CN108840896A - Stimuli responsive type parents' macromolecular and preparation method thereof - Google Patents
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Abstract
The present invention relates to a kind of stimuli responsive type parents macromoleculars and preparation method thereof.Such molecule is made of hydrophilic unit, hydrophobic units and link unit with covalent linkage, it is characterised in that the hydrophilic unit is temperature sensitive poplar bundles alkyloxy-ethers, and hydrophobic part is cholesterol liquid crystal primitive, and link portions are divided into：Carbonic acid ester bond, straight chain type alkyloxy-ethers（TEG）Or the alkyl chain containing cystine linkage.Such parents' macromolecular nano material is constructed by the method for self assembly in solution, such nano material has excellent temperature-responsive behavior or redox respondent behavior.This nano material can coat the Model Molecule of hydrophilic or hydrophobic type, under conditions of changing temperature, the temperature-responsive variation of structure causes nano material to dissociate, to make internal model molecule be released, it can be used as a kind of intelligent carrier, make such parents' macromolecular in biomedicine field, the research field of especially intellectual drug carrier has potential application.
Description
Technical field
The present invention relates to a kind of stimuli responsive type parents macromoleculars and preparation method thereof.
Background technique
Self assembly is one of building most effective means of nano material.In organic material field, due to organic molecular structure
It is easy to regulate and control, the advantages that physical and chemical performance is uniform, and stimuli responsive speed is fast, has been widely used in preparation functionalization material.
In conjunction with the method for self assembly, these Macro-Functions materials can be developed to obtain with controllable appearance（Such as spherical, rodlike and vesica
Shape etc.）And the function nano material of special properties, application range are also extended into many brand-new material fields.Typical example
Such as with the liposome molecule of parents' property, the nano material for being similar to biofilm structure can be formed by the method for self assembly,
It is non-toxic and since it is degradable in vivo, the advantages that without reproducibility is immunized, it has been commercially produced for nanometer
The fields such as drug delivery.
Stimuli responsive type nano material has been identified as nano material of new generation.This kind of new material can be in outer plus thorn
Swash, including under the action of temperature, pH, light and magnetic field etc., the change of recurring structure, shape and performance.It can be drawn according to stimulation mode
It is divided into:Physical responses type and Chemical response type.In physical responses type, responsive to temperature type applications to nanostructures range is most
Extensively, feasibility is most strong, potential using value highest.The basic principle is that changing the hydrophobe of material by regulating and controlling external temperature
Performance is to realize the change of the volume, shape, performance of material.Utilize the adjustable nano material of these stimulus response performances
Macroscopic behavior, has a very extensive application prospect, including drug conveying, intelligent drives, material selfreparing, bio-medical are contour
Sciemtifec and technical sphere.In Chemical response type, redox response is an important directions of stimuli responsive type nano material, such as
Molecule with the redox responsiveness structure such as disulfide bond can add outside reproducibility compound (such as dithiothreitol (DTT) (DTT）,
Glutathione (GSH) etc.) it is existing under the conditions of, scission of link occurs for disulfide bond, and nanometer material structure dissociates.
Develop the application prospect that novel stimuli responsive type nano material will further expand Related Research Domain.
Summary of the invention
One of the objects of the present invention is to provide parents' macromoleculars of a kind of stimuli responsive type parents macromolecular response type.
The second object of the present invention is to provide the preparation method of such parents' macromolecular.
In order to realize that the above goal of the invention, the present invention adopt the following technical scheme that：
A kind of stimuli responsive type parents macromolecular, such molecule is by hydrophilic unit, hydrophobic units and link unit with covalent bond chain
Connect composition, it is characterised in that the hydrophilic unit is temperature sensitive poplar bundles alkyloxy-ethers, and hydrophobic part is cholesterol liquid crystal primitive, link
Part is：Carbonic acid ester bond (Et-G1-Chol), straight chain type alkyloxy-ethers (Et-G1-TEG-Chol) or the alkyl chain containing cystine linkage
(Et-G1-SS-Chol), structural formula is respectively：
A method of preparing above-mentioned stimuli responsive type parents' macromolecular, it is characterised in that this method the specific steps are：
The specific method of cholesterol for preparing triethylene glycol and p-methyl benzene sulfonic chloride modification is：By p-toluenesulfonyl protection
Cholesterol (TsO-Chol) is dissolved in dioxane, and excess butanediol is added and is heated to reflux for 24 hours, washes under inert gas protection
It is filtered after washing drying, revolving removes solvent, and column Chromatographic purification obtains the cholesterol (TEG-Chol) of triethylene glycol modification.By TEG-
Chol is dissolved in dry tetrahydrofuran, and triethylamine is then added and does alkali, additional amount is the 4% of TEG-Chol mass, ice bath
Under the conditions of according to 1.5 times of molar ratios of TEG-Chol paratoluensulfonyl chloride is added, remove after ice bath that the reaction was continued at room temperature 24
H is filtered after washing is dry, and revolving removes solvent, what column Chromatographic purification obtained modifying through triethylene glycol and p-methyl benzene sulfonic chloride
Cholesterol (TsO-TEG-Chol).
