CN104255744A - Method for preparing silicon dioxide/octacalcium phosphate granules for releasing methylene blue dimer - Google Patents
Method for preparing silicon dioxide/octacalcium phosphate granules for releasing methylene blue dimer Download PDFInfo
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- CN104255744A CN104255744A CN201410436007.8A CN201410436007A CN104255744A CN 104255744 A CN104255744 A CN 104255744A CN 201410436007 A CN201410436007 A CN 201410436007A CN 104255744 A CN104255744 A CN 104255744A
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Abstract
The invention provides a method for preparing silicon dioxide/octacalcium phosphate granules for releasing methylene blue dimer, belonging to the technical field of chemical raw material production. The method comprises the following steps: sequentially adding ammonia water, methylene blue and tetraethoxysilane into a solution with water and ethanol, stirring for 4 hours, centrifuging, washing with ethanol, and preparing a silicon dioxide colloidal solution containing methylene blue by using ethanol; further adding citric acid, ethylenediamine tetraacetic acid disodium, calcium nitrate and diammonium hydrogen phosphate into the solution with water and ethanol, adjusting the pH value of the solution to be 9, further adding polyethylene glycol, stirring for one hour, pouring the silicon dioxide colloidal solution containing methylene blue, stirring for 3 hours, centrifuging, washing, and drying, thereby obtaining the silicon dioxide/octacalcium phosphate granules for releasing methylene blue dimer. The method is simple in process, low in raw material price and easy for industrialization production. The granules prepared by using the method are good in biocompatibility and easy to degrade. The methylene blue is released into a solution from interior of the granules mainly in a dimer molecule manner and is slow to release.
Description
Technical field
Discharge a preparation method for methylene blue dimeric silica/phosphoric acid eight calcium particle, belong to industrial chemicals preparation method field.
Background technology
Methylene blue is widely adopted in different field, produces singlet oxygen molecular and come the aspects such as sterilizing, also for the treatment of the disease such as malaria and urinary tract infections after being mainly used in the fluorescent tracing after biological cell dyeing and photosensitized oxidation reaction.
In aqueous, methylene blue molecule often exists with monomer, dimer and polymeric form, the accumulation shape of molecule on its fluorescence property, photosensitized oxidation reaction and redox property affect highly significant.According to people (Tardivo JP, Giglio AD, Oliveira CS, Gabrielli DS such as Tardivo JP; Junqueira HC, Tada DB, Severino D; Turchiello RF, Baptista MS, Phtodiagnosis Photodynamic Therapy 2005; 2 (3): 175-191) and people (Seo SH, Kim BM, Joe A, Han HW, Chen X, Cheng Z, Jang ES, the Biomaterials 2014 such as Seo SH; 35 (10): 3309-3318) research report methylene blue monomer and dimer have different photochemical reaction routes, be in the methylene blue monomer molecule of ground state by after optical excitation, return ground state by retreating to excite with oxygen molecule positive energy exchange, oxygen molecule then changes the singlet oxygen molecular with bactericidal action into; And the methylene blue dimer molecule being in ground state produces methylene blue free radical by intramolecule Charger transfer, methylene blue free radical can with oxygen molecule generate high reaction activity cross oxygen molecule, also other reactive oxygen species thing (reactive oxygen species can be generated, ROS), the hydroxyl radical free radical of high reaction activity is comprised.Methylene blue dimer, compared to methylene blue monomer molecule, has a clear superiority in the hypoxic tumor tissues of removal.After all in solid-state tumor tissues, the supply of oxygen and unbalanced depletion often cause the content of oxygen molecule lower.Improve methylene blue dimer concentration to realize by increasing Methylene Blue in Solution concentration, but the health of this meeting normal tissue brings adverse influence.
