CN107338049A - Biodegradable fluorescent mesoporous silicon oxide composite Nano ball and preparation method thereof - Google Patents
Biodegradable fluorescent mesoporous silicon oxide composite Nano ball and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball and preparation method thereof.Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, including following raw material, p-methyl benzenesulfonic acid cetyltrimethyl ammonium, triethanolamine, esters of silicon acis, HPO4 2‑Solion, Ca2+Solion, Eu3+Solion, wherein p-methyl benzenesulfonic acid cetyltrimethyl ammonium are template, and triethanolamine is catalyst, wherein with molar amount HPO4 2‑Solion：Ca2+Solion=2:3—5:8.Eu prepared by the application3+:HAp/MSN composite Nano balls have synthesized the spherical mesoporous material that size is 60nm -80nm, biodegradable HAp is doped in MSN skeleton using in-situ sol-gel, the larger specific surface areas of MSN and orderly pore structure are not only maintained, also imparts MSN biological degradation function；By adulterating Eu in HAp lattices3+Ion, the fluorescence mesoporous silicon oxide with red emission is obtained.Preparation technology of the present invention is simple, and reaction condition is gentle.
Description
Technical field
The present invention relates to a kind of fluorescence nano field, more particularly to a kind of Biodegradable fluorescent mesoporous silicon oxide
Composite Nano ball and preparation method thereof.
Background technology
Multifunctional nano pharmaceutical carrier can integrate the diagnosis, treatment and medicine tracking of disease, in biomedicine field
With tempting application prospect, and one of hot subject of people's research in recent years.At present, porous silicon dioxide nano material
It is considered as a kind of excellent pharmaceutical carrier, because the material has larger aperture（More than 2 nm）, huge specific surface area and
Pore volume, be advantageous to the load and storage of medicine；Good biocompatibility and hydrophilicity, is very suitable for biologic applications.
In addition, there is abundant silicone hydroxyl group on its surface, it is easy to that its surface is modified and is modified.But pure silicon dioxide material
Surface group is single（Si-OH）, and be difficult in vivo degraded, it significantly limit its biologic applications scope.
Hydroxyapatite [HAp, Ca5(PO4)3OH], it is a kind of biology with good biocompatibility and bioactivity
Material, and easily degrade in vivo.In addition, HAp or a kind of preferably luminous host material, can pass through rare earth ion
（Such as Eu3+, Tb3+Deng）Doping and obtain the fluorescent material of different emission.Therefore, if by rare earth ion doped HAp with
Mesoporous silicon oxide progress is compound, can obtain a kind of biodegradable fluorescence mesoporous silicon oxide hybrid material.Released in medicine
, can be by the imaging of hybrid material in vivo and the change of fluorescence intensity, to track and monitor medicine during putting
Release process.
But at present, the preparation method of HAp/MSN nano composite materials is usually to use post synthesis method, and HAp is deposited to
In MSN surface and duct, the method easily causes the blocking of mesopore orbit and the reduction of pore volume, and the degraded to MSN rises
Less than due effect.In addition, the size of the HAp/MSN nano-complexes prepared greatly limit mostly in 200 more than nm
Its biologic applications scope.
The content of the invention
To solve the above problems, the present invention provide a kind of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball and its
The preparation method of preparation method.The composite Nano ball have about 60nm -80nm sizes, specific surface area it is larger, it is biodegradable and
The fluorescence property of red emission.
The technical scheme is that：Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, including following raw material,
P-methyl benzenesulfonic acid cetyltrimethyl ammonium, triethanolamine, esters of silicon acis, HPO4 2-Solion, Ca2+Solion, Eu3+Ion is molten
Liquid, wherein p-methyl benzenesulfonic acid cetyltrimethyl ammonium are template, and triethanolamine is catalyst, wherein with molar amount HPO4 2-From
Sub- solution：Ca2+Solion=2:3—5:8.
With molar amount, HPO4 2-Solion：Ca2+Solion：Eu3+Solion=（50-160）：（75-256）：
（0.5-5）, toluenesulfonic acid cetyltrimethyl ammonium：Triethanolamine：Esters of silicon acis=（0.5-1）：（0.5-6.7）：（6-12）, Eu3+From
Sub- solution：Esters of silicon acis=（0.5-5）：（600-1200）.
