CN102757092A - L-tryptophan molecular imprinted TiO2 powder and preparation method thereof - Google Patents
L-tryptophan molecular imprinted TiO2 powder and preparation method thereof Download PDFInfo
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- CN102757092A CN102757092A CN201210269493XA CN201210269493A CN102757092A CN 102757092 A CN102757092 A CN 102757092A CN 201210269493X A CN201210269493X A CN 201210269493XA CN 201210269493 A CN201210269493 A CN 201210269493A CN 102757092 A CN102757092 A CN 102757092A
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Abstract
The invention relates to an L-tryptophan molecular imprinted TiO2 powder and a preparation method thereof. The preparation method thereof comprises the following steps of: taking titanic alcoxyl compound as a sol precursor and alcohol as a solvent; preparing TiO2 sol imprinted with L-tryptophan template molecules by adopting a sol-gel method; hydrolyzing the sol; leaching; drying to obtain the TiO2 powder imprinted with L-tryptophan template molecules; and finally, adding ammonia water to wash the powder, removing L-tryptophan template molecules, and thus obtaining the powder. The powder can be used for directly separating a tryptophan optical isomer in a water phase, and racemic tryptophan can be effectively separated.
Description
Technical field
The present invention relates to molecular imprinting sol gel film field, particularly a kind of L-tryptophane molecular imprinting TiO
2Powder and preparation method thereof.
Background technology
Tryptophane is a kind of indispensable amino acid that constitutes protein molecule, and it has two kinds of optical isomers.The L-tryptophane is a human indispensable amino acid, the synthetic and metabolism network adjustment of participant's body protein, and the D-tryptophane then mainly is present in mikrobe and the green plants, and content is less in the animal, and in human body, metabolism takes place hardly.The L-tryptophane has obtained admitting widely that as the purposes of treatment pellagra, schizophrenia, nutrition medicament, indispensable amino acid sheet the D-tryptophane then has different pharmaceutical uses.Therefore, the optical isomer of fractionation tryptophane all has great importance in fields such as medicine, food, health.
Molecular imprinting (Molecular Imprinting Technique) is based on manual simulation's antibody-antigen and the specificity between enzyme-substrate identification and of growing up separates and analytical technology; In this technology, can form the hole that is complementary, has multiple action point with the template molecule space structure when contacting with polymer monomer when template molecule (microsphere), the hole that after template molecule is removed, stays will have the selectivity evident characteristics to template molecule and analogue thereof.In recent years, molecular imprinting has obtained paying close attention to widely in the application of separating optical isomeric body because of characteristics such as its affinity and selectivity are high, the anti-adverse environment ability is strong, good stability, long service life.
Molecular imprinting is applied to the existing report of amino acid separation optical isomer.Like (Glad M such as Glad; Reinholdsson P; Mosbach K.Molecularly imprinted composite polymers based on trimethylolpropane trimethacrylate (TRIM) Particles for efficient enantiomeric separations [J] React; Polym.1995 (25); 47 ~ 54.) through trimethoxy propane trimethyl acrylic ester (TRIM) and MAA crosslinking copolymerization, having prepared with tertbutyloxycarbonyl-L-phenylalanine(Phe) (N-Boc-L-Phe) is the molecular blotting polymer microsphere of template.Prepared MIPs only need remove template molecule and just can directly use, and has effectively kept recognition site and void structure, the corresponding raising of extracting and separating efficient.(Yoshikawa M such as Yoshika; Izumi J; Kitao J.Enantioselective electrodialysis of amino acids with charged polar side chains through molecularly imprinted polymeric membranes containing DIDE derivatives [J] Polymer; 1997 (29), 205 ~ 210.) utilizing tetrapeptide derivative binding film technology to prepare with the tert-butoxycarbonyl-l-l-tryptophan is the molecular imprinting polymer membrane of template.But owing to the amino acid major part is insoluble in the organic solvent, and most of molecularly imprinted polymer all is a synthetic under organic system, thus all be that amino acid whose verivate is carried out trace, and the imprinted polymer compound method is comparatively complicated.
The molecular imprinting sol gel film has been taken into account the two advantage of collosol and gel and molecular imprinting; The rigidity and the relatively poor shortcoming of inertia of molecular imprinting organic polymer have been overcome; And some water miscible biomacromolecules are had good trace effect, adopt the collosol and gel molecular imprinting, (Seung-Woo Lee such as Lee; Do-Hyeon Yang, Toyoki Kunitake.Regioselective imprinting of anthracene carboxylic acids onto TiO
2Gel ultrathin films:an approach to thin film sensor [J] .Sensors and Actuators B, 2005 (104), 35 ~ 42.) at TiO
2The film surface trace several kinds of carboxylic acids, its selective separation coefficient has reached 1.7.Experiment shows inorganic nano material TiO
2Be a kind of good molecular engram material, have the big and advantages such as favorable mechanical stability and thermostability of specific surface area, be applicable to biomolecules such as amino acid are carried out imprinted material.But owing to be so that thin-film material also has adsorptive capacity little, film shortcoming such as be prone to come off.For overcoming this shortcoming, be necessary to seek a kind of direct fast and effectively amino acid whose method of trace.
