CN102319486A - The shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release - Google Patents
The shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release Download PDFInfo
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Abstract
The invention discloses a kind of shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release.Be characterized in that this method utilizes focus supersonic as stimulus; Focus on the shape memory drug-carrying polymer after making ultrasound wave through the medium conduction; The deformation recovery of the time through regulating focused ultrasound system, power, frequency, focal length, burnt territory, the sound intensity, propagation medium kind control shape memory drug-carrying polymer, control simultaneously the timing of contained medicine, quantitatively, the location discharges.Wherein focused ultrasound system is made up of signal generator, power amplifier, ultrasonic transducer, shape memory drug-carrying polymer, medium and ultrasonic signal or drug detection system.The shape memory drug-carrying polymer can make through methods such as in-situ polymerization, mechanical blending, solution blending or solution infiltrations.
Description
Technical field
The invention belongs to shape memory and drug release field, relate to a kind of novel ultrasound stimulation that utilizes and realize the controlled shape memory drug-carrying polymer material shape memory and the method for drug release.
Background technology
Shape-memory material is meant can the perception environmental change, and responds this variation, returns to the material that preestablishes shape.Shape-memory material comprises marmem, shape memory ceramics and shape-memory polymer.Wherein, Shape-memory polymer (Shape Memory Polymer; Be called for short SMP) have and can recover that deformation quantity is big, memory effect is remarkable, machine-shaping easily, use advantage such as wide, low price, be widely used in the built-in field of materials of intelligent fiber, heat-shrink tube and human body.Maximum shape-memory polymer of research is the thermotropic shape-memory polymer at present; Temperature is elevated to the glass transition temperature of material or more than the melt temperature it is carried out shaped design; Temperature reduces the interim shape of back immobilization material, and during application, the rising material temperature makes its recovery of shape.Shape-memory material can be realized through environmental stimuli means such as hot liquid stream, thermal current, irradiation, electric field or alternating magnetic fields; These stimulation means have been widened the application of shape-memory material; But under more practical situation; Get involved medical device etc. like Wicresoft, need to seek new stimulation means control shape recovery process.
Ultrasound wave is a kind of mechanical vibration wave, and frequency is 2 * 10
4-10
7Hz.Ultrasound wave is divided into low frequency ultrasound and high frequency ultrasound, and low frequency ultrasound cavitation threshold values is low, and wavelength is longer, is difficult to focus on, and can be used for cleaning, welding, disrupted cell, external stone crushing, phonochemical reaction.High frequency ultrasound cavitation threshold values is high, and wavelength is shorter, focuses on easily, can be used for media and survey (industrial ultrasound detection, medical science B ultrasonic etc.), massage treatment, oncotherapy etc.High frequency ultrasound focuses on easily; Can cross special focused transducer ultrasound wave acoustic energy is focused on ad-hoc location; Form the ultrasonic burnt territory of high-energy, moment can reach a high temperature in burnt territory, and produces cavitation, mechanical shearing effect etc.; Cause a series of physics, chemistry and biology effect, and the overseas place of focusing does not make significant difference.High intensity focused ultrasound has good penetrance, polarization and energy deposition property.Medically, focused ultrasound therapy is a kind of new technique of non-intruding treatment, promptly need not under the surgical incision situation, and external ultrasonic waves transmitted is seen through surface texture, organizes inner focusing to produce effect in vivo.Focus supersonic has been used for tumour ablation, kill cancer cell etc. clinically.
The present invention with concentration ultrasonic as the stimulation mode that triggers shape memory and drug release polymeric material simultaneously; When focus supersonic is acted on polymeric material polymer there is significant selective thermal effect; Promptly when polymeric material places water, biological tissue, blood media; Be in the polymer in the burnt territory of concentration ultrasonic can moment by ultrasonic heating to uniform temperature, and the temperature of water on every side, biological tissue, blood media environment does not have significant change.This effect is applied to the indirect shape-memory polymer by us, makes its deformation recovery.Simultaneously ultrasonic also can be through combineds effect such as mechanical vibration, cavitation, heating in polymer, improve polymer chain motor capacity, improve the diffusion rate of medicine, to the shape-memory polymer generation controlled-release function of medicine carrying.The present invention utilizes above principle, through the recovery of shape of parameters such as adjusting focused ultrasound system time, power, frequency, medium kind control medicine carrying shape memory high molecule material, controls the timing of contained medicine, quantitative, location release simultaneously.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release are provided; Be characterized in designing and preparing drug-carrying polymer, realize the location recovery of shape and the drug release function of focus supersonic through ultrasonic irradiation simultaneously with shape-memory properties.
