CN1693415B - Hydroxy phosphorite of near infrared fluorescence quantum point mark and its preparation process and application - Google Patents
Hydroxy phosphorite of near infrared fluorescence quantum point mark and its preparation process and application Download PDFInfo
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- CN1693415B CN1693415B CN 200510025590 CN200510025590A CN1693415B CN 1693415 B CN1693415 B CN 1693415B CN 200510025590 CN200510025590 CN 200510025590 CN 200510025590 A CN200510025590 A CN 200510025590A CN 1693415 B CN1693415 B CN 1693415B
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- near infrared
- hydroxyapatite
- fluorescence quantum
- infrared fluorescence
- quantum point
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Abstract
The invention discloses a method for preparing a hydroxy apatite marked by near infrared fluorescence quantum dot nano particles and application thereof in biomedicine. The invention links the near infrared fluorescence quantum dot nano particle to the hydroxy apatite by means of adsorption, ion-exchange, covalent immobilization and the like so as to be used for researches of bone growth, osteoblast transfer, and diagnosis and treatment of diseases such as coronary sclerosis and other human diseases. The near infrared fluorescence quantum dot nano particles emit near infrared fluorescence which can penetrate a tissue of centimeter level, has advantages of high quantum yield and stable optical property. The heat effect and .OH and .O2 free radicals with high activity generated by the near infrared quantum dot under the excitation of light also can be used for destroying tumor cells, and treating the tumor especially the bone cancer. The hydroxy apatite marked by near infrared fluorescence quantum dot nano particles provided by the invention has wide application in the biomedicine research field.
Description
Technical field
The present invention relates to be a kind of with the nano fluorescent marker material be attached on the hydroxyapatite method and in bio-medical applications, relate in particular to near-infrared fluorescent quantum dot nano particle is connected on the hydroxyapatite, the composite particles of hydroxyapatite of near infrared fluorescence quantum point that formed mark belongs to material and biomedical crossing domain.
Background technology
Hydroxyapatite is a kind of calcium salt of weakly alkaline phosphoric acid, is the main inorganic composition of human body and animal skeleton and tooth, and its chemical formula is Ga
10(PO
4)
6(OH)
2Hydroxyapatite crystal is six side's slant edge cylindricalitys, and the strip hydroxyapatite size in the bone is about (1.5-3.5nm) * (5.0-10.0nm) * (40.0nm-50.0nm), is natural nanostructure.
Discovering that the hydroxyapatite of synthetic has good biocompatibility and chemical stability, is a kind of ideal bone substitution material.Behind nano-grade hydroxy apatite implantable bone tissue, can form firm chemical bond with osseous tissue and combine, and have osteoconductive and osteoinductive, be widely used in the reparation of defective bone, be one of the emphasis of present embedded material research and focus.The surperficial configurational ion of hydroxyapatite is easy to adsorb ion, molecule and particle in its surrounding environment by ion-exchange or adsorption.In field of biology, hydroxyapatite also is commonly used to the medium as separation and purification of biological macromolecule.
[Zaheer A such as Zaheer A, et al.In vivo near infraredfluorescence imaging of osteoblastic activity.NatureBiotechnology, 2001,19:1148-1154] once the organic dye molecule with near-infrared fluorescent be connected on the hydroxyapatite, be used for studying the diagnosis of transfer, coronary sclerosis and other people the class disease of skeletal growth, sclerocyte.This method can in time be observed the pathology situation of growing state, cell transfer process and the tissue of bone by near-infrared fluorescent, brings great convenience to these researchs.Yet the near infrared organic dye has the defective of himself, and stable inadequately as the chemical property of dyestuff, fluorescence quantum yield is not high, fluorescent bleach speed is fast etc.
The near infrared fluorescence quantum point nanoparticle then can overcome these defectives of organic fluorescent dye, and it is stable to have a fluorescence quantum yield height, optical property, can make advantages such as the stable and persistent heat of its generation under the exciting of light.That in addition, can also utilize that near infrared fluorescence quantum point produces under optical excitation has highly active OH and an O
2Free radical comes the destroyed tumor cell.
