetrabutyl titanate to be Chemical Reagent Co., Ltd., Sinopharm Group's trade mark be 80122828 commercially available product, quadrol is the Shanghai Ling Feng chemical reagent company limited trade mark is the commercially available product of 10009518.
Embodiment 1
Anhydrous ethylenediamine is dissolved in be made into after mixing in distilled water 30mL ethylenediamine solution (
wherein quadrol 5g, water 25g), then the Methionin of 0.4g to be added in above-mentioned ethylenediamine solution and to mix formation lysine solution, then positive for 3mL (3g) metatitanic acid four butyl esters are stirred 30min forming reactions solution, and reaction soln is placed in polytetrafluoroethyllining lining inner bag stainless steel cauldron, at 100 DEG C, carries out hydro-thermal reaction be precipitated; Finally by throw out collected by centrifugation, and successively with the cleaning of distilled water, dehydrated alcohol and distilled water, and in 60 DEG C of dry 10h, obtain amination nano titanium oxide A1.
The amino content of this amination nano titanium oxide is 3mmolg
-1.
Embodiment 2
Carry out according to the method for embodiment 1, difference is Methionin is 0.3g, obtained amination nano titanium oxide A2.
The amino content of this amination nano titanium oxide is 2.7mmolg
-1.
Embodiment 3
Carry out according to the method for embodiment 1, difference is Methionin is 0.5g, obtained amination nano titanium oxide A3.
The amino content of this amination nano titanium oxide is 2.8mmolg
-1.
Embodiment 4
Carry out according to the method for embodiment 1, difference is Methionin is 0.2g, obtained amination nano titanium oxide A4.
The amino content of this amination nano titanium oxide is 2.5mmolg
-1.
Embodiment 5
Carry out according to the method for embodiment 1, difference is Methionin is 0.7g, obtained amination nano titanium oxide A5.
The amino content of this amination nano titanium oxide is 2.3mmolg
-1.
Embodiment 6
Carry out according to the method for embodiment 1, difference is the volume ratio of quadrol and water in 30mL ethylenediamine solution is 0.5:5.5, obtained amination nano titanium oxide A6.
The amino content of this amination nano titanium oxide is 2.0mmolg
-1.
Embodiment 7
Carry out according to the method for embodiment 1, difference is the volume ratio of quadrol and water in 30mL ethylenediamine solution is 0.75:5.25, obtained amination nano titanium oxide A7.
The amino content of this amination nano titanium oxide is 2.4mmolg
-1.
Embodiment 8
Carry out according to the method for embodiment 1, difference is the volume ratio of quadrol and water in 30mL ethylenediamine solution is 1.25:4.75, obtained amination nano titanium oxide A8.
The amino content of this amination nano titanium oxide is 2.6mmolg
-1.
Embodiment 9
Carry out according to the method for embodiment 1, difference is catalytic temperature is 120 DEG C, obtained amination nano titanium oxide A9.
The amino content of this amination nano titanium oxide is 2.5mmolg
-1.
Comparative example 1
Carry out according to the method for embodiment 1, difference does not add Methionin, obtained nano titanium oxide B1.
The amino content of this amination nano titanium oxide is 1mmolg
-1.Illustrate in reaction system and do not add Methionin, the amino content on nano titanium oxide surface is extremely low, and this nano titanium oxide is difficult to use as efficient fixed enzyme vector.
Comparative example 2
Carry out according to the method for embodiment 1, difference does not add anhydrous ethylenediamine, obtained nano titanium oxide B2.
The amino content of this amination nano titanium oxide is 1.7mmolg
-1.Illustrate in reaction system and do not add anhydrous ethylenediamine, the amino content on nano titanium oxide surface is extremely low, and this nano titanium oxide is difficult to use as efficient fixed enzyme vector.
Test example 1
Amination nano titanium oxide A1-A5 and nano titanium oxide B1 is carried out the detection of amino content, detected result is shown in Fig. 1.As shown in Figure 1, the content of Methionin on the amino on nano titanium oxide surface has vital impact, if do not add Methionin in reaction system, this nano titanium oxide cannot use as efficient fixed enzyme vector.Meanwhile, the consumption of Methionin is at 0.3-0.5g, and especially during 0.4g, the content of the amino on nano titanium oxide surface is maximum.This is that the existence due to Methionin is unfavorable for the synergy of anhydrous ethylenediamine and titanate due to when the consumption of Methionin is too much, have impact on the forming process of nano titanium oxide, thus causes the content of the amino on nano titanium oxide surface not high; When the consumption of Methionin is very few, in system, lack the NH of positively charged
4 +assemble with electronegative nano titanium oxide, thus cause the content of the amino on nano titanium oxide surface not high.
Test example 2
Amination nano titanium oxide A1 and nano titanium oxide B1 is carried out FT-IR detection, the results are shown in Figure 2, wherein: a curve is the infrared spectrum of nano titanium oxide A1, b curve is the infrared spectrum of nano titanium oxide B1.As shown in Figure 2, be 1400cm in wave number
-1, amination nano titanium oxide A1 has strong absorption to infrared light, thus illustrates that amino functional is rolled into a ball and is successfully connected on nano titanium oxide surface.
