KR-102959965-B1 - METHOD OF MODIFYING THE SURFACE OF METAL ORGANIC FRAMEWORKS

Abstract

The present invention relates to a method for surface modification of a metal-organic framework. The method for surface modification of a metal-organic framework according to the embodiments of the present invention can modify the surface properties of metal-organic framework nanoparticles as a one-step reaction without the need for conventional complex processes or additional reaction-promoting agents.

Inventors

• 박소정
• 샤인카루카파람빌알버트
• 강효정

Assignees

• 이화여자대학교 산학협력단

Dates

Publication Date

20260508

Application Date

20240222

Priority Date

20230706

Claims (10)

1. Reacting bromine-functionalized DNA and a metal-organic framework in a solvent to obtain a metal-organic framework with a surface modified by DNA. including, As a method for surface modification of a metal-organic framework, The above bromine-functionalized DNA is represented by the following chemical formula 1, and The above metal-organic framework comprises nitrogen having a non-covalent electron pair capable of coordination bonding, and A method for surface modification of a metal-organic framework comprising an N-alkylation reaction between the nitrogen of the metal-organic framework and the bromine-functionalized DNA: [Chemical Formula 1] ; In the above chemical formula 1, X represents a bond, or is a phosphate group, an amide group, or a polyethylene glycol group, and n is an integer from 1 to 20.
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4. In Article 1, A method for surface modification of a metal-organic framework, wherein the metal-organic framework comprises one or more selected from ZIF -8, ZIF -67, IRMOF-3, MOF-LIC-1, NH2- MIL -101(Cr), NH2 -MIL-101(Al), NH2 -MIL-101(Fe), NH2 - MIL -68(In), NH2- MIL - 88 (Al), NH2-MIL- 53 , Bio-MOF-100, NH2-MIL- 125 , Zn2 ( Atz )2, DMOF- 1 -NH2, UMCM- 1 -NH2, Zn2( CN5H2 ) 3 ( H2O ) 3 ·6H2O, NH2-CuBTC, MAF-66, CPF-13, and ZnF( Am2TAZ ).
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6. In Article 1, A method for surface modification of a metal-organic framework, wherein the solvent comprises one or more selected from water, formic acid, hydrogen fluoride, ethanol, methanol, acetic acid, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, and dimethyl sulfoxide.
7. In Article 1, A method for surface modification of a metal-organic framework, wherein the above reaction is carried out at 40°C to 70°C.
8. In Article 1, A method for surface modification of a metal-organic framework, wherein the above reaction is carried out for 5 to 25 hours.
9. A surface-modified metal-organic framework obtained by the surface modification method of a metal-organic framework according to claim 1.
10. In Article 9, Surface-modified metal-organic framework used as a drug delivery system, biosensing, bioimaging, microparticle filter, or catalytic agent.

Description

Method of Modifying the Surface of Metal Organic Frameworks The present invention relates to a method for surface modification of a metal-organic framework. Metal-organic frameworks (MOFs) are materials that have been actively researched since the report of MOF-5, a highly porous material, in 1999. Unlike conventionally known porous materials, MOFs include organic materials as major components in addition to inorganic materials. Therefore, MOFs are also referred to as organic-inorganic hybrid materials. They can contain a wide variety of metal and organic components, and particularly, the presence of highly reactive organic components enables diverse functionalization. Various MOFs can be synthesized by varying the metal components and ligands, and various MOFs with excellent porosity and stability are being studied for synthesis, functionalization, and application. Representative MOFs with excellent stability and porosity include MIL-100 (Me-BTC), MIL-101 (Cr-BDC), UiO-66 (Zr-BDC), MOF-74 (Me-dihydroxy BDC), and ZIF-8 (Zn-methyl imidazole). Conventional methods for surface modification of metal-organic frameworks (MOFs) primarily proceed through the chemical modification of organic ligands or coordination bonding with metal ions. In the case of surface modification via organic ligands, multiple reaction steps are required, or additional substances are essential to accelerate the reaction. In the case of surface modification through coordination bonding with metal ions, there is a problem in that the stability of the modified ligand is reduced due to exchange reactions with various ions in biological solutions. FIG. 1a and 1b are schematic diagrams of the synthesis of metal-organic framework (ZIF-8) nanoparticles and surface modification of metal-organic framework (ZIF-8) nanoparticles in one embodiment of the present invention. FIG. 2 is a graph of the surface charges of ZIF-8 before reaction with bromine-functionalized DNA; ZIF-8 after reaction with non-bromine-functionalized DNA (ZIF-8/fD); and ZIF-8 after reaction with bromine-functionalized DNA (ZIF-8/bD) in one embodiment of the present invention. FIG. 3 is a graph of the surface charges of ZIF-67 (ZIF-67) before reaction with bromine-functionalized DNA; ZIF-67 (ZIF-67/fD) after reaction with non-bromine-functionalized DNA; and ZIF-67 (ZIF-67/bD) after reaction with bromine-functionalized DNA, in one embodiment of the present invention. FIG. 4 is a graph of the surface charges of UiO-66 (UiO-66) before reaction with bromine-functionalized DNA; UiO-66 (UiO-66/fD) after reaction with non-bromine-functionalized DNA; and UiO-66 (UiO-66/bD) after reaction with bromine-functionalized DNA, in one embodiment of the present invention. Figures 5a and 5b are transmission electron microscope images of ZIF-8/bD nanoparticles hybridized with gold nanoparticles modified with complementary sequence DNA and non-complementary sequence DNA in one embodiment of the present invention. FIG. 6a is a transmission electron microscope image of ZIF-67/bD in one embodiment of the present invention, and FIG. 6b is a transmission electron microscope image of ZIF-67/bD nanoparticles hybridized with gold nanoparticles modified with complementary sequence DNA in one embodiment of the present invention. FIG. 7a is a transmission electron microscope image of UiO-66/bD in one embodiment of the present invention, and FIG. 7b is a transmission electron microscope image of UiO-66/bD nanoparticles hybridized with gold nanoparticles modified with complementary sequence DNA in one embodiment of the present invention. Hereinafter, embodiments and examples of the present invention are described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments and examples described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification have been given similar reference numerals. Throughout this specification, when a part is described as being "connected" to another part, this includes not only cases where they are "directly connected," but also cases where they are "electrically connected" with other elements interposed between them. Throughout this specification, when a component is described as being located "on" another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components. Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Terms of degree used in this specification, such as “about,” “substantially,” etc.