CN113956494A - Metal-polyphenol colloid and preparation method and application thereof - Google Patents
Metal-polyphenol colloid and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical synthesis of self-assembled supramolecular materials, and particularly relates to a metal-polyphenol colloid and a preparation method and application thereof. The metal-polyphenol colloid is a colloidal particle aggregate formed by complexing and coordinating tannic acid and transition metal ions; the zeta potential is-40 mV to-35 mV, and the average grain diameter is 90-150 nm. The obtained metal-polyphenol colloid has excellent dynamic stability and good interface adhesion performance, can be used as a modular unit colloid to be applied to the preparation of an interface coating material, is more convenient for industrial control, and solves the problems that only existing preparation can be used or the material utilization rate is low due to the unstable dynamics of a metal-polyphenol polymer in the existing coating preparation process.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis of self-assembled supramolecular materials, and particularly relates to a metal-polyphenol colloid and a preparation method and application thereof.
Background
The metal-polyphenol polymer is obtained by realizing material phase separation by coordination of two components in a homogeneous solvent based on a self-assembled supermolecule amorphous material formed by coordination and complexation of polyphenol molecules and catechol groups and metal ions; the self-assembly process is an assembly preparation process with rapid reaction kinetics and mild reaction conditions.
Metal-polyphenol polymers have two basic building blocks: the polyphenol molecule requires at least one catechol group as a complexing site; the metal as the crosslinking center includes various oxidation state ions such as transition metal and rare earth metal.
Because the polyphenol material has no different intrinsic adhesion to various substrates based on the molecular action generated by phenolic hydroxyl, the metal-polyphenol polymer is widely concerned by the technical field of interface engineering and is considered as an ideal interface modification material as a polydopamine mussel bionic coating.
At present, the coating formed by complexing the most economical tannin molecules and ferric ions in a constructed system has the best film-forming efficiency, and the tannin molecules serving as complex polyphenol molecules can provide more coordination crosslinking sites, have stronger deposition and adhesion capacity of a polyaromatic branched structure, have larger polymer monomer molecular weight and the like.
The prior art discloses a preparation method of a catalytic membrane, wherein the preparation method comprises the steps of respectively adding tannic acid and ferric trichloride into a Tris buffer solution to prepare a solution, wetting the membrane surface by using the ferric trichloride solution, adding the tannic acid solution, and reacting to obtain a mixed coating. In actual operation, however, after the ferric trichloride is added into the Tris buffer solution, part of iron ions are produced and precipitated, and the added tannic acid can only react with a small amount of iron ions in the system, so that the raw material utilization rate is low, and the production cost is high.
The prior art also discloses a method for preparing a composite material with silver-plated surface by surface modification of tannic acid-ferric trichloride, wherein a substrate is placed in an aqueous solution containing tannic acid and ferric trichloride and having a pH of 6-10 to obtain the substrate with poly (tannic acid-ferric trichloride) deposited on the surface. However, in the method, the aqueous solution is prepared just before use, and the modification time of the surface of the substrate is not more than 1 minute, otherwise, a large amount of metal polyphenol TA-Fe floccules are formed in the aqueous solution.
It can be seen that the existing metal-polyphenol polymer has the problems of unstable dynamics, existing preparation, low material utilization rate, difficult long-term storage and inconvenient transportation in the process of preparing a coating.
Disclosure of Invention
The first object of the present invention is to provide a metal-polyphenol colloid. The obtained metal-polyphenol colloid has excellent dynamic stability and good interface adhesion performance, can be used as a modular unit colloid to be applied to the preparation of an interface coating material, is more convenient for industrial control, and solves the problems that only existing preparation can be used or the material utilization rate is low due to the unstable dynamics of a metal-polyphenol polymer in the existing coating preparation process.
The metal-polyphenol colloid is a colloidal particle aggregate formed by complexing and coordinating tannic acid and transition metal ions, the zeta potential of the metal-polyphenol colloid is-40 mV to-35 mV, and the average particle size of the metal-polyphenol colloid is 90-150 nm.