With molar amount, HPO4 2-Solion：Ca2+Solion：Eu3+Solion=（89-90）：（135-136）：
2.5。
With molar amount, toluenesulfonic acid cetyltrimethyl ammonium：Triethanolamine：Esters of silicon acis=0.75：1.34：9.6.
With molar amount, Eu3+Solion：Esters of silicon acis=2.5：960.
The preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）With p-methyl benzenesulfonic acid cetyltrimethyl ammonium（CTAT）For template, with triethanolamine（TEA）For catalyst, using original
Position sol-gel process is by hydroxyapatite presoma and the europium ion-doped skeleton to mesoporous silicon oxide；
（2）HAp presomas and mesoporous silicon oxide skeleton high-temperature roasting with europium ion will be adulterated, obtain Biodegradable fluorescent
Mesoporous silicon oxide complex microsphere.
The step（1）For using CTAT as template, TEA is base catalyst, in esters of silicon acis（TEOS）Hydrolyze to form dioxy
In SiClx sol-process, while add Ca2+、HPO4 2-And rare earth ion Eu3+, then by gel aging obtain adulterate HAp before
Drive body and the mesoporous silicon oxide skeleton with europium ion.
The step（2）For will adulterate HAp presomas and with the mesoporous silicon oxide skeleton of europium ion air atmosphere 550~
650 oC is calcined 6~8 h, 1 DEG C/min of heating rate, obtains white powder.
Described preparation method is further comprising the steps of, by step（3）Obtained white powder carries out finely ground.
Beneficial effects of the present invention are Eu prepared by this method3+:HAp/MSN composite Nano balls have synthesized size and have been
60nm -80nm spherical mesoporous material, biodegradable HAp is doped to MSN skeleton using IN-SITU SOL-GEL
In, the larger specific surface areas of MSN and orderly pore structure are not only maintained, also imparts MSN biological degradation function；By
Eu is adulterated in HAp lattices3+Ion, the fluorescence mesoporous silicon oxide with red emission is obtained.Preparation technology of the present invention is simple,
Reaction condition is gentle.
Brief description of the drawings
Fig. 1 is Eu3+:The SEM figures of HAp/MSN composite Nano balls.
Fig. 2 is Eu3+:The TEM figures of HAp/MSN composite Nano balls.
Fig. 3 is Eu3+:The XRD spectrums of HAp/MSN composite Nano balls.
Fig. 4 is Eu3+:The FT-IR spectrums of HAp/MSN composite Nano balls.
Fig. 5 is Eu3+:The low temperature N of HAp/MSN composite Nano balls2- adsorption-desorption curve.
Fig. 6 is Eu3+:The absorption pore size distribution curve of HAp/MSN composite Nano balls.
Fig. 7 is Eu3+:The excitation spectrum of HAp/MSN composite Nano balls.
Fig. 8 is Eu3+:The emission spectrum of HAp/MSN composite Nano balls.
Fig. 9 is Eu3+:HAp/MSN was degraded in PBS solution after certain time, calcium ion concentration situation of change.
