CN111187419A - Dye/metal-organic framework composite material with fluorescence up-conversion performance, preparation method thereof and biological imaging application - Google Patents
Dye/metal-organic framework composite material with fluorescence up-conversion performance, preparation method thereof and biological imaging application Download PDFInfo
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- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 53
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- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
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- 238000005086 pumping Methods 0.000 claims description 24
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- 239000000243 solution Substances 0.000 claims description 23
- -1 carboxyphenyl Chemical group 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 9
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 8
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- VADJQOXWNSPOQA-UHFFFAOYSA-L dichlorozinc;3-n,3-n,6-n,6-n-tetramethylacridine-3,6-diamine;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Zn+2].C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 VADJQOXWNSPOQA-UHFFFAOYSA-L 0.000 claims description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 4
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 238000001228 spectrum Methods 0.000 description 4
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
- A61K49/0026—Acridine dyes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
- A61K49/003—Thiazine dyes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
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- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/005—Fluorescence in vivo characterised by the carrier molecule carrying the fluorescent agent
- A61K49/0052—Small organic molecules
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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Abstract
The invention discloses a dye/metal-organic framework composite material with fluorescence up-conversion performance, a preparation method and a biological imaging application thereof, wherein the chemical formula of the material is [ M (L)x(G)y]·(R)nWherein M is a metal ion, L is a flexible organic ligand containing a hexacarboxylic acid group, G is a solvent molecule, and R represents a dye molecule in a pore channel. The material is prepared by a solvothermal method, and under an infrared/near-infrared light pump, a frame can generate a nonlinear optical signal of second harmonic wave so as to transfer energy to dye, so that the dye which can only emit light under an ultraviolet visible light pump can also emit light under the infrared/near-infrared light pump. The advantages of infrared/near infrared light in the field of biological imaging are utilized, and the limit to exciting light is reduced(ii) a The loading of the metal-organic framework material on the dye also improves the biocompatibility and aggregation fluorescence quenching problems of the dye, and widens the application range of the dye.
Description
Technical Field
The invention relates to a dye/metal-organic framework composite material with fluorescence up-conversion performance and a preparation method thereof.
Background
Fluorescent dyes have been used in the fields of bio-imaging, fluorescent probes, cell staining, illumination LEDs, etc. due to their many kinds, convenient structural design, stable luminescence and wide spectral range; but the application is limited by the aggregation fluorescence quenching, the poor solubility and the poor biocompatibility of the organic dye molecules. Most dyes can only be excited by ultraviolet visible light, but because infrared/near infrared light is compared with an ultraviolet visible light source, the biological tissue has the advantages of high penetration rate, weak biological autofluorescence, low excitation energy, high spatial resolution and the like, and the dye has a larger application prospect in the field of biological imaging; in order to solve this contradiction in biological imaging, that is, to find a method that can make fluorescent dye emit light under infrared/near infrared light, it is very important for dye to be applied in a wider range.
Nonlinear optics provides a way to solve the excitation light source wavelength problem described above. The material with the up-conversion function can convert infrared/near infrared light into ultraviolet visible light, so as to excite the dye to emit light.
Metal-organic frameworks (MOFs) are crystalline materials formed by self-assembly of metal ions/metal clusters with organic ligands via coordination bonds. Because most MOFs materials have a microporous structure, dye molecules can be well dispersed through proper pore size design, the problem of fluorescence quenching of organic dye molecule aggregation is solved, and the toxicity problem of single dyes in biological application is improved due to the good biocompatibility of MOFs. By designing the MOFs structure, a material with nonlinear optical performance can be synthesized; particularly, MOFs materials with crystallographically asymmetric centers have Second Harmonic Generation (SHG) performance, and can convert infrared/near infrared light into ultraviolet visible light and finally excite dyes to generate fluorescence.
Disclosure of Invention
The invention aims to provide a preparation method of a dye/metal-organic framework composite material with fluorescence upconversion performance, which can be used for expanding the application range of dyes, and the upconversion performance is researched.
