CN101684179A - Double stimuli responsive type poly amino acid-based supermolecular reverse gel and method for preparing same - Google Patents
Double stimuli responsive type poly amino acid-based supermolecular reverse gel and method for preparing same Download PDFInfo
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- CN101684179A CN101684179A CN200910053747A CN200910053747A CN101684179A CN 101684179 A CN101684179 A CN 101684179A CN 200910053747 A CN200910053747 A CN 200910053747A CN 200910053747 A CN200910053747 A CN 200910053747A CN 101684179 A CN101684179 A CN 101684179A
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Abstract
The invention provides a double stimuli responsive type poly amino acid based supermolecular reverse gel used in the technical field of water gel and a method for preparing the same, wherein the method comprises the following steps of: synthesizing a linear poly(L-benzyl-glutaric acid ester)-polyethylene glycol diblock copolymer; preparing a poly(L-glutamic acid)-polyethylene glycol di-block copolymer used for forming the reverse gel; forming the supermolecular reverse micelle in which the alpha-cyclodextrin-polyethylene glycol complex serves an inner core and the poly(L-glutamic acid) servesa shell; and protonating the poly(L-glutamic acid) chain segments in an acid environment, forming crosslinking by using the mutual action of the hydrogen bonds between the poly(L-glutamic acid) chainsegments, and allowing the supermolecular reverse micelles to mutually gather to form the double stimuli responsive type poly amino acid-based supermolecular reverse gel at room temperature. Comparedwith the prior art, the elastic modulus of the gel is further improved, the gel system prepared by the method is damaged when the pH value of the gel system is higher than 8, the reverse gel can be formed again when the pH value of the gel system is adjusted to be 5, so that the pH value reversibility is good.
Description
Technical field
What the present invention relates to is chemical gel of a kind of chemical technology field and preparation method thereof, specifically is a kind of double stimuli responsive type poly amino acid-based supermolecular reverse gel and preparation method thereof.
Background technology
Different with chemical gel, the network structure in the supermolecular gel is to rely on weak interactions such as intermolecular hydrogen bonding, pi-pi accumulation, hydrophobic interaction and electrostatic interaction to form.And supramolecular hydrogel often produces bigger volume phase transition with variations such as external environment such as temperature, pH value, solvent, electromagnetic field or chemical substances.At present, supramolecular hydrogel is subjected to paying close attention to widely at aspects such as medicine sustained release, organizational project, intelligent material, biosensor, enzyme immobilizations.Based on temperature and pH value is two important factors in the physiological condition, therefore, design with construct supramolecular hydrogel and have important scientific meaning with temperature and the dual sensitivity characteristic of pH value, and will have important application prospects at medicine/gene transmission, regenerative medicine etc.
Through retrieval, do not find the similar prior art in this area to prior art.
Summary of the invention
The invention provides a kind of preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel, adopt relatively low one-tenth gum concentration to construct physicals gel preferably, compared with prior art the gel elastomer modulus is further enhanced, it is just destroyed greater than 8 o'clock in the pH value to prepare the gained gelling system simultaneously, when regulating pH value to 5 once more, reverse gel can form again again, has good pH value reversibility.
The present invention is achieved by the following technical solutions:
The present invention relates to the double stimuli responsive type poly amino acid-based supermolecular reverse gel, its component is poly-(L-L-glutamic acid)-polyoxyethylene glycol di-block copolymer (PLG
35-b-PEO), molecular formula is C
372H
708N
38O
220
The present invention relates to the preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel, may further comprise the steps:
The first step, utilize an end to have the polyoxyethylene glycol (PEO-NH of active amine
2) as the ring-opening polymerization of macromole evocating agent initiation γ-benzyl-L-L-glutamic acid-N-carboxylic acid (BLG-NCA), synthetic line style is gathered (L-benzyl-glutamate)-polyoxyethylene glycol (PBLG-b-PEO) di-block copolymer, concrete steps comprise:
(1) takes by weighing PEO-NH
2(80mg 0.016mmol) is dissolved in the N of 0.5mL, and in the dinethylformamide, dissolution process carries out in the test tube of sealing, vacuumizes logical nitrogen 3 times;
(2) (175mg 0.672mmol) places the 25mL flask, adds 1.5mLN, and dinethylformamide fully dissolves, and execution vacuumizes logical nitrogen operation 3 times to take by weighing BLG-NCA;
(3) pipette PEO-NH in the test tube with disposable syringe
2Solution, and join rapidly in the flask that is dissolved with BLG-NCA, in reaction sedimentation in the 20mL ether after 24 hours under the room temperature, obtain poly-(L-benzyl-glutamate)-polyoxyethylene glycol di-block copolymer (PBLG of line style
35-b-PEO) 201mg, 0.016mmol, transformation efficiency are 82%.