Test example 3
Amination nano titanium oxide A1 and nano titanium oxide B1 is carried out SEM detection respectively under amplification 30,000 times and 100,000 times, the results are shown in Figure 3-Fig. 6.Fig. 3 and Fig. 4 is the SEM figure of nano titanium oxide B1 under amplification 30,000 times and 100,000 times respectively, from these two figure, and the arrangement in the form of sheets of nano titanium oxide B1, but this arrangement mode is comparatively chaotic, and these nanometer sheet thickness are 40-70nm.Fig. 5 and Fig. 6 is the SEM figure of amination nano titanium oxide A1 under amplification 30,000 times and 100,000 times respectively, from these two figure, amination nano titanium oxide A1 is regular Palta type dense arrangement, and the thickness of these nanometer sheet is at about 10nm, and wherein thinnest part reaches 7nm.
Those skilled in the art know that nanometer sheet is more thin more can carry more enzyme, the thickness of nanometer sheet thus analyzes visible nano titanium oxide B1 and is not suitable as fixed enzyme vector, and amination nano titanium oxide A1 has the prospect as fixed enzyme vector.Go up known from another point of view, Methionin has the impact of outbalance to the growth of nano titanium oxide and the formation of pattern.
Test example 4
Amination nano titanium oxide A1 and nano titanium oxide B1 is carried out Tg detection respectively, the results are shown in Figure 7, wherein, a is the Tg curve of nano titanium oxide B1, and b is the Tg curve of amination nano titanium oxide A1.
As known in the figure, a curve linearly declined before 400 DEG C, and mass loss is serious, and after 400 DEG C, along with the rising of temperature, nano titanium oxide B1 almost keeps constant.B curve linearly declined before 400 DEG C, and mass loss is serious, and mass loss is 35.90%; Between 400-500 DEG C, there is a constant weight phase; Between 500-600 DEG C, mass loss is serious; After 600 DEG C, along with the rising of temperature, nano titanium oxide B1 keeps constant.Wherein, the mass loss between 500-600 DEG C 1.50% is that the amino on amination nano titanium oxide A1 surface and the thermolysis of hydroxyl cause, thus indirectly describes amination nano titanium oxide A1 rich surface containing amino and hydroxyl.
From embodiment and comparative example, the nano titanium oxide rich surface made by hydrothermal method under the synergy of Methionin, quadrol and titanate contains amino, can use as efficient fixed enzyme vector.
More than describe the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. a preparation method for amination nano titanium oxide, is characterized in that, described preparation method comprises:
A, Methionin and ethylenediamine solution are mixed with the operation of obtained lysine solution mutually;
B, tetrabutyl titanate mixed with described lysine solution and contact reacts with the operation of obtained amination nano titanium oxide.
2. the preparation method of amination nano titanium oxide according to claim 1, wherein, relative to the tetrabutyl titanate of 100 weight parts, the consumption of described Methionin is 2-20 weight part, and the consumption of the quadrol in described ethylenediamine solution is 20-300 weight part.
3. the preparation method of amination nano titanium oxide according to claim 2, wherein, relative to the tetrabutyl titanate of 100 weight parts, the consumption of described Methionin is that 5-15 measures part, and the consumption of the quadrol in described ethylenediamine solution is 80-210 weight part.
4. the preparation method of the amination nano titanium oxide according to any one in claim 1-3, wherein, before step a, described preparation method also comprises quadrol and solvent with the operation of obtained ethylenediamine solution.
5. the preparation method of amination nano titanium oxide according to claim 4, wherein, described solvent is water, and relative to the tetrabutyl titanate of 100 weight parts, the consumption of described solvent is 700-1000 weight part.
6. the preparation method of the amination nano titanium oxide according to any one in claim 1-3, wherein, described catalytic temperature of reaction is 100-120 DEG C, and the described catalytic reaction times is 10-12h.
7. an amination nano titanium oxide, is characterized in that, described amination nano titanium oxide is prepared from by the preparation method described in any one in claim 1-6.
8. the application of amination nano titanium oxide according to claim 7 in fixed enzyme vector.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943557A (en) * | 2019-03-20 | 2019-06-28 | 江西师范大学 | A kind of preparation method of immobilization chitosan enzyme and its carrier |
| CN113355317A (en) * | 2021-04-23 | 2021-09-07 | 上海师范大学 | High-efficiency enzyme immobilization method |
| CN113546091A (en) * | 2021-09-08 | 2021-10-26 | 常州市妇幼保健院 | Titanium dioxide compound with anti-tumor effect |
| CN115506536A (en) * | 2022-09-21 | 2022-12-23 | 中岩装配式建筑设计施工淮安有限公司 | Lightweight reinforced ceramsite concrete wallboard and preparation process thereof |
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| CN103030176A (en) * | 2012-12-08 | 2013-04-10 | 安徽工程大学 | Synthesizing method for controlling change of morphology and crystal form of nanoscale titanium dioxide |
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| 曹宁: ""纳米TiO2仿生合成及其固载脂肪酶的界面特性研究"", 《中国优秀硕士学位论文全文数据库 （电子期刊）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943557A (en) * | 2019-03-20 | 2019-06-28 | 江西师范大学 | A kind of preparation method of immobilization chitosan enzyme and its carrier |
| CN113355317A (en) * | 2021-04-23 | 2021-09-07 | 上海师范大学 | High-efficiency enzyme immobilization method |
| CN113546091A (en) * | 2021-09-08 | 2021-10-26 | 常州市妇幼保健院 | Titanium dioxide compound with anti-tumor effect |
| CN115506536A (en) * | 2022-09-21 | 2022-12-23 | 中岩装配式建筑设计施工淮安有限公司 | Lightweight reinforced ceramsite concrete wallboard and preparation process thereof |
| CN115506536B (en) * | 2022-09-21 | 2023-09-26 | 中岩装配式建筑设计施工淮安有限公司 | Lightweight reinforced ceramsite concrete wallboard and preparation process thereof |
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