CN103816855B - The preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting - Google Patents

The preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting Download PDF

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CN103816855B
CN103816855B CN201410080910.5A CN201410080910A CN103816855B CN 103816855 B CN103816855 B CN 103816855B CN 201410080910 A CN201410080910 A CN 201410080910A CN 103816855 B CN103816855 B CN 103816855B
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amino acid
acid whose
modified hydroxylapatite
surface grafting
preparation
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CN103816855A (en
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孙俊芬
曹桢桢
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Donghua University
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Abstract

The present invention relates to the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting, comprise: (1) configuration ethanol and water mixed solution, adjust ph, then adds KH560, stir and add nano-grade hydroxy apatite reaction 0.5-1.5h after shaking again, obtaining modified hydroxylapatite; (2) grind after above-mentioned modified hydroxylapatite washing also drying, put into the cushioning liquid controlling 6 ~ 8 containing the amino acid whose pH value of 3.0 ~ 20mg/mL again, at 35-65 DEG C, shake the acid of 20-30h grafted amino group namely obtain the amino acid whose modified hydroxylapatite of surface grafting.Preparation method of the present invention is simple, and the amino acid whose modified hydroxylapatite of the surface grafting obtained has excellent biocompatibility, large to the adsorbance of protein and enzyme, has a extensive future.

