CN105256533A - Magnetic drug-loaded fabric preparation method - Google Patents
Magnetic drug-loaded fabric preparation method Download PDFInfo
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- CN105256533A CN105256533A CN201510784975.2A CN201510784975A CN105256533A CN 105256533 A CN105256533 A CN 105256533A CN 201510784975 A CN201510784975 A CN 201510784975A CN 105256533 A CN105256533 A CN 105256533A
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Abstract
The invention discloses a magnetic drug-loaded fabric preparation method. Magnetic nano ferriferrous oxide particles are loaded to the surface of polyester fabric through the hydrothermal method, then the polyester fabric covered with ferriferrous oxide is subjected to coupling modification through a silane coupling agent, then modified beta-cyclodextrin is grafted and modified, and finally, menthol, Daktarin and other large medicine molecules are contained in a cavity of beta-cyclodextrin. The method is easy and convenient to implement, and raw materials can be saved through a reaction under a closed condition. Besides, the binding strength of beta-cyclodextrin and the polyester fabric and the medicine encapsulation rate are high, and the obtained magnetic drug-loaded fabric has no toxic and side effects on human bodies. Through an external magnetic field, release of medicine can be accelerated, pain of some sensitive parts of bodies of patients can be relieved to the largest extent, and after the loaded drug is released, the magnetic drug-loaded polyester fabric can cover medicine again and be repeatedly used.
Description
Technical field
The invention belongs to Textile Engineering technical field, be specifically related to a kind of preparation method of magnetic drug-carrying fabric.
Background technology
Magnetic nano ferroferric oxide particle, not only there is special physics and chemistry character, and there is the magnetic performances such as superparamagnetic characteristic, high magnetic susceptibility and low Curie temperature, these characteristics make tri-iron tetroxide particle be widely applied in the field such as industrial production and biological medicine.But, because the surface energy that magnetic nano-particle is huge makes it be easy to the phenomenons such as reunion and surface oxidation occur, thus affect homogeneity and the magnetic property of magnetic particle, be very limited in actual applications.Therefore, functionalization is carried out to magnetic nano particle sub-surface, such as form nucleocapsid structure and just can protect its original characteristic.Use the large molecule of supermolecule main block just can carry out functional modification to magnetic nano particle sub-surface, wherein beta-schardinger dextrin-is exactly a kind of important natural supermolecule main block compound.It has interior hydrophobic, outer hydrophilic special construction, can guest molecule that optionally inclusion size is suitable, significantly improves the dissolubility of guest molecule, plays an important role in raising stability and utilization rate.At present, people successfully by grafted by beta cyclodextrin to magnetic nano ferroferric oxide particle surface, not only reduce the specific surface energy of magnetic nano-particle, avoid the defect of the uneven and poor biocompatibility of the domain size distribution that causes because of reunion, and particle surface can be made from the invasion of external environment condition, maintain chemical stability and magnetic property, but it is also more single to use beta-schardinger dextrin-to implement the method for functional modification to magnetic nano-particle, at magnetic dacron surface grafting beta-schardinger dextrin-and the correlation technique of inclusion medicine have not been reported.
Summary of the invention
The object of this invention is to provide a kind of preparation method of magnetic drug-carrying fabric, magnetic drug-carrying fabric and contact human skin, when particularly having externally-applied magnetic field effect, magnetic drug-carrying fabric can be made to generate heat, and then realize the controlled release of the contained medicine of fabric.
The technical solution adopted in the present invention is, a kind of preparation method of magnetic drug-carrying fabric, and concrete preparation process is:
Step 1: magnetic ferroferric oxide nanoparticle is loaded to dacron surface, obtains magnetic fabric;
Step 2: coupling modifier process is carried out to step 1 gained magnetic fabric, realizes rich surface amination;
Step 3: the carboxylated modification of beta-schardinger dextrin-;
Step 4: adopt hydro-thermal method by the grafted by beta cyclodextrin of carboxylated for step 3 gained modification on step 2 gained fabric, and inclusion medicine, to obtain final product.
Feature of the present invention is also,
In step 1, the preparation process of magnetic fabric is:
Step 1.1, get dacron, according to bath raio 1:40 ~ 60, be immersed in sodium hydroxide solution, carry out dacron alkaline etching; Subsequently rinsing, oven dry are carried out to the dacron after etching;
Step 1.2, take sodium thiosulfate, ferric sulfate and urea, mix with deionized water, obtain mixed solution, for subsequent use;
Step 1.3, step 1.2 gained mixed solution and step 1.1 are processed after dacron put into reactor simultaneously, with 1 DEG C/min ~ 3 DEG C/min ramp to 110 DEG C ~ 150 DEG C after sealing, isothermal reaction 2h ~ 6h, question response still takes out dacron after naturally cooling; Subsequently dacron is put into acetone soln and soak 10 ~ 20min, with deionized water rinsing 1 ~ 3 time, then soak 10 ~ 20min in absolute ethyl alcohol, with deionized water rinsing 1 ~ 3 time, finally dry under 60 DEG C ~ 80 DEG C conditions, obtain the magnetic fabric of loaded with nano tri-iron tetroxide.