Can be there is photosensitizing chemical reaction thus can be used for removing the bacterium in water body in methylene blue, this is widely used in aquaculture field under light action.In water body, regularly input methylene blue can murder the bacterium in water body in time, effectively can keep the water body environment of aquatic products thing healthy growth.According to people (Usacheva MN, Teichert MC, Biel MA, Journal of Photochemistry and Photobiology B:Biology 2003 such as Usacheva MN; 71:87-98) report, compared to methylene blue monomer, methylene blue dimer tends to assemble at cell surface, can produce more effective photochemical reaction, and then significantly improve sterilization effect under photostimulation.But simple dependence increases concentration and provide the dimeric method of water body Methylene Blue can bring adverse influence to the health of the aquatic products thing of cultivation, also can deepen water body color simultaneously, adverse influence is brought to water body environments such as the permeabilities of water body.
If the mode of methylene blue molecule based on dimer is released in solution in particle, effectively can improve methylene blue concentration and increase the adverse effect brought, and there is not been reported can to discharge the dimeric research of methylene blue in particle.
Summary of the invention
The object of this invention is to provide a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle, for achieving the above object, the technical solution adopted in the present invention step is as follows:
(1) in the mixed solution of moisture and ethanol, stirring reaction is added after ammoniacal liquor, methylene blue and ethyl orthosilicate successively 4 hours, centrifugal and be mixed with the silica colloid solution containing methylene blue with ethanol again with after ethanol washing and depositing thing;
(2) in the mixed solution of moisture and ethanol, regulate the pH value to 9 of solution with ammoniacal liquor after adding citric acid, disodium ethylene diamine tetraacetate, nitrate of lime and diammonium hydrogen phosphate successively, add polyethylene glycol subsequently, what step (1) prepared after 1 hour by stirring reaction pours into containing the silica colloid solution of methylene blue, then stirring reaction 3 hours;
(3) reaction solution step (2) obtained is centrifugal, and with after ethanol washing and depositing thing under 70oC dry 12 hours, namely obtains release methylene blue dimeric silica/phosphoric acid eight calcium particle.
Wherein, in step (1), the volume ratio of water, ethanol, ammoniacal liquor and ethyl orthosilicate is 26.74:5:0.72:1, and the concentration of methylene blue is 2.32 mMs often liter.
In step (2), the volume ratio of water and ethanol is 3:1.The concentration of citric acid is 0.052 ~ 0.157 mM often liter, and the mol ratio of disodium ethylene diamine tetraacetate and citric acid is 1:9, and best is 0.104 mM often liter.In solution, the concentration of nitrate of lime and diammonium hydrogen phosphate is respectively 0.0567 mM often liter and 0.0349 mM often liter, and the mol ratio of the ethyl orthosilicate addition in nitrate of lime addition and step (1) is 0.68:1.The molecular weight of polyethylene glycol is 400 ~ 6000, and concentration is that 0.83 ~ 10 micromole often rises, and the molecular weight of best polyethylene glycol is 2000, and best concentration is that 2.5 micromoles often rise.When regulating the pH value to 9 of reaction solution, calcium ion in solution and phosphate anion can generate OCP, under the synergy of citric acid and polyethylene glycol, be deposited into the silica particles containing methylene blue, and then prepare release methylene blue dimeric silica/phosphoric acid eight calcium particle.
Beneficial effect of the present invention is:
(1) this method technique is simple, cost of material is low and be easy to suitability for industrialized production;
(2) preparation-obtained release methylene blue dimeric silica/phosphoric acid eight calcium particle surface is polyethylene glycol, disodium ethylene diamine tetraacetate, citric acid and OCP layer, good biocompatibility, easily degrade in aqueous environment, degraded ion is friendly ion in body, can use safely;
(3) in different solution, the all main form with dimer molecule of silica/phosphoric acid calcium granule interior as running water, deionized water and the self-contained methylene blue of phosphorus buffer solution (pH=7.2 ~ 7.4) Methylene Blue is released in solution, and the behavior expression of release is slow releasing.
Accompanying drawing explanation
Fig. 1 is standard X-ray diffraction spectrogram (b) that X-ray diffraction spectrogram (a) of the release methylene blue dimeric silica/phosphoric acid eight calcium particle that the embodiment of the present invention 1 prepares and JCPDS card are numbered the OCP of 26-1056.
Fig. 2 is the SEM electron scanning micrograph of the release methylene blue dimeric silica/phosphoric acid eight calcium particle that the embodiment of the present invention 1 prepares.
