CN113354827B - Based on Pd 6 L 8 Hexagonal nanosheet material of cage and preparation method and application thereof - Google Patents
Based on Pd 6 L 8 Hexagonal nanosheet material of cage and preparation method and application thereof Download PDFInfo
- Publication number
- CN113354827B CN113354827B CN202110455742.3A CN202110455742A CN113354827B CN 113354827 B CN113354827 B CN 113354827B CN 202110455742 A CN202110455742 A CN 202110455742A CN 113354827 B CN113354827 B CN 113354827B
- Authority
- CN
- China
- Prior art keywords
- cage
- hexagonal
- water
- preparation
- dmso
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
- A61K47/6949—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit inclusion complexes, e.g. clathrates, cavitates or fullerenes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
Abstract
The invention relates to the technical field of nano material preparation, and relates to a catalyst based on Pd 6 L 8 Hexagonal nanosheet material of the cage, and a preparation method and application thereof. The preparation method comprises the following steps: pd is added 6 L 8 And mixing the DMSO solution of the cage with water to obtain the hexagonal nanosheet material. According to the invention, the nano-sheet with an octahedral structure is converted into a hexagonal structure by adopting a nano-precipitation method, so that the dispersibility of the nano-sheet in water is remarkably changed and the nano-sheet is converted into a material which is easy to disperse in water, and the material can be loaded with an anionic photosensitizer in an aqueous solution through an ion exchange reaction, so that the photosensitizer is tightly loaded on the hexagonal nano-sheet, and the phenomenon that the photosensitizer does not fall off for a long time in the process of exerting the action of photodynamic force is ensured; the invention provides a new idea for the application of MOC in biomedicine.
Description
Technical Field
The invention relates to the technical field of nano material preparation, and relates to a catalyst based on Pd 6 L 8 Hexagonal nanosheet material of the cage, and a preparation method and application thereof.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Metal Organic Framework (MOFs) are crystalline materials with three-dimensional pore structure formed by connecting Metal atoms as centers with Organic molecules. Since the discovery of the first metal-organic framework Materials (MOFs) by Yaghi topic group in 1995, the MOFs have been the hot spot of research at home and abroad. Different MOFs structures can be obtained by utilizing different organic ligands and different inorganic metal ions or metal ion clusters; the spatial collocation of the metal atom center and various organic ligands can control the aperture size of the material and has special physical and chemical properties. The ultra-high porosity and specific surface area make the porous material have a great number of applications in the field of gas adsorption separation. In addition, the MOFs material can possess different multifunctional properties, such as magnetism, chirality, fluorescence characteristics, nonlinear optical characteristics and the like, by utilizing the functionalization of the ligand and using different metal ions, so that the application thereof is greatly expanded.
Coordinated self-assembly of metal ions with organic ligands forms a wide variety of polygons and polyhedra. Raymond et al reported tetrahedral supramolecular complexes based on Ti (IV) -and Sn (IV) -assembled with metal ions under basic conditions using a three-armed organic ligand containing pyrocatechol amide. The formation of tetrahedral cage structures was confirmed by nuclear magnetism, mass spectrometry and X-ray single crystal diffraction. Single crystal structure analysis shows that the molecular cages are positioned on a crystal triple axis, so that all metal ions are positioned in the same chiral environment; thomas et al reported that an example of cubic supramolecular complexes was assembled from 8 metallic Ru units with a 90 degree coordination geometry and 12 linear organic ligands, 4-bipyridine. NMR and ESI-MS confirmed the structure of the complex. Kinetic studies also demonstrate the stability of the complex in solution. Electrochemical tests show that the complex has three groups of reversible oxidation states. Non-chelating tridentate ligands with suitable metal centers may yield M with octahedral geometry 6 L 8 Type molecules (M stands for metal, L stands for ligand unit), whereas bidentate ligands can give M n L 2n A type molecule. However, the inventors found that almost all octahedral Metal Organic Cages (MOCs) can be dispersedly dissolved in DMSO in the form of a single cage, but are difficult to disperse in water, which limits the wide application of MOCs in biomedicine.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method based onPd 6 L 8 The invention relates to a hexagonal nanosheet material of a cage, a preparation method and application thereof 6 L 8 The nanometer sheet is converted into a nanometer sheet with a hexagonal structure, so that the dispersibility of the nanometer sheet in water is remarkably changed, the nanometer sheet is converted into a material which is easy to disperse in water, and the material can be loaded with an anionic photosensitizer in an aqueous solution through an ion exchange reaction, so that the photosensitizer is tightly loaded on the hexagonal nanometer sheet, and the phenomenon that the photosensitizer does not fall off for a long time in the process of exerting the action of photodynamic force is ensured; the invention provides a new idea for the application of MOC in biomedicine.