Second goes on foot, utilizes acetic acid (CH
3COOH) and Hydrogen bromide (HBr) mixed system, take off PBLG segment benzyl after, obtain being used to form poly-(L-L-glutamic acid)-polyoxyethylene glycol (PLG-b-PEO) di-block copolymer of reverse gel, concrete steps comprise:
(1) in the 25mL flask, adds 200mg, the PBLG of 0.016mmol
35-b-PEO, and add 7mLCH
3COOH, dissolving moments later adds 0.41g, the HBr of 0.7mL in 48 ℃ of oil baths;
(2) flask is placed 48 ℃ of oil baths react 18h, in ether, obtain 130mg, the PLG of 0.014mmol after the sedimentation
35-b-PEO, its productive rate are 85%.
The mol ratio of described HBr and benzyl is 9.2: 1;
The 3rd step, employing polyglutamic acid segment massfraction dissolve it in the alkaline environment of pH=8 earlier greater than poly-(L-L-glutamic acid)-polyoxyethylene glycol of 45% fully, then by α-CD and the effect of PEG segmental host-guest envelope, under the supramolecule effect, be gathered into the micella kernel, and the intersegmental repulsive interaction owing to its negative ion of PLG chain constitutes the micella shell, being assembled into α-CD-PEG complex compound thus is kernel, and PLG is the supermolecular reverse micella of shell;
The alkaline environment of described pH=8 is meant that the 3mol/L NaOH solution by each dropping 12 μ L～70 μ L is adjusted to 8 until the pH value.
The 4th the step, system pH is adjusted to 5, the PLG segment is protonated under sour environment, form crosslinkedly by the intersegmental interaction of hydrogen bond of PLG chain, cause supermolecular reverse micella to assemble the back mutually and under room temperature, form the double stimuli responsive type poly amino acid-based supermolecular reverse gel.
Described system pH be adjusted to 5 be meant by each dropping concentration be 3mol/L HCl solution until pH to being adjusted to 5.
The present invention has constructed the polyglutamic acid based supermolecular reverse gel by alpha-cylodextrin and intersegmental envelope mating reaction and the intersegmental interaction of hydrogen bond of PLG chain of PEG chain, and its preparation method is easy, and gel becomes glue speed fast; Proposed the construction method of supermolecular reverse gel first, reverse gel can form under slightly acidic environment fast; The physical and chemical performance of gel and reverse gel all can be by regulating as the concentration of polyglutamic acid multipolymer, the concentration of alpha-cylodextrin and the topological framework of polymkeric substance jointly; Poly amino acid-based supermolecular reverse gel has pH value and temperature dual susceptibility.
Description of drawings
Fig. 1 is the embodiment synoptic diagram.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1: preparation line style poly amino acid-based supermolecular reverse gel
Utilize an end to have the polyoxyethylene glycol (MPEO-NH of active amine
2) as the ring-opening polymerization of macromole evocating agent initiation γ-benzyl-L-L-glutamic acid-N-carboxylic acid (BLG-NCA), utilize acetic acid (CH again
3COOH) and Hydrogen bromide (HBr) mixed system, take off PBLG segment benzyl after, obtain being used to form poly-(the L-L-glutamic acid)-polyoxyethylene glycol (PLG of reverse gel
35-b-PEO) di-block copolymer, its arm length is 35 repeating units.
Adopt above-mentioned di-block copolymer (PLG
35-b-PEO 40mg) joins a 5mL volumetric flask that contains magneton, adds the 1mL deionized water, stirs the post polymerization thing and does not dissolve, and the solution muddiness has small amount of precipitate; Microsyringe is measured 12 μ L 3mol/L NaOH solution, makes its pH～8, and this moment, the system clear added 60mg α-CD then under vigorous stirring, stirred the ultrasonic 5min in back, and system has slight muddiness, as shown in Figure 1; To wherein adding 3mol/L HCl solution, each 5 μ L that add, regulate pH～5, stir the back system and in 2min, change the oyster white muddiness into, be transferred to 25 ℃ of constant temperature oil baths and leave standstill, form the oyster white gel as shown in Figure 1 behind the 5min, gel can overcome gravity and be inverted, the massfraction of this gelling system polymkeric substance is 3.6wt%, and α-CD massfraction is 5.4wt%.
