CN112979974B - ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and preparation method thereof - Google Patents

ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and preparation method thereof Download PDF

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CN112979974B
CN112979974B CN202110139698.5A CN202110139698A CN112979974B CN 112979974 B CN112979974 B CN 112979974B CN 202110139698 A CN202110139698 A CN 202110139698A CN 112979974 B CN112979974 B CN 112979974B
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CN112979974A (en
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安澜
曾虹燕
孙厚祥
刁毅
黄秀丽
张毅
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Panzhihua University Science Park Development Co ltd
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Abstract

The invention belongs to the technical field of hybrid materials, and particularly relates to a ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and a preparation method thereof. Aiming at the problem that the antibacterial activity of the existing prepared hybrid material related to chitosan can be influenced by the pH value and the acetylation degree of chitosan, the invention provides a preparation method of the hybrid material, which comprises the following steps: a. preparing a solution with the total concentration of metal ions of 0.10-0.22 mol/L, and adding urea to obtain a solution A; b. preparing a biopolymer solution B; c. and adding the solution A into the solution B, uniformly mixing, reacting for 16h at 60-80 ℃, continuously aging the obtained precipitate for 3-5h, centrifuging, washing and drying to obtain the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material. The hybrid material prepared by the invention still has antibacterial activity under the conditions that the pH is higher than 5.5, the acetylation degree of chitosan is low and the like, and has important significance.