Fig. 3 is the behavior discharged in the release methylene blue dimeric silica/phosphoric acid eight calcium particle prepared from the embodiment of the present invention 1 at running water Methylene Blue.
Fig. 4 is the behavior discharged in the release methylene blue dimeric silica/phosphoric acid eight calcium particle that methylene blue prepares from the embodiment of the present invention 1 in deionized water.
Fig. 5 is the behavior discharged in the release methylene blue dimeric silica/phosphoric acid eight calcium particle prepared from the embodiment of the present invention 1 at phosphorus buffer solution (pH=7.2 ~ 7.4) Methylene Blue.
Fig. 6 is after being released into solution in the release methylene blue dimeric silica/phosphoric acid eight calcium particle prepared from the embodiment of the present invention 1 at different solutions Methylene Blue, and methylene blue dimer is in the absorbance (A610) of 610 nanometers and ratio (A610/A664) the over time situation of monomer between 664 nanometers absorbances (A664).(a) running water; (b) deionized water; C () is in phosphorus buffer solution.
Fig. 7 be running water Methylene Blue hang oneself the embodiment of the present invention 1 step (1) preparation-obtained release methylene blue dimeric silica/phosphoric acid eight calcium particle in the behavior that discharges.
Fig. 8 is that methylene blue is hung oneself the preparation-obtained behavior containing discharging in the silica dioxide granule of methylene blue of the step (1) of the embodiment of the present invention 1 in deionized water.
Fig. 9 be phosphorus buffer solution (pH=7.2 ~ 7.4) Methylene Blue hang oneself the step (1) of the embodiment of the present invention 1 preparation-obtained containing the silica dioxide granule of methylene blue in the behavior that discharges.
Figure 10 be different solutions Methylene Blue hang oneself the step (1) of the embodiment of the present invention 1 preparation-obtained containing the silica dioxide granule of methylene blue in be released into solution after, methylene blue dimer is in the absorbance (A610) of 610 nanometers and ratio (A610/A664) the over time situation of monomer between 664 nanometers absorbances (A664).(a) running water; (b) deionized water; C () is in phosphorus buffer solution.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
(1) in the solution containing 92 milliliters of ethanol and 17.2 ml waters, add after 2.48 milliliters of ammoniacal liquor stir and add methylene blue again, stir after 10 minutes, add 3.44 milliliters of ethyl orthosilicates again, the concentration of methylene blue is made to be 2.32 mMs often liter, stirring reaction is centrifugal and with after ethanol washing and depositing thing, be mixed with the silica colloid solution containing methylene blue with ethanol after 4 hours;
(2) in the solution containing 138.3 ml waters and 46.1 milliliters of ethanol, add citric acid successively, disodium ethylene diamine tetraacetate, nitrate of lime and diammonium hydrogen phosphate, its concentration is made to be respectively 0.104 mM often liter, 0.012 mM often liter, 0.0567 mM often liter and 0.0349 mM often liter, the pH value to 9 of solution is regulated until completely dissolved with ammoniacal liquor, add the polyethylene glycol that molecular weight is 2000 again, its concentration is made to be that 2.5 micromoles often rise, the silica colloid solution containing methylene blue that step (1) prepared after 1 hour by stirring reaction is poured into, stirring reaction 3 hours,
(3) reaction solution step (2) obtained is centrifugal, and with namely obtaining release methylene blue dimeric silica/phosphoric acid eight calcium particle after ethanol washing under 70oC after dry 12 hours.
The thing phase (see figure 1) of X-ray diffraction method analysing particulates.Wherein, the broadening diffraction maximum of amorphous silicon di-oxide appears at the position of in Fig. 1 (a) about 25 degree, and finds the diffraction maximum also having OCP in Fig. 1 (a) after contrasting with Fig. 1 (b).
SEM SEM detects the pattern (see figure 2) of particle.
