CN104292475B - A kind of temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel and its preparation method and application - Google Patents
A kind of temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel and preparation method thereof, the secondary dendrimer (Me-G that the graft polymers PELG-g-(PNIPAM/ β-CD) NIPA and beta-schardinger dextrin-jointly modified modifies with diphenyl diimide2-Azo) soluble in water being mixed with obtain colloidal sol.The temperature sensitive photosensitive double-bang firecracker of the present invention should include the stimulating responsive to temperature and the stimulating responsive to light by poly-peptidyl Subjective and Objective composite intelligent hydrogel, easily prepared, in fields such as temperature control light-operated switch, the light-operated motor of temperature control, the light-operated drug releases of temperature control, there is wide application prospect.
Description
Technical field
The invention belongs to new material technology field, be specifically related to a kind of intelligent polymer material technology, relate more specifically to one
Temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel and its preparation method and application.
Background technology
Hydrogel is a very important soft material of class, has a wide range of applications in every field, and closes in recent years
Research in hydrogel is the most increasingly paid attention to by researcher.Cyclodextrin supramolecular hydrogel is that a new research is led in recent years
Territory.It is except having the fundamental characteristics of general hydrogel, such as characteristics such as biocompatibility, high-moisture, medicine carrying non-inactivations, goes back
There is self assembly and the molecular recognition properties of uniqueness, show good intelligent response, as temperature, light, pH value etc. stimulate
Response, thus conventional hydrogels is studied and will have the biggest impetus with application.By design regulation and control cyclodextrin derivative
And guest molecule, the structure of supramolecular hydrogel and intelligent can be controlled, thus meet the application requirement of different field.Li Li
Et al. substituted to alpha-cyclodextrin and mono amino diphenyl diimide is grafted on polyacrylic acid respectively, then both are compounded, utilize ring
The Binding ability of dextrin and the light sensitive characteristic of diphenyl diimide are prepared for a class and have the photo-sensitive hydrogel body of sol-gel phase in version behavior
System's (Chinese patent application: 201110359858.3).But this kind of aquogel system is the single stimuli responsive about photostimulation response
Intelligent aqueous gel capable, and the mutual conversion effect between sol-gel is macroscopically being showed the most substantially, and the biology of this system
The compatibility is the best.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes a kind of new temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent water
Gel, described hydrogel is a kind of novel double stimuli responsive intelligent aqueous gel capables, has obvious Thermo-sensitive and preferable heliosensitivity,
And there is good biocompatibility.
The temperature sensitive photosensitive double-bang firecracker that the present invention proposes should poly-peptidyl Subjective and Objective composite intelligent hydrogel, refer to that the Subjective and Objective containing poly-peptide is multiple
Closing intelligent aqueous gel capable system, it includes the secondary dendroid that graft polymers PELG-g-(PNIPAM/ β-CD) modifies with diphenyl diimide
Molecule (Me-G2-Azo)。
In the present invention, described water miscible dendrimer Me-G2-Azo be top be azo, end be that the dendroid of methyl is divided
Son, has good heliosensitivity and Thermo-sensitive (such as, its phase transition temperature is at about 60 DEG C).In the present invention, described water-soluble
The dendrimer Me-G of property2-Azo is the compound of a kind of novel structure, and its chemical structural formula is as with following formula (1) Suo Shi:
In the present invention, described graft polymers PELG-g-(PNIPAM/ β-CD) be side chain be NIPA
The graft polymers jointly modified with beta-schardinger dextrin-, its chemical structural formula is as with following formula (2) Suo Shi:
Wherein, the secondary dendrimer (Me-G that graft polymers PELG-g-(PNIPAM/ β-CD) modifies with diphenyl diimide2-Azo)
Concentration in aqueous must not be less than 0.05g/ml.
The temperature sensitive photosensitive double-bang firecracker of the present invention should poly-peptidyl Subjective and Objective composite intelligent hydrogel be a kind of temperature sensitive photosensitive double responsiveness hydrogel,
Including the stimulating responsive to temperature and the stimulating responsive to light；It has the beneficial effects such as good biocompatibility.
