CN114652854A - Double-lock MOF material and preparation and application thereof - Google Patents
Double-lock MOF material and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
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- A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
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Abstract
The invention belongs to the field of nano materials and biomedicine, and particularly relates to a double-lock MOF material and preparation and application thereof. The double-lock MOF material is a double-lock MOF material which takes ZIF-90 as a core and is externally wrapped with acid-sensitive hydrogel to form a shell-core structure and has double-lock response. The double-lock MOF material prepared by the invention has excellent simultaneous stimulation response release performance of acid and ATP. The double-lock MOF prepared by the invention has good stability and biocompatibility, and has wide application prospects in the aspects of drug delivery and disease treatment.
Description
Technical Field
The invention belongs to the field of nano materials and biomedicine, and particularly relates to a double-lock MOF material and preparation and application thereof.
Background
Bacterial colonization on surfaces and subsequent biofilm formation is one of the key global issues. Biofilms are a complex community of microorganisms in exopolysaccharide matrices that irreversibly adhere to the surface of materials, leading to biofouling and wound infection. Currently, the most common strategy for combating biofilms is the use of antibacterial drugs, however, the use of excess drug results in the emergence of resistant bacteria and increased off-target toxicity due to lack of targeting and selectivity for biofilms.
Nanocarrier-based antibiotic delivery systems have received considerable attention because of their ability to overcome toxicity caused by non-selective accumulation and to improve bioavailability of antibiotics. The selective targeted cargo release can be realized by utilizing the stimulus response surface modified nano-carrier. However, due to the complex internal environment of the human body, single-stimulus nanocarriers sometimes cannot effectively recognize the biomembrane region. For example, when acidic pH is indicative of a biofilm, acidic organelles or other external acid stimuli can also trigger cargo release, thereby increasing off-target toxicity and potential safety concerns. Therefore, further improvement of the targeting efficiency to the biofilm is crucial for precise medical treatment and imaging, and at present, nano-carriers relate to a wide range of nano-materials, such as silica nanoparticles, carbon nanotubes, gold nanoparticles and quantum, liposome and polymer, but all have response to a single stimulus, and no nano-carrier continuously responding to two stimuli has been found, and a pH/ATP double-locked nano-carrier provides a promising method for solving the problem.
Disclosure of Invention
The invention aims to provide a double-lock MOF material and preparation and application thereof, aiming at solving the problem that the existing biological membrane region cannot be effectively identified.
In order to achieve the purpose, the invention adopts the technical scheme that:
the double-lock MOF material is a double-lock MOF material which takes ZIF-90 as a core, is externally wrapped with acid-sensitive hydrogel and forms a shell-core structure and has double-lock response.
The hydrogel shell is prepared by mixing polyacrylic acid, calcium chloride and sodium carbonate according to a molar ratio of 1:1:1, and then reacting for 2-2.5 hours at normal temperature (22-25 ℃).
The core of the double-lock MOF material is ZIF-90 generated by reacting 2-formaldehyde imidazole and zinc acetate at normal temperature.
The ZIF-90 is prepared by mixing 2-formaldehyde imidazole and zinc acetate according to a molar ratio of 10:1, and then reacting for 30-35 minutes at normal temperature (22-25 ℃).
A preparation method of a double-lock MOF material comprises the steps of reacting 2-formaldehyde imidazole with zinc acetate at normal temperature to obtain ZIF-90, and then mixing the ZIF-90 with polyacrylic acid and calcium chloride to obtain the double-lock MOF material which is an acid-sensitive hydrogel and has a shell-core structure with ZIF-90 wrapped inside a shell and corresponds to double locks.
The material relation ratio of the ZIF-90 to the polyacrylic acid and the calcium chloride is 1:2:2-1:2.5: 2.5.
Use of a double-locked MOF material in drug delivery. Further, the material is applied to drug delivery and tumor treatment.
According to the invention, 2-formaldehyde imidazole and zinc acetate react at normal temperature to generate an MOF material, a fluorescent dye is wrapped in MOF, and an acid stimulus response hydrogel generated by the reaction of polyacrylic acid and calcium chloride is wrapped on the surface of the MOF to form a double-lock MOF material. Wherein the fluorescent dye Rho 6G is encapsulated within the ZIF-90 to demonstrate the stimulus-responsive properties of the double-locked MOF material.
The invention has the beneficial effects that:
according to the invention, 2-formaldehyde imidazole and zinc acetate react at normal temperature to generate an MOF material core, a fluorescent dye is wrapped in the MOF core, and acid stimulus response hydrogel generated by the reaction of polyacrylic acid and calcium chloride is wrapped on the MOF surface to form the double-lock MOF material. In a simulated biological membrane microenvironment, the double-lock MOF material shows good stimulus responsiveness, and the double-lock MOF nano carrier prepared by the invention has the continuous stimulus responsiveness of acid response and ATP response due to the special shell-core structure, and has good stability and selectivity, and is not easily interfered by a complex environment. Has wide application prospect in the aspects of drug delivery and disease treatment.