In step 1.1, the quality-volumetric concentration of sodium hydroxide solution is 80 ~ 100g/L; Dacron alkaline etching process is immersion treatment 20 ~ 40min under 80 ~ 120 DEG C of conditions; The detailed process of rinsing, oven dry is for using rinsed with deionized water 1 ~ 3 time, and under 40 DEG C of conditions, be then immersed in mass percent concentration is 30 ~ 50min in the ethanolic solution of 95%; Repeatedly clean dacron 1 ~ 3 time with deionized water again, obtain the dacron of rinsed clean, and dry under 80 DEG C ~ 100 DEG C conditions.
In step 1.2, the concentration of gained mixed solution is 540 ~ 700g/L, and wherein, the mol ratio of sodium thiosulfate and ferric sulfate is 1:0.5 ~ 1.5, and the mol ratio of urea and ferric sulfate is 1:3; The preparation process of mixed solution is: be first dissolved completely in deionized water by ferric sulfate, subsequently to wherein adding sodium thiosulfate, by magnetic stirrer to solution to clarification, finally being added by urea and stirring until dissolve completely, to obtain final product.
The detailed process of step 2 is: take ethanol water and silane resin acceptor kh-550 respectively, silane resin acceptor kh-550 is added drop-wise in ethanol water, silane resin acceptor kh-550 and ethanol water is stirred with the speed of 100 ~ 200rmp, form mixed solution, then regulate mixed solution pH value to 3.5 ~ 5.5 with glacial acetic acid, obtain coupling modifier mixed solution; Subsequently step 1 gained magnetic fabric is immersed in coupling modifier mixed solution to leave standstill after 3 ~ 8h and takes out, with washes of absolute alcohol 1 ~ 3 time, irradiate 30 ~ 60min under the ultraviolet curing lamp being then 365nm at wavelength, obtain the amidized magnetic fabric of rich surface.
Ethanol water is that absolute ethyl alcohol mixes gained with deionized water with the volume ratio of 1:8 ~ 10; The amount of taking of ethanol water is the ethanol water that every gram of fabric gets 0.025 ~ 0.05L; The consumption of silane resin acceptor kh-550 is 1 ~ 5% of fabric quality.
In step 3, the detailed process of the carboxylated modification of beta-schardinger dextrin-is: the beta-schardinger dextrin-taken respectively and maleic anhydride are dissolved in N successively, in dinethylformamide solution, stir until dissolve completely with 100 ~ 200rmp speed, then under 80 DEG C of conditions, 8 ~ 12h is reacted, after solution cooling, precipitation is separated out with chloroform extraction, by sediment acetone soln washing 3 ~ 5 times, each 5 ~ 10min, and with the multiplex vavuum pump suction filtration of recirculated water, then put into drying box vacuumize 24h under 80 DEG C of conditions, obtain carboxylated beta-schardinger dextrin-;
The mol ratio of beta-schardinger dextrin-and maleic anhydride is 0.5 ~ 1.5:1.
The detailed process of step 4 is:
Step 4.1, gets the carboxylated beta-schardinger dextrin-of step 3 gained and mixes with deionized water, poured into by mixed solution in reactor, add medicine wherein; Subsequently step 2 gained amination magnetic fabric is put into reactor, with 1 DEG C/min ~ 3 DEG C/min ramp to 100 DEG C ~ 140 DEG C after reactor sealing, with 10 ~ 50rmp rotating speed isothermal reaction 2h ~ 4h;
Step 4.2, the dacron that step 4.1 obtained take out, and wash 10 ~ 20min with the deionized water of 40 DEG C of absolute ethyl alcohols, 40 DEG C of acetone and 80 DEG C respectively, room temperature is dried naturally, obtains the magnetic dacron being loaded with medicine.
In step 4.1, the concentration of carboxylated beta-schardinger dextrin-and deionized water gained mixed solution is 1 ~ 5g/L; Medicine is menthol or Da Kening, adds the medicine of 1.5 ~ 3g in often liter of mixed solution.
The invention has the beneficial effects as follows,
(1) the present invention adopts Hydrothermal Synthesis technology, take ferric sulfate as source of iron, sodium thiosulfate is reductant, urea is precipitating agent, while preparing nano ferriferrous oxide granule, directly loaded to dacron surface, the nano ferriferrous oxide purity of generation is high, even particle size distribution, nano particle is combined firmly with dacron.
(2) the present invention introduces amino on nano ferriferrous oxide; Meanwhile, beta-schardinger dextrin-introduces carboxyl, for the graft reaction of beta-schardinger dextrin-and tri-iron tetroxide creates condition, make beta-schardinger dextrin-can be attached to dacron surface to fastness; In addition, the use of silane coupler also further promotes the bond strength of nano ferriferrous oxide granule and dacron.
