CN103816855A - Preparation method for modified hydroxyapatite with grafted amino acid on surface - Google Patents

Preparation method for modified hydroxyapatite with grafted amino acid on surface Download PDF

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

The invention relates to a preparation method for modified hydroxyapatite with grafted amino acid on the surface. The method comprises the following steps: firstly, preparing a mixed solution of ethyl alcohol and water, adjusting the pH value, then adding KH560, stirring and shaking the solution, then adding nanoscale hydroxyapatite, reacting for 0.5-1.5 h and obtaining modified hydroxyapatite; secondly, drying and grinding the modified hydroxyapatite, placing the modified hydroxyapatite in a buffered solution with the pH value controlled to be within 6-8 and amino acid of 3.0-20 mg/mL, shaking the solution for 20-30 h at 35-65 DEG C and grating amino acid to obtain the modified hydroxyapatite with grafted amino acid on the surface. According to the invention, the preparing method is simple, and the obtained modified hydroxyapatite with grafted amino acid on the surface has excellent biological compatibility, adsorbs a considerable amount of protein and enzyme, and is wide in application prospects.

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, be alkalescent, be soluble in acid and be insoluble in alkali.The crystal of hydroxyapatite belongs to P63/m space group, hexaplanar, the HAP being present in Animal Bone, Ya Deng sclerous tissues is needle-like due to its good biocompatibility, low-density, chemical stability with to the similar composition of skeleton mineral matter, hydroxyapatite is widely used in biomedical engineering.The synthetic HAP of stoichiometric is biocompatible, nontoxic, without immunogenicity, and has good biologically active.
At present, the more existing documents of the absorption of preparation modified HA P and patent are reported.The people such as Wang Yan adopt ATRP (ATRP) in the grafting of hydroxyapatite (HAP) nanoparticle surface polymethyl methacrylate (PMMA) the unit adsorbance of lysozyme (LSZ) and bovine serum albumin (BSA) is increased to (Wang Yan, Xiao Yan, Lang Meidong. the impact [N] of surface modification on 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 7thereby) react with hydroxyapatite and increased the content of surperficial P-OH and strengthened absorption (the Tanaka H of HAP to protein; Futaoka M; Hino R; et al.Structure of synthetic calcium hydroxyapatite particles modified with pyrophosphoric acid Journal of Colloid and Interface Science.2005,283 (2): 609-612); Thereby the people such as Xuejun Wang adopt the composite Nano support of PLLA and KH570 to carry out modified HA P makes the HAP after modification obtain large increase (Xuejun Wang to the adsorption capacity of albumen than the absorption of simple nanometer hydroxyapatite, Guojun Song, Tao Lou.Fabrication and characterization of nano-composite scaffold of PLLA/silane modified hydroxyapatite.Medical Engineering & Physics.2010,32 (4): 391-397); Yi Jingbo etc. (Chinese patent 201210382445.1) process HAP with silane coupler and cause amino acid ring-opening polymerisation; Zhang Shengmin etc. (Chinese patent 2003128166.4) have created organosilan decorative layer in hydroxyapatite surface, and do decorating molecule with silane derivative.
Generally speaking, along with the grafting of different modifying molecule not only can improve the mechanical property of HAP material, and its biological degradability and absorption property have been increased.About the research of preparation modified HA P protein adsorbent, directly surface grafting part is unfavorable for the dispersion of HAP.For thering is for synthetic the modified hydroxylapatite that stronger protein adsorption separates, but adopt KH560 to process HAP, thereby and then reach specific adsorption effect using amino acid as ligand-modified hydroxyapatite and but rarely have report.
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 has been improved the surface property of hydroxyapatite, overcome the shortcoming that pure ha is easily reunited, it can fully be contacted with the process of the material effect absorption such as enzyme and albumen, 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) configuration ethanol and water mixed solution, regulates pH value, then adds KH560, stir and shake after add again nano-grade hydroxy apatite to react 0.5-1.5h, obtain modified hydroxylapatite;
(2) after being washed and be dried, above-mentioned modified hydroxylapatite grinds, put into again and contain the amino acid whose pH value of 3.0～20mg/mL and be controlled at 6～8 cushioning liquid, at 35-65 ℃, shake 20-30h grafting amino acid and 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), regulating pH value 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.
The time of stirring in described step (1) and shake 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 amino acid whose modified hydroxylapatite of described step (2) gained surface grafting reaches 20～100mg/g to the adsorbance of lysozyme.
The amino acid whose modified hydroxylapatite of described step (2) gained surface grafting is for adsorbent, water treatment or the plasma purification of albumen and enzyme.
Beneficial effect:
(1) the present invention adopts silane coupler KH560 modified hydroxylapatite, improve the hydrophilicity of hydroxyapatite, thereby effectively prevent particle aggregation, make can fully contact with the process of the material absorption such as enzyme and albumen, thereby increased the absorption to albumen.
(2) the present invention has adopted specific amino acids to be grafted to as part on the KH560 of hydroxyapatite surface and has made the epoxide group generation ring-opening reaction on KH560, amino acid has the effect of the absorption of mutually combining to some protein, enzyme, endotoxin etc., be 5.68 under the similar human body environment of pH=7.35～7.45, to become electronegativity because these amino acid are its isoelectric point of amphiphilic materials, and some protein, enzyme, endotoxin etc., it generally is electropositive under human normal pH, thereby makes hydroxyapatite have adsorptivity to protein and enzyme etc.
