CN101508429A - Hydroxyapatite nano-complex particle, preparation and uses thereof - Google Patents
Hydroxyapatite nano-complex particle, preparation and uses thereof Download PDFInfo
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- CN101508429A CN101508429A CNA2009100585870A CN200910058587A CN101508429A CN 101508429 A CN101508429 A CN 101508429A CN A2009100585870 A CNA2009100585870 A CN A2009100585870A CN 200910058587 A CN200910058587 A CN 200910058587A CN 101508429 A CN101508429 A CN 101508429A
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Abstract
The invention relates to hydroxyapatite composite nanoparticles, which comprise hydroxyapatite of which mass friction is 95 to 99.5 percent and cellulose with the mass friction of between 0.5 and 5 percent, wherein the appearance of the hydroxyapatite composite nanoparticles is a needle of which the length is between 50 and 310 nanometers and the width is between 3 and 30 nanometers. A method for preparing the hydroxyapatite composite nanoparticles comprises the following technological steps: (1) taking a metallic soluble salt aqueous solution or an ammonium salt aqueous solution as a solvent to dissolve the cellulose at a temperature of between 60 and 100 DEG C; (2) adding a calcium salt aqueous solution and a phosphate aqueous solution into a cellulose-salt solution after the cellulose-salt solution prepared in the step (1) is cooled to the room temperature, controlling the mol ratio of Ca to P of a reaction system is 1.2-2.0:1, subsequently adjusting the pH value of the reaction system, stopping stirring when the pH value is stably between 10 and 12, and keeping the obtained solution stand and performing aging for at least 48 hours; and (3) collecting and drying products. The composite particles have stable dispersity in an aqueous-phase medium, and can be taken as a fluorescent molecular carrier.
Description
Technical field
The invention belongs to Mierocrystalline cellulose-hydroxyapatite composite material field, particularly a kind of hydroxyapatite nano-complex particle and preparation method thereof and application.
Background technology
The nanometer needle-like hydroxyapatite is at biomedical sectors such as tissue repair, oncotherapy, fluorescence diagnosis probe (the Qiu H that has a wide range of applications, et al., A citric acid-based hydroxyapatite composite for orthopedic implants, Biomaterials, 2006,27,5845-5854; Mondejar SP, et al.Lanthanide-doped calcium phosphatenanoparticles with high internal crystallinity and with a shell of DNA as fluorescent probes incell experiments, Journal of Materials Chemistry, 2007,17,4153-4159), conventional technology of preparing is mainly hydro-thermal or introduces hydrothermal synthesis method (the Liu HS of tensio-active agent, et al., Hydroxyapatite synthesized bya simplified hydrothermal method, Ceramics International, 1997,23,19-25), this method exists such as the energy consumption height, the products obtained therefrom poor stability, easily reunite, shortcomings such as biocompatibility difference are difficult to satisfy application demand.
The kind of Mierocrystalline cellulose-hydroxyapatite composite material seldom, at present, its preparation method mainly comprises two classes: the first is utilized the abundant oh group of Mierocrystalline cellulose, deposited hydroxyl apatite or calcium phosphate (Rhef SH on water insoluble fibre cellulose fiber or cellulose fibril, et al., Hydroxyapatite formation on cellulose cloth induced bycitric acid, Journal of Materials Science:Materials in Medicine, 2000,11 (7), 449-452); It two is that natural cellulose is carried out chemical modification, utilize its soluble derivative to synthesize preparation hydroxyapatite composite material (Zakharov NA again, et al., Hydroxyapatite-carboxymethyl cellulose nanocompositesbiomaterial, Inorganic Materials, 2005,41 (5), 509-515).Mierocrystalline cellulose-hydroxyapatite composite material that above-mentioned preparation method obtains, one class is the hydroxyapatite crystal layer that forms in the cellulose surface growth, one class is through chemical modification institute synthetic composite particles, still there is agglomeration in these matrix materials, dispersion stabilization in aqueous media is poor, seriously limits its application.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of long-time hydroxyapatite nano-complex particle stable dispersion, functionalization of energy and preparation method thereof and application in aqueous media is provided.
Hydroxyapatite nano-complex particle of the present invention contains the hydroxyapatite of massfraction 95～99.5% and the Mierocrystalline cellulose of massfraction 0.5～5%, and its pattern is needle-like, and the length of pin is 50～310nm, and the width of pin is 3～30nm.