The double-lock MOF has huge potential in the aspect of double-stimulus response release, and further can be used for drug delivery and biofilm eradication.
Drawings
FIG. 1 is a TEM image of a double-locked MOF provided in example 1 of the present invention, wherein A is rhodamine 6G @ ZIF-90, and B is rhodamine 6G @ ZIF-90@ ACC/PAA;
FIG. 2 is a TEM image of a stimulus response of double-locked MOF provided in example 1 of the present invention, wherein A is the reaction of double-locked MOF in a solution of pH 4.0 for 15min, and B is the reaction of double-locked MOF in a solution of pH 4.0 and 1mM ATP for 15 min;
FIG. 3 is a graph showing the change of fluorescence values of double-locked MOF treated at different pH values according to an embodiment of the present invention;
FIG. 4 is a graph showing the change of fluorescence values of double-locked MOF in different concentrations of ATP under an acidic environment according to an embodiment of the present invention;
FIG. 5 is a graph showing the fluorescence value of the nanocarrier according to different assembly methods.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
According to the invention, by forming the nano double-lock MOF with a specific shell-core structure, the nano carrier has the performances of continuous stimulation response of acid response and ATP response, and has good stability and selectivity, and is not easily interfered by a complex environment.
Example 1:
preparation of double-locked MOF:
1) 48.05mg of 2-imidazolecarboxaldehyde (0.5M), 4.79mg of rhodamine 6G (1mM) are dissolved in 10.0mL of DMF, stirred for 15min, and then 5.0mL of DMF containing 0.05M zinc acetate is slowly added. Then washed with DMF, ultrapure water, ethanol in sequence, and centrifuged (10000rpm,5 min). Finally, the product was dispersed in ultrapure water to give rhodamine 6G @ ZIF-90 stock solution (100mg mL)-1). (see FIG. 1A).
2) 114mg of polyacrylic acid (PAA,0.1M),111mg of calcium chloride (0.1M) and 500. mu.L of rhodamine 6G @ ZIF-90(100mg mL)-1) Added to 10.0mL of ultrapure water and stirred for 1 h. Then, 10.0mL of 0.1M Na was added2CO3The solution was added quickly and stirred for 1 h. The product obtained by centrifugation was washed with ultrapure water (10000rpm,10 minutes), and then dispersed in ultrapure water to obtain rhodamine 6G @ ZIF-90@ ACC/PAA. (see FIG. 1B).
And characterizing the prepared rhodamine 6G @ ZIF-90 and rhodamine 6G @ ZIF-90@ ACC/PAA by a Transmission Electron Microscope (TEM). As shown in FIG. 1A and FIG. 1B, rhodamine 6G @ ZIF-90 and rhodamine 6G @ ZIF-90@ ACC/PAA are all uniform nanoparticles. The rhodamine 6G @ ZIF-90 nano particle is rough in surface, uniform in size and 110-150nm in average diameter. After the polyacrylic acid/calcium chloride is coated, the size of the rhodamine 6G @ ZIF-90@ ACC/PAA material is larger than that of the rhodamine 6G @ ZIF-90, and is about 150-200 nm.
Example 2:
stimulus responsiveness of double-locked MOFs:
5 μ L of rhodamine 6G @ ZIF-90@ ACC/PAA (100mg mL) prepared in the above example was taken-1) The cells were incubated in 3mL of PBS (pH 4.0) for 15 minutes, and the morphology change was observed by TEM (see fig. 2A). 5 mu L of prepared rhodamine 6G @ ZIF-90@ ACC/PAA (100mg mL)-1) Placed in 3mL of PBS (pH 4.0) solution and incubated with 5 μ L of ATP (1M) solution for 15 minutes, and its morphological change was observed by TEM (see fig. 2B).
As shown in the figure 2A and the figure 2B, after acid treatment, the rhodamine 6G @ ZIF-90@ ACC/PAA polyacrylic acid/calcium chloride hydrogel is dissolved, the rhodamine 6G @ ZIF-90 is kept intact, the size of the hydrogel is the same as that of the figure 1A, after the acid and ATP are jointly treated, the polyacrylic acid/calcium chloride hydrogel is dissolved, and the rhodamine 6G @ ZIF-90 particles are cracked to lose the intact form, so that the stimulation responsiveness of the double-lock MOF is proved.
