CN112920426B - Rosin-based calcium salt supermolecule hydrogel, preparation method and application thereof - Google Patents
Rosin-based calcium salt supermolecule hydrogel, preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a rosin-based calcium salt supermolecular hydrogel, a preparation method and application thereof. The molecular structure of the rosin-based calcium salt supermolecule hydrogel is as follows:according to the rosin-based calcium salt supermolecular hydrogel, a tricyclic diterpene structure of rosin is combined, dehydroabietic acid is utilized to synthesize dehydroabietic acid sodium salt, and then in the presence of calcium ions, the dehydroabietic acid calcium salt supermolecular hydrogel can be formed through coordination interaction of metal ion bonds, and the dehydroabietic acid calcium salt supermolecular hydrogel has a critical gelation concentration of 1.7mM and a gelation temperature of 90 ℃, so that the high-value utilization of the rosin is greatly improved; the rosin-based calcium salt supermolecular hydrogel provided by the application has chirality, does not contain an organic solvent, has better biocompatibility and lower toxicity than organic gel, and the porous property of the three-dimensional fiber network can be used for encapsulation and delivery of therapeutic drugs such as drug molecules, proteins and cells and controllable synthesis of nano materials.
Description
Technical Field
The application relates to a rosin-based calcium salt supermolecular hydrogel, a preparation method and application thereof, and belongs to the fields of forest chemical industry and hydrogel.
Background
Hydrogels are an important class of soft materials with three-dimensional mesoscopic network structures. The hydrogel has a large number of active groups, so that the hydrogel has better adsorption performance, and strong acting forces such as hydrogen bonds, ionic bonds, hydrophobic power and the like can be formed among molecules, so that the mechanical performance of the hydrogel is improved; because of the better biocompatibility, the water content of the cell culture medium can be regulated, so that the cell culture medium has a structure similar to that of an extracellular matrix, and mild growth conditions are provided for cells. Supermolecular gels (LMGs) are typically physical gels that integrate three-dimensional network structures through intermolecular hydrogen bonding, pi-pi stacking, van der waals forces, static electricity, coordination, dipole-dipole interactions, and the like, and rely on interfacial tension, capillary action, and the like to lose mobility of solvents present therein, thereby forming viscoelastic soft solid materials. The supermolecular gel is different from the traditional covalent bond polymer gel in that the supermolecular gel is self-assembled by non-covalent bonds, the gelation of the supermolecular gel is a multistage self-assembly process of gel factors, the supermolecular gel factors are driven by the non-covalent bonds to form aggregates with smaller sizes, the aggregates continue to self-assemble to generate a nanofiber structure, the nanofibers are mutually wound to form a three-dimensional network structure, and then a large amount of solvents are wrapped to form macroscopic visible gel. Supermolecular gels tend to have good phase transition reversibility, i.e., the phase transition process between gel-sol can be controlled by the action of heat, chemicals, ultrasound, light, electricity, oxidation/reduction, shear stimulation, etc. The properties enable the gel to have great potential application value in the aspects of sensing, controlled release, catalyst loading, micro-nano material preparation and the like.
Chirality is one of the fundamental properties of nature, and has an important impact on life and human health. At present, research fields such as chiral drug synthesis, chiral catalysis, chiral separation, chiral identification, chiral materials and the like are still leading topics of scientific research. The supermolecule gel material is used as a novel intelligent material, most of the gel factors of the supermolecule gel material have chiral structures, and researches show that the chirality not only influences the assembly and formation process of the gel, but also plays an important role in the functional application of the supermolecule gel material. However, the conventional method is adopted to synthesize the novel rigid supermolecule chiral hydrogel, and the steps are complicated and the purification is complicated.
Disclosure of Invention
The application provides a rosin-based calcium salt supermolecular hydrogel, a preparation method and application thereof, wherein dehydroabietic acid raw material is used for synthesizing dehydroabietic acid sodium salt, and the supermolecular hydrogel can be formed through coordination bond interaction in the presence of calcium ions, so that the preparation is simple and easy to control; the hydrogel provided by the application is used as a template, so that the metal sulfide nano material can be prepared, the controllable synthesis of the nano material is realized, and the method has important significance.
In order to solve the technical problems, the technical scheme adopted by the application is as follows:
a rosin-based calcium salt supermolecule hydrogel has a molecular structure as follows:
the hydrophobic group of the hydrogel is of a full rigid structure.
