IPC분류정보
국가/구분 |
United States(US) Patent
등록
|
국제특허분류(IPC7판) |
|
출원번호 |
US-0679645
(2008-10-01)
|
등록번호 |
US-10065979
(2018-09-04)
|
우선권정보 |
FR-07 06873 (2007-10-01) |
국제출원번호 |
PCT/FR2008/001366
(2008-10-01)
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§371/§102 date |
20100505
(20100505)
|
국제공개번호 |
WO2009/077670
(2009-06-25)
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발명자
/ 주소 |
- Horcajada-Cortes, Patricia
- Ferey, Gérard
- Serre, Christian
- Gref, Ruxandra
- Couvreur, Patrick
|
출원인 / 주소 |
- CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE-CNRS
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대리인 / 주소 |
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인용정보 |
피인용 횟수 :
0 인용 특허 :
7 |
초록
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The invention relates to nanoparticles made from organometallic hybrid materials made from iron carboxylates, used for example as contrast agents. The particles can also be used for the encapsulation and vectoring of molecules of interest such as active3 pharmaceutical agents, cosmetically interesti
The invention relates to nanoparticles made from organometallic hybrid materials made from iron carboxylates, used for example as contrast agents. The particles can also be used for the encapsulation and vectoring of molecules of interest such as active3 pharmaceutical agents, cosmetically interesting compounds and markers. Apart from the intrinsic properties thereof for imaging, said nanoparticles give good results in terms of capacity for loading with medicaments and in biocompatibility.
대표청구항
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1. A process for preparing isoreticular porous crystalline MOF nanoparticles comprising a three-dimensional succession of units having formula (I) below: FemOkXlLp Formula (I) in which: Fe represents the metallic ion Fe3+ or Fe2+;m is 1 to 4;k is 0 to 4;l is 0 to 4;p is 1 to 4;X is a ligand chosen
1. A process for preparing isoreticular porous crystalline MOF nanoparticles comprising a three-dimensional succession of units having formula (I) below: FemOkXlLp Formula (I) in which: Fe represents the metallic ion Fe3+ or Fe2+;m is 1 to 4;k is 0 to 4;l is 0 to 4;p is 1 to 4;X is a ligand chosen from the group comprising OH−, Cl−, F−, I−, Br, SO42−, NO3−, ClO4−, PF6−, BF3−, R1—(COO)n−, R1—(SO3)n−, R1—(PO3)n−, in which R1 is a hydrogen atom, an optionally substituted, linear or branched C1 to C12 alkyl, n=1 to 4;L is a spacer ligand comprising a radical R bearing q carboxylate groups in which q is 1, 2, 3, 4, 5 or 6;* denotes the point of attachment of the carboxylate to the radical R;# denotes the possible points of attachment of the carboxylate to the metal ion;R represents:(i) a C1-12alkyl, C2-12alkene or C2-12alkyne radical;(ii) a fused or non-fused monocyclic or polycyclic aryl radical, comprising 6 to 50 carbon atoms;(iii) a fused or non-fused monocyclic or polycyclic heteroaryl, comprising 1 to 50 carbon atoms;(iv) an organic radical comprising a metal element chosen from the group comprising ferrocene, porphyrin, phthalocyanin and a Schiff's base RX1RX2—C═N—RX3, in which RX1 and RX2 are independently a hydrogen atom, a linear, branched or cyclic, optionally substituted C1-12alkyl, C2-12alkene or C2-12alkyne radical, or an optionally branched and/or substituted monocyclic or polycyclic aryl comprising 6 to 50 carbon atoms;and RX3 is a linear, branched or cyclic, optionally substituted C1-12alkyl, C2-12alkene or C2-12alkyne radical, or an optionally branched and/or substituted monocyclic or polycyclic aryl comprising 6 to 50 carbon atoms; the radical R being optionally substituted with one or more groups R2 independently chosen from the group comprising C1-10alkyl; C2-10alkene; C2-10alkyne; C3-10cycloalkyl; C1-10heteroalkyl; C1-10haloalkyl; C6-10aryl; C3-10heteroaryl; C5-20heterocycle; C1-10alkylC6-10aryl; C1-10alkylC3-10heteroaryl; C1-10alkoxy; C6-10aryloxy; C3-10heteroalkoxy; C3-10heteroaryloxy; C1-10alkylthio; C6-10arylthio; C1-10heteroalkylthio; C3-10heteroarylthio; F; Cl; Br; I; —NO2; —CN; —CF3; —CH2CF3; —CHCl2; —OH; —CH2OH; —CH2CH2OH; —NH2; —CH2NH2; —NHCOH; —COOH; —CONH2; —SO3H; —CH2SO2CH3; —PO3H2; —B(ORG1)2; or a function -GRG1 in which G is —O—, —S—, —NRG2—, —C(═O)—, —S(═O)—, —SO2—, —C(═O)O—, —C(═O)NRG2—, —OC(═O)—, —NRG2C(═O)—, —OC(═O)O—, —OC(═O)NRG2—, —NRG2C(═O)O—, —NRG2C(═O)NRG2—, —C(═S)—, —C(═S)S—, —SC(═S)—, —SC(═S)S—, —C(═NRG2)—, —C(═NRG2)O—, —C(═NRG2)NRG3—, —OC(═NRG2)—, —NRG2C(═NRG3)—, —NRG2SO2—, —NRG2SO2NRG3—, —NRG2C(═S)—, —SC(═S)NRG2—, —NRG2C(═S)S—, —NRG2C(═S)NRG2—, —SC(═NRG2)—, —C(═S)NRG2—, —OC(═S)NRG2—, —NRG2C(═S)O—, —SC(═O)NRG2—, —NRG2C(═O)S—, —C(═O)S—, —SC(═O)—, —SC(═O)S—, —C(═S)O—, —OC(═S)—, —OC(═S)O— or —SO2NRG2—, in which each occurrence of RG1, RG2 and RG3 is, independently of the other occurrences of RG1, a hydrogen atom; a halogen atom; or a linear, branched or cyclic, optionally substituted C1-12alkyl, C1-12heteroalkyl, C2-10alkene or C2-10alkyne group; or a group C6-10aryl, C3-10heteroaryl, C5-10heterocycle, C1-10alkylC6-10aryl or C1-10alkylC3-10heteroaryl in which the aryl, heteroaryl or heterocyclic radical is optionally substituted; or alternatively, when G represents —NRG2—, RG1 and RG2 together with the nitrogen atom to which they are attached form an optionally substituted heterocycle or heteroaryl; the process comprising at least one reaction step (i) that consists in mixing in a polar solvent: at least one solution comprising at least one metallic inorganic precursor in the form of iron metal, an iron(III) salt, an iron(II) salt or a coordination complex comprising the metal ion Fe3+,at least one ligand L′ comprising a di-, tri-, tetra- or hexadentate ligand selected from the group consisting of: In which R3 is selected from the group consisting of a radical —OH, a radical —OY in which Y represents an alkali metal cation, a halogen or a radical —OR4, —O—C(═O)R4 or —NR4R4′, in which R4 and R4′, identical or different, represent C1-12 alkyl radicals,X1 represents O or S,s represents an integer from 1 to 4,each occurrence of t independently represents an integer from 1 to 4,u represents an integer from 1 to 7,RL1 and RL2 independently represent H, a halogen or a C1 to C6 alkyl, andeach occurrence of RL3 independently represents H, a halogen, OH, NH2, NO2 or a C1 to C6 alkyl,so as to obtain the said nanoparticles, wherein,when the process is carried out via the solvothermal route, the reaction temperature is between 20 and 200° C., the reaction time is between 30 minutes and 72 hours, the concentration of ligand L′ and of metallic inorganic precursor is—between 1 and 200 mmol/L, a monocarboxylic acid cosolvent is added in the course of synthesis of the MOF nanoparticle to stop crystal growth of the MOF nanoparticle, before the end of the synthesis; andwhen the process is carried out via the ultrasonication route, the reaction temperature is between −5° C. and 20° C., the reaction time is between 15 minutes and 2 hours, the concentration of ligand L′ and of metallic inorganic precursor is between 10 mol/l and 10−2 mol/l, and a monocarboxylic acid is added. 2. The process for preparing nanoparticles as claimed in claim 1, in which the ligand L′ used represents a di-, tri- or tetracarboxylic acid selected from the group consisting of: C2H2(CO2H)2 (fumaric acid), C2H4(CO2H)2 (succinic acid), C3H6(CO2H)2 (glutaric acid), C4H4(CO2H)2 (muconic acid), C4H8(CO2H)2 (adipic acid), C7H14(CO2H)2 (azelaic acid), C5H3S(CO2H)2 (2,5-thiophenedicarboxylic acid), C6H4(CO2H)2 (terephthalic acid), C6H2N2(CO2H)2 (2,5-pyrazinedicarboxylic acid), C10H6(CO2H)2 (naphthalene-2,6-dicarboxylic acid), C12H8(CO2H)2 (biphenyl-4,4′-dicarboxylic acid), C12H8N2(CO2H)2 (azobenzenedicarboxylic acid), C6H3(CO2H)3 (benzene-1,2,4-tricarboxylic acid), C6H3(CO2H)3 (benzene-1,3,5-tricarboxylate acid), C24H15(CO2H)3 (benzene-1,3,5-tribenzoic acid), C6H2(CO2H)4 (benzene-1,2,4,5-tetracarboxylic acid), C10H4(CO2H)4 (naphthalene-2,3,6,7-tetracarboxylic acid), C10H4(CO2H)4 (naphthalene-1,4,5,8-tetracarboxylic acid), C12H6(CO2H)4 (biphenyl-3,5,3′,5′-tetracarboxylic acid), and modified analogs chosen from the group comprising 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-methylterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 2,5-dihydroxoterephthalic acid, tetrafluoroterephthalic acid, 2,5-dicarboxyterephthalic acid, dimethyl-4,4′-biphenyldicarboxylic acid, tetramethyl-4,4′-biphenyldicarboxylic acid, dicarboxy-4,4′-biphenyldicarboxylic acid, 2,5-pyrazinedicarboxylic acid, 2,5-diperfluoroterephthalic acid, azobenzene-4,4′-dicarboxylic acid, 3,3′-dichloroazobenzene-4,4′-dicarboxylic acid, 3,3′-dihydroxoazobenzene-4,4′-dicarboxylic acid, 3,3′-diperfluoroazobenzene-4,4′-dicarboxylic acid, 3,5,3′,5′-azobenzenetetracarboxylic acid, 2,5-dimethylterephthalic acid, and perfluoroglutaric acid. 3. The process for preparing nanoparticles as claimed in claim 1, in which the reaction step (i) is performed with at least one of the reaction conditions below: (a) a reaction temperature from 0° C. to 220° C.;(b) a stirring speed from 0 to 1000 rpm;(c) a reaction time from 1 minute to 96 hours;(d) a pH from 0 to 7;(e) the addition of at least one monocarboxylic acid cosolvent to the solvent, to the precursor, to the ligand or to the mixture thereof, said monocarboxylic acid cosolvent being selected from the group consisting of acetic acid, formic acid and benzoic acid;(f) the solvent is selected from the group consisting of water, alcohols RS—OH in which RS is a linear or branched C1 to C6 alkyl radical, dimethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, diethylformamide, chloroform, cyclohexane, acetone, cyanobenzene, dichloromethane, nitrobenzene, ethylene glycol, dimethylacetamide, and mixtures of these solvents, which may be miscible or immiscible;(g) in a supercritical medium;(h) under microwaves and/or under ultrasound;(i) under electrochemical electrolysis conditions;(j) under conditions using a roll mill;(k) in a gas stream. 4. The process for preparing nanoparticles as claimed in claim 1, further comprising a step (ii) of introducing into said nanoparticle at least one molecule of interest which may be a pharmaceutically active principle and/or a compound of cosmetic interest and/or marker. 5. The process for preparing nanoparticles as claimed in claim 4, further comprising a step (iii) of binding to said nanoparticle at least one organic surface agent selected from the group consisting of an oligosaccharide, a polysaccharide, a glycosaminoglycan, a polymer, a surfactant, a vitamin, a coenzyme, an antibody or antibody fragment, an amino acid and a peptide.
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