The invention firstly provides the construction idea of the modular metal-polyphenol colloid assembly unit, avoids the procedure defects that the material precursor liquid is required to be prepared freshly and mixed and dissolved discretely in the traditional method, and the obtained colloid can be dispersed in water or an organic solvent for long-term storage, is convenient to carry and transport, and is expected to be suitable for various processes for obtaining coatings by desolvation. The modular design concept provided by the invention is beneficial to bringing innovation to the surface modification technology in the field of material chemistry assisted by the metal-polyphenol complex.
Preferably, the transition metal ion is Fe3+、Cu2+、Al3+Or Zr4+。
The second purpose of the invention is to provide a preparation method of the metal-polyphenol colloid.
The preparation method of the metal-polyphenol colloid comprises the following steps: under the action of a buffer solution, the tannic acid and transition metal ions carry out a complex reaction; firstly, dissolving tannic acid in a buffer solution to form a precursor solution A, and then adding a precursor solution B containing transition metal ions into the precursor solution A.
In practical research, the technicians of the invention find that after a large amount of metal polyphenol TA-Fe flocs are formed by directly contacting a tannic acid solution and an iron chloride solution, most of the flocs cannot be redispersed by adjusting the pH of a system even though a Tris buffer solution is added, so that a large amount of flocs cannot be utilized, a supernatant can be obtained only by filtering, and residual molecules in the supernatant are utilized and then the Tris buffer solution is added to adjust the pH to a proper range for preparing a coating. This not only results in a large amount of material waste, but also greatly reduces the concentration of the metal-polyphenol polymer. When the Tris buffer solution is firstly contacted with Fe ions, the alkalinity of Tris can cause the rapid formation of ferric hydroxide precipitate, and the added tannic acid cannot form complex coordination with the iron ions.
Through tests, the inventor finds that the tannin is firstly mixed with the buffer solution, and then the transition metal ions are added, and through the material mixing mode, the system does not produce precipitates or floccules; and obtaining the micelle module with excellent dynamic stability and good interface adhesion performance under the synergistic action of Tris mediation and tannic acid on the complexation of transition metal ions.
Further studies have found that the contribution to the stable colloidal state is not due to the weak alkaline environment of the buffer, because the use of Phosphate Buffered Saline (PBS) at the same pH, or the direct replacement of Tris buffer with NaOH solution at the same pH, is not equally effective and still forms TA-Fe flocs. In the invention, the buffer solution is one or more selected from Tris (hydroxymethyl) aminomethane Tris buffer solution, Bis (2-hydroxyethylamino) Tris (hydroxymethyl) methane Bis-Tris buffer solution or 2- [ [ Tris (hydroxymethyl) methyl ] amino ] ethanesulfonic acid TES buffer solution. The buffer solutions provide weak base, neutral environment and mediated environment of supporting colloid form for complex coordination, and guarantee the obtaining of colloid.
Further preferably, the pH of the precursor liquid a is controlled to be 6-11, and the molar concentration of the buffer solution is at least 5 times of that of the transition metal ions, so that the complexing reaction process is more stable, the condition that the pH of the system is reduced and floccules are generated due to the addition of the transition metal ions is effectively prevented, and the method is more favorable for obtaining a discrete, uniform-scale and dynamically stable metal-polyphenol colloid. Still more preferably, the molar ratio of the buffer to the transition metal ion is (5-20): 1.
preferably, the pH of the system of the complexation reaction is controlled to be between 6.5 and 10, so as to ensure a dominant coordination mode with strong adhesive capacity of colloid.
Preferably, the concentration of the tannic acid in the precursor liquid A is 0.1-5.0 mM.
The precursor liquid B is a salt solution containing transition metal ions, and the salt is preferably hydrochloride. The concentration of transition metal ions in the salt solution is 0.1-20 mM.
Preferably, during the preparation of the precursor solution a, tannic acid is slowly added into the buffer solution under the condition of vigorous stirring to ensure sufficient dissolution.
The third object of the present invention is to provide an aqueous dispersion containing a metal-polyphenol colloid, which is obtained by removing an excessive amount of a buffer reagent and excessive metal ions from the dispersion containing a metal-polyphenol colloid obtained by the above-mentioned preparation method by dialysis.
The aqueous dispersion containing the metal-polyphenol colloid is purple black, the pH value is 5.0-6.5, the zeta potential is-55 mV to-40 mV, and the particle size of the colloid is less than 150 nm. The solvent in the obtained water system dispersion liquid is only water, and belongs to environment-friendly liquid, but the colloid is still stable, and the subsequent stable use does not depend on a buffer system any more.