The specific method of chloro-carbonic acid cholesterol for preparing the modification of bis- sulphur diethanol of 2,2'- is：By 2,2 '-two sulphur diethanols
With cholesteryl chloroformate according to 1:1.5 molar ratio is dissolved in dry methylene chloride, and triethylamine is added later and makees alkali, adds
Enter 50% that amount is 2,2 '-two sulphur diethanol quality；Under inert gas protection, it reacts 3 hours at room temperature；Wash drying
After filter, revolving remove solvent, column Chromatographic purification obtain 2,2'-, bis- sulphur diethanol modification chloro-carbonic acid cholesterol (OH-SS-
Chol)。
The specific method for preparing Et-G1-Chol is：By generation poplar bundles alkyloxy-ethers benzylalcohol and cholesteryl chloroformate according to
1:1.5 molar ratio is dissolved in dry methylene chloride, and triethylamine is added later and makees alkali, additional amount is generation poplar bundles alcoxyl
The 24% of ether benzylalcohol quality；Under inert gas protection, it reacts 24 hours at room temperature；It is filtered after washing is dry, revolving removes
Solvent, column Chromatographic purification obtain target macromolecule Et-G1-Chol.
The specific method for preparing Et-G1-TEG-Chol is：Generation poplar bundles alkyloxy-ethers benzylalcohol is dissolved in dry tetrahydro furan
In muttering, it is separately added into potassium iodide, 15- crown- 5- ether and sodium hydride later, after stirring and dissolving, according to generation poplar bundles alkyloxy-ethers benzyl
The cholesterol (TsO-TEG-Chol) modified through TEG and p-methyl benzene sulfonic chloride is added in 1.5 times of molar ratios of alcohol, in inert gas
Under protection, react 24 hours at room temperature；It is filtered after washing is dry, revolving removes solvent, and column Chromatographic purification obtains target and divides greatly
Sub- Et-G1-TEG-Chol.
The specific method for preparing Et-G1-SS-Chol is：Generation poplar bundles alkyloxy-ethers carboxylic acid is dissolved in dry dichloromethane
In alkane, the cholesterol modified through 2,2'-, bis- sulphur diethanol is added according to 1.5 times of molar ratios of generation poplar bundles alkyloxy-ethers carboxylic acid
(OH-SS-Chol), catalyst 4-dimethylaminopyridine (DMAP) then is added, EDC is added after 20 min in stirring and dissolving.
Under inert gas protection, it reacts 24 hours at room temperature；It is filtered after washing is dry, revolving removes solvent, and column Chromatographic purification obtains
To target macromolecule Et-G1-SS-Chol.
It is a kind of with spherical or club shaped structure nano material, formed using above-mentioned stimuli responsive type parents' macromolecular
Core-shell structure, it is characterised in that the nano material shell is the hydrophilic unit of stimuli responsive type parents' macromolecular, and core is containing having
The hydrophobic units of liquid crystalline phase ordered arrangement, size are greater than 1 nm and less than 2000 nm.
A method of preparing above-mentioned has spherical or club shaped structure nano material, it is characterised in that the tool of this method
Body step is：Stimuli responsive type parents' macromolecular is dissolved in 1,4- dioxane and is configured to concentration as 0.05 wt% ~ 0.2
The solution of wt%, 20 oC ~ 25 oUnder C, it is slowly added dropwise selective solvent deionized water thereto, the volume of deionized water and 1,
The volume ratio of 4- dioxane is 1.1：1；Organic phase 1,4- dioxane, which is removed, finally by the method for dialysis obtains described receive
Rice material.