Description

The preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting
Technical field
The invention belongs to the preparation field of hydroxyapatite material, particularly the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting.
Background technology
The molecular formula of hydroxyapatite (hydroxyapatite is called for short HAP) is Ca 10(PO 4) 6(OH) 2, density is 3.16g/cm 3, property is crisp, and refractive index is 1.64 ~ 1.65.Be slightly soluble in pure water, in alkalescent, be soluble in acid and be insoluble in alkali.The crystal of hydroxyapatite belongs to P63/m space group, hexaplanar, the HAP be present in Animal Bone, Ya Deng sclerous tissues is that needle-like is due to its good biocompatibility, low-density, chemical stability and the similar composition to skeleton mineral matter, hydroxyapatite is widely used in biomedical engineering.The HAP of stoichiometric synthesis is biocompatible, nontoxic, without immunogenicity, and has good biologically active.
At present, prepare the absorption of modified HA P and have some documents and patent is reported.The people such as Wang Yan have adopted ATRP (ATRP) in the grafting of hydroxyapatite (HAP) nanoparticle surface, and the unit adsorbance of polymethyl methacrylate (PMMA) to lysozyme (LSZ) and bovine serum albumin (BSA) increases (Wang Yan, Xiao Yan, Lang Meidong. surface modification is on the impact [N] of hydroxyapatite protein adsorption. East China University of Science's journal (natural science edition), 2011-5-13(5)); The people such as Tanaka are by a certain amount of pyrophosphoric acid (H 4p 2o 7) to react with hydroxyapatite thus the content adding surperficial P-OH enhances the absorption (TanakaH of HAP to protein; FutaokaM; HinoR; etal.Structureofsyntheticcalciumhydroxyapatiteparticlesm odifiedwithpyrophosphoricacidJournalofColloidandInterfac eScience.2005,283 (2): 609-612); The people such as XuejunWang adopt the composite Nano support of PLLA and KH570 to carry out modified HA P thus make modified HAP obtain large increase (XuejunWang to the adsorption capacity of albumen than the absorption of simple nanometer hydroxyapatite, GuojunSong, TaoLou.Fabricationandcharacterizationofnano-compositesca ffoldofPLLA/silanemodifiedhydroxyapatite.MedicalEngineer ing & Physics.2010,32 (4): 391-397); Yi Jingbo etc. (Chinese patent 201210382445.1) silane coupler process HAP causes amino acid ring-opening polymerisation; Zhang Shengmin etc. (Chinese patent 2003128166.4) create organosilan decorative layer in hydroxyapatite surface, and do decorating molecule with silane derivative.
Generally speaking, the grafting along with different modifying molecule not only can improve the mechanical property of HAP material, and increases its biological degradability and absorption property.About the research of preparation modified HA P protein adsorbent, direct surface grafting part is unfavorable for the dispersion of HAP.For in order to synthesize the modified hydroxylapatite that there is stronger protein adsorption and be separated, but adopt KH560 process HAP, and then reach specific adsorption effect but rarely have report using amino acid as ligand-modified hydroxyapatite.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting, the method improve the surface property of hydroxyapatite, overcome the shortcoming that pure ha is easily reunited, can fully contacting in the process that itself and enzyme and the material effects such as albumen are adsorbed, is the promising medical material of tool and sorbing material.
The preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting of the present invention, comprising:
(1) configure ethanol and water mixed solution, adjust ph, then adds KH560, stirs and adds nano-grade hydroxy apatite again after shaking and react 0.5-1.5h, obtain modified hydroxylapatite;
(2) grind after above-mentioned modified hydroxylapatite washing also drying, put into the cushioning liquid controlling 6 ~ 8 containing the amino acid whose pH value of 3.0 ~ 20mg/mL again, at 35-65 DEG C, shake the acid of 20-30h grafted amino group namely obtain the amino acid whose modified hydroxylapatite of surface grafting.
In described step (1), the volume ratio of second alcohol and water is 9:1, and pH value is adjusted to 4 ~ 6.5.
In described step (1), adjust ph agents useful for same is glacial acetic acid.
In described step (1), the mass volume ratio of KH560 and ethanol and water mixed solution is 2.5 ~ 10g:100mL.
To stir in described step (1) and the time of shaking is that 30 ~ 40min is to make KH560 complete hydrolysis.
In described step (1), the mass volume ratio of nano-grade hydroxy apatite and ethanol and water mixed solution is 1.5 ~ 3.5g:100mL.
Amino acid in described step (2) is one or more in serine, arginine, lysine, leucine.
The adsorbance of the amino acid whose modified hydroxylapatite of described step (2) gained surface grafting to lysozyme reaches 20 ~ 100mg/g.
The amino acid whose modified hydroxylapatite of described step (2) gained surface grafting is used for the adsorbent of albumen and enzyme, water treatment or plasma purification.
Beneficial effect:
(1) the present invention adopts silane coupler KH560 modified hydroxylapatite, improve the hydrophilicity of hydroxyapatite, thus effectively prevent particle aggregation, make can fully contact with enzyme and the process of the species adsorbs such as albumen, thus increase the absorption to albumen.
(2) present invention employs epoxide group generation ring-opening reaction specific amino acids is grafted to hydroxyapatite surface KH560 as part made on KH560, amino acid has the effect of the absorption that be combined with each other to some protein, enzyme, endotoxin etc., because these amino acid are its isoelectric point of amphiphilic species is 5.68 become electronegativity under the similar human body environment of pH=7.35 ~ 7.45, and some protein, enzyme, endotoxin etc., it generally is electropositive under human normal pH, thus makes hydroxyapatite have adsorptivity to protein and enzyme etc.
(3) the modified hydroxylapatite powder that obtains of the present invention, has excellent biocompatibility, large to the adsorbance of protein and enzyme, is a kind of novel sorbing material.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 4 with glacial acetic acid, accurately take 2.5%(w/v with electronic balance again) KH5602.5g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 1.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 35 DEG C of reaction 0.5h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.0.3gL-serine is fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, be 4 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 35 DEG C, reaction 24h.The adsorbance of this L-ser-KH560-HAP to lysozyme (LSZ) is 20mg/g.
Embodiment 2
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 5 with glacial acetic acid, accurately take 5.0%(w/v with electronic balance again) KH5605g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 2.5%(w/v) nano-HAP powder 2.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 45 DEG C of reaction 1h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.1g leucine is fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, be 5 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 45 DEG C, reaction 24h.The adsorbance of this L-ser-KH560-HAP to lysozyme (LSZ) is 30mg/g.
Embodiment 3
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 6 with glacial acetic acid, accurately take 7.0%(w/v with electronic balance again) KH5607g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 3.5%(w/v) nano-HAP powder 3.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 55 DEG C of reaction 1.5h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.1.5g arginine is fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, be 6 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 55 DEG C, reaction 24h.The adsorbance of this L-ser-KH560-HAP to lysozyme (LSZ) is 40mg/g.
Embodiment 4
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 6.5 with glacial acetic acid, accurately take 10%(w/v with electronic balance again) KH56010g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 1.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 65 DEG C of reaction 0.5h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.2g lysine is fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing slow joining in dissolved liquid 100ml control its volume proportion, be 6.5 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 55 DEG C, reaction 24h.The adsorbance of this L-ser-KH560-HAP to lysozyme (LSZ) is 50mg/g.
Embodiment 5
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 4 with glacial acetic acid, accurately take 2.5%(w/v with electronic balance again) KH5601.5g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 2.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 35 DEG C of reaction 1h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.0.15gL-serine and 0.15g leucine are fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, be 4 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 55 DEG C, reaction 24h.The adsorbance of this L-ser-KH560-HAP to lysozyme (LSZ) is 60mg/g.
Embodiment 6
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 5 with glacial acetic acid, accurately take 2.5%(w/v with electronic balance again) KH5602.5g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 2.5%(w/v) nano-HAP powder 3.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 45 DEG C of reaction 1.5h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.0.5g leucine and 0.5g arginine are fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, be 5 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 65 DEG C, reaction 24h.The adsorbance of this L-ser-KH560-HAP to lysozyme (LSZ) is 70mg/g.
Embodiment 7
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 6 with glacial acetic acid, accurately take 2.5%(w/v with electronic balance again) KH5607g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 3.5%(w/v) nano-HAP powder 1.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 55 DEG C of reaction 0.5h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.0.75g arginine and 0.75g lysine are fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing slow joining in dissolved liquid 100ml control its volume proportion, be 6 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 55 DEG C, reaction 24h.The adsorbance of this Leu-KH560-HAP to lysozyme (LSZ) is 80mg/g.
Embodiment 8
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 6.5 with glacial acetic acid, accurately take 2.5%(w/v with electronic balance again) KH56010g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 2.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 65 DEG C of reaction 1h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.1g leucine and 1g lysine are fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing slow joining in dissolved liquid 100ml control its volume proportion, be 6.5 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 55 DEG C, reaction 24h.The adsorbance of this Arg-KH560-HAP to lysozyme (LSZ) is 90mg/g.
Embodiment 9
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and regulate solution to make its pH value be 4 with glacial acetic acid, accurately take 2.5%(w/v with electronic balance again) KH56010g be fully blended in constant temperature shaking device under stir 30min and make KH560 complete hydrolysis, then by 2.5%(w/v) nano-HAP powder 3.5g adds in flask, open magnetic agitation to make it to be uniformly dispersed, bath temperature controls at 50 DEG C of reaction 1.5h.After reaction terminates, with absolute ethyl alcohol repeatedly fully washed product suction filtration, the product obtained puts into vacuum drying oven, 80 DEG C of vacuum drying 24h.2g lysine is fully dissolved in the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing slow joining in dissolved liquid 100ml control its volume proportion, be 5.5 by glacial acetic acid adjust ph, get modified HA P1g and add in flask and control bath temperature 55 DEG C, reaction 24h.The adsorbance of this Lys-KH560-HAP to lysozyme (LSZ) is 100mg/g.

