CN114652854B - 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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- CN114652854B CN114652854B CN202210208303.7A CN202210208303A CN114652854B CN 114652854 B CN114652854 B CN 114652854B CN 202210208303 A CN202210208303 A CN 202210208303A CN 114652854 B CN114652854 B CN 114652854B
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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 takes ZIF-90 as a core, and the outer part of the material wraps acid sensitive hydrogel to form the double-lock MOF material with a shell-core structure and double-lock response. The double-lock MOF material prepared by the invention has excellent acid and ATP simultaneous stimulus response release performance. The double-lock MOF prepared by the invention has good stability and biocompatibility, and has wide application prospect in 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 the surface and subsequent biofilm formation are one of the critical global issues. Biofilms are complex communities of microorganisms in extracellular polysaccharide matrices that adhere irreversibly to material surfaces, resulting in biofouling and wound infection. At present, the most common strategy for combating biofilms is the use of antibacterial drugs, however, due to lack of targeting and selectivity for biofilms, the use of excessive amounts of drugs leads to the emergence of drug resistant bacteria and increased off-target toxicity.
Nanocarrier-based antibiotic delivery systems are of great interest because of their ability to overcome toxicity caused by non-selective accumulation and to increase bioavailability of antibiotics. The nano-carrier is modified by the stimulus response surface, so that the selective targeted cargo release can be realized. However, single-stimulus nanocarriers sometimes cannot effectively identify biofilm areas due to the complex internal environment of the human body. For example, when acidic pH is used as an indicator of biofilm, acidic organelles or other external acid stimuli may also trigger cargo release, thereby increasing off-target toxicity and potential safety issues. Therefore, further improvement of the targeting efficiency of the biological membrane is crucial for accurate medical treatment and imaging, the nano-carriers at present relate to a wide range of nano-materials such as silica nano-particles, carbon nano-tubes, gold nano-particles and quanta, liposomes and polymers, but are only responsive to a single stimulus, no nano-carriers which continuously respond to two stimuli are found yet, and the pH/ATP double-lock 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 the problem that the existing biological film area can not be effectively identified.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a double-lock MOF material takes ZIF-90 as a core, and the outer part of the core is wrapped with acid-sensitive hydrogel to form a double-lock MOF material with a shell-core structure and 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 dual-lock MOF material core is ZIF-90 generated by the normal temperature reaction of 2-formaldehyde imidazole and zinc acetate.
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 with double-lock corresponding to the acid-sensitive hydrogel, wherein the acid-sensitive hydrogel is a shell-core structure with the ZIF-90 wrapped inside a shell.
The material relation ratio of ZIF-90 to polyacrylic acid and calcium chloride is 1:2:2-1:2.5:2.5.
Use of a double-lock MOF material for the delivery of a drug. Further, the use of said materials in drug delivery and in tumor therapy.
According to the invention, 2-formaldehyde imidazole and zinc acetate react at normal temperature to generate the MOF material, fluorescent dye is wrapped in the MOF, and acid stimulus response hydrogel generated by the reaction of polyacrylic acid and calcium chloride is wrapped on the surface of the MOF to form the double-lock MOF material, so that the prepared double-lock MOF material has excellent acid and ATP continuous stimulus response release performance. Wherein, the ZIF-90 is internally wrapped with a fluorescent dye Rho 6G to confirm the stimulus response performance of the double-lock 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, 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 surface of the MOF to form a double-lock MOF material, so that the prepared double-lock MOF material has excellent acid and ATP continuous stimulus response release performance. In the simulated biological membrane microenvironment, the double-lock MOF material shows good stimulus response, and the double-lock MOF nano-carrier prepared by the invention has the continuous stimulus response performance of acid response and ATP response due to the special shell-core structure, has good stability and selectivity, and is not easy to be interfered by complex environments. Has wide application prospect in the aspects of drug delivery and disease treatment.
The double-lock MOF has great potential in the aspect of double-stimulus response release, and can be further used for drug delivery and biomembrane eradication.
Drawings
FIG. 1 is a TEM image of a double-lock MOF provided in embodiment 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 the stimulus response of the double-lock MOF provided in example 1 of the present invention, wherein a is the double-lock MOF reacted in a solution with ph=4.0 for 15min, B is the double-lock MOF reacted in a solution with ph=4.0, 1mm ATP for 15min;
FIG. 3 is a graph showing the change of fluorescence values at different pH treatments of the double-lock MOF according to the embodiment of the present invention;
FIG. 4 is a graph showing the change of fluorescence values of double-lock MOFs in the acidic environment where ATP is treated at different concentrations according to the embodiment of the present invention;
FIG. 5 is a graph showing the change of fluorescence values of nanocarriers according to different assembly methods.