In order to achieve the above object, a first aspect of the present invention provides a Pd-based catalyst 6 L 8 The preparation method of the hexagonal nanosheet material of the cage specifically comprises the following steps: pd is added 6 L 8 Mixing the DMSO solution of the cage with water to obtain a hexagonal nanosheet material;
the second aspect of the invention provides a Pd-based catalyst prepared by the method 6 L 8 Hexagonal nanoplatelets of the cage.
The third aspect of the invention provides a preparation method of a photosensitive hexagonal nanosheet composite material, which specifically comprises the following steps:
based on Pd 6 L 8 And mixing the hexagonal nanosheet material of the cage with an anionic photosensitizer in an aqueous solution, and fully reacting to obtain the photosensitive hexagonal nanosheet composite material.
The fourth aspect of the invention provides a photosensitive hexagonal nanosheet composite material obtained by the preparation method.
The fifth aspect of the invention provides an application of the photosensitive hexagonal nanosheet composite material in tumor photodynamic therapy.
One or more embodiments of the present invention have at least the following advantageous effects:
(1) according to the invention, the hexagonal nanosheet with the nanometer size is obtained by a nanometer coprecipitation method, so that the problems that MOC is poor in dispersibility in water and is limited in application in the field of biomedicine are solved, and the metal organic cage has good dispersibility in water, so that more excellent biocompatibility is obtained.
(2) According to the invention, the anionic photosensitizer is loaded on the hexagonal nanosheets, and the anionic photosensitizer can perform ion exchange with nitrate ions in the hexagonal nanosheets, so that the photosensitizer is tightly loaded on the hexagonal nanosheets, long-term non-shedding is ensured, and the service life is prolonged.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a structural formula of an oxadiazole heterocycle bridged organic ligand of example 1 of the present invention;
FIG. 2 shows Pd in example 1 of the present invention 6 L 8 The structural formula of the octahedral nanocage;
FIG. 3 is a transmission electron microscope image (the scale is 100 nm) of a Pd-MOC hexagonal nanosheet in example 1 of the present invention;
FIG. 4 is a graph showing a particle size distribution of Pd-MOC and Pd-MOC-ICG in an example of the present invention;
FIG. 5 is a transmission electron micrograph (scale bar 200 nm) of spherical nanoparticles prepared in example 2 of the present invention;
FIG. 6 is a transmission electron micrograph (scale bar 200 nm) of the acicular material prepared in example 3 of the present invention;
FIG. 7 is a transmission electron micrograph (scale bar 100 nm) of Pd-MOC-ICG prepared in example 4 of the present invention;
FIG. 8 is a graph showing UV absorption of Pd-MOC, Pd-MOC-ICG and ICG according to an example of the present invention;
FIG. 9 is a graph showing the particle size distribution of Pd-MOC and Pd-MOC-ICG after 30 days of storage in examples of the present invention;
FIG. 10 is a photograph comparing before and after Pd-MOC and Pd-MOC-ICG are left in water for thirty days;
FIG. 11 is a graph showing the photodynamic properties of Pd-MOC-ICG in example 4 of the present invention;
FIG. 12 is a graph showing the measurement of the photodynamic properties of Pd-MOC in example 4 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, almost all octahedral Metal Organic Cages (MOC) can be dispersed and dissolved in DMSO in the form of a single cage, but are difficult to disperse in water, which limits the wide application of MOC in biomedicine.