Because hydroxyapatite nano-complex particle of the present invention contains Mierocrystalline cellulose, thereby its surface carries oh group, can be used as fluorescence molecule carrier and pharmaceutical carrier.
Experiment shows that hydroxyapatite nano-complex particle of the present invention has stable dispersing property (seeing embodiment 7) in aqueous media.
Mierocrystalline cellulose in the hydroxyapatite nano-complex particle of the present invention source is very extensive, at least a in bamboo cellulose, wood cellulose, cotton cellulose, draft Mierocrystalline cellulose, the bacteria cellulose.
The preparation method of hydroxyapatite nano-complex particle of the present invention, processing step is as follows successively:
(1) cellulosic dissolving
The proportioning of Mierocrystalline cellulose and solvent is: Mierocrystalline cellulose quality: solvent volume=1:250～1500, cellulosic mass unit is a milliliter for the volume unit of gram, solvent, or cellulosic mass unit is that the volume unit of kilogram, solvent is for rising, described solvent is the metal soluble salt aqueous solution or ammonium salt aqueous solution, and its concentration is 1～5mol/L;
Mierocrystalline cellulose is joined in the solvent, it is dissolved fully, solvent temperature is controlled at 60～100 ℃;
(2) reaction is synthetic
After the Mierocrystalline cellulose-salts solution of step (1) preparation is cooled to room temperature, under agitation in this solution, add calcium saline solution and aqueous phosphatic, the add-on of calcium saline solution, aqueous phosphatic is exceeded with the mol ratio=1.2～2.0:1 of Ca/P in the reaction system, continue after the pH value of conditioned reaction system, when the pH of reaction system value stabilization 10～12 the time, stop to stir under room temperature, normal pressure still aging at least 48 hours;
(3) product collection is with dry
After the still aging end, adopt the mode collecting reaction product of filtering separation or centrifugation, then reaction product is carried out drying, promptly obtain hydroxyapatite nano-complex particle.
In the aforesaid method, Mierocrystalline cellulose is at least a in bamboo cellulose, wood cellulose, cotton cellulose, draft Mierocrystalline cellulose, the bacteria cellulose, and cellulosic granularity is 300 orders to the maximum, and the metal soluble salt is NaNO
3, NaBr, NaI, KBr, Mg (NO
3)
2, MgCl
2, CaCl
2, SrCl
2, ZnCl
2, FeCl
3In at least a, ammonium salt is NH
4NO
3, NH
4Br, NH
4At least a among the I.
In the aforesaid method, calcium salt is Ca (NO
3)
24H
2O or CaCl
2, phosphoric acid salt is Na
2HPO
412H
2O, (NH
4)
2HPO
42H
2O, NaH
2PO
42H
2O, K
2HPO
43H
2O, KH
2PO
4, NH
4H
2PO
4In a kind of.
In the aforesaid method, during the pH value of conditioned reaction system, with the NaOH aqueous solution and hydrochloric acid or ammoniacal liquor and hydrochloric acid.
The present invention has following beneficial effect:
1, hydroxyapatite nano-complex particle of the present invention is needle-like, has good aqueous media dispersiveness, can in water, PBS damping fluid, physiological saline, cell culture medium etc., keep the stable dispersion state for a long time, not produce agglomeration (seeing embodiment 7).
2,, thereby aspect injectable drug carrier, gene nano-carrier, having broad application prospects because hydroxyapatite nano-complex particle of the present invention has good aqueous media dispersiveness.
3, because the plain active group of the nanostructure of hydroxyapatite nano-complex particle of the present invention and surface fiber, but thereby load fluorescence molecule (seeing embodiment 8), use as the fluorescence molecule carrier.
4, the method for the invention starting material wide material sources, cost is low, and preparation technology is simple, environmental friendliness.