The present invention realizes that through following technical measures wherein said raw material mark is parts by weight except that certain illustrated:
The shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release; It is characterized in that: this method prepares the shape memory drug-carrying polymer; According to actual needs design and produce various deformation through stretching, compression and bend mode at it more than the shape memory transition temperature, be cooled to it then and make interim fixed in shape below the shape memory transition temperature; Signal generator sends an electronic signal; Change ultrasonic signal into by power amplifier; Ultrasound wave through focused transducer generation certain frequency and intensity conducts the deformation position that focuses on the shape memory drug-carrying polymer through medium, under the stimulation of concentration ultrasonic; The shape memory drug-carrying polymer is replied its permanent shape, discharges embedding medicinal simultaneously; Control the timing of shape memory drug-carrying polymer deformation recovery speed and embedding medicinal, quantitative, location release through focus supersonic time, power, frequency, focal length, burnt territory, the sound intensity and propagation medium.
This shape memory drug-carrying polymer is composed of the following components:
(A) shape-memory polymer is 100 parts;
Its shape memory transition temperature is Tz, 35 ℃≤Tz≤85 ℃.
(B) medicine is 0.1～80 part.
The polymeric matrix of shape memory drug-carrying polymer is any in polynorbornene, polyethylene glycol oxide, PSB, using trans-polyisoprene, polyethylene-vinyl acetate copolymer, polyethylene glycol oxalate, crosslinked polyethylene, polymethacrylates-acrylic acid esters co-polymer, polyurethane, polylactic acid, polycaprolactone, nylon, polylactic acid-caprolactone copolymer or the polyvinyl alcohol.
The medicine of shape memory drug-carrying polymer is any in commercialization medicine or calcium, magnesium, potassium, the copper metallic salt medicine; Medicine dissolves through the method for processing, solution soaking or in-situ polymerization or is dispersed in the polymeric matrix.
The method for preparing of shape memory drug-carrying polymer is:
(1) thermoplastic processing
Polymer and medicine are through after the melting mixing, through extruding or injection or compression molding;
(2) solution blending
With polymer be dissolved in the solvent with medicine through mechanical agitation or sonic oscillation uniform mixing, remove and desolvate, through extruding or inject or casting or compression molding;
(3) in-situ polymerization
With medicine with pour in the mould polymerization forming at a certain temperature after polymerization system mixes into, wherein polymerization system comprises monomer, cross-linking agent, initiator;
(4) solution infiltration
The shape-memory polymer matrix that makes is in advance immersed in the drug solution, and medicine makes through penetrating into the polymer network after drying.
The focused ultrasound devices of the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release comprises signal generator (1), power amplifier (2), focused transducer (3), propagation medium (4), shape memory drug-carrying polymer (5) and ultrasonic signal or drug release detection system (6); Signal generating system links to each other with power amplifying system, and power amplifying system links to each other with focused transducer, and ultrasonic signal or drug release detection system link to each other with signal generator; According to the needs of shape memory and drug release, set the signal procedure of focus supersonic, further carry out power amplification, through focused transducer the signal of telecommunication is converted into the mechanical energy signal, in the sonic propagation medium, produce ultrasound wave;
Wherein, a) sine, cosine wave, square wave, impulse wave and the continuous wave signal that produce of signal generating system; B) the controlled power scope of power amplifying system generation is 1～2000 watt, and frequency range is 500 KHzs～50 megahertzes; C) the focused transducer subject distance range is 2～30cm; D) the sonic propagation medium is a water, any in ultrasonic body mould and the biological tissue.
Have the following advantages:
(1) the present invention is the ideal long-range stimulation mode that shape memory drug-carrying polymer Wicresoft gets involved medical device for invading and non-intrusion type;
(2) can be focused, realize Long-distance Control;
(3) compare with photostimulation, penetration depth is big;
(4) parameter that changes focused ultrasound devices can be regulated and control ultrasonication position and action time;
(5) safe;
(6) system features in convenient, controllability is strong.