In order to solve the technical problems, the invention provides a Pd-based catalyst in a first aspect 6 L 8 The preparation method of the hexagonal nanosheet material of the cage specifically comprises the following steps: pd is added 6 L 8 And mixing the DMSO solution of the cage with water to obtain the hexagonal nanosheet material.
The conventional octahedral metal organic cage can be dispersed and dissolved in DMSO and is not easy to disperse in water, so that the octahedral metal organic cage is difficult to apply to a water environment, and the octahedral metal organic cage not only can be directly applied to the water environment, but also can be loaded with other functional materials in the water environment, and the wide application of the octahedral metal organic cage material is limited.
In order to change the characteristic of hard water solubility of an octahedral metal organic cage, Pd is adopted 6 L 8 The DMSO solution in the cage is mixed with water, and Pd is treated by the combined action of the water and the DMSO 6 L 8 The cage structure is modified to change the structure from octahedral cage to hexagonal cageThe rice flakes can be well dispersed in water and can be kept for a long time without sedimentation.
As a preferred embodiment, the Pd 6 L 8 The cage structure is an octahedral metal nano cage which takes an oxadiazole heterocyclic ring bridged organic ligand and Pd (II) ions as coordination sites, and the molecular formula of the bridged organic ligand is C 33 N 9 O 3 And assembling the organic ligand and palladium nitrate in DMSO to obtain a DMSO solution of the nanocage.
In one or more embodiments of the invention, the Pd 6 L 8 The volume ratio of the DMSO solution to the water in the cage is 3: 2; the invention is found by experiments that only Pd is adopted 6 L 8 With a solvent at a ratio of 3:2 to obtain hexagonal nano-sheets, and mixing Pd 6 L 8 With water in a ratio of greater than or less than 3:2, irregular particles are obtained, hexagonal nanosheets cannot be obtained, and good dispersibility in water is difficult to ensure when the shape is changed.
Pd 6 L 8 The DMSO solution concentration of the cage was: 4.17X 10 -3 mol/L；
Furthermore, the mixing of DMSO and water needs to be carried out quickly, so that the DMSO and water can be quickly mixed to play a role, and the prepared hexagonal nanosheets are more uniform in size.
To mix DMSO with water uniformly and Pd simultaneously 6 L 8 The cages are fully contacted, the invention is to use Pd 6 L 8 Mixing the DMSO solution in the cage with water, and stirring for 3-4h preferably at a constant stirring temperature of 24-25 ℃;
further, after stirring, obtaining the hexagonal nanosheet material through centrifugation, wherein the rotation speed of the centrifugation is 10000-.
The second aspect of the invention provides Pd-based catalyst prepared by the method 6 L 8 The hexagonal nanosheet material of the cage has remarkable excellent dispersibility in water, and solves the problem of the existing Pd through the change of the structure 6 L 8 The octahedral metal organic cage is difficult to disperse in water,thereby improving the effect of photodynamic therapy.
The third aspect of the invention provides a preparation method of a photosensitive hexagonal nanosheet composite material, which specifically comprises the following steps:
based on Pd 6 L 8 And mixing the hexagonal nanosheet material of the cage with an anionic photosensitizer in an aqueous solution, and fully reacting to obtain the photosensitive hexagonal nanosheet composite material.