(3) the inventive method gained magnetic drug-carrying dacron, by externally-applied magnetic field, can accelerate the release of medicine, and after treating contained insoluble drug release, magnetic drug-carrying dacron can inclusion medicine again, and iterative cycles uses.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the embodiment of the present invention 3 gained magnetic drug-carrying dacron;
Fig. 2 is the X-ray diffraction spectrogram of the embodiment of the present invention 3 gained magnetic drug-carrying dacron;
Fig. 3 is the magnetization curve of the embodiment of the present invention 3 gained magnetic drug-carrying dacron;
Fig. 4 is the diffuse reflection spectrum of the embodiment of the present invention 3 gained magnetic drug-carrying dacron;
Fig. 5 is the differential scanning calorimetric curve of the embodiment of the present invention 3 gained magnetic drug-carrying dacron;
Fig. 6 is the menthol release rate curve of the embodiment of the present invention 3 gained magnetic drug-carrying dacron.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of a kind of magnetic drug-carrying fabric of the present invention, concrete preparation process is:
Step 1: magnetic ferroferric oxide nanoparticle is loaded to dacron surface, obtains magnetic fabric:
Step 1.1, get dacron, according to bath raio 1:40 ~ 60, be immersed in sodium hydroxide solution, carry out dacron alkaline etching; Subsequently rinsing, oven dry are carried out to the dacron after etching; Wherein, the quality-volumetric concentration of sodium hydroxide solution is 80 ~ 100g/L; Dacron alkaline etching process is immersion treatment 20 ~ 40min under 80 ~ 120 DEG C of conditions; The detailed process of rinsing, oven dry is for using rinsed with deionized water 1 ~ 3 time, and under 40 DEG C of conditions, be then immersed in mass percent concentration is 30 ~ 50min in the ethanolic solution of 95%; Repeatedly clean dacron 1 ~ 3 time with deionized water again, obtain the dacron of rinsed clean, and dry under 80 DEG C ~ 100 DEG C conditions;
Step 1.2, take sodium thiosulfate, ferric sulfate and urea, mix with deionized water, obtain mixed solution, the concentration of gained mixed solution is 540 ~ 700g/L, wherein, the mol ratio of sodium thiosulfate and ferric sulfate is 1:0.5 ~ 1.5, and the mol ratio of urea and ferric sulfate is 1:3; The preparation process of mixed solution is: be first dissolved completely in deionized water by ferric sulfate, subsequently to wherein adding sodium thiosulfate, by magnetic stirrer to solution to clarification, finally being added by urea and stirring until dissolve completely;
Step 1.3, step 1.2 gained mixed solution and step 1.1 are processed after dacron put into reactor simultaneously, with 1 DEG C/min ~ 3 DEG C/min ramp to 110 DEG C ~ 150 DEG C after sealing, isothermal reaction 2h ~ 6h, question response still takes out dacron after naturally cooling; Subsequently dacron is put into acetone soln and soak 10 ~ 20min, with deionized water rinsing 1 ~ 3 time, then soak 10 ~ 20min in absolute ethyl alcohol, with deionized water rinsing 1 ~ 3 time, finally dry under 60 DEG C ~ 80 DEG C conditions, obtain the magnetic fabric of loaded with nano tri-iron tetroxide.
Step 2: coupling modifier process is carried out to step 1 gained magnetic fabric, realizes rich surface amination:
Take ethanol water and silane resin acceptor kh-550 respectively, silane resin acceptor kh-550 is added drop-wise in ethanol water, silane resin acceptor kh-550 and ethanol water is stirred with the speed of 100 ~ 200rmp, form mixed solution, then regulate mixed solution pH value to 3.5 ~ 5.5 with glacial acetic acid, obtain coupling modifier mixed solution; Subsequently step 1 gained magnetic fabric is immersed in coupling modifier mixed solution to leave standstill after 3 ~ 8h and takes out, with washes of absolute alcohol 1 ~ 3 time, irradiate 30 ~ 60min under the ultraviolet curing lamp being then 365nm at wavelength, obtain the amidized magnetic fabric of rich surface.Wherein, ethanol water is that absolute ethyl alcohol mixes gained with deionized water with the volume ratio of 1:8 ~ 10; The amount of taking of ethanol water is the ethanol water that every gram of fabric gets 0.025 ~ 0.05L; The consumption of silane resin acceptor kh-550 is 1 ~ 5% of fabric quality.