(3) the modified hydroxylapatite powder that the present invention obtains, has good biocompatibility, large to the adsorbance of protein and enzyme, is a kind of novel sorbing material.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 4, accurately take 2.5%(w/v with electronic balance again) KH5602.5g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 1.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 35 ℃ of reaction 0.5h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.0.3gL-serine is fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, regulating pH value with glacial acetic acid is 4, gets modified HA P1g and adds in flask and control 35 ℃ of bath temperatures, reacts 24h.This L-ser-KH560-HAP is 20mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 2
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 5, accurately take 5.0%(w/v with electronic balance again) KH5605g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 2.5%(w/v) nano-HAP powder 2.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 45 ℃ of reaction 1h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.1g leucine is fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, regulating pH value with glacial acetic acid is 5, gets modified HA P1g and adds in flask and control 45 ℃ of bath temperatures, reacts 24h.This L-ser-KH560-HAP is 30mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 3
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 6, accurately take 7.0%(w/v with electronic balance again) KH5607g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 3.5%(w/v) nano-HAP powder 3.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 55 ℃ of reaction 1.5h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.1.5g arginine is fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, regulating pH value with glacial acetic acid is 6, gets modified HA P1g and adds in flask and control 55 ℃ of bath temperatures, reacts 24h.This L-ser-KH560-HAP is 40mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 4
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 6.5, accurately take 10%(w/v with electronic balance again) KH56010g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 1.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 65 ℃ of reaction 0.5h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.2g lysine is fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4slow joining in dissolved liquid 100ml of mixing control its volume proportion, regulating pH value with glacial acetic acid is 6.5, gets modified HA P1g and adds in flask and control 55 ℃ of bath temperatures, reacts 24h.This L-ser-KH560-HAP is 50mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 5
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 4, accurately take 2.5%(w/v with electronic balance again) KH5601.5g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 2.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 35 ℃ of reaction 1h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.0.15gL-serine and 0.15g leucine are fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, regulating pH value with glacial acetic acid is 4, gets modified HA P1g and adds in flask and control 55 ℃ of bath temperatures, reacts 24h.This L-ser-KH560-HAP is 60mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 6
Configuration 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 5, accurately take 2.5%(w/v with electronic balance again) KH5602.5g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 2.5%(w/v) nano-HAP powder 3.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 45 ℃ of reaction 1.5h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.0.5g leucine and 0.5g arginine are fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4mixing cushioning liquid 100ml in control its volume proportion, regulating pH value with glacial acetic acid is 5, gets modified HA P1g and adds in flask and control 65 ℃ of bath temperatures, reacts 24h.This L-ser-KH560-HAP is 70mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 7
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 6, accurately take 2.5%(w/v with electronic balance again) KH5607g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 3.5%(w/v) nano-HAP powder 1.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 55 ℃ of reaction 0.5h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.0.75g arginine and 0.75g lysine are fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4slow joining in dissolved liquid 100ml of mixing control its volume proportion, regulating pH value with glacial acetic acid is 6, gets modified HA P1g and adds in flask and control 55 ℃ of bath temperatures, reacts 24h.This Leu-KH560-HAP is 80mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 8
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 6.5, accurately take 2.5%(w/v with electronic balance again) KH56010g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 1.5%(w/v) nano-HAP powder 2.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 65 ℃ of reaction 1h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.1g leucine and 1g lysine are fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4slow joining in dissolved liquid 100ml of mixing control its volume proportion, regulating pH value with glacial acetic acid is 6.5, gets modified HA P1g and adds in flask and control 55 ℃ of bath temperatures, reacts 24h.This Arg-KH560-HAP is 90mg/g to the adsorbance of lysozyme (LSZ).
Embodiment 9
Put 9:1(v/v) the mixed solution 100ml of alcohol-water, and to make its pH value with glacial acetic acid regulator solution be 4, accurately take 2.5%(w/v with electronic balance again) KH56010g be fully blended in and under constant temperature shaking device, stir 30min and make KH560 complete hydrolysis, then by 2.5%(w/v) nano-HAP powder 3.5g adds in flask, open magnetic agitation and make it to be uniformly dispersed, bath temperature is controlled at 50 ℃ of reaction 1.5h.After reaction finishes, with repeatedly abundant washed product suction filtration of absolute ethyl alcohol, the product obtaining is put into vacuum drying oven, 80 ℃ of vacuum drying 24h.2g lysine is fully dissolved in to the Na of the 0.2mol/L of preparation 2hPO 4and NaH 2pO 4slow joining in dissolved liquid 100ml of mixing control its volume proportion, regulating pH value with glacial acetic acid is 5.5, gets modified HA P1g and adds in flask and control 55 ℃ of bath temperatures, reacts 24h.This Lys-KH560-HAP is 100mg/g to the adsorbance of lysozyme (LSZ).