The anion type photosensitizer is a material capable of carrying out anion exchange, the anion type photosensitizer can carry out ion exchange with nitrate ions in the hexagonal nanosheets in an aqueous solution, and Pd-based photosensitizer can be realized through an anion exchange process 6 L 8 The hexagonal nanosheets of the cage are tightly combined with the photosensitizer, and the good dispersibility of the hexagonal nanosheets in water provides a stable environment for anion exchange reaction; the anionic photosensitizer is one or more of congo red, indocyanine green, sunset yellow and carmine, and is preferably indocyanine green in order to further improve the photosensitive effect, because the indocyanine green belongs to a near-infrared dye, has a longer excitation wavelength, has good singlet oxygen generation capacity, and can solve the problem of insufficient depth of light source penetrating tissues.
Furthermore, the mixing process is completed in a dark environment, so that the situation that the photosensitizer is activated by light irradiation to influence the loading effect in the process of loading the photosensitizer can be avoided.
Further, stirring is required in the mixing process, and the stirring time is 24-25 hours; after stirring, the mixture was centrifuged and washed until the supernatant was completely colorless.
The fourth aspect of the invention provides a photosensitive hexagonal nanosheet composite material obtained by the preparation method, wherein the particle size is 155-165nm, and the composite material has good singlet oxygen generation capacity, can solve the problem of insufficient tissue penetration depth of a light source in photodynamic therapy and improves the treatment effect.
The fifth aspect of the invention provides an application of the photosensitive hexagonal nanosheet composite material in tumor photodynamic therapy.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) Oxadiazole heterocyclic bridged organic ligand (40mg, structure shown in figure 1) and palladium nitrate (12.7mg) were assembled in DMSO to give a composition comprising Pd 6 L 8 DMSO from octahedral nanocages (structure shown in FIG. 2) is designated as solution A.
(2) Taking 150 mu L of the solution A, quickly adding 100 mu L of water, stirring for four hours, centrifuging for ten minutes at 13300rmp to obtain a hexagonal nanosheet, and recording as Pd-MOC; the morphology of the prepared Pd-MOC is shown in figure 3, the Pd-MOC can be seen to be hexagonal nanosheets, and figure 4 shows that the particle size of the material is about 160 nm.
Example 2
Take 150. mu.L of solution A, add 1500. mu.L of water quickly, stir for four hours, 13300rmp centrifugation for ten minutes to get spherical nanoparticles, as shown in FIG. 5.
Example 3
mu.L of solution A was taken, 75. mu.L of water was rapidly added thereto, stirred for four hours, and centrifuged at 13300rmp for ten minutes to obtain a needle-like material, as shown in FIG. 6.
Example 4
(1) The hexagonal nanosheet Pd-MOC obtained in example 1 was dispersed in 10mL of an aqueous solution, 10mg of indocyanine green was added, and the mixture was stirred in the dark at a constant temperature of 25 ℃ for 24 hours. After completion of the reaction, the reaction mixture was centrifuged at 13300rmp for 10 minutes, and washed with water until the supernatant was colorless.
(2) The solid obtained by centrifugation was collected and designated as Pd-MOC-ICG.
The morphology of Pd-MOC-ICG is shown in FIG. 7, it can be seen that the Pd-MOC-ICG material is a hexagonal nanosheet, and FIG. 4 shows that the particle size of the material is about 160 nm. UV absorption of ICG, Pd-MOC and Pd-MOC-ICG As shown in FIG. 8, the UV absorption of Pd-MOC-ICG showed a significant red shift compared to the ICG UV absorption.
Pd-MOC and Pd-MOC-ICG were allowed to stand in water for thirty days as shown in FIG. 9, the particle diameters remained substantially unchanged, indicating that no significant aggregation and sedimentation were found, demonstrating good dispersibility in water, and photographs before and after thirty days of standing in water are shown in FIG. 10.
