CN112979841B - Double-titration preparation method of two-dimensional metal hydroxide-chitosan supermolecule hybrid material - Google Patents
Double-titration preparation method of two-dimensional metal hydroxide-chitosan supermolecule hybrid material Download PDFInfo
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention belongs to the technical field of hybrid materials, and particularly relates to a double-titration preparation method of a two-dimensional metal hydroxide-chitosan supermolecule hybrid material. Aiming at the problem that the antibacterial activity of the chitosan hybrid material prepared by the existing method can also be influenced by the pH value and the acetylation degree of chitosan, the invention provides a double-titration preparation method of a two-dimensional metal hydroxide-chitosan supramolecular hybrid material, which comprises the following steps: a. preparing a mixed solution A of a zinc chloride solution and an aluminum chloride solution; b. preparing NaOH and Na 2 CO 3 And a chitosan solution with low acetylation degree; c. and (3) taking the solution A and the solution B, slowly dripping the solution A and the solution B at the same time, keeping for 3 hours, aging, filtering, washing and drying to obtain the two-dimensional metal hydroxide-chitosan supramolecular hybrid material. The invention adopts the double titration method, which is beneficial to forming a large number of weak crystal heterojunction structures of different types and promotes the easy and rapid dispersion of metal ions in a medium, thereby improving the antibacterial activity.
Description
Technical Field
The invention belongs to the technical field of hybrid materials, and particularly relates to a double-titration preparation method of a two-dimensional metal hydroxide-chitosan supramolecular hybrid material.
Background
Recent epidemiological studies have shown that infections caused by multiple drug resistant bacteria continue to increase. Recently, in the fight against antimicrobial resistance, hybrid materials in the ultra-nanometer scale are an increasingly used method by many people. The construction of organic-inorganic hybrid materials is a rapidly developing field in the field of material chemistry, aiming at producing advanced materials with improved structure and function. The bio-inorganic hybrid may exhibit not only the characteristics of different components but also further enhanced characteristics and new synergistic characteristics due to the interaction between the bio-molecules and the inorganic material.
In selecting the raw materials for forming supramolecular hybrid materials, layered double hydroxides LDH (ZnAl, inorganic) and chitosan (CS, organic) are more studied, mainly because of their unique properties, such as non-toxicity and allergenicity, good thermal stability, biocompatibility, and better favourability for intercalation and ion exchange. At the same time, they also have the ability to have an excellent combination of physical, chemical and mechanical properties. In addition, chitosan exhibits potent antibacterial and antifungal activity against a variety of microorganisms, as compared to other polymers and biopolymers. It has three types of functional nucleophilic groups, each consisting of C-2NH 2 A group, a secondary C-3OH group and a C-6 primary OH group. Chitosan is a biopolymer with reactive functional groups that are easily chemically modified and has been shown to be a functional polymer that can covalently graft antioxidant/antimicrobial activity onto its backbone. Layered double hydroxide (ZnH) ZnAl heterostructure nanomaterials consist of positively charged brucite-type divalent and trivalent metal hydroxide layers, their excess positive charge, znAl hydroxide (depending on its method of synthesis) being an effective antibacterial agent against bacteria such as e. Hydroxyl (-OH) and metal cations, wherein Zn 2+ Is one of the most active metals and has strong micro-kinetic characteristics. Thus, CS polymers have a large number of primary amines and hydroxyl groups, which make them highly affinity for metal ions. It can be bound by simple chelation or ion exchange, making it an excellent support for Layered Double Hydroxide (LDH) synthesis. In order to improve the antibacterial performance of the two compounds, the inorganic/natural polymer composite material based on inorganic nano has the characteristics of inorganic and natural polymers, the physical and chemical properties break through the limitation of a single material to a certain extent, and better antibacterial activity is provided by better performance.
However, in the hybrid material related to chitosan prepared at present, the antibacterial activity is also influenced by the pH value and the acetylation degree of chitosan, and the antibacterial activity of the hybrid material cannot be ensured.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the antibacterial activity of the chitosan hybrid material prepared by the existing method is also influenced by the pH value and the acetylation degree of chitosan, and the antibacterial activity is unstable.