Description of drawings
Fig. 1 is the sem photograph of hydroxyapatite nano-complex particle of the present invention (embodiment 1 preparation);
Fig. 2 is the transmission electron microscope picture of hydroxyapatite nano-complex particle of the present invention (embodiment 1 preparation);
Fig. 3 is the x x ray diffration pattern x of hydroxyapatite nano-complex particle of the present invention (embodiment 1 preparation);
Fig. 4 is the dispersing property experimental result photo of hydroxyapatite nano-complex particle of the present invention (embodiment 1 preparation) in different aqueous medias (A cell culture medium, B deionized water, C physiological saline, DPBS buffered soln);
Fig. 5 is the uv absorption spectra of hydroxyapatite nano-complex particle of the present invention (embodiment 1 preparation) and conventional hydrothermal method synthetic nanometer needle-like hydroxyapatite contrast marker fluorescence molecule (FITC), among the figure, A is the uv absorption spectra of hydroxyapatite nano-complex particle of the present invention, and B is the uv absorption spectra of conventional hydrothermal method synthetic nanometer needle-like hydroxyapatite.
Embodiment
Below by embodiment hydroxyapatite nano-complex particle of the present invention and preparation method thereof and application are described further.Among the following embodiment, all with the deionized water preparation, room temperature is 25～30 ℃ to the aqueous solution.
Embodiment 1
In the present embodiment, the processing step of preparation hydroxyapatite nano-complex particle is as follows successively:
(1) cellulosic dissolving
Get 0.05g500 purpose mao bamboon cellulose powder, join the NaI-NaNO that 12.50mL concentration is 1.0mol/L
3In-NaBr the aqueous solution (the amount of substance concentration of three kinds of sodium salts is 1.0mol/L in the solution), (stirring velocity is 400 rev/mins) is heated to 60 ℃ and temperature is remained on 60 ℃ make the mao bamboon cellulose powder dissolve (about 6 hours) fully under magnetic agitation, forms Mierocrystalline cellulose-salt homogeneous phase aqueous solution;
(2) reaction is synthetic
After the mao bamboon Mierocrystalline cellulose-salts solution of step (1) preparation is cooled to room temperature, under 400 rev/mins speed stir, add the Ca (NO of concentration 0.06mol/L
3)
24H
2The Na of the O aqueous solution, concentration 0.05mol/L
2HPO
412H
2Each 25mL of the O aqueous solution, the Ca/P=1.2:1 of reaction system;
Continue after, with the pH value of the HCl conditioned reaction system of the NaOH aqueous solution of concentration 0.1mol/L and concentration 0.1mol/L, when the pH of reaction system value stabilization 10 the time, stop stirring, still aging 48 hours;
(3) product collection is with dry
After the still aging end, 1000 rev/mins of centrifugal collecting precipitations are used the collected precipitation of deionized water wash 3～5 times, will wash postprecipitation then and place vacuum drying oven, 40 ℃ of vacuum-dryings (negative pressure is 0.1Mpa) 36 hours, promptly obtain hydroxyapatite nano-complex particle.
With scanning electronic microscope (HITACHI S-4800) and transmission electron microscope (JEM-100CX) obtaining hydroxyapatite nano-complex particle being carried out pattern characterizes, the result shows that the pattern of this nano-complex particle is needle-like, the mean length of pin is 230nm, and the width average of pin is 15nm (seeing Fig. 1, Fig. 2); (DX-1000) analyzes obtaining hydroxyapatite nano-complex particle with the x x ray diffractometer x, and the result shows has hydroxyapatite and Mierocrystalline cellulose to have (see figure 3) simultaneously; Analyzed the relative content of Mierocrystalline cellulose and hydroxyapatite in the nano-complex particle with thermogravimetric analyzer TG (STA 449C), the result shows that in the prepared composite particles of present embodiment, cellulosic massfraction is 5%, and the massfraction of hydroxyapatite is 95%.
