CN112742300A

CN112742300A - CO containing disulfide bond2/N2And redox stimulus response type worm micelle system and preparation method thereof

Info

Publication number: CN112742300A
Application number: CN202011603999.0A
Authority: CN
Inventors: 蒋建中; 张建新; 徐倩倩
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2020-12-29
Filing date: 2020-12-29
Publication date: 2021-05-04

Abstract

The invention discloses a CO containing disulfide bond₂/N₂And a redox stimuli-responsive worm micellar system and a preparation method thereof, the preparation method comprising: adding an anionic surfactant into the cystamine-based bicarbonate mother liquor, and stirring until the anionic surfactant is completely dissolved to obtain the worm micelle system; wherein the anionic surfactant is C₆～C₁₈Mono-or di-long-chain alkyl radicals, straight-or branched, saturated or unsaturated, with or without aromatic ringsAnd one or a mixture of more of sulfate, sulfonate, carboxylate and phosphate. Disulfide bond-containing CO of the present invention₂/N₂And redox stimuli responsive worm micellar system with CO-pairing properties₂/N₂Redox stimuli responsiveness; the raw materials are simple in composition and low in price, and complicated steps such as organic synthesis, separation and purification and the like are not needed; the formed worm micelle has high viscosity and has great application prospect in the fields of fracturing fluid, material preparation, drug release and the like.

Description

Containing disulfide bondCO2/N2And redox stimulus response type worm micelle system and preparation method thereof

Technical Field

The invention relates to a CO containing disulfide bond₂/N₂And a redox stimulus response type worm micelle system and a preparation method thereof, belonging to the technical field of colloid and interface chemistry.

Background

Wormlike micelles (wormlike micelles) are one of the association structures of amphiphilic molecules in aqueous solution. When the surfactant is self-assembled in solution after increasing the solution concentration or adding a counter-ion salt, the formed flexible network-like structure micelles, which exhibit significant viscoelastic properties similar to flexible polymers, are a model of "equilibrium polymers" (or "living" polymers) that can be repeatedly broken down and formed to extend the linear structure. In the last two decades, wormlike micelles have attracted great interest, and the research range is continuously expanded from theoretical research to industrial technical application, such as a large number of application examples in the relevant fields of heat carriers, hard surface cleaners, drag reducers, petroleum fracturing fluids, solid delivery, personal care products and the like.

The classification into single-component worm-like micelles and multi-component worm-like micelles is based on the component constituting the worm-like micelle system. The surfactant with a special geometric structure can spontaneously form worm-like micelles at a specific temperature or concentration by virtue of non-covalent bond forces such as hydrogen bonds, van der waals forces, hydrophobic forces and the like. The most widely used wormlike micellar systems contain long aliphatic chain cationic surfactants such as octadecyl trimethyl ammonium bromide.

Compared with the traditional wormlike micelle system, the environment stimulation response type wormlike micelle can control the formation or the destruction of the wormlike micelle by changing the external environment of the solution, and realize the controllable change of the viscoelastic performance macroscopically. The redox reaction process occurs continuously in every living body, so the redox response mechanism has good biocompatibility. In 2017, Zhang et al synthesized a novel selenium-containing surfactant (C)₁₁-Se-C₁₁) And constructs a worm-like micelle containing a redox stimulus response mechanism with a conventional surfactant CTAB in the market. By redox reaction between selenium and selenium ether, C₁₁-Se-C₁₁The CTAB system can reversibly switch between worm and rod micelles more than three times. In 2018, Zhang et al used sodium dodecyl sulfate propyl sulfate (SDSePS) and tertiary benzyl amine (BTA) for the first time to construct worm-like micelles containing redox switch response. In the SDSePS-BTA system, the state of the SDSePS hydrophilic head group is changed through oxidation-reduction reaction, so that reversible formation and destruction of worm-like micelles are realized.

Disulfide bonds (-S-S-) are widely present in biological macromolecules and proteins, have certain oxidation-reduction property, can be broken in a reducing environment to form sulfhydryl groups, and have good biocompatibility and biodegradability, and the breakage of disulfide bonds is a hot point of research in the aspect of drug release and tumor treatment. Fan et al and Mizuhashi et al can control the self-assembled morphology of surfactants by the cleavage and reformation of disulfide bonds after the introduction of disulfide bonds in the surfactant molecule. Asakawa et al have synthesized a dithiogemini surfactant [ C₁₂H₂₅N(CH₃)₂CH₂CH₂S-SCH₂CH₂N(CH₃)₂C₁₂H₂₅]2Br (abbreviation C)₁₂SSC₁₂) And the micellization behavior and redox reversibility of disulfide bonds were investigated. In the presence of a reducing agent, C₁₂SSC₁₂In (2) disulfide bond cleavage to form monomeric surfactant [ C ]₁₂H₂₅N(CH₃)₂CH₂CH₂SH]Br (abbreviation C)₁₂SH). The responsive aggregate containing disulfide bonds has great significance for drug delivery and release, so that the redox-responsive wormlike micelle has wider research space. The disulfide surfactant needs to be subjected to multiple steps of organic synthesis and separation and purification, and has the problems of high cost and the like.

