Novel metal-organic framework and preparation method thereof

Abstract

The present invention relates to a novel metal-organic framework (MOF) and a preparation method thereof, and specifically to a surface-modified novel metal-organic framework which, compared to a metal-organic framework which has not been surface-modified, has an increased specific surface area and a large pore diameter. In addition, the surface-modified metal-organic framework prepared by the preparation method for a novel metal-organic framework according to the present invention has an excellent binding effect with nucleic acids, and thus can be used as a carrier for nucleic acids.

Description

Novel metal-organic framework and method for preparing the same

[0001] The present invention relates to a novel metal-organic framework and a method for producing the same.

[0002] Organic-inorganic hybrid nanoporous materials, so-called metal-organic frameworks (MOFs), are commonly referred to as “porous coordination polymers” or “porous organic-inorganic hybrids.”

[0003] The above metal-organic frameworks have recently begun to be newly developed through the combination of molecular coordination bonds and material science, and the above metal-organic frameworks have high surface areas and molecular-sized or nano-sized pores, so they have applications in adsorbents, gas storage materials, sensors, membranes, functional thin films, drug delivery materials, catalysts, and catalyst carriers, and they can also be used to capture guest molecules smaller than the pore size or to separate molecules according to their sizes using the pores, so they have been actively studied recently.

[0004] In addition, the metal-organic framework has the advantage of having nano-sized pores and thus providing a high surface area, and is therefore mainly used for the purpose of adsorbing substances or carrying and delivering compositions within the pores.

[0005] For the metal-organic frameworks described above, there is a need to develop novel metal-organic frameworks and methods for producing the same with improved efficiency for application to various purposes.

[0006] [Prior Art Literature]

[0007] [Patent Document]

[0008] KR 10-2232255 B1

[0009] The purpose of the present invention is to provide a novel metal-organic framework (MOF) and a method for preparing the same.

[0010] Another object of the present invention is to provide a novel metal-organic framework having a surface modification, which has an increased specific surface area and a larger pore diameter compared to a metal-organic framework without surface modification.

[0011] Another object of the present invention is to provide a method for producing a novel metal-organic framework, wherein the surface-modified metal-organic framework produced by the method has an excellent binding effect with nucleic acids and thus can be utilized as a nucleic acid delivery vehicle.

[0012] To achieve the above object, the present invention relates to a novel metal-organic framework surface-modified with a compound represented by the following chemical formula 1:

[0013] [Chemical Formula 1]

[0014]

[0015] Here,

[0016] n is an integer from 0 to 4,

[0017] X1 is C(R4) or N,

[0018] R1 to R4 are the same or different from each other, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0019] In addition, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 2:

[0020] [Chemical Formula 2]

[0021]

[0022] Here,

[0023] n, X1 and R3 are as defined in the above chemical formula 1.

[0024] In addition, the metal-organic framework is a metal selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi or Li + , Na + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 3+ , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn2+ , Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ and Bi + It may include a metal ion selected from the group consisting of:

[0025] Additionally, the metal-organic framework may be selected from the group consisting of aluminum-based metal-organic frameworks, iron-based metal-organic frameworks, zirconium-based metal-organic frameworks, and mixtures thereof.

[0026] In addition, the metal-organic frameworks are UIO-66, UIO-66-NH2, UIO-67, UIO-67-NH2, PCN-128, PCN-222, PCN-223, PCN-224, MOF-525, MOF-545, MOF-801, MOF-808, MOF-867, Al-MIL-53, Al-MIL-53-NH2, Al-MIL-88, Al-MIL-88-NH2, Al-MIL-100, Al-MIL-100-NH2, Al-MIL-101, Al-MIL-101-NH2, Al-MIL-125, Al-MIL-125-NH2, Fe-MIL-53, Fe-MIL-53-NH2, Fe-MIL-88, It can be selected from the group consisting of Fe-MIL-88-NH2, Fe-MIL-100, Fe-MIL-100-NH2, Fe-MIL-101, Fe-MIL-101-NH2, Fe-MIL-125 and Fe-MIL-125-NH2.

[0027] In addition, the specific surface area of ​​the metal-organic framework is 1,400 m 2 / g to 1,500 m 2 / g may be.

[0028] Additionally, the pore diameter of the metal-organic framework may be 1 nm to 3 nm.