Detailed Description
The following description of the embodiments of the present invention is further provided in connection with the accompanying examples, and it should be noted that the embodiments described herein are for the purpose of illustration and explanation only, and are not limiting of the invention.
According to the invention, by forming the nano double-lock MOF with a specific shell-core structure, the nano carrier has the performance of continuous stimulus response of acid response and ATP response, has good stability and selectivity, and is not easy to be interfered by complex environments.
Example 1:
preparation of double-lock MOF:
1) 48.05mg of 2-imidazole-formaldehyde (0.5M), 4.79mg of rhodamine 6G (1 mM) were dissolved in 10.0mL of DMF and stirred for 15min, followed by slow addition of 5.0mL of DMF containing 0.05M zinc acetate. Then washed sequentially with DMF, ultrapure water and ethanol, and centrifuged (10000 rpm,5 min). Finally, the product was dispersed in ultrapure water to give rhodamine 6G@ZIF-90 stock solution (100 mg mL) -1 ). (see FIG. 1A).
2) 114mg polyacrylic acid (PAA, 0.1M), 111mg calcium chloride (0.1M) and 500. Mu.L rhodamine 6G@ZIF-90 (100 mg mL) -1 ) Added to 10.0mL of ultrapure water and stirred for 1 hour. Then, 10.0mL of 0.1M Na was added 2 CO 3 The solution was added rapidly and stirred for 1h. The resultant product was centrifuged and washed with ultrapure water (10000 rpm,10 minutes), and redispersed in ultrapure water to obtain rhodamine 6G@ZIF-90@ACC/PAA. (see FIG. 1B).
The morphology of the prepared rhodamine 6G@ZIF-90 and rhodamine 6G@ZIF-90@ACC/PAA was characterized by a Transmission Electron Microscope (TEM). As shown in FIGS. 1A and 1B, both rhodamine 6G@ZIF-90 and rhodamine 6G@ZIF-90@ACC/PAA are uniform nanoparticles. Rhodamine 6G@ZIF-90 nano particles are rough in surface, uniform in size and 110-150nm in average diameter. After being wrapped by polyacrylic acid/calcium chloride, the size of the rhodamine 6G@ZIF-90@ACC/PAA material is larger than that of the rhodamine 6G@ZIF-90, and the size is about 150-200nm.
Example 2:
stimulus responsiveness of double-lock MOF:
mu.L of rhodamine 6G@ZIF-90@ACC/PAA prepared in the above example (100 mg mL) was taken -1 ) Incubation was performed for 15min in 3mL of PBS (ph=4.0) solution, and morphological changes were observed by TEM (see fig. 2A). mu.L of prepared rhodamine 6G@ZIF-90@ACC/PAA (100 mg mL) was taken -1 ) Placed in 3mL of PBS (ph=4.0) solution and incubated with 5 μl of ATP (1M) solution for 15 minutes, the morphological changes were observed by TEM (see fig. 2B).
As shown in fig. 2A and 2B, the rhodamine 6g@zif-90@acc/PAA polyacrylic acid/calcium chloride hydrogel after the acid treatment was dissolved, the rhodamine 6g@zif-90 remained intact and the dimensions were the same as in fig. 1A, and the polyacrylic acid/calcium chloride hydrogel was dissolved and the rhodamine 6g@zif-90 particles were cleaved to lose the intact morphology after the acid and ATP co-treatment, demonstrating the stimulus responsiveness of the double-lock MOF.
Example 3:
stimulus responsiveness of double-locked MOF at different pH:
mu.L of rhodamine 6G@ZIF-90@ACC/PAA (1 mg mL) -1 ) Respectively adding 240 mu L of PBS buffer solutions with different pH values, adding 10 mu L of ATP (1 mM) solution, carrying out oscillation reaction for 60min, and measuring the fluorescence intensity of the solution at the excitation wavelength of 525nm and the emission wavelength of 552 nm. As can be seen from fig. 3, the fluorescence value of the double-lock MOF nanomaterial increases with time, and the release equilibrium can be reached in about 30 minutes.
Example 4:
stimulus responsiveness of double-locked MOF at different ATP concentrations:
mu.L of rhodamine 6G@ZIF-90@ACC/PAA (1 mg mL) -1 ) Add 240. Mu.L of pHAnd adding 10 mu L of ATP solution with different concentrations into PBS buffer solutions of other 4.0 and 6.0, carrying out oscillation reaction for 60min, and measuring the fluorescence intensity of the solution at the excitation wavelength of 525nm and the emission wavelength of 552 nm. As can be seen from FIG. 4, under acidic conditions, the fluorescence value increases with the increase of the ATP concentration, and the system has generated a more obvious fluorescence response at the ATP concentration of 1. Mu.M, which proves that rhodamine 6G@ZIF-90@ACC/PAA nanoparticles have sensitive ATP responsiveness.