Step 3: the carboxylated modification of beta-schardinger dextrin-:
Be that the beta-schardinger dextrin-that takes respectively of 0.5 ~ 1.5:1 and maleic anhydride are dissolved in N successively in molar ratio, in dinethylformamide solution, stir until dissolve completely with 100 ~ 200rmp speed, then under 80 DEG C of conditions, 8 ~ 12h is reacted, after solution cooling, precipitation is separated out with chloroform extraction, by sediment acetone soln washing 3 ~ 5 times, each 5 ~ 10min, and with the multiplex vavuum pump suction filtration of recirculated water, then put into drying box vacuumize 24h under 80 DEG C of conditions, obtain carboxylated beta-schardinger dextrin-;
Step 4: adopt hydro-thermal method by the grafted by beta cyclodextrin of carboxylated for step 3 gained modification on step 2 gained fabric, and inclusion medicine:
Get the carboxylated beta-schardinger dextrin-of step 3 gained to mix with deionized water, mixed solution is poured in reactor, add medicine wherein; Wherein, the concentration of carboxylated beta-schardinger dextrin-and deionized water gained mixed solution is 1 ~ 5g/L; Medicine is menthol or Da Kening, adds the medicine of 1.5 ~ 3g in often liter of mixed solution.Subsequently step 2 gained amination magnetic fabric is put into reactor, with 1 DEG C/min ~ 3 DEG C/min ramp to 100 DEG C ~ 140 DEG C after reactor sealing, with 10 ~ 50rmp rotating speed isothermal reaction 2h ~ 4h; After cooling, will walk fabric and take out, wash 10 ~ 20min with the deionized water of 40 DEG C of absolute ethyl alcohols, 40 DEG C of acetone and 80 DEG C respectively, room temperature is dried naturally, obtains the magnetic dacron being loaded with medicine.
Embodiment 1
Step 1: the NaOH taking 80g, is mixed with the deionized water of 1L the sodium hydroxide solution that quality-volumetric concentration is 80g/L; According to bath raio 1:40, take the dacron of 17g, be immersed in 20min in the sodium hydroxide solution of 80 DEG C, then rinsed with deionized water is used 1 time, be immersed in 30min in 40 DEG C of mass percent concentration 95% ethanolic solutions, washed with de-ionized water 1 time, 80 DEG C of oven dry; According to sodium thiosulfate, ferric sulfate and urea mol ratio 0.5:1:3, take the urea of the sodium thiosulfate of 79g, the ferric sulfate of 400g and 60g, ferric sulfate is dissolved completely in the deionized water of 1L, add sodium thiosulfate and by magnetic stirrer to solution to clarification, finally urea added in solution until dissolve completely; Mixed solution obtained above is poured in the quartz glass reaction inner bag of 1.2L, add the dacron of alkaline etching process, with 1 DEG C/min ramp to 110 DEG C after reactor sealing, isothermal reaction 6h, question response still takes out dacron after naturally cooling, 10min is soaked in acetone soln, deionized water rinsing 1 time, soaks 10min in absolute ethyl alcohol, deionized water rinsing 1 time, in 60 DEG C of oven dry, obtain the dacron of loaded with nano tri-iron tetroxide.
Step 2: according to absolute ethyl alcohol and deionized water volume ratio 1:8, the ethanol water of preparation 0.425L; The silane resin acceptor kh-550 of 0.17g is taken according to 1% of dacron quality; Silane coupler is added drop-wise in ethanol water, and stirs with 100rmp speed and form mixed solution, be then 3.5 by acetic acid regulator solution pH value, obtain coupling modifier mixed solution; The dacron of load tri-iron tetroxide is immersed in coupling modifier mixed solution, take out after 3h and use washes of absolute alcohol 1 time, then be placed on the ultraviolet curing light irradiation 30min with dominant wavelength 365nm on glass dish, obtain the dacron of the amidized magnetic nano ferroferric oxide of rich surface.
Step 3: according to beta-schardinger dextrin-and maleic anhydride mol ratio 0.5:1, takes the beta-schardinger dextrin-of 567g and the maleic anhydride of 98g; Beta-schardinger dextrin-and maleic anhydride are dissolved in successively the N of 1L, in dinethylformamide solution, stir until dissolve completely with 100rmp speed, under 80 DEG C of conditions, react 8h, after solution cooling, precipitation is separated out with chloroform extraction, sediment acetone soln is washed 3 times, each 5min, put into drying box through vavuum pump suction filtration, vacuumize 24h under 80 DEG C of conditions, obtains carboxy-modified beta-schardinger dextrin-.
Step 4: take the carboxylated beta-schardinger dextrin-of 1g and added in the deionized water of 1L, then the menthol of 1.5g is added, finally add amination magnetic dacron, dacron is transferred in quartz glass reaction still together with solution and seals, with 1 DEG C/min ramp to 100 DEG C, with 10rmp rotating speed isothermal reaction 4h, after question response terminates, fabric is taken out, successively with the deionized water washing 10min of 40 DEG C of absolute ethyl alcohols, 40 DEG C of acetone and 80 DEG C, room temperature is dried naturally, obtains the magnetic dacron being loaded with menthol medicine.
The deionized water that the magnetic dacron of the present embodiment gained is placed in 100mL is carried out adding thermal distillation, distillate ethanolic solution absorbs, then mixed solution is mixed with than toner, measure the absorbance of this menthol distillate, the menthol concentration being calculated this medicine carrying fabric inclusion by regression curve is 0.65g/L.