The temperature sensitive photosensitive double-bang firecracker of the present invention should poly-peptidyl Subjective and Objective composite intelligent hydrogel, when temperature is increased to 40 DEG C, colloidal sol change
For hydrogel, temperature is returned to room temperature, and gel breaks down returns back to collosol state；When temperature rises to 60 DEG C, there is precipitation in bottom,
Can not form gel, temperature returns back to room temperature, and system is again transformed into colloidal sol.
The temperature sensitive photosensitive double-bang firecracker of the present invention should poly-peptidyl Subjective and Objective composite intelligent hydrogel, be warming up to 40 DEG C formed hydrogels, protect
Holding temperature-resistant, the ultraviolet light using wavelength to be 365nm is after it is irradiated, and lucifuge is placed and be there will be gel-sol conversion；Again
The colloidal sol formed is irradiated by the visible ray using wavelength to be 450nm, stands and gel back again occurs.
The invention allows for a kind of noval chemical compound, it is the dendrimer Me-G that water miscible diphenyl diimide is modified2-Az, it is
Top be azo, end be the dendrimer of methyl, shown in its chemical structural formula such as formula (1):
The present invention also provide for a kind of temperature sensitive photosensitive double-bang firecracker should the preparation method of poly-peptidyl Subjective and Objective composite intelligent hydrogel, by poly-(N-
N-isopropylacrylamide) and the graft polymers PELG-g-(PNIPAM/ β-CD) that jointly modifies of beta-schardinger dextrin-modify with diphenyl diimide
Secondary dendrimer (Me-G2-Azo) soluble in water being mixed with obtain colloidal sol.
Preparation method of the present invention comprises the steps:
The first step, with Pidolidone and 2-chloroethyl alcohol as initial feed, passes sequentially through NCA (a-amino acid-N-carboxyl inner-acid anhydride) open loop
Polymerization, azido reaction and click chemistry reaction, prepare graft polymers PELG-g-(PNIPAM/ β-CD), its molecule
Shown in structural formula such as formula (2)；
Second step, formula (2) glycerol polymerization that NIPA obtained above and beta-schardinger dextrin-are modified jointly
Secondary dendrimer (the Me-G that thing PELG-g-(PNIPAM/ β-CD) modifies with the diphenyl diimide shown in formula (1)2-Azo) molten
Yu Shuizhong, is mixed with and obtains colloidal sol；It is further advanced by regulation variations in temperature and/or regulating illumination change, obtains temperature sensitive photosensitive
Double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel.
In the present invention, the colloidal sol that above-mentioned second step is obtained, by regulation variations in temperature, prepare the poly-peptidyl of temperature sensitive response
Subjective and Objective composite intelligent hydrogel.Wherein, described regulation variations in temperature is to carry out with the form of water bath with thermostatic control；Prepare molten under room temperature
Glue, when rising high-temperature to 40 DEG C, colloidal sol is changed into hydrogel, and temperature is returned to room temperature, and gel breaks down returns back to collosol state；
When temperature rises to 60 DEG C, there is precipitation in bottom, it is impossible to forming gel, temperature returns back to room temperature, and system is again transformed into colloidal sol.
In the present invention, the system of the colloidal sol obtained by above-mentioned second step is warming up to 40 DEG C and forms hydrogel, keeps temperature-resistant, institute
State regulating illumination to change i.e. by alternately irradiating ultraviolet light and visible ray, prepare photosensitive response poly-peptidyl Subjective and Objective composite intelligent
Hydrogel.Wherein, described alternately irradiating ultraviolet light and visible ray are that described gel is shone by the ultraviolet light with wavelength as 365nm
Penetrate until returning back to collosol state, then the radiation of visible light with wavelength as 450nm is until being transformed into gel.
The temperature sensitive photosensitive response poly-peptidyl Subjective and Objective composite intelligent hydrogel that the present invention prepares can realize the temperature sensitive of intelligent aqueous gel capable
The effect of photosensitive pair of stimuli responsive.