[0029] According to another embodiment of the present invention, a method for producing a novel metal-organic framework comprises the steps of: suspending a metal-organic framework in a first organic solvent to prepare a metal-organic framework mixed solution; dissolving a compound represented by the following chemical formula 1 in a second organic solvent to prepare a surface-modifying solution; and mixing and stirring the metal-organic framework mixed solution and the surface-modifying solution.

[0030] [Chemical Formula 1]

[0031]

[0032] Here,

[0033] n is an integer from 0 to 4,

[0034] X1 is C(R4) or N,

[0035] R1 to R4 are the same or different from each other, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0036] In addition, the stirring step may be performed at 80°C to 120°C for 4 to 8 hours to surface-modify the metal-organic framework.

[0037] In addition, after the stirring step, a surface-modified metal-organic framework can be manufactured by washing and drying.

[0038] In addition, the washing step may include a first centrifugation step of the reactant prepared by the stirring step at 5,000 rpm to 15,000 rpm for 1 to 10 minutes; a first washing step of suspending the precipitate separated by the first centrifugation step in a third organic solvent and then centrifuging the precipitate at 5,000 rpm to 15,000 rpm for 1 to 10 minutes, repeated 1 to 5 times; and a second washing step of suspending the precipitate separated by the first washing step in a fourth organic solvent and then centrifuging the precipitate at 5,000 rpm to 15,000 rpm for 1 to 10 minutes, repeated 1 to 5 times.

[0039] Additionally, the drying step may dry the lower layer particles separated by the second washing step in an oven at 60°C to 100°C for 2 to 6 hours.

[0040] In the present invention, “nucleic acid” is RNA, DNA, siRNA (short interfering RNA), mRNA (messenger RNA), aptamer, antisense oligodeoxynucleotide (ODN), antisense RNA, ribozyme, or DNAzyme.

[0041] In the present invention, “hydrogen” is hydrogen, light hydrogen, deuterium or tritium, unless specifically limited.

[0042] In the present invention, “halogen group” is fluorine, chlorine, bromine or iodine.

[0043] In the present invention, “alkyl” refers to a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, and hexyl.

[0044] In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0045] In the present invention, “alkynyl” refers to a monovalent substituent derived from an unsaturated hydrocarbon having 2 to 40 carbon atoms and a straight or branched chain having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0046] In the present invention, “alkylthio” means the above-described alkyl group bonded via a sulfur linkage (-S-).

[0047] In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a single ring or a combination of two or more rings. In addition, it may also include a form in which two or more rings are simply attached to each other (pendant) or condensed, and specifically, it may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, phenalenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. The fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.

[0048] In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, at least one carbon atom in the ring, preferably 1 to 3 carbon atom(s), is substituted with a heteroatom such as N, O, S, or Se. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included, and a form condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0049] In the present invention, “aryloxy” is a monovalent substituent represented by RO-, wherein R represents aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0050] In the present invention, “alkoxy” may be straight chain, branched chain, or cyclic chain. The carbon number of the alkoxy is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but is not limited thereto.

[0051] As used herein, "aralkyl" refers to an aryl-alkyl group, where aryl and alkyl are as defined above. Preferred aralkyl groups include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl, and naphthalenylmethyl. Bonding to the parent moiety is via the alkyl group.

[0052] In the present invention, “arylamino group” means an amine substituted with an aryl group having 6 to 30 carbon atoms.

[0053] In the present invention, “alkylamino group” means an amine substituted with an alkyl group having 1 to 30 carbon atoms.

[0054] In the present invention, “aralkylamino group” means an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

[0055] In the present invention, “heteroarylamino group” means an amine group substituted with an aryl group and a heterocyclic group having 6 to 30 carbon atoms.

[0056] In the present invention, “heteroaralkyl group” means an aryl-alkyl group substituted with a heterocyclic group.

[0057] In the present invention, “cycloalkyl” refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0058] In the present invention, “heterocycloalkyl” means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, wherein at least one carbon atom in the ring, preferably 1 to 3 carbon atom(s), is substituted with a heteroatom such as N, O, S or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

[0059] In the present invention, “alkylsilyl” means silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” means silyl substituted with aryl having 6 to 60 carbon atoms.

[0060] In the present invention, “fused ring” means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

[0061] In the present invention, “forming a ring by bonding with adjacent groups” means forming a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; a substituted or unsubstituted aromatic heterocycle; or a condensed ring thereof by bonding with adjacent groups.

