CN113512423A - Fluorescent carbon quantum dot based on metal organic framework and preparation method thereof - Google Patents
Fluorescent carbon quantum dot based on metal organic framework and preparation method thereof Download PDFInfo
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Abstract
The invention discloses fluorescent carbon quantum dots (MOF-CDs) based on a metal organic framework and a preparation method thereof. The MOF-CDs have the pore size structure and the nanometer size of Metal Organic Frameworks (MOFs) on one hand, and can realize the loading of drugs and the targeting of specific disease parts; on the other hand, the excellent fluorescence properties of Carbon Dots (CDs) can be used to monitor the distribution of MOF-CDs in vivo. The preparation method of the MOF-CDs comprises the following steps: firstly, metal ions and organic ligands are utilized to synthesize MOFs, and then MOF-CDs are synthesized in one step by a high-temperature carbonization method. The preparation method disclosed by the invention is low in energy consumption and simple to operate, and the prepared MOF-CDs have excellent fluorescence properties. The method of the invention endows the MOFs with fluorescence property, solves the technical problem that the application of the current MOFs material is difficult to monitor, and provides more possibilities for the application of the MOFs material.
Description
Technical Field
The invention belongs to carbon quantum dots and preparation thereof, and particularly relates to fluorescent carbon quantum dots (MOF-CDs) based on a metal organic framework and a preparation method thereof.
Background
Metal Organic Frameworks (MOFs) are novel nanomaterials with porous structures formed by connecting metal nodes and organic ligands, have the advantages of variable and flexible structures, easily adjustable pore sizes, simple surface modification, convenient and controllable synthesis process and the like, and are widely applied to the fields of gas separation and storage, energy storage and conversion, ion exchange, catalysis, sensing, drug delivery and the like. One characteristic advantage of the MOFs is that they have unique pore size structure and large specific surface area, which makes them possible to serve as excellent drug carriers to carry different drugs. MOFs have great advantages over traditional drug carriers. Firstly, the pore size structure and the larger specific surface area make the carrier have the potential of loading more drugs; secondly, the diversity of the structure, the size and the shape can provide more choices, different MOFs can be selected according to different drug properties and different disease characteristics, and the surface modification of the MOFs can enhance the binding capacity of the MOFs and the drugs and the targeting capacity of the MOFs to specific diseases; in addition, different metal elements also give different MOFs some unique properties, for example, iron and copper based MOFs are capable of undergoing Fenton-like reaction and can catalyze H2O2OH with strong oxidizing ability is generated by reaction, and MOFs based on zinc has higher biocompatibility and biodegradability and can be degraded under acidic conditions. With the above-mentioned various superior properties of MOFs, researchers have developed various MOFs-based drug delivery systems that show great potential for use in the field of drug delivery. However, there are some problems in the application of MOFs, and currently applied MOFs materials are difficult to detect, and thus, the distribution and metabolic processes in vivo are not easy to control.
Carbon Dots (CDs) are a new group of materials of interest in recent years, with particle sizes less than 10nm, mainly comprising: graphene quantum dots, carbon nanodots, and polymer dots. The carbon dots have the advantages of simple synthesis, easily available raw materials, stable chemical properties, long in-vivo circulation time, good water solubility, easy modification and the like, and more importantly, the carbon dots have excellent fluorescence properties, so that the carbon dots are widely applied to various fields of chemical sensing, biological sensing, light emitting diodes, photocatalysis, fluorescence imaging and the like. Compared with the traditional semiconductor quantum dots and fluorescent dyes, the carbon dots have more stable fluorescence property, strong resistance to photobleaching, better biocompatibility and safety. Therefore, carbon dots have greater potential for use in bioimaging.
Combining MOFs with CDs is a feasible approach to address the difficult monitoring of MOFs materials. The currently applied method for combining the MOFs and the CDs mainly loads the CDs in the aperture structure of the MOFs, and then realizes the monitoring of the MOFs through the fluorescence property of the CDs. Firstly, the method needs to synthesize MOFs and CDs respectively and then load the CDs into the MOFs, so that the operation is too complicated; secondly, the use of MOFs as drug carriers to deliver various therapeutic drugs is a major aspect of their application, and loading CDs may affect the loading efficiency of drugs, limiting the application of MOFs; finally, when the MOFs are disintegrated and released at a specific disease site (such as under tumor acidic conditions), CDs loaded in the MOFs are also released, so that the spatial distribution of CDs and MOFs in vivo is not completely consistent, and the fluorescence of CDs cannot truly reflect the in vivo distribution of the MOFs. Therefore, the preparation method of the MOFs-based fluorescent CDs, which is simple to synthesize, high in drug loading and accurate in monitoring, is urgently designed.