Embodiment 2
In the present embodiment, the processing step of preparation hydroxyapatite nano-complex particle is as follows successively:
(1) cellulosic dissolving
Get 0.03kg400 purpose pine cellulose powder, join the ZnCl that 45L concentration is 5mol/L
2In the aqueous solution, (stirring velocity is 400 rev/mins) is heated to 100 ℃ and temperature is remained on 100 ℃ make the pine cellulose powder dissolve (about 2 hours) fully under magnetic agitation, forms Mierocrystalline cellulose-salt homogeneous phase aqueous solution;
(2) reaction is synthetic
After the pine Mierocrystalline cellulose-salts solution of step (1) preparation is cooled to room temperature, under 400 rev/mins speed stir, add the Ca (NO of concentration 0.5mol/L
3)
24H
2(the NH of the O aqueous solution, concentration 0.25mol/L
4)
2HPO
42H
2Each 2.5L of the O aqueous solution, the Ca/P=2.0:1 of reaction system;
Continue after, with the pH value of the HCl conditioned reaction system of the ammoniacal liquor of concentration 1.0mol/L and concentration 1.0mol/L, when the pH of reaction system value stabilization 12 the time, stop stirring, still aging 78 hours;
(3) product collection is with dry
After the still aging end, 1000 rev/mins of centrifugal collecting precipitations are used the collected precipitation of deionized water wash 3～5 times, will wash postprecipitation then and place vacuum drying oven, 50 ℃ of vacuum-dryings (negative pressure is 0.1Mpa) 24 hours, promptly obtain hydroxyapatite nano-complex particle.
With scanning electronic microscope (HITACHI S-4800) and transmission electron microscope (JEM-100CX) obtaining hydroxyapatite nano-complex particle being carried out pattern characterizes, the result shows that the pattern of this nano-complex particle is needle-like, the mean length of pin is 190nm, and the width average of pin is 20nm; (DX-1000) analyzes obtaining hydroxyapatite nano-complex particle with the x x ray diffractometer x, and the result shows has hydroxyapatite and Mierocrystalline cellulose to exist simultaneously; Analyzed the relative content of Mierocrystalline cellulose and hydroxyapatite in the nano-complex particle with thermogravimetric analyzer TG (STA449C), the result shows in the prepared composite particles of present embodiment, cellulosic massfraction is 0.5%, and the massfraction of hydroxyapatite is 99.5%.
Embodiment 3
In the present embodiment, the processing step of preparation hydroxyapatite nano-complex particle is as follows successively:
(1) cellulosic dissolving
Get 0.10g300 purpose degreasing cotton cellulose powder, join the ZnCl of 50mL concentration 2mol/L
2-Mg (NO
3)
2-MgCl
2In the aqueous solution (the amount of substance concentration of three kinds of metal-salts is 2mol/L), (stirring velocity is 400 rev/mins) is heated to 80 ℃ and temperature is remained on 80 ℃ make the degreasing cotton cellulose powder dissolve (about 4 hours) fully under magnetic agitation, forms Mierocrystalline cellulose-salt homogeneous phase aqueous solution;
(2) reaction is synthetic
After the degreasing cotton Mierocrystalline cellulose-salts solution of step (1) preparation is cooled to room temperature, under 400 rev/mins speed stir, add the Ca (NO of concentration 1mol/L
3)
24H
2The NaH of the O aqueous solution, concentration 0.6mol/L
2PO
42H
2Each 15mL of the O aqueous solution, the Ca/P=1.67:1 of reaction system;
Continue after, with the pH value of the hydrochloric acid conditioned reaction system of the ammoniacal liquor of concentration 0.1mol/L and concentration 0.1mol/L, when the pH of reaction system value stabilization 11 the time, stop stirring, still aging 90 hours;
(3) product collection is with dry
After the still aging end, 1000 rev/mins of centrifugal collecting precipitations are used the collected precipitation of deionized water wash 3～5 times, will wash postprecipitation then and place vacuum drying oven, 60 ℃ of vacuum-dryings (negative pressure is 0.1Mpa) 16 hours, promptly obtain hydroxyapatite nano-complex particle.
With scanning electronic microscope (HITACHI S-4800) and transmission electron microscope (JEM-100CX) obtaining hydroxyapatite nano-complex particle being carried out pattern characterizes, the result shows that the pattern of this nano-complex particle is needle-like, the mean length of pin is 210nm, and the width average of pin is 18nm; (DX-1000) analyzes obtaining hydroxyapatite nano-complex particle with the x x ray diffractometer x, and the result shows has hydroxyapatite and Mierocrystalline cellulose to exist simultaneously; Analyzed the relative content of Mierocrystalline cellulose and hydroxyapatite in the nano-complex particle with thermogravimetric analyzer TG (STA 449C), the result shows in the prepared composite particles of present embodiment, cellulosic massfraction is 4.1%, and the massfraction of hydroxyapatite is 95.9%.