Visible spectrophotometry is determined at the behavior (seeing Fig. 3, Fig. 4 and Fig. 5 respectively) from the release of release methylene blue dimeric silica/phosphoric acid eight calcium granule interior of running water, deionized water and phosphorus buffer solution Methylene Blue, and the dimer discharged is in the absorbance (A610) of 610 nanometers and ratio (A610/A664) the over time situation (see figure 6) of methylene blue monomer between the absorbance (A664) of 664 nanometers.
For the purpose of contrast, the silica colloid solution containing methylene blue prepared by the step (1) through embodiment 1 obtains precipitum through centrifugal, obtains the silica dioxide granule containing methylene blue under 70oC after dry 12 hours.Visible spectrophotometry is determined at the behavior (seeing Fig. 7, Fig. 8 and Fig. 9 respectively) of the silica dioxide granule inside release of running water, deionized water and the self-contained methylene blue of phosphorus buffer solution Methylene Blue, and the dimer discharged is in the absorbance (A610) of 610 nanometers and ratio (A610/A664) the over time situation (see figure 10) of methylene blue monomer between the absorbance (A664) of 664 nanometers.
Test through heat analysis method, calculating methylene blue what prepare through the step (1) of embodiment 1 is 111.4 mg/g containing the parcel amount in the silica dioxide granule of methylene, and the intragranular parcel amount of release methylene blue dimeric silica/phosphoric acid eight calcium that methylene blue is preparing through embodiment 1 is 96.1 mg/g.
Find after tested, in different solutions (running water, deionized water and phosphorus buffer solution), methylene blue mainly with dimeric form from silica/phosphoric acid eight calcium granule interior slow releasing.
Claims (9)
1. discharge a preparation method for methylene blue dimeric silica/phosphoric acid eight calcium particle, it is characterized in that comprising the following steps:
Step 1. containing in the solution of second alcohol and water, to add after ammoniacal liquor, methylene blue and ethyl orthosilicate stirring reaction 4 hours successively, centrifugal and be mixed with the silica colloid solution containing methylene blue with ethanol again with after ethanol washing and depositing thing;
Step 2. is in the solution of moisture and ethanol, regulate the pH value to 9 of solution with ammoniacal liquor after adding citric acid, disodium ethylene diamine tetraacetate, nitrate of lime and diammonium hydrogen phosphate successively, add polyethylene glycol subsequently, what step 1 prepared after 1 hour by stirring reaction pours into containing the silica colloid solution of methylene blue, then stirring reaction 3 hours;
The reaction solution that step 2 obtains by step 3. is centrifugal, and with after ethanol washing and depositing thing under 70oC dry 12 hours, namely obtains release methylene blue dimeric silica/phosphoric acid eight calcium particle.
2. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: in step 1, the volume ratio of water, ethanol, ammoniacal liquor and ethyl orthosilicate is 26.74:5:0.72:1.
3. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: the concentration of step 1 Methylene Blue is 2.32 mMs often liter.
4. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: in step 2, the volume ratio of water and ethanol is 3:1.
5. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, it is characterized in that: in step 2, the concentration of citric acid is 0.052 ~ 0.157 mM often liter, the mol ratio of disodium ethylene diamine tetraacetate and citric acid is 1:9.
6. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: in step 2, the concentration of nitrate of lime and diammonium hydrogen phosphate is respectively 0.0567 mM often liter and 0.0349 mM often liter.
7. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: the mol ratio of the ethyl orthosilicate addition in step 2 in nitrate of lime addition and step 1 is 0.68:1.
8. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: in step 2, the concentration of polyethylene glycol is that 0.83 ~ 10 micromole often rises.
9. a kind of preparation method discharging methylene blue dimeric silica/phosphoric acid eight calcium particle according to claim 1, is characterized in that: in step 2, the molecular weight of polyethylene glycol is 400 ~ 6000 grams every mole.
