CN107987282A - A kind of hydrostable lanthanide series metal-organic framework materials and preparation and application - Google Patents
A kind of hydrostable lanthanide series metal-organic framework materials and preparation and application Download PDFInfo
- Publication number
- CN107987282A CN107987282A CN201711313250.0A CN201711313250A CN107987282A CN 107987282 A CN107987282 A CN 107987282A CN 201711313250 A CN201711313250 A CN 201711313250A CN 107987282 A CN107987282 A CN 107987282A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal
- framework materials
- preparation
- hydrostable
- 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.)
- Granted
Links
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
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
A kind of hydrostable lanthanide series metal organic framework materials and preparation method thereof and chemical sensitisation application, chemical formula is { [Eu (TDA) (H2BTEC)0.5(H2O)3]·H2O}n, wherein H2TDA is 2,4 tetrahydro-thiazoles diacid, H4BTEC is 1,2,4,5 benzene tertacarbonic acids；Its preparation method is that 2,4 tetrahydro-thiazoles diacid and 1,2,4,5 benzene tertacarbonic acids are added to the water, and target product is obtained after hydro-thermal reaction by six nitric hydrate europiums；Quantitative detection available for 3 acetic acid of 5 hydroxyl color amine of carcinoid tumor biomarker and 5 oxyindole.It is an advantage of the invention that：Product preparation is simple, reaction condition is gentle, cost is low, and the metal-organic framework material of preparation has preferable water stability, and the detection to 3 acetic acid of 5 hydroxyl color amines and 5 oxyindole has higher sensitivity and relatively low test limit.
Description
Technical field
The present invention relates to the preparation of metal-organic framework materials, particularly hydrostable metal-organic framework materials and
Its preparation method and application.
Background technology
Carcinoid tumor is a kind of rare, slow-growing epithelial cell tumour, is one group and betides intestines and stomach and other devices
The neoformation of official's chromaffin cell.Such a tumour can secrete the bioactie agents such as serotonine, kassinin kinin class, histamine, cause
Vasomotor disturbance (visible flush), gastrointestinal symptom, damaged heart valve, asthma etc., are known as carcinoid syndrome.Class cancer
In diet 60% tryptophan transfer can be turned to serotonine by knurl patient.Main generation in blood serotonine and its urine
It is its main biochemical feature to thank to the rise of thing 5-OHi -3- acetic acid.5-OHi -3- acetic acid can exceed ginseng sometimes in urine
Examine the decades of times of value.Therefore, 5-OHi -3- acetic acid can be as the effective of carcinoid tumor in serotonine and urine in blood
Biomarker.
Metal-organic framework is as fluorescence probe come to detect biomarker be a kind of new trial.Metal-organic framework
(MOFs) be acted on by metal ion or metal cluster with organic ligand by coordinate bond formed there is three-dimensional net structure
Crystalline material.In recent years, MOFs is received people and is widely closed due to its rich and changeful chemical constitution and excellent performance
Note.MOFs because the diversity of its structure, the controllability of pore size and in the storage including gas and separation, heterogeneous urge
The numerous areas such as change, optics, electronics and magnetic material, chemical sensitisation, drug delivery and biomedicine, which all has, potentially should
With value.Fluorescence MOFs is as emerging optical material, since its component units has extensive selectivity, its frame structure
With Modulatory character, its luminescent properties can be regulated and controled on this basis, and fluorescence MOFs materials also have porosity
Design feature so that its to the different selective detection identification functions of guest molecule, therefore in fluorescence probe or
The fields such as sensor all have very tempting application prospect.
The luminosity of MOFs directly depends on metal ion and organic ligand and its coordination mode.Different types of object
Molecule by coordinate bond, intermolecular interaction for example dipole-dipole, dipole induced dipole, ion-dipole, π-π interaction,
Hydrogen bond etc. can all have an impact its luminosity, this has established theoretical foundation for applications of the MOFs in fluorescence identifying.MOFs
The adjustability in duct and its potential functional site such as Lewis soda acids site can effectively strengthen it to organic molecule and the moon
The Selective recognition of cation.Some porous fluorescence MOFs can by reaching testing goal with exchanging for analyte, and
It can reuse.In recent years, potential applications of the fluorescence MOFs in terms of chemical sensitisation, such as zwitterion, organic molecule,
The detection etc. of volatile organic compounds (VOCs), energy-containing compound, biomarker all achieves important progress.
