CN109897129A - The new method of the light-operated temperature sensitive macromolecule PNIPAm of azobenzene small molecule self assembly in water - Google Patents
The new method of the light-operated temperature sensitive macromolecule PNIPAm of azobenzene small molecule self assembly in water Download PDFInfo
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- CN109897129A CN109897129A CN201910203628.4A CN201910203628A CN109897129A CN 109897129 A CN109897129 A CN 109897129A CN 201910203628 A CN201910203628 A CN 201910203628A CN 109897129 A CN109897129 A CN 109897129A
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Abstract
The present invention provides a kind of more easy method realize light heat of the heat-sensible high polymer PNIPAm in water system can anti-phase be isolated from the respondent behavior of assembling, by photoresponse small molecule, heat-sensible high polymer and deionized water are blended, it realizes from the light-operated PNIPAm self assembly of small molecule isomery, and photoresponse is different from reported system, under the conditions of ultraviolet, PNIPAm self assembly aggregation；Radiation of visible light, PNIPAm dissolution.The photoresponse behavior more fits in drug release demand, is expected to really be applied to intellectual drug release field.
Description
Technical field
This patent provides small molecule photoresponse induction temperature sensitive polymer poly(N-isopropylacrylamide) (PNIPAm) certainly
A kind of new method of assembling.Using water-soluble azo phenyl small molecule isomery induce temperature sensitive macromolecule PNIPAm assemble in water and
The phase separation of dissolution, i.e., when radiation of visible light, PNIPAm is dissolved in water；And the PNIPAm aggregation analysis when ultraviolet light
Out, phase separation temperature is close to human body temperature (30 DEG C -45 DEG C).Compared to azobenzene functionalized polymeric, which is provided
The new method of one more simple control temperature sensitive polymer PNIPAm self assembly, and its photoresponse behavior and azobenzene are high
Molecular system is on the contrary, the biologic applications closer to PNIPAm require.
Background technique
Poly(N-isopropylacrylamide) (PNIPAm), as stimulating responsive " intelligence " polymeric families it is main at
LCST (Lower Critical Solution Temperature) lower critical solution temperature phenomenon is presented in member in aqueous solution,
I.e. low temperature is molten, high temperature is insoluble, simultaneously because it is used widely with good bio-compatibility, such as drug release, instead
Should control, ion identification, automatically cleaning driving etc..Wherein, photoresponse is since light is with remote controllability, non-contact exact positioning
The characteristics of and become the ideal intelligent switch in the fields such as medicine, intelligence, control.There is research by azobenzene photoresponse functional group
The side-chain structure of polymer P NIPAm is introduced, when ultraviolet irradiation, cis- polymeric system is dissolved in water, and when radiation of visible light
The trans- polymer is not soluble in water.But under the operating condition in more bio-pharmaceuticals release field, it is desirable that cis- polymerization
Object is not soluble in water, volume-diminished, opens conduction pathway, so that the further intelligent biological application of research is hindered.Though in addition,
Right azobenzene structure and content have important influence for photoresponse temperature and rate, but because of azobenzene polymerization inhibitor
Polymerization process is difficult to control, therefore restricts the further development of research.Therefore, the bottleneck of azo-based phenyl photoresponse development,
The quasi- photoresponse self-assembly system for proposing new method building PNIPAm of researcher: water-soluble azobenzene small molecule light is used
Control PNIPAm self assembly.
Applicant proposes earliest adjusts polymer poly (methyl-prop using the functionalized ionic liquid small molecule of azobenzene
Olefin(e) acid benzyl ester) the LCST phase separation of (PBnMA) and its derivative in ionic liquid.But not yet study small point of azobenzene
Son induces the self assembly of PNIPAm in water system, and being primarily due to azobenzene, dissolubility is very poor in water.Therefore research introduces
The structure of glyoxaline cation and hydrophilic anion modified azobenzene small molecule, makes it have hydrophily.Use the hydrophily
Small molecule isomery induced polymer self assembly, it has been found that azobenzene small molecule can realize that PNIPAm ultraviolet irradiation is insoluble, can
Light-exposed irradiation dissolution, and phase transition temperature, at 35-40 DEG C, the photoresponse with azobenzene polymerization system completely on the contrary, meet just
The requirement of drug release.In conclusion this patent is quasi- to propose a kind of new method building thermal response polymer P NIPAm
Meet the intelligent light-controlled phase-separated system of biologic applications, the development for srnart biomaterials is provided fundamental basis and experimental data.