The chemical structural formula of the generation poplar bundles alkyloxy-ethers benzylalcohol is：；
The chemical structural formula of the generation poplar bundles alkyloxy-ethers carboxylic acid is：;
The chemical structural formula of the cholesteryl chloroformate is：；
The chemical structural formula of the cholesterol modified through triethylene glycol and p-methyl benzene sulfonic chloride is：；
The chemical structural formula of chloro-carbonic acid cholesterol through the modification of bis- sulphur diethanol of 2,2'- is：。
Important component in stimuli responsive type nano material includes responsive to temperature type and oxidation-reduction type nano material
Deng.Wherein, responsive to temperature type nano material is by regulating and controlling external temperature, i.e., the hydrophilicity and hydrophobicity of changeable material is to realize material
Expect controllable responsiveness micro-nano structure variation.Compound containing disulfide bond has the ability of redox response, can be in outer plus reduction
Property compound (such as dithiothreitol (DTT) (DTT), glutathione (GSH)) it is existing under the conditions of, scission of link, nanometer material occur for disulfide bond
Material structure dissociates.There are intelligent nano material according to the present invention apparent temperature response characteristics or redox to respond
Characteristic not only can change the temperature-responsive section of formed nano material by changing intermolecular link primitive, can also be with
Assign material different respondent behaviors, it is even more important that the temperature of environment can carry out the pattern of this kind of Nanoscale assemblies
Regulation, as a kind of intelligent carrier being adjusted by temperature, is cured to discharge the internal effective component wrapped up in biology
The research field in medicine field, especially intellectual drug carrier has potential application.
A kind of brand new has been synthesized using cholesterol liquid crystal primitive and the design of poplar bundles alkyloxy-ethers in this patent, there is liquid
Brilliant performance and the excellent parents' macromolecular of biocompatibility, can prepare novel temperature-sensitive nano material by way of self assembly.
Wherein, cholesterol molecule is a kind of hydrophobic nature rigid molecule, has liquid crystal ordered arrangement under solid phase, and poplar bundles alkyloxy-ethers
It is the temperature sensitive macromolecular of a kind of hydrophily, two kinds of structural motifs are by Covalent bonding together to obtain a kind of novel parental type compound.
This parents' macromolecular in the solution self assembly when, using cholesteryl at liquid crystal phase separation be driving force controllably formed
The nanoscale assembly of size, morphology controllable.And the ordered arrangement of liquid crystalline phase is similar to a kind of physical crosslinking inside assembly,
The stability of assembly can be greatly improved.Alkyloxy-ethers molecule is not only hydrophilic and has temperature response performance, the structural motif
Introducing so that nanometer assembled material is provided with intelligent response performance.Meanwhile the structure by changing link primitive not only can be with
Change the range of temperature-responsive, it is often more important that multiple stimulation response structure can be introduced, such as introduce the alkane containing disulfide bond
Base chain is as link primitive, so that nano material has both redox corresponding ability while with temperature-responsive, so that
Nano material is more intelligent.In addition to this, the nano material that thus two kinds of primitives construct has good bio-compatible
Property, it can be used as a kind of intelligent nano material that structure adjusting is carried out by temperature and be applied to the fields such as drug intelligent delivery.
The present invention has following outstanding feature and remarkable advantage：
1. being linked cholesterol primitive and poplar bundles alkyloxy-ethers primitive to obtain a kind of parents' macromolecular by covalent bond.
2. the assembly aqueous solution of parents' macromolecular shows excellent temperature sensitive behavior.
3. the macromolecular with different stimulated respondent behavior can be obtained by changing intermolecular link primitive, such as
Introducing two sulphur structures can be obtained the macromolecular with redox respondent behavior.
3. parents' macromolecular forms stable and microcosmic by two kinds of driving forces of ordered arrangement of hydrophobe effect and cholesterol
The nanometer materials of structure-controllable, such as spherical and club shaped structure.
4. the preparation method of intellectual material is simple, structure is easy to regulate and control, and physical and chemical performance is uniform, stimuli responsive speed
Degree is fast.
5. such intellectual material can carry out the package of Model Molecule, discharged rapidly under conditions of changing temperature.
Detailed description of the invention
Fig. 1 is parents' macromolecular Et-G1- Chol's1H NMR spectra.
Fig. 2 is parents' macromolecular Et-G1-TEG-Chol's1H NMR spectra.
Fig. 3 is parents' macromolecular Et-G1-SS-Chol's1H NMR spectra.
