CN101591442A - A kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle - Google Patents
A kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle Download PDFInfo
- Publication number
- CN101591442A CN101591442A CNA2009100321016A CN200910032101A CN101591442A CN 101591442 A CN101591442 A CN 101591442A CN A2009100321016 A CNA2009100321016 A CN A2009100321016A CN 200910032101 A CN200910032101 A CN 200910032101A CN 101591442 A CN101591442 A CN 101591442A
- Authority
- CN
- China
- Prior art keywords
- macromole
- aqueous solution
- pvp
- self
- micella
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle, belongs to the numerator self-assembly technique field.The present invention be simple and easy to random copolymer polypropylene acid-co-vinylbenzene (P (AA-co-St)) be simple and easy to homopolymer polyethylene pyrrolidone (PVP) form by the strong interaction self-assembly of hydrogen at aqueous phase and have in the globular macromolecule micellar process of nucleocapsid structure, induce by adding ionogenic surfactant, obtain the bar-shaped macromole micella that axial length changes in 20～80nm range-controlled at the variation of 100～400nm range-controlled, radical length.Characteristics of the present invention are: induce by ionogenic surfactant, be simple and easy to macromole form the non-globular macromolecule micella of nano level by easy molecule self-assembling method; Make the macromole self assembling process finish at aqueous phase but not in solvent phase, finish, friendly more to environment.
Description
Technical field
A kind of ionogenic surfactant that utilizes induces the binary macromolecular aqueous solution self-assembly to form bar-shaped macromole micellar method, the present invention be simple and easy to random copolymer polypropylene acid-co-vinylbenzene (P (AA-co-St)) be simple and easy to homopolymer polyethylene pyrrolidone (PVP) form by the strong interaction self-assembly of hydrogen at aqueous phase and have in the globular macromolecule micellar process of nucleocapsid structure, induce by adding ionogenic surfactant, obtain axial length and change in 100～400nm range-controlled, the bar-shaped macromole micella that radical length changes in 20～80nm range-controlled.Belong to the numerator self-assembly technique field.
Background technology
By the supramolecular aggregation with nucleocapsid structure and specified shape that the self-assembly behavior of amphiphilic polymer in solution forms, promptly the macromole micella has caused extensive studies interest.Micella has extremely tempting application prospect, especially at biomedicine field, as the carrier of useful as drug sustained release, target administration.And, can or concentrate organic substance at the hydrophobic interior parcel because of it at the macromole micella that aqueous phase can stable existence, and organic molecule there is stronger adsorptive power, can be used for sewage disposal, environmental purification and as the carrier of catalyzer etc.
Utilize segmented copolymer self-assembly in selective solvent can obtain the macromole micella.Domestic more simple micellization method i.e. " non-segmented copolymer route " is being proposed then aspect the micella self-assembly, use be simple and easy to homopolymer to or homopolymer and the macromole micella of multipolymer to having obtained by self-assembly being connected with non covalent bond between the nucleocapsid." have the self-assembly behavior of special interactional blend polymer in selective solvent, the chemistry journal, 2000, the self-assembly behavior in methyl alcohol of sulfonated polystyrene and poly 4 vinyl pyridine has been discussed 58 (1): 118-121 ", and it is spherical that the macromole micella that utilizes this self-assembling method to form mostly is greatly.In order to satisfy different practical application request, the macromole micella that obtains variform has become another branch direction of research.The special construction of small molecules tensio-active agent can induce the macromole micella to reach the purpose of conversion shape, does not see the report that utilizes tensio-active agent to induce the macromole micellar conformation to change in non covalent bond rubber alloy bundle system both at home and abroad as yet.
The present invention utilizes above-mentioned " non-segmented copolymer route ", with be simple and easy to random copolymers P (AA-co-St) be simple and easy to homopolymer PVP form globular macromolecule micella with nucleocapsid structure in the aqueous phase self-assembly, induce by adding anionic or cationic surfactant in the micellization process again, make binary macromolecular aqueous solution change the self-assembly mode and obtain bar-shaped macromole micella.
Summary of the invention
The object of the invention is: provide a kind of anionic or cationic surfactant of utilizing to induce macromole aggregate aqueous phase to generate bar-shaped macromole micellar method.This method forms in the globular macromolecule micellar process by the strong effect of hydrogen self-assembly at aqueous phase with random copolymers P (AA-co-St) and homopolymer PVP, by adding anionic or cationic surfactant, induces it to generate bar-shaped macromole micella.