Many studies on environment-responsive worm micelles have been reported in the literature, but few studies have been reported on the construction of environment-responsive worm micelles using inexpensive organic compounds. The adoption of cheap organic compounds is beneficial to reducing the use cost of the worm micelle, avoids complicated organic synthesis and separation and purification steps, and has important significance for developing potential applications in the fields of drag reducers, petroleum fracturing fluids, solid delivery, personal care products and the like.

Disclosure of Invention

The technical problem to be solved by the invention is to provide CO containing disulfide bond₂/N₂And redox stimuli-responsive worm micellar systems.

In order to solve the technical problems, the invention provides the following technical scheme:

in a first aspect, the present invention provides a CO containing disulfide bonds₂/N₂And a method for preparing a redox stimuli-responsive worm micellar system, comprising:

adding an anionic surfactant into the cystamine bicarbonate mother liquor, and stirring until the anionic surfactant is completely dissolved to obtain the worm micelle system;

wherein the anionic surfactant is C₆～C₁₈One or more of sulfate, sulfonate, carboxylate and phosphate of linear or branched, saturated or unsaturated, and mono-or di-long-chain alkyl containing or not containing aromatic ring.

Further, the anionic surfactant includes, but is not limited to, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecylcarboxylate.

Further, the cystamine bicarbonate includes, but is not limited to, cystamine bicarbonate, N '-tetramethylcystamine bicarbonate, N' -tetraethylcystamine bicarbonate, N '-tetrapropylcystamine bicarbonate, and one or more mixtures of N, N' -tetrabutylcystamine bicarbonate.

Further, the cystine bicarbonate is prepared from CO₂Introducing water soluble solution containing one or more of cystamine, N, N, N ', N' -tetramethyl cystamine, N, N, N ', N' -tetraethyl cystamine, N, N, N ', N' -tetrapropyl cystamine and N, N, N ', N' -tetrabutyl cystamineFormed in the liquid.

Furthermore, in the worm micelle system, the molar concentration of the cystine-based bicarbonate is 20-200 mmol/L, and the molar concentration of the anionic surfactant is 30-600 mmol/L.

In a second aspect, the invention also provides the CO containing the disulfide bond prepared by the method₂/N₂And redox stimuli-responsive worm micellar systems.

Further, nitrogen is introduced into the wormlike micelles, and when the wormlike micelles are heated to above 40 ℃, the wormlike micelles are completely disintegrated; when carbon dioxide is introduced, the wormlike micelle system recovers.

Further, adding a reducing agent into the worm micelle system, and decomposing worm-like micelles; after addition of the reducing agent, the wormlike micellar system is restored.

Further, the reducing agent includes, but is not limited to, dithiothreitol, glutathione, sodium dithionite, vitamin C, sodium borohydride, potassium borohydride, lithium aluminum hydride, and one or a mixture of more of sulfurous acid, and the addition amount is 0.5-3.0 times of the mole number of the cystine bicarbonate.

Further, the oxidant includes but is not limited to benzoyl peroxide, hydrogen peroxide, potassium permanganate, potassium dichromate, potassium permanganate, fuming sulfuric acid, lead dioxide, sodium bismuthate, periodic acid, cobalt trifluoride, sodium ferrate, sodium hypochlorite, sodium persulfate and potassium persulfate, and the addition amount is 0.5-3.0 times of the mole number of the cysteamine bicarbonate.

In a third aspect, the invention also provides a preparation method of the pH-responsive wormlike micelle system, which specifically comprises the following steps: adding a cystamine compound into one or a mixture of more of hydrochloric acid, sulfuric acid and phosphoric acid to form a cystamine-based salt, and mixing the cystamine-based salt with an anionic surfactant to obtain a pH-responsive vermicular micelle system.

Wherein, the cystamine compound includes but is not limited to one or a mixture of several of cystamine, N, N, N ', N' -tetramethyl cystamine, N, N, N ', N' -tetraethyl cystamine, N, N, N ', N' -tetrapropyl cystamine and N, N, N ', N' -tetrabutyl cystamine.