The Application Areas of quantum dot nano particle has related to pharmacy, cytobiology, genomics, proteomics, molecular biology etc., and its research will produce huge and far-reaching influence to biomedical sector.
Summary of the invention
At the deficiency that prior art exists, one of purpose of the present invention is to provide a kind of hydroxyapatite of near infrared nano-luminescent material mark;
Two of purpose of the present invention is to provide the preparation method of this hydroxyapatite;
Three of purpose of the present invention is to provide the hydroxyapatite of this near infrared nano-luminescent material mark in bio-medical applications.
Goal of the invention of the present invention is achieved through the following technical solutions:
A kind of hydroxyapatite of near infrared fluorescence quantum point mark, wherein being connected of near infrared fluorescence quantum point nanoparticle and hydroxyapatite is to carry out in the mixed solution of water or organic phase or water and organic phase, in this liquid-phase system, the concentration of hydroxyapatite is 5 μ g/mL～0.25g/mL, and the concentration of near infrared fluorescence quantum point is 1ng/mL～15mg/mL.
Described near infrared fluorescence quantum point is main by the elementary composition semiconductor nano crystallite at the near-infrared region emitting fluorescence of II-VI family or III-V family.Comprise near infrared fluorescence quantum point nanoparticle that single semiconductor material forms, be nuclear with a kind of semi-conductor nano particles, another kind of inorganic materials is one or more the combination in the nano-complex particle of the core-shell type near infrared fluorescence quantum point nano-complex particle of shell or near infrared fluorescence quantum point quantum well structure.
Described hydroxyapatite is a kind of weakly alkaline calcium phosphate salt, comprises the hydroxyapatite of the nature of the hydroxyapatite of synthetic or animal, is needle-like or bar-shaped, or spherical or round pie or other are irregularly shaped.Described calcium phosphate salt also comprise phosphatic rock, calcium orthophosphate base bone cement.Described hydroxyapatite is synthetic or high temperature solid-state synthetic method acquisition by water, comprise hydrothermal method, hydrolysis method, coprecipitation method, sol-gel method, aerosol processing, acid-base reaction method, spray-drying process, synthetic in micro emulsion, aqueous phase is synthetic and by in the method for pyrolytic decomposition calcium containing compound in wet air any one in liposome, or by natural bone in the animal body is carried out high-temperature calcination obtains, the hydroxyapatite that obtains is a needle-like or bar-shaped, or spherical.
Described near infrared fluorescence quantum point is meant main by the elementary composition semiconductor nano crystallite at the near-infrared region emitting fluorescence of II-VI family or III-V family, comprises the near infrared fluorescence quantum point nanoparticle that single semiconductor material is formed; With a kind of semi-conductor nano particles is nuclear, and another kind of inorganic materials is the core-shell type near infrared fluorescence quantum point nano-complex particle of shell; And a kind of or several combination arbitrarily in the nano-complex particle of near infrared fluorescence quantum point quantum well structure.The near infrared fluorescence quantum point nanoparticle surface can be modified the molecule that can strengthen particle stability, as hydrophilic macromolecule, hydrophobic polymer, tensio-active agent etc.
The preparation method of the hydroxyapatite of near infrared fluorescence quantum point mark is as follows:
The present invention is connected to near-infrared fluorescent quantum dot nano particle on the hydroxyapatite by any one or a few method in absorption, ion-exchange, the covalent bonding, the composite particles of hydroxyapatite of near infrared fluorescence quantum point that formed mark.Being connected of near infrared fluorescence quantum point nanoparticle and hydroxyapatite be at liquid-phase system as in the mixed solution of water or organic phase or water and organic phase, carrying out.