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Cited By (6)
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| CN107022207A (en) * | 2017-04-24 | 2017-08-08 | 山东理工大学 | A kind of preparation method of hydroxyapatite@ferric tannates/titanium dioxide viridine green containing methylene blue |
| CN107213885A (en) * | 2017-06-22 | 2017-09-29 | 山东理工大学 | A kind of preparation method for the Silica-coated particle containing methylene blue for preventing methylene blue from outwards discharging |
| CN108888765A (en) * | 2018-07-16 | 2018-11-27 | 山东理工大学 | A kind of silica containing methylene blue/shellac composite particles preparation method discharging methylene blue aggregation |
| CN109207141A (en) * | 2018-09-19 | 2019-01-15 | 山东理工大学 | A method of there are the silica containing methylene blue/shellac composite particles of high fluorescent by heat treatment auxiliary preparation |
| CN109233806A (en) * | 2018-09-25 | 2019-01-18 | 山东理工大学 | A method of there is the silica dioxide granule containing methylene blue of high fluorescent using heat treatment auxiliary preparation |
| JP2021517982A (en) * | 2018-02-09 | 2021-07-29 | エシロール アテルナジオナール | Encapsulated light absorber nanoparticles, their preparation method, and spectacle lenses containing the nanoparticles |
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| CN101401951A (en) * | 2008-11-17 | 2009-04-08 | 昆明理工大学 | Calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof |
| CN103923037A (en) * | 2014-04-24 | 2014-07-16 | 山东理工大学 | Method for reducing copper ions in methylene blue solution by using calcium phosphate |
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Patent Citations (3)
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| CN101401950A (en) * | 2008-11-17 | 2009-04-08 | 昆明理工大学 | Nano-calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof |
| CN101401951A (en) * | 2008-11-17 | 2009-04-08 | 昆明理工大学 | Calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof |
| CN103923037A (en) * | 2014-04-24 | 2014-07-16 | 山东理工大学 | Method for reducing copper ions in methylene blue solution by using calcium phosphate |
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| CN107022207A (en) * | 2017-04-24 | 2017-08-08 | 山东理工大学 | A kind of preparation method of hydroxyapatite@ferric tannates/titanium dioxide viridine green containing methylene blue |
| CN107022207B (en) * | 2017-04-24 | 2018-05-25 | 山东理工大学 | A kind of preparation method of hydroxyapatite@tannic acid-iron/titanium dioxide viridine green containing methylene blue |
| CN107213885A (en) * | 2017-06-22 | 2017-09-29 | 山东理工大学 | A kind of preparation method for the Silica-coated particle containing methylene blue for preventing methylene blue from outwards discharging |
| CN107213885B (en) * | 2017-06-22 | 2020-07-07 | 山东理工大学 | Preparation method of silica-coated particle containing methylene blue for preventing methylene blue from being released outwards |
| JP2021517982A (en) * | 2018-02-09 | 2021-07-29 | エシロール アテルナジオナール | Encapsulated light absorber nanoparticles, their preparation method, and spectacle lenses containing the nanoparticles |
| JP7110363B2 (en) | 2018-02-09 | 2022-08-01 | エシロール アテルナジオナール | Nanoparticles of encapsulated light absorbers, methods for their preparation, and ophthalmic lenses containing nanoparticles |
| CN108888765A (en) * | 2018-07-16 | 2018-11-27 | 山东理工大学 | A kind of silica containing methylene blue/shellac composite particles preparation method discharging methylene blue aggregation |
| CN108888765B (en) * | 2018-07-16 | 2021-02-26 | 山东理工大学 | Preparation method of methylene blue aggregate-releasing silicon dioxide/shellac composite particle containing methylene blue |
| CN109207141A (en) * | 2018-09-19 | 2019-01-15 | 山东理工大学 | A method of there are the silica containing methylene blue/shellac composite particles of high fluorescent by heat treatment auxiliary preparation |
| CN109207141B (en) * | 2018-09-19 | 2021-04-06 | 山东理工大学 | Method for preparing methylene blue-containing silicon dioxide/shellac composite particles with high fluorescence intensity through heat treatment assistance |
| CN109233806A (en) * | 2018-09-25 | 2019-01-18 | 山东理工大学 | A method of there is the silica dioxide granule containing methylene blue of high fluorescent using heat treatment auxiliary preparation |
| CN109233806B (en) * | 2018-09-25 | 2021-09-17 | 山东理工大学 | Method for preparing silicon dioxide particles containing methylene blue with high fluorescence intensity by heat treatment assistance |
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