[0062] Examples of the “aromatic hydrocarbon ring” in the present invention include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, etc.

[0063] In the present invention, “aliphatic heterocycle” means an aliphatic ring containing at least one heteroatom.

[0064] In the present invention, “aromatic heterocycle” means an aromatic ring containing at least one heteroatom.

[0065] In the present invention, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of substitution is not limited as long as it is a position where a hydrogen atom is replaced, i.e., a position where a substituent can be substituted, and when two or more are substituted, the two or more substituents may be the same or different from each other. The above substituent is hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 6 to It may be substituted with one or more substituents selected from the group consisting of 30 arylsilyl groups and substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, but is not limited to the above examples.

[0066] The present invention is a novel metal-organic framework having a surface modified metal-organic framework, wherein the metal-organic framework has an increased specific surface area and a larger average pore diameter than a metal-organic framework without surface modification.

[0067] In addition, a method for producing a novel metal-organic framework is provided, and the surface-modified metal-organic framework produced by the method has an excellent binding effect with nucleic acids and can be utilized as a nucleic acid carrier.

[0068] FIG. 1 is a schematic diagram of a metal-organic framework according to one embodiment of the present invention.

[0069] Figure 2 is a scanning electron microscope observation result of a metal-organic framework according to one embodiment of the present invention.

[0070] Figure 3 shows the results of X-ray diffraction analysis of a metal-organic framework according to one embodiment of the present invention.

[0071] Figure 4 shows the results of BET analysis through N2 adsorption of a metal-organic framework according to one embodiment of the present invention.

[0072] Figure 5 shows the FT-IR measurement results of a metal-organic framework according to one embodiment of the present invention.

[0073] Figure 6 shows the NMR (13C) measurement results of a metal-organic framework according to one embodiment of the present invention.

[0074] Figure 7 is a schematic diagram of a metal-organic framework according to one embodiment of the present invention.

[0075] Figure 8 is a scanning electron microscope observation result of a metal-organic framework according to one embodiment of the present invention.

[0076] Figure 9 is an X-ray diffraction analysis result of a metal-organic framework according to one embodiment of the present invention.

[0077] Figure 10 shows the results of BET analysis through N2 adsorption of a metal-organic framework according to one embodiment of the present invention.

[0078] Figure 11 shows the FT-IR measurement results of a metal-organic framework according to one embodiment of the present invention.

[0079] Figure 12 shows the NMR (13C) measurement results of a metal-organic framework according to one embodiment of the present invention.

[0080] Figure 13 is a schematic diagram of a metal-organic framework according to one embodiment of the present invention.

[0081] Figure 14 is a scanning electron microscope observation result of a metal-organic framework according to one embodiment of the present invention.

[0082] Figure 15 is an X-ray diffraction analysis result of a metal-organic framework according to one embodiment of the present invention.

[0083] Figure 16 shows the results of BET analysis through N2 adsorption of a metal-organic framework according to one embodiment of the present invention.

[0084] Figure 17 shows the FT-IR measurement results of a metal-organic framework according to one embodiment of the present invention.

[0085] Figure 18 shows the NMR (13C) measurement results of a metal-organic framework according to one embodiment of the present invention.

[0086] Figure 19 shows the electrophoresis results of an mRNA-MOF complex according to one embodiment of the present invention.

[0087] Figure 20 shows the electrophoresis results of an mRNA-MOF complex according to one embodiment of the present invention.

[0088] The present invention relates to a novel metal-organic framework surface-modified with a compound represented by the following chemical formula 1:

[0089] [Chemical Formula 1]

[0090]

[0091] Here,

[0092] n is an integer from 0 to 4,

[0093] X1 is C(R4) or N,

[0094] R1 to R4 are the same or different from each other, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0095] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0096] In the present invention, a metal-organic framework (MOF) refers to a porous material in which a metal cluster and an organic linker (or organic bridging ligand) are connected by coordination bonds to form a three-dimensional structure, and various MOFs can be created depending on the selection of metal ions and organic ligands.

[0097] The above MOF has the characteristic of being porous with empty spaces within the structure, and the pore size, porosity, three-dimensional structure, surface area, etc. can be designed in various ways depending on the type and bonding method of the metal ions and organic ligands that make up the MOF.