Description of drawings
Fig. 1 is focus supersonic-shape memory and drug delivery system installation drawing
Fig. 2. the recovery of shape rate of gathering (methyl methacrylate-butyl acrylate)/copper sulfate medicine carrying shape memory polymer system is schemed over time
The specific embodiment
Below in conjunction with embodiment the present invention is done specific descriptions.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1:
(1) focused ultrasound devices as shown in Figure 1, its parameter is respectively: ultrasonic power is 0-500w, and transducer diameter is 39mm, and focal length is 2cm, and frequency is 500kHz, and focused spot diameter is 3mm, and the ultrasonication mode is the continous way square wave.
(2) will gather the preparation of (methyl methacrylate-butyl acrylate)/copper sulfate medicine carrying shape-memory polymer: with 66 parts of methymethacrylates, 34 parts of butylacrylate, 1.12 parts of ethylene glycol dimethacrylates (EGDMA), 0.56 part of azodiisobutyronitrile (AIBN) and 10 parts of copper sulfate mix homogeneously; Be cast in the plate glass mould, polymerization was taken out after 24 hours in 55 ℃ of water-baths.It is 46 ℃ that differential scanning calorimetry records its transfer of shapes temperature.This material is heated to 80 ℃ in baking oven, be bent into square after, reduce to fixing its temporary transient shape of room temperature rapidly.
(3) gather recovery of shape behavior and the medicine sustained release behavior of (methyl methacrylate-butyl acrylate)/copper sulfate medicine carrying shape-memory polymer under High Intensity Focused Ultrasound: the polymer for preparing is placed the tubular glass container, and place 37 ℃ of water-baths.Open ultrasonic instrument, ultrasonic power is 20W, and ultrasonic sound beam focusing is in polymeric matrix.Under ultrasonication, gathering (methyl methacrylate-butyl acrylate)/copper sulfate medicine carrying shape-memory polymer heats up rapidly; The concurrent deformation position begins to produce recovery of shape; In 40 seconds, reply after 90%, 3 minute and reply 98%, its recovery of shape rate is as shown in Figure 2 with the variation of ultrasonic time.Meanwhile medicine copper sulfate discharges from polymeric matrix under ultrasonic stimulation.Behind the ultrasonication 15min,, have the copper sulfate of 1wt% from polymeric matrix, to discharge approximately, and not ultransonic comparative sample was soaked after 15 minutes, did not observe the release of copper sulfate in 37 ℃ of water-baths through the atomic absorption spectrum test.
Embodiment 2:
(1) focused ultrasound devices as shown in Figure 1, its parameter is respectively: ultrasonic power is 500-1000w, and transducer diameter is 39mm, and focal length is 10cm, and frequency is 1.1MHz, and focused spot diameter is 3mm, and the ultrasonication mode is that pulsed is sinusoidal wave.
(2) preparation of polyurethane/curcumin shape memory polymer system:, add 25.0 gram methyl diphenylene diisocyanates and 6.6 grams, 1,4 butanediol, then with pouring flat plate mold into behind its mix homogeneously, 120 ℃ of following polymerizations 24 hours at 95.1 gram polycaprolactones.Polymer is taken out mould, and immersion contains in the alcoholic solution of 10% curcumin, soaks after 7 days polymer is taken out, and drying makes the shape memory polyurethane material that contains the 40wt% curcumin.Its original shape is a strip, and the shape memory transition temperature is 55 ℃.This material is heated to 80 ℃, be bent into S shape after, immerse fixing its temporary transient shape in the mixture of ice and water.
(3) recovery of shape behavior and the medicine sustained release behavior of polyurethane/curcumin medicine carrying shape-memory polymer under High Intensity Focused Ultrasound: the polymer for preparing is fixed in the tubular glass vessel.Open ultrasonic instrument, ultrasonic power is 15W, and ultrasonic sound beam focusing is in polymeric matrix.Polymer heats up rapidly under the ultrasonication, and the post polymerization thing was replied its strip in about 3 minutes.Continue behind the ultrasonic 20min about 2% curcumin and discharge from polymeric matrix that (release rate adopts the UV-Vis3010 type ultraviolet-visible spectrophotometer of HIT to measure: scanning speed: 600nm/min, slit width: 1nm).