Fig. 4 is the temperature sensitive phase transformation Haze curve figure of parents' macromolecular Et-G1- Chol.
Fig. 5 is transmission electron microscope (TEM) photo of parents' macromolecular Et-G1- Chol nano material.
Fig. 6 is the change of size figure of the nano material of parents' macromolecular Et-G1- Chol formation at different temperatures.
Fig. 7 is the temperature sensitive phase transformation Haze curve figure of parents' macromolecular Et-G1- TEG-Chol.
Fig. 8 is transmission electron microscope (TEM) photo of parents' macromolecular Et-G1- TEG-Chol nano material.
Fig. 9 is transmission electron microscope (TEM) photo of parents' macromolecular Et-G1- SS-Chol nano material.
Figure 10 is the cooling releasing curve diagram after Et-G1- Chol nano material packing model molecule FITC.
Specific embodiment
Details are as follows for the preferred embodiment of the present invention：
Embodiment one：
The synthesis of target molecule Et-G1- Chol
The generation poplar bundles alkyloxy-ethers benzylalcohol of ethyl capping is added into 25 dry mL reaction flasks, methylene chloride stirring is added
After dissolution, triethylamine is added dropwise with liquid-transfering gun, stirring and dissolving rear substitution nitrogen three times and keeps nitrogen atmosphere, and chloro-carbonic acid gallbladder is consolidated
Alcohol ester is dissolved in methylene chloride, is added drop-wise in reaction flask dropwise under condition of ice bath, is dripped off recession and is removed ice bath, continues to stir at room temperature
React 18h.After the reaction was completed, rotary evaporation removes solvent, and column Chromatographic purification obtains product Et-G1-Chol.Nucleus magnetic hydrogen spectrum figure ginseng
See Fig. 1.
Embodiment two：
The synthesis of target molecule Et-G1-TEG- Chol
The generation poplar bundles alkyloxy-ethers benzylalcohol of ethyl capping is added into 25 dry mL reaction flasks, tetrahydrofuran stirring is added
After dissolution, potassium iodide, 15- crown- 5- ether and sodium hydride are sequentially added, continues stirring and dissolving rear substitution nitrogen three times and keeps nitrogen
The cholesterol that triethylene glycol and p-methyl benzene sulfonic chloride are modified is dissolved in tetrahydrofuran, drips dropwise under condition of ice bath by gas atmosphere
It is added in reaction flask, drips off recession and remove ice bath, continue to be stirred to react 24 h at room temperature.After the reaction was completed, rotary evaporation removes molten
Agent, column Chromatographic purification obtain product Et-G1-TEG-Chol.Nucleus magnetic hydrogen spectrum figure is referring to fig. 2.
Embodiment three：
The synthesis of target molecule Et-G1-SS- Chol
The generation poplar bundles alkyloxy-ethers carboxylic acid of ethyl capping is added into 25 dry mL reaction flasks, methylene chloride stirring is added
After dissolution, it is added cholesterol modify through 2,2'-, bis- sulphur diethanol, after stirring and dissolving, addition catalyst DMAP；By 20 min
Afterwards, EDC is added.Under inert gas protection, it reacts 24 hours at room temperature；It is filtered after washing is dry, revolving removes solvent, column
Chromatographic purification obtains target macromolecule Et-G1-SS-Chol.Nucleus magnetic hydrogen spectrum figure is referring to Fig. 3.
Example IV：
This example is related to a kind of method using self assembly in solution and prepares spherical or rod-like nano material, and specific implementation process is such as
Under：Keeping temperature 20oC-25 oUnder conditions of C, by above-mentioned parents' macromolecular Et-G1- Chol, Et-G1-TEG- Chol
Or Et-G1-SS- Chol (2.0 mg) is dissolved in respectively in Isosorbide-5-Nitrae-dioxane (1.0 mL), wiring solution-forming slightly shakes
Deionized water (10 μ L/min), the dialysis for being 3500Da with molecular cut off by mixed solution after dripping are slowly added dropwise simultaneously
Bag dialysis, finally obtains spherical or rod-like nano material aqueous solution.