Embodiment 2
Step 1: the NaOH taking 100g, is mixed with the deionized water of 1L the sodium hydroxide solution that quality-volumetric concentration is 100g/L; According to bath raio 1:60, take the dacron of 25g, be immersed in 40min in the sodium hydroxide solution of 120 DEG C, then rinsed with deionized water is used 3 times, be immersed in 50min in 40 DEG C of mass percent concentration 95% ethanolic solutions, washed with de-ionized water 3 times, 100 DEG C of oven dry; According to sodium thiosulfate, ferric sulfate and urea mol ratio 1.5:1:3, take the urea of the sodium thiosulfate of 237g, the ferric sulfate of 400g and 60g, ferric sulfate is dissolved completely in the deionized water of 1L, add sodium thiosulfate and by magnetic stirrer to solution to clarification, finally urea added in solution until dissolve completely; Mixed solution obtained above is poured in the quartz glass reaction inner bag of 1.2L, add the dacron of alkaline etching process, with 3 DEG C/min ramp to 150 DEG C after reactor sealing, isothermal reaction 2h, question response still takes out dacron after naturally cooling, 20min is soaked in acetone soln, deionized water rinsing 3 times, soaks 20min in absolute ethyl alcohol, deionized water rinsing 3 times, in 80 DEG C of oven dry, obtain the dacron of loaded with nano tri-iron tetroxide.
Step 2: according to absolute ethyl alcohol and deionized water volume ratio 1:10, the ethanol water of preparation 1.25L; The silane resin acceptor kh-550 of 1.25g is taken according to 5% of dacron quality; Silane coupler is added drop-wise in ethanol water, and stirs with 200rmp speed and form mixed solution, be then 5.5 by acetic acid regulator solution pH value, obtain coupling modifier mixed solution; The dacron of load tri-iron tetroxide is immersed in coupling modifier mixed solution, take out after 8h and use washes of absolute alcohol 3 times, then be placed on the ultraviolet curing light irradiation 60min with dominant wavelength 365nm on glass dish, obtain the dacron of the amidized magnetic nano ferroferric oxide of rich surface.
Step 3: according to beta-schardinger dextrin-and maleic anhydride mol ratio 1.5:1, takes the beta-schardinger dextrin-of 1700g and the maleic anhydride of 98g; Beta-schardinger dextrin-and maleic anhydride are dissolved in successively the N of 1L, in dinethylformamide solution, stir until dissolve completely with 200rmp speed, under 80 DEG C of conditions, react 12h, after solution cooling, precipitation is separated out with chloroform extraction, sediment acetone soln is washed 5 times, and each 10min, puts into drying box through vacuum filtration, vacuumize 24h under 80 DEG C of conditions, obtains carboxy-modified beta-schardinger dextrin-.
Step 4: take the carboxylated beta-schardinger dextrin-of 5g and added in the deionized water of 1L, then the menthol of 3g is added, finally add amination magnetic dacron, dacron is transferred in quartz glass reaction still together with solution and seals, with 3 DEG C/min ramp to 140 DEG C, with 50rmp rotating speed isothermal reaction 2h, after question response terminates, fabric is taken out, successively with the deionized water washing 20min of 40 DEG C of absolute ethyl alcohols, 40 DEG C of acetone and 80 DEG C, room temperature is dried naturally, obtains the magnetic dacron being loaded with menthol medicine.
The deionized water that the magnetic dacron of the present embodiment gained is placed in 100mL is carried out adding thermal distillation, distillate ethanolic solution absorbs, then mixed solution is mixed with than toner, measure the absorbance of this menthol distillate, the menthol concentration being calculated this medicine carrying fabric inclusion by regression curve is 1.12g/L.
Embodiment 3
Step 1: the NaOH taking 90g, is mixed with the deionized water of 1L the sodium hydroxide solution that quality-volumetric concentration is 90g/L; According to bath raio 1:50, take the dacron of 20g, be immersed in 30min in the sodium hydroxide solution of 100 DEG C, then rinsed with deionized water is used 2 times, be immersed in 40min in 40 DEG C of mass percent concentration 95% ethanolic solutions, washed with de-ionized water 2 times, 90 DEG C of oven dry; According to sodium thiosulfate, ferric sulfate and urea mol ratio 1:1:3, take the urea of the sodium thiosulfate of 158g, the ferric sulfate of 400g and 60g, ferric sulfate is dissolved completely in the deionized water of 1L, add sodium thiosulfate and by magnetic stirrer to solution to clarification, finally urea added in solution until dissolve completely; Mixed solution obtained above is poured in the quartz glass reaction inner bag of 1.2L, add the dacron of alkaline etching process, with 2 DEG C/min ramp to 130 DEG C after reactor sealing, isothermal reaction 4h, question response still takes out dacron after naturally cooling, 15min is soaked in acetone soln, deionized water rinsing 2 times, soaks 15min in absolute ethyl alcohol, deionized water rinsing 2 times, in 70 DEG C of oven dry, obtain the dacron of loaded with nano tri-iron tetroxide.