Claims (9)

1. a preparation method for the amino acid whose modified hydroxylapatite of surface grafting, comprising:
(1) configuration ethanol and water mixed solution, regulates pH value, then adds KH560, stir and shake after add again nano-grade hydroxy apatite to react 0.5-1.5h, obtain modified hydroxylapatite;
(2) after being washed and be dried, above-mentioned modified hydroxylapatite grinds, put into again and contain the amino acid whose pH value of 3.0～20mg/mL and be controlled at 6～8 cushioning liquid, at 35-65 ℃, shake 20-30h grafting amino acid and obtain the amino acid whose modified hydroxylapatite of surface grafting.
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, and pH value is adjusted to 4～6.5.
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), regulating pH value 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: the middle time of stirring and shake of described step (1) 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 amino acid in described step (2) is one or more in serine, arginine, lysine, leucine.
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 reaches 20～100mg/g to the adsorbance of lysozyme.
9. 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 for adsorbent, water treatment or the plasma purification of albumen and enzyme.
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CN108786713A (en) * 2018-06-08 2018-11-13 南京师范大学 A kind of nano hydroxyapatite adsorbent and its preparation method and application that parents' absorbent-type is sulfhydryl modified
CN108925367A (en) * 2018-09-21 2018-12-04 浙江世荣农业开发有限公司 A kind of black fungus rich in selenium culture medium and black fungus rich in selenium
CN109225162A (en) * 2018-11-09 2019-01-18 华东理工大学 A kind of preparation method of the modified walnut shell adsorbent of aspartic acid
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
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CN115591525A (en) * 2022-10-28 2023-01-13 西安交通大学（Cn） Surface grafting modification method based on animal bone apatite and adsorbent

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Publication number Priority date Publication date Assignee Title
CN104774331A (en) * 2015-04-24 2015-07-15 东华大学 Method for preparing polyimide (PI)/surface graft amino acid modified hydroxyapatite (HAP) hybrid membrane
CN107440913A (en) * 2017-07-27 2017-12-08 武汉大学 A kind of preparation method of coloured hydroxyapatite available for the detection of dentistry bleaching agent effectiveness
CN108786713A (en) * 2018-06-08 2018-11-13 南京师范大学 A kind of nano hydroxyapatite adsorbent and its preparation method and application that parents' absorbent-type is sulfhydryl modified
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
CN108925367A (en) * 2018-09-21 2018-12-04 浙江世荣农业开发有限公司 A kind of black fungus rich in selenium culture medium and black fungus rich in selenium
CN109225162A (en) * 2018-11-09 2019-01-18 华东理工大学 A kind of preparation method of the modified walnut shell adsorbent of aspartic acid
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
CN113351165A (en) * 2021-04-29 2021-09-07 中石化石油工程技术服务有限公司 Defluorination process for drinking water in mining area
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
CN115591525A (en) * 2022-10-28 2023-01-13 西安交通大学（Cn） Surface grafting modification method based on animal bone apatite and adsorbent
CN115591525B (en) * 2022-10-28 2024-04-26 西安交通大学 Surface grafting modification method and adsorbent based on animal bone apatite

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