The above anionic surfactant is C₆～C₁₈One or more of sulfate, sulfonate, carboxylate and phosphate of linear or branched, saturated or unsaturated, and mono-or di-long-chain alkyl containing or not containing aromatic ring. For example, the anionic surfactant may be sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecylcarboxylate.

The wormlike micelle system has pH responsiveness, and when the pH is more than 10.24, the wormlike micelle is disintegrated; when pH <6, wormlike micelles recover.

Compared with the prior art, the invention has the beneficial effects that:

the worm micelle system with disulfide bond and stimulus response of the invention has the function of resisting CO₂/N₂And redox dual stimuli responsiveness; the raw materials are simple in composition and low in price, and complicated steps such as organic synthesis, separation and purification and the like are not needed; the formed worm micelle has high viscosity, and has important significance for the application of the worm micelle in the fields of drag reducers, petroleum fracturing fluids, solid conveying, personal care products and the like.

Drawings

FIG. 1 is a photograph of an appearance: (a) photographs of the appearance of an aqueous solution of TMCDD (100 mM); (b) photographs of the appearance of an aqueous SDS (300mM) solution; (c) photographs of the appearance of a binary solution of TMCDD-SDS (100/300 mM);

FIG. 2 is a response appearance diagram of TMCDD-SDS vermicular micelle solution sequentially added with introduced nitrogen and carbon dioxide;

FIG. 3 shows TMCDD-SDS vermicular micelle solution CO₂/N₂A steady-state rheogram (a) and a dynamic rheogram (b) before and after the response;

FIG. 4 is a diagram showing the response appearance of TMCDD-SDS vermicular micelle solution before and after addition of a reducing agent;

FIG. 5 is a steady-state rheogram (a) and a dynamic rheogram (b) before and after adding a reducing agent into TMCDD-SDS worm-like micelles;

FIG. 6 is a cryo-TEM image of TMCDD-SDS solution under different conditions: (a) before the stimulus response; (b) after the nitrogen stimulates the response; (c) after the response of the reduction stimulus;

fig. 7 is an appearance graph of the response of the pH-responsive vermicular micelle system of example 9 at pH 5.42(a) and pH 10.24 (b);

wherein TMCDD is the abbreviation of N, N, N ', N' -tetramethyl cystamine bicarbonate, and SDS is the abbreviation of sodium dodecyl sulfate.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.

₂ ₂Preparation of CO/N and redox stimulus responsive worm micelle system

Example 1

Introducing carbon dioxide into the cystamine aqueous solution to form a cystamine bicarbonate aqueous solution; adding sodium dodecyl sulfate into a cystamine bicarbonate aqueous solution, wherein the concentration of cystamine is 20-200 mmol, the concentration of sodium dodecyl sulfate is 30-600 mmol/L, and completely dissolving to obtain a vermicular micelle system.

Example 2

Introducing carbon dioxide into the N, N, N ', N' -tetramethyl cystamine aqueous solution to form an N, N, N ', N' -tetramethyl cystamine bicarbonate aqueous solution; adding sodium dodecyl sulfate into the N, N, N ', N' -tetramethyl cystamine bicarbonate aqueous solution, wherein the concentration of the N, N, N ', N' -tetramethyl cystamine is 20 mmol-200 mmol, the concentration of the sodium dodecyl sulfate is 30-600 mmol/L, and obtaining a vermicular micelle system after complete dissolution, as shown in figure 1 (c).

Example 3

Introducing carbon dioxide into the N, N, N ', N' -tetramethyl cystamine aqueous solution to form an N, N, N ', N' -tetramethyl cystamine bicarbonate aqueous solution; adding sodium dodecyl benzene sulfonate into the N, N, N ', N' -tetramethyl cystamine bicarbonate aqueous solution, wherein the concentration of the N, N, N ', N' -tetramethyl cystamine is 20 mmol-200 mmol, and the concentration of the sodium dodecyl benzene sulfonate is 30-600 mmol/L, and completely dissolving to obtain the vermicular micelle system.

Example 4

Introducing carbon dioxide into the aqueous solution of N, N, N ', N' -tetraethylcystamine to form an aqueous solution of N, N, N ', N' -tetraethylcystamine bicarbonate; adding sodium dodecyl benzene sulfonate into the N, N, N ', N' -tetraethylcystamine bicarbonate aqueous solution, wherein the concentration of the N, N, N ', N' -tetraethylcystamine is 20 mmol-200 mmol, and the concentration of the sodium dodecyl benzene sulfonate is 30-600 mmol/L, and obtaining the vermicular micelle system after complete dissolution.

