CN102757092B - 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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- CN102757092B CN102757092B CN201210269493.XA CN201210269493A CN102757092B CN 102757092 B CN102757092 B CN 102757092B CN 201210269493 A CN201210269493 A CN 201210269493A CN 102757092 B CN102757092 B CN 102757092B
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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 engram sol gel film field, particularly a kind of L-Trp molecular engram TiO
2powder and preparation method thereof.
Background technology
Tryptophan is a kind of essential amino acid that forms protein molecule, and it has two kinds of optical isomers.L-Trp is the essential amino acid of human body, and participant's body protein is synthetic to be regulated with metabolism network, and D-trp is mainly present in microorganism and green plants, and in animal, content is less, and in human body, metabolism occurs hardly.L-Trp obtained admitting widely as the purposes for the treatment of bark favus, schizophrenia, nutrition medicament, essential amino acid sheet, and D-trp has different medical values.Therefore, the optical isomer of fractionation tryptophan all has great importance in fields such as medicine, food, health.
Molecular imprinting (Molecular Imprinting Technique) is that the specific recognition between antibody-antigen and the enzyme-substrate based on manual simulation and grow up one separate and analytical technology, in this technology, in the time that template molecule (microsphere) contacts with polymer monomer, can form the hole that matches, has multiple action point with template molecule space structure, the hole staying after template molecule is removed will have selective evident characteristics to template molecule and analog thereof.In recent years, molecular imprinting has obtained paying close attention to widely because of features such as its compatibility and selective high, anti-adverse environment ability strong, good stability, long service life in the application of separating optical isomeric body.
Molecular imprinting is applied to amino acid separation optical isomer and has been reported.As (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.) by trimethoxy propane trimethyl acrylic ester (TRIM) and MAA crosslinking copolymerization, prepared the molecular blotting polymer microsphere take tertbutyloxycarbonyl-L-Phe (N-Boc-L-Phe) as template.Prepared MIPs only needs to remove template molecule and just can directly apply, and has effectively retained recognition site and void structure, the corresponding raising of extract and separate efficiency.(the 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.) utilize tetrapeptide derivative binding film technology to prepare the molecular imprinting polymer membrane take tert-butoxycarbonyl-l-l-tryptophan as template.But because amino acid major part is insoluble in organic solvent, and most of molecularly imprinted polymer is all synthetic under organic system, thus be all that amino acid whose derivative is carried out to trace, and imprinted polymer synthetizing method is comparatively complicated.
Molecular engram sol gel film has been taken into account the two advantage of collosol and gel and molecular engram, overcome the poor shortcoming of the rigidity of molecular engram organic polymer and inertia, and some water miscible large biological molecules are had to good trace effect, adopt collosol and gel molecular imprinting, (the 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
2film surface trace several carboxylic acids, its Selective Separation coefficient has reached 1.7.Experiment shows inorganic nano material TiO
2be a kind of well molecular engram material, there is the large and good advantage such as mechanical stability and heat endurance of specific area, be applicable to the biomolecule such as amino acid to carry out imprinted material.But owing to being so that thin-film material also has adsorbance little, the film shortcoming such as easily come off.For overcoming this shortcoming, be necessary to seek the one direct amino acid whose method of trace fast and effectively.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of directly TiO of separating tryptophane optical isomer in water
2powder and preparation method thereof, utilizes this powder can make racemic tryptophan effectively separate.
In order to address the above problem, the technical solution used in the present invention is:
A kind of L-Trp molecular engram TiO
2powder, this TiO
2powder have be close on space structure with L-Trp mate also can with the three-D space structure of L-Trp selective binding.The preparation method of this powder carries out according to following steps:
(1) TiO of trace L-Trp template molecule
2the preparation of colloidal sol
Adopt sol-gel process, the alkyl oxide of the titanium that is 1:0.015 ~ 0.18 by mass ratio and L-Trp template molecule join in 500mL alcohols solvent, stir solid is all dissolved, and continue to stir 24h, and making trace has the TiO of L-Trp template molecule
2colloidal sol;
(2) TiO of trace L-Trp template molecule
2the preparation of powder
The trace that step (1) is obtained has the TiO of L-Trp template molecule
2the ratio mix and blend 24h that colloidal sol is 1:5.88 according to the mass ratio of the alkyl oxide of titanium and water, has the TiO of L-Trp template molecule by obtaining trace after the white precipitate suction filtration obtaining, oven dry
2powder;
(3) removing of L-Trp template molecule
The trace that step (2) is obtained has the TiO of L-Trp template molecule
2powder is eluted to its supernatant liquor fluorescence spectrum with the ammonia spirit that volume ratio is 1% does not absorb at 350nm place, collects this powder, washs to neutrality by deionized water, and 60 ℃ of oven dry obtain having the TiO of L-Trp molecular engram
2powder.
As limitation of the invention, the alkyl oxide of the titanium described in step (1) is tetra-n-butyl titanate, and described alcohols solvent is absolute ethyl alcohol.