In the present invention, described graft polymers PELG-g-(PNIPAM/ β-CD) is prepared in the following manner: with Pidolidone with
2-chloroethyl alcohol is that initiation material prepares side base by NCA (a-amino acid-N-carboxyl inner-acid anhydride) ring-opening polymerisation and azido reaction and is
The PELG of azido, then use click chemistry reaction (Click) by the previously prepared PNIPAM (poly-N-isopropyl containing alkynes end group
Acrylamide) and the cyclodextrin functional molecular of band alkynyl be grafted on PELG main chain, thus obtain target product: PNIPAM
The graft polymers PELG-g-(PNIPAM/ β-CD) jointly modified with β-CD.Wherein, described poly-N-isopropyl acrylamide
(PNIPAM) it is to be prepared by Transfer Radical Polymerization (ATRP).
Specifically, the temperature sensitive photosensitive double-bang firecracker of the present invention should the preparation method of poly-peptidyl Subjective and Objective composite intelligent hydrogel include, by poly-(N-
N-isopropylacrylamide) and the graft polymers PELG-g-(PNIPAM/ β-CD) that jointly modifies of beta-schardinger dextrin-modify with diphenyl diimide
Secondary dendrimer (Me-G2-Azo) soluble in water being mixed with obtain colloidal sol.On the one hand, it is increased to 40 DEG C when temperature
Time, colloidal sol is changed into hydrogel, and temperature is returned to room temperature, and gel breaks down returns back to collosol state.When temperature rises to 60 DEG C, the end
There is precipitation in portion, it is impossible to forming gel, temperature returns back to room temperature, and system is again transformed into colloidal sol, thus prepares temperature sensitive sound
Ying Xingju peptidyl Subjective and Objective composite intelligent hydrogel；On the other hand, system is warming up to 40 DEG C and forms hydrogel, keep temperature not
Becoming, the ultraviolet light using wavelength to be 365nm is after it is irradiated, and lucifuge is placed and be there will be gel-sol conversion.Use wavelength again
For 450nm visible ray to formed colloidal sol irradiate, stand gel back occurs again, the present invention have preferable Thermo-sensitive and
Heliosensitivity.Thus prepare the poly-peptidyl Subjective and Objective composite intelligent aquogel system that a kind of novel temperature is controlled with illumination.
In one embodiment of the present invention, after obtaining colloidal sol, system temperature is increased to 40 DEG C, until colloidal sol is changed into hydrogel,
Temperature is returned to room temperature, and gel breaks down returns back to collosol state.When system temperature rises to 60 DEG C, there is precipitation in bottom, it is impossible to shape
Becoming gel, temperature returns back to room temperature, and system is again transformed into colloidal sol, obtains described temperature sensitive stimuli responsive poly-peptidyl Subjective and Objective and is combined
Intelligent aqueous gel capable.The hydrogel obtained by change liter high-temperature, reduction temperature sequence in implementation process of the present invention is respectively provided with well
Temperature sensitive performance.And repeat to implement the present invention and rise high-temperature and reduce temperature again 20 times, hydrogel still keeps good temperature sensitive performance.
In one embodiment of the present invention, system is warming up to 40 DEG C of ultraviolet lights obtained after hydrogel with wavelength as 365nm to institute
State gel to be irradiated until returning back to collosol state, then the radiation of visible light with wavelength as 450nm is until being transformed into gel,
To described photosensitive stimuli responsive poly-peptidyl Subjective and Objective composite intelligent hydrogel.In implementation process of the present invention by change ultraviolet light, can
See that the hydrogel that the radiation modality order of light obtains is respectively provided with good photosensitive property.And repeat to implement ultraviolet light of the present invention with visible
Light alternately exposes to 20 times, and hydrogel still keeps good photosensitive property.
In a specific embodiment, the temperature sensitive photosensitive double-bang firecracker of the present invention should the preparation side of poly-peptidyl Subjective and Objective composite intelligent hydrogel
Method, specifically includes following steps:
(1) graft polymers PELG-g-(PNIPAM/ β-CD) is prepared:
NCA (a-amino acid-N-carboxyl inner-acid anhydride) ring-opening polymerisation and Azide is passed through for initial feed with Pidolidone and 2-chloroethyl alcohol
Reaction prepares the PELG that side base is azido, then uses click chemistry reaction, adds in advance in 50mL reaction bulb
Preparation is containing the poly-N-isopropyl acrylamide (PNIPAM) (1.00g, 0.238mmol) of alkynes end group, the cyclodextrin merit of band alkynyl
Can molecule (mono-6-Propargyl-β-CD) (0.12g, 0.102mmol), PELG-N3(0.052g) and 10mL DMF,
Stir, under nitrogen atmosphere is protected, then add CuBr (0.041g, 0.28mmol) and part PMDETA (60 μ L).