Disclosure of Invention
The invention aims to provide fluorescent carbon quantum dots (MOF-CDs) based on a metal organic framework and a preparation method thereof.
The MOF-CDs have the dual advantages of both Metal Organic Framework (MOFs) materials and Carbon Dots (CDs). As MOFs, MOF-CDs can realize larger drug load and can be specifically distributed to specific disease parts such as tumors and the like through passive targeting; as CDs, under the irradiation of proper exciting light, MOF-CDs can emit strong fluorescence, and the enrichment and in-vivo distribution of the fluorescence at disease sites can be monitored.
The preparation method of the MOF-CDs synthesizes the MOF-CDs with fluorescence property by directly carbonizing MOFs materials, and is simple to operate. The MOF-CDs prepared by the method have good water solubility, high fluorescence quantum yield, good stability and excellent photobleaching resistance, more importantly, the MOF-CDs prepared by the method retain the skeleton structure of MOFs, the drug loading performance of the MOFs cannot be influenced, the MOF-CDs have fluorescence, and the fluorescence property of the MOFs can accurately reflect the distribution and metabolic process of the MOFs in vivo.
In order to achieve the above purpose, the preparation method of the fluorescent carbon quantum dots (MOF-CDs) based on the metal organic framework specifically comprises the following steps: a) metal elements are used as nodes, and organic ligands are used as bridges to synthesize Metal Organic Frameworks (MOFs); b) obtaining pure MOFs through centrifugation, supernatant liquid removal and repeated cleaning; c) dissolving the obtained MOFs in ultrapure water; d) MOF-CDs are synthesized in one step by a high-temperature carbonization method.
In the preparation method of the MOF-CDs, the metal element in the step a) is one or more than two of zinc, iron, copper, cobalt, chromium, aluminum and nickel; the organic ligand in the step a) is an organic substance rich in heteroatoms (such as N, O, S), and comprises one or more than two of 2-methylimidazole, 4-imidazole dithiocarboxylic acid and triazole.
In the preparation method of the MOFs, the centrifugation rotating speed in the step b) is 5000rpm, the centrifugation time is 3min, and the obtained MOFs are obtained by collecting precipitates after centrifugation and cleaning.
In the preparation method of the MOF-CDs, the high-temperature carbonization time in the step d) is 6 h.
In the preparation method of the MOF-CDs, the high-temperature carbonization temperature and the pH of the reaction solution in the step d) are optimized, the optimized carbonization temperature is 180 ℃ and 200 ℃, and the optimized pH of the reaction solution is alkaline (pH 12) and neutral (pH 7).
The MOF-CDs synthesized under different optimized conditions have stronger blue-green fluorescence, and the comparison of the fluorescence intensity under various conditions shows that the MOF-CDs synthesized under the conditions of pH 12 and temperature 200 ℃ have the strongest fluorescence, so that the MOF-CDs synthesized under the conditions of pH 12 and temperature 200 ℃ are taken as the optimal conditions for the subsequent synthesis of the MOF-CDs.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, organic ligands in Metal Organic Frameworks (MOFs) are used as carbon sources, and are directly carbonized to prepare fluorescent carbon dots, so that the MOFs are directly endowed with fluorescence, and extra carbon dots are not required to be loaded, thus the preparation process of MOF-CDs is simplified, and the time required by preparation is saved. Meanwhile, as no new carbon point is introduced, the MOF-CDs prepared by the method have high safety, and the problem of toxicity possibly caused by the introduction of the carbon point is avoided.
(2) Although the conventional method for loading CDs by MOFs can introduce fluorescence property into the MOFs, the CDs are released while the MOFs releases the drugs, and the CDs and the MOFs are not at the same position in space, so the fluorescence of the CDs cannot reflect the distribution of the MOFs. The method directly endows the MOFs with excellent fluorescence property, the fluorescence is the MOFs, and the fluorescent signal can accurately reflect the distribution condition of the MOFs in vivo.