Description

ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and preparation method thereof
Technical Field
The invention belongs to the technical field of hybrid materials, and particularly relates to a ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and a preparation method thereof.
Background
Recently, in the fight against antimicrobial resistance, hybrid materials in the ultra-nanoscale 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. Bio-inorganic hybrids can exhibit not only the properties of different components, but also further enhanced properties and new synergistic properties due to the interaction between biomolecules and inorganic materials.
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 susceptible to chemical modification 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 synthesis method) 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 affected 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 existing prepared hybrid material related to chitosan is also influenced by pH value and acetylation degree of chitosan, and the antibacterial activity is unstable.
The technical scheme for solving the technical problems comprises the following steps: provides a preparation method of a ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material. The method comprises the following steps:
a. preparation of Zn (NO) 3 ) 2 ·6H 2 O solution and Al (NO) 3 ) 3 ·9H 2 O solution with the total concentration of metal ions of 0.10-0.22 mol/L and Zn 2+ And Al 3+ The molar ratio of (A) to (B) is 1/3-5.0; adding urea into the solution, and uniformly stirring to obtain a solution A;
b. dissolving chitosan with low acetylation degree in lactic acid water solution to prepare biopolymer solution B, and adjusting pH of the biopolymer solution to 10 with sodium hydroxide;
c. and adding the solution A into the solution B, uniformly mixing, reacting for 16 hours at 60-80 ℃, continuously aging the obtained precipitate for 3-5 hours, repeatedly centrifuging, separating to obtain a white solid product, washing and drying to obtain the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the adding amount of urea in the step a is as follows: urea/NO 3- And the molar ratio is 4.
In the preparation method of the ZnAl 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 preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the lactic acid aqueous solution in the step b is stirred for more than 30 min.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the concentration of chitosan in the step b is 0.5-2g/L.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the addition amount of sodium hydroxide in the step b is as follows: CS/NaOH = 1.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the operation in the step c is carried out under the protection of nitrogen.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the speed of adding the solution in the step c is 20mL/h.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the washing in the step c is washed by decarburized water, and the drying condition is that the drying is carried out for 24 hours at 90-110 ℃.
The invention also provides the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material prepared by the method.
The invention has the beneficial effects that:
the invention provides a novel ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material which is synthesized by a urea method, and the antibacterial activity can be improved and pathogenic microorganisms can be better eliminated by hybridizing the ZnAl two-dimensional metal hydroxide and chitosan. The hybrid material of the invention maintains activation and enhances the antimicrobial activity of chitosan, avoiding no antimicrobial activity at pH >5.5 or at chitosan Deacetylation Degree (DD) of 90-99.5. The antibacterial hybrid material synthesized by the urea method has the following advantages: good thermal stability, low sensitivity to medium, permanent surface charge, relatively low viscosity, high antibacterial activity, etc. In addition, the preparation method is simple and convenient, is low in cost and has a relatively high application prospect.
Drawings
FIG. 1 shows the FTIR spectra of the hybrid materials in the examples: (ii) (a) pure CS, (b) U-LDH and (c) ZnAl-LDH/CS hybrid; FIG. 1 shows that CS has been incorporated into the ZnAl-LDH/CS hybrid and affects the structure of the ZnAl-LDH/CS hybrid, further confirming that CS and ZnAl-LDH have bound to form a ZnAl-LDH/CS complex.
FIG. 2 shows the UV-Vis DRS spectrum of the hybrid material in the example: (a) pure CS, (b) ZnAl-LDH and (c) ZnAl-LDH/CS; as the concentration of CS used to prepare the ZnAl-LDH/CS increases, the thermal resistance of the ZnAl-LDH/CS hybrid decreases.
Fig. 3 shows the XRD pattern of the hybrid material in example: (a) thermogravimetric and differential thermogravimetric TGA-DTG curves of pure CS; (b) ZnAl-LDH; (c) ZnAl-LDH/CS. The XRD pattern of the ZnAl/CS mixture shows reflections attributed to ZnAl-LDH, indicating that the addition of CS does not affect the crystal structure of ZnAl-LDH.
Fig. 4 shows the XRD pattern of the hybrid material in the example: XRD patterns of (a) pure CS, (b) ZnAl-LDH and (c) ZnAl-LDH/CS; SEM images confirmed that the morphology of the ZnAl-LDH/CS hybrid differs from that of ZnAl and CS, indicating the formation of a ZnAl-LDH and CS based hybrid.
Fig. 5 shows SEM images of the hybrid materials in the examples: (a) pure CS, (b) ZnAl-LDH5 and (c) ZnAl-LDH/CS (. Times.20,000). The release of potassium in the cell culture medium indicates the presence of the CS molecule, while the zinc ion (Zn) 2+ ) Indicates the presence of active oxygen species (ZnO, al) 2 O 3 ) Is produced by the combination of ZnAl-LDH and CS.
Fig. 6 shows the concentrations of (a) zinc ions and (b) potassium released from the cell culture medium comprising the ZnAl-LDH/CS hybrid in the examples (n = 3). Due to the binding of the molecules, the antibacterial activity of ZnAl-LDH/CS is much greater than that of CS and ZnAl-LDH. The results show that the hybrid of chitosan and ZnAl-LDH can maintain and improve the antibacterial ability of both compounds in cell culture media with pH higher than 5.5.
Fig. 7 shows the effect of CS, znAl and ZnAl/CS on (a) penicillium (scale bar =0.5 cm).
Fig. 8 shows the effect of CS, znAl and ZnAl/CS on e.coli (b) (scale bar =0.5 cm).
Detailed Description
The invention adopts a urea 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.
The invention provides a preparation method of a ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, which comprises the following steps:
a. preparation of Zn (NO) 3 ) 2 ·6H 2 O solution and Al (NO) 3 ) 3 ·9H 2 O solution with the total concentration of metal ions of 0.10-0.22 mol/L and Zn 2+ And Al 3+ The molar ratio of (A) to (B) is 1/3-5.0; adding urea into the solution, and uniformly stirring to obtain a solution A;
b. dissolving chitosan with low acetylation degree in lactic acid water solution to prepare biopolymer solution B, and adjusting pH value of the biopolymer solution to 10 by using sodium hydroxide;
c. and adding the solution A into the solution B, uniformly mixing, reacting for 16h at 60-80 ℃, continuously aging the obtained precipitate for 3-5h, repeatedly centrifuging, separating to obtain a white solid product, washing and drying to obtain the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the adding amount of urea in the step a is as follows: urea/NO 3- And the molar ratio is 4.