Embodiment 4
In the present embodiment, the processing step of preparation hydroxyapatite nano-complex particle is as follows successively:
(1) cellulosic dissolving
Get 0.02kg 500 purpose draft cellulose powders (wheat stalk fiber), join the KBr-CaCl of 20.0L concentration 1.5mol/L
2-SrCl
2-FeCl
3In the aqueous solution (the amount of substance concentration of four kinds of metal-salts is 1.5mol/L), (stirring velocity is 400 rev/mins) is heated to 70 ℃ and temperature is remained on 70 ℃ make the plain powder of draft fiber powder dissolve (about 5 hours) fully under magnetic agitation, forms Mierocrystalline cellulose-salt homogeneous phase aqueous solution;
(2) reaction is synthetic
After the draft Mierocrystalline cellulose-salts solution of step (1) preparation is cooled to room temperature, under 400 rev/mins speed stir, add the CaCl of concentration 0.45mol/L
2The K of the aqueous solution, concentration 0.3mol/L
2HPO
43H
2Each 2.5L of the O aqueous solution, the Ca/P=1.5:1 of reaction system;
Continue after, with the pH value of the hydrochloric acid conditioned reaction system of the ammoniacal liquor of concentration 0.1mol/L and concentration 0.1mol/L, when the pH of reaction system value stabilization 10 the time, stop stirring, still aging 60 hours;
(3) product collection is with dry
After the still aging end, 1000 rev/mins of centrifugal collecting precipitations are used the collected precipitation of deionized water wash 3～5 times, and the precipitation lyophilize after will washing then 48 hours promptly obtains hydroxyapatite nano-complex particle.
With scanning electronic microscope (HITACHI S-4800) and transmission electron microscope (JEM-100CX) obtaining hydroxyapatite nano-complex particle being carried out pattern characterizes, the result shows that the pattern of this nano-complex particle is needle-like, the mean length of pin is 200nm, and the width average of pin is 25nm; (DX-1000) analyzes obtaining hydroxyapatite nano-complex particle with the x x ray diffractometer x, and the result shows has hydroxyapatite and Mierocrystalline cellulose to exist simultaneously; Analyzed the relative content of Mierocrystalline cellulose and hydroxyapatite in the nano-complex particle with thermogravimetric analyzer TG (STA 449C), the result shows in the prepared composite particles of present embodiment, cellulosic massfraction is 3.6%, and the massfraction of hydroxyapatite is 96.4%.
Embodiment 5
Among the embodiment, the processing step of preparation hydroxyapatite nano-complex particle is as follows successively:
(1) cellulosic dissolving
Get the NH that 0.2g 500 purpose bacteria cellulose powder (acetobacter xylinum is a bacterial classification, and Sucus Cocois is a substratum) join 50mL concentration 2mol/L
4NO
3-NH
4Br-NH
4In the I aqueous solution (the amount of substance concentration of three kinds of ammonium salts is 2mol/L), (stirring velocity is 400 rev/mins) is heated to 90 ℃ under magnetic agitation, and temperature remained on 90 ℃, and make the plain powder of bacterial fibers powder dissolve (about 3 hours) fully, form Mierocrystalline cellulose-salt homogeneous phase aqueous solution;
(2) reaction is synthetic
After the bacteria cellulose-salts solution of step (1) preparation is cooled to room temperature, under 400 rev/mins speed stir, add the Ca (NO of concentration 0.5mol/L
3)
24H
2The KH of the O aqueous solution, concentration 0.3mol/L
2PO
4Each 25mL of the aqueous solution, the Ca/P=1.67:1 of reaction system;
Continue after, with the pH value of the hydrochloric acid conditioned reaction system of the ammoniacal liquor of concentration 0.1mol/L and concentration 0.1mol/L, when the pH of reaction system value stabilization 11 the time, stop stirring, still aging 120 hours;
(3) product collection is with dry
After the still aging end, 1000 rev/mins of centrifugal collecting precipitations are used the collected precipitation of deionized water wash 3～5 times, and the precipitation lyophilize after will washing then 48 hours promptly obtains hydroxyapatite nano-complex particle.
