CN105732678A - Rare-earth organic framework material for fluorescent temperature sensation imaging in biological tissue and cells and preparation method thereof - Google Patents
Rare-earth organic framework material for fluorescent temperature sensation imaging in biological tissue and cells and preparation method thereof Download PDFInfo
- Publication number
- CN105732678A CN105732678A CN201610168091.9A CN201610168091A CN105732678A CN 105732678 A CN105732678 A CN 105732678A CN 201610168091 A CN201610168091 A CN 201610168091A CN 105732678 A CN105732678 A CN 105732678A
- Authority
- CN
- China
- Prior art keywords
- rare
- rare earth
- temperature
- organic framework
- earth
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 73
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 71
- 239000013384 organic framework Substances 0.000 title claims abstract description 54
- 238000003384 imaging method Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims description 10
- 230000035807 sensation Effects 0.000 title abstract 2
- -1 rare-earth ions Chemical class 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 229910001868 water Inorganic materials 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical group [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 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 5
- MSFXUHUYNSYIDR-UHFFFAOYSA-N 4-[4,6-bis(4-carboxyphenyl)-1,3,5-triazin-2-yl]benzoic acid Chemical class C1=CC(C(=O)O)=CC=C1C1=NC(C=2C=CC(=CC=2)C(O)=O)=NC(C=2C=CC(=CC=2)C(O)=O)=N1 MSFXUHUYNSYIDR-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 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
- ZBGLGVFYHCSILI-UHFFFAOYSA-N acetic acid;europium Chemical compound [Eu].CC(O)=O ZBGLGVFYHCSILI-UHFFFAOYSA-N 0.000 claims description 4
- KNFUDJRDHMKNRO-UHFFFAOYSA-N acetic acid;terbium Chemical compound [Tb].CC(O)=O KNFUDJRDHMKNRO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 4
- SFUGYLCQBSSLPC-UHFFFAOYSA-N 2-[4,6-bis(2-carboxyphenyl)-1,3,5-triazin-2-yl]benzoic acid Chemical class OC(=O)C1=CC=CC=C1C1=NC(C=2C(=CC=CC=2)C(O)=O)=NC(C=2C(=CC=CC=2)C(O)=O)=N1 SFUGYLCQBSSLPC-UHFFFAOYSA-N 0.000 claims description 3
- OSJBEEZVQCXAGO-UHFFFAOYSA-N 3-[4,6-bis(3-carboxyphenyl)-1,3,5-triazin-2-yl]benzoic acid Chemical class C(=O)(O)C=1C=C(C=CC=1)C1=NC(=NC(=N1)C1=CC(=CC=C1)C(=O)O)C1=CC(=CC=C1)C(=O)O OSJBEEZVQCXAGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- ILRSCQWREDREME-UHFFFAOYSA-N lauric acid amide propyl betaine Natural products CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VJNBQNKBLZXMQD-UHFFFAOYSA-N [Eu].[Tb] Chemical compound [Eu].[Tb] VJNBQNKBLZXMQD-UHFFFAOYSA-N 0.000 claims description 2
- 229950003988 decil Drugs 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract 2
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 125000004306 triazinyl group Chemical group 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 18
- 230000035945 sensitivity Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 230000001413 cellular effect Effects 0.000 description 8
- 238000002595 magnetic resonance imaging Methods 0.000 description 8
- 238000004861 thermometry Methods 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 230000004083 survival effect Effects 0.000 description 5
- 230000003834 intracellular effect Effects 0.000 description 4
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 238000002271 resection Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000012307 MRI technique Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003501 co-culture Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000010259 detection of temperature stimulus Effects 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CMBJJRLWNDIJTC-UHFFFAOYSA-N nitric acid;terbium Chemical group [Tb].O[N+]([O-])=O CMBJJRLWNDIJTC-UHFFFAOYSA-N 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
-
- 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
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/006—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using measurement of the effect of a material on microwaves or longer electromagnetic waves, e.g. measuring temperature via microwaves emitted by the object
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a rare-earth organic framework material for fluorescent temperature sensation imaging in biological tissue and cells. The rare-earth organic framework material has the long-range ordered crystal structure and regular pores. The chemical formula is [LnLx(G)(H2O)].(G)n, wherein Ln is rare earth Eu or Tb, L is an organic ligand simultaneously containing benzene carboxylic acid group and triazinyl group, G represents a solvent molecule which is coordinated with rare-earth ions or in the crystal pores, x=1-3, and n=1-4. The rare-earth organic framework material is prepared by the solvothermal method which is simple and has higher yield. The micro/nano rare-earth organic framework material has the characterized light emissions of two types of rare-earth ions; the strength ratio of the two peaks has favorable exponential relation to the temperature; the temperature detection range is 20-80 DEG C; as the temperature increases, the luminous color can turn red from green; and the rare-earth organic framework material has favorable biocompatibility and heat stability, can implement real-time temperature imaging in biological tissues, and is hopeful to be applied in the aspects of biomedical treatment and the like.