Embodiment
Embodiment 1：
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 5 × 10-4Mol~10 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyl ammoniums（CTAT）Add in three-necked bottle, then
Add 20~80 mL deionized waters and 5 × 10-4Mol~6.7 × 10-3Mol triethanolamines（TEA）, 70~90 DEG C of magnetic agitations
40~60 min, the template micella in reaction system is made；
（2）In step（1）5 × 10 are added in template micella in obtained reaction system-4Mol~1.6 × 10-3mol
HPO4 2-Solion, 70~90 DEG C of 30~50min of magnetic agitation.Then under 600~1000 turns/min mechanical agitations, by 1
Drop/sec~2 drops/sec of speed is added dropwise 6 × 10-3Mol~1.2 × 10-2Mol esters of silicon acis, after stirring 3~10 min, rapidly
Add 7.5 × 10-4Mol~2.56 × 10-3mol Ca2+Solion and 5 × 10-6Mol~5 × 10-5Mol Eu3+Ion is molten
Liquid, 70~90 DEG C of water-baths continue the h of stirring 4~6, are cooled to centrifugation after room temperature and obtain sediment, sediment uses deionized water respectively
With absolute ethyl alcohol washing precipitation 2~3 times, 50 DEG C~70 DEG C vacuum drying 8 h~15 h；Wherein with molar amount HPO4 2-Ion
Solution：Ca2+Solion=2:3—5:8；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 550~650 DEG C of 6~8 h of roasting of air atmosphere,
0.5 DEG C/min~2 DEG C of heating rate/min.White powder sample is obtained, is Eu3+:HAp/MSN powder, be it is obtained can
Biodegradable fluorescence mesoporous silicon oxide composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 2
（1）Take 0.342 g p-methyl benzenesulfonic acid cetyltrimethyl ammoniums（CTAT）Add in 100 mL three-necked bottles, then add
50mL deionized waters, the min of ultrasonic disperse 5, obtain transparent homogeneous mixed solution.The ethanol of 0.2 g tri- is being added into mixed liquor
Amine（TEA）, sealing, 80 DEG C of min of water-bath magnetic agitation 40, the template micella in reaction system is made；
（2）Walk then up in solution and add 0.32 g Na2HPO4•12H2O, continue to stir 30 min.With 1000 turns/min
Rotating speed mechanical agitation under, 2.0 mL tetraethyl orthosilicates (TEOS) are added dropwise with 1 drop/s speed, dripped in 5 min
Finish, continue to stir 3 min.Then the anhydrous CaCl of 0.15 g are rapidly added2It is the EuCl that 50 μ L concentration are 0.5 mol/L with volume3
Solution, 80 DEG C of water-baths continue to stir 4 h, are cooled to room temperature, are centrifuged to obtain sediment with 5000 turns/min rotating speed, sink
Starch is washed 3 times with deionized water and absolute ethyl alcohol respectively, 60 DEG C of 12 h of vacuum drying；
（3）By step（2）Sediment after obtained washing is placed in ceramic crucible, 650 DEG C of air atmosphere in tube type resistance furnace
Roasting 6 hours, heating rate is 1 DEG C/min, obtains white powder sample, is Eu3+:HAp/MSN powder, it is obtained
Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to,
Preserved after vacuum drying.
Embodiment 3
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 0.360 g p-methyl benzenesulfonic acid cetyltrimethyl ammoniums（CTAT）Add in three-necked bottle, add 80 mL deionizations
Water and 1.0 g triethanolamines（TEA）, 90 DEG C of min of magnetic agitation 60, the template micella in reaction system is made；
（2）In step（1）0.50g Na are added in template micella in obtained reaction system2HPO4•12H2O, 70~90 DEG C
30~50min of magnetic agitation.Then under 1000 turns/min mechanical agitations, the positive silicon of 3.0mL is added dropwise by 2 drops/sec of speed
Sour methyl esters, after stirring 3~10 min, it is rapidly added 0.2g Ca (NO3)2Powder and volume are that 100 μ L concentration are 0.5 mol/L
EuCl3Solution, 90 DEG C of water-baths continue to stir 5 h, centrifuge after being cooled to room temperature, washed respectively with deionized water and absolute ethyl alcohol
Precipitation 2 times, 50 DEG C of 15 h of vacuum drying；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 550 DEG C of 8 h of roasting of air atmosphere, heating rate
0.5 DEG C/min, white powder sample is obtained, is Eu3+:HAp/MSN powder, it is that obtained Biodegradable fluorescent is mesoporous
Silica composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 4
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 5 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyls ammonium is added in three-necked bottle, then adds 40mL deionized waters,
