CN102068706B - Preparation method of silicon dioxide (SiO2) ultrasonic imaging radiography material - Google Patents
Preparation method of silicon dioxide (SiO2) ultrasonic imaging radiography material Download PDFInfo
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Abstract
The invention relates to a preparation method of a silicon dioxide (SiO2) ultrasonic imaging radiography material. The preparation method comprises the following steps: hydrolyzing a non-functional silicon source and an amino-functional silicon source in a water-alcohol system by utilizing a hard template so as to obtain silicon spheres with amino on surfaces; removing the hard template by extraction to obtain hollow SiO2 spheres with amino on surfaces with uniform particle sizes; and carrying out surface modification by coupling the amino group on the surfaces of the SiO2 spheres with a carboxyl group in polyethylene glycol (PEG) so as to modify the PEG with good biocompatibility on the surfaces of the spheres, and finally obtaining the SiO2 ultrasonic imaging radiography material which has the advantages of good dispersibility, good biocompatibility, suitable cavity dimension and shell thickness and is applicable to ultrasonic imaging.
Description
Technical field
The present invention relates to ultra sonic imaging radiography material field, be specially a kind of method for preparing of silicon dioxide ultra sonic imaging radiography material.
Background technology
Ultrasonic contrast is the for the third time revolution of ultrasonic technique after two-dimentional gray scale ultrasound, CDFI; It is to utilize external substance to inject in body cavity, pipeline or the blood vessel; According to the marked difference between the different or acoustic characteristic impedance of echo between infusion and tissue, thereby strengthen demonstration to internal organs or pathological changes.Extension and development and the development of molecular image technology and the improvement of ultra sonic imaging instrument performance along with Protocols in Molecular Biology; The ultrasonic contrast technology is can effectively strengthen the two-dimensional ultrasonic imaging of each internal organs; Reflection normal structure blood perfusion, contrast agent distribution and the image dynamic change situation different with pathological tissues, the superiority aspect pathological changes diagnosis and discriminating more and more is a people institute extensive concern.
First generation microbubble contrast agent is selected free gas for use, like air, nitrogen etc., because the persistent period is extremely short in blood circulation, microvesicle is not of uniform size, can not fail in wide clinical application through shortcomings such as pulmonary circulation; Second filial generation microbubble contrast agent is shell component or stabilizing agent outside the microvesicle periphery superscribes protein or liposome etc. then, and that more representative is Albunex and Levovist; Third generation microbubble contrast agent has then been done very big improvement at the aspects such as gas componant of the low spread macromolecule of the toughness of elastic housing and employing; The gas that adopts is hexane, perfluoropropane, sulfur hexafluoride etc.; Outer shell component is a polymer; Like polyethylene glycol, polybutylcyanoacrylate etc., this type of contrast agent mainly contains Ecogen, Optison, Sonoveue etc.
But, the microvesicle that these adopt organic molecule or polymer to assemble, its particle diameter heterogeneity is difficult to control the form that obtains homogeneous; Under action of ultrasonic waves, this flexible vesicle very easily breaks, and causes imaging time short, can't long-term follow observe pathological tissues.In addition, the liposome of functionalization or polymer costs an arm and a leg.And the nearest nanoscale microvesicle of reporting is except existing above problem, and resistance to pressure in blood circulation and stability are desirable not enough, and the lar nanometric cavities volume of its formation is big inadequately, causes echoing characteristic relatively poor, and reinforced effects is not obvious.
The porous silicon dioxide nano material is extensively thought to have excellent biological compatibility, chemistry and thermodynamic stability, has bigger specific surface area, advantage such as the aperture is adjustable; And be easy to get at the silicon source of its duct and surface by utilizing functionalization and be modified with amino, carboxyl or sulfydryl isoreactivity functional group, can further combine with medicine or luminescent substance etc., obtain the multifunctional nano material.In addition, utilize methods such as opposite charges adsorption-condensation method, self assembly template layer by layer to make the SiO of hollow
2The constantly research and development of technology of microsphere.But, at present both at home and abroad to the research of silicon dioxide microsphere mainly at the transportation of medicine or DNA and the aspects such as release of medicine, and at the rarely seen report of the applied research in ultra sonic imaging field, thereby await us it studied.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing of silicon dioxide ultra sonic imaging radiography material.