Description
Technical field
The present invention relates to a kind of rare earth organic framework materials and preparation method thereof, in particular for biological tissue and intracellular
Rare earth organic framework materials of micro/nano-scale of portion's fluorescence temperature sensing imaging and preparation method thereof.
Background technology
Temperature is a common and very important physical parameter, and the detection of temperature is to many Science and Technology fields all
There is outstanding meaning.Particularly at biomedical sector, tissue or intracellular temperature measurement and control are for disease
Prevention and treatment are most important, such as, utilizing High Intensity Focused Ultrasound (HIFU, high intensity focused
Ultrasound), the when of carrying out tumor resection, detection and the control of local temperature are the most extremely important, and temperature is the lowest, is unable to reach
Preferably therapeutic effect, and too Gao Zehui causes carbonized and may damage tissue around.Implementing high strong-focusing at present
The temperature imaging technology mainly used time ultrasonic is nuclear magnetic resonance (MRI, Magnetic Resonance Imaging) technology.
But use MRI technique when biological tissue is carried out temperature imaging, motion artifacts can be caused, to temperature due to the motion of tissue
The accuracy of imaging produces impact.And its equipment is heavy and expensive, so one can replace MRI technique in biological tissue
The research and development of the technology carrying out temperature imaging are extremely urgent.
Fluorescence temperature detection and imaging, as a kind of novel temperature sensing means, relative to traditional thermometer, have
Non-cpntact measurement, high sensitivity, electromagnetism interference, the advantages such as spatial resolution is high.And if as fluorescence temperature detection and
The Biocompatibility of imaging is good, and size is little, then the most intracellular temperature in just can realizing organizing with these materials
Detection and imaging.Utilize fluorescence temperature detection and imaging, the defect of MRI temperature imaging can be overcome, be expected to substitute MRI as newly
The temperature imaging technology in organism of type.
Rare earth organic framework materials is that the one being self-assembly of by coordination by rare earth ion and organic ligand is new
Shaped material, it has an abundant characteristics of luminescence, stable luminescence, and sensitivity of thermometry is high, and spatial resolution is high, and it is latent to be that one has very much
The fluorescence temperature detection material of power.There is the organic ligand of suitable triplet energy level, it is possible to effectively pass energy to rare earth ion, from
And obtain that there is strong characteristic fluorescence and launch and highly sensitive rare earth organic framework materials.It addition, at double rare earth organic frame materials
In material, the energy transmission between two kinds of rare earth elements (such as terbium and europium) is thermally sensitive, thus two kinds of rare earth ions
Fluorescence intensity variation with temperature can present different variation tendencies.Relative to single rare earth organic framework materials, due to two kinds
The fluorescence intensity of rare earth ion presents different trend with temperature, measures temperature by the ratio of two fluorescence intensities, can
To eliminate the error that the detection external factor such as substrate concentration, excitation intensity is brought, thus realize highly sensitive self calibration fluorescence temperature
Degree detection.Due to the different trend of the variations in light of two kinds of rare earth ions, the color meeting of the fluorescence of double rare earth organic framework materials
Present change along with the change of temperature, thus real-time temperature imaging can be realized with double rare earth organic framework materials.
Due to above-mentioned advantage, double rare earth organic framework materials are the most potential temperature sensing of one and image forming material,
And the temperature imaging being expected to be used in organism.But thermometric accuracy is wanted by biological field and other high-tech areas
Seeking Truth is the highest, the most inadequate due to the sensitivity of thermometry in Physiological temperatures range of double rare earth organic framework materials at present
Height, it changes the most obvious with the color of temperature, is still unable to reach the requirement of actual application so that its actual thermometric with
The application of imaging receives limitation.Further, undersized rare earth organic framework materials is difficult to prepare, and more limits it at biology
The application of medical domain.So at present, the sensitivity of thermometry of double rare earth organic framework materials is improved so that it is color change is the brightest
Aobvious, reduce its size simultaneously, it just can be made to obtain actual application.