The min of ultrasonic disperse 4, obtain transparent homogeneous mixed solution.Into mixed solution 6.7 × 10-3Mol triethanolamines, 70 DEG C of magnetic force
50 min are stirred, the template micella in reaction system is made；
（2）In step（1）1.6 × 10 are added in template micella in obtained reaction system-3mol Na2HPO4•12H2O,
90 DEG C of magnetic agitation 30min.Then under 800 turns/min mechanical agitations, 1.2 × 10 are added dropwise by 2 drops/sec of speed-2mol
Tetraethyl orthosilicate, stir 3 min after, be rapidly added 2.56 × 10-3Mol Ca (NO3)2With 5 × 10-6Mol EuCl3, 90
DEG C water-bath continues to stir 4h, after being cooled to room temperature centrifugation obtain sediment, sediment uses deionized water and absolute ethyl alcohol water respectively
Washing precipitation 2 times, 60 DEG C of vacuum drying 8h；Wherein with molar amount HPO4 2-Solion；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 550 DEG C of roasting 7.5h of air atmosphere, heating rate
0.8℃/min.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is that obtained Biodegradable fluorescent is mesoporous
Silica composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 5：
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 10 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyls ammonium is added in three-necked bottle, adds 80 mL deionized waters
With 5 × 10-4Mol triethanolamines, 90 DEG C of min of magnetic agitation 50, the template micella in reaction system is made；
（2）In step（1）5 × 10 are added in template micella in obtained reaction system-4Mol volumes K2HPO4•12H2O, 80
DEG C magnetic agitation 50min.Then under 600 turns/min mechanical agitations, 6 × 10 are added dropwise by 1.5 drops/sec of speed-3Mol's
Four (2- ethylhexyls) esters of silicon acis, after stirring 3~10 min, it is rapidly added 7.5 × 10-4Mol CaCl2With 5 × 10-5Mol's
EuCl3, 75 DEG C of water-baths continue to stir 4.5h, are cooled to centrifugation after room temperature and obtain sediment, sediment is washed with deionized water respectively
Wash twice, absolute ethyl alcohol water washing precipitates 3 times, 65 DEG C of vacuum drying 14h；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 600 DEG C of 6.5 h of roasting of air atmosphere, heating speed
1.2 DEG C/min of rate.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is that obtained Biodegradable fluorescent is situated between
Hole silica composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 6：
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 7.5 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyl ammoniums（CTAT）Add in three-necked bottle, add 30 mL and go
Ionized water and 1.34 × 10-3Mol triethanolamines（TEA）, 70~90 DEG C of min of magnetic agitation 40~60, it is made in reaction system
Template micella；
（2）In step（1）1.6 × 10 are added in template micella in obtained reaction system-3Mol Na2HPO4•12H2O,
70~90 DEG C of 30~50min of magnetic agitation.Then under 600~1000 turns/min mechanical agitations, by 1 drop/sec~2 drops/sec
Speed is added dropwise 9.6 × 10-3Mol methyl silicates, after stirring 3~10 min, it is rapidly added 2.56 × 10-3Mol CaCl2
With 2.5 × 10-5Mol EuCl3, 85 DEG C of water-baths continue to stir 5.5 h, are cooled to centrifugation after room temperature and obtain sediment, sediment
Precipitated 3 times with deionized water and absolute ethyl alcohol water washing respectively, 65 DEG C of 10 h of vacuum drying；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 580 DEG C of 7 h of roasting of air atmosphere, heating rate
0.9℃/min.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is that obtained Biodegradable fluorescent is mesoporous
Silica composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 7
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 9 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyls ammonium add three-necked bottle in, add 70 mL deionized waters and
6.5×10-3Mol triethanolamines, 75 DEG C of magnetic agitation 55min, the template micella in reaction system is made；
（2）In step（1）1.05 × 10 are added in template micella in obtained reaction system-3Mol Na2HPO4•
12H2O, 70 DEG C of magnetic agitation 35min.Then under 600 turns/min mechanical agitations, 8 × 10 are added dropwise by 1 drop/sec of speed-3Mol tetraethyl orthosilicates, after stirring 6min, it is rapidly added 1.60 × 10-3Mol Ca (NO3)2With 1 × 10-5Mol EuCl3, 85
DEG C water-bath continues to stir 4.5h, after being cooled to room temperature centrifugation obtain sediment, sediment uses deionized water and absolute ethyl alcohol respectively