With scanning electronic microscope (HITACHI S-4800) and transmission electron microscope (JEM-100CX) obtaining hydroxyapatite nano-complex particle being carried out pattern characterizes, the result shows that the pattern of this nano-complex particle is needle-like, the mean length of pin is 220nm, and the width average of pin is 15nm; (DX-1000) analyzes obtaining hydroxyapatite nano-complex particle with the x x ray diffractometer x, and the result shows has hydroxyapatite and Mierocrystalline cellulose to exist simultaneously; Analyzed the relative content of Mierocrystalline cellulose and hydroxyapatite in the nano-complex particle with thermogravimetric analyzer TG (STA 449C), the result shows in the prepared composite particles of present embodiment, cellulosic massfraction is 2.3%, and the massfraction of hydroxyapatite is 97.7%.
Embodiment 6
Among the embodiment, the processing step of preparation hydroxyapatite nano-complex particle is as follows successively:
(1) cellulosic dissolving
Get 0.01kg 400 purpose pine cellulose powders and 0.01kg 500 purpose draft cellulose powders (wheat stalk Mierocrystalline cellulose), join the NH of 20L 1mol/L
4NO
3In the aqueous solution, (stirring velocity is 400 rev/mins and is heated to 100 ℃, and temperature is remained on 100 ℃, makes the plain powder of pine fiber powder dissolve (about 2 hours) fully with the wheat stalk cellulose powder, formation Mierocrystalline cellulose-salt homogeneous phase aqueous solution under magnetic agitation;
(2) reaction is synthetic
When after the pine Mierocrystalline cellulose-draft Mierocrystalline cellulose-salts solution is cooled to room temperature of step (1) preparation, under 400 rev/mins speed stir, add the Ca (NO of concentration 0.45mol/L
3)
24H
2The NH of the O aqueous solution, concentration 0.3mol/L
4H
2PO
4Each 1.5L of the aqueous solution, the Ca/P=1.5:1 of reaction system;
Continue after, with the ammoniacal liquor of concentration 1.0mol/L and the pH value of concentration 1.0mol/L HCl hydrochloric acid conditioned reaction system, when the pH of reaction system value stabilization 12 the time, stop stirring, still aging 78 hours;
(3) product collection is with dry
After the still aging end, 1000 rev/mins of centrifugal collecting precipitations are used the collected precipitation of deionized water wash 3～5 times, will wash postprecipitation then and place vacuum drying oven, 50 ℃ of vacuum-dryings (negative pressure is 0.1Mpa) 24 hours, promptly obtain hydroxyapatite nano-complex particle.
With scanning electronic microscope (HITACHI S-4800) and transmission electron microscope (JEM-100CX) obtaining hydroxyapatite nano-complex particle being carried out pattern characterizes, the result shows that the pattern of this nano-complex particle is needle-like, the mean length of pin is 180nm, and the width average of pin is 20nm; (DX-1000) analyzes obtaining hydroxyapatite nano-complex particle with the x x ray diffractometer x, and the result shows has hydroxyapatite and Mierocrystalline cellulose to exist simultaneously; Analyzed the relative content of Mierocrystalline cellulose and hydroxyapatite in the nano-complex particle with thermogravimetric analyzer TG (STA 449C), the result shows in the prepared composite particles of present embodiment, cellulosic massfraction is 1.6%, and the massfraction of hydroxyapatite is 98.4%.
Embodiment 7
Each 0.5mg of hydroxyapatite nano-complex particle that gets embodiment 1 preparation joins respectively among 5mL water, 5mL PBS damping fluid, 5mL physiological saline, the 5mL cell culture medium, and at room temperature ultra-sonic dispersion is 5 minutes, leaves standstill 45 days for 25 times.The result shows that raphioid fiber element-hydroxyapatite nano-complex particle all keeps the dispersion state (see figure 4) at initial stage among water, PBS damping fluid, physiological saline, cell culture medium, and no reunion throw out produces.
This experiment shows, invents described hydroxyapatite nano-complex particle and has good aqueous media dispersiveness.