In order effectively to construct the TiO with L-Trp molecule casting mold
2powder, the alkyl oxide of titanium and the mass ratio of L-Trp are 1:0.015 ~ 0.18, both mass ratioes are during higher than 1:0.015, at TiO
2powder on can not effectively construct the casting mold of L-Trp molecule, when both mass ratioes are less than 1:0.18, not only waste too much L-Trp, affect equally TiO
2the casting mold of L-Trp molecule on powder, the alkyl oxide of titanium and the optimum quality ratio of L-Trp: 1:0.05 ~ 0.15.
Principle of the present invention is as shown in Figure of description Fig. 1, and the carboxylic acid group on tetra-n-butyl titanate and tryptophan and amino Hydrogenbond, be wrapped in template molecule tryptophan in the network structure of colloidal sol, adds water and makes tetra-n-butyl titanate hydrolysis generate TiO
2after powder, TiO
2in Ti-O bond polarity larger, the water of adsorption is because of polarization generation dissociation, form hydroxyl, with carboxyl and the amino hydrogen bond that forms on tryptophan, tryptophan is wrapped in the structure of Ti-O-Ti, after template molecule is removed, can leave the hole matching with template molecule and form specific recognition site, thereby reach the object of selective identification.
The present invention is with inorganic material TiO
2for trace monomer synthetic molecules trace compound, realize the fractionation to two kinds of optical isomers of tryptophan under aqueous systems, powder body material has improved adsorbance greatly, makes it at chiral separation packed column, and there is good application prospect sensor aspect.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is L-Trp molecular engram TiO
2the preparation flow figure of powder, wherein a is the structure of L-Trp, and b is the structure of positive four butyl esters of metatitanic acid, and c is the TiO of trace L-Trp template molecule
2the structure of colloidal sol, d is the TiO of trace L-Trp template molecule
2the structure of powder, e is the TiO with L-Trp molecular engram
2the structure of powder, T is template molecule L-Trp.
The specific embodiment
The present invention is further detailed explanation in conjunction with the embodiments now.
Embodiment 1
(1) TiO of trace L-Trp template molecule
2the preparation of colloidal sol
Take 1.28g L-Trp, 85.0g tetra-n-butyl titanate adds in 500mL absolute ethyl alcohol, stir solid is all dissolved, continue stir 24h, make the abundant combination of amino acid and tetra-n-butyl titanate, obtain the TiO of trace L-Trp template molecule
2colloidal sol;
(2) TiO of trace L-Trp template molecule
2the preparation of powder
The trace that step (1) is obtained has the TiO of L-Trp template molecule
2the ratio mix and blend 24h that colloidal sol is 1:5.88 according to the mass ratio of the alkyl oxide of titanium and water, has the TiO of L-Trp molecule by obtaining trace after the white precipitate suction filtration obtaining, oven dry
2powder;
(3) removing of L-Trp template molecule
The trace that step (2) is obtained has the TiO of L-Trp molecule
2the ammonia spirit wash-out that powder is 1% by volume ratio, in order to guarantee effectively to remove tryptophan, can be by cleaning solution 0.5molL
-1hCl regulate pH to 6 ~ 7, to the not absorption at 350nm place of the fluorescence spectrum of its supernatant liquor, collect this powder, wash to neutrality by deionized water, 60 ℃ of oven dry obtain having the TiO of L-Trp molecular engram
2powder.
In order to evaluate the TiO with L-Trp casting mold
2the separating effect of powder to L-Trp and D-trp, the present invention uses the TiO with L-Trp casting mold
2powder is weighed the variation of tryptophan solution fluorescence intensity before and after L-Trp and the absorption of D-trp solution respectively, and concrete assay method is to take the TiO with L-Trp molecular engram that two parts of quality are 0.10g
2powder, the concentration that is placed in respectively 30mL pH=6 is 0.1mmolL
-1l-Trp and the aqueous solution of D-trp in, after stirring and adsorbing 4h, with fluorescent spectrophotometer assay adsorbance (excitation wavelength measured of tryptophan is 282nm, and emission wavelength is 350nm), calculate Selective Separation coefficient (α) simultaneously.
Selective Separation coefficient is defined as α=(m
1-m
2)/(m
3-m
4), wherein m
1, m
2quality before representing L-Trp absorption and after absorption, m
3, m
4quality before representing D-trp absorption and after absorption, selectively the evaluating trace powder take Selective Separation coefficient as index.Concrete outcome is as shown in table 1: the TiO that measures this example and have L-Trp molecular engram
2powder is 3.19mg/g to the adsorbance of L-Trp, and the adsorbance of D-trp is 2.29mg/g, and Selective Separation factor alpha is 1.39.
Embodiment 2
L-Trp addition in embodiment 1 is changed into 2.55g, and all the other conditions are all identical with embodiment 1.Measure the TiO with L-Trp molecular engram that the present embodiment makes
2powder is 3.06mg/g to the adsorbance of L-Trp, is 1.89mg/g to the adsorbance of D-trp, and Selective Separation factor alpha is 1.62, as shown in table 1.
Embodiment 3
L-Trp addition in embodiment 1 is become to 5.10g, and all the other conditions are all identical with embodiment 1.Measure the TiO with L-Trp molecular engram that the present embodiment makes
2powder is 2.90mg/g to the adsorbance of L-Trp, is 1.60mg/g to the adsorbance of D-trp, and Selective Separation factor alpha is 1.82, as shown in table 1.