[0098] Due to this porosity, MOFs not only have a very large surface area but also have an open pore structure, enabling the movement of large quantities of molecules or solvents compared to other known porous materials. Furthermore, when used as catalysts or gas storage media, they have the advantage of having many active sites, which can maximize efficiency. Furthermore, MOFs are resistant to deformation at high temperatures and have a rigid framework, resulting in excellent chemical and thermal stability.

[0099] The present invention relates to a novel MOF, which is not a conventionally known MOF, but rather a surface-modified MOF. As described below, the MOF surface-modified with the novel compound is characterized by not only a larger surface area but also larger pore diameters compared to conventional MOFs. Unlike conventional MOFs, the novel MOF, due to surface modification with the novel compound, not only binds to nucleic acids more easily, as described below, but can also be used as a more effective nucleic acid delivery vehicle in the body.

[0100] That is, it is known that conventional MOFs can be utilized as drug delivery vehicles due to their large surface area and numerous pores, but in the present invention, the surface of the MOF is modified to facilitate the binding of nucleic acids, thereby increasing the efficiency as a nucleic acid delivery vehicle.

[0101] When the novel MOF of the present invention is used as a nucleic acid delivery vehicle as described above, conventional LNPs for delivering nucleic acids into the body were important in temperature conditions during storage due to particle instability, but when the novel MOF of the present invention is used, it can be used as a more stable nucleic acid delivery vehicle.

[0102] Specifically, the novel MOF of the present invention can be surface-modified with a compound represented by the following chemical formula 1:

[0103] [Chemical Formula 1]

[0104]

[0105] Here,

[0106] n is an integer from 0 to 4,

[0107] X1 is C(R4) or N,

[0108] R1 to R4 are the same or different from each other, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0109] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 2:

[0110] [Chemical Formula 2]

[0111]

[0112] Here,

[0113] n, X1 and R3 are as defined in the above chemical formula 1.

[0114] The compound represented by the above chemical formula 2 may be a compound represented by the following chemical formulas 3 to 5:

[0115] [Chemical Formula 3]

[0116]

[0117] [Chemical Formula 4]

[0118]

[0119] [Chemical Formula 5]

[0120]

[0121] Here,

[0122] m and p are equal to or different from each other and are each independently an integer from 0 to 4,

[0123] o is an integer from 0 to 3,

[0124] L1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms,

[0125] R5 to R8 are the same or different from each other, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0126] The compound represented by the above chemical formula 1 may be selected from the group consisting of compounds represented by the following chemical formulas:

[0127]

[0128] The N of the -NH2 group commonly included in the above compounds contains an unshared electron pair, and can form a coordination bond with the MOF by the unshared electron pair, so that the compounds can bind to the surface of the MOF.

[0129] As described above, the present invention can surface-modify MOF through bonding by unshared electron pairs of compounds.

[0130] The above MOF is a metal selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi or Li + , Na + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 3+ , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+, Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ and Bi + It may include a metal ion selected from the group consisting of:

[0131] The above metal-organic framework can be selected from the group consisting of aluminum-based MOF, iron-based MOF, zirconium-based MOF, and mixtures thereof.

[0132] The MOF is UIO-66, UIO-66-NH2, UIO-67, UIO-67-NH2, PCN-128, PCN-222, PCN-223, PCN-224, MOF-525, MOF-545, MOF-801, MOF-808, MOF-867, Al-MIL-53, Al-MIL-53-NH2, Al-MIL-88, Al-MIL-88-NH2, Al-MIL-100, Al-MIL-100-NH2, Al-MIL-101, Al-MIL-101-NH2, Al-MIL-125, Al-MIL-125-NH2, Fe-MIL-53, Fe-MIL-53-NH2, Fe-MIL-88, It can be selected from the group consisting of Fe-MIL-88-NH2, Fe-MIL-100, Fe-MIL-100-NH2, Fe-MIL-101, Fe-MIL-101-NH2, Fe-MIL-125 and Fe-MIL-125-NH2, preferably UIO-66, but is not limited to the above examples, and any MOF capable of forming a coordination bond with the compound represented by the above chemical formula 1 can be used without limitation.

[0133] Additionally, the specific surface area of ​​the above MOF is 1,400 m 2 / g to 1,500 m 2 / g, and the pore diameter may be 1 nm to 3 nm. The MOF of the present invention is characterized by having a larger specific surface area and pore diameter than a non-surface-modified MOF due to surface modification.

[0134] The MOF of the present invention can be used as a nucleic acid delivery vehicle as described above. The nucleic acid is specifically mRNA, but is not limited to the above examples, and any nucleic acid that can be bound to the surface-modified MOF of the present invention can be used without limitation. The MOF of the present invention can easily bind nucleic acids and exhibit stable MOF release after being injected into the body, so it can be utilized as an excellent nucleic acid delivery vehicle.

[0135] A method for producing a novel metal-organic framework according to another embodiment of the present invention may include the steps of: suspending a metal-organic framework in a first organic solvent to produce a metal-organic framework mixed solution; dissolving a compound represented by the following chemical formula 1 in a second organic solvent to produce a surface-modifying solution; and mixing and stirring the metal-organic framework mixed solution and the surface-modifying solution.

[0136] [Chemical Formula 1]

[0137]

[0138] Here,

[0139] n is an integer from 0 to 4,

[0140] X1 is C(R4) or N,

[0141] R1 to R4 are the same or different from each other, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0142] The above MOF is as described above, and can be manufactured using a conventional MOF manufacturing method, and is not limited to the MOF manufacturing method.

[0143] Specifically, the above MOF can be suspended in a first organic solvent to prepare a metal-organic framework mixed solution. At this time, the first organic solvent is toluene, but is not limited to toluene, and any organic solvent that can be used to suspend the MOF and prepare a metal-organic framework mixed solution can be used without limitation.

[0144] Thereafter, the step of preparing a surface modification solution can be prepared by dissolving the compound represented by the above chemical formula 1 in a second organic solvent. The compound represented by the above chemical formula 1 is as described above. The compound represented by the above chemical formula 1 can be purchased and used, or can be synthesized and used, and can be synthesized using a conventional synthesis method.

[0145] Although the above second organic solvent is toluene, it is not limited to toluene, and any organic solvent that can be prepared as a surface modification solution by mixing the compound represented by the above chemical formula 1 can be used without limitation.

[0146] Thereafter, the metal-organic framework mixed solution and the surface modification solution may be mixed and stirred. The stirring step may be performed at 80°C to 120°C for 4 to 8 hours so that the compound represented by the chemical formula 1 may be bound to the surface of the metal-organic framework through a coordination bond.

[0147] The above stirring conditions may be stirring at 80°C to 120°C for 4 to 8 hours, stirring at 90°C to 110°C for 5 to 7 hours, or stirring at 100°C for 6 hours. Under the above stirring conditions, the compound represented by the above chemical formula 1 can be coordinately bonded to the surface of the MOF.

[0148] After the above stirring step, the surface-modified metal-organic framework can be manufactured by washing and drying.

[0149] More specifically, the washing step may include a first centrifugation step of the reactant prepared by the stirring step at 5,000 rpm to 15,000 rpm for 1 to 10 minutes; a first washing step of suspending the precipitate separated by the first centrifugation step in a third organic solvent and then centrifuging the precipitate at 5,000 rpm to 15,000 rpm for 1 to 10 minutes, repeated 1 to 5 times; and a second washing step of suspending the precipitate separated by the first washing step in a fourth organic solvent and then centrifuging the precipitate at 5,000 rpm to 15,000 rpm for 1 to 10 minutes, repeated 1 to 5 times.

[0150] The third organic solvent may be toluene, and the fourth organic solvent may be ethanol, but is not limited to the above examples, and any organic solvent capable of washing the synthesized surface-modified MOF may be used without limitation.

[0151] Additionally, the drying step may dry the lower layer particles separated by the second washing step in an oven at 60°C to 100°C for 2 to 6 hours.

[0152]

[0153] Manufacturing example

[0154] Manufacturing of novel MOFs

[0155] Benzoic acid (11.2 g) and benzene-1,4-dicarboxylic acid (BDC) were added to 250 ml of N,N-dimethylformamide (DMF) and stirred. 2.12 g of zirconium(IV) chloride (ZrCl4) was added to the solution and stirred. The mixture was then allowed to react in an oven at 120°C for 24 hours. The reactant was obtained and centrifuged at 10,000 rpm for 5 minutes, after which the supernatant was removed. The centrifuged precipitate was resuspended in 30 ml of DMF, and the washing process of centrifuging at 10,000 rpm for 5 minutes was repeated three times. The above DMF was removed, resuspended in 30 ml of ethanol, and centrifuged at 10,000 rpm for 5 minutes. This washing process was repeated three times. The ethanol was removed, and the lower layer particles were dried in an oven at 80°C for 4 hours to obtain a powder (UIO-66).

[0156] 200 mg of the powder obtained above was weighed and suspended in 10 ml of toluene to prepare a toluene suspension.

[0157] 3-Aminobenzyl alcohol (ABA), 2-methoxy-4-nitroaniline (MN), and 2-aminopyridine (APD) were weighed so that each amount was 0.6 mmol, and then dissolved in 40 ml of toluene to prepare a toluene solution.

[0158] The above toluene suspension and toluene solution were placed in a round flask, the flask was connected to a reflux condenser, and the reaction product was prepared by stirring at 100°C for 6 hours.

[0159] The above reaction product was obtained, centrifuged at 10,000 rpm for 5 minutes, and the supernatant was removed. The centrifuged precipitate was resuspended in 30 ml of toluene, and the washing process of centrifuging at 10,000 rpm for 5 minutes was repeated three times.

[0160] The same washing process was repeated three times using ethanol instead of toluene.

[0161] In the final washing process, the supernatant ethanol was removed, and the particles in the lower layer were dried in an oven at 80°C for 4 hours to obtain the final product, powder.

[0162] The product obtained by surface-modifying the above ABA was called UIO66ABA, the product obtained by surface-modifying the above MN was called UIO66MN, and the product obtained by surface-modifying the above APD was called UIO66APD.

[0163]

[0164] Experimental Example 1

[0165] Analysis of synthetic results

[0166] For scanning electron microscope (SEM) measurements, powder samples were placed in 2-3 mg Eppen tubes, 100 μl of ethanol was added, and bath sonication was performed. 10 μl was then spotted onto a silicon wafer and dried in an oven at 80°C. The dried silicon wafer was then attached to an SEM mount using carbon tape and moved to an SEM device for image capture (Company name: Zeiss / Model name: ULTRA PLUS).

[0167] Next, for X-ray diffraction (XRD) measurement, the powder sample was carefully placed on the XRD sample holder, and the sample was compressed by pressing it with an appropriate force using a glass slide glass. After that, all powder scattered around the sample holder was carefully removed, and the sample holder was moved to the equipment, set up, and measurements were performed in the range of 2℃ to 30℃ (Company name: Bruker / Model name: D2 phaser).

[0168] Next, for N2 adsorption isotherm and BET specific surface area-pore measurement, about 40 mg of completely dried sample was prepared and carefully placed in a glass sampler using a glass funnel, and all powder adhering around the glass tube except for the lower sample container was removed. After that, the upper filter cap was attached, and degas was performed by vacuum and heat treatment at 120℃ for 12 hours in a pretreatment device. The weight of the pretreated sample was measured using a microbalance, and the weight of the empty cell that was weighed in advance was subtracted to calculate the weight of the intact sample. The glass sampler was attached to the N2 adsorption-desorption device and the measurement was performed (Company name: MICROTAAC / Model name: BELSORP MINI X).

[0169] The structural schematic diagram of the above UIO66ABA particles is as shown in Fig. 1. The scanning electron microscope observation results for the above UIO66ABA are as shown in Fig. 2. In addition, the X-ray diffraction analysis results are as shown in Fig. 3, which confirmed that the manufactured particles were synthesized with the crystal structure of UIO66ABA. In addition, the BET (Brunauer-Emmett-Teller) analysis results through N2 adsorption showed that the specific surface area of ​​the UIO66ABA particles was 1481 m 2 / g, and the pore diameter is 2.110 nm (Fig. 4).

[0170] The FT-IR measurement results of UIO66ABA are as shown in Fig. 5. Fig. 6 shows the NMR (13C) measurement results for the synthesized UIO66ABA particles.

[0171] The structural schematic diagram of the particles of the above UIO66MN is as shown in Fig. 7. The results of scanning electron microscopy observation of the above UIO66MN are as shown in Fig. 8. In addition, the results of X-ray diffraction analysis are as shown in Fig. 9, which confirmed that the manufactured particles were synthesized with the crystal structure of UIO66MN. In addition, the results of BET (Brunauer-Emmett-Teller) analysis through N2 adsorption showed that the specific surface area of ​​the UIO66MN particles was 1449 m 2 / g, and the pore diameter is 2.044 nm (Fig. 10).

[0172] The FT-IR measurement results of UIO66MN are as shown in Fig. 11. Fig. 12 shows the NMR (13C) measurement results for the synthesized UIO66MN particles.

[0173] The structural schematic diagram of the particles of the above UIO66APD is as shown in Fig. 13. The results of scanning electron microscopy observation of the above UIO66APD are as shown in Fig. 14. In addition, the results of X-ray diffraction analysis are as shown in Fig. 15, which confirmed that the manufactured particles were synthesized with the crystal structure of UIO66APD. In addition, the results of BET (Brunauer-Emmett-Teller) analysis through N2 adsorption showed that the specific surface area of ​​the UIO66APD particles was 1481 m 2 / g, and the pore diameter is 2.110 nm (Fig. 16).

[0174] The FT-IR measurement results of UIO66APD are as shown in Fig. 17. Fig. 18 shows the NMR (13C) measurement results for the synthesized UIO66APD particles.

[0175] The specific surface area of ​​UIO-66 is typically 1,180 m 2 / g to 1,240 m 2 / g, and the specific surface area of ​​the UIO66ABA particles of the present invention is 1481 m 2 / g, and the specific surface area of ​​UIO66MN particles is 1449 m 2 / g, and the specific surface area of ​​UIO66APD particles is 1481 m 2 / g, it was confirmed that there was a large difference in the specific surface area compared to UIO-66 without surface modification.

[0176] In addition, the pore diameter of UIO-66 is 0.6 nm, and as described above, the pore diameter of UIO66ABA particles is 2.110 nm, the pore diameter of UIO66MN particles is 2.044 nm, and the pore diameter of UIO66APD particles is 2.110 nm, confirming that there is a large difference in pore diameter compared to UIO-66 without surface modification.

[0177] Experimental Example 2

[0178] Formation of m-RNA-MOF complex and confirmation test of m-RNA-MOF complex formation

[0179] A 1% agarose gel was prepared by adding 1.0 g of agarose to 100 ml of 1×TAE buffer and melting it at high temperature. 7 ul of Dyne StainingSTAR (an EtBr substitute) was added to the agarose gel solution, mixed thoroughly, and then the solution was placed in an electrophoresis gel forming mold and solidified.

[0180] The solidified agarose gel was placed in an electrophoresis device, and 1×TAE buffer was added to sufficiently submerge the gel.

[0181] The above UIO66MN and UIO66APD were suspended in each DW at a concentration of 10 mg / ml, and then diluted to concentrations of 10 mg / ml, 5 mg / ml, 2.5 mg / ml, 1.25 mg / ml, 0.625 mg / ml, and 0.312 mg / ml.

[0182] A 200 ng / ul mRNA solution was prepared by adding 80 ul of 10 mM NaOAC to 20 ul of mRNA (1 ug / ul). 1 ul of the mRNA solution and 10 ul each of UIO66MN and UIO66APD solutions were mixed and incubated at room temperature for 10 minutes to prepare mRNA-MOF complexes (mRNA-UIO66MN complex and mRNA-UIO66APD complex).

[0183] An mRNA control was prepared by mixing 1 ul of mRNA solution and 10 ul of DI.

[0184] After mixing 5 ul of DNA ladder (50 bp) and 1 ul of DNA loading buffer, 5 ul was loaded onto an agarose gel. 5 ul of mRNA control and 5 ul each of mRNA-MOF complexes (mRNA-UIO66MN complex and mRNA-UIO66APD complex) were mixed in 1 ul of DNA loading buffer, and 5 ul was loaded onto an agarose gel.

[0185] The results of electrophoresis for 15 minutes under 35 V conditions are as shown in Figs. 19 and 20.

[0186] Figure 19 shows the results of mRNA binding according to concentration for the mRNA-UIO66MN complex. Compared to the mRNA control, no mRNA was detected, confirming that the mRNA-UIO66MN complex was well bound to mRNA.

[0187] Figure 20 shows the results of mRNA binding according to concentration for the mRNA-UIO66APD complex. Compared to the mRNA control, no mRNA was detected, confirming that the mRNA-UIO66 APD complex is well bound to mRNA.

[0188] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

[0189] This project (outcome) is the result of a local government-university collaboration-based regional innovation project, supported by the National Research Foundation of Korea and funded by the Ministry of Education in 2024 (2021RIS-001).

[0190] [Project ID] 1345370811

[0191] [Project Number] 2021RIS-001

[0192] [Ministry Name] Ministry of Education (P13)

[0193] [Name of Project Management (Specialist) Institution] National Research Foundation of Korea

[0194] [Research Project Name] Local Government-University Cooperation-Based Regional Innovation Project

[0195] [Research Project Name] Local Government-University Cooperation-Based Regional Innovation Project (Chungbuk Regional Innovation Platform)

[0196] [Contribution rate]

[0197] [Name of Project Performing Organization] (Chungbuk Regional Innovation Platform) Chungbuk National University

[0198] [Research Period] March 1, 2024 - February 28, 2025

[0199] The present invention relates to a novel metal-organic framework and a method for producing the same.

Claims

1. A novel metal-organic framework surface-modified with a compound represented by the following chemical formula 1: [Chemical Formula 1] Here, n is an integer from 0 to 4, X1 is C(R4) or N, R1 to R4 are the same or different, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

2. In paragraph 1, The compound represented by the above chemical formula 1 is a novel metal-organic framework represented by the following chemical formula 2: [Chemical formula 2] Here, n, X1 and R3 are as defined in paragraph 1.

3. In paragraph 1, The above metal-organic framework is a metal selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, or Li. + , Na + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 3+ , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ and Bi + Containing a metal ion selected from the group consisting of A novel metal-organic framework.

4. In paragraph 1, The above metal-organic framework is selected from the group consisting of aluminum-based metal-organic frameworks, iron-based metal-organic frameworks, zirconium-based metal-organic frameworks, and mixtures thereof. A novel metal-organic framework.

5. In paragraph 1, The above metal-organic frameworks are UIO-66, UIO-66-NH2, UIO-67, UIO-67-NH2, PCN-128, PCN-222, PCN-223, PCN-224, MOF-525, MOF-545, MOF-801, MOF-808, MOF-867, Al-MIL-53, Al-MIL-53-NH2, Al-MIL-88, Al-MIL-88-NH2, Al-MIL-100, Al-MIL-100-NH2, Al-MIL-101, Al-MIL-101-NH2, Al-MIL-125, Al-MIL-125-NH2, Fe-MIL-53, Fe-MIL-53-NH2, Fe-MIL-88, Selected from the group consisting of Fe-MIL-88-NH2, Fe-MIL-100, Fe-MIL-100-NH2, Fe-MIL-101, Fe-MIL-101-NH2, Fe-MIL-125 and Fe-MIL-125-NH2 A novel metal-organic framework.

6. In paragraph 1, The specific surface area of ​​the above metal-organic framework is 1,400 m 2 / g to 1,500 m 2 / g person A novel metal-organic framework.

7. In paragraph 1, The pore diameter of the above metal-organic framework is 1 nm to 3 nm. A novel metal-organic framework.

8. A step of suspending a metal-organic framework in a first organic solvent to prepare a metal-organic framework mixed solution; A step of preparing a surface modification solution by dissolving a compound represented by the following chemical formula 1 in a second organic solvent; and A step of mixing and stirring the above metal-organic framework mixture solution and the surface modification solution. Method for preparing novel metal-organic frameworks: [Chemical Formula 1] Here, n is an integer from 0 to 4, X1 is C(R4) or N, R1 to R4 are the same or different, and each independently represent hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

9. In paragraph 8, The above stirring step is to surface modify the metal-organic framework by stirring at 80°C to 120°C for 4 to 8 hours. A method for preparing a novel metal-organic framework.

10. In paragraph 8, After the above stirring step, the surface-modified metal-organic framework is manufactured by washing and drying. A method for preparing a novel metal-organic framework.

11. In paragraph 10, The above washing step is, A step of first centrifuging the reactant prepared by the above stirring step at 5,000 rpm to 15,000 rpm for 1 to 10 minutes; A first washing step in which the precipitate separated by the first centrifugation step is suspended in a third organic solvent and then centrifuged at 5,000 rpm to 15,000 rpm for 1 to 10 minutes is repeated 1 to 5 times; and A second washing step is performed by suspending the precipitate separated by the first washing step in a fourth organic solvent and then performing a second centrifugation at 5,000 rpm to 15,000 rpm for 1 to 10 minutes, repeated 1 to 5 times. A method for preparing a novel metal-organic framework.

12. In paragraph 10, The above drying step is, The lower layer particles separated by the second washing step are dried in an oven at 60°C to 100°C for 2 to 6 hours. A method for preparing a novel metal-organic framework.

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