Preferably, the dialysis adopts a dialysis bag with the molecular weight of cut-off filtration of 100-10000, and the dialysis time is 10-80 h.
The fourth object of the present invention is to provide an organic dispersion containing a metal-polyphenol colloid, which is obtained by concentrating the aqueous dispersion containing a metal-polyphenol colloid and then replacing it with an organic solvent.
Preferably, the organic solvent is selected from methanol, ethanol, isopropanol, dimethyl sulfoxide, N-dimethylformamide, acetonitrile, etc., and the colloid in the organic dispersion obtained after the replacement is still stable.
Further preferably, the replacement volume ratio of water to the organic solvent in the aqueous dispersion of the metal-polyphenol colloid is 1 (0.2 to 10).
A fifth object of the present invention is to provide the use of the above metal-polyphenol colloid, aqueous dispersion containing metal-polyphenol colloid, and organic dispersion containing metal-polyphenol colloid in an interface coating material.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adjusts the material adding sequence in the existing preparation of the metal-polyphenol polymer, obtains metal-polyphenol colloid with stable dynamics and uniform size under the synergistic action of Tris-like buffer molecule mediation and tannin on the complexation of transition metal ions, and has universality on the transition metal ions with various valence states.
2) The metal-polyphenol colloid and the dispersion liquid thereof have wide adaptability, can be stable in a wide environment range, such as a pH stable range of 2.5-11 and a temperature stable range of 20-80 ℃, and can be suitable for various chemical and biological research systems.
3) The method can proportionally increase the concentration of the tannic acid, the metal ions and the Tris buffer solution in the system to 5-10 times and keep the stability, and is more favorable for improving the utilization rate of a colloid assembly unit.
4) The metal-polyphenol colloid prepared by the invention still retains good interface adhesion capability due to the dominant coordination mode caused by controlling the synthetic pH, and is a construction unit of a potential interface coating material.
Drawings
FIG. 1 is a scanning electron micrograph of the particle morphology of TA-Fe colloid.
FIG. 2 is a graph showing a distribution of the particle size of TA-Fe colloid.
Fig. 3 is a photograph of tyndall phenomenon of organic dispersions of four metal-polyphenol colloids. Wherein (a) represents a TA-Fe colloidal dispersion liquid, (b) represents a TA-Cu colloidal dispersion liquid, (c) represents a TA-Al colloidal dispersion liquid, and (d) represents a TA-Zr colloidal dispersion liquid.
FIG. 4 is a graph showing the visible absorption spectra of organic dispersions of four metal-polyphenol colloids.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
As one embodiment of the present invention, the method for preparing a metal-polyphenol colloid comprises:
s1: formulation of competitive ligand buffers
Weighing 0.1-9.6 g of tris (hydroxymethyl) aminomethane, dissolving in 800mL of deionized water, preparing 1.0-100.0 mM tris (hydroxymethyl) aminomethane solution, and regulating and controlling the pH of the buffer solution to 7.0-10.0 for later use;
weighing 0.17-16.7 g of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane, dissolving in 800mL of deionized water, preparing 1.0-100.0 mM of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane solution, and regulating the pH of the buffer solution to 7.0-10.0 for later use;
weighing 0.18-18.34 g of 2- [ [ tris (hydroxymethyl) methyl ] amino ] ethanesulfonic acid and dissolving in 800mL of deionized water to prepare 1.0-100.0 mM of 2- [ [ tris (hydroxymethyl) methyl ] amino ] ethanesulfonic acid solution, and regulating the pH of the buffer solution to 7.0-10.0 for later use;
s2: preparation of tannin assembly precursor liquid A
Respectively measuring 100mL of trihydroxymethyl aminomethane buffer solution, bis (2-hydroxyethylamino) tris (hydroxymethyl) methane buffer solution and 2- [ [ tris (hydroxymethyl) methyl ] amino ] ethanesulfonic acid; 0.02-0.85 g of tannic acid powder is weighed, and is slowly added into three types of buffer solutions respectively under the stirring state of magnetons to ensure the sufficient dissolution of tannic acid, wherein the stirring time is as follows: stirring for 0.5-24 h until the residence time stops disturbance, carrying out anaerobic packaging to obtain the tannin assembly precursor liquid A, and controlling the preservation time within 0.5-5 h. The concentration of the preparation is 0.1-5.0 mM.