The dye/metal-organic framework composite material with fluorescence upconversion performance has a long-range ordered crystal structure and regular pore channels, and the chemical formula of the dye/metal-organic framework composite material is [ M (L) ]x(G)y]·(R)nWherein M is a metal ion comprising La, Ce, Pr, Nd, Sm, Eu, Gd, Tb; l is a flexible organic ligand containing a six carboxylic acid group, hexyl [4- (carboxyphenyl) carbonyl]-3-oxan, x ═ 0.5; g represents a solvent molecule coordinated with the metal ion or in the pore channel of the crystal, and is water, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide; y is 0-10, R represents dye molecules in the pore channel and comprises neutral red, basic blue 17, basic orange 14 and quinacridone, and n is 1-50.
The preparation method of the dye/metal-organic framework composite material with fluorescence upconversion performance comprises the following steps:
adding metal nitrate and an organic ligand into deionized water and an organic solvent together to obtain a mixed solution, adding 1-3 mL of an acid solution, putting the obtained solution into a liner of a reaction kettle, heating and reacting at 140-180 ℃ for 3-5 days, centrifuging and washing to obtain a metal-organic framework material; and soaking the obtained metal-organic framework material in a dye aqueous solution, and placing the metal-organic framework material in an oven at the temperature of 40-60 ℃ for heat preservation for 2-7 days to obtain the dye/metal-organic framework composite material with fluorescence upconversion performance for expanding the application range of the dye.
In the invention, the metal nitrate is lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate and terbium nitrate.
In the present invention, the flexible organic ligand containing a hexacarboxylic acid group is hexyl [4- (carboxyphenyl) carbonyl ] -3-oxane; the structural formula is as follows:
in the invention, the structural formula of the dye is as follows: (a) neutral red; (b) basic blue 17; (c) basic orange 14; (d) a quinacridone.
In the present invention, the organic solvent used is any one of N, N-dimethylformamide, N-dimethylacetamide, or N, N-diethylformamide.
In the invention, the molar ratio of metal ions to organic ligands in the metal nitrate is 1-3: 1.
in the invention, the volume ratio of the organic solvent to the deionized water is 5-10: 1.
in the invention, the acid in the acid solution can be nitric acid, hydrochloric acid, sulfuric acid or acetic acid, and the solvent is water and has the concentration of 0.5-2M.
According to the dye/metal-organic framework composite material with the fluorescence up-conversion performance, the wavelength of pump light is located in an infrared/near-infrared region, and the metal-organic framework material can generate a nonlinear optical signal of second harmonic; this signal further energizes the dye, causing the organic dye to emit fluorescence. In this way, dyes that would otherwise only emit light under ultraviolet visible light pumping can also emit light under infrared/near infrared light pumping.
The invention has the following specific beneficial effects:
1. dyes have been used in the fields of bio-imaging, illumination LEDs, etc. because of their many types, convenient structural design, stable luminescence and wide spectral range; however, the defects of quenching of aggregation fluorescence, poor solubility, excitation of most dyes only by ultraviolet and visible light and the like limit the application of the dye in a wider range. Compared with an ultraviolet visible light source, the infrared/near infrared light source has the advantages of high penetration rate of biological tissues to the light source, weak biological autofluorescence, low excitation energy, high spatial resolution and the like, and has a wider application prospect in the field of biological imaging. The method can be used for expanding the application range of the dye, reducing the limit on the excitation wavelength, converting infrared/near infrared light into ultraviolet visible light by using the dye/metal-organic framework composite material with the fluorescence up-conversion performance, and further absorbing the ultraviolet visible light by the dye to finally emit the fluorescence of the dye.
2. Compared with the commercial up-conversion fluorescence biological imaging dye, under the same test condition, the fluorescence emission intensity of the dye/metal-organic framework composite material with the fluorescence up-conversion performance is more than 10 times of that of the dye/metal-organic framework composite material with the fluorescence up-conversion performance. The composite material of the invention has higher efficiency and is more hopeful to be applied to biological imaging.