The concrete preparation method of the hydroxyapatite of near infrared fluorescence quantum point mark provided by the invention is: hydroxyapatite is dispersed in the aqueous solution or organic solution such as methyl alcohol, ethanol, trichloromethane etc.; then in protection of inert gas or directly in the aqueous solution or the organic solution that in the hydroxyapatite suspension, add near infrared fluorescence quantum point under the air atmosphere, stir 1min～10 day.Calcium ion by hydroxyapatite surface or generation ion-exchange such as the metal ion on other configurational ions and near infrared fluorescence quantum point surface such as cadmium ion are adsorbed onto hydroxyapatite surface with near infrared fluorescence quantum point.Or making hydroxyapatite surface and near infrared fluorescence quantum point surface band dissimilar charges, the attraction by dissimilar charges is adsorbed onto hydroxyapatite surface with near infrared fluorescence quantum point.
Second method of the present invention is: modify organic molecule in hydroxyapatite surface; in protection of inert gas or directly under air atmosphere, with near infrared fluorescence quantum point generation chemical bonding or adsorption near infrared fluorescence quantum point is connected with hydroxyapatite, stir 1min～10 day by the functional group on the organic molecule.The described organic molecule of modifying in hydroxyapatite surface, be meant the organic molecule that has the polar functionalities group, as have hydroxyl, carboxyl, sulfonic group, amido, itrile group and can with organic molecules such as the polymer of one or more groups among O, the N etc. of metal ion generation coordination or small molecules, comprise various coupling agents and polyelectrolyte.Modifying method comprises physical adsorption and chemical reaction.
The third method of the present invention is: hydroxyapatite and near infrared fluorescence quantum point together are scattered in water be scattered in organic phase or be scattered in organic solution and the mixed solution of water in, obtain the hydroxyapatite micro-sphere of embedding near infrared fluorescence quantum point by spraying drying.Spray-dired condition is: inlet temperature is 30～250 ℃, and air outlet temperature is regulated automatically according to inlet temperature and input speed, and input speed is 0.1～200mLmin
-1, spraying drying is indoor to be rare gas element or air.Before the spraying drying, can in mixing solutions, add the agent of biocompatible glue connection.The product that obtains can be further dry, or further heating makes glue crosslinking agent molecule generation sex change.The agent of described biocompatible glue connection, be meant the organic molecule that has the polar functionalities group, as have hydroxyl, carboxyl, sulfonic group, amido, itrile group and can with organic molecules such as the polymer of one or more groups among O, the N etc. of metal ion generation coordination or small molecules.In the mixed solution, glue crosslinking agent concentration is 0～20wt%.
After near infrared fluorescence quantum point and hydroxyapatite effect, by centrifugal or filter or dialysis or self sedimentation or the isolating method of post are removed near infrared fluorescence quantum point and other impurity of not absorption.The hydroxyapatite composite particles of the near infrared fluorescence quantum point mark that obtains exists with water, or exist with the dried powder state.
Near infrared fluorescence quantum point is sterilized after being connected on the hydroxyapatite, and sterilization method is a kind of in heat sterilization or pressure sterilizing or Entkeimung or uv light irradiation or other aseptic techniques.
The hydroxyapatite of near infrared fluorescence quantum point mark of the present invention, it is applied as biomedical sector, especially is used for studying transfer, and the Clinics and Practices of other people class disease of skeletal growth, sclerocyte.
The hydroxyapatite of near infrared fluorescence quantum point mark provided by the invention has bigger superiority than the hydroxyapatite of existing mark organic fluorescent dye, the near-infrared fluorescent of its emission has advantages such as fluorescence quantum yield height, optical property be stable, and quantum dot under optical excitation, produce have highly active OH and an O
2Free radical can also be used to the destroyed tumor cell, can be used for tumor treatment.The hydroxyapatite of near infrared fluorescence quantum point mark provided by the invention has important scientific research value and wide biomedical applications prospect.
