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CN103788946A - Method for preparing europium-doped hydroxyapatite nanorod - Google Patents

Method for preparing europium-doped hydroxyapatite nanorod Download PDF

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Publication number
CN103788946A
CN103788946A CN201410078332.1A CN201410078332A CN103788946A CN 103788946 A CN103788946 A CN 103788946A CN 201410078332 A CN201410078332 A CN 201410078332A CN 103788946 A CN103788946 A CN 103788946A
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solution
europium
distilled water
preparation
beaker
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孙康宁
徐欣
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Shandong University
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Shandong University
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Abstract

The invention discloses a method for preparing a europium-doped hydroxyapatite nanorod. According to the method, diammonium hydrogen phosphate, cetyl trimethyl ammonium bromide, anhydrous calcium chloride and europium oxide are used as raw materials, a mixed solution of the anhydrous calcium chloride and europium nitrate is dropwise added to a mixed solution of the diammonium hydrogen phosphate and the cetyl trimethyl ammonium bromide, the mixed solutions react at a certain temperature, after the reaction is over, precipitate is washed in distilled water and distilled water for multiple times and dried in the suction filtration process, and then the europium-doped hydroxyapatite nanorod is obtained. According to the method, the reaction temperature is low, the requirement for equipment is low, operation is simple, and the prepared material is controllable in shape, high in purity, good in crystallinity, dispersity and luminescence property, and wide in application prospect.

Description

A kind of preparation method of europium doped hydroxyapatite nanometer rod
Technical field
The present invention relates to a kind of preparation method of europium doped hydroxyapatite nanometer rod, belong to the preparation field of biomaterial and luminescent material.
Background technology
Hydroxyapatite (Hydroxyapatite, HA) has good biological activity and certain mechanical property, has become one of biomaterial of investigation of materials person's close attention.HA is the main component of vertebrates bone and tooth, wherein in dentary, accounts for 97%, in people's bone, accounts for 75%.Nano level HA is aspect bone reparation, as alveolar ridge increases, the replacement of ear ossiculum, tooth-planting, vertebrae replacement etc. have broad application prospects.In addition,, due to good biocompatibility, chemical stability and the surface property of nano level HA, it has been widely used in antitumor and pharmaceutical carrier field.
HA is easily easily loose under the effect of implantation initial stage at body fluid as bone renovating material, causes nano level HA particle to run off and enters in organism.Meanwhile, nano level HA is during as pharmaceutical carrier, when after drug release, as the nanometer HA of carrier also may stable existence in organism.Because hydroxyapatite itself does not have obvious fluorescent characteristic, for probing into nanometer HA circulation and deposition in vivo, can utilize Eu3+ to replace the Ca in HA 2+, reach fluorescently-labeled object.The existing complicated process of preparation about mixing europium hydroxyapatite, condition harshness, crystallinity, fluorescence intensity and the dispersiveness of prepared material are difficult to reach good unification.
Summary of the invention
For prior art, the object of the present invention is to provide a kind of preparation method of europium doped hydroxyapatite nanometer rod.
The preparation method of europium doped hydroxyapatite nanometer rod of the present invention, step is:
(1) europium nitrate solution of preparation 0.2mol/L, for subsequent use;
(2) prepare solution 1 by following proportional, take 1.584g Secondary ammonium phosphate and 1g cetyl trimethylammonium bromide joins in beaker, the distilled water that measures 50ml joins in beaker and dissolves, and its pH value is adjusted to 12 with the NaOH solution of 1mol/L;
(3) prepare solution 2 by following proportional, take 1.998g~2.109g Calcium Chloride Powder Anhydrous and join in another beaker, then add 25ml distilled water to dissolve, the europium nitrate solution that measures step (1) preparation of 1~10ml joins in beaker, mixes;
(4) solution of preparation 2 is slowly added drop-wise in the solution 1 that continues to stir, then mixing solutions is heated to 100 ℃, react 6 ± 1 hours;
(5) after having reacted, gained suspension liquid is left standstill to 3~5 hours, then in suction filtration process, with distilled water and ethanol, throw out is washed 5~10 times, under 80 ℃ of conditions, be dried 10~12 hours, obtain europium doped hydroxyapatite nanometer rod.
In the preparation method of above-mentioned europium doped hydroxyapatite nanometer rod: preferably 0.034mol/L of cetyl trimethylammonium bromide concentration in the solution described in step (2).
It is raw material that the present invention adopts Secondary ammonium phosphate, cetyl trimethylammonium bromide, Calcium Chloride Powder Anhydrous and europium sesquioxide, Calcium Chloride Powder Anhydrous and europium nitrate mixing solutions are dropwise joined in Secondary ammonium phosphate and cetyl trimethylammonium bromide mixing solutions, reaction at a certain temperature, after reaction finishes, then with distilled water and ethanol, throw out washing is also dry for several times in suction filtration process, obtain europium doped hydroxyapatite nanometer rod.The inventive method temperature of reaction is low, low for equipment requirements, simple to operate, and the material pattern of preparation is controlled, and purity is high, and crystallinity, dispersiveness and luminescent properties are good, have a extensive future.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the europium doped hydroxyapatite nanometer rod prepared in the present invention.
Fig. 2 is the transmission electron microscope photo of the europium doped hydroxyapatite nanometer rod prepared in the present invention.
Fig. 3 is the europium doped hydroxyapatite nanometer rod prepared in the present invention utilizing emitted light spectrogram under 250nm ultraviolet excitation.
Embodiment
In order to further illustrate this invention, be described in detail below in conjunction with the preparation method of the concrete disclosed europium doped hydroxyapatite nanometer rod of embodiment.
Embodiment 1
Take the europium sesquioxide of 1.7597g, adding afterwards 30ml concentration is rare nitric acid of 4mol/L, stirs 30 minutes under heating condition, after dissolving completely, is made into the europium nitrate solution of 0.2mol/L.
Take 1.584g Secondary ammonium phosphate and 1g cetyl trimethylammonium bromide joins in beaker, the distilled water that measures 50ml joins in beaker and dissolves, and pH value is adjusted to 12 with the NaOH solution of 1mol/L, is solution 1.Take 2.109g Calcium Chloride Powder Anhydrous and join in another beaker, add 25ml distilled water to dissolve, the europium nitrate solution of having prepared that measures 5ml with transfer pipet joins in beaker, is solution 2.Then solution 2 is slowly added drop-wise to and continues, in stirred solution 1, mixing solutions to be heated to 100 ℃, react 6 hours.After having reacted, suspension liquid is left standstill to 3 hours, then in suction filtration process, with distilled water and ethanol, throw out is washed 8 times, under 80 ℃ of conditions, be dried 10 hours, obtain europium doped hydroxyapatite nanometer rod.
The X-ray diffractogram of sample is referring to Fig. 1, consistent with the standard diffraction spectra (JCPDS NO.74-0566) of HA.Fig. 1 illustrates that product purity is high, without other impurity.
The transmission electron microscope photo of sample is referring to Fig. 2, and synthetic europium doped hydroxyapatite nanometer rod is wide is 40-50nm, and long is 120-200nm, favorable dispersity.
The emmission spectrum of sample under 250nm excites is referring to Fig. 3, and sample, under 250nm ultraviolet excitation, can be observed the apparent fluorescent orange of naked eyes.
Embodiment 2
Take the europium sesquioxide of 1.7597g, adding afterwards 30ml concentration is rare nitric acid of 4mol/L, stirs 30 minutes under heating condition, after dissolving completely, is made into the europium nitrate solution of 0.2mol/L.
Take 1.584g Secondary ammonium phosphate and 1g cetyl trimethylammonium bromide joins in beaker, the distilled water that measures 50ml joins in beaker and dissolves, and pH value is adjusted to 12 with the NaOH solution of 1mol/L, is solution 1.The Calcium Chloride Powder Anhydrous that takes 2.198g joins in another beaker, adds 25ml distilled water to dissolve, and the europium nitrate solution of having prepared that measures 1ml with transfer pipet joins in beaker, is solution 2.Then solution 2 is slowly added drop-wise to and continues, in stirred solution 1, mixing solutions to be heated to 100 ℃, react 6 hours.After having reacted, suspension liquid is left standstill to 3 hours, then in suction filtration process, with distilled water and ethanol, throw out is washed 5 times, under 80 ℃ of conditions, be dried 10 hours, obtain europium doped hydroxyapatite nanometer rod.
Embodiment 3
Take the europium sesquioxide of 1.7597g, adding afterwards 30ml concentration is rare nitric acid of 4mol/L, stirs 30 minutes under heating condition, after dissolving completely, is made into the europium nitrate solution of 0.2mol/L.
Take 1.584g Secondary ammonium phosphate and 1g cetyl trimethylammonium bromide joins in beaker, the distilled water that measures 50ml joins in beaker and dissolves, and pH value is adjusted to 12 with the NaOH solution of 1mol/L, is solution 1.The Calcium Chloride Powder Anhydrous that takes 1.998g joins in another beaker, adds 25ml distilled water to dissolve, and the europium nitrate solution of having prepared that measures 10ml with transfer pipet joins in beaker, is solution 2.Then solution 2 is slowly added drop-wise to and continues, in stirred solution 1, mixing solutions to be heated to 100 ℃, react 6 hours.After having reacted, suspension liquid is left standstill to 3 hours, then in suction filtration process, with distilled water and ethanol, throw out is washed 10 times, under 80 ℃ of conditions, be dried 10 hours, obtain europium doped hydroxyapatite nanometer rod.
Embodiment 4
Take 1.584g Secondary ammonium phosphate and 1g cetyl trimethylammonium bromide joins in beaker, the distilled water that measures 50ml joins in beaker and dissolves, and pH value is adjusted to 12 with the NaOH solution of 1mol/L, is solution 1.The Calcium Chloride Powder Anhydrous that takes 2.22g joins in another beaker, adds 30ml distilled water to dissolve, and is solution 2.Then solution 2 is slowly added drop-wise to and continues, in stirred solution 1, mixing solutions to be heated to 100 ℃, react 6 hours.After having reacted, suspension liquid is left standstill to 3 hours, then in suction filtration process, with distilled water and ethanol, throw out is washed 6 times, under 80 ℃ of conditions, be dried 10 hours, obtain pure ha nanometer rod.
The explanation of above embodiment just helps to understand method of the present invention and core concept thereof.It should be pointed out that for the person of ordinary skill of the art, do not depart from the present invention away from prerequisite under, can also carry out some improvement and modification to the present invention, these improvement and modify also fall in the protection domain of the claims in the present invention.