The content of the invention
It is an object of the invention to provide it is a kind of it is easy to operate, cost is low, convenient and efficient and can quantify detection carcinoid tumor life
The hydrostable metal-organic framework materials and its preparation side of thing marker serotonine and 5-OHi -3- acetic acid
Method and application.
Technical scheme：
A kind of hydrostable metal-organic framework materials, chemical formula are { [Eu (TDA) (H2BTEC)0.5(H2O)3]·
H2O}n, in formula：N arrives just infinite natural number, wherein H for 12TDA is 2,4- tetrahydro-thiazoles diacid, H4BTEC is 1,2,4,5- benzene
Tetrabasic carboxylic acid；The metal-organic framework materials are by Eu3+Ion forms three-dimensional net structure with organic ligand by coordinate bond, wherein
Organic ligand is 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids；It is only comprising a crystallography in minimum asymmetric cell
Vertical Eu3+, a TDA2-Ligand, half of H2BTEC2-Ligand, three water of coordination molecule and a free hydrone；Adjacent
Eu3+Ion passes through TDA2-Ligand connects to form two-dimension plane structure；Pass through H2BTEC2-Further connection forms three-dimensional framework knot
Structure simultaneously has one-dimensional passage；There is free object hydrone in duct.Fig. 1 is the metal-organic framework materials of the present invention
Single crystal diffraction structure chart, wherein：Fig. 1 (a) is the minimum asymmetric cell figure of the metal-organic framework materials, and Fig. 1 (b) is Eu3+
Coordination mode figure.Fig. 2 is by Eu3+And TDA2-、H2BTEC2-Three-dimensional framework figure and its one-dimensional pipe with the compound of structure
Shape duct figure.
A kind of preparation method of hydrostable metal-organic framework materials, comprises the following steps：
1) six nitric hydrate europiums, 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids are added in distilled water, mixed
Conjunction uniformly obtains mixed liquor；
2) above-mentioned mixed liquor is placed in heavy wall pressure bottle, when heating 24-36 is small at 80-100 DEG C after sealing, filtered
To colourless web crystal；
3) above-mentioned crystal is washed with distilled water 3-5 times, you can hydrostable metal-organic framework materials are made.
Six nitric hydrate europiums, 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids are in molar ratio in the mixture
0.8-1.2:1:1；The amount ratio of six nitric hydrate europiums and distilled water is 0.1mmol：8-12mL.
A kind of application of hydrostable metal-organic framework materials, for serotonine and 5-OHi-
The quantitative detection of 3- acetic acid, method are to carry out excitation and the hair of solid fluorescence to the metal-organic framework materials of preparation at room temperature
Penetrate spectrum test；Serotonine and 5-OHi -3- acetic acid are added gradually to the metal-organic framework material prepared respectively
Expect that in aqueous solution (1mg/mL), ultrasonic 10-30min forms suspension, tests its fluorescence light by excitation wavelength of 280nm at room temperature
Spectrum.
It is an advantage of the invention that：1) preparation process of the metal-organic framework materials is simple, reaction condition is gentle, yield
Height, cost are low；2) material has preferable water stability, keeps stablizing in aqueous, is conducive to practical application；3) in room temperature
Under, serotonine and 5-OHi -3- acetic acid are to response of the material with fluorescent quenching, with before good application
Scape.
Brief description of the drawings
Fig. 1 is the single crystal diffraction structure chart of the metal-organic framework materials of the present invention, wherein：Fig. 1 (a) is the metal-have
The minimum asymmetric cell figure of machine frame frame material, Fig. 1 (b) are Eu3+Coordination mode figure.
Fig. 2 is by Eu3+And TDA2-、H2BTEC2-The three-dimensional framework figure of the compound of structure and its one-dimensional tubulose duct
Figure.
Fig. 3 is the stability test figure of the metal-organic framework materials of embodiment 1, including the metal-organic framework materials
Immersion in water 48 it is small when after powder diagram.
Fig. 4 is that the solid fluorescence of the metal-organic framework materials of embodiment 2 at room temperature excites and launch spectrogram.
Fig. 5 (a) is that the metal-organic framework materials of embodiment 2 are immersed in the serotonine aqueous solution of various concentrations
Fluorescence spectra, Fig. 5 (b) are the I of embodiment 20/ I vs.5- hydroxyl color amine concentration maps.