S3: preparation of precursor liquid B for four metal salt assembly
Weighing 0.002-0.32 g FeCl3Dissolving in 100mL of deionized water to prepare 0.1-20 mM FeCl3Keeping the water solution for 15min, and regulating pH to be less than 3;
weighing 0.001-0.26 g of CuCl2Dissolving in 100mL of deionized water to prepare 0.1-20 mM CuCl2An aqueous solution;
weighing 0.001-0.26 g AlCl3Dissolving in 100mL of deionized water to prepare 0.1-20 mM AlCl3An aqueous solution;
weighing 0.002-0.47 g ZrCl4Dissolving in 100mL deionized water to prepare 0.1-20 mM ZrCl4An aqueous solution.
S4: preparation of metal-polyphenol colloidal dispersion
Respectively adding 100mL of FeCl with good constant volume310-1000 mL of tris (hydroxymethyl) aminomethane and bis (2-hydroxyethylamino) tris (tert-butyl-tert-butyl) are quickly poured into the assembly precursor solution BHydroxymethyl) methane, 2- [ [ tris (hydroxymethyl) methyl]Amino group]Stirring 1-30 min in a precursor solution A assembled by tannic acid of three buffer systems of ethanesulfonic acid to obtain a TA-Fe metal polyphenol colloid dispersion solution;
100mL of CuCl with constant volume is added2Quickly pouring the assembly precursor solution into 10-1000 mL of trihydroxymethyl aminomethane buffer system tannic acid assembly precursor solution, and stirring for 1-30 min to obtain TA-Cu metal polyphenol colloid dispersion liquid;
100mL of AlCl with a constant volume is added3Quickly pouring the assembly precursor solution into 10-1000 mL of trihydroxymethyl aminomethane buffer system tannic acid assembly precursor solution, and stirring for 1-30 min to obtain TA-Al metal polyphenol colloid dispersion liquid;
100mL of ZrCl with good constant volume is added4And quickly pouring the assembly precursor solution into 10-1000 mL of the trihydroxymethyl aminomethane buffer system tannic acid assembly precursor solution, and stirring for 1-30 min to obtain the TA-Zr metal polyphenol colloid dispersion solution.
As one embodiment of the present invention, the aqueous dispersion of the metal polyphenol colloid is prepared by the following method (purification):
respectively filling 200mL of TA-Fe, TA-Cu, TA-Al and TA-Zr metal polyphenol colloid dispersion liquid into dialysis bags with molecular filtration amount of 100-10000, sinking the dialysis bags into a beaker filled with 2L of deionized water, filling magnetons at the bottom of the beaker, stirring, and dialyzing for 10-80 h; the pH of the water dispersion of the metal polyphenol colloid obtained after dialysis is stabilized at 6.0-7.5, and the water dispersion can be stored for a long time.
As one embodiment of the present invention, the organic dispersion of the metal-polyphenol colloid is obtained by the following method (solvent substitution):
measuring 6 parts of TA-Fe metal-polyphenol colloid dispersed aqueous solution with the volume of 10mL, respectively adding 2-100 mL of methanol, ethanol, isopropanol, dimethyl sulfoxide, N-dimethylformamide and acetonitrile into the six parts of solution, wherein the water/organic solvent ratio is 1: (0.2-10) preparing the metal polyphenol organic dispersion liquid.
Specific examples of the preparation of four groups of TA-Fe, TA-Cu, TA-Al, TA-Zr colloids during the course of the study of the present invention are provided below.