In the above-mentioned reverse gel system, the shared massfraction of polymkeric substance and α-CD is all low than concentration of component of the prior art, the Young's modulus of gained reverse gel (G ') value is about 27000Pa, has good physicals, compared with prior art the gel elastomer modulus wants big, therefore, present embodiment adopts relatively low one-tenth gum concentration to construct physicals gel preferably;
It is just destroyed greater than 8 o'clock in the pH value that the while present embodiment prepares the gained gelling system, and when regulating pH value to 5 once more, reverse gel can form again again, has good pH value reversibility.
Embodiment 2: preparation has the poly amino acid-based supermolecular reverse gel of eight arms
Utilize an end to have the methoxy poly (ethylene glycol) (MPEO-D of 8 support arm amino
3) as the ring-opening polymerization of macromole evocating agent initiation γ-benzyl-L-L-glutamic acid-N-carboxylic acid (BLG-NCA), utilize acetic acid (CH again
3COOH) and Hydrogen bromide (HBr) system, take off after the PBLG segment benzyl protection, obtain being used to form poly-(the L-L-glutamic acid)-polyoxyethylene glycol (D3-PBLG of eight arms of reverse gel
13-b-PEO) di-block copolymer, its arm length is 13 repeating units.
Adopt above-mentioned di-block copolymer (D3-PLG
13-b-PEO 40mg) joins a 5mL volumetric flask that contains magneton, adds the 1mL deionized water, stirs the post polymerization thing and does not dissolve, and the solution muddiness has small amount of precipitate; Microsyringe is measured 70 μ L 3mol/L NaOH solution, makes its pH=8, and this moment, the system clear added 54mg α-CD then under vigorous stirring, stirred the ultrasonic 5min in back, and system has slight muddiness; To wherein adding 3mol/L HCl solution, each 5 μ L that add, regulate pH=5, stir the back system and in 2min, change the oyster white muddiness into, being transferred to 25 ℃ of constant temperature oil baths leaves standstill, form the oyster white gel behind the 12min, the massfraction of this gelling system polymkeric substance is 3.6wt%, and α-CD massfraction is 4.9wt%.
In the above-mentioned reverse gel system, the shared massfraction of polymkeric substance and α-CD is all low than concentration of component of the prior art, the Young's modulus of gained reverse gel (G ') value is about 30000Pa, has good physicals, line style reverse gel Young's modulus than example 1 is big, therefore, has constructed physicals gel preferably with relatively low one-tenth gum concentration, and, improved the Young's modulus of gel by introducing branched structure; Simultaneously, this gelling system is just destroyed greater than 8 o'clock in the pH value, and during re-adjustment pH value to 5, reverse gel can form again again, also has good pH value reversibility.
Claims (7)
1, a kind of double stimuli responsive type poly amino acid-based supermolecular reverse gel is characterized in that, its component is poly-(L-L-glutamic acid)-polyoxyethylene glycol di-block copolymer, and molecular formula is C
372H
708N
38O
220
2, a kind of preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel according to claim 1 is characterized in that, may further comprise the steps:
The first step, utilize polyoxyethylene glycol that an end has an active amine to cause the ring-opening polymerization of γ-benzyl-L-L-glutamic acid-N-carboxylic acid, poly-(L-benzyl-glutamate)-polyoxyethylene glycol di-block copolymer of synthetic line style as macromole evocating agent;
Second step, utilize acetic acid and Hydrogen bromide mixed system, take off poly benzyl glutamate segment benzyl after, obtain being used to form poly-(L-the L-glutamic acid)-polyoxyethylene glycol di-block copolymer of reverse gel;
The 3rd step, employing polyglutamic acid segment massfraction dissolve it in the alkaline environment of pH=8 earlier greater than poly-(L-L-glutamic acid)-polyoxyethylene glycol of 45% fully, host-guest envelope effect by alpha-cylodextrin and polyoxyethylene glycol segment then, under the supramolecule effect, be gathered into the micella kernel, constitute the micella shell and gather the intersegmental repulsive interaction of (L-L-glutamic acid) chain owing to its negative ion, being assembled into alpha-cylodextrin-polyoxyethylene glycol complex compound thus is kernel, and poly-(L-L-glutamic acid) is the supermolecular reverse micella of shell;
The 4th the step, system pH is adjusted to 5, poly-(L-L-glutamic acid) segment is protonated under sour environment, form crosslinkedly by the poly-intersegmental interaction of hydrogen bond of (L-L-glutamic acid) chain, cause supermolecular reverse micella to assemble the back mutually and under room temperature, form the double stimuli responsive type poly amino acid-based supermolecular reverse gel.