React 72 hours under the conditions of keeping 50 DEG C.Stopped reaction, is spin-dried for DMF, adds dichloromethane, concentrates organic facies, in second
Precipitating in ether, sucking filtration, vacuum drying collection obtains white solid powder 0.91g, productivity 77.8%.Described graft polymers PELG-g-
(PNIPAM/ β-CD) is the graft polymers that side chain is NIPA and beta-schardinger dextrin-is modified jointly, step
(1) reaction scheme, as shown below:
(2) preparing temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel:
The secondary dendroid that the graft polymers PELG-g-(PNIPAM/ β-CD) step (1) prepared modifies with diphenyl diimide
Molecule (Me-G2-Azo) soluble in water being mixed with obtains colloidal sol.On the one hand, when temperature is increased to 40 DEG C, colloidal sol is changed into
Hydrogel, temperature is returned to room temperature, and system returns back to collosol state.When temperature rises to 60 DEG C, it is impossible to forming gel, temperature is returned
Multiple to room temperature, system is again transformed into colloidal sol, obtains described temperature sensitive response poly-peptidyl Subjective and Objective composite intelligent hydrogel；Another
Aspect, system is warming up to 40 DEG C formed hydrogels, keep temperature-resistant, use wavelength be 365nm ultraviolet light its shine
After penetrating, occur that gel-sol is changed.The visible ray using wavelength the to be 450nm again colloidal sol to being formed irradiates, and gel again occurs
Reply, obtain described photosensitive response poly-peptidyl Subjective and Objective composite intelligent aquogel system.
In preparation method of the present invention, the secondary dendroid that graft polymers PELG-g-(PNIPAM/ β-CD) modifies with diphenyl diimide is divided
Son (Me-G2-Azo) concentration in aqueous must not be less than 0.05g/ml.
Wherein, described cyclodextrin is beta-schardinger dextrin-.
Wherein, the described poly-N-isopropyl acrylamide containing alkynes end group (PNIPAM) and the cyclodextrin functional molecular of band alkynyl
The mol ratio of (mono-6-Propargyl-β-CD) is 1: 1.2～1.5.
Wherein, the described precipitant used in the reaction of graft polymers click chemistry of preparing is ether.
The invention allows for the temperature sensitive photosensitive response poly-peptidyl Subjective and Objective composite intelligent hydrogel that the method that is prepared as described above obtains.
The invention allows for temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel light-operated motor, light-operated switch,
The application in the fields such as light-operated drug release.
Beneficial effect of the present invention includes, utilizes the inclusion characteristic of cyclodextrin, the light isomery characteristic of diphenyl diimide and diphenyl diimide to modify
The temperature sensitive performance that secondary dendrimer is good with PNIPAM, being prepared for a kind of novel temperature sensitive photosensitive double-bang firecracker should poly-peptidyl host and guest
Bluk recombination intelligent aqueous gel capable system.The preparation method of subject hydrogel is easy, easily controllable, wherein synthesized glycerol polymerization
Thing, structure is unique, and good biocompatibility, bio-toxicity is low.Temperature and ultraviolet-visible are had by the hydrogel prepared by the method
There is the most double stimulating responsive.Subject hydrogel is applied widely, its most light-operated motor of optical element, light-operated switch,
The aspect tool wide application prospect such as light-operated drug release.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of the graft polymers PELG-g-(PNIPAM/ β-CD) of embodiment 1 preparation.
Fig. 2 is that in embodiment 3, temperature sensitive photosensitive double-bang firecracker should the scanning electron microscope (SEM) photograph of poly-peptidyl Subjective and Objective composite intelligent hydrogel.
Fig. 3 is that in embodiment 3, temperature sensitive photosensitive double-bang firecracker should G ', the G of poly-peptidyl Subjective and Objective composite intelligent hydrogel " and viscosity is with scanning
Frequency variation diagram；Fig. 3 A show in whole test frequency range the storage modulus (G ') of hydrogel be far longer than loss modulus (G "),
This just confirms the formation of inventive gel system；Fig. 3 B shows that the viscosity of gel increases along with the increase of shearing frequency, card
Bright its has the performance of shear thickening.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail, and the protection content of the present invention is not limited to
In following example.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage
All it is included in the present invention, and with appending claims as protection domain.Implement the process of the present invention, condition, examination
Agent, experimental technique etc., outside the lower content mentioned specially, be universal knowledege and the common knowledge of this area, the present invention
Content is not particularly limited.
The preparation method of a kind of temperature sensitive photosensitive response of the present invention poly-peptidyl Subjective and Objective composite intelligent hydrogel, comprises the steps:
(1) graft polymers PELG-g-(PNIPAM/ β-CD) is prepared
NCA (a-amino acid-N-carboxyl inner-acid anhydride) ring-opening polymerisation and Azide is passed through for initial feed with Pidolidone and 2-chloroethyl alcohol
Reaction prepares the PELG-N that side base is azido3, then use click chemistry reaction, add pre-in 50mL reaction bulb
First prepare the poly-N-isopropyl acrylamide (PNIPAM) (1.00g, 0.238mmol) containing alkynes end group, the cyclodextrin of band alkynyl
Functional molecular (mono-6-Propargyl-β-CD) (0.12g, 0.102mmol), PELG-N3 (0.052g) and 10mL DMF,
Stir, under nitrogen atmosphere is protected, then add CuBr (0.041g, 0.28mmol) and part PMDETA (60 μ L).
React 72 hours under the conditions of keeping 50 DEG C.Stopped reaction, is spin-dried for DMF, adds dichloromethane, concentrates organic facies, in second
Precipitating in ether, sucking filtration, vacuum drying collection obtains white solid powder 0.91g, productivity 77.8%.Finally obtain target product side
The graft polymers PELG-g-(PNIPAM/ β-CD) that chain is NIPA and beta-schardinger dextrin-is modified jointly.
Wherein, the poly-N-isopropyl acrylamide (PNIPAM) containing alkynes end group and the cyclodextrin functional molecular (mono-6-of band alkynyl
Propargyl-β-CD) mol ratio be 1: 1.2～1.5.
Wherein, preparing the precipitant used in the reaction of graft polymers click chemistry is ether.
The graft polymers PELG-g-(PNIPAM/ β-CD) that step (1) prepares is NIPA
The graft polymers jointly modified with beta-schardinger dextrin-.
(2) preparing temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel
Secondary dendrimer (the Me-G that graft polymers PELG-g-(PNIPAM/ β-CD) is modified with diphenyl diimide2-Azo)
Soluble in water being mixed with obtains colloidal sol.On the one hand, when temperature is increased to 40 DEG C, colloidal sol is changed into hydrogel, and temperature is replied
To room temperature, gel breaks down returns back to collosol state.When temperature rises to 60 DEG C, there is precipitation in bottom, it is impossible to form gel, temperature
Returning back to room temperature, system is again transformed into colloidal sol, thus prepares temperature sensitive response poly-peptidyl Subjective and Objective composite intelligent hydrogel；
On the other hand, system is warming up to 40 DEG C formed hydrogels, keep temperature-resistant, use wavelength be 365nm ultraviolet light its enter
After row irradiates, lucifuge is placed and be there will be gel-sol conversion.The visible ray using wavelength the to be 450nm again colloidal sol to being formed irradiates,
Standing and gel back again occur, the present invention has preferable Thermo-sensitive and heliosensitivity.Thus prepare a kind of novel temperature
The poly-peptidyl Subjective and Objective composite intelligent aquogel system controlled with illumination.
The temperature sensitive photosensitive double-bang firecracker prepared should poly-peptidyl Subjective and Objective composite intelligent hydrogel be a kind of double stimuli responsive intelligence water-setting
Glue, including the double stimuli responsive performance of temperature and illumination.Wherein, graft polymers PELG-g-(PNIPAM/ β-CD) and diphenyl diimide
Secondary dendrimer (the Me-G modified2-Azo) concentration in aqueous must not be less than 0.05g/ml.
Embodiment 1 prepares graft polymers PELG-g-(PNIPAM/ β-CD)
The present embodiment preparation process, as with shown in following formula (3):
NCA (a-amino acid-N-carboxyl inner-acid anhydride) ring-opening polymerisation and Azide is passed through for initial feed with Pidolidone and 2-chloroethyl alcohol
Reaction prepares the PELG-N that side base is azido3, then use click chemistry reaction, add pre-in 50mL reaction bulb
First prepare the poly-N-isopropyl acrylamide (PNIPAM) (1.00g, 0.238mmol) containing alkynes end group, the cyclodextrin of band alkynyl
Functional molecular (mono-6-Propargyl-β-CD) (0.12g, 0.102mmol), PELG-N3 (0.052g) and 10mL DMF,
Stir, under nitrogen atmosphere is protected, then add CuBr (0.041g, 0.28mmol) and part PMDETA (60 μ L).
React 72 hours under the conditions of keeping 50 DEG C.Stopped reaction, is spin-dried for DMF, adds dichloromethane, concentrates organic facies, in second
Precipitating in ether, sucking filtration, vacuum drying collection obtains white solid powder 0.91g, productivity 77.8%.Finally obtain target product side
The graft polymers PELG-g-(PNIPAM/ β-CD) that chain is NIPA and beta-schardinger dextrin-is modified jointly.1H-NMR(CDCl3, δ): nucleus magnetic hydrogen spectrum figure is it can be seen that the peak-to-peak signal of 6.49ppm is on graft polymers in PNIPAM
The signal peak (a) of the Hydrogen Proton of-NH-, and at 4.60ppm be on 6,7 hydroxyls of poly-peptide side chain beta-schardinger dextrin-H and
-COCH2CH2The signal peak of-(c), is-NH-CH-(i) on-CH-CO-(e) and side chain PNIPAM on poly-peptide main chain at 4.05ppm
Signal peak, H and-COCH on poly-3 carbon of peptide side-chain radical beta-schardinger dextrin-2CH2The signal peak of-(b) occurs in 3.75ppm
Place, occurs in that beta-schardinger dextrin-2, the Hydrogen Proton signal peak of 4,5,6 at 3.10 simultaneously.
The present embodiment product nuclear magnetic spectrogram is as shown in Figure 1, it is seen that prepare is i.e. poly-(the N-isopropyl acrylamide of target product
Amine) and the graft polymers PELG-g-(PNIPAM/ β-CD) that jointly modifies of beta-schardinger dextrin-.
Embodiment 2 prepares temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel
The secondary dendroid that the graft polymers PELG-g-(PNIPAM/ β-CD) embodiment 1 prepared modifies with diphenyl diimide
Molecule (Me-G2-Azo) soluble in water being mixed with obtain colloidal sol.System temperature is increased to 40 DEG C, and colloidal sol is changed into hydrogel,
Temperature is returned to room temperature, and gel breaks down returns back to collosol state.When system temperature rises to 60 DEG C, there is precipitation in bottom, it is impossible to shape
Becoming gel, temperature returns back to room temperature, and system is again transformed into colloidal sol, obtains described temperature sensitive stimuli responsive poly-peptidyl Subjective and Objective and is combined
Intelligent aqueous gel capable.The method identifying obtained photosensitive hydrogel is: sample bottle is inverted 5min, this system energy gram
Take gravity to be steady statue and occur without any flowing, thereby determine that and define the temperature sensitive stimuli responsive of the present invention poly-peptidyl Subjective and Objective again
Close intelligent aqueous gel capable.
System be warming up to 40 DEG C obtain hydrogel after ultraviolet light with wavelength as 365nm described gel is irradiated, return back to molten
Gluey state, then the radiation of visible light with wavelength as 450nm, system transition becomes gel, obtains the described poly-peptidyl of photosensitive stimuli responsive
Shown in Subjective and Objective composite intelligent hydrogel.The method identifying obtained photosensitive hydrogel is: be inverted by sample bottle
5min, this system can overcome gravity to be steady statue and occur without any flowing, thereby determines that defining photosensitive stimulation of the present invention rings
Should poly-peptidyl Subjective and Objective composite intelligent hydrogel.