And (3) measuring the photodynamic performance:
the Pd-MOC-ICG obtained above was dispersed in an ethanol solution to prepare a dispersion of 10. mu.g/mL. 1,3 diphenyl isobenzofuran (DPBF) was used as the singlet oxygen scavenger. 2mL of the Pd-MOC-ICG ethanol dispersion was added to 100. mu.L of 1mM DPBF ethanol solution, and mixed well. Using a 808nm laser (100 mW/cm) 2 ) The absorbance of the solution was recorded every 1 minute with an ultraviolet absorptiometer upon irradiation, as shown in FIG. 11. 1,3 Diphenylisobenzofuran can be reacted with 1 O 2 The reaction produced colorless 1, 2-phenylenebis (benzophenone), resulting in a decrease in absorbance at 414nm, indicating that Pd-MOC-ICG has good photodynamic properties. Similarly, 10. mu.g/mL of Pd-MOC ethanol dispersion was used to determine the singlet oxygen generating capacity according to the above method, and as shown in FIG. 12, the absorption curve did not change, indicating that the initial Pd-MOC did not have photodynamic properties.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a hexagonal nanosheet material based on a Pd6L8 cage is characterized by comprising the following steps: mixing the DMSO solution of the Pd6L8 cage with water to obtain a hexagonal nanosheet material;
the Pd6L8 cage is an octahedral metal nano cage which takes an oxadiazole heterocyclic bridge as an organic ligand and takes Pd (II) ions as coordination sites, the molecular formula of the bridged organic ligand is C33N9O3, and the organic ligand and palladium nitrate are assembled in DMSO to obtain a DMSO solution of the nano cage;
the volume ratio of the DMSO solution of the Pd6L8 cage to water is 3: 2;
the DMSO concentration of Pd6L8 cage was: 4.17X 10-3 mol/L;
the mixing of DMSO and water is carried out rapidly.
2. The method of claim 1, wherein:
mixing DMSO and water, and stirring for 3-4h at a constant stirring temperature of 24-25 deg.C;
after stirring, obtaining the hexagonal nanosheet material by centrifugation at the rotation speed of 13300-13500 rmp.
3. Hexagonal nanoplatelets based on Pd6L8 cages obtained by the preparation method according to any of claims 1-2.
4. A preparation method of a photosensitive hexagonal nanosheet composite material is characterized by comprising the following steps: mixing the hexagonal nanosheet material based on Pd6L8 cages as claimed in claim 3 with an anionic photosensitizer in an aqueous solution, and obtaining photosensitive hexagonal nanosheets through anion exchange, wherein the mixing process is completed in a dark environment.
5. The method of claim 4, wherein: the anionic photosensitizer is one or more of congo red, indocyanine green, sunset yellow and carmine.
6. The method of claim 4, wherein: the anionic photosensitizer is indocyanine green.
7. The method of claim 4, wherein:
stirring is required in the mixing process, and the stirring time is 24-25 hours;
after completion of the stirring, centrifugation was carried out and washing was carried out until the supernatant was completely colorless.
8. The photosensitive hexagonal nanosheet composite obtained by the preparation method of any one of claims 4 to 7, having a particle size of 155-165 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110455742.3A CN113354827B (en) | 2021-04-26 | 2021-04-26 | Based on Pd 6 L 8 Hexagonal nanosheet material of cage and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110455742.3A CN113354827B (en) | 2021-04-26 | 2021-04-26 | Based on Pd 6 L 8 Hexagonal nanosheet material of cage and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113354827A CN113354827A (en) | 2021-09-07 |
| CN113354827B true CN113354827B (en) | 2022-09-06 |
Family
ID=77525568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110455742.3A Active CN113354827B (en) | 2021-04-26 | 2021-04-26 | Based on Pd 6 L 8 Hexagonal nanosheet material of cage and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113354827B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020011913A (en) * | 2018-07-13 | 2020-01-23 | 国立大学法人京都大学 | Synthesis of transition metal dichalcogenide nanosheet carrying photosensitizer and its application to cancer phototherapy |