The preparation method of the rosin-based calcium salt supermolecule hydrogel comprises the following steps:
1) Preparing sodium dehydroabietate from dehydroabietic acid;
2) The sodium dehydroabietate and calcium ions form rosin-based calcium salt supermolecular hydrogel.
The rosin-based calcium salt supermolecule hydrogel does not need a complex reaction process, and the preparation method is very simple.
The dehydroabietic acid calcium hydrogel is rosin-based calcium salt supermolecule hydrogel.
The application reasonably utilizes the tricyclic diterpene structure of rosin biomass resources to synthesize the rosin-based calcium salt supermolecule hydrogel, which meets the development requirements of green chemistry; the synthesis method of the supermolecular hydrogel is simple, sodium dehydroabietate is synthesized by dehydroabietic acid, and then the supermolecular hydrogel can be formed through coordination interaction with calcium ions.
When the concentration is more than 1.7mM, stable calcium dehydroabietate hydrogel can be formed, the critical gel concentration is low, the hydrogel forms a fiber structure, and the calcium dehydroabietate hydrogel can be used as a template to prepare a nanomaterial to realize the controllable synthesis of the nanomaterial, such as the preparation of a metal sulfide nanomaterial.
The step 1) is as follows: dehydroabietic acid reacts with NaOH in a solvent to prepare sodium dehydroabietate.
In order to facilitate the operation and simultaneously give consideration to environmental protection and product yield, in the step 1), the solvent is absolute ethyl alcohol; the mole ratio of dehydroabietic acid to NaOH is 1: (1-1.2), most preferably, dehydroabietic acid is equimolar reacted with NaOH.
In order to improve the reaction efficiency and the product purity, the reaction temperature in the step 1) is 55-65 ℃, the reaction time is 4-8 hours, after the reaction is finished, the reaction is cooled to room temperature, the solvent is removed by rotary evaporation, and then ethanol is used for recrystallization, so that the sodium dehydroabietate solid is obtained.
In order to increase the success rate of the reaction, the step 2) is as follows: and uniformly mixing and cooling the dehydroabietic acid sodium, the soluble calcium salt and the sodium hydroxide aqueous solution at the temperature of 55-65 ℃ to obtain the rosin-based calcium salt supermolecular hydrogel.
In order to improve the uniformity of the product, as one of the preferred implementation schemes, the step 2) is to mix the water solution of the soluble calcium salt with the water solution of sodium hydroxide uniformly, heat up to 55-65 ℃, then add the dehydroabietyl sodium, mix uniformly, cool down to room temperature, namely the rosin-based calcium salt supermolecule hydrogel.
In order to improve the uniformity of the product, the soluble calcium salt, the dehydroabietyl sodium and the like can be added in the form of an aqueous solution.
The soluble calcium salt is preferably calcium chloride.
Preferably, in the above step 2), the molar ratio of sodium dehydroabietate to calcium ion is 2 (1 to 1.2).
mM of the present application means millimoles per liter.
One of the uses of the rosin-based calcium salt supramolecular hydrogel of the application is: the method is used for preparing the transition metal sulfide nano particles.
The transition metal sulfide nanoparticles can be prepared by the following method:
1) Transition metal salts and CaCl 2 Mixing the aqueous solutions, adding a sodium hydroxide solution with a certain concentration, heating to 55-65 ℃, then adding sodium dehydroabietate, uniformly mixing, and cooling to room temperature to form hydrogel;
2) Na is added to the top of the hydrogel obtained in the step 1 2 S·9H 2 O or Na 2 S solution, na 2 S diffuses into the gel network, and after 8-12 hours, transition metal sulfide nano particles are generated inside the hydrogel network.
In order to increase the efficiency, na is preferably added in step 2) 2 S solution.
The transition metal salt in the step 1) is preferably CdCl 2 、Zn(ClO 4 ) 2 、Co(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O or CrCl 2 。
The technology not mentioned in the present application refers to the prior art.
According to the rosin-based calcium salt supermolecular hydrogel, a tricyclic diterpene structure of rosin is combined, dehydroabietic acid is utilized to synthesize dehydroabietic acid sodium salt, and then in the presence of calcium ions, the dehydroabietic acid calcium salt supermolecular hydrogel can be formed through coordination interaction of metal ion bonds, and the dehydroabietic acid calcium salt supermolecular hydrogel has a critical gelation concentration of 1.7mM and a gelation temperature of 90 ℃, so that the high-value utilization of the rosin is greatly improved; the rosin-based calcium salt supermolecular hydrogel provided by the application has chirality, does not contain an organic solvent, has better biocompatibility and lower toxicity than organic gel, and the porous property of the three-dimensional fiber network can be used for encapsulation and delivery of therapeutic drugs such as drug molecules, proteins and cells and controllable synthesis of nano materials.
Drawings
FIG. 1 is a phase diagram of calcium dehydroabietate supramolecular hydrogels of the present application at different concentrations;
FIG. 2 is a cryo-electron micrograph of a calcium dehydroabietate hydrogel having a concentration of 5mM according to the present application;
FIG. 3 is a CD spectrum of a calcium dehydroabietate hydrogel of the present application;
FIG. 4 is a phase diagram of the preparation of a metal sulfide nanomaterial using a calcium dehydroabietate hydrogel as a template in accordance with the present application;
Detailed Description
For a better understanding of the present application, the following examples are further illustrated, but are not limited to the following examples.
Example 1
Equal molar amounts of dehydroabietic acid (3 g,0.01 mol), naOH (0.4 g,0.01 mol) and absolute ethyl alcohol (50 mL) are weighed, put into a flask with a magnetic rotor, a reflux device is connected, the temperature is raised to 60 ℃, the reaction is carried out for 6 hours, the reaction liquid is cooled to room temperature, the ethanol is removed by rotary evaporation, and the dehydroabietic acid sodium solid is obtained by recrystalization twice by the ethanol. The sodium dehydroabietate solid was weighed, distilled water was added, and 50mM,40mM,30mM,20mM and 10mM aqueous solutions of sodium dehydroabietate were prepared, respectively, for use.
Example 2
Preparing dehydroabietic acid calcium supermolecule hydrogel:
CaCl was prepared at 25mM, 20mM, 15mM, 10mM, 5mM 2 An aqueous solution;
1mL of CaCl 25mM was removed by pipetting gun 2 Adding 1mL of 100mM sodium hydroxide aqueous solution into the aqueous solution, heating to 60 ℃ in a water bath, adding 1mL of 50mM sodium dehydroabietate aqueous solution, uniformly mixing, taking out and cooling to 25 ℃, and forming 8.3mM calcium dehydroabietate hydrogel, carrying out circular dichroism test on the obtained hydrogel, and exploring the chirality of the hydrogel, wherein a CD spectrum chart of the hydrogel is shown in figure 3; the structural formula of the dehydroabietic acid calcium hydrogel isThe same method was used to prepare calcium dehydroabietate supramolecular hydrogels of different concentrations, the phase diagram of which is shown in fig. 1.
TABLE 1 sodium dehydroabietate solutions and CaCl corresponding to calcium dehydroabietate hydrogels of different concentrations 2 Solution
The freeze transmission electron microscope test is carried out on the calcium dehydroabietate hydrogel with the concentration of 30mM and the concentration of 5mM, as shown in figure 2, the freeze transmission electron microscope shows obvious fiber structure and accords with the characteristics of the hydrogel, and the calcium dehydroabietate hydrogel with other concentrations also shows obvious fiber structure after the test, thus the calcium dehydroabietate hydrogel can be used for the encapsulation and delivery of therapeutic drugs such as drug molecules, proteins, cells and the like and the controllable synthesis of nano materials.
Example 3
The calcium dehydroabietate hydrogel is used as a template to prepare a metal sulfide nano material:
0.1mL of a transition metal salt (Cu (NO) 3 ) 2 ·3H 2 O、Zn(ClO 4 ) 2 、Co(NO 3 ) 2 ·6H 2 O、CrCl 2 Or CdCl 2 ) Solution (20 mM) with 1.9mL CaCl 2 Mixing (20 mM) aqueous solution, adding 1mL of NaOH (100 mM) solution, heating to 60 ℃ in water bath, adding 2mL of dehydroabietic acid sodium aqueous solution (40 mM), mixing uniformly, taking out, and cooling to 25 ℃ to form hydrogel; after 45 minutes, 1mLNa was added on top of the gel layer 2 S (20 mM) solution was allowed to diffuse through the gel network and after 12 hours, as shown in FIG. 4, a translucent gel of different colors was formed, indicating the presence of nano transition metal sulfides within the hydrogel network.
Claims (8)
1. A preparation method of rosin-based calcium salt supermolecule hydrogel is characterized by comprising the following steps: the molecular structure of the rosin-based calcium salt supermolecule hydrogel is as follows:
the preparation method of the rosin-based calcium salt supermolecule hydrogel comprises the following steps:
1) Preparing sodium dehydroabietate from dehydroabietic acid;
2) And uniformly mixing and cooling the dehydroabietic acid sodium, the soluble calcium salt and the sodium hydroxide aqueous solution at the temperature of 55-65 ℃ to obtain the rosin-based calcium salt supermolecular hydrogel.
2. The method of manufacturing according to claim 1, wherein: the step 1) is as follows: dehydroabietic acid reacts with NaOH in a solvent to prepare sodium dehydroabietate.
3. The method of manufacturing as claimed in claim 2, wherein: in the step 1), the solvent is absolute ethyl alcohol; the mole ratio of dehydroabietic acid to NaOH is 1: (1-1.2).
4. A method of preparation as claimed in claim 3, wherein: in the step 1), the reaction temperature is 55-65 ℃, the reaction time is 4-8 hours, after the reaction is finished, the reaction is cooled to room temperature, the solvent is removed by rotary evaporation, and then ethanol is used for recrystallization, so that the sodium dehydroabietate solid is obtained.
5. The method of any one of claims 1-4, wherein: the step 2) is as follows: mixing the water solution of soluble calcium salt with the water solution of sodium hydroxide, heating to 55-65 ℃, then adding sodium dehydroabietate, mixing uniformly, and cooling to room temperature, thus obtaining the rosin-based calcium salt supermolecule hydrogel.
6. The method of any one of claims 1-4, wherein: in the step 2), the molar ratio of the dehydroabietyl sodium to the calcium ions is 2 (1-1.2).
7. The method of any one of claims 1-4, wherein: the rosin-based calcium salt supermolecular hydrogel is used for preparing transition metal sulfide nano-particles.
8. The method of manufacturing according to claim 7, wherein: the preparation method of the transition metal sulfide nano-particles comprises the following steps:
1) Mixing transition metal salt, soluble calcium salt and sodium hydroxide aqueous solution uniformly, heating to 55-65 ℃, then adding sodium dehydroabietate, mixing uniformly, and cooling to room temperature to form hydrogel;
2) Adding Na to the hydrogel obtained in step 1) 2 S·9H 2 O or Na 2 S solution, na 2 S diffuses into the gel network, and after 8-12 hours, transition metal sulfide nano particles are generated inside the hydrogel network.
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Citations (4)
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| JP2003041236A (en) * | 2001-08-01 | 2003-02-13 | Arakawa Chem Ind Co Ltd | Organic gelatinizer |
| JP2005132959A (en) * | 2003-10-30 | 2005-05-26 | Arakawa Chem Ind Co Ltd | Siloxane gel and method for producing the same |
| CN104016882A (en) * | 2014-05-09 | 2014-09-03 | 上海大学 | 12-oxime ether dehydroabietic acid compound and synthetic method thereof |
| CN109627191A (en) * | 2019-01-04 | 2019-04-16 | 江南大学 | A kind of supramolecular hydrogel of abietyl micro-molecular hydrogel agent and its formation |
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| WO2020140326A1 (en) * | 2019-01-04 | 2020-07-09 | 江南大学 | Rosin-based small molecule hydrogel agent and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041236A (en) * | 2001-08-01 | 2003-02-13 | Arakawa Chem Ind Co Ltd | Organic gelatinizer |
| JP2005132959A (en) * | 2003-10-30 | 2005-05-26 | Arakawa Chem Ind Co Ltd | Siloxane gel and method for producing the same |
| CN104016882A (en) * | 2014-05-09 | 2014-09-03 | 上海大学 | 12-oxime ether dehydroabietic acid compound and synthetic method thereof |
| CN109627191A (en) * | 2019-01-04 | 2019-04-16 | 江南大学 | A kind of supramolecular hydrogel of abietyl micro-molecular hydrogel agent and its formation |
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| Title |
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| 松香基聚丙烯酰胺水凝胶的药物释放性能及其动力学研究;张海波;蒋建新;高宏;商士斌;宋湛谦;;林产化学与工业(第03期);25-32 * |
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