Embodiment 3:
Focused ultrasound devices as shown in Figure 1, its parameter is respectively: ultrasonic power is 1000-1500w, and transducer diameter is 39mm, and focal length is 20cm, and frequency is 10MHz, and focused spot diameter is 3mm, and the ultrasonication mode is the continous way cosine wave.
(2) preparation of polylactic acid/ibuprofen shape memory polymer system: with the banburying on two roller banburies of 80 parts of ibuprofen of 100 parts of polylactic acid, treat that hot pressing was colded pressing 10 minutes in 15 minutes again after the abundant mixing, promptly make drug-carrying polymer sheet material.Its original shape is a strip, and the shape memory transition temperature is 65 ℃, and this material is heated to 100 ℃, be bent into square after, immerse fixing its temporary transient shape in the mixture of ice and water.
(3) recovery of shape behavior and the medicine sustained release behavior of polylactic acid/ibuprofen medicine carrying shape-memory polymer under High Intensity Focused Ultrasound.The polymer for preparing is fixed in the tubular glass vessel.Open ultrasonic instrument, ultrasonic power is 10W, and ultrasonic sound beam focusing is in polymeric matrix.Polymer heats up rapidly under the ultrasonication, and the post polymerization thing was replied its strip in about 5 minutes.Continue behind the ultrasonic 20min about 5% ibuprofen and from polymeric matrix, discharge, stopping ultrasonic back 20min has 0.1% ibuprofen from polymeric matrix, to discharge approximately, and continuing ultrasonic 20min has 4% ibuprofen from polymeric matrix, to discharge approximately.(release rate adopts the UV-Vis3010 type ultraviolet-visible spectrophotometer of HIT to measure: scanning speed: 600nm/min, slit width: 1nm)
Embodiment 4:
(1) focused ultrasound devices as shown in Figure 1, its parameter is respectively: ultrasonic power is 1500-2000w, and transducer diameter is 39mm, and focal length is 30cm, and frequency is 50MHz, and focused spot diameter is 3mm, and the ultrasonication mode is that pulsed is sinusoidal wave.
(2) preparation of polyvinyl alcohol/ciprofloxacin medicine carrying shape memory polymer system: 100 parts of polyvinyl alcohol 1799 are dissolved in 98 ℃ of water, and polyvinyl alcohol dissolves fully after 6 hours, adds aqueous hydrochloric acid solution and regulates pH value to 4., add 10 parts of ciprofloxacins, 4 parts of glutaraldehydes again, stir and pour in the mould after 3 minutes, under 25 ℃ of conditions of room temperature, leave standstill and made it crosslinked in 36 hours.Add the capacity distilled water again and regulate pH value to neutrality, drying is removed moisture, makes the shape memory polyvinyl alcohol material that contains ciprofloxacin.Its original shape is a strip, and the shape memory transition temperature is about 60 ℃.This material is heated to 120 ℃, be deformed into V-type after, be cooled to fixing its temporary transient shape of room temperature.
(3) recovery of shape behavior and the medicine sustained release behavior of polyvinyl alcohol/ciprofloxacin medicine carrying shape memory polymer system under High Intensity Focused Ultrasound: the polymer for preparing is fixed in the tubular glass vessel.Open ultrasonic instrument, ultrasonic power is 20W, and ultrasonic wave acoustic beam focuses on polymeric matrix.Polymer heats up rapidly under the ultrasonication, and the post polymerization thing was replied its strip in about 3 minutes.Continue behind the ultrasonic 30min about 0.5% ciprofloxacin and discharge from polymeric matrix that (release rate adopts the UV-Vis3010 type ultraviolet-visible spectrophotometer of HIT to measure: scanning speed: 600nm/min, slit width: 1nm).
Embodiment 5:
(1) focused ultrasound devices as shown in Figure 1, its parameter is respectively: ultrasonic power is 500-1000w, and transducer diameter is 39mm, and focal length is 25cm, and frequency is 5MHz, and focused spot diameter is 3mm, and the ultrasonication mode is the continous way square wave.
(2) preparation of LDPE/SEBS/ ethacridine lactate medicine carrying shape memory polymer system: 100 parts of SEBS, 5 parts of PE waxes, 0.24 part of cumyl peroxide, 2 parts of maleic anhydrides are vulcanized on torque rheometer; 200 ℃ of temperature; Rotating speed is 40r/min, cure time 10 minutes.Mixing with 100 parts of LDPE, 5 parts of ethacridine lactate again, melting temperature is 160 ℃, and rotating speed is 40r/min, cure time 10 minutes.Mixing evenly after, 200 ℃ of preheatings 10 minutes, 10Mpa pressure pressed made sample in 10 minutes with hot press.Its original shape is a S shape, and the shape memory transition temperature is about 78 ℃.This material is heated to 100 ℃, be stretched as strip after, be cooled to fixing its temporary transient shape of room temperature.
(3) recovery of shape behavior and the medicine sustained release behavior of LDPE/SEBS/ ethacridine lactate medicine carrying shape-memory polymer under High Intensity Focused Ultrasound: the polymer for preparing is fixed in the tubular glass vessel.Open ultrasonic instrument, ultrasonic power is 700W, and ultrasonic wave acoustic beam focuses on polymeric matrix.Polymer heats up rapidly under the ultrasonication, and the post polymerization thing was replied its S shape in about 1 minute.Continue after ultrasonic 1 hour about 0.4% ethacridine lactate and discharge from polymeric matrix that (release rate adopts the UV-Vis3010 type ultraviolet-visible spectrophotometer of HIT to measure: scanning speed: 600nm/min, slit width: 1nm).
Embodiment 6:
(1) focused ultrasound devices as shown in Figure 1, its parameter is respectively: ultrasonic power is 500-1000w, and transducer diameter is 39mm, and focal length is 15cm, and frequency is 1.1MHz, and focused spot diameter is 3mm, and the ultrasonication mode is that pulsed is sinusoidal wave.
(2) preparation of ethene-vinyl acetate/enoxacin shape memory drug-carrying polymer system: with 100 parts of ethene-vinyl acetates (28wt% vinyl acetate) and 0.16 part of cumyl peroxide, 10 parts of enoxacins in being connected with the Haake torque rheometer of batch mixer under 100 ℃ of temperature with the speed melting mixing of 50rpm 5 minutes, hot-forming under 100 ℃ of temperature again.Again elevated temperature to 190 ℃ crosslinked 20 minutes both sample.Its shape memory transition temperature is about 70 ℃.Cutting obtains L type sample, and material is warming up to 100 ℃, be stretched as strip after, cooling makes its fixing temporary transient shape.
(3) recovery of shape behavior and the medicine sustained release behavior of ethene-vinyl acetate/enoxacin shape memory drug-carrying polymer under High Intensity Focused Ultrasound: the polymer for preparing is fixed in the tubular glass vessel.Open ultrasonic instrument, ultrasonic power is 700W, and ultrasonic wave acoustic beam focuses on polymeric matrix.Polymer heats up rapidly under the ultrasonication, and the post polymerization thing was replied its L shape in about 2 minutes.Continue after ultrasonic half an hour about 1% enoxacin and discharge from polymeric matrix that (release rate adopts the UV-Vis3010 type ultraviolet-visible spectrophotometer of HIT to measure: scanning speed: 600nm/min, slit width: 1nm).
Claims (6)
1. the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release; It is characterized in that: this method prepares the shape memory drug-carrying polymer; According to actual needs design and produce various deformation through stretching, compression and bend mode at it more than the shape memory transition temperature, be cooled to it then and make interim fixed in shape below the shape memory transition temperature; Signal generator sends an electronic signal; Change ultrasonic signal into by power amplifier; Ultrasound wave through focused transducer generation certain frequency and intensity conducts the deformation position that focuses on the shape memory drug-carrying polymer through medium, under the stimulation of concentration ultrasonic; The shape memory drug-carrying polymer is replied its permanent shape, discharges embedding medicinal simultaneously; Control the timing of shape memory drug-carrying polymer deformation recovery speed and embedding medicinal, quantitative, location release through focus supersonic time, power, frequency, focal length, burnt territory, the sound intensity and propagation medium.
2. the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release according to claim 1, it is characterized in that: this shape memory drug-carrying polymer is composed of the following components, is by weight:
(A) shape-memory polymer is 100 parts;
Its shape memory transition temperature is Tz, 35 ℃≤Tz≤85 ℃.
(B) medicine is 0.1～80 part.