Embodiment five：
The parents molecule Et-G1- Chol prepared such as example IV has apparent temperature-responsive ability, and phase transition temperature is quantitative
Characterization is implemented as follows：Utilize ultraviolet/visible spectrophotometer（UV/Vis）The turbidity of the aqueous solution at different temperatures is carried out
Test, ramp rates preferably 0.2oC/min.As a result referring to fig. 4, solution transmitance during cooling increases rapidly, then
It is warming up to 28oCertain dehydration aggregation can occur when C so that transmitance reduces.Using transmission electron microscope to this solution
Microscopic appearance is observed, and prepares sample at different temperatures respectively, obtains having various sizes of globular nanostructures, referring to
Fig. 5,25oWhen C, having a size of 250-500nm, 5oWhen C, size is about 10nm, and 35oWhen C, having a size of 50-
200nm.Dynamic light scattering test is carried out to the partial size of spherical nano material at different temperatures respectively, referring to Fig. 6, test knot
It is consistent that fruit with transmission electron microscope measures result.
Embodiment six：
Such as the temperature-responsive section generation significant change of parents molecule Et-G1-TEG- Chol prepared by example IV, as a result join
See Fig. 7,24-28 is changed into phase transformation sectionoC illustrates the link primitive by changing molecule, and the section of temperature-responsive can occur
Variation can adjust temperature-responsive range by adjusting link primitive.Using transmission electron microscope to the microcosmic of this solution
Pattern is observed, 35oSample is prepared when C, obtains rodlike nanostructure, and referring to Fig. 8, length is about 200-1000
Nm, width are about 80 nm.
Embodiment seven：
The parents molecule Et-G1-SS- Chol prepared such as example IV has the ability of certain reduction response, is embodied
Journey is as follows：Reproducibility will be added in the aqueous solution (1 mL) of the obtained spherical nano material of Et-G1-SS- Chol in example IV
Compound DTT (1.54 mg) is observed after shaking 24 h by TEM, as a result referring to Fig. 9, before DTT is added, the nano material
For the chondritic of size 150-200 nm, after DTT is added, chondritic size becomes smaller, about 10-50 nm, illustrates due to double
The chondritic of the fracture of sulfide linkage, script dissociates.
Embodiment eight：
In the present embodiment, a kind of fluorescein molecule FITC is selected to carry out parents' macromolecular in embodiment one as fluorescence probe
The load release experiment of Et-G1-Chol.Specific implementation process is as follows：Keeping temperature 20oUnder conditions of C, by parents' molecule
Et-G1-Chol (2.0 mg) is dissolved in Isosorbide-5-Nitrae-dioxane (1.0 mL), and the aqueous solution of FITC is slowly added dropwise in wiring solution-forming
(1.0 mL, concentration are 0.1 mg/mL), while slight concussion is kept, drop rate is 10 μ L/min.It will mixing after dripping
Solution is dialysed with the bag filter that molecular cut off is 3500Da, to remove uncoated FITC, finally obtains load fluorescein
The aqueous solution of the spherical nano material of FITC, takes wherein 2mL, is divided into two parts, it is 3500 that every part of 1mL, which is placed in molecular cut off,
In the bag filter of Da, bag filter is respectively put into the conical flask equipped with 100 mL deionized waters, it is 25 that temperature, which is distinguished constant,oC
With 10oC takes 100 times of solution and dilution in 50 μ L bag filters at regular intervals, tests its fluorescence intensity, calculate and draw
The curve of cumulative release amount, referring to Figure 10, (10 under the conditions of temperature is loweroC), which can pass through temperature-responsive
It is dissociated faster, to achieve the purpose that release.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
Innovation and creation purpose according to the present invention makes a variety of variations, what the Spirit Essence and principle of all technical solutions according to the present invention were done
Changes, modifications, substitutions, combinations, simplifications should be equivalent substitute mode, as long as meeting goal of the invention of the invention, as long as not
Away from the technical principle and inventive concept of the preparation method and application of the intelligent parents' molecule nano material of the present invention, this is belonged to
The protection scope of invention.
Claims (4)
1. a kind of stimuli responsive type parents' macromolecular, such molecule is by hydrophilic unit, hydrophobic units and link unit with covalent bond
Link is constituted, it is characterised in that the hydrophilic unit is temperature sensitive poplar bundles alkyloxy-ethers, and hydrophobic part is cholesterol liquid crystal primitive, chain
Socket part is divided into：Carbonic acid ester bond (Et-G1-Chol), straight chain type alkyloxy-ethers (Et-G1-TEG-Chol) or the alkyl chain containing cystine linkage
(Et-G1-SS-Chol), structural formula is respectively：
。
2. a kind of method for preparing stimuli responsive type parents macromolecular according to claim 1, it is characterised in that this method
The specific steps are：
Link primitive is adjusted using cholesteryl chloroformate or modified cholesterol；
By poplar bundles alcoxyl ether moiety and cholesterol moiety by simple esterification or etherification reaction, can be prepared
Parents' macromolecular with different stimulated response performance.