Summary of the invention
The technical problem that the present invention will solve provide a kind of can be directly at the TiO of aqueous phase separating tryptophane optical isomer
2Powder and preparation method thereof utilizes this powder that racemic tryptophane is effectively separated.
In order to address the above problem, the technical scheme that the present invention adopts is:
A kind of L-tryptophane molecular imprinting TiO
2Powder, this TiO
2Powder have with the L-tryptophane on space structure, be close to coupling and can with the three-D space structure of L-tryptophane selective binding.The preparation method of this powder carries out according to following steps:
(1) TiO of trace L-tryptophane template molecule
2The preparation of colloidal sol
Adopting sol-gel method, is that the alkyl oxide and the L-tryptophane template molecule of the titanium of 1:0.015 ~ 0.18 joins in the 500mL alcoholic solvent with mass ratio, stirs solid is all dissolved, and continues to stir 24h, makes the TiO that trace has L-tryptophane template molecule
2Colloidal sol;
(2) TiO of trace L-tryptophane template molecule
2The preparation of powder
The trace that step (1) is obtained has the TiO of L-tryptophane template molecule
2Colloidal sol is the mixed stirring 24h of 1:5.88 according to the alkyl oxide of titanium and the mass ratio of water, with promptly obtaining the TiO that trace has L-tryptophane template molecule after the white precipitate suction filtration that obtains, the oven dry
2Powder;
(3) L-tryptophane template molecule removes
The trace that step (2) is obtained has the TiO of L-tryptophane template molecule
2It is fluorescence spectrum not absorption at 350nm place that 1% ammonia soln is eluted to its supernatant liquid that powder uses volume ratio, collects this powder, and to neutrality, 60 ℃ of oven dry promptly obtain having the TiO of L-tryptophane molecular imprinting with deionized water wash
2Powder.
As to qualification of the present invention, the alkyl oxide of the titanium described in the step (1) is a tetra-n-butyl titanate, and described alcoholic solvent is an absolute ethyl alcohol.
In order to construct TiO effectively with L-tryptophane molecule casting mold
2Powder, the mass ratio of the alkyl oxide of titanium and L-tryptophane is 1:0.015 ~ 0.18, when both mass ratioes are higher than 1:0.015, at TiO
2Powder on can not construct the casting mold of L-tryptophane molecule effectively, both mass ratioes are not only wasted too much L-tryptophane during less than 1:0.18, influence TiO equally
2The casting mold of L-tryptophane molecule on the powder, the optimum quality ratio of the alkyl oxide of titanium and L-tryptophane: 1:0.05 ~ 0.15.
Principle of the present invention such as Figure of description are shown in Figure 1, and carboxylic acid group on tetra-n-butyl titanate and the tryptophane and amino hydrogen bonded are wrapped in the template molecule tryptophane in the network structure of colloidal sol, add water and make the tetra-n-butyl titanate hydrolysis generate TiO
2Behind the powder, TiO
2In the Ti-O bond polarity bigger; The water of surface adsorption dissociates because of polarization; Form hydroxyl, carboxyl and the amino hydrogen bond that forms with on the tryptophane are wrapped in tryptophane in the structure of Ti-O-Ti; Can stay the hole that is complementary with template molecule after template molecule is removed and form specific recognition site, thereby reach the purpose that selectivity is discerned.
The present invention is with inorganic materials TiO
2Be trace monomer synthetic molecules trace compound, realized that under aqueous systems to the fractionation of two kinds of optical isomers of tryptophane, powder body material has improved adsorptive capacity greatly, makes it at the chiral separation packed column, there is good prospects for application aspects such as transmitter.
Description of drawings
Below in conjunction with accompanying drawing the present invention is further specified.
Fig. 1 is L-tryptophane molecular imprinting TiO
2The preparation flow figure of powder, wherein a is the structure of L-tryptophane, and b is the structure of positive four butyl esters of metatitanic acid, and c is the TiO of trace L-tryptophane template molecule
2The structure of colloidal sol, d is the TiO of trace L-tryptophane template molecule
2The structure of powder, e is the TiO with L-tryptophane molecular imprinting
2The structure of powder, T is a template molecule L-tryptophane.
Embodiment
Combine embodiment that the present invention is done further detailed explanation now.
Embodiment 1
(1) TiO of trace L-tryptophane template molecule
2The preparation of colloidal sol
Take by weighing in 1.28g L-tryptophane, the 85.0g tetra-n-butyl titanate adding 500mL absolute ethyl alcohol, stirring is all dissolved solid, continues to stir 24h, and amino acid is fully combined with tetra-n-butyl titanate, obtains the TiO of trace L-tryptophane template molecule
2Colloidal sol;
(2) TiO of trace L-tryptophane template molecule
2The preparation of powder
The trace that step (1) is obtained has the TiO of L-tryptophane template molecule
2Colloidal sol is the mixed stirring 24h of 1:5.88 according to the alkyl oxide of titanium and the mass ratio of water, with promptly obtaining the TiO that trace has L-tryptophane molecule after the white precipitate suction filtration that obtains, the oven dry
2Powder;
(3) L-tryptophane template molecule removes
The trace that step (2) is obtained has the TiO of L-tryptophane molecule
2Powder use volume ratio is 1% ammonia soln wash-out, in order to guarantee to remove effectively tryptophane, can washings be used 0.5molL
-1HCl regulate pH to 6 ~ 7, to fluorescence spectrum not absorption of its supernatant liquid, collect this powder at 350nm place, to neutrality, 60 ℃ of oven dry promptly obtain having the TiO of L-tryptophane molecular imprinting with deionized water wash
2Powder.
In order to estimate TiO with L-tryptophane casting mold
2Powder is to the separating effect of L-tryptophane and D-tryptophane, and the present invention uses the TiO with L-tryptophane casting mold
2Powder is weighed the variation of tryptophane solution fluorescence intensity before and after L-tryptophane and the D-tryptophane solution absorbs respectively, and concrete measuring method is to take by weighing the TiO with L-tryptophane molecular imprinting that two parts of quality are 0.10g
2Powder places the concentration of 30mL pH=6 to be 0.1mmolL respectively
-1The aqueous solution of L-tryptophane and D-tryptophane in, behind the whip attachment 4h,, calculate selective separation coefficient (α) simultaneously with fluorescent spectrophotometer assay adsorptive capacity (excitation wavelength measured of tryptophane is 282nm, and emission wavelength is 350nm).
The selective separation coefficient be defined as α=(m
1-m
2)/(m
3-m
4), m wherein
1, m
2Expression L-tryptophane adsorbs the quality after preceding and the absorption, m
3, m
4Expression D-tryptophane adsorbs the quality after preceding and the absorption, is that index is estimated the selectivity of trace powder with the selective separation coefficient.Concrete outcome is as shown in table 1: measure the TiO that this instance has L-tryptophane molecular imprinting
2Powder is 3.19mg/g to the adsorptive capacity of L-tryptophane, and the adsorptive capacity of D-tryptophane is 2.29mg/g, and the selective separation alpha is 1.39.
Embodiment 2
L-tryptophane add-on among the embodiment 1 is changed into 2.55g, and all the other conditions are all identical with embodiment 1.Measure the TiO that present embodiment makes with L-tryptophane molecular imprinting
2Powder is 3.06mg/g to the adsorptive capacity of L-tryptophane, is 1.89mg/g to the adsorptive capacity of D-tryptophane, and the selective separation alpha is 1.62, and is as shown in table 1.
Embodiment 3
L-tryptophane add-on among the embodiment 1 is become 5.10g, and all the other conditions are all identical with embodiment 1.Measure the TiO that present embodiment makes with L-tryptophane molecular imprinting
2Powder is 2.90mg/g to the adsorptive capacity of L-tryptophane, is 1.60mg/g to the adsorptive capacity of D-tryptophane, and the selective separation alpha is 1.82, and is as shown in table 1.
L-tryptophane add-on among the embodiment 1 is become 10.2g, and all the other conditions are all identical with embodiment 1.Measure the TiO that present embodiment makes with L-tryptophane molecular imprinting
2Powder is 2.73mg/g to the adsorptive capacity of L-tryptophane, is 1.13mg/g to the adsorptive capacity of D-tryptophane, and the selective separation alpha is 2.42, and is as shown in table 1.
Embodiment 5
L-tryptophane add-on among the embodiment 1 is become 12.8g, and all the other conditions are all identical with embodiment 1.Measure the TiO that present embodiment makes with L-tryptophane molecular imprinting
2Powder is 2.64mg/g to the adsorptive capacity of L-tryptophane, is 1.32mg/g to the adsorptive capacity of D-tryptophane, and the selective separation alpha is 2.00, and is as shown in table 1.
Embodiment 6
L-tryptophane add-on among the embodiment 1 is become 15.3g, and all the other conditions are all identical with embodiment 1.Measure the TiO that present embodiment makes with L-tryptophane molecule casting mold
2Powder is 2.52mg/g to the adsorptive capacity of L-tryptophane, is 1.42mg/g to the adsorptive capacity of D-tryptophane, and the selective separation alpha is 1.77, and is as shown in table 1.
Comparative example 1
L-tryptophane add-on among the embodiment 1 is become 0g, and all the other conditions are all identical with embodiment 1.The non-trace powder that the mensuration present embodiment makes is 1.14mg/g to the adsorptive capacity of L-tryptophane, and the adsorptive capacity of D-tryptophane is 1.05mg/g, and selectivity coefficient α is 1.09, and is as shown in table 1.
Table 1 preparation L-tryptophane molecular imprinting TiO
2The material quantity of powder reaches the selective separation coefficient to the L-tryptophane
Claims (4)
1. L-tryptophane molecular imprinting TiO
2Powder is characterized in that this TiO
2Powder have with the L-tryptophane on space structure, be close to coupling and can with the three-D space structure of L-tryptophane selective binding.
2. a kind of L-tryptophane molecular imprinting TiO as claimed in claim 1
2The preparation method of powder is characterized in that this method carries out according to following steps:
(1) TiO of trace L-tryptophane template molecule
2The preparation of colloidal sol
Adopting sol-gel method, is that the alkyl oxide and the L-tryptophane template molecule of the titanium of 1:0.015 ~ 0.18 joins in the 500mL alcoholic solvent with mass ratio, stirs solid is all dissolved, and continues to stir 24h, obtains the TiO that trace has L-tryptophane template molecule
2Colloidal sol;
(2) TiO of trace L-tryptophane template molecule
2The preparation of powder
The trace that step (1) is obtained has the TiO of L-tryptophane template molecule
2Colloidal sol is the mixed stirring 24h of 1:5.88 according to the alkyl oxide of titanium and the mass ratio of water, with promptly obtaining the TiO that trace has L-tryptophane template molecule after the white precipitate suction filtration that obtains, the oven dry
2Powder;
(3) L-tryptophane template molecule removes
The trace that step (2) is obtained has the TiO of L-tryptophane template molecule
2It is fluorescence spectrum not absorption at 350nm place that 1% ammonia soln is eluted to its supernatant liquid that powder uses volume ratio, collects this powder, and to neutrality, 60 ℃ of oven dry promptly obtain having the TiO of L-tryptophane molecular imprinting with deionized water wash
2Powder.
3. a kind of L-tryptophane molecular imprinting TiO as claimed in claim 2
2The preparation method of powder, the alkyl oxide that it is characterized in that described titanium is a tetra-n-butyl titanate, described alcoholic solvent is an absolute ethyl alcohol.
4. a kind of L-tryptophane molecular imprinting TiO as claimed in claim 2
2The preparation method of powder is characterized in that the alkyl oxide of titanium and the optimum quality ratio of L-tryptophane are 1:0.05 ~ 0.15.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664901A (en) * | 2016-02-22 | 2016-06-15 | 河南师范大学 | Preparation method of targeted titanium dioxide catalyst |
| WO2022224772A1 (en) * | 2021-04-23 | 2022-10-27 | 日産化学株式会社 | Method for producing titanium oxide particles using amphoteric substance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008104467A1 (en) * | 2007-02-27 | 2008-09-04 | Basf Se | Method of forming a (rutile) titanium dioxide-coated platelet-like pigment |
| CN101264928A (en) * | 2008-04-23 | 2008-09-17 | 华中师范大学 | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface thereof functionalization |
| CN101624188A (en) * | 2008-07-09 | 2010-01-13 | 东丽纤维研究所（中国）有限公司 | Nanometer silicon dioxide and titanium dioxide compound microparticle and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008104467A1 (en) * | 2007-02-27 | 2008-09-04 | Basf Se | Method of forming a (rutile) titanium dioxide-coated platelet-like pigment |
| CN101264928A (en) * | 2008-04-23 | 2008-09-17 | 华中师范大学 | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface thereof functionalization |
| CN101624188A (en) * | 2008-07-09 | 2010-01-13 | 东丽纤维研究所（中国）有限公司 | Nanometer silicon dioxide and titanium dioxide compound microparticle and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 范浩军等: "纳米级TiO2或SiO2的鞣革机理及鞣性的研究", 《皮革科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664901A (en) * | 2016-02-22 | 2016-06-15 | 河南师范大学 | Preparation method of targeted titanium dioxide catalyst |
| WO2022224772A1 (en) * | 2021-04-23 | 2022-10-27 | 日産化学株式会社 | Method for producing titanium oxide particles using amphoteric substance |
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