Embodiment 8
Present embodiment is the FITC labelling experiment, with reference to Roman and co-worker thereof the method for Mierocrystalline cellulose mark is also slightly made an amendment (Dong S, Roman M, Fluorescently labeled cellulose nanocrystals for biomagingapplications, Journal of American Chemical Society, 2007,129,13810-13811), Hydrothermal Preparation nanometer needle-like hydroxyapatite sample in contrast.Concrete steps are as follows:
Get the hydroxyapatite nano-complex particle of 1.5mg embodiment 1 preparation, add the 2mL epoxy chloropropane, 2mL 2MNaOH, 60 ℃ are reacted 4-16h down; Above-mentioned reaction is dialysed after finishing.The after product of will dialysing is added in the 10mL round-bottomed flask, adds 0.01M NaOH 2mL, and 60 ℃ are reacted 4～16h down; Above-mentioned reaction is dialysed after finishing, and the dialysis product joins in the 10mL round-bottomed flask, to wherein adding the borate buffer solution (pH=10) that 2mL prepares in advance, again to wherein adding 0.83mgFITC, stirring reaction 14～72h; Reaction was dialysed 5～8 days after finishing.
Get 1.5mg Hydrothermal Preparation nanometer needle-like hydroxyapatite, add the 2mL epoxy chloropropane, 2mL 2M NaOH, 60 ℃ are reacted 4-16h down; Above-mentioned reaction is dialysed after finishing.The after product of will dialysing is added in the 10mL round-bottomed flask, adds 0.01M NaOH 2mL, and 60 ℃ are reacted 4～16h down; Above-mentioned reaction is dialysed after finishing, and the dialysis product joins in the 10mL round-bottomed flask, to wherein adding the borate buffer solution (pH=10) that 2mL prepares in advance, again to wherein adding 0.83mg FITC, stirring reaction 14～72h; Reaction was dialysed 5～8 days after finishing.
The mark effect is by the UV spectrophotometer measuring evaluation, and the result as shown in Figure 5.As can be seen from Figure 5, the present invention's ability of preparing hydroxyapatite nano-complex particle institute load fluorescence molecule is higher than the nanometer needle-like hydroxyapatite of Hydrothermal Preparation far away.
Experimental result shows that hydroxyapatite nano-complex particle of the present invention can be used as the fluorescence molecule carrier.
Claims (9)
1, a kind of hydroxyapatite nano-complex particle, it is characterized in that described composite particles contains the hydroxyapatite of massfraction 95～99.5% and the Mierocrystalline cellulose of massfraction 0.5～5%, its pattern is needle-like, and the length of pin is 50～310nm, and the width of pin is 3～30nm.
2, hydroxyapatite nano-complex particle according to claim 1 is characterized in that described composite particles surface carries oh group, has stable dispersing property in aqueous media.
3, hydroxyapatite nano-complex particle according to claim 1 and 2 is characterized in that Mierocrystalline cellulose is at least a in bamboo cellulose, wood cellulose, cotton cellulose, draft Mierocrystalline cellulose, the bacteria cellulose.
4, the described hydroxyapatite nano-complex particle of claim 1 is as the application of fluorescence molecule carrier.
5, a kind of preparation method of hydroxyapatite nano-complex particle is characterized in that processing step is as follows successively:
(1) cellulosic dissolving
The proportioning of Mierocrystalline cellulose and solvent is: the Mierocrystalline cellulose quality: solvent volume=1: 250～1500, cellulosic mass unit is a milliliter for the volume unit of gram, solvent, or cellulosic mass unit is that the volume unit of kilogram, solvent is for rising, described solvent is the metal soluble salt aqueous solution or ammonium salt aqueous solution, and its concentration is 1～5mol/L;
Mierocrystalline cellulose is joined in the solvent, it is dissolved fully, solvent temperature is controlled at 60～100 ℃;
(2) reaction is synthetic
After the Mierocrystalline cellulose-salts solution of step (1) preparation is cooled to room temperature, under agitation in this solution, add calcium saline solution and aqueous phosphatic, the add-on of calcium saline solution, aqueous phosphatic is exceeded with the mol ratio=1.2～2.0:1 of Ca/P in the reaction system, continue after the pH value of conditioned reaction system, when the pH of reaction system value stabilization 10～12 the time, stop to stir under room temperature, normal pressure still aging at least 48 hours;
(3) product collection is with dry
After the still aging end, collecting reaction product carries out drying with reaction product then, promptly obtains hydroxyapatite nano-complex particle.
6, the preparation method of hydroxyapatite nano-complex particle according to claim 5 is characterized in that Mierocrystalline cellulose is at least a in bamboo cellulose, wood cellulose, cotton cellulose, draft Mierocrystalline cellulose, the bacteria cellulose, and the metal soluble salt is NaNO
3, NaBr, NaI, KBr, Mg (NO
3)
2, MgCl
2, CaCl
2, SrCl
2, ZnCl
2, FeCl
3In at least a, ammonium salt is NH
4NO
3, at least a among NH4Br, the NH4I.