The technical scheme for solving the technical problems comprises the following steps: provides a double titration preparation method of a two-dimensional metal hydroxide-chitosan supermolecule hybrid material. The method comprises the following steps:
a. preparing a mixed solution A of a zinc chloride solution and an aluminum chloride solution, wherein the total concentration of metal ions in the mixed solution A is 1.2mol/L, and Zn in the mixed solution A 2+ And Al 3+ The molar ratio of (A) to (B) is 1/3-5.0;
b. preparing NaOH and Na 2 CO 3 And a chitosan solution with low acetylation degree;
c. taking the solution A and the solution B with the same volume, and slowly dropping the solution A and the solution B into a three-neck flask at the same time under the condition of vigorous stirring at 60 ℃; keeping for 3 hours after the dropwise addition is finished, aging the precipitate for 12 hours at 80 ℃, filtering and washing to be neutral, and drying for 24 hours at 90 ℃ to obtain the two-dimensional metal hydroxide-chitosan supramolecular hybrid material.
In the double titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the concentration of NaOH in the step b is 1.75 mol.L -1 。
Wherein in the double titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the Na in the step b 2 CO 3 Has a concentration of 0.75 mol. L -1 。
In the double-titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the chitosan with low acetylation degree in the step b is chitosan with deacetylation degree of 90-99.5%.
In the double titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the concentration of chitosan in the step b is 0.5-3 g/L.
In the double titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the chitosan solution in the step b is prepared by dissolving chitosan in 1.0wt% of acetic acid.
The invention has the beneficial effects that:
the invention provides a method for preparing a ZnAl two-dimensional metal hydroxide-chitosan supermolecule hybrid material by adopting a double titration method, and the antibacterial activity can be improved and pathogenic microorganisms can be better killed by hybridizing the ZnAl two-dimensional metal hydroxide and chitosan. The hybrid material of the present invention maintains activation and enhances the antimicrobial activity of chitosan, avoiding the need to work at pH>Has no antibacterial activity at 5.5 or at chitosan Deacetylation Degree (DD) of 90-99.5. The invention adopts a double titration method to be beneficial to forming a large number of different types of weak crystallization heterojunction structures (ZnO, al) 2 O 3 ,ZnAl 2 O 4 ,Zn 2+ ,Al 3+ ) Promote the easy and fast dispersion of metal ions in the medium, thereby improving the antibacterial activity. The antibacterial hybrid material synthesized by the double titration method has the following advantages: good thermal stability, low sensitivity to media, permanent surface charge, relatively low viscosity, high antibacterial activity, and the like.
Drawings
FIG. 1 shows an XRD pattern of an example; (a) an XRD pattern representing pure CS; (b) Represents an XRD mode of LDH-ZnAl and LDH-ZnAl/CS mixed materials;
FIG. 2 shows FTIR spectra of pure CS, LDH-ZnAl and LDH-ZnAl/CS blends;
FIG. 3 shows SEM images of LDH-ZnAl and LDH-ZnAl/CS samples,. Times.15000;
FIG. 4 shows the storage modulus G' (a) and loss modulus G "(b) for pure CS, LDH-ZnAl and LDH-ZnAl/CS samples;
FIG. 5 shows TGA-DTG curves for pure CS thermogravimetry and differential thermogravimetry;
FIG. 6 shows the TGA-DTG curves for the thermogravimetry and the differential thermogravimetry of LDH-ZnAl;
FIG. 7 shows LDH-ZnAl/CS 0.5 TGA-DTG curves of thermogravimetry and differential thermogravimetry of;
FIG. 8 shows LDH-ZnAl/CS 1 TGA-DTG curves of thermogravimetry and differential thermogravimetry of;
FIG. 9 shows LDH-ZnAl/CS 1.5 TGA-DTG curves of thermogravimetry and differential thermogravimetry of;
FIG. 10 shows LDH-ZnAl/CS 2 TGA-DTG curves of thermogravimetry and differential thermogravimetry of;
FIG. 11 shows LDH-ZnAl/CS 3 TGA-DTG curves of thermogravimetry and differential thermogravimetry of;
FIG. 12 is a graph showing the inhibition zones and the bacteriostatic activity against E.coli (E.coli) for U-LDH/CS samples;
FIG. 13 is a graph showing the inhibition zones and bacteriostatic activity against Staphylococcus aureus (S.aureus) for the U-LDH/CS samples;
fig. 14 shows the inhibition zones and the bacteriostatic activity against penicillium (p. Cyclopium) for the U-LDH/CS sample.
Detailed Description
The invention adopts a double titration method to prepare an LDH-ZnAl/biopolymer Chitosan (CS) hybrid material which can be used for actively eliminating pathogenic microorganisms. The invention maintains and enhances the antibacterial activity of chitosan, and can also avoid the influence of a microorganism culture medium on the antibacterial activity of chitosan. For example, conventional chitosan has no antibacterial activity at pH >5.5, and chitosan microspheres have no antibacterial activity at a Degree of Deacetylation (DD) of 90-99.5, but the LDH-ZnAl/biopolymer Chitosan (CS) hybrid material prepared by the method of the present invention has antibacterial activity in both cases.
Specifically, the double titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material comprises the following steps:
a. preparing a mixed solution A of a zinc chloride solution and an aluminum chloride solution, wherein the total concentration of metal ions in the mixed solution A is 1.2mol/L, and Zn in the mixed solution A 2+ And Al 3+ The molar ratio of (A) to (B) is 1/3-5.0;
b. preparing NaOH and Na 2 CO 3 And a chitosan solution with low acetylation degree; the concentration of NaOH in the solution B was 1.75 mol. L -1 Said Na 2 CO 3 Has a concentration of 0.75 mol. L -1 The concentration of the chitosan is 0.5-3 g/L;
c. taking the solution A and the solution B with the same volume, and slowly dropping the solution A and the solution B into a three-neck flask at the same time under the condition of vigorous stirring at 60 ℃; keeping for 3 hours after the dropwise addition is finished, aging the precipitate for 12 hours at 80 ℃, filtering and washing to be neutral, and drying for 24 hours at 90 ℃ to obtain the two-dimensional metal hydroxide-chitosan supramolecular hybrid material.
In the double-titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the chitosan with low acetylation degree in the step b is chitosan with deacetylation degree of 90-99.5%.
In the double-titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the chitosan solution in the step b is prepared by dissolving chitosan in 1.0wt% of acetic acid.
The invention combines LDH-ZnAl and chitosan for the first time to prepare the antibacterial hybrid material. In the hybrid material, LDH-ZnAl (hydrotalcite or hydrotalcite-like compound) provides a large surface area, has good capability of fixing biological molecules, has good compatibility with the biological molecules, and simultaneously has excellent electronic conduction and signal amplification characteristics. The natural biological polymer chitosan has antifungal and antibacterial activity, excellent film forming property, strong water permeability and no toxicity. According to the invention, two compounds are combined through a complex chemical bond to form the hybrid material with wider antibacterial range and enhanced antibacterial activity. The antibacterial range of the invention includes gram-negative bacteria, gram-positive bacteria and mould, and the band gap of the obtained hybrid allows the hybrid to have activity in the UV region and the outside, and is environment-friendly and low in cost.
Compared with the existing domestic antibiotic preparation method, the ZnAl-LDH prepared by the invention has excellent ion release (Zn) 2+ ) Protection, conduction and signal amplification characteristics combined with excellent characteristicsFilm-forming property, extremely strong micro-dynamic property and biocompatibility of natural polymer chitosan. Positively charged (NH) 3+ Cations) interfere with the negatively charged bacterial cell membrane. This interaction with the bacterial membrane results in changes in cell permeability and membrane lysis. The hybrid may activate sequestration of nutrients by chitosan, resulting in essential metals inhibiting the growth of microorganisms. Hybrids can also lyse microorganisms by their metal compounds generating Reactive Oxygen Species (ROS). The production of ROS is believed to be a major contributor to the antimicrobial activity of various metal oxides. The reactive species is a superoxide anion (O) 2 ) Hydrogen peroxide (H) 2 O 2 ) And Hydroxides (OH) - ). The toxicity of these substances is related to the destruction of cellular components (such as lipids, DNA and proteins) due to their internalization into the bacterial cell membrane.
The following examples are given to further illustrate the embodiments of the present invention, but are not intended to limit the scope of the present invention to the examples.
EXAMPLE 1 preparation of ZnAl-LDH hybrid Material
By mixing compounds having different Zn/Al molar ratios (Zn) 2+ +Al 3+ ＝1.2mol·L -1 ) To prepare solution A (200 ml) as a solution of Zn and Al metal chlorides. By adding NaOH (1.75 mol. L) -1 ) And Na 2 CO 3 (0.75mol·L -1 ) Solution B was prepared in 200mL of deionized water. Then, the solutions a and B were dropped into an empty three-necked flask at 60 ℃ with vigorous stirring. The precipitate was aged at 80 ℃ for 12 hours, filtered and washed to neutrality, and then dried at 90 ℃ for 24 hours to obtain a sample which was a ZnAl-LDH hybrid material.
Example 2 preparation of ZnAl two-dimensional Metal hydroxide-Chitosan hybrid Material
The specific operation steps are as follows:
a. preparing a mixed solution A of a zinc chloride solution and an aluminum chloride solution, wherein the total concentration of metal ions in the mixed solution A is 1.2mol/L, and Zn in the mixed solution A 2+ And Al 3+ The molar ratio of (A) to (B) is 1/3-5.0;
b. preparing NaOH and Na 2 CO 3 And a chitosan solution with low acetylation degree; the concentration of NaOH in the solution B was 1.75 mol. L -1 Said Na 2 CO 3 Has a concentration of 0.75 mol. L -1 ；
c. Taking the solution A and the solution B with the same volume, and slowly dropping the solution A and the solution B into a three-neck flask at the same time of 60 ℃ under vigorous stirring; keeping for 3 hours after the dropwise addition is finished, aging the precipitate for 12 hours at 80 ℃, filtering and washing to be neutral, and drying for 24 hours at 90 ℃ to obtain the two-dimensional metal hydroxide-chitosan supramolecular hybrid material.
In example 2, chitosan solutions with different concentrations, namely 0.5g/L, 1g/L, 1.5g/L, 2g/L and 3g/L, were used, and the chitosan solutions were prepared by dissolving chitosan in 1.0wt% acetic acid.
Example 3 determination of antibacterial Activity of different hybrid materials
The bacteria AS target organisms are escherichia coli (e.coli, gram negative bacteria, ATCC 35218), staphylococcus aureus (Staphylococcus aureus, gram positive bacteria, ST 398) and penicillium (p. Cyclopium, fungi), AS 3.4513. All from the general collection center for microorganisms of Hunan Tan university.
The p. Cyclopium strain was maintained in Potato Dextrose (PD) medium at 28 ℃ for 72 hours. Coli and s.aureus strains were maintained in Mineral Salt (MS) medium at pH 7.0 at 37 ℃ for 24 hours. All samples were measured to obtain their OD 600nm values to calculate the inhibitory concentration. The control test contained a nutrient medium with a bacterial suspension but no antimicrobial agent.
The antimicrobial efficacy of ZnAl/CS was evaluated by determining the antimicrobial susceptibility of the bacteria after exposure to the test samples by the agar well diffusion method. Gram-negative E.coli and Cyclosporium were used as target organisms. All antimicrobial experiments involving both cultures were performed in sterile 250mL shake flasks or 90mm agar plates. In fact, for the antimicrobial tests, 100mL of culture fractions of the cyclosporine and escherichia coli strains were transferred onto PD and MS medium. The plates were incubated in E.coli for 24 hours at 37 ℃ and in Cyclosporium for 72 hours at 28 ℃. Finally, the zone of inhibition (in millimeters) around the wells was measured to assess antimicrobial activity.
The XRD patterns of the different samples in the examples are shown in fig. 1. XRD results show that the adoption of double titration method and the addition of CS as a soft template is beneficial to the heterojunction structure ZnO-Zn (OH) 2 Resulting in high antibacterial activity against bacteria and high adhesion of CS molecules.
FTIR spectra of different samples in the examples are shown in FIG. 2. The FT-IR spectrum shows that ZnAl-LDH and CS are organically combined to form the hydrotalcite-chitosan composite material.
SEM images of different samples in the examples are shown in fig. 3. SEM images show that the CS content has a certain influence on the microstructure of the LDH-ZnAl/CS hybrid material.
The storage modulus G' (a) and loss modulus G "(b) of the different samples of the examples are shown in FIG. 4. It can be seen from FIG. 4 that this non-terminal behavior is probably due to the fact that the intercalated LDH-ZnAl layer weakens the mobility of the CS chains and then limits their long-range relaxation, which is LDH-ZnAl/CS 3 Showing the reason for maintaining the close fragility.
The thermogravimetric and differential thermogravimetric TGA-DTG curves for the different samples in the examples are shown in FIGS. 5-11. TGA-DTG curves for thermogravimetry and differential thermogravimetry show that increasing the concentration of CS to produce LDH-ZnAl/CS leads to a decrease in the thermal resistance of the LDH-ZnAl/CS hybrid.
The results of the bacteriostatic activity are shown in table 1 below. The bacteriostatic effect profiles are shown in fig. 12-14.
TABLE 1 antibacterial Activity of LDH-ZnAl/CS hybrid materials
The lattice parameters and basal planes of the two-dimensional metal hydroxide-chitosan supramolecular hybrid materials prepared in the examples are calculated as shown in table 2.
TABLE 2 LDH-ZnAl, LDH-ZnAl/CS 0.5 ，LDH-ZnAl/CS 1 ，LDH-ZnAl/CS 1.5 ，LDH-ZnAl/CS 2 ， LDH-ZnAl/CS 3 Calculation of lattice parameters and basal planes of
From the above results, it can be seen that the LDH-ZnAl/CS hybrid material prepared by the method of the present invention has antibacterial activity superior to that of pure chitosan and LDH-ZnAl groups, but when the concentration of CS reaches or exceeds 2g/L, the layered double hydroxide is insufficient or cannot be firmly attached and protects the chitosan from the influence of medium pH, and at this time, the antibacterial activity is almost the same as that of pure chitosan. It can also be seen from Table 2 that the content of chitosan affects the crystallization of the LDH-ZnAl/CS hybrid material. It can be seen that the hybrid material of the present invention requires strict requirements for the concentration of CS when prepared.
The hybrid material with enhanced antibacterial activity is prepared by the method, and has important economic value.
Claims (4)
1. The double titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material is characterized by comprising the following steps of:
a. preparing a mixed solution A of a zinc chloride solution and an aluminum chloride solution, wherein the total concentration of metal ions in the mixed solution A is 1.2mol/L, and Zn in the mixed solution A 2+ And Al 3+ The molar ratio of (A) is 1/3-1/5.0;
b. preparing NaOH and Na 2 CO 3 And a chitosan solution with low acetylation degree;
c. taking the solution A and the solution B with the same volume, and slowly dripping the solution A and the solution B into a three-neck flask at the temperature of 60 ℃ under vigorous stirring; keeping for 3 hours after the dropwise addition is finished, aging the precipitate for 12 hours at 80 ℃, filtering and washing to be neutral, and drying for 24 hours at 90 ℃ to obtain a two-dimensional metal hydroxide-chitosan supramolecular hybrid material;
the concentration of the chitosan in the step b is 0.5-1 g/L;
the chitosan with low acetylation degree in the step b is chitosan with deacetylation degree of 90-99.5%.
2. The double-titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, wherein: the concentration of NaOH in the step b is 1.75 mol.L -1 。
3. The double-titration preparation method of two-dimensional metal hydroxide-chitosan supramolecular hybrid materials as claimed in claim 1, characterized in that: na as described in step b 2 CO 3 Has a concentration of 0.75 mol. L -1 。
4. The double-titration preparation method of the two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, wherein: the chitosan solution in the step b is prepared by dissolving chitosan in 1.0wt% of acetic acid.
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