Summary of the invention
The purpose of the present invention is to provide a kind of more easy method construct temperature sensitive macromolecule PNIPAm light in water/
Thermal reversion mutually separates respondent behavior.This method has raw material simple and easy to get, and preparation method is simple, and content is controllable, and response is rapidly, warm
Many advantages, such as degree is suitable for, is easier to realize scientific and technological conversion, is expected to provide scientific guidance and theory for the development of biological intellectual material
Foundation.
The PNIPAm polymer phase temperature containing azobenzene system reported before is lower, and ultraviolet dissolution, it is seen that
Light is precipitated, and is not suitable for the requirement of PNIPAm polymeric medicine delivery systme construction, and the structure by changing azobenzene, position
It sets, fails the photoresponse for changing PNIPAm system.Therefore, the requirement of Yao Shixian bio-pharmaceutical release, needs to change photic phase
The mechanism and composition of separation system construct.Research experience based on early period, small point of the water-soluble azobenzene of this research proposed adoption
Son is used as light responsive material, and PNIPAm constructs the new photosensitive temperature sensitive of PNIPAm as solvent as heat-sensible high polymer, deionized water
Smart system, each substance proportion of the present invention are as follows: the high molecular mass fraction of thermal response is 0-20wt%, and azobenzene is small
The mass fraction of molecule is 0-10wt%, remaining is deionized water.
Production method of the invention is achieved in that
(1) [the Azo-CH of certain mass is taken2-Imi4][BF4] or [Azo-CH2-Imi4][PF6], PNIPAm and deionization
Water is placed in weighing disk, and rotor is added, is sealed with sealed membrane, room temperature magnetic agitation 12h makes it sufficiently dissolve and be uniformly dispersed.
(2) it takes a small amount of solution in (1) to be placed on the glass slide with a thickness of 30 μm of grooves, gently covers another coverslip,
It is placed in thermal station, keeps the temperature 12h respectively under 20 DEG C of dark/ultraviolet irradiation conditions；Heating rate 1 DEG C/min, temperature range 20-
50℃；365nm, 15mw/cm is respectively adopted in light source2And 450nm, 30mw/cm2LED (Light Emitting Diode) it is cold
Light source irradiation measures the solution transmitance variation with temperature trend under different light conditions in conjunction with spectral investigator；Respectively
Take it is dark, ultraviolet under the conditions of the place 565nm, transmitance be the temperature at 80% as phase separation temperature, be denoted as trans- respectively
Tcp、cis-Tcp。
(3) it calculates and surveys ultraviolet poor with phase separation temperature under dark condition, the temperature of referred to as photic phase separation in (2)
Section (Δ Tcp).Alternately irradiated in the section by ultraviolet light and visible light, it can be achieved that the phased soln of PNIPAm with mutually separate
The photic phase-separated system of PNIPAm is successfully constructed in cyclic process.
The invention has the following advantages:
Material fabrication process of the invention is relatively simple, is not necessarily to azobenzene monomer polymerization, and simple small molecule is only needed to add
Photosensitive system can be constructed by adding.
The mutually separation of material phase transformation temperature range of the invention at 30-45 DEG C, under realizing from room temperature to higher temperature conditions
Temperature accuracy controlling.
Phase separation temperature of present invention under the conditions of ultraviolet is lower than the phase separation temperature under visible light conditions, and is reported before
Phase transformation law of the PNIPAm macromolecule in road in water system is opposite, and (phase transition temperature under the conditions of i.e. ultraviolet is higher than under visible light conditions
Phase transition temperature), be more suitable for biologic applications development requirement.
Detailed description of the invention
Fig. 1 is the phase separating mechanism figure of each case study on implementation；
Fig. 2 be case study on implementation 5 light heat responsive materials under different illumination conditions transmitance vary with temperature tendency chart；
Fig. 3 is phase transformation law figure of the case study on implementation 1-5 in the case where becoming PNIPAm concentration levels, under different illumination conditions；
Fig. 4 is case study on implementation 3,6-8 in change [Azo-CH2-Imi4][BF4] under concentration levels, the phase under different illumination conditions
Become rule figure；
Fig. 5 is the photo-induced reversible phase transformation figure at 38 DEG C of case study on implementation 6；
Specific embodiment
The present invention relates to a kind of light heat responsive materials and preparation method thereof, for clearer invention clearly of the invention
Purpose, technical solution and effect below will be further described invention, but should not be understood as to enforceable range of the present invention
Restriction.
Case study on implementation 1
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 5.00wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 0.20wt%.
Weigh 0.10g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 1.90g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 4.00mg PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Case study on implementation 2
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 5.00wt%, thermal response macromolecule (PNIPAm) is dense
Spend the light heat responsive materials of 1.00wt%.
Weigh 0.10g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 1.88g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 0.02g PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Case study on implementation 3
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 5.00wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 5.00wt%.