Example 3:
stimulus responsiveness of double-locked MOFs at different pH:
50 μ L of rhodamine 6G @ ZIF-90@ ACC/PAA (1mg mL)-1) Adding 240 μ L of PBS buffer solution with different pH, adding 10 μ L of ATP (1mM) solution, shaking for 60min, and measuring the fluorescence intensity of the solution at excitation wavelength of 525nm and emission wavelength of 552 nm. As can be seen from fig. 3, the fluorescence value of the double-locked MOF nano material increases with time, the release equilibrium can be reached in about 30 minutes, in addition, the change of the fluorescence of the nanoparticles is greatly different in different pH environments, and the release of the fluorescent molecules gradually increases with the increase of the acidity of the environmental system, thus showing good pH stimulus responsiveness.
Example 4:
stimulus responsiveness of double-locked MOF at different ATP concentrations:
50 μ L of rhodamine 6G @ ZIF-90@ ACC/PAA (1mg mL)-1) Adding 240 μ L PBS buffer solution with pH of 4.0 and 6.0 respectively, adding 10 μ L ATP solution with different concentrations, shaking for 60min, and measuring fluorescence intensity of the solution at excitation wavelength of 525nm and emission wavelength of 552 nm. As can be seen from FIG. 4, under acidic conditions, the fluorescence value increases with the increase of ATP concentration, and the system generates a relatively obvious fluorescence response at the ATP concentration of 1 μ M, which proves that the rhodamine 6G @ ZIF-90@ ACC/PAA nanoparticles have sensitive ATP responsiveness.
Example 5:
the fluorescence responsiveness of the nano-carrier prepared by different assembly methods:
1) 48.05mg of 2-imidazolecarboxaldehyde (0.5M), 4.79mg of rhodamine 6G (1mM) are dissolved in 10.0mL of DMF, stirred for 15min, and then 5.0mL of DMF containing 0.05M zinc acetate is slowly added. Then sequentially washing with ultrapure water, dispersing the product in the ultrapure water to obtain rhodamine 6G @ ZIF-90 stock solution (100mg mL)-1). 114mg of polyacrylic acid (PAA,0.1M),111mg of calcium chloride (0.1M) and 500. mu.L of rhodamine 6G @ ZIF-90(100mg mL)-1) Added to 10.0mL of ultrapure water and stirred for 1 h. Then, 10.0mL of 0.1M Na was added2CO3The solution was added quickly and stirred for 1 h. The resulting product was centrifuged and washed with ultrapure water, which was a material prepared by preparation method 1, i.e., example 1.
2) 114mg of polyacrylic acid (PAA,0.1M),111mg of calcium chloride (0.1M) and 4.79mg of rhodamine 6G (1mM) were added to 10.0mL of ultrapure water and stirred for 1 h. Then, 10.0mL of 0.1M Na was added2CO3The solution was added quickly and stirred for 1 h. The resulting product was centrifuged and washed with ultrapure water to obtain a stock solution (100mg mL)-1). 48.05mg of 2-imidazolecarboxaldehyde (0.5M) and 50. mu.L of stock solution (100mg mL)-1) Dissolved in 10.0mL of DMF, stirred for 15min, then 5.0mL of DMF containing 0.05M zinc acetate was added slowly. Then, the product was dispersed in ultrapure water by successively washing with ultrapure water, which was preparation method 2.
mu.L of each of the nanomaterials prepared in the above examples was placed in 3mL of PBS (pH 4.0), 5. mu.L of ATP (1M) was added thereto, the resulting mixture was incubated for 15 minutes, the change in fluorescence was observed, and the resulting mixture was left for 14 days to observe the fluorescence again. The result shows that only the assembly mode of the preparation method 1 can synthesize the target nano-carrier with double stimulation, the nano-carrier has good stability, and the fluorescence value is not obviously changed after the nano-carrier is soaked for 14 days.
Claims (7)
1. A double-locked MOF material, comprising: the double-lock MOF material is a double-lock MOF material which takes ZIF-90 as a core and is externally wrapped with acid-sensitive hydrogel to form a shell-core structure and has double-lock response.
2. A double-locked MOF material according to claim 1, wherein: the hydrogel shell is prepared by mixing polyacrylic acid, calcium chloride and sodium carbonate according to a molar ratio of 1:1:1, and then reacting for 2-2.5 hours at normal temperature (22-25 ℃).
3. A double-locked MOF material according to claim 1, wherein: the core of the double-lock MOF material is ZIF-90 generated by reacting 2-formaldehyde imidazole and zinc acetate at normal temperature.
4. A process for the preparation of a double-locked MOF material according to claim 3, wherein: the ZIF-90 is prepared by mixing 2-formaldehyde imidazole and zinc acetate according to a molar ratio of 10:1, and then reacting for 30-35 minutes at normal temperature (22-25 ℃).