Example 1
The embodiment provides a preparation method of TA-Fe colloid, which comprises the following steps:
(1) formulation of competitive ligand buffers
Preparing a 10mM buffer solution of trihydroxymethyl aminomethane, and regulating the pH value of the buffer solution to 7.0-10.0 for later use;
preparing a buffer solution of 10mM bis (2-hydroxyethylamino) tris (hydroxymethyl) methane, and regulating the pH of the buffer solution to 7.0-10.0 for later use;
preparing 10mM buffer solution of 2- [ [ tri (hydroxymethyl) methyl ] amino ] ethanesulfonic acid, and regulating the pH of the buffer solution to 7.0-10.0 for later use;
(2) preparation of precursor solution for tannin assembly
Respectively measuring 100mL of a buffer solution of tris (hydroxymethyl) aminomethane, a buffer solution of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane and a buffer solution of 2- [ [ tris (hydroxymethyl) methyl ] amino ] ethanesulfonic acid;
preparing a tannin water solution with the concentration of 0.6 mM;
under the stirring state of magnetons, slowly adding the mixture into three types of buffer solutions respectively to ensure the sufficient dissolution of the tannic acid; stirring for 0.6h, stopping stirring until the retention time is reached, packaging in an anaerobic environment to obtain 0.6mM of tannin assembly precursor solution, and keeping the preservation time within 0.5 h.
(3) Preparation of metal salt assembly precursor liquid
Preparation of 1.8mM FeCl3Keeping the water solution for 15 min;
(4) preparation of metal-polyphenol colloidal dispersion
100mL of FeCl with good constant volume is added3100mL of tris (hydroxymethyl) aminomethane, bis (2-hydroxyethylamino) tris (hydroxymethyl) methane and 2- [ [ tris (hydroxymethyl) methyl ] are quickly poured into the assembly precursor solution]Amino group]The precursor solution of the ethanesulfonic acid buffer system tannic acid assembly is stirred for 5min to obtain TA-Fe metal polyphenol colloid dispersion liquid;
(5) purification of metal-polyphenol colloids
Putting 200mL of TA-Fe metal polyphenol colloid dispersion liquid into a dialysis bag with the molecular filtration amount of 1000, sinking the dialysis bag into a beaker filled with 2L of deionized water, putting magnetons at the bottom of the beaker, stirring, and dialyzing for 72 hours; the pH value of all the metal polyphenol colloid dispersion liquid after dialysis is stabilized at 6.0-7.5, and the metal polyphenol colloid dispersion liquid can be stored for a long time.
(6) Solvent displacement of metal-polyphenol colloidal dispersion
10mL of TA-Fe colloidal dispersion aqueous solution was measured, and 40mL of methanol was added to the solution at a water/organic solvent ratio of 1: 4 preparing an organic dispersion of the metal-polyphenol colloid.
Example 2
This example provides a method for preparing TA-Cu colloid, which is different from example 1 in that:
preparing a 10mM buffer solution of tris (hydroxymethyl) aminomethane, and regulating the pH of the buffer solution to 7.0-10.0;
preparing 0.6mM of tannic acid assembly precursor solution;
1.8mM CuCl was prepared2An aqueous solution;
100mL of CuCl with constant volume is added2Quickly pouring the aqueous solution into 100mL of tannin assembly precursor solution in a tris buffer system, and stirring for 5min to obtain aqueous dispersion of TA-Cu metal polyphenol colloid.
Example 3
This example provides a method for preparing TA — Al colloid, which is different from example 1 in that:
preparing a 10mM buffer solution of tris (hydroxymethyl) aminomethane, and regulating the pH of the buffer solution to 7.0-10.0;
preparing 0.6mM of tannic acid assembly precursor solution;
1.8mM AlCl was prepared3An aqueous solution;
100mL of AlCl with a constant volume is added3And quickly pouring the assembly precursor solution into 1000mL of the trihydroxymethyl aminomethane buffer system tannic acid assembly precursor solution, and stirring for 5min to obtain the TA-Al metal polyphenol colloid dispersion solution.
Example 4
This example provides a method for preparing TA — Zr colloid, which is different from example 1 in that:
preparing a 10mM buffer solution of tris (hydroxymethyl) aminomethane, and regulating the pH of the buffer solution to 7.0-10.0;
preparing 0.6mM of tannic acid assembly precursor solution;
1.8mM ZrCl was prepared4An aqueous solution;
100mL of ZrCl with good constant volume is added4And quickly pouring the assembly precursor solution into 100mL of the tannic acid assembly precursor solution of the tris buffer system, and stirring for 5min to obtain the TA-Zr metal polyphenol colloid dispersion solution.
Effect verification
1. Structure and particle size
Directly infiltrating the monodisperse solution of the TA-Fe colloid in example 1 with a copper mesh, and fishing, wherein TA-Fe colloidal particle aggregates with certain particle size can be directly observed through a scanning electron microscope SEM (shown in figure 1); dynamic light scattering also demonstrated an average particle size of the TA-Fe colloid of <150nm, as shown in figure 2.