Claims (8)

1. a preparation method for the amino acid whose modified hydroxylapatite of surface grafting, comprising:
(1) configure ethanol and water mixed solution, adjust ph, then adds KH560, stirs and adds nano-grade hydroxy apatite again after shaking and react 0.5-1.5h, obtain modified hydroxylapatite; Wherein, pH value is adjusted to 4 ~ 6.5;
(2) grind after above-mentioned modified hydroxylapatite washing also drying, put into the cushioning liquid controlling 6 ~ 8 containing the amino acid whose pH value of 3.0 ~ 20mg/mL again, at 35-65 DEG C, shake the acid of 20-30h grafted amino group namely obtain the amino acid whose modified hydroxylapatite of surface grafting; Wherein, amino acid is one or more in serine, arginine, lysine, leucine.
2. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: in described step (1), the volume ratio of second alcohol and water is 9:1.
3. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: in described step (1), adjust ph agents useful for same is glacial acetic acid.
4. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: in described step (1), the mass volume ratio of KH560 and ethanol and water mixed solution is 2.5 ~ 10g:100mL.
5. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: stir in described step (1) and the time of shaking is that 30 ~ 40min is to make KH560 complete hydrolysis.
6. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: in described step (1), the mass volume ratio of nano-grade hydroxy apatite and ethanol and water mixed solution is 1.5 ~ 3.5g:100mL.
7. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: the adsorbance of the amino acid whose modified hydroxylapatite of described step (2) gained surface grafting to lysozyme reaches 20 ~ 100mg/g.
8. the preparation method of the amino acid whose modified hydroxylapatite of a kind of surface grafting according to claim 1, is characterized in that: the amino acid whose modified hydroxylapatite of described step (2) gained surface grafting is used for the adsorbent of albumen and enzyme, water treatment or plasma purification.
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CN104774331B (en) * 2015-04-24 2017-05-03 东华大学 Method for preparing polyimide (PI)/surface graft amino acid modified hydroxyapatite (HAP) hybrid membrane
CN107440913B (en) * 2017-07-27 2020-02-14 武汉大学 Application of colored hydroxyapatite in dental bleaching agent effect detection
CN108786713B (en) * 2018-06-08 2021-04-27 南京师范大学 Amphiphilic adsorption type sulfhydryl modified nano hydroxyapatite adsorbent and preparation method and application thereof
CN108925367B (en) * 2018-09-21 2021-04-09 浙江世荣农业开发有限公司 Selenium-rich black fungus culture medium and selenium-rich black fungus
CN109225162B (en) * 2018-11-09 2022-03-01 华东理工大学 Preparation method of aspartic acid modified walnut shell adsorbent
CN113181430A (en) * 2021-04-12 2021-07-30 北京冬曦既驾科技咨询有限公司 Medical ceramic slurry for additive manufacturing and medical article prepared from medical ceramic slurry
CN113351165B (en) * 2021-04-29 2023-04-14 中石化石油工程技术服务有限公司 Defluorination process for drinking water in mining area

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CN101301489A (en) * 2008-06-23 2008-11-12 中国科学院长春应用化学研究所 Method for preparing nano hydroxylapatite hybridized material with surface grafting polypeptide
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