In the preparation method of the ZnAl 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 preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the lactic acid aqueous solution in the step b is stirred for more than 30 min.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the concentration of chitosan in the step b is 0.5-2g/L.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the addition amount of sodium hydroxide in the step b is as follows: CS/NaOH = 1.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the operation in the step c is carried out under the protection of nitrogen.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the speed of adding the solution in the step c is 20mL/h.
In the preparation method of the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material, the washing in the step c is washed by decarburized water, and the drying condition is that the drying is carried out for 24 hours at 90-110 ℃.
The invention also provides the ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material prepared by the method.
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 activities, 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 comprises 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, thereby being 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+ ) The characteristics of protection, conduction and signal amplification are combined with excellent film-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 cell permeability and membrane lysisAnd (6) changing. 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 Hydroxide (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+ Solution a (200 ml) prepared from 0.10 to 0.22mol · L-1) of Zn and Al metal chloride solution the mixed solution was poured into a three-necked round-bottom flask and urea (solution B: urea/NO 3- The molar ratio is 4: 1).
The A and B solutions were then added dropwise to 200mL of deionized water at 60-80 ℃ while stirring vigorously. The reaction solution was magnetically stirred at 110 ℃ for 12h. Filtering and washing to neutrality, and then drying for 24 hours at 80 ℃, wherein the obtained sample is ZnAl-LDH hybrid material.
Example 2 preparation of ZnAl two-dimensional Metal hydroxide-Chitosan hybrid Material
a. Zn (NO) with metal ion concentration of 0.10-0.22 mol/L is prepared 3 ) 2 ·6H 2 O solution and Al (NO) 3 ) 3 ·9H 2 Adding urea into the solution, and uniformly stirring, wherein the molar ratio of urea/NO 3-is 4;
b. a biopolymer solution was prepared by dissolving 0.5g/L of chitosan with a low (10% or less) acetylation degree in an aqueous lactic acid solution (2 mL) stirred for 30 minutes; adding sodium hydroxide into the biopolymer solution to make the pH value reach 10; the adding amount of the sodium hydroxide is as follows: CS/NaOH = 1;
c. the reaction was carried out under nitrogen atmosphere to avoid contamination. Pouring the solution obtained in the step a into a three-neck round-bottom flask containing the solution obtained in the step b at the speed of 20mL/h. 100m of the solution from step b were added dropwise to the mixed salt solution at room temperature under stirring (300 rpm) at pH 8.5. After dropwise addition, the reaction temperature was raised to 103 ℃ with stirring for 12h and aged for 3-5h. After reaction, crystallizing the mixture at 80 ℃ for 18 hours, filtering, washing, and then drying at 90 ℃ for 6 hours to obtain the ZnAl two-dimensional metal hydroxide-chitosan hybrid material.
Example 3 preparation of ZnAl two-dimensional Metal hydroxide-Chitosan hybrid Material
a. Zn (NO) with metal ion concentration of 0.10-0.22 mol/L is prepared 3 ) 2 ·6H 2 O solution and Al (NO) 3 ) 3 ·9H 2 Adding urea into the solution, and uniformly stirring, wherein the molar ratio of urea/NO 3-is 4;
b. dissolving 1g/L of chitosan with low acetylation degree (less than 10%) in lactic acid aqueous solution (2 mL) stirred for 30 minutes to prepare biopolymer solution; adding sodium hydroxide into the biopolymer solution to make the pH value reach 10; the adding amount of the sodium hydroxide is as follows: CS/NaOH = 1;
c. the reaction was carried out under nitrogen atmosphere to avoid contamination. Pouring the solution obtained in the step a into a three-neck round-bottom flask filled with the solution obtained in the step b at the speed of 20mL/h. 100m of the solution from step b were added dropwise to the mixed salt solution at room temperature under stirring (300 rpm) at pH 8.5. After the dropwise addition, the reaction temperature was raised to 103 ℃ with stirring for 12h and aged for 3-5h. After reaction, crystallizing the mixture at 80 ℃ for 18 hours, filtering, washing and drying the mixture at 90 ℃ for 6 hours to obtain the ZnAl two-dimensional metal hydroxide-chitosan hybrid material.
Example 4 preparation of ZnAl two-dimensional Metal hydroxide-Chitosan hybrid Material
a. Zn (NO) with metal ion concentration of 0.10-0.22 mol/L is prepared 3 ) 2 ·6H 2 O solution and Al (NO) 3 ) 3 ·9H 2 Adding urea into the solution, and uniformly stirring the solution to obtain an O solution, wherein the molar ratio of urea to NO3-Example 4;
b. dissolving 3g/L of chitosan with low acetylation degree (less than 10%) in lactic acid aqueous solution (2 mL) stirred for 30 minutes to prepare biopolymer solution; adding sodium hydroxide into the biopolymer solution to make the pH value reach 10; the adding amount of the sodium hydroxide is as follows: CS/NaOH = 1;
c. the reaction was carried out under nitrogen atmosphere to avoid contamination. Pouring the solution obtained in the step a into a three-neck round-bottom flask filled with the solution obtained in the step b at the speed of 20mL/h. 100m of the solution from step b were added dropwise to the mixed salt solution at room temperature under stirring (300 rpm) at pH 8.5. After dropwise addition, the reaction temperature was raised to 103 ℃ with stirring for 12h and aged for 3-5h. After reaction, crystallizing the mixture at 80 ℃ for 18 hours, filtering, washing, and then drying at 90 ℃ for 6 hours to obtain the ZnAl two-dimensional metal hydroxide-chitosan hybrid material.
Example 5 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 of microorganisms of Hunan Tan university.
P. cyclopium strains were maintained in Potato Dextrose (PD) medium at 28 ℃ for 72 hours. Coli and s.aureus strains were maintained in a Mineral Salt (MS) medium at ph7.0 at 37 ℃ for 24 hours. All samples were measured to obtain their OD 600nm values to calculate the inhibitory concentration. The control test contained nutrient medium with bacterial suspension but no antimicrobial agent.
The antimicrobial efficiency 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 e.coli strains were transferred onto PD and MS media. 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 well was measured to assess antimicrobial activity. The results are shown in table 1 below and in fig. 1-7.
TABLE 1 antibacterial Activity of LDH-ZnAl/CS hybrid materials
Figure GDA0004104915200000081
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 be seen that the hybrid material of the present invention requires strict CS concentration in the preparation. The hybrid material with enhanced antibacterial activity is prepared by the method, and has important economic value.