Summary of the invention
It is an object of the invention to provide that a kind of sensitivity of thermometry is high, color is changed significantly can be used in biological tissue and thin
Rare earth organic framework materials of micro/nano-scale of intracellular portion fluorescence temperature sensing imaging and preparation method thereof.
The rare earth organic framework materials sensing imaging for biological tissue and cell interior fluorescence temperature of the present invention, has
The crystal structure of long-range order and the duct of rule, its molecular formula is [LnLx(G)(H2O)]·(G)n, wherein Ln is rare earth Eu
Or Tb；L be 2,4,6-tri-(4-carboxyl phenyl)-1,3,5-triazines, 2,4,6-tri-(3-carboxyl phenyl)-1,3,5-triazines, 2,4,
6-tri-(2-carboxyl phenyl)-1,3,5-triazines or 2,4,6-tri-(3,5-dicarboxyphenyi)-1,3,5-triazines；G represents with dilute
Soil ion coordination or the solvent molecule in crystal duct, for DMF (DMF), N,N-dimethylacetamide
Or N, N-diethylformamide (DEF) (DMA)；X=1～3；N=1～4.
The system of the rare earth organic framework materials sensing imaging for biological tissue and cell interior fluorescence temperature of the present invention
Preparation Method, uses solvent thermal process, comprises the following steps:
By rare-earth europium salt and rare earth terbium salt europium in molar ratio: the mixing of terbium=1:99～1:1, then with contain benzene carboxylic acid base simultaneously
Be dissolved in organic solvent together with group and the organic ligand of triazine group and surfactant, two of which rare-earth salts mole always
The mol ratio measuring, containing simultaneously benzene carboxylic acid group and the organic ligand of triazine group and surfactant is 2:1:12, then
Adding deionized water and methanol, the volume ratio of deionized water, methanol and organic solvent is 1:4:20, obtains mixed solution, will be mixed
Close solution and put in airtight vial, in 40 DEG C-140 DEG C stirring reactions 20-120 minute, centrifugal, washing, obtain for giving birth to
Fabric texture and the rare earth organic framework materials of cell interior fluorescence temperature sensing imaging.
In the present invention, described rare-earth europium salt is europium nitrate, Europium chloride or acetic acid europium；Described rare earth terbium salt is nitric acid
Terbium, terbium chloride or acetic acid terbium.
In the present invention, described while organic ligand containing benzene carboxylic acid group and triazine group be structural formula be (a)
2,4,6-tri-(4-carboxyl phenyl)-1,3,5-triazines, structural formula be the 2 of (b), 4,6-tri-(3-carboxyl phenyl)-1,3,5-triazines,
Structural formula is the 2 of (c), and 4,6-tri-(2-carboxyl phenyl)-1,3,5-triazines or structural formula are the 2 of (d), 4,6-tri-(3,5-bis-
Carboxyl phenyl)-1,3,5-triazines；
In the present invention, described surfactant can be cetyl trimethylammonium bromide, dodecanamide propyl diformazan
Amine second lactone or lauryl alcohol phosphate ester potassium.
Double rare earth organic framework materials sensitivity of thermometry of the present invention are high, it is possible to realize relatively in 20-80 DEG C of temperature range
Change for obvious color, when temperature is in time being increased to 80 DEG C for 20 DEG C, and its glow color has changed to redness from green, with the naked eye or
Person's CCD camera just can identify, and its size is at micro/nano-scale, it is possible to meets the requirement of biomedical aspect application, thus
Make it have the highest practical value.The reason of its high sensitivity of thermometry is the triplet energy level height of the organic ligand selected
Degree is 22857.1cm-1, with the emission level of rare earth ion terbium5D4(20500cm-1) closely, so that the energy between them
Amount transmits sensitivity unusual to temperature.The incorporation of europium ion further adds the thermometric of this pair of rare earth organic framework materials
Sensitivity, and due to the incorporation of two kinds of rare earth ions, it is possible to realize self-alignment temperature sensing so that such temperature sensing
The most credible.And this pair of rare earth organic framework materials good biocompatibility, size is at micro/nano-scale, it is possible to be employed
Temperature sensing and imaging is carried out at tissue or cell interior.