Step 2: according to absolute ethyl alcohol and deionized water volume ratio 1:9, the ethanol water of preparation 0.95L; The silane resin acceptor kh-550 of 1g is taken according to 2.5% of dacron quality; Silane coupler is added drop-wise in ethanol water, and stirs with 150rmp speed and form mixed solution, be then 4 by acetic acid regulator solution pH value, obtain coupling modifier mixed solution; The dacron of load tri-iron tetroxide is immersed in coupling modifier mixed solution, take out after 5h and use washes of absolute alcohol 2 times, then be placed on the ultraviolet curing light irradiation 50min with dominant wavelength 365nm on glass dish, obtain the dacron of the amidized magnetic nano ferroferric oxide of rich surface.
Step 3: according to beta-schardinger dextrin-and maleic anhydride mol ratio 1:1, takes the beta-schardinger dextrin-of 1135g and the maleic anhydride of 98g; Beta-schardinger dextrin-and maleic anhydride are dissolved in successively the N of 1L, in dinethylformamide solution, stir until dissolve completely with 150rmp speed, under 80 DEG C of conditions, react 10h, after solution cooling, precipitation is separated out with chloroform extraction, sediment acetone soln is washed 4 times, each 7min, and use vavuum pump suction filtration, then put into drying box vacuumize 24h under 80 DEG C of conditions, obtain carboxy-modified beta-schardinger dextrin-.
Step 4: take the carboxylated beta-schardinger dextrin-of 3g and added in the deionized water of 1L, then the menthol of 2g is added, finally add amination magnetic dacron, dacron is transferred in quartz glass reaction still together with solution and seals, with 2 DEG C/min ramp to 120 DEG C, with 30rmp rotating speed isothermal reaction 3h, after question response terminates, fabric is taken out, successively with the deionized water washing 15min of 40 DEG C of absolute ethyl alcohols, 40 DEG C of acetone and 80 DEG C, room temperature is dried naturally, must be loaded with the magnetic dacron of menthol medicine.
Fig. 1 is the stereoscan photograph of the present embodiment gained magnetic drug-carrying dacron.Can find out, graft beta-cyclodextrin and after inclusion menthol dacron surface wrapped up the thicker organic substance of one deck, should be beta-schardinger dextrin-, and be dispersed with some tiny particles, should be nano ferriferrous oxide granule aggregate.Fig. 2 is the X-ray diffractogram of magnetic drug-carrying dacron.Test result shows, the angle of diffraction 2 θ is at 18 °, and 23 ° and about 26 ° is the characteristic diffraction peak of dacron, correspond to respectively (010), (-110) and (110) crystal face; Also there is obvious diffraction maximum 30 °, 36 °, 43 °, 54 °, 57 ° and about 63 ° simultaneously, consistent with magnetic iron ore tri-iron tetroxide No.19-0629 in standard diagram JCPDS, for anti-cubic spinel phase, correspond to respectively (220) of tri-iron tetroxide, (311), (400), (422), (511) and (440) crystal face.Therefore the nano particle of known dacron area load is spinel-type tri-iron tetroxide.Fig. 3 is the B-H loop of magnetic drug-carrying dacron.Test result shows, magnetic drug-carrying dacron has more weak anti-ferromagnetism, and saturation magnetization is 2.6emu/g, coercivity is 0.56emu/g, remanent magnetization is 170Oe, therefore can be heated medicine carrying dacron by externally-applied magnetic field, accelerates the release of medicine.Fig. 4 is the spectrogram that diffuses of magnetic drug-carrying dacron.Can find out, dacron is obviously different to the absorption of light after different operation process, shows often through a procedure, and fabric face has corresponding material to exist.Fig. 5 is the differential scanning calorimetric curve of magnetic drug-carrying dacron.Test result shows, containing menthol volatile medicine in magnetic drug-carrying dacron.Fig. 6 is magnetic drug-carrying dacron menthol release rate profile.Can find out, magnetic drug-carrying dacron is placed after 90 days still containing a certain amount of menthol medicine.
The deionized water that the magnetic dacron of the present embodiment gained is placed in 100mL is carried out adding thermal distillation, distillate ethanolic solution absorbs, then mixed solution is mixed with than toner, measure the absorbance of this menthol distillate, the menthol concentration being calculated this medicine carrying fabric inclusion by regression curve is 1.45g/L.