Embodiment
How further specify the present invention below in conjunction with specific embodiment realizes:
Embodiment 1:
The hydroxyapatite of elder generation's synthesis nano in the aqueous solution: accurately take by weighing Ca (NO
3)
24H
2O 7.8877g uses the 30mL deionized water dissolving, and regulates its pH=10.5 with ammoniacal liquor.Accurately take by weighing (NH
4)
2HPO
42.6412g, use the 50mL deionized water dissolving, also regulate its pH=10.5 with ammoniacal liquor.Under 70 ℃ of conditions with (NH
4)
2HPO
4Drips of solution is added to Ca (NO
3)
24H
2In the O solution, mix with magnetic agitation.Drip off (NH
4)
2HPO
4The back continuation is stirred 3h down at 70 ℃, obtains oyster white colloidal sol, behind the naturally cooling, by the centrifugal colloidal sol precipitation that makes, should precipitate 3 times with deionized water wash.X-ray diffraction (XRD) analysis revealed, the product of acquisition is the hydroxyapatite of hexagonal system, transmission electron microscope (TEM) observations shows that the product that is obtained is the acicular nanometer particle of length between 50～240nm.
Synthetic near infrared fluorescence quantum point: under nitrogen protection; with chlorination every with sodium hydrogen telluride and a kind of small molecules with coordination ability be raw material by the aqueous solution of certain molar ratio at pH=11 in reaction obtain brown transparent cadmium telluride (CdTe) nano-particle solution; further slaking and Passivation Treatment; the maximum emission wavelength that obtains fluorescence emission spectrum is at the 680nm place, and fluorescence trails to 800nm.
Under nitrogen protection the CdTe aqueous solution is added drop-wise in the hydroxyapatite colloidal sols, in mixed system, hydroxyapatite concentration is 200 μ g/mL, and CdTe concentration is 20 μ g/mL, magnetic agitation, and respectively at 1min, 2h and sampling in 10 days.
Experiment finds that brown transparent CdTe precipitates because of being adsorbed onto on the hydroxyapatite colloidal sols.The sample of absorption 1min, through centrifugal, supernatant liquor is a light brown, lower floor is a brown precipitate.The sample of absorption 2h and 10 days, without centrifugal i.e. precipitation fully, the upper strata is the achromaticity and clarification clear solution, lower floor is a brown precipitate.Find down that at transmission electron microscope (TEM) the acicular hydroxyapatite surface of nanometer has been adsorbed tiny particle.Fluorescence spectrum detects and shows that the CdTe that is adsorbed on the hydroxyapatite still has very strong fluorescence and very strong stability.Fluorescence emission spectrum does not have remarkable displacement.
Embodiment 2:
Get the hydroxyapatite and the CdTe solution of embodiment 1 preparation, respectively through dilution and concentration, then they are mixed, in the mixed system of dilution, the concentration of hydroxyapatite is 5 μ g/mL, and the concentration of CdTe is 1ng/mL.In the spissated mixed system, the concentration of hydroxyapatite is 0.25g/mL, and the concentration of near infrared fluorescence quantum point is 15mg/mL.Vibration 30min, through centrifugal, precipitation has all been adsorbed nano particle as a result through tem observation on the hydroxyapatite, and in spissated adsorbed product, hydroxyapatite has taken place more seriously to assemble.
Embodiment 3:
By embodiment 1 preparation concentration is the nano hydroxyapatite colloidal sols of 500 μ g/mL, carries out spraying drying then under following condition:
(1) inlet temperature is 150 ℃, and air outlet temperature is 95～105 ℃, and input speed is 3mL/min, and the atomizing disk rotating speed is 20000r/min.
(2) inlet temperature is 250 ℃, and air outlet temperature is 100～110 ℃, and input speed is 200mL/min, and the atomizing disk rotating speed is 20000r/min.
(3) inlet temperature is 30 ℃, and air outlet temperature is 25～30 ℃, and input speed is 0.1mL/min, and the atomizing disk rotating speed is 20000r/min.
Tem observation is the result show, the dried powder of acquisition is sphere and the patty particle of 3～20 μ m, and a large amount of tiny holes are arranged in the particle.