Water washing precipitates 2 times, 55 DEG C of vacuum drying 9h；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 650 DEG C of roasting 6h of air atmosphere, heating rate 2
℃/min.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is the mesoporous dioxy of obtained Biodegradable fluorescent
SiClx composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 8
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 6 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyls ammonium is added in three-necked bottle, adds 40mL deionized waters and 7
×10-4Mol triethanolamines, 70 DEG C of min of magnetic agitation 60, the template micella in reaction system is made；
（2）In step（1）8 × 10 are added in template micella in obtained reaction system-4Mol K2HPO4Solution, 70~
90 DEG C of 30~50min of magnetic agitation.Then under 600~1000 turns/min mechanical agitations, by 1 drop/sec~2 drops/sec of speed
It is added dropwise 1.0 × 10-2Mol methyl silicates, after stirring 3~10 min, it is rapidly added 1.28 × 10-3Mol Ca（NO3）2
Solution and 2 × 10-5Mol EuCl3, 75 DEG C of water-baths continue to stir 5 h, are cooled to centrifugation after room temperature and obtain sediment, sediment
Precipitation is washed with deionized water and absolute ethyl alcohol 2 times, 60 DEG C of 12 h of vacuum drying respectively；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 620 DEG C of 6.8 h of roasting of air atmosphere, heating speed
1.5 DEG C/min of rate.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is that obtained Biodegradable fluorescent is situated between
Hole silica composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 9
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 7 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyls ammonium add three-necked bottle in, add 50 mL deionized waters and
3×10-3Mol triethanolamines, 80 DEG C of magnetic agitation 50min, the template micella in reaction system is made；
（2）In step（1）9 × 10 are added in template micella in obtained reaction system-4Mol Na2HPO4•12H2O, 70
~90 DEG C of 30~50min of magnetic agitation.Then under 600~1000 turns/min mechanical agitations, by 1 drop/sec~2 drops/sec of speed
Degree is added dropwise 6 × 10-3Mol~1.2 × 10-2Mol four [2- (2- methoxyethoxies) ethyl] esters of silicon acis, stirring 3~10
After min, 1.35 × 10 are rapidly added-3CaCl2With 4 × 10-5Mol EuCl3, 85 DEG C of water-baths continue stir 4.2h, be cooled to
Centrifugation obtains sediment after room temperature, and sediment is precipitated 3 times with deionized water and absolute ethyl alcohol water washing respectively, 50 DEG C of vacuum drying
8 h；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 580 DEG C of roasting 7h of air atmosphere, heating rate
1.2℃/min.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is that obtained Biodegradable fluorescent is mesoporous
Silica composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Embodiment 10
A kind of preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, comprises the following steps,
（1）Take 8.5 × 10-4Mol p-methyl benzenesulfonic acid cetyltrimethyls ammonium is added in three-necked bottle, adds 30mL deionized waters
With 2 × 10-3Mol triethanolamines（TEA）, 75 DEG C of magnetic agitation 45min, the template micella in reaction system is made；
（2）In step（1）8.5 × 10 are added in template micella in obtained reaction system-4Mol K2HPO4•12H2O,
85 DEG C of magnetic agitation 35min.Then under 800 turns/min mechanical agitations, 1.0 × 10 are added dropwise by 1 drop/sec of speed-2mol
Four (1- Methylethyls) esters of silicon acis, stir 6min after, be rapidly added 1.36 × 10-3Mol Ca (NO3)2With 3 × 10-5Mol's
EuCl3, 80 DEG C of water-baths continue to stir 6 h, are cooled to centrifugation after room temperature and obtain sediment, sediment uses deionized water and nothing respectively
Water-ethanol water washing precipitates 2 times, 60 DEG C of vacuum drying 9h；
（3）By step（2）Sediment after obtained washing is placed in Muffle furnace, 650 DEG C of roasting 6h of air atmosphere, heating rate 1
℃/min.White powder sample is obtained, is Eu3+:HAp/MSN powder, it is the mesoporous dioxy of obtained Biodegradable fluorescent
SiClx composite Nano ball, it is further finely ground in agate mortar after room temperature being cooled to.
Experiment detection
50 mg Eu made from Example 2- embodiments 103+:HAp/MSN powder is detected.