The temperature sensitive photosensitive double-bang firecracker of embodiment 3 should poly-peptidyl Subjective and Objective composite intelligent hydrogel relevant characterization
Fig. 2 show the SEM photograph of the poly-peptidyl Subjective and Objective composite intelligent hydrogel formed.After lyophilization, this water
Gel present the most through loose structure, pore size is about about 10 μm.Be can be seen that to a certain degree by figure
Fragmentation with subside, this may with physical crosslinking active force impact relevant.
Additionally, the present invention characterizes the viscoelasticity behavior of this kind of Subjective and Objective composite intelligent hydrogel also by dynamic mechanical test,
As shown in Figure 3.As the viscoelastic gel systems of document report, by flow graph, this system is carried out dynamic frequency scanning,
In whole test frequency range, the storage modulus (G ') of hydrogel is far longer than loss modulus (G "), this just confirms the present invention
The formation of gel rubber system.And may certify that the Subjective and Objective composite intelligent hydrogel that the present invention constructs has preferable mechanical property, because of
This is advantageous as tissue engineering bracket etc..On the other hand it will be seen that the viscosity of hydrogel increases along with the increase of shearing frequency
Add, it was demonstrated that it has the performance of shear thickening, it was demonstrated that this Subjective and Objective compound system of the present invention belongs to dilatant fluid.
Claims (9)
1. a temperature sensitive photosensitive double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel, it is characterised in that it includes graft polymers
The secondary dendrimer Me-G that PELG-g-(PNIPAM/ β-CD) modifies with diphenyl diimide2-Azo；Wherein, described diphenyl diimide
The secondary dendrimer Me-G modified2-Azo is as shown in formula (1):
Described graft polymers PELG-g-(PNIPAM/ β-CD) is as shown in formula (2):
Temperature sensitive photosensitive double-bang firecracker the most as claimed in claim 1 should poly-peptidyl Subjective and Objective composite intelligent hydrogel, it is characterised in that described
The secondary dendrimer Me-G that graft polymers PELG-g-(PNIPAM/ β-CD) modifies with described diphenyl diimide2-Azo is at water
Concentration in solution must not be less than 0.05g/ml.
Temperature sensitive photosensitive double-bang firecracker the most as claimed in claim 1 should poly-peptidyl Subjective and Objective composite intelligent hydrogel, it is characterised in that work as temperature
When degree is increased to 40 DEG C, colloidal sol is changed into hydrogel, and temperature is returned to room temperature, and gel breaks down returns back to collosol state；Work as temperature
Degree rises to 60 DEG C, and precipitation occurs in bottom, it is impossible to forming gel, temperature returns back to room temperature, and system is again transformed into colloidal sol.
Temperature sensitive photosensitive double-bang firecracker the most as claimed in claim 1 should poly-peptidyl Subjective and Objective composite intelligent hydrogel, it is characterised in that by it
Being warming up to 40 DEG C and form hydrogels, keep temperature-resistant, the ultraviolet light using wavelength to be 365nm after it is irradiated, is kept away
Light is placed and be there will be gel-sol conversion；The visible ray using wavelength the to be 450nm again colloidal sol to being formed irradiates, and stands again
Secondary there is gel back.
5. a temperature sensitive photosensitive double-bang firecracker should the preparation method of poly-peptidyl Subjective and Objective composite intelligent hydrogel, it is characterised in that include as follows
Step:
The first step: with Pidolidone and 2-chloroethyl alcohol as initial feed, pass sequentially through NCA (a-amino acid-N-carboxyl inner-acid anhydride) open loop
Polymerization, azido reaction and click chemistry reaction, prepare the graft polymers PELG-g-shown in formula (2)
(PNIPAM/β-CD)；
Second step: the graft polymers PELG-g-that above-mentioned prepared NIPA and beta-schardinger dextrin-are modified jointly
The secondary dendrimer Me-G that (PNIPAM/ β-CD) modifies with the diphenyl diimide shown in formula (1)2-Azo mixing soluble in water
Prepare colloidal sol, changed by regulation variations in temperature and/or regulating illumination, obtain as claimed in claim 1 temperature sensitive photosensitive
Double-bang firecracker should poly-peptidyl Subjective and Objective composite intelligent hydrogel.