(3) The MOFs-CDs prepared by the method have excellent fluorescence property while the excellent drug loading property of the MOFs is kept. On one hand, considerable amount of therapeutic drugs can be loaded by utilizing the porous structure and the nanometer size of the MOFs, and the excellent properties of the MOFs can be utilized to enhance the therapeutic effect of the therapeutic drugs, for example, the MOFs can be specifically targeted to tumor tissues through the high permeability and retention effect (EPR effect) of solid tumor tissues, so that the killing of the antitumor drugs on the tumor tissues is promoted; on the other hand, carbonization imparts fluorescence properties to MOFs, and distribution of MOFs in vivo can be monitored by fluorescence.
Drawings
FIG. 1 is a schematic diagram of synthesis of fluorescent carbon quantum dots based on metal organic framework
FIG. 2 Transmission Electron microscopy results for Metal organic frameworks
FIG. 3 Transmission Electron microscopy results for fluorescent carbon Quantum dots based on Metal organic frameworks
FIG. 4 particle size comparison of metal organic frameworks and fluorescent carbon quantum dots based on metal organic frameworks
FIG. 5 comparison of potentials of metal-organic frameworks and fluorescent carbon quantum dots based on metal-organic frameworks
FIG. 6 UV-VIS absorption spectra of metal-organic frameworks and metal-organic framework-based fluorescent carbon quantum dots
FIG. 7 Infrared contrast plot of metal organic framework synthesis raw materials, metal organic framework and fluorescent carbon quantum dots based on metal organic framework
FIG. 8 fluorescence emission spectrum of fluorescent carbon quantum dots based on metal organic framework
FIG. 9 is a fluorescence emission spectrum of metal organic framework-based fluorescent carbon quantum dots under different excitation wavelengths
FIG. 10 shows fluorescence emission spectra of metal organic framework based fluorescent carbon quantum dots synthesized under different reaction conditions
Detailed Description
The present invention is further described in detail with reference to the following specific embodiments, which are provided for the purpose of facilitating understanding of the present invention and are not to be construed as limiting the scope of the present invention, and those skilled in the art can make some non-essential modifications and improvements to the present invention based on the above disclosure.
The instruments and equipment used in the following examples are as follows:
ultraviolet-visible spectrophotometer Ultra 6600A (Rigol, china); spectrofluorometer RF-5301(Shimadzu, japan); a Fourier transform Infrared Spectroscopy Nicolet iS5(Thermo Fisher Scientific, USA); transmission electron microscope JEM-1200EX TEM (JEOL, japan); laser particle sizer Zetasizer Nano ZS90(Malvern, uk).
In the following examples, the metal organic framework is ZIF-8, and the fluorescent carbon quantum dots based on the metal organic framework are ZIF-8 carbon dots (ZCD).
Example 1 preparation of a fluorescent carbon Quantum dot based on a Metal organic framework
(1) Preparation of ZIF-8
568.2mg of zinc nitrate were weighed into a round-bottomed flask, and dissolved by adding 20mL of methanol. 2463.12mg of 2-methylimidazole were weighed into a centrifuge tube and dissolved in 40mL of methanol. The 2-methylimidazole solution is added into the zinc nitrate solution dropwise, stirred at 500rpm and reacted for 2 hours at 40 ℃. After the reaction is finished, taking out the reaction solution, centrifuging for 3min in two 50mL centrifuge tubes at the rotation speed of 5000rpm, discarding the supernatant, respectively adding 30mL methanol for cleaning for 3 times, and then adding 30mL deionized water for dissolving.
(2) Preparation of ZCD
And (3) putting 10mL of the ZIF-8 solution into an EP (ethylene propylene glycol) tube, adjusting the pH value of the solution to 7, transferring the solution into an autoclave, placing the autoclave in a muffle furnace, and reacting for 6 hours at 180 ℃.