Menthol concentration and the menthol release rate curve acquisition process of gained magnetic drug-carrying dacron inclusion of the present invention are:
Prepare aqueous sulfuric acid according to the concentrated sulfuric acid and deionized water volume ratio 1.6:1, add p-dimethylamino benzaldehyde according to 5.0g/L consumption, after mixing, make colorimetric agent solution.With the menthol standard liquid of volumetric flask accurate formulation 1g/L, 3g/L, 4g/L, 6g/L, 8g/L and 10g/L, measure each 1mL of menthol standard liquid of variable concentrations, mix with 5mL colorimetric agent solution respectively, then be placed in boiling water bath and heat 2min, rapid cooling, now solution presents grape redness.The ethanol water (ethanol and deionized water volume ratio are 1:1) of 1mL is mixed as reference with the ratio toner of 5mL, measure the absorbance of above-mentioned red solution with visible spectrophotometer at 550nm place, and draw menthol standard liquid absorbance curve.The deionized water that the magnetic dacron being loaded with menthol is placed in 100mL is carried out adding thermal distillation, distillate ethanolic solution absorbs, because menthol can all spin off 100 DEG C time from beta-schardinger dextrin-cavity, then be mixed with mixed solution with than toner, measure the absorbance of this menthol distillate.Magnetic drug-carrying dacron is placed certain number of days, adopting the way of distillation to collect the menthol of inclusion in beta-schardinger dextrin-, the release profiles of menthol can be obtained by measuring absorbance.
The present invention adopts Hydrothermal Synthesis technology, take ferric sulfate as source of iron, sodium thiosulfate is reductant, urea is precipitating agent, while preparing nano ferriferrous oxide granule, is directly loaded to dacron surface, and adopt single-factor analysis therapy, by controlling reaction temperature and time, ferric sulfate, sodium thiosulfate and amount of urea, the best modified technique of optimization dacron loaded with nano tri-iron tetroxide and formula.The nano ferriferrous oxide purity that the present invention generates is high, even particle size distribution, and nano particle is combined very firm with dacron, and after 50 standard wash, dacron surface is still coated with a large amount of nano particles.Use the dacron of silane resin acceptor kh-550 coupling modifier tri-iron tetroxide load, nano ferriferrous oxide is introduced amino; Meanwhile, use maleic anhydride to carry out modification beta-schardinger dextrin-, beta-schardinger dextrin-introduces carboxyl, for the graft reaction of beta-schardinger dextrin-and tri-iron tetroxide creates condition, makes beta-schardinger dextrin-can be attached to dacron surface to fastness.In addition, the use of silane coupler also further promotes the bond strength of nano ferriferrous oxide granule and dacron.Adopt hydro-thermal one-step method, while by carboxy-modified grafted by beta cyclodextrin to dacron surface, also by menthol (or Da Kening) medicine inclusion in beta-schardinger dextrin-inner chamber.This method is simple and easy to do, react in confined conditions and not only can save raw material, and beta-schardinger dextrin-and dacron binding strength, menthol (or Da Kening) inclusion rate is high, the magnetic drug-carrying dacron obtained does not have toxic and side effect to human body, by externally-applied magnetic field, the release of medicine can be accelerated, patient's misery can be alleviated to greatest extent for some human body sensitive parts.After treating contained insoluble drug release, magnetic drug-carrying dacron can inclusion medicine again, and iterative cycles uses.
Claims (10)
1. a preparation method for magnetic drug-carrying fabric, is characterized in that, concrete preparation process is:
Step 1: magnetic ferroferric oxide nanoparticle is loaded to dacron surface, obtains magnetic fabric;
Step 2: coupling modifier process is carried out to step 1 gained magnetic fabric, realizes rich surface amination;
Step 3: the carboxylated modification of beta-schardinger dextrin-;
Step 4: adopt hydro-thermal method by the grafted by beta cyclodextrin of carboxylated for step 3 gained modification on step 2 gained fabric, and inclusion medicine, to obtain final product.
2. the preparation method of a kind of magnetic drug-carrying fabric according to claim 1, is characterized in that, in step 1, the preparation process of magnetic fabric is:
Step 1.1, get dacron, according to bath raio 1:40 ~ 60, be immersed in sodium hydroxide solution, carry out dacron alkaline etching; Subsequently rinsing, oven dry are carried out to the dacron after etching;
Step 1.2, take sodium thiosulfate, ferric sulfate and urea, mix with deionized water, obtain mixed solution, for subsequent use;
Step 1.3, step 1.2 gained mixed solution and step 1.1 are processed after dacron put into reactor simultaneously, with 1 DEG C/min ~ 3 DEG C/min ramp to 110 DEG C ~ 150 DEG C after sealing, isothermal reaction 2h ~ 6h, question response still takes out dacron after naturally cooling; Subsequently dacron is put into acetone soln and soak 10 ~ 20min, with deionized water rinsing 1 ~ 3 time, then soak 10 ~ 20min in absolute ethyl alcohol, with deionized water rinsing 1 ~ 3 time, finally dry under 60 DEG C ~ 80 DEG C conditions, obtain the magnetic fabric of loaded with nano tri-iron tetroxide.