Technical scheme of the present invention: a kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle, in random copolymers P (AA-co-St) and homopolymer PVP binary macromolecular aqueous solution, form in the globular macromolecule micellar process, induce it to generate bar-shaped macromole micella by adding ionogenic surfactant by the strong effect of hydrogen self-assembly;
Aniorfic surfactant is selected carboxylic acid type, sulfonate type, sulfuric acid type or phosphate ester salt type for use; Cationic surfactant is selected amine salt type or quaternary amine type for use; Technology is:
Under ultrasonic and mechanical stirring condition, tetrahydrofuran (THF) (THF) solution and a small amount of ionogenic surfactant aqueous solution of a small amount of P (AA-co-St) dropwise are added drop-wise in the aqueous solution of PVP simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 4.5～450mg/L, PVP 9～4500mg/L, ionogenic surfactant 0.2～14mmol/L, stirred 10 minutes, and made light blue transparent macromole micellar solution, generated bar-shaped macromole micella through the Electronic Speculum test shows;
The molecular weight control of used random copolymers P (AA-co-St) is 5000～100000, and wherein AA segmental mol mark is 0.1～0.6.
The concentration of used P (AA-co-St) in tetrahydrofuran solution is 100～10000mg/L, and the concentration of PVP in the aqueous solution is 10～5000mg/L.
Used anion surfactant is a sulfuric acid type tensio-active agent.
Used sulfuric acid type tensio-active agent is sodium lauryl sulphate (SDS), and its concentration of aqueous solution is 5～300mmol/L.
Used cationic surfactant is a quaternary amine type tensio-active agent.
Used quaternary amine type tensio-active agent is cetyl trimethylammonium bromide (CTAB), and its concentration of aqueous solution is 5～300mmol/L.
The macromole micellar conformation characterizes: a macromole micellar solution is dropped on the copper mesh of carbon film covering, seasoning is with transmission electron microscope observing macromole micellar form.
Beneficial effect of the present invention: induce by ionogenic surfactant, be simple and easy to macromole form the non-globular macromolecule micella of nano level by easy self-assembling method; Make the macromole self assembling process finish at aqueous phase but not in solvent phase, finish, friendly more to environment.
Description of drawings
The macromole micellar transmission electron microscope picture that Fig. 1 embodiment 1 obtains, 48mg/LP when not adding tensio-active agent (AA-co-St) and the globular macromolecule micellar TEM with nucleocapsid structure that 95mg/L PVP forms scheme, the macromole micella is the regular sphere with nucleocapsid structure, the about 100nm of diameter.
The macromole micellar transmission electron microscope picture that Fig. 2 embodiment 2 obtains, 0.45mmol/L SDS makes 45mg/LP (AA-co-St) and 900mg/L PVP mixed system form bar-shaped macromole micellar TEM figure, the macromole micella is a club shaped structure, the about 200nm of axial length, the about 40nm of radical length.
The macromole micellar transmission electron microscope picture that Fig. 3 embodiment 9 obtains, 0.45mmol/L CTAB makes 45mg/L P (AA-co-St) and 900mg/L PVP mixed system form bar-shaped macromole micellar TEM figure, the macromole micella is a club shaped structure, the about 200nm of axial length, the about 20nm of radical length.
Embodiment
Embodiment 1:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 20000, AA segmental mol mark is 0.25) THF solution dropwise be added drop-wise in the PVP aqueous solution, each component ultimate density is respectively in the mixed system: P (AA-co-St) 48mg/L, PVP 95mg/L, stirred 10 minutes, and made light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
Fig. 1 is the macromole micellar transmission electron microscope picture that embodiment 1 obtains, and does not add tensio-active agent, and the macromole micella is the regular sphere with nucleocapsid structure, the about 100nm of diameter.
Embodiment 2:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 20000, AA segmental mol mark is 0.25) the THF solution and the SDS aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 45mg/L, PVP 900mg/L, SDS 0.45mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
Fig. 2 is the macromole micellar transmission electron microscope picture that embodiment 2 obtains, and the macromole micella is a club shaped structure, the about 200nm of axial length, the about 40nm of radical length.
Embodiment 3:
Under ultrasound condition and mechanical stirring, with P (AA-co-St) (molecular weight 100000, AA segmental mol mark is 0.6) the THF solution and the SDS aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 4.5mg/L, PVP 9mg/L, SDS 0.2mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
Bar-shaped macromole micella size is little, and dispersity is bigger.
Embodiment 4:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 50000, AA segmental mol mark is 0.1) the THF solution and the SDS aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 450mg/L, PVP 4500mg/L, SDS 14mmol/L stirred 10 minutes, make light blue transparent micellar solution, utilize transmission electron microscope to characterize micellar conformation.