Example 2 preparation of fluorescent carbon quantum dots based on metal organic frameworks
(1) Preparation of ZIF-8
568.2mg of zinc nitrate were weighed into a round-bottomed flask, and dissolved by adding 20mL of methanol. 2463.12mg of 2-methylimidazole were weighed into a centrifuge tube and dissolved in 40mL of methanol. The 2-methylimidazole solution is added into the zinc nitrate solution dropwise, stirred at 500rpm and reacted for 2 hours at 40 ℃. After the reaction is finished, taking out the reaction solution, centrifuging for 3min in two 50mL centrifuge tubes at the rotation speed of 5000rpm, discarding the supernatant, respectively adding 30mL methanol for cleaning for 3 times, and then adding 30mL deionized water for dissolving.
(2) Preparation of ZCD
And (3) putting 10mL of the ZIF-8 solution into an EP (ethylene propylene glycol) tube, adjusting the pH value of the solution to be 12, transferring the solution into an autoclave, placing the autoclave in a muffle furnace, and reacting for 6 hours at 180 ℃.
Example 3 preparation of fluorescent carbon Quantum dots based on Metal organic frameworks
(1) Preparation of ZIF-8
568.2mg of zinc nitrate were weighed into a round-bottomed flask, and dissolved by adding 20mL of methanol. 2463.12mg of 2-methylimidazole were weighed into a centrifuge tube and dissolved in 40mL of methanol. The 2-methylimidazole solution is added into the zinc nitrate solution dropwise, stirred at 500rpm and reacted for 2 hours at 40 ℃. After the reaction is finished, taking out the reaction solution, centrifuging for 3min in two 50mL centrifuge tubes at the rotation speed of 5000rpm, discarding the supernatant, respectively adding 30mL methanol for cleaning for 3 times, and then adding 30mL deionized water for dissolving.
(2) Preparation of ZCD
And (3) putting 10mL of the ZIF-8 solution into an EP (ethylene propylene glycol) tube, adjusting the pH value of the solution to 7, transferring the solution into an autoclave, placing the autoclave in a muffle furnace, and reacting for 6 hours at the temperature of 200 ℃.
Example 4 preparation of fluorescent carbon Quantum dots based on Metal organic frameworks
(1) Preparation of ZIF-8
568.2mg of zinc nitrate were weighed into a round-bottomed flask, and dissolved by adding 20mL of methanol. 2463.12mg of 2-methylimidazole were weighed into a centrifuge tube and dissolved in 40mL of methanol. The 2-methylimidazole solution is added into the zinc nitrate solution dropwise, stirred at 500rpm and reacted for 2 hours at 40 ℃. After the reaction is finished, taking out the reaction solution, centrifuging for 3min in two 50mL centrifuge tubes at the rotation speed of 5000rpm, discarding the supernatant, respectively adding 30mL methanol for cleaning for 3 times, and then adding 30mL deionized water for dissolving.
(2) Preparation of ZCD
And (3) putting 10mL of the ZIF-8 solution into an EP (ethylene propylene glycol) tube, adjusting the pH value of the solution to be 12, transferring the solution into an autoclave, placing the autoclave in a muffle furnace, and reacting for 6 hours at the temperature of 200 ℃.
ZIF-8 is taken as a representative of a metal organic framework, ZIF-8 carbon dots (ZCD) are taken as a representative of fluorescent carbon quantum dots based on the metal organic framework, and the characteristics are as follows:
FIG. 1 is a schematic of the synthesis of ZCD.
FIG. 2 is a transmission electron micrograph of ZIF-8, showing that ZIF-8 is a polyhedron having a uniform size and a particle diameter of about 100 nm.
FIG. 3 is a transmission electron micrograph of ZCD, which shows that ZCD is in the shape of hollow nanometer flower with a particle size of about 200nm and uniform size.
FIG. 4 shows the particle sizes of ZIF-8 and ZCD measured by a Malvern laser granulometer, showing that the particle size of ZIF-8 is about 260nm, the particle size of ZCD is about 270nm, and the particle size of ZCD is slightly larger. The grain sizes of the two are larger than those of the transmission electron microscope results in fig. 2 and 3, and the reason is that the malvern particle sizer measures the hydrated grain size of the material.
FIG. 5 is a comparison of the ZIF-8 and ZCD potentials measured by a Malvern laser granulometer, showing that the ZIF-8 potential is around 4mV and the ZCD potential is around-45 mV, and the material potential drops significantly after carbonization to carbon spots due to the presence of a large number of carboxyl groups on the surface of the carbon spots after carbonization.