New Si O of the present invention
2The ultra sonic imaging contrast agent material is to make through following method: utilize hard template; In water alcohol system, hydrolysis non-functionalized silicon source and the functionalized silicon source that has amino, thus obtain the amino silicon ball of surface band; Hard template is removed in extraction, obtains the very amino SiO of surface band of homogeneous hollow of particle diameter
2Ball; Again through its surperficial amino and Polyethylene Glycol (PEG) carboxyl mutually coupling carry out finishing; Just can be in its finishing the good Polyethylene Glycol of biocompatibility; Obtain dispersibility and biocompatibility is fine, have suitable cavity size and shell thickness, applicable to the SiO of ultra sonic imaging
2The ultra sonic imaging radiography material.
Step comprises:
(1) hard template is scattered in the mixed liquor of water and alcohol, adds non-functionalized silicon source and have amino functionalized silicon source, both weight ratios are 8～20: 1, regulate PH to 8～10 with ammonia, stir hydrolysis, get deposition and obtain the amino SiO of surface band
2Microsphere; Described alcohol is preferably isopropyl alcohol; Described non-functionalized silicon source is positive tetraethyl orthosilicate, tetramethoxy-silicane or vinyltrimethoxy silane, is preferably positive tetraethyl orthosilicate; The described functionalized silicon source, functionalized silicon source that has amino is 3-aminopropyl silane, γ-An Jibingjisanyiyangjiguiwan or 3-sulfydryl propyl trimethoxy silicane, is preferably 3-aminopropyl silane;
Described hard template is the positively charged polymer globules in surface, and particle diameter is 100nm～1.2 μ m, can select polystyrene (PS) microsphere, polylactic acid-glycolic guanidine-acetic acid copolymer (PLGA) microsphere or polyamide-amide (PAMAM) microsphere for use;
(2) hard template is removed in extraction, obtains the amino hollow SiO of surface band
2Microsphere;
Stating the method that extraction removes hard template is: the SiO that the surface band is amino
2Microsphere is dispersed in the oxolane, and 15～60 ℃ extracted 8～10 hours down; The amino SiO of surface band
2Microsphere and oxolane amount ratio are 0.5～2mg/ml;
(3) Polyethylene Glycol is dissolved in the organic solvent, adds condensing agent and bridging agent, stir 1～3hr, activated carboxyl adds the amino hollow SiO of surface band again
2Microsphere stirs 6～10hr, and deposition is got in washing;
Amino mol ratio with Polyethylene Glycol is 1: 0.8～1.2;
Organic solvent can be selected dimethyl sulfoxide for use.
The mol ratio of condensing agent and bridging agent is 1: 1～3; Condensing agent is selected from 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) or N, N ,-dicyclohexylcarbodiimide (DCC, Dicyclohexylcarbodiimide); Bridging agent is selected from N-maloyl imines (NHS).
In this method, use hard template earlier, hydrolysis silicon source in water and system is at the amino hollow SiO of preparation surface band
2Be template with the polystyrene microsphere during microsphere, template is removed through extraction again in hydrolysis silicon source in water and isopropyl alcohol system, obtains the SiO of hollow
2Microsphere; Then at normal temperatures with the abundant activation of the carboxyl of PEG, the SiO that the method thus of being connected to obtains
2The microspherulite diameter homogeneous, good dispersion, good water solubility.And raw materials used have a low toxicity or nontoxic, advantage such as cheap.
The face finish material that the present invention selected for use is a Polyethylene Glycol, and it is the biomacromolecule of generally acknowledged good biocompatibility, and its price is suitable, and is nontoxic, often be used in the biological medicine research, and be a kind of very good biological organic macromolecule.
In this method, prepare polyethyleneglycol modified SiO
2During microsphere, employing be at the room temperature activated carboxyl, again with the method for amino reaction.Because this experiment must be abundant with activated carboxylic, just can let itself and amino react fully completely, so one step of activated carboxyl is very important.
The present invention makes SiO
2Nano microsphere, uniform particle diameter, mean diameter are 960nm, and shell thickness is suitable, is 30～50nm, and good dispersion has suitable cavity size, is applicable to ultra sonic imaging, and is highly stable under this material room temperature, and biocompatibility is very good.
The present invention can prepare good dispersion, particle diameter is even, cavity is suitable, shell is appropriate hollow Nano microsphere under simple and common experimental provision condition.Response time is short, and required raw material is easy to get, and is cheap, and operating process is simple, and by-product is nuisanceless.This invention provides a kind of economy and practical new for the synthetic preparation of nanometer ultra sonic imaging contrast agent material.
Description of drawings
Fig. 1 is the prepared SiO of embodiment 1
2The transmission electron microscope picture of hollow microsphere.