3. Biocompatibility is an important criterion for assessing whether a material can be used in the biomedical field. The dye/metal-organic framework composite material with fluorescence upconversion performance has good biocompatibility and the cell survival rate is maintained to be more than 80%. Compared with the simple toxicity of the dye, the toxicity is obviously reduced (more than 2 times) after the dye is loaded into a metal-organic framework.
4. Compared with inorganic compounds, complexes or organic molecules, the metal-organic framework material is a crystalline material with ordered micropores, and has a long-range ordered crystal structure and regular pore channels. The micropore characteristics of the MOFs are verified through a nitrogen isothermal adsorption curve. And after the dye is loaded, BET is obviously reduced, and evidence is provided for the dye to occupy MOFs pore channels. The dye molecules can be uniformly dispersed in the frame, so that the fluorescent quenching caused by molecular agglomeration is avoided, and the luminous efficiency can be improved by more than 30 times.
Drawings
FIG. 1 is a graph of the second harmonic signal of the Gd-HCOO metal-organic framework material with second harmonic properties of the present invention under different wavelength laser pumping, compared to potassium dihydrogen phosphate (KDP);
FIG. 2 is a nitrogen isothermal adsorption curve of Gd-HCOO, a dye loaded Gd-HCOO metal-organic framework material with second harmonic performance of the present invention;
FIG. 3 is a graph of the spectrum of a dye/metal-organic framework composite with fluorescence upconversion capability of the present invention loaded with different concentrations of neutral red dye under 900nm laser pumping compared to pure dye powder/solution under the same test conditions;
FIG. 4 is a biocompatibility characterization of the metal-organic framework material Gd-HCOO, neutral red loaded Gd-HCOO, pure dye with second harmonic performance of the present invention;
FIG. 5 is a spectrum of a dye/metal-organic framework composite with fluorescent upconversion capability loaded with quinacridone dye under 1060nm laser pumping in accordance with the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Example 1:
the metal-organic framework material is synthesized by a solvothermal method by utilizing gadolinium nitrate and hexyl [4- (carboxyphenyl) carbonyl ] -3-dioxane, and a specific synthetic route is as follows:
0.1mmol of gadolinium nitrate and 0.1mmol of hexyl [4- (carboxyphenyl) carbonyl]-3-Oxane dissolved in 7mL of LDMF and 1mL of H2O mixed solvent, then 1mL HNO is added3Aqueous solution (1M). The solution is packaged in a 20mL polytetrafluoroethylene reaction kettle and placed in a 160 ℃ oven for reaction for 72 hours. Cooling to room temperature, washing with DMF for 3 times to obtain colorless needle-like metal-organic framework material Gd2L(DMF)2·(H2O)5(DMF)3(abbreviated Gd-HCOO). 40mg of the crystals were put into 0.001mol L-1Deionized water solution of Neutral Red (NR). And putting the mixture into a 15mL glass bottle, putting the glass bottle into a 60 ℃ oven for reaction for 3 days, taking out the glass bottle, filtering to remove the dye solution, washing the glass bottle with deionized water for 3 times, and putting the glass bottle into the oven for drying at 60 ℃ to obtain the metal-organic framework material containing the organic dye, wherein the dye content is 1.8 wt%. By fluorescent lightThe spectra also show that the quantum efficiency of the dye after being loaded is improved from 2.64% to 74.26% of the powder, which also reduces the limit to the use environment of the dye to a certain extent.
For Gd2L(DMF)2·(H2O)5(DMF)3The second harmonic performance of (a) was characterized. As can be seen from FIG. 1, under 960-1140nm laser pumping, MOFs can exhibit much higher second harmonic signals than the KDP reference. The material can convert infrared/near infrared light into ultraviolet visible light and can be applied to upconversion optics. The nitrogen isothermal adsorption curves before and after loading the MOFs with the dye show that the BET is 314.2929m2The/g is reduced to 97.7216m2(ii) in terms of/g. The dye occupied a fraction of the channel positions, resulting in a reduction of the channels of the MOFs (fig. 2), also indirectly demonstrating the successful loading of the dye.