Example 5

Introducing carbon dioxide into the N, N, N ', N' -tetrapropyl cystamine aqueous solution to form N, N, N ', N' -tetrapropyl cystamine bicarbonate aqueous solution; adding sodium hexadecyl carboxylate into the N, N, N ', N' -tetrapropyl cystamine bicarbonate aqueous solution, wherein the concentration of the N, N, N ', N' -tetrapropyl cystamine is 20 mmol-200 mmol, and the concentration of the sodium hexadecyl carboxylate is 30-600 mmol/L, and obtaining the vermicular micelle system after complete dissolution.

Wormlike micellar System test

Example 6: CO of TMCDD-SDS vermicular micelle system₂/N₂Redox stimulus response performance

(1)CO₂/N₂Response performance

When nitrogen gas was introduced into the TMCDD-SDS vermicular micelle system prepared in example 2 and heated to 40 deg.C, the vermicular system became a solution with good fluidity, as shown in FIG. 2,the steady state rheology and the dynamic rheology profile are shown in figure 3. Before nitrogen is introduced, the solution has the characteristic of shear thinning, the viscosity of the system is basically unchanged at a low shear rate, the zero shear viscosity can reach about 2000 mPa.s, and the viscosity of the solution exceeds 25.85s at the shear rate^-1Then rapidly descending; after nitrogen is introduced, the viscosity of the system is obviously reduced, no shear thinning is carried out under high shear rate, the viscosity is kept constant at 10mPa & s, and the Newtonian fluid belongs to the Newtonian fluid. In the dynamic rheological diagram, no intersection point exists between the solutions G 'and G' after the nitrogen is introduced, and the system has no transition between viscosity and elasticity, which indicates that the worm-like micelle is destroyed and is converted from the Maxwell fluid into the Newtonian fluid.

(2) Redox response performance

After a reducing agent Dithiothreitol (DTT) is added into the vermicular micelle system (the molar ratio of the DTTT to TMCDD is 0.1: 1-10: 1), the viscosity of the solution is obviously reduced, and the solution becomes a flowing liquid without viscoelasticity, as shown in figure 4, the vermicular micelle of TMCDD-SDS has reduction stimulation responsiveness. Rheological tests were performed on the TMCDD-SDS (100/300mM) solutions before and after DTT addition, as shown in FIG. 5a, the viscosity of the solution was reduced to about 5 mPas after DTT reduction of the disulfide bonds, which was 3 orders of magnitude lower than the zero shear viscosity of the solution before DTT addition. As the shear rate is increased, the zero shear viscosity of the system is almost unchanged, and the shear thinning phenomenon disappears, which indicates that the wormlike micelle structure is destroyed.

Further, the dynamic rheology can also react with structural changes before and after DTT (the molar ratio of DTT to TMCDD is 0.1: 1-10: 1). As shown in FIG. 5b, before addition of DTT, the viscous modulus curve and the elastic modulus curve of a TMCDD-SDS (100/300mM) solution have a cross-over point at an angular frequency of 117 rad/s. To the left of the intersection point, the viscous modulus curve is always above the elastic modulus, indicating that viscosity is dominant at stress failure. As the angular frequency increases, the value of G' gradually approaches and exceeds G ", the solution switches to elastic dominated. After the DTT is added, irregular jump points appear in the data of G 'and G', although the values of G 'and G' are infinitely close to each other along with the increase of the angular frequency, G 'is always larger than G', the Cole-Cole model of the worm-like micelle is not met any more, the worm-like micelle structure is destroyed, and the TMCDD-SDS worm-like micelle system has the response of redox stimulation. Adding an oxidant hydrogen peroxide (the molar ratio of hydrogen peroxide to DTT is 0.5: 1-5: 1) and recovering the wormlike micelle system.

Example 7 Redox stimulus response Properties of wormlike micellar System

After a reducing agent sodium dithionite (the molar ratio of sodium dithionite to TMCDD is 0.1: 1-10: 1) is added into the vermicular micelle system, the system becomes a solution with good fluidity, and the vermicular micelle is destroyed. Continuously adding an oxidant benzoyl peroxide (the molar ratio of the benzoyl peroxide to the sodium hydrosulfite is 0.5: 1-10: 1), fully dissolving and reacting in a water bath, and cooling to 25 ℃ to form clear viscoelastic worm-like micelles again.

Example 8 Redox stimulus response Properties of wormlike micellar System

After a reducing agent sodium borohydride (the molar ratio of the sodium borohydride to TMCDD is 0.1: 1-10: 1) is added into the wormlike micelle system, the system becomes a solution with good fluidity, and wormlike micelles are destroyed. Continuously adding an oxidant potassium persulfate (the molar ratio of potassium persulfate to sodium borohydride is 0.5: 1-10: 1) into the system, fully dissolving and reacting in a water bath, and cooling to 25 ℃ to form the viscoelastic worm-shaped micelle again.

preparation of pH response type wormlike micelle system

Example 9

Adding hydrochloric acid into an aqueous solution of N, N, N ', N' -tetramethyl cystamine to form an aqueous solution of N, N, N ', N' -tetramethyl cystamine hydrochloride; adding sodium dodecyl sulfate into an aqueous solution of N, N, N ', N' -tetramethyl cystamine hydrochloride, wherein the concentration of the N, N, N ', N' -tetramethyl cystamine is 20 mmol-200 mmol, the concentration of the sodium dodecyl sulfate is 30-600 mmol/L, and a pH response type vermicular micelle system can be obtained after complete dissolution. As shown in fig. 7, the worm-like micelles collapsed when pH >10.24 and recovered when pH < 6.

The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims

1. CO containing disulfide bond₂/N₂And a method for preparing a redox stimulus-responsive worm micellar system, comprising:

adding an anionic surfactant into the cystamine-based hydrogen carbonate mother liquor, and stirring until the anionic surfactant is completely dissolved to obtain the worm micelle system;

2. The disulfide bond-containing CO of claim 1₂/N₂And a preparation method of the redox stimulus response type worm micelle system, which is characterized in that the anionic surfactant is sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or sodium hexadecyl carboxylate.

3. The disulfide bond-containing CO of claim 1₂/N₂And a preparation method of a redox stimulus response type worm micelle system, which is characterized in that the cystamine bicarbonate is one or a mixture of more of cystamine bicarbonate, N, N, N ', N' -tetramethyl cystamine bicarbonate, N, N, N ', N' -tetraethyl cystamine bicarbonate, N, N, N ', N' -tetrapropyl cystamine bicarbonate and N, N, N ', N' -tetrabutyl cystamine bicarbonate.

4. A disulfide bond-containing CO as claimed in claim 3₂/N₂And a preparation method of a redox stimulus response type worm micelle system, which is characterized in that the cysteaminyl bicarbonate is prepared from CO₂Introducing cystamine and N, N, N ', N' -tetramethyl cystamineAnd N, N, N ', N' -tetraethylcystamine, N, N, N ', N' -tetrapropylcystamine, N, N, N ', N' -tetrabutylcystamine.

5. The disulfide bond-containing CO of claim 1₂/N₂And a preparation method of the redox stimulus response type worm micelle system, which is characterized in that in the worm micelle system, the molar concentration of the cysteamine bicarbonate is 20-200 mmol/L, and the molar concentration of the anionic surfactant is 30-600 mmol/L.

6. Disulfide bond-containing CO prepared by the method of any one of claims 1 to 5₂/N₂And redox stimuli-responsive worm micellar systems.

7. The disulfide-bond containing CO of claim 6₂/N₂And an oxidation-reduction stimulus-responsive wormlike micelle system, characterized in that the wormlike micelle is completely disintegrated by introducing nitrogen gas into the wormlike micelle and heating to a temperature of more than 40 ℃; when carbon dioxide is introduced, the wormlike micelle system recovers.

8. The disulfide-bond containing CO of claim 6₂/N₂And an oxidative stimulus-responsive worm micelle system, wherein a reducing agent is added to the worm micelle system to decompose the worm-like micelles; after addition of the reducing agent, the wormlike micellar system is restored.

9. The disulfide-bond containing CO of claim 8₂/N₂And the oxidation stimulation response type worm micelle system is characterized in that the reducing agent is one or a mixture of more of dithiothreitol, glutathione, sodium dithionite, vitamin C, sodium borohydride, potassium borohydride, lithium aluminum hydride and sulfurous acid, and the addition amount of the reducing agent is 0.5-3.0 times of the mole number of the cystine-based bicarbonate.

10. The disulfide-bond containing CO of claim 8₂/N₂And the oxidation stimulation response type worm micelle system is characterized in that the oxidant is one or a mixture of more of benzoyl peroxide, hydrogen peroxide, potassium permanganate, potassium dichromate, potassium permanganate, fuming sulfuric acid, lead dioxide, sodium bismuthate, periodic acid, cobalt trifluoride, sodium ferrate, sodium hypochlorite, sodium persulfate and potassium persulfate, and the addition amount of the oxidant is 0.5-3.0 times of the mole number of the cysteamine bicarbonate.