5. A process for the preparation of a double-locked MOF material according to claim 1, wherein: reacting 2-formaldehyde imidazole with zinc acetate at normal temperature to obtain ZIF-90, and mixing the ZIF-90 with polyacrylic acid and calcium chloride to obtain the acid-sensitive hydrogel which is a double-lock MOF material with a shell-core structure wrapped with the ZIF-90 in the shell and corresponding to double locks.
6. A process for the preparation of a double-locked MOF material according to claim 5, characterized in that: the material relation ratio of the ZIF-90 to the polyacrylic acid and the calcium chloride is 1:2:2-1:2.5: 2.5.
7. Use of the double-locked MOF material of claim 1, wherein: use of said material in drug delivery.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115819165A (en) * | 2022-12-20 | 2023-03-21 | 郑州大学 | Copper azide composite initiating explosive block material and preparation method thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017078609A1 (en) * | 2015-11-05 | 2017-05-11 | Su Holding Ab | One-pot synthesis of metal-organic frameworks with encapsulated target-molecule and their use |
CN108456241A (en) * | 2018-01-17 | 2018-08-28 | 南开大学 | Porous framework material is used for the storage and transportation and preparation of biological products |
CN110538345A (en) * | 2019-10-11 | 2019-12-06 | 上海交通大学医学院附属第九人民医院 | biological material, preparation method thereof and application thereof in bone repair |
CN111265533A (en) * | 2019-11-25 | 2020-06-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of core-shell nanoparticles based on lipid membrane and metal organic framework |
CN111269516A (en) * | 2020-04-02 | 2020-06-12 | 北京航空航天大学 | MXene composite gel material, preparation method and application |
CN111643480A (en) * | 2020-04-20 | 2020-09-11 | 武汉大学 | Metal organic framework composite nano material with targeting property and pH responsiveness and preparation method and application thereof |
CN112999352A (en) * | 2021-03-09 | 2021-06-22 | 安徽工程大学 | RGD/PTX @ ZIF-90 drug delivery system and preparation method thereof |
CN113307990A (en) * | 2021-06-09 | 2021-08-27 | 上海科技大学 | Composite material and preparation method and application thereof |
WO2021261966A1 (en) * | 2020-06-26 | 2021-12-30 | 숙명여자대학교 산학협력단 | Cyclodextrin-based composite composition for oral administration and method for producing same |
-
2022
- 2022-03-04 CN CN202210208303.7A patent/CN114652854B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017078609A1 (en) * | 2015-11-05 | 2017-05-11 | Su Holding Ab | One-pot synthesis of metal-organic frameworks with encapsulated target-molecule and their use |
CN108456241A (en) * | 2018-01-17 | 2018-08-28 | 南开大学 | Porous framework material is used for the storage and transportation and preparation of biological products |
CN110538345A (en) * | 2019-10-11 | 2019-12-06 | 上海交通大学医学院附属第九人民医院 | biological material, preparation method thereof and application thereof in bone repair |
CN111265533A (en) * | 2019-11-25 | 2020-06-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of core-shell nanoparticles based on lipid membrane and metal organic framework |
CN111269516A (en) * | 2020-04-02 | 2020-06-12 | 北京航空航天大学 | MXene composite gel material, preparation method and application |
CN111643480A (en) * | 2020-04-20 | 2020-09-11 | 武汉大学 | Metal organic framework composite nano material with targeting property and pH responsiveness and preparation method and application thereof |
WO2021261966A1 (en) * | 2020-06-26 | 2021-12-30 | 숙명여자대학교 산학협력단 | Cyclodextrin-based composite composition for oral administration and method for producing same |
CN112999352A (en) * | 2021-03-09 | 2021-06-22 | 安徽工程大学 | RGD/PTX @ ZIF-90 drug delivery system and preparation method thereof |
CN113307990A (en) * | 2021-06-09 | 2021-08-27 | 上海科技大学 | Composite material and preparation method and application thereof |
Non-Patent Citations (4)
Title |
---|
CHENGYUAN XU等: "Biodegradable Nanoparticles of Polyacrylic Acid–Stabilized Amorphous CaCO3 for Tunable pH-Responsive Drug Delivery and Enhanced Tumor Inhibition", 《ADV. FUNCT. MATER.》 * |
RAN MO等: "ATP-triggered anticancer drug delivery", 《NATURE COMMUNICATIONS》 * |
YINGWEN WANG等: "Precise Localization and Simultaneous Bacterial Eradication of Biofilms Based on Nanocontainers with Successive Responsive Property toward pH and ATP", 《APPL. MATER. INTERFACES》 * |
李旭飞等: "沸石咪唑酯骨架材料ZIF-90的合成及应用研究进展", 《化工新型材料》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115819165A (en) * | 2022-12-20 | 2023-03-21 | 郑州大学 | Copper azide composite initiating explosive block material and preparation method thereof |
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