7,, it is characterized in that calcium salt is Ca (NO according to the preparation method of claim 5 or 6 described hydroxyapatite nano-complex particles
3)
24H
2O or CaCl
2, phosphoric acid salt is Na
2HPO
412H
2O, (NH
4)
2HPO
42H
2O, NaH
2PO
42H
2O, K
2HPO
43H
2O, KH
2PO
4, NH
4H
2PO
4In a kind of.
8, according to the preparation method of claim 5 or 6 described hydroxyapatite nano-complex particles, when it is characterized in that the pH value of conditioned reaction system, with the NaOH aqueous solution and hydrochloric acid or ammoniacal liquor and hydrochloric acid.
9, the preparation method of hydroxyapatite nano-complex particle according to claim 7 is when is characterized in that the pH value of conditioned reaction system, with the NaOH aqueous solution and hydrochloric acid or ammoniacal liquor and hydrochloric acid.
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| CN104958766A (en) * | 2015-06-03 | 2015-10-07 | 四川大学 | Sodium alginate-hydroxyapatite hybridization nano particle and preparing method thereof |
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| CN103159961A (en) * | 2013-04-01 | 2013-06-19 | 钟春燕 | Preparation method of mineralized bacterial cellulose/polyvinyl alcohol composite aquagel cartilage repairing material |
| CN104958766B (en) * | 2015-06-03 | 2018-05-25 | 四川大学 | Sodium alginate-hydroxyapatite hybridized nano-particle and preparation method thereof |
| CN104958766A (en) * | 2015-06-03 | 2015-10-07 | 四川大学 | Sodium alginate-hydroxyapatite hybridization nano particle and preparing method thereof |
| CN106827851A (en) * | 2016-12-20 | 2017-06-13 | 当涂县金龙机械有限公司 | A kind of fast print type containing nanometer hydroxyapatite prepared by magnetic activated water exempts from alcohol concentration fountain solution and preparation method thereof |
| CN110114309A (en) * | 2017-02-28 | 2019-08-09 | 新东工业株式会社 | The manufacturing method and composite material molded body of composite material molded body containing needle-like hydroxyapatite |
| CN110114309B (en) * | 2017-02-28 | 2022-11-01 | 新东工业株式会社 | Method for producing composite material molded body containing needle-like hydroxyapatite, and composite material molded body |
| WO2019033594A1 (en) * | 2017-08-16 | 2019-02-21 | 西安电子科技大学 | Ph-responsive ultrasensitive fluorescent nanoprobe and preparation method therefor |
| US11291736B2 (en) | 2017-08-16 | 2022-04-05 | Xidian University | pH-responsive ultrasensitive fluorescent nanoprobe, preparation and using method thereof |
| CN107473194A (en) * | 2017-10-10 | 2017-12-15 | 周益铭 | A kind of preparation method of nanometer hydroxyapatite |
| CN108607116A (en) * | 2018-05-21 | 2018-10-02 | 湖南师范大学 | A kind of bamboo fibre/nano-apatite composite material and preparation method |
| CN108607116B (en) * | 2018-05-21 | 2020-12-22 | 湖南师范大学 | Bamboo fiber/nano apatite composite material and preparation method thereof |
| CN109381746A (en) * | 2018-10-15 | 2019-02-26 | 湖南师范大学 | A kind of preparation method and applications of lignin modification nanometer hydroxyapatite |
| CN112194111A (en) * | 2020-01-05 | 2021-01-08 | 天津科技大学 | Preparation method of hydroxyapatite nanotube |
| CN111690155A (en) * | 2020-01-11 | 2020-09-22 | 天津科技大学 | Preparation method of nano-cellulose/hydroxyapatite nanospheres |
| CN117378598A (en) * | 2023-12-08 | 2024-01-12 | 金宝医学科技(深圳)有限公司 | Oocyte cryopreservation liquid and preparation method thereof |
| CN117378598B (en) * | 2023-12-08 | 2024-03-19 | 金宝医学科技(深圳)有限公司 | Oocyte cryopreservation liquid and preparation method thereof |
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