Under 900nm laser pumping, dye-loaded MOFs showed both a second harmonic signal of 450nm and a broad spectrum fluorescence signal of 600nm for the dye, whereas neither the dye powder nor the solution showed fluorescence under the same conditions. It was confirmed that energy transfer by near infrared-SHG-fluorescence occurred in the composite material. By the mode, a plurality of dyes which can only emit light under ultraviolet visible light pumping originally can also emit light under infrared/near infrared light pumping, and the application range of the dyes is greatly expanded.
The biocompatibility of the MOFs after the dye loading is characterized, and the cell survival rates of the MOFs material and the MOFs after the dye loading can be maintained to be more than 80% under the concentration of 100 mu g/mL; whereas pure dye at the same concentration is only 30%. The biocompatibility of the loaded dye is obviously improved, and the designed composite material is expected to be applied to a biological system.
Example 2:
the metal-organic framework material is synthesized by a solvothermal method by utilizing gadolinium nitrate and hexyl [4- (carboxyphenyl) carbonyl ] -3-dioxane, and a specific synthetic route is as follows:
0.1mmol of gadolinium nitrate and 0.1mmol of hexyl [4- (carboxyphenyl) carbonyl]-3-Oxane dissolved in 7mL of LDMF and 1mL of H2O mixed solvent, then 1 is addedmL HNO3Aqueous solution (1M). The solution is packaged in a 20mL polytetrafluoroethylene reaction kettle and placed in a 160 ℃ oven for reaction for 72 hours. Cooling to room temperature, washing with DMF for 3 times to obtain colorless needle-like metal-organic framework material Gd2L(DMF)2·(H2O)5(DMF)3(Gd-HCOO). 40mg of the crystals were placed in 0.001mol L-1A deionized water solution of quinacridone (Qu). Putting the mixture into a 15mL glass bottle, putting the glass bottle into a 60 ℃ oven for reaction for 3 days, taking out the glass bottle, filtering to remove the dye solution, washing the glass bottle with deionized water for 3 times, and putting the glass bottle into the oven for drying at 60 ℃ to obtain the metal-organic framework material containing the organic dye, wherein the dye content is 1.42 wt%. The fluorescence spectrum also shows that the quantum efficiency of the loaded dye is improved from 0.75% to 58.23% of the powder, which also reduces the limit to the use environment of the dye to a certain extent.
Under 1060nm laser pumping, MOFs loaded by dye simultaneously displays a second harmonic signal of 530nm and a wide-spectrum fluorescent signal of 600nm of the dye, so that a plurality of dyes which can only emit light under ultraviolet visible light pumping can emit light under infrared/near infrared light pumping, and the application range of the dyes is greatly expanded.
Example 3:
the metal-organic framework material is synthesized by a solvothermal method by utilizing gadolinium nitrate and hexyl [4- (carboxyphenyl) carbonyl ] -3-dioxane, and a specific synthetic route is as follows:
0.1mmol of gadolinium nitrate and 0.1mmol of hexyl [4- (carboxyphenyl) carbonyl]-3-Oxane dissolved in 7mL of LDMF and 1mL of H2O mixed solvent, then 1mL HNO is added3Aqueous solution (1M). The solution is packaged in a 20mL polytetrafluoroethylene reaction kettle and placed in a 160 ℃ oven for reaction for 72 hours. Cooling to room temperature, washing with DMF for 3 times to obtain colorless needle-like metal-organic framework material Gd2L(DMF)2·(H2O)5(DMF)3(Gd-HCOO). 40mg of the crystals were placed in 0.001mol L-1Deionized water solution of Neutral Red (NR). Putting the mixture into a 15mL glass bottle, putting the glass bottle into a 60 ℃ oven for reaction for 3 days, taking out the glass bottle, filtering to remove the dye solution, washing the glass bottle with deionized water for 3 times, putting the glass bottle into the oven for drying at 60 ℃ to obtain the dye solutionA metal-organic framework material containing an organic dye, the dye content being 1.8% by weight. The fluorescence spectrum also shows that the quantum efficiency of the loaded dye is improved from 2.64% to 74.26% of the powder, which also reduces the limit to the use environment of the dye to a certain extent.