FIG. 6 is a graph showing UV-VIS absorption spectra of ZIF-8 and ZCD, in which the UV absorption peak of ZCD is slightly blue-shifted as compared with ZIF-8, because part of the imidazole ring structure in ZIF-8 is destroyed by carbonization.
FIG. 7 is an infrared contrast chart of ZIF-8 and ZCD, showing that the infrared peak of ZIF-8 shows a strong imidazole ring structure characteristic of 425cm-1The nearby Zn-N bond indicates the doping of Zn, while the structural feature of the imidazole ring of the infrared peak of ZCD is weaker, indicating that part of the imidazole ring is damaged by carbonization and 3300cm-1And 3570cm-1The strong characteristic peak of carboxyl groups in between indicates successful carbonization.
FIG. 8 is a fluorescence emission spectrum of ZCD under 365nm excitation, and the result shows that ZCD can emit strong blue-green fluorescence in the spectrum range of 370-600nm, and the maximum emission peak is around 450 nm.
Fig. 9 is a fluorescence emission spectrum of ZCD at different excitation wavelengths, and the result shows that the emission peak of ZCD has a certain shift under the excitation of laser with different wavelengths, that is, the fluorescence emission of ZCD has excitation wavelength dependence, which is one of the characteristic properties of carbon dots, and can prove the successful synthesis of carbon dots.
FIG. 10 is a fluorescence emission spectrum of ZCD synthesized under different reaction conditions, showing that the positions of fluorescence emission peaks of ZCD synthesized under different conditions are almost the same, while ZCD synthesized under the conditions of 200 ℃ temperature and 12 pH has the strongest fluorescence emission peak, so this condition is taken as the best condition for synthesizing ZCD.
Claims (14)
1. Fluorescent carbon quantum dots (MOF-CDs) based on metal organic frameworks, characterized by having the superior properties of both Metal Organic Frameworks (MOFs) and Carbon Dots (CDs).
2. The MOF-CDs of claim 1, wherein the pore size structure and large specific surface area of the MOFs are preserved enabling larger dose drug loading.
3. MOF-CDs according to claim 1, wherein the nanometric size of the MOFs is preserved, allowing passive targeting of specific diseases such as tumors.
4. The MOF-CDs of claim 1, having excellent fluorescence properties of CDs, wherein the fluorescent signal can be used to trace MOFs-CDs materials and monitor their distribution in vivo.
5. The MOF-CDs of claim 1, wherein the method of preparation comprises the steps of:
a) metal elements are used as nodes, and organic ligands are used as bridges to synthesize Metal Organic Frameworks (MOFs);
b) obtaining pure MOFs through centrifugation, supernatant liquid removal and repeated cleaning;
c) dissolving the obtained MOFs in ultrapure water;
d) MOF-CDs are synthesized in one step by a high-temperature carbonization method.
6. The method of making MOF-CDs of claim 5, wherein the metallic element in step a) is one or more of zinc, iron, copper, cobalt, chromium, aluminum, nickel.
7. The method for preparing MOF-CDs according to claim 5, wherein the organic ligand in step a) is a heteroatom (e.g. N, O, S) -rich organic compound comprising one or more of 2-methylimidazole, 4-imidazolyldithiocarboxylic acid and triazole.
8. The method of making MOF-CDs according to claim 5, wherein the centrifugation speed in step b) is 5000rpm and the centrifugation time is 3 min.
9. The process for the preparation of MOF-CDs according to claim 5, wherein the high temperature carbonization time in step d) is 6 h.
10. The method of making MOF-CDs according to claim 5, wherein the high temperature carbonization temperature and reaction solution pH in step d) are optimized.
11. A process for the preparation of MOF-CDs according to claim 5 and claim 10 wherein the optimized carbonization temperature is 180 ℃ and 200 ℃.
12. A method for the preparation of MOF-CDs according to claim 5 and claim 10, wherein the optimized reaction solution pH is alkaline (pH 12) and neutral (pH 7).
13. A method for the preparation of MOF-CD according to claim 11 and claim 12, wherein MOF-CD synthesized under different conditions has better fluorescence properties.
14. A method of making MOF-CD according to claim 11 and claim 12 wherein the MOF-CD synthesized at 200 ℃ and pH 12 has the strongest fluorescence.
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