Fig. 6 (a) is that the metal-organic framework materials of embodiment 2 are immersed in the 5-OHi -3- acetic acid water of various concentrations
The fluorescence spectra of solution, Fig. 6 (b) are the I of embodiment 20/ I vs.5- oxyindole -3- acetic acid concentration figures.
The cycle performance figure that Fig. 7 (a) detects serotonine for the metal-organic framework materials of embodiment 2, Fig. 7 (b)
The cycle performance figure detected for the metal-organic framework materials of embodiment 2 to 5-OHi -3- acetic acid.
Embodiment
Embodiment 1：
A kind of hydrostable metal-organic framework materials, chemical formula are { [Eu (TDA) (H2BTEC)0.5(H2O)3]·
H2O}n, in formula：N arrives just infinite natural number, wherein H for 12TDA is 2,4- tetrahydro-thiazoles diacid, H4BTEC is 1,2,4,5- benzene
Tetrabasic carboxylic acid；The metal-organic framework materials are by Eu3+Ion forms three-dimensional net structure with organic ligand by coordinate bond, wherein
Organic ligand is 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids；It is only comprising a crystallography in minimum asymmetric cell
Vertical Eu3+, a TDA2-Ligand, half of H2BTEC2-Ligand, three water of coordination molecule and a free hydrone；Adjacent
Eu3+Ion passes through TDA2-Ligand connects to form one-dimensional chain structure；Pass through H2BTEC2-Further connection forms three-dimensional frame structure
And there is one-dimensional passage；There is free object hydrone in duct.
The preparation method of the metal-organic framework materials to ph stability, comprises the following steps：
1) by the 1,2,4 of the six nitric hydrate europiums of 0.1mmol, the 2,4- tetrahydro-thiazoles diacid of 0.1mmol and 0.1mmol,
5- benzene tertacarbonic acids, add in 10 milliliters of distilled water, are uniformly mixed and obtain mixed liquor；
2) above-mentioned mixed liquor is placed in 35mL heavy wall pressure bottles, when heating 36 is small at 80 DEG C after sealing, be obtained by filtration
Colourless web crystal；
3) above-mentioned crystal is washed with distilled water 3 times, you can hydrostable metal-organic framework materials are made, are based on
2,4- tetrahydro-thiazoles diacid yield is 76%.
The structure determination of the metal-organic framework materials：
Crystal structure is measured by Supernova type X-rays single crystal diffractometer, using by graphite monochromator monochromatization
Mo-KαRayFor Incident Irradiation Source, withScan mode collects point diffraction, is repaiied by least square method
Just their coordinate and its anisotropic parameters, the position of hydrogen atom are obtained by theory hydrogenation, and all calculating uses SHELXL-
97 program bags carry out.With reference to elemental analysis, thermogravimetric analysis, and Advances in crystal X-ray diffraction data determine final point of the compound
Minor.The result shows that:The structural formula of the metal-organic framework materials is { [Eu (TDA) (H2BTEC)0.5(H2O)3]·H2O}n, belong to
Monoclinic system, space group P21/ c, cell parameter are
α=γ=90 °, β=90.581 (2) °, unit cell volume areZ=4, Dc=2.301g/cm3.The gold of preparation
The mono-crystalline structures figure of category-organic framework materials is shown in Fig. 1 and Fig. 2, wherein：Fig. 1 (a) is Eu in the metal-organic framework materials3+'s
Coordination context diagram, Fig. 1 (b) are Eu3+Coordination mode figure.Fig. 2 is by Eu3+And TDA2-、H2BTEC2-With the compound of structure
Three-dimensional framework figure and its one-dimensional tubulose duct figure.A crystal is included in the minimum asymmetric cell of the metal-organic framework
Learn independent Eu3+, a TDA2-Ligand, half of H2BTEC2-Ligand, three water of coordination molecule and a free hydrone.Eu3 +With nine coordination environment { EuO8N }, an oxygen atom comes from H2BTEC2-Ligand, an oxygen atom and a nitrogen-atoms come from
In TDA2-Ligand, is left four oxygen atoms and comes from three water of coordination molecule and a dissociating water molecule.Eu3+Pass through TDA2-Match somebody with somebody
Body connects to form two-dimension plane structure；Pass through H2BTEC2-The further connection of ligand forms three-dimensional frame structure and with one-dimensional
, there is free object hydrone in duct in passage.
Fluorescent detection capabilities：
By in the metal-organic framework soaking water of acquisition 48 it is small when after, crystal is filtered, is dried in atmosphere, and is carried out
Powder X-ray RD is tested.As shown in Figure 3：The peak position of the diffraction spectrogram of the sample soaked and peak type are spread out with what single crystal data was simulated
Penetrate the peak position of spectrogram and peak type is coincide very good, show that the frame structure of material remains unchanged, metal of the invention-organic
Frame material has preferable water stability.
Embodiment 2
A kind of application of hydrostable metal-organic framework materials, for quantitatively detecting biomarker 5- hydroxyls
Primary colours amine and 5-OHi -3- acetic acid, method are：At room temperature, solid fluorescence is carried out to the metal-organic framework materials of preparation
Excitation and emission spectra test；Respectively by serotonine and 5-OHi -3- acetic acid be added gradually to prepare metal -
In organic framework materials aqueous solution (1mg/mL), ultrasonic 30min forms suspension, tests its fluorescence spectrum at room temperature.
Fig. 4 is that the excitation and emission spectra that the metal-organic framework materials are carried out with solid fluorescence is tested, 280nm's
Under excitation wavelength excitation, four main emission peaks are showed, respectively in 592,616,652 and 697nm, corresponding to Eu3+Ion
's5D0→7FJ(J=1-4) transition.Fig. 5 (a) and Fig. 6 (a) is 5- hydroxyl of the metal-organic framework materials in various concentrations respectively
Fluorescence spectrum in primary colours amine and 5-OHi -3- acetic acid aqueous solutions, shows in figure：Serotonine and 5-OHi-
The introducing of 3- acetic acid can result in fluorescent quenching.Fig. 5 (b) and Fig. 6 (b) is I respectively0/ I is to serotonine and 5- hydroxyls Yin
The curve of diindyl -3- acetic acid concentrations, in low strength range (0-0.3mml/L), I0/ I and serotonine and 5-OHi -3-
The concentration of acetic acid meets relational expression I0/ I=1+KSV[C](I0For no addition serotonine and 5-OHi -3- acetic acid
Fluorescence intensity, I are the fluorescence intensity added after serotonine and 5-OHi -3- acetic acid, [C] represent serotonine and
The molar concentration of 5-OHi -3- acetic acid), the wherein K of serotonineSVFor 7.1 × 103mol-1, 5-OHi -3- second
The K of acidSVFor 9.1 × 103mol-1.With the increase of serotonine and 5-OHi -3- acetic acid concentrations, I0/ I and concentration
Change is gradually upwardly deviated from original straight line, and index of coincidence relational expression I0/ I=aexp (k [C])+b (I0It is respectively with I
The fluorescence intensity before and after serotonine and 5-OHi -3- acetic acid is added, [C] represents serotonine and 5- hydroxyls Yin
The molar concentration of diindyl -3- acetic acid, a, b, k are constant), this illustrates being quenched for serotonine and 5-OHi -3- acetic acid
Phenomenon is the process triggered by self-absorption or energy transfer.
Fig. 7 (a) and Fig. 7 (b) is respectively the metal-organic framework materials to serotonine and 5-OHi -3- second
The cycle performance figure of acid detection, fluorescence intensity has almost no change after circulating six times, shows the metal-organic framework materials pair
The detection of serotonine and 5-OHi -3- acetic acid has good cyclical stability.The metal-organic framework materials can
For quantitatively detecting the concentration of serotonine and 5-OHi -3- acetic acid.
Claims (4)
1. a kind of hydrostable metal-organic framework materials, it is characterised in that chemical formula is { [Eu (TDA) (H2BTEC)0.5
(H2O)3]·H2O}n, in formula：N arrives just infinite natural number, wherein H for 12TDA is 2,4- tetrahydro-thiazoles diacid, H4BTEC is 1,
2,4,5- benzene tertacarbonic acids；The metal-organic framework materials are by Eu3+Ion forms three-dimensional network knot with organic ligand by coordinate bond
Structure, wherein organic ligand are 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids；One is included in minimum asymmetric cell
The Eu of crystallography independence3+, a TDA2-Ligand, half of H2BTEC2-Ligand, three water of coordination molecule and a free moisture
Son；Adjacent Eu3+Ion passes through TDA2-Ligand bridging forms two-dimension plane structure；Pass through H2BTEC2-Further connection forms three
Dimension frame structure simultaneously has one-dimensional passage；There is free object hydrone in duct.