Claims (2)

1. a preparation method for europium doped hydroxyapatite nanometer rod, step is:
(1) europium nitrate solution of preparation 0.2mol/L, for subsequent use;
(2) prepare solution 1 by following proportional, take 1.584g Secondary ammonium phosphate and 1g cetyl trimethylammonium bromide joins in beaker, the distilled water that measures 50ml joins in beaker and dissolves, and its pH value is adjusted to 12 with the NaOH solution of 1mol/L;
(3) prepare solution 2 by following proportional, take 1.998g~2.109g Calcium Chloride Powder Anhydrous and join in another beaker, then add 25ml distilled water to dissolve, the europium nitrate solution that measures step (1) preparation of 1~10ml joins in beaker, mixes;
(4) solution of preparation 2 is slowly added drop-wise in the solution 1 that continues to stir, then mixing solutions is heated to 100 ℃, react 6 ± 1 hours;
(5) after having reacted, gained suspension liquid is left standstill to 3~5 hours, then in suction filtration process, with distilled water and ethanol, throw out is washed 5~10 times, under 80 ℃ of conditions, be dried 10~12 hours, obtain europium doped hydroxyapatite nanometer rod.
2. the preparation method of europium doped hydroxyapatite nanometer rod according to claim 1, is characterized in that: in the solution described in step (2), cetyl trimethylammonium bromide concentration is 0.034mol/L.
CN201410078332.1A 2014-03-05 2014-03-05 Method for preparing europium-doped hydroxyapatite nanorod Pending CN103788946A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN105018086A (en) * 2015-07-03 2015-11-04 武汉理工大学 Rare-earth-doped calcium phosphate fluorescent nanoparticles, and preparation method and application thereof
CN105412934A (en) * 2015-12-23 2016-03-23 山东建筑大学 Multifunctional drug carrier material based on nanometer rare earth doped with hydroxyapatite
CN105950147A (en) * 2015-12-31 2016-09-21 陕西科技大学 Preparation method of strontium-containing hydroxylapatite fluorescent material
RU2628610C1 (en) * 2016-06-17 2017-08-21 Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) Method for production of nano-dimensional high-luminescent apatite with europium (eu) impurity
CN111732087A (en) * 2020-06-24 2020-10-02 三峡大学 Europium selenium double-doped hydroxyapatite and its application in the preparation of drugs for monitoring and treating osteosarcoma
CN111748337A (en) * 2020-07-27 2020-10-09 吉林大学 A kind of preparation method of fluorescent marker for osteoporosis
CN112830464A (en) * 2021-01-20 2021-05-25 山东大学 A kind of strontium-doped hydroxyapatite microtube and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018086A (en) * 2015-07-03 2015-11-04 武汉理工大学 Rare-earth-doped calcium phosphate fluorescent nanoparticles, and preparation method and application thereof
CN105412934A (en) * 2015-12-23 2016-03-23 山东建筑大学 Multifunctional drug carrier material based on nanometer rare earth doped with hydroxyapatite
CN105950147A (en) * 2015-12-31 2016-09-21 陕西科技大学 Preparation method of strontium-containing hydroxylapatite fluorescent material
RU2628610C1 (en) * 2016-06-17 2017-08-21 Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) Method for production of nano-dimensional high-luminescent apatite with europium (eu) impurity
CN111732087A (en) * 2020-06-24 2020-10-02 三峡大学 Europium selenium double-doped hydroxyapatite and its application in the preparation of drugs for monitoring and treating osteosarcoma
CN111748337A (en) * 2020-07-27 2020-10-09 吉林大学 A kind of preparation method of fluorescent marker for osteoporosis
CN112830464A (en) * 2021-01-20 2021-05-25 山东大学 A kind of strontium-doped hydroxyapatite microtube and preparation method thereof
CN112830464B (en) * 2021-01-20 2022-10-04 山东大学 A kind of strontium-doped hydroxyapatite microtube and preparation method thereof

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Application publication date: 20140514