Claims (7)

  1. A preparation method of a ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material is characterized by comprising the following steps:
    a. preparation of Zn (NO) 3 ) 2 ·6H 2 O solution and Al (NO) 3 ) 3 ·9H 2 O solution with the total concentration of metal ions of 0.10-0.22 mol/L and Zn 2+ And Al 3+ The molar ratio of (A) to (B) is 1/3-5.0; adding urea into the solution, and uniformly stirring to obtain a solution A;
    b. dissolving chitosan with low acetylation degree in lactic acid water solution to prepare biopolymer solution B, and adjusting pH value of the biopolymer solution to 10 by using sodium hydroxide; the adding amount of the sodium hydroxide in the step b is as follows: CS/NaOH = 1; the concentration of the chitosan in the step b is 0.5-2g/L;
    c. adding the solution A into the solution B, uniformly mixing, reacting for 16h at 60-80 ℃, continuously aging the obtained precipitate for 3-5h, repeatedly centrifuging, separating to obtain a white solid product, washing and drying to obtain a ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material; and c, washing by adopting decarburized water, and drying for 24 hours at the temperature of 90-110 ℃.
  2. 2. The preparation method of ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, characterized in that: the adding amount of the urea in the step a is as follows: urea/NO 3 - And the molar ratio is 4.
  3. 3. The preparation method of ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, characterized in that: the chitosan with low acetylation degree in the step b is chitosan with deacetylation degree of 90-99.5%.
  4. 4. The preparation method of ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, characterized in that: and c, stirring the lactic acid aqueous solution in the step b for more than 30 min.
  5. 5. The preparation method of ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, characterized in that: and c, performing the operation in the step c under the protection of nitrogen.
  6. 6. The preparation method of ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material as claimed in claim 1, characterized in that: the rate of addition of the solution in step c was 20mL/h.
  7. 7. ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material prepared by the preparation method of any one of claims 1 to 6.
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