A kind of 2. preparation method of hydrostable metal-organic framework materials as claimed in claim 1, it is characterised in that including
Following steps：
1) six chloride hydrate europiums, 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids are added in distilled water, mixing is equal
It is even to obtain mixed liquor；
2) above-mentioned mixed liquor is placed in heavy wall pressure bottle, when heating 24-36 is small at 80-100 DEG C after sealing, nothing is obtained by filtration
Color strip-shaped crystal；
3) above-mentioned crystal is washed with distilled water 3-5 times, you can hydrostable metal-organic framework materials are made.
3. the preparation method of hydrostable metal-organic framework materials according to claim 2, it is characterised in that：It is described
Six chloride hydrate europiums, 2,4- tetrahydro-thiazoles diacid and 1,2,4,5- benzene tertacarbonic acids are 0.8-1.2 in molar ratio in mixture:1:1；
The amount ratio of six chloride hydrate europiums and distilled water is 0.1mmol：8-12mL.
A kind of 4. application of hydrostable metal-organic framework materials as claimed in claim 1, it is characterised in that：For 5-
The quantitative detection of hydroxyl color amine and 5-OHi -3- acetic acid, method be at room temperature to the metal-organic framework materials of preparation into
The excitation and emission spectra test of row solid fluorescence；Serotonine and 5-OHi -3- acetic acid are added gradually to respectively
In the aqueous solution of the metal-organic framework materials 1mg/mL of preparation, ultrasonic 10-30min forms suspension, at room temperature with 280nm
Its fluorescence spectrum is tested for excitation wavelength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711313250.0A CN107987282B (en) | 2017-12-12 | 2017-12-12 | Water-stable lanthanide metal-organic framework material, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711313250.0A CN107987282B (en) | 2017-12-12 | 2017-12-12 | Water-stable lanthanide metal-organic framework material, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107987282A true CN107987282A (en) | 2018-05-04 |
| CN107987282B CN107987282B (en) | 2020-07-24 |
Family
ID=62037591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711313250.0A Expired - Fee Related CN107987282B (en) | 2017-12-12 | 2017-12-12 | Water-stable lanthanide metal-organic framework material, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107987282B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867780A (en) * | 2019-03-05 | 2019-06-11 | 北京化工大学 | It is a kind of to keep the organic polymer of MOFs pattern, preparation method and application |
| CN110586190A (en) * | 2019-08-28 | 2019-12-20 | 南京理工大学 | Two-dimensional conductive metal organic compound array, preparation method and application |
| CN111087415A (en) * | 2020-01-19 | 2020-05-01 | 福建医科大学 | Europium-doped organic framework material and preparation method and application thereof |
| CN112458795A (en) * | 2020-11-24 | 2021-03-09 | 陕西科技大学 | Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080121105A1 (en) * | 2006-11-24 | 2008-05-29 | Basf Aktiengesellschaft | Method for the separation of carbon dioxide using a porous metal-organic framework material |
| CN104151335A (en) * | 2014-08-01 | 2014-11-19 | 南开大学 | MOFs (Metal-Organic Frameworks) with ph stability as well as preparation method and application of MOFs |
| CN105924460A (en) * | 2016-05-20 | 2016-09-07 | 南开大学 | Metal-organic framework material good in acid and alkali stability and preparation method and application thereof |
| CN106317092A (en) * | 2016-08-19 | 2017-01-11 | 安阳师范学院 | Europium complex of pyromellitic acid ligand as well as preparation method and application thereof |
-
2017
- 2017-12-12 CN CN201711313250.0A patent/CN107987282B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080121105A1 (en) * | 2006-11-24 | 2008-05-29 | Basf Aktiengesellschaft | Method for the separation of carbon dioxide using a porous metal-organic framework material |
| CN104151335A (en) * | 2014-08-01 | 2014-11-19 | 南开大学 | MOFs (Metal-Organic Frameworks) with ph stability as well as preparation method and application of MOFs |
| CN105924460A (en) * | 2016-05-20 | 2016-09-07 | 南开大学 | Metal-organic framework material good in acid and alkali stability and preparation method and application thereof |