3. the preparation method of a kind of magnetic drug-carrying fabric according to claim 2, is characterized in that, in step 1.1, the quality-volumetric concentration of sodium hydroxide solution is 80 ~ 100g/L; Dacron alkaline etching process is immersion treatment 20 ~ 40min under 80 ~ 120 DEG C of conditions; The detailed process of rinsing, oven dry is for using rinsed with deionized water 1 ~ 3 time, and under 40 DEG C of conditions, be then immersed in mass percent concentration is 30 ~ 50min in the ethanolic solution of 95%; Repeatedly clean dacron 1 ~ 3 time with deionized water again, obtain the dacron of rinsed clean, and dry under 80 DEG C ~ 100 DEG C conditions.
4. the preparation method of a kind of magnetic drug-carrying fabric according to claim 2, it is characterized in that, in step 1.2, the concentration of gained mixed solution is 540 ~ 700g/L, wherein the mol ratio of sodium thiosulfate and ferric sulfate is 1:0.5 ~ 1.5, and the mol ratio of urea and ferric sulfate is 1:3; The preparation process of mixed solution is: be first dissolved completely in deionized water by ferric sulfate, subsequently to wherein adding sodium thiosulfate, by magnetic stirrer to solution to clarification, finally being added by urea and stirring until dissolve completely, to obtain final product.
5. the preparation method of a kind of magnetic drug-carrying fabric according to claim 1, it is characterized in that, the detailed process of step 2 is: take ethanol water and silane resin acceptor kh-550 respectively, silane resin acceptor kh-550 is added drop-wise in ethanol water, silane resin acceptor kh-550 and ethanol water is stirred with the speed of 100 ~ 200rmp, form mixed solution, then regulate mixed solution pH value to 3.5 ~ 5.5 with glacial acetic acid, obtain coupling modifier mixed solution; Subsequently step 1 gained magnetic fabric is immersed in coupling modifier mixed solution to leave standstill after 3 ~ 8h and takes out, with washes of absolute alcohol 1 ~ 3 time, irradiate 30 ~ 60min under the ultraviolet curing lamp being then 365nm at wavelength, obtain the amidized magnetic fabric of rich surface.
6. the preparation method of a kind of magnetic drug-carrying fabric according to claim 5, is characterized in that, described ethanol water is that absolute ethyl alcohol mixes gained with deionized water with the volume ratio of 1:8 ~ 10; The amount of taking of ethanol water is the ethanol water that every gram of fabric gets 0.025 ~ 0.05L; The consumption of silane resin acceptor kh-550 is 1 ~ 5% of fabric quality.
7. the preparation method of a kind of magnetic drug-carrying fabric according to claim 1, it is characterized in that, in step 3, the detailed process of the carboxylated modification of beta-schardinger dextrin-is: the beta-schardinger dextrin-taken respectively and maleic anhydride are dissolved in N successively, in dinethylformamide solution, stir until dissolve completely with 100 ~ 200rmp speed, then under 80 DEG C of conditions, 8 ~ 12h is reacted, after solution cooling, precipitation is separated out with chloroform extraction, by sediment acetone soln washing 3 ~ 5 times, each 5 ~ 10min, and with the multiplex vavuum pump suction filtration of recirculated water, then drying box vacuumize 24h under 80 DEG C of conditions is put into, obtain carboxylated beta-schardinger dextrin-.
8. the preparation method of a kind of magnetic drug-carrying fabric according to claim 7, is characterized in that, the mol ratio of beta-schardinger dextrin-and maleic anhydride is 0.5 ~ 1.5:1.
9. the preparation method of a kind of magnetic drug-carrying fabric according to claim 1, is characterized in that, the detailed process of step 4 is:
Step 4.1, gets the carboxylated beta-schardinger dextrin-of step 3 gained and mixes with deionized water, poured into by mixed solution in reactor, add medicine wherein; Subsequently step 2 gained amination magnetic fabric is put into reactor, with 1 DEG C/min ~ 3 DEG C/min ramp to 100 DEG C ~ 140 DEG C after reactor sealing, with 10 ~ 50rmp rotating speed isothermal reaction 2h ~ 4h;
Step 4.2, dacron step 4.1 obtained takes out, and wash 10 ~ 20min with the deionized water of 40 DEG C of absolute ethyl alcohols, 40 DEG C of acetone and 80 DEG C respectively, room temperature is dried naturally, obtains the magnetic dacron being loaded with medicine.
10. the preparation method of a kind of magnetic drug-carrying fabric according to claim 9, is characterized in that, in step 4.1, the concentration of carboxylated beta-schardinger dextrin-and deionized water gained mixed solution is 1 ~ 5g/L; Medicine is menthol or Da Kening, adds the medicine of 1.5 ~ 3g in often liter of mixed solution.
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Application publication date: 20160120 Assignee: Weinan Hongxing Chemical Machinery Co.,Ltd. Assignor: XI'AN POLYTECHNIC University Contract record no.: X2023980034832 Denomination of invention: A preparation method of magnetic drug loaded fabric Granted publication date: 20170825 License type: Common License Record date: 20230421 |
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