3. it is a kind of with spherical or club shaped structure nano material, it is big using the stimuli responsive type parents according to claim
The core-shell structure that molecule is formed, it is characterised in that the nano material shell is the hydrophilic unit of stimuli responsive type parents' macromolecular, core
For containing the hydrophobic units with liquid crystalline phase ordered arrangement, size is greater than 1 nm and less than 2000 nm.
4. a kind of prepare the method according to claim 1 with spherical or club shaped structure nano material, feature exists
In this method the specific steps are：Stimuli responsive type parents' macromolecular is dissolved in 1,4- dioxane be configured to concentration be 0.05
The solution of the wt% of wt% ~ 0.2,20 oC ~ 25 oUnder C, selective solvent deionized water, deionized water are slowly added dropwise thereto
Volume and 1,4- dioxane volume ratio be 1.1：1；Organic phase 1,4- dioxane is removed finally by the method for dialysis
Obtain the nano material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912811A (en) * | 2019-03-29 | 2019-06-21 | 安徽省农业科学院蚕桑研究所 | A kind of preparation method of amphiphilic sericin polymer and the application of polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870719A (en) * | 2010-05-21 | 2010-10-27 | 中国科学院上海有机化学研究所 | Organic functional compound having disulfide chemical bond and steroids skeleton, preparation method thereof and use thereof |
| CN106883360A (en) * | 2017-02-14 | 2017-06-23 | 上海大学 | Can functionalization stimulating responsive polymer and preparation method thereof |
| CN106967203A (en) * | 2017-02-14 | 2017-07-21 | 上海大学 | Volume can temperature adjustment polymer and preparation method thereof |
| CN107141404A (en) * | 2017-06-20 | 2017-09-08 | 上海大学 | SiRNA carrier based on temperature sensitive cationic polymer and preparation method thereof |
| WO2017201528A1 (en) * | 2016-05-20 | 2017-11-23 | The University Of Chicago | Nanoparticles for chemotherapy, targeted therapy, photodynamic therapy, immunotherapy, and any combination thereof |
-
2018
- 2018-04-23 CN CN201810364517.7A patent/CN108840896A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870719A (en) * | 2010-05-21 | 2010-10-27 | 中国科学院上海有机化学研究所 | Organic functional compound having disulfide chemical bond and steroids skeleton, preparation method thereof and use thereof |
| WO2017201528A1 (en) * | 2016-05-20 | 2017-11-23 | The University Of Chicago | Nanoparticles for chemotherapy, targeted therapy, photodynamic therapy, immunotherapy, and any combination thereof |
| CN106883360A (en) * | 2017-02-14 | 2017-06-23 | 上海大学 | Can functionalization stimulating responsive polymer and preparation method thereof |
| CN106967203A (en) * | 2017-02-14 | 2017-07-21 | 上海大学 | Volume can temperature adjustment polymer and preparation method thereof |
| CN107141404A (en) * | 2017-06-20 | 2017-09-08 | 上海大学 | SiRNA carrier based on temperature sensitive cationic polymer and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 《精讲精练》编写组: "《精讲精练》", 31 December 2014, 黄河出版传媒集团宁夏人民教育出版社出版 * |
| 化学工业出版社《化工百科全书》编: "《化工百科全书》", 31 August 1996, 化学工业出版社 * |
| 卢悦等: "智能响应型大分子的设计合成与自组装", 《2016年全国高分子材料科学与工程研讨会论文摘要集》 * |
| 涂料工艺编委会编: "《涂料工艺（第三版）上册》", 31 December 1997, 化学工业出版社 * |
| 王国建: "《高分子现代合成方法与技术》", 31 July 2013, 同济大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912811A (en) * | 2019-03-29 | 2019-06-21 | 安徽省农业科学院蚕桑研究所 | A kind of preparation method of amphiphilic sericin polymer and the application of polymer |
| CN109912811B (en) * | 2019-03-29 | 2021-04-06 | 安徽省农业科学院蚕桑研究所 | Preparation method of amphiphilic sericin polymer and application of polymer |
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