| CN110894298A (en) * | 2018-09-13 | 2020-03-20 | 北京大学深圳研究生院 | Preparation method of MOFs nano material and derivative thereof |
-
2021
- 2021-04-26 CN CN202110455742.3A patent/CN113354827B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020011913A (en) * | 2018-07-13 | 2020-01-23 | 国立大学法人京都大学 | Synthesis of transition metal dichalcogenide nanosheet carrying photosensitizer and its application to cancer phototherapy |
| CN110894298A (en) * | 2018-09-13 | 2020-03-20 | 北京大学深圳研究生院 | Preparation method of MOFs nano material and derivative thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113354827A (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Titanium-oxide host clusters with exchangeable guests | |
| Debata et al. | Development of coordination driven self-assembled discrete spherical ensembles | |
| Rahim et al. | Surface-confined amorphous films from metal-coordinated simple phenolic ligands | |
| Monama et al. | Palladium deposition on copper (II) phthalocyanine/metal organic framework composite and electrocatalytic activity of the modified electrode towards the hydrogen evolution reaction | |
| Liu et al. | Superior absorption capacity of tremella like ferrocene based metal-organic framework in removal of organic dye from water | |
| Yu et al. | Coordination‐Induced Emission from Tetraphenylethylene Units and Their Applications | |
| Pichon et al. | Octa-and nonanuclear nickel (II) polyoxometalate clusters: synthesis and electrochemical and magnetic characterizations | |
| Hu et al. | A luminescent mg-metal–organic framework for sustained release of 5-fluorouracil: appropriate host–guest interaction and satisfied acid–base resistance | |
| Liu et al. | Hexavalent octahedral template: a neutral high-nucleus silver alkynyl nanocluster emitting infrared light | |
| CN107759803A (en) | A kind of four sulfydryl porphyrin compounds and its production and use | |
| CN111748340B (en) | Fluorescent silver nanocluster and synthesis method and application thereof | |
| Zhao et al. | Insights into the binding mechanism of 2D copper-tetrakis-(4-carboxyphenyl)-porphyrin metal-organic framework nanosheets with Rhodamine B: Spectroscopic and thermodynamics studies | |
| Liu et al. | A robust polyoxometalate-templated four-fold interpenetrating metal–organic framework showing efficient organic dye photodegradation in various pH aqueous solutions | |
| Chai et al. | Five Mesoporous Lanthanide Metal–Organic Frameworks: Syntheses, Structures, and Fluorescence Sensing of Fe3+, Cr2O72–, and H2O2 and Electrochemical Sensing of Trinitrophenol | |
| Li et al. | Total structural determination of [Au 1 Ag 24 (Dppm) 3 (SR) 17] 2+ comprising an open icosahedral Au 1 Ag 12 core with six free valence electrons | |
| CN113354827B (en) | Based on Pd 6 L 8 Hexagonal nanosheet material of cage and preparation method and application thereof | |
| CN107828066B (en) | Tetramercaptoporphyrin modified metal organic framework nano material and preparation method and application thereof | |
| Lin et al. | An ultrastable {SiNb18O54}-based hybrid polyoxoniobate framework for selective removal of crystal violet from aqueous solution and proton-conduction | |
| Burger et al. | Luminescent Porphyrinic Metal–Organic Frameworks for Oxygen Sensing: Correlation of Nanostructure and Sensitivity | |
| Tajnšek et al. | Design and degradation of permanently porous vitamin C and zinc-based metal-organic framework | |
| Long et al. | Advances in gigantic polyoxomolybdate chemistry | |
| Icten | Preparation of Gadolinium‐Based Metal‐Organic Frameworks and the Modification with Boron‐10 Isotope: A Potential Dual Agent for MRI and Neutron Capture Therapy Applications | |
| Lin et al. | Modulation of Hierarchical Pores in Metal–Organic Frameworks for Improved Dye Adsorption and Electrocatalytic Performance | |
| JP2017036919A (en) | Preparation method of sample for crystal structure analysis and determination method of molecular structure of metabolite | |
| Bakhshi et al. | Ultrasound-assisted efficient synthesis of a novel Nd–MOF polymer as a new candidate for electrocatalytic activity in hydrogen storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |