CN104739927A - Medical anticancer macromolecule slow release medicine and preparation method thereof - Google Patents
Medical anticancer macromolecule slow release medicine and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of medical biological material and particularly relates to a medical anticancer macromolecule slow release medicine and a preparation method thereof. The medical anticancer macromolecule slow release medicine comprises the following substances in parts by weight: 20-30 parts of Sculellaria barbata, 13-20 parts of astragalus polysaccharide, 5-8 parts of burdock, 10-15 parts of Ganoderma lucidum spore, 7-12 parts of liquorice, 40-60 parts of Nitrosoureas medicine and 60-80 parts of PLA-b-PNIPAM-b-PLA (a triblock copolymer of PLA and PNIPAM). The medicine has the beneficial effects that the medicine is a western-Chinese conjugation medicine, small in piston for patients and good in effect; the medicine is released according to the diseased region, the traditional process of using pure western medicine or pure traditional Chinese medicine to treat the cancer patient is broken through, the pain of the patient is relieved and the lifespan of the cancer patient can be prolonged after the medicine is taken for a long time.
Description
Technical field
The present invention relates to medical biomaterial technical field, be specifically related to a kind of medical anticancer high molecular slow-release medicine and preparation method thereof.
Background technology
The Drug therapy of cancer has achieved significant progress in recent years, but the successful cancer therapy drug of clinical practice is mostly cytotoxic drug at present, while inhibition tumor cell propagation, the propagation of organism normal cell is also suppressed, as hematopoietic stem cell etc., thus cause bone marrow hematogenesis impaired mechanical, leucocyte level is low, inhibit the propagation of tumor often, but also destroy the immunity of patient, the lighter causes alopecia, vomiting, severe one causes high heat, arrhythmia etc., finally be difficult to obtain good therapeutic effect, also limit the clinical practice of chemotherapeutics.In order to improve safety and the high efficiency of medication, avoid toxic medicament (so multi-resistance tumour medicine) to Normocellular injury, the Co ntrolled release of medicine has become an important topic of domestic and international pharmaceutical arts at present.As the macromolecular material of drug release carrier, needing to have biocompatibility and biological degradability, can degradation in vivo be namely micromolecular compound, thus by organism metabolism, absorption or excretion, to human non-toxic's side effect, and degradation process occur time confidential suitable.In the past few years, along with block copolymer is without the extensive investigation and application of carrier micelle, traditional carrier micelle can not meet the demand of people, discharge in human body periodically, concentration can be fluctuated, easily cause toxic and side effects, and utilization rate is low, large quantifier elimination has turned to the polymer drug carrier with environmental stimulus response.
Polylactic acid PLA has good biocompatibility and degradability, and first form oligomer by C-O unstable on main chain hydrolysis during its degraded, then under the effect of enzyme, carbon dioxide and water is degraded to further, excrete finally by respiratory tract and perspiration etc., completely harmless to human body, overcome the shortcoming must taken out from human body after other non-degradable type drug carrier materials release medicine.Therefore PLA is considered to the most promising degradable high polymer material in bio-medical field.PLA be used as pharmaceutical carrier mainly by with other polymer copolymerization, form copolymer nano particle to realize, by introducing the Co ntrolled release that the segment with environmental stimulus correspondence realizes medicine in the copolymer, thus the effective curative effect of medication that improves reduces poisonous side effect of medicine.
Poly-N-isopropylacrylamide (PNIPAM) is a kind of important temperature sensing polymer, owing to there is hydrophobic group and hydrophilic radical simultaneously, makes the difference of the dissolubility meeting Yin Wendu of PNIPAM in water and changes.PNIPAM is dissolved completely in water at low temperatures, and along with the rising of temperature, its dissolubility can decline gradually, and when being warming up to a certain temperature, PNIPAM can be separated and Precipitation; Otherwise, when the temperature is lowered, its dissolubility can improve again thereupon, thus reversibly return to original consoluet state, this temperature undergone phase transition is designated as the lowest critical solution temperature of PNIPAM, the lowest critical solution temperature of PNIPAM homopolymer in pure water is between 30-35 DEG C, because the lowest critical solution temperature of PNIPAM is near Human Physiology temperature 37 DEG C, therefore in recent years, PNIPAM homopolymer or PNIPAM and functional monomer copolymerization have been applied in the field such as Protein Separation, targeted drug delivery.
And traditional cancer therapy drug or be pure Chinese medicinal preparation at present, or be Western medicine preparation, Chinese medicine preparation effect is slow, inadequate to the inhibitory action of cancerous cell, the metastasis and extension of cancerous cell may be caused during this period, common Western medicine preparation is very large to human injury, while killing and wounding cancerous cell, also create the harm of can not ignore to other cells in human body, and this is also the problem needing at present to be solved further.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of medical anticancer high molecular slow-release medicine and preparation method thereof, it is a kind of Chinese and Western bound drug, patient is poisoned little, good effect, carries out drug release for diseased region, breaks through existing medicine carries out pure Western medicine or pure treatment by Chinese herbs tradition to cancer patient, alleviate the misery of patient, long-term taking can by the life of cancer patient.
To achieve these goals, the present invention adopts following technical scheme:
A kind of medical anticancer high molecular slow-release medicine, is characterized in that the composition of each material and parts by weight are: triblock copolymer PLA-b-PNIPAM-b-PLA 60-80 part of Herba Scutellariae Barbatae 20-30 part, astragalus polysaccharides 13-20 part, Fructus Arctii 5-8 part, Ganoderma spore powder 10-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 40-60 part, PLA and PNIPAM.
Described nitrosourea medicament is the one in streptozocin, nimustine, carmustine, estramustine, lomustine, methyl lomustine, NSC 353451.
The composition of each material and parts by weight are: triblock copolymer PLA-b-PNIPAM-b-PLA 65-75 part of Herba Scutellariae Barbatae 25-28 part, astragalus polysaccharides 15-17 part, Fructus Arctii 5-8 part, Ganoderma spore powder 12-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 43-55 part, PLA and PNIPAM.
A kind of medical anticancer high molecular slow-release process for preparing medicine, it is characterized in that comprising the steps: Herba Scutellariae Barbatae 20-30 part, astragalus polysaccharides 13-20 part, Fructus Arctii 5-8 part, Ganoderma spore powder 10-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 40-60 part, triblock copolymer PLA-b-PNIPAM-b-PLA60-80 part is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2 μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament.
Described triblock copolymer PLA-b-PNIPAM-b-PLA is obtained by HO-PNIPAM-OH, lactide polymerization, is specially: take HO-PNIPAM-OH, lactide, Sn (Oct) at 1: 1.2: 0.35 in mass ratio
2be dissolved in toluene, nitrogen pump drainage three final vacuum tube sealings, be placed in 135 DEG C of oil for reacting 24h, after stopped reaction, product be dissolved in chloroform, precipitate three times in absolute ether, obtaining the thick product of block copolymer of white; Then be dissolved in deionized water, with the micro-pore-film filtration that aperture is 0.2 μm, to remove PLA, micellar solution is transferred in bag filter (MWCO=14000), at room temperature to dialyse 24h with deionized water, to remove PNIPAM and small-molecule substance, by product lyophilization, obtain the triblock copolymer of white powder.
Described HO-PNIPAM-OH process is: be take NIPAM and 2 mercapto ethanol at 1: 3 in molar ratio, taking azo-initiator is that the 0.5-2% of total weight of monomer is in single port bottle, add ethanol, tube sealing after nitrogen pump drainage 20min, electromagnetic agitation 8h in 70-75 DEG C of water-bath, stopped reaction, reacted mixed liquor is moved into beaker, be placed in 4 DEG C of refrigerators, inject deionized water until white precipitate dissolves completely, mixed solution is transferred in bag filter (MWCO=8000-12000), at room temperature dialyse one week with deionized water, by the product lyophilization after dialysis to constant weight, obtain the HO-PNIPAM-OH homopolymer of white powder.
This slow releasing pharmaceutical is slow releasing injection or sustained-release implant.
The invention has the beneficial effects as follows: Ganoderma spore powder, for chemicotherapy Patients Before And After of performing the operation, improves leukocyte, alleviates chemicotherapy side effect, prevent postoperative recurrence from shifting; The Radix Astragali has obvious stimulation to interferon system, himself has certain antineoplastic action, and astragalus polysaccharides can significantly enhancing non-specific immunity function and humoral immune function, target cell can be protected to resist T cell active; Radix Glycyrrhizae can control treating disorders in five ZANG-organs six internal organs cold and heat pathogen, hard muscles and bones, longue meat, times strength, removing toxic substances, and clothes are made light of one's life by commiting suicide and prolonged life for a long time, slow healthy energy, yin nourishing blood, tonifying the spleen and stomach, and lung moistening, can promote cell regeneration; Containing antimutagen in Fructus Arctii, the active anticancer of medicine can be improved; Herba Scutellariae Barbatae reaches 100% to JTc-26 oncocyte extracorporeal inhibiting rate, its to Normocellular suppression ratio then instrument be 50%, even the late tumor to the weary art for the treatment of, be also improved symptom, Tumor suppression propagation and extend the effect of patient vitals; Nitrosourea medicament is a kind of anticancer significant Western medicine.The present invention by Chinese medicine and Western medicine in conjunction with anticancer, part Western medicine anticarcinogen is replaced with part Traditional Chinese Drug Anticancer medicine, the existing medicine that cancerous cell is killed in formula, also the medicine promoting cell regeneration is had, can take good care of health while anticancer and nourish, removing toxic substances, patient is poisoned little, avoid some drugs to gastrointestinal zest, good effect, biodegradability is good, carbon dioxide and water is become after degraded, do not need to use additive method to be excreted, break through existing medicine only carries out western medicine or simple treatment by Chinese herbs tradition to cancer patient, alleviate the misery of patient, long-term taking can by the life of cancer patient.Use the structure of nucleocapsid parcel, utilize its distinctive temperature-sensing property, slow release temperature is between 37-38 DEG C simultaneously, release is dissolved at the position that medicine only reaches 37-38 DEG C at cancer site equitemperature, realize local release, anticancer effect is with strong points, has breakthrough progress.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is explained.
The invention provides a kind of medical anticancer high molecular slow-release medicine, it is characterized in that the composition of each material and parts by weight are: triblock copolymer PLA-b-PNIPAM-b-PLA 60-80 part of Herba Scutellariae Barbatae 20-30 part, astragalus polysaccharides 13-20 part, Fructus Arctii 5-8 part, Ganoderma spore powder 10-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 40-60 part, PLA and PNIPAM.
Described nitrosourea medicament is the one in streptozocin, nimustine, carmustine, estramustine, lomustine, methyl lomustine, NSC 353451.
The composition of each material and parts by weight are: triblock copolymer PLA-b-PNIPAM-b-PLA 65-75 part of Herba Scutellariae Barbatae 25-28 part, astragalus polysaccharides 15-17 part, Fructus Arctii 5-8 part, Ganoderma spore powder 12-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 43-55 part, PLA and PNIPAM.
A kind of medical anticancer high molecular slow-release process for preparing medicine, is characterized in that comprising the steps:
The preparation of HO-PNIPAM-OH: be take NIPAM and 2 mercapto ethanol at 1: 3 in molar ratio, taking azo-initiator is that the 0.5-2% of total weight of monomer is in single port bottle, add ethanol, tube sealing after nitrogen pump drainage 20min, electromagnetic agitation 8h in 70-75 DEG C of water-bath, stopped reaction, reacted mixed liquor is moved into beaker, be placed in 4 DEG C of refrigerators, inject deionized water until white precipitate dissolves completely, mixed solution is transferred in bag filter (MWCO=8000-12000), at room temperature dialyse one week with deionized water, by the product lyophilization after dialysis to constant weight, obtain the HO-PNIPAM-OH homopolymer of white powder.
The polymerization of the preparation of triblock copolymer PLA-b-PNIPAM-b-PLA: HO-PNIPAM-OH, lactide obtains, and is specially: take HO-PNIPAM-OH, lactide, Sn (Oct) at 1: 1.2: 0.35 in mass ratio
2be dissolved in toluene, nitrogen pump drainage three final vacuum tube sealings, be placed in 135 DEG C of oil for reacting 24h, after stopped reaction, product be dissolved in chloroform, precipitate three times in absolute ether, obtaining the thick product of block copolymer of white; Then be dissolved in deionized water, with the micro-pore-film filtration that aperture is 0.2 μm, to remove PLA, micellar solution is transferred in bag filter (MWCO=14000), at room temperature to dialyse 24h with deionized water, to remove PNIPAM and small-molecule substance, by product lyophilization, obtain the triblock copolymer of white powder.
The preparation of slow releasing pharmaceutical: by Herba Scutellariae Barbatae 20-30 part, astragalus polysaccharides 13-20 part, Fructus Arctii 5-8 part, Ganoderma spore powder 10-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 40-60 part, triblock copolymer PLA-b-PNIPAM-b-PLA 60-80 part is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2. μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament.
In medicine composition, the preparation method of PLA-b-PNIPAM-b-PLA is the same with above-mentioned method and condition, only lists the embodiment of several different pharmaceutical composition different treatment effects below.
Embodiment 1:
By Herba Scutellariae Barbatae 20 parts, astragalus polysaccharides 15 parts, Fructus Arctii 8 parts, Ganoderma spore powder 12 parts, 9 parts, Radix Glycyrrhizae, nitrosourea medicament nimustine 48 parts, triblock copolymer PLA-b-PNIPAM-b-PLA 65 parts is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2 μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament, envelop rate is 48%, under human body temperature, release amount of medicine reached 20% at 10 hours, and reach 46% when 20h, to typeⅡ pneumocyte transplanted tumor in nude mice growth inhibitory action compare do not use this medicine time, the life of nude mice 15%.
Embodiment 2:
By Herba Scutellariae Barbatae 30 parts, astragalus polysaccharides 13 parts, Fructus Arctii 5 parts, Ganoderma spore powder 15 parts, 7 parts, Radix Glycyrrhizae, nitrosourea medicament estramustine 60 parts, triblock copolymer PLA-b-PNIPAM-b-PLA 80 parts is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2 μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament, envelop rate is 56%, under human body temperature, release amount of medicine reached 20% at 10 hours, and reach 54% when 20h, to typeⅡ pneumocyte transplanted tumor in nude mice growth inhibitory action compare do not use this medicine time, the life of nude mice 13%.
Embodiment 3:
By Herba Scutellariae Barbatae 22 parts, astragalus polysaccharides 20 parts, Fructus Arctii 6 parts, Ganoderma spore powder 10 parts, 12 parts, Radix Glycyrrhizae, nitrosourea medicament NSC 353451 40 parts, triblock copolymer PLA-b-PNIPAM-b-PLA 60 parts is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2 μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament, envelop rate is 40%, under human body temperature, release amount of medicine reached 18% at 10 hours, and reach 42% when 20h, to typeⅡ pneumocyte transplanted tumor in nude mice growth inhibitory action compare do not use this medicine time, the life of nude mice 15%.
Embodiment 4:
By Herba Scutellariae Barbatae 26 parts, astragalus polysaccharides 16 parts, Fructus Arctii 7 parts, Ganoderma spore powder 14 parts, 10 parts, Radix Glycyrrhizae, nitrosourea medicament estramustine 48 parts, triblock copolymer PLA-b-PNIPAM-b-PLA 70 parts is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2. μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament, envelop rate is 54%, under human body temperature, release amount of medicine reached 22% at 10 hours, and reach 60% when 20h, to typeⅡ pneumocyte transplanted tumor in nude mice growth inhibitory action compare do not use this medicine time, the life of nude mice 25%.
The micellar structure that self assembly is formed with PNIPAM is in aqueous shell for the block copolymer of PNIPAM and hydrophobic chain segment PLA, hydrophobic segment PLA is core.By PNIPAM and PLA copolymerization, the block copolymer obtained not only has the Thermo-sensitive of PNIPAM, but also combine biocompatibility and the degradability of PLA, below the phase transition temperature of copolymer, PNIPAM is hydrophilic segment, and PLA is hydrophobic chain segment, copolymer self assembly can form the micelle with " core-shell structure copolymer " structure in aqueous.PLA is hydrophobic kernel, PNIPAM is hydrophilic shell, the copolymer micelle of this " core-shell structure copolymer " structure is used as pharmaceutical carrier, effectively can improve drug effect and reduce the toxic and side effects of medicine, simultaneously based on the temperature-responsive of PNIPAM, G realizes the Co ntrolled release to medicine, therefore by conjunction with the temperature-responsive of PNIPAM and the biocompatibility of PLA and degradability, the block copolymer of preparation PNIPAM and PLA, and use it for the Co ntrolled release system of medicine, highlight great researching value.
Slow release principle: oil-soluble medicine is embedded in hydrophobic kernel, by local heating to destroy micellar structure, thus can discharge medicine.Namely at lowest critical solution temperature once; the PNIPAM shell of high degree of hydration is as a protective layer; prevent between hydrophobic core and core and gathering in core and system between other hydrophobic components, bonding; make hydrophobic cores and medicine energy stable existence in micelle; delay the rate of release to medicine simultaneously; when temperature is elevated to more than lowest critical solution temperature; the micellar shell of solvation is destroyed; PNIPAM assembles and shrinks; cave at core surface, thus medicine is discharged from kernel.
The catabolite of this product not instrument can be absorbed by the body metabolism, and its catabolite has therapeutical effect and nutritive effect to human body.