3. the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release according to claim 1 or claim 2, it is characterized in that: the polymeric matrix of this shape memory drug-carrying polymer is any in polynorbornene, polyethylene glycol oxide, PSB, using trans-polyisoprene, polyethylene-vinyl acetate copolymer, polyethylene glycol oxalate, crosslinked polyethylene, polymethacrylates-acrylic acid esters co-polymer, polyurethane, polylactic acid, polycaprolactone, nylon, polylactic acid-caprolactone copolymer or the polyvinyl alcohol.
4. the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release according to claim 1 or claim 2, the medicine that it is characterized in that the shape memory drug-carrying polymer are any in commercialization medicine or calcium, magnesium, potassium, the copper metallic salt medicine; Medicine dissolves through the method for processing, solution soaking or in-situ polymerization or is dispersed in the polymeric matrix.
5. the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and the method for drug release according to claim 1, it is characterized in that: the method for preparing of shape memory drug-carrying polymer is:
(1) thermoplastic processing
Polymer and medicine are through after the melting mixing, through extruding or injection or compression molding;
(2) solution blending
With polymer be dissolved in the solvent with medicine through mechanical agitation or sonic oscillation uniform mixing, remove and desolvate, through extruding or inject or casting or compression molding;
(3) in-situ polymerization
With medicine with pour in the mould polymerization forming at a certain temperature after polymerization system mixes into, wherein polymerization system comprises monomer, cross-linking agent, initiator;
(4) solution infiltration
The shape-memory polymer matrix that makes is in advance immersed in the drug solution, and medicine makes through penetrating into the polymer network after drying.
6. the focused ultrasound devices of the method for the shape memory of focus supersonic Synchronization Control shape memory drug-carrying polymer and drug release according to claim 1, it is characterized in that: this device comprises that focus supersonic is by signal generator (1), power amplifier (2), focused transducer (3), propagation medium (4), shape memory drug-carrying polymer (5) and ultrasonic signal or drug release detection system (6); Signal generating system links to each other with power amplifying system, and power amplifying system links to each other with focused transducer, and ultrasonic signal or drug release detection system link to each other with signal generator; According to the needs of shape memory and drug release, set the signal procedure of focus supersonic, further carry out power amplification, through focused transducer the signal of telecommunication is converted into the mechanical energy signal, in the sonic propagation medium, produce ultrasound wave;
Wherein, a) sine, cosine wave, square wave, impulse wave and the continuous wave signal that produce of signal generating system; B) the controlled power scope of power amplifying system generation is 1～2000 watt, and frequency range is 500 KHzs～50 megahertzes; C) the focused transducer subject distance range is 2～30cm; D) the sonic propagation medium is a water, any in ultrasonic body mould and the biological tissue.
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| CN108359201A (en) * | 2018-01-23 | 2018-08-03 | 复旦大学 | A kind of hydro-thermal double-bang firecracker answers the preparation method of shape memory polymer material |
| CN108553300A (en) * | 2018-01-10 | 2018-09-21 | 哈尔滨工业大学 | A kind of drug release method printing shape-memory polymer structure based on 4D |
| CN108618285A (en) * | 2018-05-22 | 2018-10-09 | 哈尔滨工业大学 | A kind of load medicine ornaments for penetrating skin-worn based on shape-memory polymer |
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| CN108553300A (en) * | 2018-01-10 | 2018-09-21 | 哈尔滨工业大学 | A kind of drug release method printing shape-memory polymer structure based on 4D |
| CN108359201A (en) * | 2018-01-23 | 2018-08-03 | 复旦大学 | A kind of hydro-thermal double-bang firecracker answers the preparation method of shape memory polymer material |
| CN108359201B (en) * | 2018-01-23 | 2021-01-26 | 复旦大学 | Preparation method of hydrothermal double-response shape memory polymer material |
| CN108618285A (en) * | 2018-05-22 | 2018-10-09 | 哈尔滨工业大学 | A kind of load medicine ornaments for penetrating skin-worn based on shape-memory polymer |
| CN114247046A (en) * | 2021-12-14 | 2022-03-29 | 中国人民解放军战略支援部队特色医学中心 | Focused ultrasound-polymer micelle controllable drug release device |
| CN114247046B (en) * | 2021-12-14 | 2023-11-17 | 中国人民解放军战略支援部队特色医学中心 | Focusing ultrasonic-polymer micelle controllable drug release device |
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