Fig. 2 is the prepared SiO of embodiment 1
2The field emission scanning electron microscope figure of hollow microsphere.
Fig. 3 is the prepared SiO of embodiment 1
2The infrared spectrogram of hollow microsphere.Infrared spectrum is seen 3443cm from figure
-1The place is the stretching vibration characteristic peak of N-H, 2918cm
-1Be the asymmetrical stretching vibration characteristic peak of C-H, 2845cm
-1Be the symmetrical stretching vibration characteristic peak of C-H, 1640cm
-1Be stretching vibration characteristic peak in the face of N-H, 1068cm
-1Be the stretching vibration characteristic peak of Si-O-Si, 465cm
-1Stretching vibration characteristic peak for Si-O.Hence one can see that, and embodiment 1 microspheres prepared is the amino SiO of surface band
2Microsphere.
Fig. 4 is the prepared SiO of embodiment 3
2The field emission scanning electron microscope figure of ultra sonic imaging contrast agent material can be found out that by figure significant change does not almost take place its form after modifying.
Fig. 5 is the prepared SiO of embodiment 3
2The infrared spectrogram of ultra sonic imaging contrast agent material.See 3445cm from figure
-1The place is the stretching vibration characteristic peak of N-H, 2918cm
-1Be the asymmetrical stretching vibration characteristic peak of C-H, 2845cm
-1Be the symmetrical stretching vibration characteristic peak of C-H, 1640cm
-1Be stretching vibration characteristic peak in the face of N-H, 1070cm
-1Be the stretching vibration characteristic peak of C-O-C in the stretching vibration characteristic peak of Si-O-Si and the Polyethylene Glycol, 465cm
-1Stretching vibration characteristic peak for Si-O.Hence one can see that, the SiO that embodiment 2 is prepared
2Polyethylene Glycol has successfully been modified on the hollow microsphere surface.
Fig. 6 is the prepared SiO of embodiment 3
2The Zeta potential figure of ultra sonic imaging contrast agent material, left figure (A) and right figure (B) are respectively embodiment 2 prepared SiO
2Hollow microsphere and embodiment 3 have wrapped up the SiO of PEG
2Ultra sonic imaging contrast agent material Zeta potential figure.SiO before modifying
2Microsphere institute is electrically charged to be 29.4mV, and its surface charge is 22.2 after modifying Polyethylene Glycol, further specifies Polyethylene Glycol and successfully has been modified at SiO
2The hollow microsphere surface.
Fig. 7 is the prepared SiO of embodiment 3
2External supersonic image under the radiography condition can be found out prepared SiO by figure
2The ultra sonic imaging contrast agent material can be in the contrast of external obvious enhancing ultra sonic imaging.
Fig. 8 is the prepared SiO of embodiment 3
2The ultra sonic imaging contrast agent material is at external two-dimentional gray scale ultrasound image.
The specific embodiment
In order to understand essence of an invention better, specify the technology contents of invention below through embodiment, but content of the present invention is not limited thereto.The also available polylactic acid-glycolic guanidine-acetic acid of polystyrene microsphere copolymer (PLGA) microsphere or polyamide-amide (PAMAM) microsphere replace; Positive tetraethyl orthosilicate can replace with tetramethoxy-silicane or vinyltrimethoxy silane, and perhaps 3-aminopropyl silane replaces with γ-An Jibingjisanyiyangjiguiwan or 3-sulfydryl propyl trimethoxy silicane, and effect is identical.
Embodiment 1
Measure 0.25mL commercial polystyrene microsphere (particle diameter is 1 μ m) (5%, wt/v), add the 7mL distilled water; The isopropyl alcohol of 30mL; 0.1ml positive tetraethyl orthosilicate (TEOS) (93mg), the 3-aminopropyl silane (9.5mg) of 0.01mL and 0.2mL (mass concentration is 25%～28%) ammonia is adjusted into 8～10 with pH value, stirring at normal temperature 3h; Centrifugal, washing just can obtain the amino SiO of surface band
2Microsphere.
Get the amino SiO of 50mg above-mentioned surface band
2Microsphere is dispersed in the 30mL tetrahydrofuran solution, and 25 ℃ extract 8～10h down, remove the polystyrene microsphere hard template, obtains the amino SiO of surface band
2Tiny balloon.
Obtaining its amino density through amino density measurement is 8.65*10
-4Mol/g.