Under nitrogen protection and room temperature condition, spray-dired hydroxyapatite powder is distributed in the CdTe aqueous solution magnetic agitation 2h respectively.
Brown CdTe of result and hydroxyapatite together precipitate, and tem observation shows that as seen hydroxyapatite surface has fine particle.Fluorescence spectrum detects and to show, the fluorescence emission spectrum that is adsorbed on the CdTe on the hydroxyapatite of spherical and patty does not also have remarkable displacement.
Embodiment 4:
Press the embodiment 1 preparation nano hydroxyapatite colloidal sols and the nanometer CdTe aqueous solution, these two kinds of nano-particle solution are mixed with poly(lactic acid), PLA concentration is 0.5mg/mL in the mixed solution.In air atmosphere, be that 150 ℃, air outlet temperature are that 100～105 ℃, input speed are that 3mL/min, atomizing disk rotating speed are that the condition of 20000r/min is carried out spraying drying then with inlet temperature.
The result obtains the spherical and patty particle powder of about 3～25 μ m, and it is brown that powder is.
Embodiment 5:
Press the embodiment 1 preparation nano hydroxyapatite colloidal sols and the nanometer CdTe aqueous solution, these two kinds of nano-particle solution are mixed with bovine serum albumin (BSA), BSA concentration is 2mg/mL in the mixed solution.In air atmosphere, be that 100 ℃, air outlet temperature are that 80～85 ℃, input speed are that 3mL/min, atomizing disk rotating speed are that the condition of 20000r/min is carried out spraying drying then with inlet temperature.The powder that obtains is further at 120 ℃ of heat treated 1h.
The result obtains the spherical and patty particle powder of 3～30 μ m, and depression or hole are arranged in most of spheroidal particle, and it is brown that powder is.
Embodiment 6:
Press the sphere of embodiment 2 preparations 3～20 μ m and the hydroapatite particles of patty, then the porous hydroxyapatite of 200mg is immersed in an amount of fused molecular-weight average and is in about 100,000 the poly(lactic acid) and carry out blend, obtain macromolecule modified toughness reinforcing hydroxyapatite composite particles.Then polylactic acid modified hydroxyapatite is joined in 80 ℃ the CdTe aqueous solution, the nitrogen protection lower magnetic force stirs 15min.Remove the CdTe nanoparticle that is not attached on the hydroxyapatite composite particles by the centrifugation mode, collecting precipitation, the hydroxyapatite of CdTe that promptly obtained mark.This hydroxyapatite surface is light brown, and visible CdTe has been attached on the hydroxyapatite composite particles.
Claims (6)
1. the hydroxyapatite of a near infrared fluorescence quantum point mark, be being connected of near infrared fluorescence quantum point nanoparticle and hydroxyapatite in the mixed solution of water or organic phase or water and organic phase, to carry out, in this liquid-phase system, the concentration of hydroxyapatite is that every milliliter of 5 microgram are to every milliliter of 0.25 gram, the concentration of near infrared fluorescence quantum point is every milliliter to 15 milligrams every milliliter of 1 nanogram, wherein, described near infrared fluorescence quantum point is main by the elementary composition semiconductor nano crystallite at the near-infrared region emitting fluorescence of II-VI family or III-V family.
2. the hydroxyapatite of a kind of near infrared fluorescence quantum point mark according to claim 1, it is characterized in that: described near infrared fluorescence quantum point is the near infrared fluorescence quantum point nanoparticle formed of single semiconductor material, be nuclear with a kind of semi-conductor nano particles, and another kind of inorganic materials is one or more the combination in the nano-complex particle of the core-shell type near infrared fluorescence quantum point nano-complex particle of shell or near infrared fluorescence quantum point quantum well structure.
3. the hydroxyapatite of a kind of near infrared fluorescence quantum point mark according to claim 1, it is characterized in that: described hydroxyapatite is the hydroxyapatite of the nature of artificial synthetic hydroxyapatite or animal, be needle-like or bar-shaped, or spherical or round pie or irregularly shaped in a kind of.
4. at the preparation method of the hydroxyapatite of claim 1,2 or 3 described a kind of near infrared fluorescence quantum point marks, the steps include: near-infrared fluorescent quantum dot nano particle is connected on the hydroxyapatite by any one or a few method in absorption, ion-exchange, the covalent bonding composite particles of hydroxyapatite of near infrared fluorescence quantum point that formed mark.
5. the preparation method of the hydroxyapatite of near infrared fluorescence quantum point mark according to claim 4; it is characterized in that: hydroxyapatite is dispersed in the aqueous solution or the organic solution; then in protection of inert gas or directly in the aqueous solution or the organic solution that in the hydroxyapatite suspension, add near infrared fluorescence quantum point under the air atmosphere; stir 1min～10 day; by the calcium ion of hydroxyapatite surface or the metal ion generation ion-exchange on other configurational ions and near infrared fluorescence quantum point surface near infrared fluorescence quantum point is adsorbed onto hydroxyapatite surface; or making hydroxyapatite surface and near infrared fluorescence quantum point surface band dissimilar charges, the attraction by dissimilar charges is adsorbed onto hydroxyapatite surface with near infrared fluorescence quantum point.
6. the preparation method of the hydroxyapatite of near infrared fluorescence quantum point mark according to claim 4; it is characterized in that: modify organic molecule in hydroxyapatite surface; in protection of inert gas or directly under air atmosphere, can with near infrared fluorescence quantum point generation chemical bonding or adsorption near infrared fluorescence quantum point be connected with hydroxyapatite with the O of metal ion generation coordination, any one or a few combination among the N on by organic molecule, stirring 1min～10 day.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255335B (en) * | 2008-04-10 | 2010-06-02 | 浙江大学 | Preparation of Tb surface finished hydroxyl apatite fluorescent nano-particle |
| CN101643645B (en) * | 2009-07-24 | 2012-12-26 | 华中科技大学 | Calcium phosphate material marked by fluorescein isothiocyanate and preparation method thereof |
| CN105778918B (en) * | 2015-12-31 | 2018-01-12 | 浙江理工大学 | A kind of amorphous calcium phosphate/quantum dot composite material prepared using oyster shell whiting and preparation method thereof |
| CN108344738B (en) * | 2018-01-22 | 2021-07-27 | 翰飞骏德（北京）医疗科技有限公司 | Imaging method for hydroxyapatite and device thereof |
| CN112225189A (en) * | 2020-09-15 | 2021-01-15 | 上海摩漾生物科技有限公司 | Active calcium-phosphorus nano material containing defect sites and preparation and application thereof |
| CN114272438B (en) * | 2021-12-30 | 2023-02-17 | 上海大学 | Preparation method of high-activity mineralized aggregate fluorescence enhanced bone repair tracer material |
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| CN1374132A (en) * | 2002-03-22 | 2002-10-16 | 上海交通大学 | Prepn of core-shell type nano compound hydroxyapatiti-liposome particle |
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| CN1560633A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of quantum point microspheric for bio-medical fluorescence probe |
| US6869593B2 (en) * | 2000-10-27 | 2005-03-22 | Beth Israel Deaconess Medical Center | Non-isotopic detection of osteoblastic activity in vivo using modified bisphosphonates |
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|---|---|---|---|---|
| US6869593B2 (en) * | 2000-10-27 | 2005-03-22 | Beth Israel Deaconess Medical Center | Non-isotopic detection of osteoblastic activity in vivo using modified bisphosphonates |
| CN1374132A (en) * | 2002-03-22 | 2002-10-16 | 上海交通大学 | Prepn of core-shell type nano compound hydroxyapatiti-liposome particle |
| CN1559656A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of nucleous-shell type nanometer composite particle of magnetic micro particle and quantum point |
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