For Gd2L(DMF)2·(H2O)5(DMF)3The second harmonic performance of (a) was characterized. As can be seen from FIG. 1, under 960-1140nm laser pumping, MOFs can exhibit much higher second harmonic signals than the KDP reference. The material can convert infrared/near infrared light into ultraviolet visible light and can be applied to upconversion optics. The nitrogen isothermal adsorption curves before and after loading the MOFs with the dye show that the BET is 314.2929m2The/g is reduced to 97.7216m2(ii) in terms of/g. The dye occupied a fraction of the channel positions, resulting in a reduction of the channels of the MOFs (fig. 2), also indirectly demonstrating the successful loading of the dye.
To confirm that the composite material can be applied under infrared/near infrared laser pumping, we also tested the optical signal of the composite material under 1000, 1100nm laser pumping, and found that the dye-loaded MOFs showed both the second harmonic signal and the broad spectrum fluorescence signal of the dye, whereas under the same conditions neither the dye powder nor the solution showed fluorescence. It was confirmed that energy transfer by near infrared-SHG-fluorescence occurred in the composite material. By the mode, a plurality of dyes which can only emit light under ultraviolet visible light pumping originally can also emit light under infrared/near infrared light pumping, and the application range of the dyes is greatly expanded.
The biocompatibility of the MOFs after the dye loading is characterized, and the cell survival rates of the MOFs material and the MOFs after the dye loading can be maintained to be more than 80% under the concentration of 100 mu g/mL; whereas pure dye at the same concentration is only 30%. The biocompatibility of the loaded dye is obviously improved, and the designed composite material is expected to be applied to a biological system.
Example 4:
europium nitrate and hexyl [4- (carboxyl phenyl) carbonyl ] -3-dioxane are utilized to synthesize the metal-organic framework material by a solvothermal method, and the specific synthetic route is as follows:
0.1mmol of europium nitrate and 0.1mmol of hexyl [4- (carboxyphenyl) carbonyl]-3-Oxane dissolved in 7mL of LDMF and 1mL of H2O mixed solvent, then 1mL HNO is added3Aqueous solution (1M). The solution is packaged in a 20mL polytetrafluoroethylene reaction kettle and placed in a 160 ℃ oven for reaction for 72 hours. Cooling to room temperature, washing with DMF for 3 times to obtain colorless acicular metal-organic framework material Eu2L(DMF)2·(H2O)3(DMF)3. 40mg of the crystals were placed in 0.001mol L-1Deionized water solution of neutral red. And putting the mixture into a 15mL glass bottle, putting the glass bottle into a 60 ℃ oven for reaction for 3 days, taking out the glass bottle, filtering to remove the dye solution, washing the glass bottle with deionized water for 3 times, and putting the glass bottle into a 60 ℃ oven for drying to obtain the metal-organic framework material containing the organic dye. Fluorescence spectrum also shows that the quantum efficiency of the loaded dye is obviously improved, and the limit on the use environment of the dye is reduced to a certain extent.
To Eu2L(DMF)2·(H2O)3(DMF)3The second harmonic performance of (a) was characterized. Both MOFs can exhibit much higher second harmonic signals than the KDP reference under infrared/near-infrared laser pumping. The material can convert infrared/near infrared light into ultraviolet visible light and can be applied to upconversion optics. The nitrogen isothermal adsorption curves before and after loading the dye on the MOFs show that the dye occupies part of pore channel positions, so that the pore channels of the MOFs are reduced, and the successful loading of the dye is indirectly proved.