L-Trp addition in embodiment 1 is become to 10.2g, and all the other conditions are all identical with embodiment 1.Measure the TiO with L-Trp molecular engram that the present embodiment makes
2powder is 2.73mg/g to the adsorbance of L-Trp, is 1.13mg/g to the adsorbance of D-trp, and Selective Separation factor alpha is 2.42, as shown in table 1.
Embodiment 5
L-Trp addition in embodiment 1 is become to 12.8g, and all the other conditions are all identical with embodiment 1.Measure the TiO with L-Trp molecular engram that the present embodiment makes
2powder is 2.64mg/g to the adsorbance of L-Trp, is 1.32mg/g to the adsorbance of D-trp, and Selective Separation factor alpha is 2.00, as shown in table 1.
Embodiment 6
L-Trp addition in embodiment 1 is become to 15.3g, and all the other conditions are all identical with embodiment 1.Measure the TiO with L-Trp molecule casting mold that the present embodiment makes
2powder is 2.52mg/g to the adsorbance of L-Trp, is 1.42mg/g to the adsorbance of D-trp, and Selective Separation factor alpha is 1.77, as shown in table 1.
Comparative example 1
L-Trp addition in embodiment 1 is become to 0g, and all the other conditions are all identical with embodiment 1.The non-trace powder that mensuration the present embodiment makes is 1.14mg/g to the adsorbance of L-Trp, and the adsorbance of D-trp is 1.05mg/g, and selectivity factor α is 1.09, as shown in table 1.
Table 1 is prepared L-Trp molecular engram TiO
2the material quantity of powder and the Selective Separation coefficient to L-Trp
Claims (4)
1. a L-Trp molecular engram TiO
2powder, is characterized in that this TiO
2powder have be close on space structure with L-Trp mate also can with the three-D space structure of L-Trp selective binding; This TiO
2the preparation method of powder carries out according to following steps:
(1) TiO of trace L-Trp template molecule
2the preparation of colloidal sol
Adopt sol-gel process, the alkyl oxide of the titanium that is 1:0.015～0.18 by mass ratio and L-Trp template molecule join in 500mL alcohols solvent, stir solid is all dissolved, and continue to stir 24h, and obtaining trace has the TiO of L-Trp template molecule
2colloidal sol;
(2) TiO of trace L-Trp template molecule
2the preparation of powder
The trace that step (1) is obtained has the TiO of L-Trp template molecule
2the ratio mix and blend 24h that colloidal sol is 1:5.88 according to the mass ratio of the alkyl oxide of titanium and water, has the TiO of L-Trp template molecule by obtaining trace after the white precipitate suction filtration obtaining, oven dry
2powder;
(3) removing of L-Trp template molecule
The trace that step (2) is obtained has the TiO of L-Trp template molecule
2powder is eluted to its supernatant liquor fluorescence spectrum with the ammonia spirit that volume ratio is 1% does not absorb at 350nm place, collects this powder, washs to neutrality by deionized water, and 60 ℃ of oven dry obtain having the TiO of L-Trp molecular engram
2powder.
2. a kind of L-Trp molecular engram TiO as claimed in claim 1
2the preparation method of powder, is characterized in that the method carries out according to following steps:
(1) TiO of trace L-Trp template molecule
2the preparation of colloidal sol
Adopt sol-gel process, the alkyl oxide of the titanium that is 1:0.015～0.18 by mass ratio and L-Trp template molecule join in 500mL alcohols solvent, stir solid is all dissolved, and continue to stir 24h, and obtaining trace has the TiO of L-Trp template molecule
2colloidal sol;
(2) TiO of trace L-Trp template molecule
2the preparation of powder
The trace that step (1) is obtained has the TiO of L-Trp template molecule
2the ratio mix and blend 24h that colloidal sol is 1:5.88 according to the mass ratio of the alkyl oxide of titanium and water, has the TiO of L-Trp template molecule by obtaining trace after the white precipitate suction filtration obtaining, oven dry
2powder;
(3) removing of L-Trp template molecule
The trace that step (2) is obtained has the TiO of L-Trp template molecule
2powder is eluted to its supernatant liquor fluorescence spectrum with the ammonia spirit that volume ratio is 1% does not absorb at 350nm place, collects this powder, washs to neutrality by deionized water, and 60 ℃ of oven dry obtain having the TiO of L-Trp molecular engram
2powder.
3. a kind of L-Trp molecular engram TiO as claimed in claim 2
2the preparation method of powder, is characterized in that the alkyl oxide of described titanium is tetra-n-butyl titanate, and described alcohols solvent is absolute ethyl alcohol.
4. a kind of L-Trp molecular engram 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-Trp are 1:0.05～0.15.
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| 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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| 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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| Title |
|---|
| 纳米级TiO2或SiO2的鞣革机理及鞣性的研究;范浩军等;《皮革科学与工程》;20030228;第13卷(第1期);18-21 * |
| 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》.2003,第13卷(第1期),18-21. |
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