The about 400nm of bar-shaped macromole micella axial length, the about 80nm of radical length.
Embodiment 5:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 10000, AA segmental mol mark is 0.4) the THF solution and the SDS aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 200mg/L, PVP 2500mg/L, SDS 7mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 300nm of bar-shaped macromole micella axial length, the about 50nm of radical length.
Embodiment 6:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 30000, AA segmental mol mark is 0.2) the THF solution and the dodecyl carboxylic acid sodium aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 150mg/L, PVP 2000mg/L, dodecyl carboxylic acid sodium 0.6mmol/L, stirred 10 minutes, make transparent slightly milky macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 220nm of bar-shaped macromole micella axial length, the about 40nm of radical length.
Embodiment 7:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 40000, AA segmental mol mark is 0.3) THF solution and sodium dodecyl benzene sulfonate aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 350mg/L, PVP 3000mg/L, Sodium dodecylbenzene sulfonate 1mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 250nm of rod-shaped micelle axial length, the about 40nm of radical length.
Embodiment 8:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 8000, AA segmental mol mark is 0.2) THF solution and 1-isobutyl-3,5-dimethylhexylphosphoric acid two aqueous solutions of potassium dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 400mg/L, PVP 3500mg/L, 1-isobutyl-3,5-dimethylhexylphosphoric acid dipotassium 0.5mmol/L, stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 260nm of bar-shaped macromole micella axial length, the about 40nm of radical length.
Embodiment 9:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 20000, AA segmental mol mark is 0.25) the THF solution and the CTAB aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 45mg/L, PVP 900mg/L, CTAB 0.45mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
Fig. 3 is the macromole micellar transmission electron microscope picture that embodiment 9 obtains, and the macromole micella is a club shaped structure, the about 200nm of axial length, the about 20nm of radical length.
Embodiment 10:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 6000, AA segmental mol mark is 0.1) the THF solution and the CTAB aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 4.5mg/L, PVP 9mg/L, CTAB 0.2mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
Bar-shaped macromole micella size is little, and dispersity is bigger.
Embodiment 11:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 80000, AA segmental mol mark is 0.5) the THF solution and the CTAB aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 450mg/L, PVP 1000mg/L, CTAB 14mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 400nm of bar-shaped macromole micella axial length, the about 80nm of radical length.
Embodiment 12:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 60000, AA segmental mol mark is 0.1) the THF solution and the CTAB aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 200mg/L, PVP 500mg/L, CTAB 7mmol/L stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 300nm of bar-shaped macromole micella axial length, the about 50nm of radical length.
Embodiment 13:
Under ultrasonic and mechanical stirring condition, with P (AA-co-St) (molecular weight 50000, AA segmental mol mark is 0.3) THF solution and lauryl amine acetate aqueous solution dropwise be added in the PVP aqueous solution simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 100mg/L, PVP 3500mg/L, lauryl amine acetate 0.8mmol/L, stirred 10 minutes, make light blue transparent macromole micellar solution, utilize transmission electron microscope to characterize the macromole micellar conformation that obtains.
The about 240nm of bar-shaped macromole micella axial length, the about 20nm of radical length.
Claims (6)
1. a binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle, it is characterized in that in random copolymer polypropylene acid-co-vinylbenzene (P (AA-co-St)) and homopolymer polyethylene base pyrrolidone (PVP) binary macromolecular aqueous solution, forming in the globular macromolecule micellar process, induce it to generate bar-shaped macromole micella by adding ionogenic surfactant by the strong effect of hydrogen self-assembly;
Aniorfic surfactant is selected carboxylic acid type, sulfonate type, sulfuric acid type or phosphate ester salt type for use; Cationic surfactant is selected amine salt type or quaternary amine type for use; Technology is:
Under ultrasonic and mechanical stirring condition, tetrahydrofuran solution and a small amount of ionogenic surfactant aqueous solution of a small amount of P (AA-co-St) dropwise are added drop-wise in the aqueous solution of PVP simultaneously, each component ultimate density is respectively in the mixed system: P (AA-co-St) 4.5～450mg/L, PVP 9～4500mg/L, ionogenic surfactant 0.2～14mmol/L, stirred 10 minutes, and made light blue transparent macromole micellar solution, generated bar-shaped macromole micella through the Electronic Speculum test shows;
The molecular weight control of used random copolymers P (AA-co-St) is 5000～100000, and wherein AA segmental mo1 mark is 0.1～0.6.