Weigh 0.20g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 3.60g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.0.2g PNIPAm is weighed to be dissolved in equipped with magnetic agitation
It in the above-mentioned solution of son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat sound
Answer material.
Case study on implementation 4
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 5.00wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 9.00wt%.
Weigh 0.10g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 1.72g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 0.18g PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Case study on implementation 5
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 5.00wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 15.00wt%.
Weigh 0.10g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 1.60g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 0.30g PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Case study on implementation 6
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 1.25wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 5.00wt%.
Weigh 0.03g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 1.88g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 0.10g PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Case study on implementation 7
Prepare photoresponse small molecule [Azo-CH2-Imi4][BF4] concentration 2.50wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 5.00wt%.
Weigh 0.05g [Azo-CH2-Imi4][BF4] be added in the weighing disk equipped with 1.85g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 0.10g PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Case study on implementation 8
Prepare photoresponse small molecule [Azo-CH2-Imi4] [BF4] concentration 3.75wt%, thermal response macromolecule (PNIPAm)
The light heat responsive materials of concentration 5.00wt%.
Weigh 0.08g [Azo-CH2-Imi4] [BF4] be added in the weighing disk equipped with 1.83g deionized water, it is placed in 50
Ultrasonic vibration 12h in DEG C constant-temperature ultrasonic washer, makes it be uniformly dispersed.It weighs 0.10g PNIPAm and is dissolved in and stirred equipped with magnetic force
It in the above-mentioned solution for mixing son, is sealed with sealed membrane, room temperature magnetic agitation 12h, keeps its fully dispersed uniformly, obtain a kind of light heat
Responsive materials.
Claims (3)
1. azobenzene small molecule regulation heat-sensible high polymer poly(N-isopropylacrylamide) PNIPAm self assembly in water is new
The general structure of method, the azobenzene small molecule and heat-sensible high polymer is as follows:
2. self assembly new method as described in claim 1, it is characterised in that: the light heat responsive materials are mainly by thermal response height
The photosensitive small molecule of molecule, azobenzene and water composition, it is 0- that each content of material, which is respectively as follows: the high molecular mass fraction of thermal response,
20wt%, and the mass fraction of azobenzene small molecule is 0-10wt%, remaining is deionized water.
3. the test result of self assembly new method as claimed in claim 2, it is characterised in that: use small point of water-soluble azo phenyl
Sub- isomery induces temperature sensitive macromolecule PNIPAm to assemble the phase separation with dissolution, the i.e. PNIPAm when radiation of visible light in water
It is dissolved in water；And the PNIPAm segregation when ultraviolet light, phase separation temperature close to human body temperature (30 DEG C -45 DEG C),
And its phase separation temperature can be changed by the mass fraction of each component to adjust.
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| CN201910203628.4A CN109897129B (en) | 2019-03-18 | 2019-03-18 | Method for self-assembling azophenyl micromolecule photo-control temperature-sensitive macromolecule PNIPAm in water |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0140376B1 (en) * | 1983-11-02 | 1991-01-23 | Ocg Microelectronic Materials, Inc. | Thermally stable positive resist |
| JPH05247709A (en) * | 1992-03-06 | 1993-09-24 | Sekisui Jushi Co Ltd | Artificial flower |
| CN102443199A (en) * | 2011-09-22 | 2012-05-09 | 四川大学 | Photoresponsive polymer microsphere system and preparation method thereof |
| CN104292475A (en) * | 2014-09-30 | 2015-01-21 | 华东师范大学 | Temperature-sensitive and photosensitive dual-response polypeptide based host-guest composite intelligent hydrogel as well as preparation method and application thereof |
-
2019
- 2019-03-18 CN CN201910203628.4A patent/CN109897129B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0140376B1 (en) * | 1983-11-02 | 1991-01-23 | Ocg Microelectronic Materials, Inc. | Thermally stable positive resist |
| JPH05247709A (en) * | 1992-03-06 | 1993-09-24 | Sekisui Jushi Co Ltd | Artificial flower |
| CN102443199A (en) * | 2011-09-22 | 2012-05-09 | 四川大学 | Photoresponsive polymer microsphere system and preparation method thereof |
| CN104292475A (en) * | 2014-09-30 | 2015-01-21 | 华东师范大学 | Temperature-sensitive and photosensitive dual-response polypeptide based host-guest composite intelligent hydrogel as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHENG WANG ET AL: "Photo- and thermo-responsive multicompartment hydrogels for synergistic delivery of gemcitabine and doxorubicin", 《JOURNAL OF CONTROLLED RELEASE》 * |
| 罗春华等: "温度和光双重敏感的含偶氮苯端基的聚N-异丙基丙烯酰胺研究", 《高分子学报》 * |
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