Above several example of the present invention has been described in detail, but described interior looks being preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (7)
1. a medical anticancer high molecular slow-release medicine, is characterized in that the composition of each material and parts by weight are: triblock copolymer PLA-b-PNIPAM-b-PLA 60-80 part of Herba Scutellariae Barbatae 20-30 part, astragalus polysaccharides 13-20 part, Fructus Arctii 5-8 part, Ganoderma spore powder 10-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 40-60 part, PLA and PNIPAM.
2. medical anticancer high molecular slow-release medicine according to claim 1, is characterized in that described nitrosourea medicament is the one in streptozocin, nimustine, carmustine, estramustine, lomustine, methyl lomustine, NSC 353451.
3. medical anticancer high molecular slow-release medicine according to claim 2, is characterized in that the composition of each material and parts by weight are: triblock copolymer PLA-b-PNIPAM-b-PLA 65-75 part of Herba Scutellariae Barbatae 25-28 part, astragalus polysaccharides 15-17 part, Fructus Arctii 5-8 part, Ganoderma spore powder 12-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 43-55 part, PLA and PNIPAM.
4. medical anticancer high molecular slow-release medicine according to claim 1, is characterized in that described slow releasing pharmaceutical is slow releasing injection or sustained-release implant.
5. a medical anticancer high molecular slow-release process for preparing medicine, it is characterized in that comprising the steps: Herba Scutellariae Barbatae 20-30 part, astragalus polysaccharides 13-20 part, Fructus Arctii 5-8 part, Ganoderma spore powder 10-15 part, Radix Glycyrrhizae 7-12 part, nitrosourea medicament 40-60 part, triblock copolymer PLA-b-PNIPAM-b-PLA60-80 part is dissolved in DMF, after stirring 1.5h, this solution is added dropwise in deionized water gradually, continue to keep stirring after 2 hours, solution being transferred to molecular cut off is in the bag filter of 4000mg/mol, dialyse more than 24 hours in deionized water at 15 DEG C, micellar solution aperture is the micro-pore-film filtration of 0.2 μm afterwards, obtain the PLA-b-PNIPAM-b-PLA polypeptide drug-loaded micelle solution being coated with anti-lung-cancer medicament.
6. medical anticancer high molecular slow-release process for preparing medicine according to claim 5, it is characterized in that described triblock copolymer PLA-b-PNIPAM-b-PLA is polymerized by HO-PNIPAM-OH, lactide to obtain, be specially: take HO-PNIPAM-OH, lactide, Sn (Oct) at 1: 1.2: 0.35 in mass ratio
2be dissolved in toluene, nitrogen pump drainage three final vacuum tube sealings, be placed in 135 DEG C of oil for reacting 24h, after stopped reaction, product be dissolved in chloroform, precipitate three times in absolute ether, obtaining the thick product of block copolymer of white; Then be dissolved in deionized water, with the micro-pore-film filtration that aperture is 0.2 μm, to remove PLA, micellar solution is transferred in bag filter (MWCO=14000), at room temperature to dialyse 24h with deionized water, to remove PNIPAM and small-molecule substance, product is frozen in dry, obtains the triblock copolymer of white powder.
7. medical anticancer high molecular slow-release process for preparing medicine according to claim 6, it is characterized in that described HO-PNIPAM-OH process is: be take NIPAM and 2 mercapto ethanol at 1: 3 in molar ratio, taking azo-initiator is that the 0.5-2% of total weight of monomer is in single port bottle, add ethanol, tube sealing after nitrogen pump drainage 20min, electromagnetic agitation 8h in 70-75 DEG C of water-bath, stopped reaction, reacted mixed liquor is moved into beaker, be placed in 4 DEG C of refrigerators, inject deionized water until white precipitate dissolves completely, mixed solution is transferred in bag filter (MWCO=8000-12000), at room temperature dialyse one week with deionized water, by the product lyophilization after dialysis to constant weight, obtain the HO-PNIPAM-OH homopolymer of white powder.
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| CN101264328A (en) * | 2008-05-07 | 2008-09-17 | 济南基福医药科技有限公司 | Anticancer sustained-release gel injection containing stines medicine |
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| CN101264328A (en) * | 2008-05-07 | 2008-09-17 | 济南基福医药科技有限公司 | Anticancer sustained-release gel injection containing stines medicine |
| CN103417872A (en) * | 2013-08-19 | 2013-12-04 | 王锦生 | TCM composition for treatment of lung cancer and preparation method thereof |
| CN104072697A (en) * | 2014-07-08 | 2014-10-01 | 成都市绿科华通科技有限公司 | Polylactic acid (PLA) medicinal polymer with hexagonal columnar porous structure |
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Application publication date: 20150701 |