2. method according to claim 1 is characterized in that the concentration of used P (AA-co-St) in tetrahydrofuran solution is 100～10000mg/L, and the concentration of PVP in the aqueous solution is 10～5000mg/L.
3. method according to claim 1 is characterized in that used anion surfactant is a sulfuric acid type tensio-active agent.
4. method according to claim 3 is characterized in that used sulfuric acid type tensio-active agent is sodium lauryl sulphate (SDS), and its concentration of aqueous solution is 5mmol/L～300mmol/L.
5. method according to claim 1 is characterized in that used cationic surfactant is a quaternary amine type tensio-active agent.
6. method according to claim 5 is characterized in that used quaternary amine type tensio-active agent is cetyl trimethylammonium bromide (CTAB), and its concentration of aqueous solution is 5mmol/L～300mmol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100321016A CN101591442A (en) | 2009-07-09 | 2009-07-09 | A kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100321016A CN101591442A (en) | 2009-07-09 | 2009-07-09 | A kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101591442A true CN101591442A (en) | 2009-12-02 |
Family
ID=41406329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100321016A Pending CN101591442A (en) | 2009-07-09 | 2009-07-09 | A kind of binary macromolecular aqueous solution self-assembly forms the method for rod-shaped micelle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101591442A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792564A (en) * | 2010-03-04 | 2010-08-04 | 吉林大学 | Anti-scratch coating and preparation method thereof |
-
2009
- 2009-07-09 CN CNA2009100321016A patent/CN101591442A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792564A (en) * | 2010-03-04 | 2010-08-04 | 吉林大学 | Anti-scratch coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Naqvi et al. | Modification strategies for improving the solubility/dispersion of carbon nanotubes | |
| Huang et al. | Engineered PES/SPES nanochannel membrane for salinity gradient power generation | |
| Fujigaya et al. | Non-covalent polymer wrapping of carbon nanotubes and the role of wrapped polymers as functional dispersants | |
| Anjali et al. | Carbon-based hydrogels: synthesis and their recent energy applications | |
| Bo et al. | Morphology-controlled fabrication of polypyrrole hydrogel for solid-state supercapacitor | |
| Mallakpour et al. | Surface functionalization of carbon nanotubes: fabrication and applications | |
| Punetha et al. | Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene | |
| Giacalone et al. | New concepts and applications in the macromolecular chemistry of fullerenes | |
| Zou et al. | A general strategy to disperse and functionalize carbon nanotubes using conjugated block copolymers | |
| CN103897183B (en) | Binary carbon material-conductive composite nano-polymers air-sensitive film and preparation method thereof | |
| Peng et al. | Ferrocene-based supramolecular structures and their applications in electrochemical responsive systems | |
| Zou et al. | Cucurbit [8] uril‐Based Polymers and Polymer Materials | |
| Sun et al. | Supramolecular hybrids of carbon dots with doxorubicin: synthesis, stability and cellular trafficking | |
| Li et al. | Pillararene-based molecular-scale porous materials | |
| CN101811696B (en) | Graphene-supported cobaltosic oxide nano composite material and preparation method thereof | |
| CN100572267C (en) | A kind of oxidation modifying method of carbon nanotube | |
| CN104495780A (en) | Hydrophilic graphene-carbon nano-tube composite super-light elastic aerogel and preparation method thereof | |
| Cui et al. | Near-infrared absorbing amphiphilic semiconducting polymers for photoacoustic imaging | |
| Ahamed et al. | Biocompatible mediated bioanode prepared by using poly (3, 4-ethylene dioxythiophene) poly (styrene sulfonate)(PEDOT: PSS) and sulfonated graphene oxide integrated enzyme for biofuel cells applications | |
| CN103980122B (en) | Parents' post [5] aromatic hydrocarbons self-assembly forms vesica and the reversibility of depolymerization, the control method of controllability | |
| Choudhury et al. | High performance polymer chemical hydrogel-based electrode binder materials for direct borohydride fuel cells | |
| Amin et al. | Effects of chain length on the size, stability, and electronic structure of redox-active organic–inorganic hybrid polyoxometalate micelles | |
| CN102875978A (en) | Preparation method of gold nanoparticle/poly(3,4-dioxyethyl)thiophene (PEDOT) composite material | |
| Priyangga et al. | Morphology and topography studies of composite membranes developed from chitosan/phthaloyl chitosan consisting multi-walled carbon nanotube/montmorillonite as filler | |
| CN102532538A (en) | Size-controllable polypyrrole nano particle and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091202 |