6. preparation method as claimed in claim 5, it is characterised in that the colloidal sol that described second step obtains by regulation variations in temperature,
Obtain temperature sensitive response poly-peptidyl Subjective and Objective composite intelligent hydrogel；Wherein, described regulation variations in temperature is with water bath with thermostatic control
Form is carried out；Preparing colloidal sol under room temperature, when rising high-temperature to 40 DEG C, colloidal sol is changed into hydrogel, and temperature is returned to room temperature,
Gel breaks down returns back to collosol state；When temperature rises to 60 DEG C, there is precipitation in bottom, it is impossible to form gel, and temperature is replied
To room temperature, system is again transformed into colloidal sol.
7. preparation method as claimed in claim 5, it is characterised in that the change of described regulating illumination refers to obtain described second step
Colloidal sol, be warming up to 40 DEG C formed hydrogels, keep temperature-resistant, by alternately irradiating ultraviolet light and visible ray, obtain light
Quick response poly-peptidyl Subjective and Objective composite intelligent hydrogel；Wherein, described alternately irradiating ultraviolet light and visible ray are to be with wavelength
Described gel is irradiated until returning back to collosol state by the ultraviolet light of 365nm, then the visible ray with wavelength as 450nm shines
Penetrate until being transformed into gel.
8. the temperature sensitive photosensitive response poly-peptidyl Subjective and Objective composite intelligent hydrogel that a method as described in claim 5 prepares.
Light-operated motor, light-operated prepared by temperature sensitive photosensitive response the most as claimed in claim 1 poly-peptidyl Subjective and Objective composite intelligent hydrogel
Application in switch, light-operated medicine.
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| CN105153864A (en) * | 2015-08-19 | 2015-12-16 | 中国科学院深圳先进技术研究院 | Photothermally-induced shape memory composite and preparation method thereof |
| CN106008754A (en) * | 2016-05-30 | 2016-10-12 | 昆明理工大学 | Mono-(6-propargylamino-deoxy)-beta-cyclodextrin function monomer and preparation method thereof |
| CN107022048B (en) * | 2017-05-22 | 2019-02-22 | 国家纳米科学中心 | A kind of temperature sensitive driver of macromolecular and its preparation method and application |
| CN107216468B (en) * | 2017-05-22 | 2019-06-07 | 华中科技大学 | A kind of supramolecular hydrogel and preparation method thereof |
| CN107474191A (en) * | 2017-08-29 | 2017-12-15 | 华南理工大学 | A kind of photoresponse type intelligent nano switch and preparation method and application |
| CN107759824B (en) * | 2017-11-13 | 2021-01-05 | 广州智妥科技有限公司 | Preparation method of automatic continuous expansion-contraction porous hydrogel actuator |
| CN107814973B (en) * | 2017-11-13 | 2021-01-05 | 广州智妥科技有限公司 | Preparation method of automatic continuous expansion-contraction porous hydrogel spheres |
| CN108484832B (en) * | 2018-04-17 | 2020-10-16 | 西北大学 | Preparation method of self-healing hydrogel with ultraviolet and pH sensitivity |
| CN109705368B (en) * | 2018-12-24 | 2021-03-23 | 西北师范大学 | Supermolecule based on benzimidazole iodonium salt and preparation method thereof |
| CN109897129B (en) * | 2019-03-18 | 2021-05-04 | 四川大学 | Method for self-assembling azophenyl micromolecule photo-control temperature-sensitive macromolecule PNIPAm in water |
| CN109970933B (en) * | 2019-03-28 | 2021-09-28 | 南京林业大学 | Amphiphilic block copolymer with temperature and light response in ionic liquid and preparation method thereof |
| CN110372887B (en) * | 2019-07-30 | 2022-01-28 | 西安石油大学 | Self-healing photoresponse supramolecular fluorescent hydrogel and preparation method and application thereof |
| CN117752850A (en) * | 2021-09-23 | 2024-03-26 | 齐鲁工业大学(山东省科学院) | Photosensitive and temperature-sensitive mixed antibacterial hydrogel |
| CN114558528B (en) * | 2022-02-06 | 2024-04-12 | 河南师范大学 | Preparation method of ionic liquid counter ion-mixed surfactant UV light and heat dual-response gel |
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