Projection Electronic Speculum figure such as Fig. 1; Field emission scanning electron microscope figure such as Fig. 2; Infrared spectrogram such as Fig. 3 see 3443cm from figure
-1The place is the stretching vibration characteristic peak of N-H, 2918cm
-1Be the asymmetrical stretching vibration characteristic peak of C-H, 2845cm
-1Be the symmetrical stretching vibration characteristic peak of C-H, 1640cm
-1Be stretching vibration characteristic peak in the face of N-H, 1068cm
-1Be the stretching vibration characteristic peak of Si-O-Si, 465cm
-1Stretching vibration characteristic peak for Si-O.Hence one can see that, and embodiment 1 microspheres prepared is the amino SiO of surface band
2Hollow microsphere.
Embodiment 2
The consumption of positive tetraethyl orthosilicate (TEOS) is 0.2ml (186mg), and all the other are with embodiment 1.Detect through infrared spectrum, projection Electronic Speculum and field emission scanning electron microscope, microspheres prepared is the amino SiO of surface band
2Hollow microsphere.Obtaining its amino density through amino density measurement is 4.85*10
-4Mol/g.
Get 6mg (3.46*10
-5Mol) PEG2000 is dissolved in the dimethyl sulfoxide (DMSO) of 20mL, and according to PEG: EDC: NHS=1: 1: 2.5 mol ratio adds EDC (5mg) and NHS (10mg), and stirring 1～3h is in order to activated carboxyl.
Add 1 amino SiO of synthetic surface band of 40mg embodiment
2Hollow microsphere (mol ratio of its surface amino groups and PEG carboxyl is 1: 1), room temperature slowly stirs 6-10h, washing, centrifugal, lyophilization, it is extraordinary to obtain biocompatibility, the hollow SiO of Polyethylene Glycol in the finishing
2Microsphere is to be used for ultra sonic imaging.Uniform particle diameter, mean diameter are 960nm, and shell thickness is suitable, is 30～50nm.
Field emission scanning electron microscope figure such as Fig. 4 can find out that significant change does not almost take place its form after modifying.
Infrared spectrogram such as Fig. 5.See 3445cm from figure
-1The place is the stretching vibration characteristic peak of N-H, 2918cm
-1Be the asymmetrical stretching vibration characteristic peak of C-H, 2845cm
-1Be the symmetrical stretching vibration characteristic peak of C-H, 1640cm
-1Be stretching vibration characteristic peak in the face of N-H, 1070cm
-1Be the stretching vibration characteristic peak of C-O-C in the stretching vibration characteristic peak of Si-O-Si and the Polyethylene Glycol, 465cm
-1Stretching vibration characteristic peak for Si-O.Hence one can see that, the SiO that embodiment 2 is prepared
2Polyethylene Glycol has successfully been modified on the hollow microsphere surface.
Zeta potential figure such as Fig. 6, left figure (A) and right figure (B) are respectively embodiment 2 prepared SiO
2Hollow microsphere and embodiment 3 have wrapped up the SiO of PEG
2Ultra sonic imaging contrast agent material Zeta potential figure.SiO before modifying
2Microsphere institute is electrically charged to be 29.4mV, and its surface charge is 22.2 after modifying Polyethylene Glycol, further specifies Polyethylene Glycol and successfully has been modified at SiO
2The hollow microsphere surface.
External supersonic image such as Fig. 7 under the radiography condition can find out prepared SiO by figure
2Microsphere can be in the contrast of external obvious enhancing ultra sonic imaging.At external two-dimentional gray scale ultrasound image such as Fig. 8.
Embodiment 4
Get 6mg (3.46*10
-5Mol) PEG2000 is dissolved in the dimethyl sulfoxide (DMSO) of 20mL, and according to PEG: EDC: NHS=1: 1: 2.5 mol ratio adds EDC (5mg) and NHS (10mg), and stirring 1～3h is in order to activated carboxyl.
Add 2 amino SiO of synthetic surface band of 71mg embodiment
2Hollow microsphere (mol ratio of its surface amino groups and PEG carboxyl is 1: 1), all the other steps are with embodiment 3.
The result shows, obtains the hollow SiO of Polyethylene Glycol in the finishing
2Microsphere can be used in the ultra sonic imaging.Uniform particle diameter, mean diameter are 960nm, and shell thickness is suitable, is 30～50nm.