3, the preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel according to claim 2 is characterized in that, described the first step concrete steps comprise:
(1) take by weighing 80mg, the polyoxyethylene glycol macromole evocating agent of 0.016mmol is dissolved in the N of 0.5mL, and in the dinethylformamide, dissolution process carries out in the test tube of sealing, vacuumizes logical nitrogen 3 times;
(2) take by weighing 175mg, γ-benzyl of 0.672mmol-L-L-glutamic acid-N-carboxylic acid places the 25mL flask, adds 1.5mL N, and dinethylformamide fully dissolves, and execution vacuumizes logical nitrogen operation 3 times;
(3) pipette polyoxyethylene glycol initiator solution in the test tube with disposable syringe, and join rapidly in the flask that is dissolved with γ-benzyl-L-L-glutamic acid-N-carboxylic acid, in reaction sedimentation in the 20mL ether after 24 hours under the room temperature, obtain poly-(L-benzyl-glutamate)-polyoxyethylene glycol di-block copolymer 201mg of line style, 0.016mmol transformation efficiency is 82%.
4, the preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel according to claim 2 is characterized in that, the described second step concrete steps comprise:
(1) add 200mg in the 25mL flask, the line style of 0.016mmol is gathered (L-benzyl-glutamate)-polyoxyethylene glycol di-block copolymer, and adds 7mL acetic acid, and dissolving moments later adds 0.41g, the Hydrogen bromide of 0.7mL in 48 ℃ of oil baths;
(2) flask is placed 48 ℃ of oil baths react 18h, in ether, obtain 130mg after the sedimentation, poly-(L-L-glutamic acid)-polyoxyethylene glycol di-block copolymer of 0.014mmol, its productive rate is 85%.
5, the preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel according to claim 2 is characterized in that, the mol ratio of Hydrogen bromide described in the first step and benzyl is 9.2: 1.
6, the preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel according to claim 2, it is characterized in that the alkaline environment of the pH=8 described in the 3rd step is meant that the 3mol/L sodium hydroxide solution by each dropping 12 μ L～70 μ L is adjusted to 8 until the pH value.
7, the preparation method of double stimuli responsive type poly amino acid-based supermolecular reverse gel according to claim 2, it is characterized in that, the 4th the step described in system pH be adjusted to 5 be meant by each dropping concentration be the 3mol/L hydrochloric acid soln until pH to being adjusted to 5.
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Cited By (7)
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| CN102964593A (en) * | 2012-12-17 | 2013-03-13 | 中国科学院长春应用化学研究所 | Block polymer, preparation method thereof and electrically active hydrogel |
| CN104592511A (en) * | 2015-01-19 | 2015-05-06 | 华东师范大学 | Hydrogel containing cyclodextrin and polyethylene glycol block polypeptide molecular brush as well as preparation method and application of hydrogel |
| CN104817548A (en) * | 2015-03-19 | 2015-08-05 | 郑州轻工业学院 | Small organic molecule capable of realizing visual and selective recognition of lithium hydroxide, sodium hydroxide and potassium hydroxide |
| CN104817548B (en) * | 2015-03-19 | 2017-12-01 | 郑州轻工业学院 | A kind of organic molecule that Selective recognition is visualized to lithium hydroxide, sodium hydroxide, potassium hydroxide |
| CN107556450A (en) * | 2016-06-30 | 2018-01-09 | 翁秋梅 | A kind of dynamic aggregation thing and application with hybrid cross-linked network |
| CN107556450B (en) * | 2016-06-30 | 2020-11-24 | 翁秋梅 | Dynamic polymer with hybrid cross-linked network and application thereof |
| CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
| CN109206620A (en) * | 2017-07-06 | 2019-01-15 | 香港理工大学深圳研究院 | Bionical water-responsive shape memory polyaminoacid material and preparation method thereof |
| CN109206620B (en) * | 2017-07-06 | 2021-08-20 | 香港理工大学深圳研究院 | Bionic water response shape memory polyamino acid material and preparation method thereof |
| CN108546308A (en) * | 2018-04-17 | 2018-09-18 | 华南理工大学 | Multiple response ionic gel and preparation method thereof based on super amphiphile, amphiphilic molecule |
| CN108546308B (en) * | 2018-04-17 | 2020-02-18 | 华南理工大学 | Multi-responsiveness ionic gel based on super-amphiphilic molecules and preparation method thereof |
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