XRD spectrum test uses the model of instrument：D8 FOCUS（German Bruker）, the use of excitation and emission spectra figure
INSTRUMENT MODEL is：FLS920P（Edinburgh, Britain）, Fourier transform infrared spectroscopy use INSTRUMENT MODEL for：（U.S.'s thermoelectricity）, N2
Adsorption/desorption isotherms test uses INSTRUMENT MODEL：ASAP 2020 HD88（Merck ＆ Co., Inc of the U.S.）, SEM photograph
The INSTRUMENT MODEL that piece uses for：Quanta 200（FEI Co. of the U.S.）, the INSTRUMENT MODEL of transmission electron microscope photo use
For：JEM 1200EX（JEOL）.The INSTRUMENT MODEL that icp analysis uses for：Agilent 7500ce（U.S.'s Agilent）.
SEM is tested：Eu made from Example 2- embodiments 103+:HAp/MSN carries out SEM tests, does not occur reuniting now
As.
Such as embodiment 2, Fig. 1 is Eu made from embodiment 23+:The Flied emission scanning electron microscopy of HAp/MSN composite Nano balls
Mirror photo.As seen from the figure, Eu made from embodiment 23+:HAp/MSN composite Nanos ball is uniform nanosphere, and is not occurred
Agglomeration, show Eu made from embodiment 23+:The dispersiveness of HAp/MSN composite Nano balls is preferably.Show HAp introducing, and
Without the pattern for substantially changing MSN.
TEM is tested：Eu made from Example 2- embodiments 103+:HAp/MSN carries out TEM tests, Eu3+:HAp/MSN is answered
Nanosphere is closed as the spherical of rule, diameter is about 60 nm -80 nm, Eu3+:HAp/MSN composite Nanos ball is loose structure, and
Not it was observed that substantial amounts of HAp occurs.
Such as embodiment 2, Fig. 2 is Eu made from embodiment 23+:The TEM photos of HAp/MSN composite Nano balls.It can be seen that implement
Eu made from example 23+:HAp/MSN composite Nano balls are well-regulated spherical, and diameter is about 70 nm.By Fig. 2 it can also be seen that receiving
Rice ball has obvious loose structure.Meanwhile TEM figures do not observe that substantial amounts of HAp occurs, and shows that HAp is uniformly distributed to
In MSN skeleton or duct, this is consistent with SEM characterization result.
XRD is tested：Eu made from Example 2- embodiments 103+:HAp/MSN carries out XRD tests, Eu3+:HAp/MSN exists
There is a wider diffraction maximum at 2 22 ° of θ ≈, meanwhile, there is stronger diffraction maximum in 2 θ=25 °, 31 °, 40 °, 46 ° and 49 °.
Such as embodiment 2, Fig. 3 is Eu made from embodiment 23+:The XRD spectra of HAp/MSN composite Nano balls.Can be with from Fig. 3
Find out, Eu made from embodiment 23+:HAp/MSN has a wider diffraction maximum at 22 ° of 2 θ ≈, and this is unformed MSN feature
Diffraction maximum.Meanwhile having stronger diffraction maximum in 2 θ=25 °, 31 °, 40 °, 46 ° and 49 °, this is hexagonal phase hydroxyapatite Ca5
(PO4)3(OH) characteristic diffraction peak（PDF#:09-0432）, show on the MSN that HAp has successfully been loaded to.
FT-IR is tested：50 mg Eu made from Example 2- embodiments 103+:HAp/MSN carries out FT-IR tests, sample
In 3390 cm-1—3410 cm-1There is absworption peak, be because Eu3+:Si-OH stretching vibration in HAp/MSN composite Nano balls；
1072 cm-1—1087 cm-1Absworption peak be present, be because Eu3+:Si-O-Si stretching vibration in HAp/MSN composite Nano balls；
In 555 cm-1—570 cm-1Absworption peak be present, be the asymmetric bending vibration for Si-O-Ca.
Such as embodiment 2, Fig. 4 is Eu made from embodiment 23+:The FT-IR collection of illustrative plates of HAp/MSN composite Nano balls.From Fig. 4
As can be seen that sample is in 3400 cm-1Absworption peak come from Eu3+:Si-OH stretching vibration in HAp/MSN composite Nano balls,
1080 cm-1Absorption belong to Eu3+:Si-O-Si stretching vibration, 563 cm in HAp/MSN composite Nano balls-1For Si-O-
Ca asymmetric bending vibration.FT-IR results show stronger chemical bond between HAp and MSN be present, and HAp passes through covalent bond effect
In the skeleton for the MSN being doped to.
N2Adsorption-desorption isothermal is tested：Eu made from Example 2- embodiments 103+:HAp/MSN carries out N2Absorption-de-
Attached isothermal test, Eu3+:HAp/MSN adsorption isotherm is the adsorption isotherm of typical mesoporous material, shows the composite wood
Expect for typical mesoporous material, and Eu is calculated by BET formula3+:The specific surface area of HAp/MSN composite Nano balls is 800
m2/g -815 m2/ g, pore volume are 0.73 cm3/g -0.80cm3/g。Eu3+:HAp/MSN composite Nano ball apertures are about 2.5
Nm-3.2 nm, and obtained Eu in each embodiment3+:The pore-size distribution relatively narrower of HAp/MSN composite Nano balls.
Such as embodiment 2, Fig. 5 is Eu made from embodiment 23+:The low temperature N of HAp/MSN composite Nano balls2Adsorption-desorption etc.
Warm line.As seen from Figure 5, Eu made from embodiment 23+:HAp/MSN adsorption isotherm is the adsorption isotherm of typical mesoporous material
Line, it is typical mesoporous material to show the composite.Eu made from the embodiment 2 be calculated as BET formula3+:HAp/MSN
The specific surface area of composite Nano ball is 809 m2/ g, pore volume 0.76cm3/g.From Eu made from embodiment 23+:HAp/MSN is answered
Close the absorption graph of pore diameter distribution of nanosphere（Fig. 6）As can be seen that Eu made from embodiment 23+:HAp/MSN aperture is about 3 nm,
And pore-size distribution relatively narrower, show Eu made from embodiment 23+:The aperture ratio of HAp/MSN composite Nano balls is more uniform.
Fluorescent emission and excitation spectrum test：Eu made from Example 2- embodiments 103+:HAp/MSN carries out fluorescence hair
Penetrate and tested with excitation spectrum, sample has the last one in the range of 350-450 nm scanning wavelengths at the nm of 392 nm -400
Emission peak, be Eu3+Typical excitation peak.Meanwhile to launch peak-to-peak value as excitation wavelength, obtain Eu3+:HAp/MSN's is glimmering
Optical emission spectroscopy, there is stronger emission peak at the nm of 610nm -620, be Eu3+Typical emission peak, show embodiment 2- implement
Eu made from example 103+:HAp/MSN has stronger red light emitting phosphor performance.
Such as embodiment 2, Fig. 7 is Eu made from embodiment 23+:HAp/MS fluorescence excitation spectrum, it can be seen that sample exists
In the range of 350-450 nm scanning wavelengths, there is the emission peak of the last one at 395 nm, this is Eu3+Typical excitation peak.Meanwhile
We obtain Eu made from embodiment 2 using 395 nm as excitation wavelength3+:HAp/MSN fluorescence emission spectrum (Fig. 8).By Fig. 8
It can be seen that Eu made from embodiment 23+:HAp/MSN has stronger emission peak at 615 nm, and this is Eu3+Typical emission peak, table
Eu made from bright embodiment 23+:HAp/MSN has stronger red light emitting phosphor performance.
Biodegradation experiment
50 mg Eu made from Example 2- embodiments 103+:HAp/MSN powder adds 10 mL phosphate and delayed in centrifugation
Rush solution（PBS, pH=5.0）, ultrasonic wave disperse 3 min after be placed in 37oIn C water bath with thermostatic control shaking tables, degrade the regular hour
Afterwards, centrifuge, collect supernatant liquor and precipitation, be deposited in 60oC is dried in vacuo 12 h.
ICP is tested：By carrying out ICP tests, Eu made from embodiment 2- embodiments 103+:HAp/MSN PBS (pH=
5.0) degraded in solution, with the extension of degradation time, Ca2+Concentration become larger, after -14 hours about 10 hours,
Ca2+Change in concentration be held essentially constant, illustrate Eu made from embodiment 2- embodiments 103+:HAp/MSN has preferably raw
Thing degradation property.
Such as embodiment 2, Fig. 9 is Eu made from embodiment 23+:HAp/MSN degrades necessarily in PBS (pH=5.0) solution
Time after, Ca in solution2+Change in concentration situation map.As can be seen that with the extension of degradation time, Ca2+Concentration it is gradual
Become big, after degrading 12 hours, Ca2+Change in concentration be held essentially constant, this shows Eu made from embodiment 23+:HAp/MSN exists
There is preferable biodegradability in PBS.
Above-described is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
Under the premise of general idea of the present invention is not departed from, some changes and improvements can also be made, these should also be considered as the present invention's
Protection domain.
Claims (9)
1. Biodegradable fluorescent mesoporous silicon oxide composite Nano ball, it is characterised in that：Including following raw material, p-methyl benzenesulfonic acid
Cetyltrimethyl ammonium, triethanolamine, esters of silicon acis, HPO4 2-Solion, Ca2+Solion, Eu3+Solion, wherein right
Toluenesulfonic acid cetyltrimethyl ammonium is template, and triethanolamine is catalyst, wherein with molar amount HPO4 2-Solion：Ca2+
Solion=2:3—5:8.
2. Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 1, it is characterised in that：To rub
That gauge, HPO4 2-Solion：Ca2+Solion：Eu3+Solion=（50-160）：（75-256）：（0.5-5）, toluene
Sulfonic acid cetyltrimethyl ammonium：Triethanolamine：Esters of silicon acis=（0.5-1）：（0.5-6.7）：（6-12）, Eu3+Solion：Silicic acid
Ester=（0.5-5）：（600-1200）.
3. Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 2, it is characterised in that：To rub
That gauge, HPO4 2-Solion：Ca2+Solion：Eu3+Solion=（89-90）：（135-136）：2.5.
4. Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 2, it is characterised in that：To rub
That gauge, toluenesulfonic acid cetyltrimethyl ammonium：Triethanolamine：Esters of silicon acis=0.75：1.34：9.6.
5. Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 2, it is characterised in that：To rub
That gauge, Eu3+Solion：Esters of silicon acis=2.5：960.
6. Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 1-5 any claims
Preparation method, it is characterised in that：Comprise the following steps,
（1）With p-methyl benzenesulfonic acid cetyltrimethyl ammonium（CTAT）For template, with triethanolamine（TEA）For catalyst, using original
Position sol-gel process is by hydroxyapatite presoma and the europium ion-doped skeleton to mesoporous silicon oxide；
（2）HAp presomas and mesoporous silicon oxide skeleton high-temperature roasting with europium ion will be adulterated, obtain Biodegradable fluorescent
Mesoporous silicon oxide complex microsphere.
7. the preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 6, it is special
Sign is：The step（1）For using CTAT as template, TEA is base catalyst, in esters of silicon acis（TEOS）Hydrolyze to form dioxy
In SiClx sol-process, while add Ca2+、HPO4 2-And rare earth ion Eu3+, then by gel aging obtain adulterate HAp before
Drive body and the mesoporous silicon oxide skeleton with europium ion.
8. the preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 6, it is special
Sign is：The step（2）For, will adulterate HAp presomas and with the mesoporous silicon oxide skeleton of europium ion air atmosphere 550~
650 oC is calcined 6~8 h, 1 DEG C/min of heating rate, obtains white powder.
9. the preparation method of Biodegradable fluorescent mesoporous silicon oxide composite Nano ball according to claim 6, it is special
Sign is：Described preparation method is further comprising the steps of, by step（3）Obtained white powder carries out finely ground.
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Non-Patent Citations (2)
| Title |
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| PIAOPING YANG ET AL.: "Bioactive, luminescent and mesoporous europium-doped hydroxyapatite as a drug carrier", 《BIOMATERIALS》 * |
| XIAOHONG HAO ET AL.: "Hybrid Mesoporous Silica-Based Drug Carrier Nanostructures with Improved Degradability by Hydroxyapatite", 《ACS NANO》 * |
Cited By (2)
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|---|---|---|---|---|
| CN109568675A (en) * | 2018-12-13 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Degradation rate can fluorescent marker the preparation of polyester/periodic mesoporous bone filled composite materials and product and application |
| CN109568675B (en) * | 2018-12-13 | 2021-06-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of polyester/periodic mesoporous bone filling composite material with fluorescence-labeled degradation rate, product and application |
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