| CN106317092A (en) * | 2016-08-19 | 2017-01-11 | 安阳师范学院 | Europium complex of pyromellitic acid ligand as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| QINGYANG GU ET AL: ""Eu3+ luminescence enhancement by intercalation of benzenepolycarboxylic guests into Eu3+-doped layered gadolinium hydroxide"", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867780A (en) * | 2019-03-05 | 2019-06-11 | 北京化工大学 | It is a kind of to keep the organic polymer of MOFs pattern, preparation method and application |
| CN109867780B (en) * | 2019-03-05 | 2020-09-11 | 北京化工大学 | Organic polymer keeping MOFs appearance, preparation method and application |
| CN110586190A (en) * | 2019-08-28 | 2019-12-20 | 南京理工大学 | Two-dimensional conductive metal organic compound array, preparation method and application |
| CN111087415A (en) * | 2020-01-19 | 2020-05-01 | 福建医科大学 | Europium-doped organic framework material and preparation method and application thereof |
| CN111087415B (en) * | 2020-01-19 | 2022-05-20 | 福建医科大学 | Europium-doped organic framework material and preparation method and application thereof |
| CN112458795A (en) * | 2020-11-24 | 2021-03-09 | 陕西科技大学 | Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107987282B (en) | 2020-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107987282A (en) | A kind of hydrostable lanthanide series metal-organic framework materials and preparation and application | |
| Xu et al. | Eu (III) functionalized Zr-based metal-organic framework as excellent fluorescent probe for Cd2+ detection in aqueous environment | |
| CN104804027B (en) | A kind of rare earth metal organic framework materials and preparation method and application | |
| CN112029496B (en) | Fluorescent array sensor for distinguishing and detecting metal ions and preparation method thereof | |
| CN106674534A (en) | Europium rare earth metal-organic frame material and preparation method and application thereof | |
| CN108276383B (en) | Fluorescent probe for identifying iodide ions and preparation method and identification method thereof | |
| CN107421932B (en) | Utilize the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI | |
| CN107082785A (en) | Application process is closed in a kind of fluorescence probe for detecting cyanide ion and its synthesis | |
| CN105175417B (en) | There is one-dimensional organic semiconductor nanotube of fluorescence response and its preparation method and application to organic amine gas | |
| Li et al. | An Eu-based MOF as fluorescent probe for the sensitive detection of L-tryptophan | |
| CN106366131A (en) | Preparation method and application of physiological pH (potential of hydrogen) sensing dinuclear ruthenium complex | |
| Wang et al. | Thiadiazole-functionalized metal-organic frameworks multifunction-architectonics for dual-target sensing of ethylamine and gossypol | |
| Li et al. | A lanthanide metal–organic framework as ratio fluorescence probe to detect pesticides in water | |
| CN107141491A (en) | It is a kind of to detect atmosphere pollution SO with fluorescent test paper2And its method for derivative | |
| CN111205470B (en) | Azole functionalized divalent copper frame coordination material, preparation method and application thereof, and p-nitrophenol detection method | |
| CN114636746B (en) | Pb detection2+Carboxyl ligand-induced annihilation ratio electrochemiluminescence aptamer sensing method | |
| CN106706588B (en) | A kind of accurate multiphase photocatalysis resonance fluorescence method for detecting determination of trace uranium in environmental water sample | |
| CN104949949B (en) | Compound and preparation method and application containing rhodamine group and benzofuraxan group | |
| Weng et al. | Novel multi-component photofunctional nanohybrids for ratio-dependent oxygen sensing | |
| CN103865519A (en) | Preparation method for up-conversion luminescent nano-probe and application of up-conversion luminescent nano-probe to measurement of antioxidant activity of substance | |
| CN110878100B (en) | Cyanide ion probe capable of being recognized by naked eyes, preparation method thereof and application of cyanide ion probe in detection of cyanide ions in water-containing system | |
| CN104262351B (en) | The preparation method of N-(dinitrophenyl group)-rhodamine B hydrazides and the application of detection Cu (II) thereof | |
| CN105778897B (en) | PH sensitive fluorescence dyes and its preparation method and application | |
| CN110776523B (en) | Ultra-stable three-dimensional luminous zinc (II) metal organic framework material and preparation method and application thereof | |
| CN105510286A (en) | Application of transition metal manganese complex in detection of aromatic amine pollutants |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200724 Termination date: 20201212 |