Under infrared/near infrared laser pumping, dye-loaded MOFs show both second harmonic signals and broad spectrum fluorescence signals of the dye, whereas neither dye powder nor solution shows fluorescence under the same conditions. It was confirmed that energy transfer by near infrared-SHG-fluorescence occurred in the composite material. By the mode, a plurality of dyes which can only emit light under ultraviolet visible light pumping originally can also emit light under infrared/near infrared light pumping, and the application range of the dyes is greatly expanded. The MOFs after dye loading has excellent biocompatibility, so that the designed composite material is expected to be applied to biological systems.
Claims (10)
1. The dye/metal-organic framework composite material with fluorescence upconversion performance is characterized in that the material has a long-range ordered crystal structure and regular pore channels, and the chemical formula of the material is [ M (L) ]x(G)y]·(R)nWherein M is a metal ion comprising La, Ce, Pr, Nd, Sm, Eu, Gd, Tb; l is a flexible organic ligand hexyl [4- (carboxyphenyl) carbonyl group containing a hexacarboxylic acid group]-3-oxan, x ═ 0.5; g represents a solvent molecule coordinated with the metal ion or in the pore channel of the crystal, and is water, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide; y is 0-10, R represents dye molecules in the pore channel and comprises neutral red, basic blue 17, basic orange 14 and quinacridone, and n is 1-50.
2. A method for preparing the dye/metal-organic framework composite material with fluorescent upconversion capability of claim 1, comprising the steps of:
adding metal nitrate and a flexible organic ligand containing a hexacarboxylic acid group into deionized water and an organic solvent together to obtain a mixed solution, adding 1-3 mL of an acid solution, putting the obtained solution into an inner container of a reaction kettle, heating and reacting at 140-180 ℃ for 3-5 days, centrifuging, and washing to obtain a metal-organic framework material; and soaking the obtained metal-organic framework material in a dye aqueous solution, and placing the metal-organic framework material in an oven at the temperature of 40-60 ℃ for heat preservation for 2-7 days to obtain the dye/metal-organic framework composite material with the fluorescence up-conversion performance.
3. The method for preparing the dye/metal-organic framework composite material with fluorescence upconversion performance according to claim 2, wherein the metal nitrate is lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, or terbium nitrate.
4. The method for preparing the dye/metal-organic framework composite material with fluorescence upconversion performance according to claim 2, wherein the flexible organic ligand containing a hexacarboxylic acid group is hexyl [4- (carboxyphenyl) carbonyl ] -3-oxane; the structural formula is as follows:
5. the method for preparing the dye/metal-organic framework composite material with fluorescence upconversion performance according to claim 2, wherein the dye is an aqueous solution of: (a) neutral red; or (b) basic blue 17; or (c) basic orange 14; or (d) a quinacridone; the structural formula is as follows:
6. the method for preparing the dye/metal-organic framework composite material with the fluorescence upconversion performance according to claim 2, wherein the organic solvent in the mixed solution is any one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide; and the volume ratio of the organic solvent to the deionized water is 5-10: 1.
7. the preparation method of the dye/metal-organic framework composite material with fluorescence upconversion performance according to claim 2, wherein a molar ratio of metal ions to organic ligands in the metal nitrate is 1-3: 1.
8. the method for preparing the dye/metal-organic framework composite material with fluorescence upconversion performance according to claim 2, wherein an acid in the acid solution is nitric acid, hydrochloric acid, sulfuric acid or acetic acid, a solvent is water, and the concentration of the solvent is 0.5-2M.
9. Use of a dye/metal-organic framework composite material with fluorescence upconversion properties, wherein the material is the material according to claim 1 or the material prepared by the method according to any one of claims 2 to 8, and the material is used for expanding the application range of dyes and has less limitation on excitation light.
10. The use of the dye/metal-organic framework composite material with fluorescence upconversion capability of claim 9, wherein the material loaded with organic dye can generate a second harmonic nonlinear optical signal under infrared/near infrared pumping, so as to transfer energy to the dye, so that the dye that can only emit light under ultraviolet visible pumping can emit light under infrared/near infrared pumping, and can be applied to biological imaging.
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