Claims (2)
1. the method for preparing of a silicon dioxide ultra sonic imaging radiography material is characterized in that, comprises the steps:
(1) hard template is scattered in the mixed liquor of water and alcohol, adds non-functionalized silicon source and have amino functionalized silicon source, both weight ratios are 8～20: 1, regulate pH to 8～10 with ammonia, stir hydrolysis, get deposition and obtain the amino SiO of surface band
2Microsphere; Described hard template is the positively charged polymer globules in surface, and particle diameter is 100nm～1.2 μ m;
Said hard template is polystyrene microsphere, polylactic acid-glycolic guanidine-acetic acid copolymer microsphere or polyamide-amide microsphere; Described alcohol is isopropyl alcohol;
Described non-functionalized silicon source is positive tetraethyl orthosilicate, tetramethoxy-silicane or vinyltrimethoxy silane;
The described functionalized silicon source that has amino is 3-aminopropyl silane, γ-An Jibingjisanyiyangjiguiwan or 3-sulfydryl propyl trimethoxy silicane;
(2) hard template is removed in extraction, obtains the amino hollow SiO of surface band
2Microsphere;
The method that hard template is removed in said extraction is: the SiO that the surface band is amino
2Microsphere is dispersed in the oxolane, and 15～60 ℃ extracted 8～10 hours down;
(3) Polyethylene Glycol is dissolved in the organic solvent, adds condensing agent and bridging agent, stir 1～3hr, activated carboxyl adds the amino hollow SiO of surface band again
2Microsphere stirs 6～10hr, and deposition is got in washing;
Amino mol ratio with Polyethylene Glycol is 1: 0.8～1.2; The mol ratio of condensing agent and bridging agent is 1: 1～3;
Said condensing agent is selected from 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide or N, N ,-dicyclohexylcarbodiimide; Said bridging agent is selected from N-maloyl imines; Said organic solvent is a dimethyl sulfoxide.
2. the method for preparing of the said silicon dioxide ultra sonic imaging of claim 1 radiography material is characterized in that, the amino SiO of the band of surface described in the step (2)
2Microsphere and oxolane amount ratio are 0.5～2mg/ml.
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| CN102380110A (en) * | 2011-11-11 | 2012-03-21 | 上海师范大学 | SiO2 hollow sphere ultrasonic imaging contrast agent material and preparation method and application thereof |
| CN102389576A (en) * | 2011-11-11 | 2012-03-28 | 上海师范大学 | Magnetic-ultrasonic difunctional SiO2 hollow sphere contrast agent and preparation method and application thereof |
| CN102441179B (en) * | 2011-12-07 | 2013-07-17 | 中国科学院上海硅酸盐研究所 | Silicon dioxide base ultrasonic contrast medium/high intensity focused ultrasound (HIFU) synergist and preparation method thereof |
| CN104436228A (en) * | 2013-09-16 | 2015-03-25 | 成都市绿科华通科技有限公司 | Novel magnetic ferric oxide hollow microsphere contrast agent |
| CN104784698A (en) * | 2015-03-09 | 2015-07-22 | 江苏大学 | Hierarchical porous polylactic acid drug carrier and preparation method thereof |
| CN105056233B (en) * | 2015-08-12 | 2018-03-13 | 苏州大学 | Multi-functional mesoporous silicon dioxide nano particle with near-infrared photo-thermal and internal fluorescence imaging characteristic and its preparation method and application |
| CN108210981A (en) * | 2016-12-22 | 2018-06-29 | 南通蓝智新材料科技有限公司 | Bioactivity glass microballoon and preparation method thereof |
| CN108210980A (en) * | 2016-12-22 | 2018-06-29 | 南通蓝智新材料科技有限公司 | Bioactivity glass microballoon and preparation method thereof |
| CN109602917B (en) * | 2019-01-02 | 2021-07-02 | 大连理工大学 | Mesoporous titanium peroxide nano-drug composition with lung cancer targeting and enhanced photodynamic therapy effects and preparation method thereof |
| CN110064063B (en) * | 2019-03-15 | 2021-11-19 | 徐州医科大学 | Double-layer hydrophobic-hydrophilic modified hollow nano silicon ball, and preparation method and application thereof |
| CN115300643B (en) * | 2022-10-12 | 2022-12-09 | 山东百多安医疗器械股份有限公司 | Gastrointestinal tract ultrasonic examination development assisting agent and preparation method thereof |
| CN115317629B (en) * | 2022-10-13 | 2022-12-20 | 山东百多安医疗器械股份有限公司 | Two-component development assisting agent for ultrasonic examination of stomach and preparation method thereof |
| CN116813930B (en) * | 2023-08-29 | 2023-12-15 | 鲁东大学 | Preparation method of high molecular weight hyperbranched dendrimer metal ion adsorbent |
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