Example 5:
fluorescence responsivity of nanocarriers prepared by different assembly methods:
1) 48.05mg of 2-imidazole-formaldehyde (0.5M), 4.79mg of rhodamine 6G (1 mM) were dissolved in 10.0mL of DMF and stirred for 15min, followed by slow addition of 5.0mL of DMF containing 0.05M zinc acetate. Then washing with ultrapure water sequentially, dispersing the product in the ultrapure water to obtain rhodamine 6G@ZIF-90 stock solution (100 mg mL) -1 ). 114mg polyacrylic acid (PAA, 0.1M), 111mg calcium chloride (0.1M) and 500. Mu.L rhodamine 6G@ZIF-90 (100 mg mL) -1 ) Added to 10.0mL of ultrapure water and stirred for 1 hour. Then, 10.0mL of 0.1M Na was added 2 CO 3 The solution was added rapidly and stirred for 1h. The resultant product was centrifuged and washed with ultrapure water, which is a material obtained in 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 (1 mM) were added to 10.0mL of ultrapure water and stirred for 1 hour. Then, 10.0mL of 0.1M Na was added 2 CO 3 The solution was added rapidly and stirred for 1h. Centrifuging the obtained product and washing with ultrapure water to obtain stock solution (100 mg mL) -1 ). 48.05mg of 2-imidazole formaldehyde (0.5M), 50. Mu.L of stock solution (100 mg mL) -1 ) Dissolved in 10.0mL DMF and stirred for 15min before slowly adding 5.0mL DMF containing 0.05M zinc acetate. Then washed with ultrapure water in this order, and the product was dispersed in ultrapure water, which is preparation method 2.
mu.L of the nanomaterial prepared in the above example was placed in 3mL of PBS (pH=4.0) solution, and 5. Mu.L of ATP (1M) solution was added to incubate for 15 minutes, and the change in fluorescence was observed, and the fluorescence was again observed for 14 days. The result shows that the target nano-carrier with double stimulus can be synthesized only by the assembly mode of the preparation method 1, and the nano-carrier has good stability, and the fluorescence value is not changed obviously after soaking for 14 days.
Claims (3)
1. A double lock MOF material, characterized by: the double-lock MOF material takes ZIF-90 as a core, and the outer part of the material wraps acid sensitive hydrogel to form a double-lock MOF material with a shell-core structure and double-lock response;
the preparation method comprises the following steps:
1) 48.05mg of 2-imidazole-formaldehyde, 4.79mg of rhodamine 6G are dissolved in 10.0mL of DMF and stirred for 15min, and then 5.0mL of DMF containing 0.05M zinc acetate is slowly added; washing with DMF, ultrapure water and ethanol in sequence, and centrifuging at 10000rpm for 5min; finally, dispersing the product in ultrapure water to obtain rhodamine 6G@ZIF-90 stock solution;
2) 114mg of polyacrylic acid, 111mg of calcium chloride and 500. Mu.L of rhodamine 6G@ZIF-90 were added to 10.0mL of ultrapure water and stirred for 1 hour; then, 10.0mL of 0.1M Na was added 2 CO 3 The solution is added and stirred for 1h; the product obtained was centrifuged at 10000rpm for 10min and washed with ultrapure water, and redispersed in ultrapure water to obtain rhodamine 6G@ZIF-90@ACC/PAA.
2. A method of preparing a double-lock MOF material according to claim 1, wherein:
1) 48.05mg of 2-imidazole-formaldehyde, 4.79mg of rhodamine 6G are dissolved in 10.0mL of DMF and stirred for 15min, and then 5.0mL of DMF containing 0.05M zinc acetate is slowly added; washing with DMF, ultrapure water and ethanol in sequence, and centrifuging at 10000rpm for 5min; finally, dispersing the product in ultrapure water to obtain rhodamine 6G@ZIF-90 stock solution;
2) 114mg of polyacrylic acid, 111mg of calcium chloride and 500. Mu.L of rhodamine 6G@ZIF-90 were added to 10.0mL of ultrapure water and stirred for 1 hour; then, 10.0mL of 0.1M Na was added 2 CO 3 The solution is added and stirred for 1h; the product obtained was centrifuged at 10000rpm for 10min and washed with ultrapure water, and redispersed in ultrapure water to obtain rhodamine 6G@ZIF-90@ACC/PAA.
3. Use of the double lock MOF material of claim 1, wherein: the use of said material as a carrier in drug delivery.
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