CN102357261B - Surface modification method of nanometer hydroxyapatite mediated by APTS - Google Patents
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- CN102357261B CN102357261B CN201110176322.8A CN201110176322A CN102357261B CN 102357261 B CN102357261 B CN 102357261B CN 201110176322 A CN201110176322 A CN 201110176322A CN 102357261 B CN102357261 B CN 102357261B
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Abstract
The invention relates to a surface modification method of nanometer hydroxyapatite mediated by APTS, which includes (1) mixing the nanometer hydroxyapatite n-HA with ethanol and dispersing the mixture through ultrasonic wave to obtain n-HA ethanol suspending liquid; (2) adding the APTS into the n-HA ethanol suspending liquid in dropwise mode and conducting centrifuging, washing, separating and precipitating on the suspending liquid after reaction is finished under room temperature condition to obtain n-HA-APTS nanometer particles; or further conducting acetylation or carboxylation on the n-HA-APTS nanometer particles. The surface modification method is mild in condition and simple in process. Products are easy to separate, and the used modification agent is environment-friendly silane materials. The obtained n-HA-APTS, n-HA-APTS.AC and n-HA-APTS.SAH nanometer particles have different active groups on the surfaces, have good biocompatibility and blood cell stability and are wide in application prospect.
Description
Technical field
The invention belongs to the modification field on nanometer hydroxyapatite surface, particularly a kind of surface modification method of nanometer hydroxyapatite of APTS mediation.
Background technology
In recent years, nano-particle has been subject to extensive concern in the application in the fields such as biomedicine, electrochemical sensor, molecular image.Nanometer hydroxyapatite (Nanohydroxyaptite, n-HA, molecular formula: Ca
10(PO
4)
6(OH)
2) be the main inorganic composition of mammal tooth and skeleton, there is the good characteristics such as good biological activity and bone conductibility.The great specific surface area that n-HA has, make its can adsorbed proteins, lipid, polysaccharide isoreactivity material; And n-HA can also carry out ion exchange with the surrounding liquid environment.These good characteristics of n-HA make it be with a wide range of applications in fields such as gene transfection, bone tissue engineer, pharmaceutical carrier, plastic surgeries.
Along with progressively going deep into of research, the defect that n-HA self exists also progressively highlights.The problems such as easy reunion low such as toughness, that surface modificability is poor and nanoparticle itself has, these drawbacks limit the application of n-HA.For seeking the new way addressed the above problem, researcher has been carried out much work.These research work mainly comprise and use polymer reunion (as the nanofiber containing n-HA or thin film etc.) in liquid phase or connect a kind of Multifunctional matter on the n-HA surface with the surface modificability that improves n-HA etc. for template restriction n-HA.By polymer, it is the reunion that template can well limit nano-particle, but often under external force simply by n-HA and polymer mixed, and a little less than inevitably there will be polymer and n-HA intermediate force, or cause the problems such as n-HA structural damage are occurred.Thereby, by chemical method, at some Multifunctional matters of n-HA finishing, be one of method preferably of expanding the n-HA application.
APTS (aminopropyl triethoxysilane) is a kind of common silanization coupling agent, is usually used in solid is carried out the modifications such as surface silicon alkanisation or amination.Document has reported that APTS is to magnetic nanoparticle, TiO
2finishing Deng nano-particle.The people such as Balasundaram have reported under the APTS mediation, with arginine-glycine-aspartic acid (RGD), hydroxyapatite briquetting (HA-compacts) is modified, and proved that the hydroxyapatite briquetting after modification RGD can promote osteoblastic adhesion (the hydroxyapatite briquetting of matched group for not modifying through RGD) better.This research has illustrated carries out the feasibility of finishing to hydroxyapatite by APTS.
The research work that history faces south seminar early stage successfully neutralizes the amino of the polymine that is modified at the multi-wall carbon nano-tube tube-surface, and (J Phys.Chem.C 113 (8): 3150-3156) can effectively to reduce the toxicity of multi-walled carbon nano-tubes.
But up to now, still do not have bibliographical information to carry out the APTS finishing to bar-shaped n-HA, the one-step functional of going forward side by side is modified, and also there is no the report of its cytotoxicity of overall merit and blood compatibility.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of nanometer hydroxyapatite surface modification method of APTS mediation, the method experimental condition gentleness, and technique is simple, and the product easy operating separates, and dressing agent used is eco-friendly silane material; Resulting n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH nano grain surface have different active groups, and have good biocompatibility and hemocyte stability, have a extensive future.
A kind of nanometer hydroxyapatite surface modification method of APTS mediation comprises:
(1) by n-HA and ethanol according to mass volume ratio 0.8-1.2: 0.8-1.2mg/mL mixes, and then with ultrasound wave, disperses to obtain the n-HA/ alcohol suspension;
(2) then APTS is dropped in said n-HA/ alcohol suspension, react at ambient temperature 10-15h; After reaction finishes, centrifugal, washing, precipitation separation, obtain the n-HA-APTS nano-particle; Wherein n-HA with the APTS amount of substance than 1: 3～1: 5.
The time that ultrasound wave described in step (1) disperses is 1-5h, and power is 30-80W.
N-HA described in step (1) is commercial n-HA, and its TEM picture is as shown in accompanying drawing 4 (a).
Washing described in step (1) is followed successively by water washing 2 times, washing with alcohol 3～5 times.
Before APTS being dropped to said n-HA/ alcohol suspension, first, to the ultra-pure water that drips 1～5mL in described n-HA/ alcohol suspension, can improve reaction rate in step (2).
Centrifugal described in step (2), be preferably speed 5000-7000r/min, time 3-8min.
In step (2), the acetylation method of the n-HA-APTS nano-particle of gained is: by the n-HA-APTS nano-particle of gained, by mass volume ratio, being that 1.5-15: 1mg/mL is ultrasonic is dispersed in DMSO; then add the 0.5-3mL triethylamine; add again the DMSO solution containing acetic anhydride; magnetic agitation reaction 18-30h; centrifugal after reaction finishes, washing, precipitation separation, obtain the n-HA-APTS.Ac nano-particle.
The mol ratio of above-mentioned acetic anhydride and n-HA-APTS is 5: 1～10: 1; Volume ratio containing acetic anhydride in the DMSO solution of acetic anhydride and DMSO is 5: 1～10: 1.
In step (2), the carbonylation process of the n-HA-APTS nano-particle of gained is: by the n-HA-APTS nano-particle of gained, by mass volume ratio, be that 1.5-5: 1mg/mL is dispersed in DMSO, add again the DMSO solution containing succinic anhydrides, reaction 20-30h, centrifugal after reaction finishes, washing, precipitation separation, obtain the n-HA-APTS.SAH nano-particle.
The mol ratio of above-mentioned succinic anhydrides and n-HA-APTS is 5: 1～10: 1; Volume ratio containing succinic anhydrides in the DMSO solution of succinic anhydrides and DMSO is 5: 1～10: 1.
The present invention is easy to operation, has increased number and the kind of n-HA surface functional group, has strengthened the modifiability of n-HA, for solving better the defect that n-HA in use exists, provides reference.
The present invention use transmission electron microscope (TEM), elementary analysis (ICP-AES), Fourier transform infrared spectroscopy (FITR), proton nmr spectra (
1h-NMR), the feasibility of the characterization method checking the inventive method such as X-ray diffraction (XRD), zeta potential measurement.The biocompatibility of material and blood compatibility utilize MTT colorimetry and the means such as phase contrast microscope, hemolytic test to be estimated.Concrete test result is as follows:
(1) test result of Fourier transform infrared spectroscopy (FTIR)
In FTIR collection of illustrative plates shown in above accompanying drawing 1,961cm
-1, 1032cm
-1and 1088cm
-1the absworption peak that place occurs is PO in the n-HA lattice
4 3-the eigen vibration peak, 3570cm
-1the weak peak at place is OH in the n-HA lattice
-stretching vibration peak; Accompanying drawing 1 below figure is 1250cm
-1～1700cm
-1the enlarged drawing of part; Can see 1327cm in spectral line (2) from enlarged drawing
-1the absworption peak at the place stretching vibration peak that is C-N in APTS, proved that APTS successfully is connected to the surface of n-HA by covalent, in (3) and (4) spectral line at 1636cm
-1the new absworption peak that place occurs can be summed up as the stretching vibration peak of C=O, and this absworption peak has also illustrated that the success of acetylation and carboxylation reaction carries out intuitively.In addition, the 1445cm occurred in spectral line
-1and 1415cm
-1, 1560cm
-1the absworption peak that place occurs is respectively because the CO that nano-particle adsorbs from air
2with moisture, produce.
(2) proton nmr spectra (
1hNMR) analyze
The present invention passes through
1h NMR further determines the feasibility of n-HA finishing reaction, as shown in Figure 2.Spectrogram (a), (b) and (c) representative (a) n-HA-APTS respectively, (b) n-HA-APTS.Ac and (c) n-HA-APTS.SAH
1h NMR spectrogram.The last one signal peak all occurs at chemical shift 2.0ppm place in three spectrograms, can attribution be in the n-HA lattice-proton signal of OH, and 0.47,1.6 and the proton signal at 2.82ppm place can be classified as APTS in the signal of proton on the diverse location methylene.It should be noted that; a new proton signal has respectively appearred in the 2.3ppm place in the 1.87ppm in spectrogram (b) and spectrogram (c); after can being attributed to acetylation and carboxylation reaction respectively; the signal peak of proton on the carbon atom be connected with amido link, this is also the feasible strong evidence of proof the present invention program.
(3) elementary analysis (ICP-AES) test result
The ICP-AES test result shows, in sample n-HA-APTS, the composition of calcium and element silicon is respectively 382.8 μ g/mg and 14.3 μ g/mg.According to formula
Can calculate with the quality of the APTS that is connected to the n-HA surface is 6.96% of the own quality of n-HA.In above-mentioned formula, ω
aPTSthe quality (accounting for the mass fraction of n-HA itself) of the APTS that representative is reacted with n-HA; m
n-HAand m
aPTSrepresent respectively the quality of n-HA and APTS in the n-HA-APTS sample; ω
siand ω
carepresent respectively the mass fraction of elemental silicon and element calcium in the n-HA-APTS sample, M
siand M
carepresent respectively the relative atomic mass of silicon and calcium.It should be noted that M ' in above-mentioned formula
aPTSand M '
n-HAafter representing respectively APTS and n-HA reaction, APTS and n-HA be the correction value of relative atomic mass separately.According to equation a and b (seeing accompanying drawing 9), the silanol formed after the APTS hydrolysis and the hydroxyl reaction of n-HA nano grain surface, thereby, M ' in formula 1
aPTSand M '
n-HAvalue be respectively 134 and 953.
(4) test result of transmission electron microscope (TEM)
The TEM test result show (a) n-HA, (b) n-HA-APTS, (c) n-HA-APTS.Ac and (d) the n-HA-APTS.SAH nano-particle all be the corynebacterium structure, as shown in Figure 3.With the n-HA (figure (a)) without any modification, compare, after finishing is processed, the corynebacterium structure of nano-particle and the length of rod-shpaed particle and diameter do not occur significantly to change, and the surface modification method of this explanation the present invention report can not destroy the pattern of n-HA granule.
(5) test result of X-ray diffraction (XRD)
By comparison and the analysis to diffracting spectrum (accompanying drawing 4), the collection of illustrative plates (JCPD 09-0432) of the spectrogram of (b) n-HA-APTS after modification, (c) n-HA-APTS.Ac and (d) n-HA-APTS.SAH and not modified (a) n-HA is consistent, each crystal plane is coincide, and shows that the method for modifying that the present invention reports can not change the crystal structure of n-HA.
(6) Zeta electric potential test
Study verified, the periphery amino of nano-particle can produce cytotoxicity and with the cell membrane non-specific binding, thereby limited the biologic applications of these nano-particle.In the present invention, we,, by the peripheral amino of n-HA-APTS being carried out to acetylation or carboxylated its surface potential one-tenth neutrality or electronegative that makes, can improve the biocompatibility of nano-particle.The surface potential measurement result has confirmed the feasibility of this operation.The surface potential measurement result shows, the surface potential of n-HA is-8.22mV, and the surface potential of n-HA-APTS is+7.14mV.After acetylation and carboxylation reaction, drop to respectively+1.31mV of surface potential and-21.8mV, illustrated that the success of acetylation and carboxylation reaction is carried out.
(7) MTT and phase contrast microscope cell morphology are observed the biocompatibility of estimating n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH
Measure the vigor of KB cell (a kind of cell strain of human epithelium's cancer) by MTT, with the cytotoxicity of evaluating material.Process is as follows: take density as 10
4cells/well is to inoculating cell in 96 porocyte culture plates, cultivate after 24 hours for 37 ℃, add n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH (concentration is that 0,10,50 and 100 μ g/mL, temperature are 37 ℃) and cultivate altogether 24h in each hole respectively.Then, add 10 μ LMTT colour developings in every hole, ultraviolet-visible spectrophotometer reads the light absorption value (OD value, this OD value is directly proportional to the living cells number) at 570nm place, and assay is the impact of different materials on the KB cell viability under above-mentioned same culture conditions.
Analyzing the result (accompanying drawing 5) of MTT can find; with matched group, compare; in the experimental concentration scope (0～100 μ g/mL), n-HA-APTS has suppressed the propagation of KB cell to a certain extent, but follow-up acetylation and carboxylated modification can be eliminated this inhibitory action.The MTT result modified rear n-HA-APTS.Ac of proof and n-HA-APTS.SAH have good biocompatibility.
The present invention has observed pattern and the growth conditions of cell by inverted phase contrast microscope.From accompanying drawing 6, can find out, when 100 μ g/mL, n-HA, n-HA-APTS.Ac and n-HA-APTS.SAH process KB Growth of Cells after 24h good (Fig. 6 (a), (b), (d) and (e)).And the cell (Fig. 6 (c)) of processing through n-HA-APTS has part to start apoptosis (cell stops division, and spherical in shape).That from inverted phase contrast microscope, observes found that, n-HA after surface modification produces certain inhibitory action the propagation of cell except n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH on the propagation of KB cell without obvious impact, this shows to compare with modifying front n-HA, and n-HA-APTS.Ac and n-HA-APTS.SAH still have biocompatibility preferably.
(8) hemolytic experiment is estimated the blood compatibility of n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH.
Blood compatibility is an important indicator weighing the material application performance.The present invention is by the blood compatibility of hemolytic experiment evaluating material, be dissolved in n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH respectively in PBS, the solution (10～500 μ g/mL) of preparation variable concentrations, and PBS group is set and the pure water group is matched group.The human blood cell is mixed and hatches 2h under 37 ℃ of conditions with material, then centrifugal (8000r/min, 2min), (inferior light absorption value is directly proportional to the content of hemoglobin to get the light absorption value of supernatant measurement at the 570nm place, the human blood cell will discharge intracellular hemoglobin after rising brokenly, and hemoglobin is soluble in PBS, and at the 570nm place, maximum absorption value is arranged).Analyze accompanying drawing 7 known, when experimental concentration is 250 μ g/mL, experimental group (b) PBS, (c) n-HA, (d) n-HA-APTS, (e) n-HA-APTS.Ac and (f) n-HA-APTS.SAH obvious haemolysis does not all occur.Accompanying drawing 8 for by UV-Vis, record in 10～500 μ g/mL scopes, the content of hemoglobin in the PBS after every group of material processed.Analysis chart 8 is known, material under human red cell and each experimental concentration is cultivated 2h and altogether after centrifugal, in supernatant, the content of hemoglobin is compared with matched group (distilled water) and is all existed significant difference (p<0.01), show in 10～500 μ g/mL scopes, n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH all can not make the human blood cell produce haemolysis, and above-mentioned material has good blood compatibility in 10～500 μ g/mL scopes.
beneficial effect
(1) the present invention adopts simply, the auxiliary method of APTS realizes the surperficial multifunction of n-HA is modified, the experimental condition gentleness, technique is simple, and the product easy operating separates, dressing agent used is eco-friendly silane material, has the prospect of industrialized implementation;
(2) the resulting n-HA-APTS of the present invention, n-HA-APTS.Ac and n-HA-APTS.SAH nano grain surface have different active groups, and there is good biocompatibility and hemocyte stability, can be and solve better the defect that n-HA in use exists, and bring into play its premium properties.
The accompanying drawing explanation
The Fourier transform infrared spectroscopy figure that the upper figure of Fig. 1 is the nano-particle that the present invention relates to, figure below is 1250cm in upper figure
-1～1800cm
-1the enlarged drawing of part;
Fig. 2 is the nano-particle that the present invention relates to
1h NMR spectrogram: (a) n-HA-APTS, (b) n-HA-APTS.Ac and (c) n-HA-APTS.SAH;
The transmission electron microscope picture that Fig. 3 is the nano-particle that the present invention relates to: (a) n-HA, (b) n-HA-APTS, (c) n-HA-APTS.Ac and (d) n-HA-APTS.SAH;
The X-ray diffractogram that Fig. 4 is the nano-particle that the present invention relates to: (a) n-HA, (b) n-HA-APTS, (c) n-HA-APTS.Ac and (d) n-HA-APTS.SAH;
Fig. 5 is the cell viability of KB cell after PBS buffer (contrast), n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH process 24h that the test of MTT colorimetry obtains;
Fig. 6 is through (a) PBS buffer (contrast), (b) n-HA, (c) n-HA-APTS, (d) n-HA-APTS.Ac and the inverted phase contrast microscope picture (concentration of nano-particle is 100 μ g/mL) of the KB cell after (e) n-HA-APTS.SAH processes 24h;
Fig. 7 is the digital pictures (concentration of nano-particle is 250 μ g/mL) of human blood cell's haemolysis after (a) deionized water (contrast), (b) PBS buffer (contrast), (c) n-HA, (d) n-HA-APTS, (e) n-HA-APTS.Ac and (f) n-HA-APTS.SAH processing 2h;
The haemolysis effect that Fig. 8 is human blood cell after PBS buffer (contrast), deionized water (contrast), n-HA, n-HA-APTS, n-HA-APTS.Ac and n-HA-APTS.SAH process 2h;
Fig. 9 is that a is that the APTS hydrolysis forms silanol; The hydroxyl reaction that b is silanol and n-HA nano grain surface.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
190mg n-HA is mixed with the 200mL dehydrated alcohol, and be aided with ultrasound wave dispersion (80W, 1.5h), preparation n-HA/ alcohol suspension; 200 μ L APTS are slowly dropped in said n-HA/ alcohol suspension, and be aided with at ambient temperature magnetic agitation reaction 12h, reaction finishes.The suspension that reaction is obtained, after centrifugal (6000r/min, 5min), washing (distilled water wash 2 times, absolute ethanol washing 3 times), precipitation separation, obtains the n-HA-APTS nano-particle.
200mgn-HA is mixed with the 200mL dehydrated alcohol, and be aided with ultrasound wave dispersion (50W, 2h), preparation n-HA/ alcohol suspension.Drip the 5mL ultra-pure water in above-mentioned n-HA/ alcohol suspension.After magnetic agitation is even, 235 μ LAPTS are slowly dropped in said n-HA/ alcohol suspension, and be aided with at ambient temperature magnetic agitation reaction 12h, reaction finishes.The suspension that reaction is obtained, after centrifugal (6000r/min, 5min), washing (distilled water wash 2 times, absolute ethanol washing 3 times), precipitation separation, obtains the n-HA-APTS nano-particle.
The n-HA-APTS nano-particle of 200mg embodiment 1 preparation in dispersed and 15mL DMSO, is slowly dripped to the 1mL triethylamine by ultrasonic assosting effect under the condition of magnetic agitation, continue to stir 30min, make it fully to mix with the n-HA-APTS dispersion liquid.Then, slowly add the DMSO solution of 500 μ L containing 50 μ L acetic anhydride, be aided with at ambient temperature magnetic agitation reaction 24h, reaction finishes.The suspension that reaction is obtained, after centrifugal (6000r/min, 5min), washing (distilled water wash 2 times, absolute ethanol washing 3 times), precipitation separation, obtains the n-HA-APTS.Ac nano-particle.
The 50mg succinic anhydrides fully is dissolved in 10mLDMSO, then the n-HA-APTS of 100mg embodiment 2 preparations is joined in the DMSO of above-mentioned succinic anhydrides, and be aided with at ambient temperature magnetic agitation reaction 24h, reaction finishes; The suspension that reaction is obtained, after centrifugal (6000r/min, 5min), washing (distilled water wash 2 times, absolute ethanol washing 3 times), precipitation separation, obtains the n-HA-APTS.SAH nano-particle.
The n-HA-APTS nano-particle of 100mg embodiment 2 preparations is dispersed in 33mLDMSO, add again the 10mL DMSO solution containing the 80mg succinic anhydrides, reaction 24h, centrifugal after reaction finishes, washing, precipitation separation, obtain the n-HA-APTS.SAH nano-particle.
Claims (7)
1. the nanometer hydroxyapatite surface modification method of APTS mediation comprises:
(1) nanometer hydroxyapatite is mixed according to mass volume ratio 0.8-1.2:0.8-1.2mg/mL with ethanol, then with ultrasound wave, disperse to obtain nanometer hydroxyapatite/alcohol suspension;
(2) then APTS is dropped in above-mentioned nanometer hydroxyapatite/alcohol suspension, react at ambient temperature 10-15h; After reaction finishes, centrifugal, washing, precipitation separation, obtain the n-HA-APTS nano-particle; Wherein nanometer hydroxyapatite with the APTS amount of substance than 1:3～1:5; In step (2) before APTS is dropped to above-mentioned nanometer hydroxyapatite/alcohol suspension, first to the ultra-pure water that drips 1～5mL in described nanometer hydroxyapatite/alcohol suspension;
N-HA-APTS nano-particle acetylation by gained in step (2), operational approach is: by the n-HA-APTS nano-particle of gained, by mass volume ratio, being that 1.5-15:1mg/mL is ultrasonic is dispersed in DMSO, then add the 0.5-3mL triethylamine, add again the DMSO solution containing acetic anhydride, magnetic agitation reaction 18-30h, centrifugal after reaction finishes, washing, precipitation separation, obtain the n-HA-APTS.Ac nano-particle;
Perhaps that the n-HA-APTS nano-particle of gained in step (2) is carboxylated, operational approach is: by the n-HA-APTS nano-particle of gained, by mass volume ratio, be that 1.5-15:1mg/mL is dispersed in DMSO, add again the DMSO solution containing succinic anhydrides, reaction 20-30h, centrifugal after reaction finishes, washing, precipitation separation, obtain the n-HA-APTS.SAH nano-particle.
2. the nanometer hydroxyapatite surface modification method that a kind of APTS according to claim 1 mediates is characterized in that: the time that the ultrasound wave described in step (1) disperses is 1-5h, and power is 30-80W; Described washing is followed successively by water washing 2 times, washing with alcohol 3～5 times.
3. the nanometer hydroxyapatite surface modification method of a kind of APTS mediation according to claim 1 is characterized in that: centrifugal described in step (2), and its speed is 6000r/min, the time is 5min.
4. the nanometer hydroxyapatite surface modification method that a kind of APTS according to claim 1 mediates, it is characterized in that: the mol ratio of described acetic anhydride and n-HA-APTS is 5:1～10:1.
5. the nanometer hydroxyapatite surface modification method that a kind of APTS according to claim 1 mediates is characterized in that: the described volume ratio containing acetic anhydride in the DMSO solution of acetic anhydride and DMSO is 5:1～10:1.
6. the nanometer hydroxyapatite surface modification method that a kind of APTS according to claim 1 mediates, it is characterized in that: the mol ratio of described succinic anhydrides and n-HA-APTS is 5:1～10:1.
7. the nanometer hydroxyapatite surface modification method that a kind of APTS according to claim 1 mediates is characterized in that: the described volume ratio containing succinic anhydrides in the DMSO solution of succinic anhydrides and DMSO is 5:1～10:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475280A (en) * | 2003-06-17 | 2004-02-18 | 武汉理工大学 | Method of establishing nano organic silane dressing layer on hydroxy apatite surfac |
| CN101829341A (en) * | 2009-03-13 | 2010-09-15 | 上海交通大学医学院附属第九人民医院 | Hydroxyapatite nanoparticle radionuclide marked product and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475280A (en) * | 2003-06-17 | 2004-02-18 | 武汉理工大学 | Method of establishing nano organic silane dressing layer on hydroxy apatite surfac |
| CN101829341A (en) * | 2009-03-13 | 2010-09-15 | 上海交通大学医学院附属第九人民医院 | Hydroxyapatite nanoparticle radionuclide marked product and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张胜民.HA/PLA复合生物材料界面的分子设计、构建与相关性能.《中国优秀博硕士学位论文全文数据库（博士）工程科技I辑》.2003,(第02期),B020-5页. * |
| 龙跃.乙酰化法.《简明有机分析》.郑州大学出版社,2009,第157-158页. * |
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