Similarly, the SEM and particle size diagrams of the monodisperse dispersions of the colloids obtained in examples 2 to 4 also show the corresponding structures and particle size.
2. Tyndall phenomenon
Tndall phenomenon can be observed in the dispersion liquid of four colloids of TA-Fe, TA-Cu, TA-Al and TA-Zr, as shown in figure 3;
the ultraviolet-visible spectrum shows that the four colloid dispersion solutions have obvious absorbance enhancement in the range of 400-800nm in the visible region compared with the tannin assembly precursor solution with the same concentration, which shows that the tannin and the metal ions realize complex coordination through electron transfer, as shown in fig. 4.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A metal-polyphenol colloid characterized by a micelle aggregate formed by the complex coordination of tannic acid and a transition metal ion; the zeta potential is-40 mV to-35 mV, and the average grain diameter is 90-150 nm.
2. The metal-polyphenol colloid of claim 1, wherein the transition metal ion is Fe3+、Cu2+、Al3+Or Zr4+。
3. A method for preparing a metal-polyphenol colloid, comprising: under the action of a buffer solution, the tannic acid and transition metal ions carry out a complex reaction; firstly, dissolving tannic acid in a buffer solution to form a precursor solution A, and then adding a precursor solution B containing transition metal ions into the precursor solution A.
4. The method of claim 3, wherein the buffer is one or more selected from Tris (hydroxymethyl) aminomethane Tris buffer, Bis (2-hydroxyethylamino) Tris (hydroxymethyl) methane Bis-Tris buffer, and 2- [ [ Tris (hydroxymethyl) methyl ] amino ] ethanesulfonic acid TES buffer.
5. The method for producing a metal-polyphenol colloid according to claim 4, wherein the pH of the precursor liquid a is controlled to 6 to 11, and the molar concentration of the buffer is at least 5 times or more the transition metal ion;
preferably, the molar ratio of the buffer to the transition metal ion is (5-20): 1.
6. the method for preparing a metal-polyphenol colloid as claimed in claim 5, wherein the pH of the system of the complexation reaction is controlled to be between 6.5 and 10.
7. An aqueous dispersion containing a metal-polyphenol colloid, which is obtained by removing an excessive amount of a buffer reagent and an excessive amount of metal ions from the dispersion containing a metal-polyphenol colloid obtained by the production method according to any one of claims 3 to 6 by dialysis.
8. The aqueous dispersion of metal-polyphenol containing colloids of claim 7 wherein the aqueous dispersion of metal-polyphenol containing colloids is purple black, has a pH of 5 to 6.5, a zeta potential of-55 mV to-40 mV, and a colloid particle size of <150 nm;
preferably, the dialysis adopts a dialysis bag with the molecular weight of cut-off filtration of 100-10000, and the dialysis time is 10-80 h.
9. An organic dispersion containing a metal-polyphenol colloid, which is obtained by concentrating the aqueous dispersion containing a metal-polyphenol colloid according to claim 7 or 8 and then replacing it with an organic solvent;
preferably, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, dimethyl sulfoxide, N-dimethylformamide or acetonitrile.
10. Use of a metal-polyphenol colloid of claim 1 or 2 or an aqueous dispersion comprising a metal-polyphenol colloid of claim 7 or 8 or an organic dispersion comprising a metal-polyphenol colloid of claim 9 in an interfacial coating material.
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| CN115606606A (en) * | 2022-10-08 | 2023-01-17 | 河海大学 | Novel metal polyphenol network loaded metal oxide antibacterial nanoparticles, preparation method and application |
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| CN109939246A (en) * | 2019-04-19 | 2019-06-28 | 西安交通大学 | A kind of gadolinium of small size-polyphenol polymer nano particle and its preparation method and application |
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| CN114948996A (en) * | 2022-06-13 | 2022-08-30 | 国家纳米科学中心 | Antibacterial agent and preparation method and application thereof |
| CN115606606A (en) * | 2022-10-08 | 2023-01-17 | 河海大学 | Novel metal polyphenol network loaded metal oxide antibacterial nanoparticles, preparation method and application |
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