Relative to MRI temperature imaging technology, double rare earth organic framework materials is used to carry out fluorescence temperature imaging, it is possible to effectively
The motion artifacts that causes due to histokinesis of elimination, and method is simple, and equipment is the most less expensive, is expected to substitute
MRI temperature imaging technology carries out detection and the imaging of temperature in vivo, thus can assist and carry out some disease and control
Treating, such as auxiliary HIFU carries out tumor resection, reaches the purpose of actual application.
Concrete the having the beneficial effects that of the present invention:
1, double rare earth organic framework materials of the present invention have high sensitivity of thermometry in the range of 20-80 DEG C, and it is with temperature
The color change highly significant of degree, has the highest practical value.
2, the size of the rare earth organic framework materials of the present invention is in the rank of micro/nano-scale.Organic relative to conventional rare earth
Frame material, its undersized advantage can enter tissue or cell interior carries out fluorescence temperature sensing and imaging, it is ensured that
It can be used in biomedical sector.
3, can bio-toxicity be to evaluate a kind of material be applied to the major criterion of biomedical sector, and the present invention's is dilute
Soil organic framework materials bio-toxicity is low.During with cell co-culture, even if the concentration of rare earth organic framework materials is higher, cell
Survival rate the highest, it was demonstrated that it is the least to the damage of biological cell, it is possible to be applied to biological field.
4, the rare earth organic framework materials of the present invention can keep long Stability Analysis of Structures in water.Eight are soaked in water
After hour, its x-ray diffractogram of powder spectrum still can good corresponding with before not soaking, it was demonstrated that it has preferably
Water stability, it is ensured that it is in the application of biomedical sector.
5, the rare earth organic framework materials Heat stability is good of the present invention, good cycling stability, repeatedly after thermal cycle still
Thermometric performance accurately can be kept, it was demonstrated that it can be used for temperature sensing and imaging and credibility is higher, it is also possible to weight
Multiple utilization.
6, compared with inorganic rare earth compound, coordination compound or organic molecule, rare earth organic framework materials of the present invention is a kind of
There is the crystalline material of orderly micropore, there is crystal structure and the duct of rule of long-range order, it is possible to by frame structure
The regulation of design and pore size obtains bigger interionic distance, such that it is able to the fluorescent quenching of suppression rare earth ion, sends
Light intensity is high, and identification is high, and the life-span is long, and quantum efficiency is high, is highly suitable as temperature sensing and image forming material.
7, compared with MRI temperature imaging technology, the rare earth organic framework materials of the present invention is used to carry out temperature imaging, will not
Produce motion artifacts because of the motion of tissue so as to get temperature data the most credible, and method is simple, equipment phase
To less expensive, it be expected to substitute MRI temperature imaging technology in biological tissue, carry out detection and the imaging of temperature, so that its
Can assist and carry out some disease treatment, such as auxiliary HIFU carries out tumor resection, reaches the purpose of actual application.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the rare earth organic framework materials of the present invention.
Fluorescence photo in cellular environment when Fig. 2 is the rare earth organic framework materials different temperatures of the present invention, wherein a is
Rare earth organic framework materials is the fluorescence photo in cellular environment when 20 degree, b be rare earth organic framework materials when 40 degree
Fluorescence photo in cellular environment.
Fig. 3 is being total to of the PC12 cell after 6 hours of the rare earth organic framework materials co-cultivation with the 100 μ g/mL present invention
Focus on photo.
Detailed description of the invention
Embodiment 1:
Utilize europium nitrate and Terbium nitrate (Tb(NO3)3) and 2,4,6-tri-(4-carboxyl phenyl)-1,3,5-triazines, closed by solvent thermal process
Becoming the rare earth organic framework materials of micro/nano-scale, its concrete synthetic route is as follows:
By europium nitrate and Terbium nitrate (Tb(NO3)3) (mol ratio Eu of 0.0885mmol of 0.0615mmol3+:Tb3+=41:59),
The 2 of 0.075mmol, the cetyl trimethylammonium bromide of 4,6-tri-(4-carboxyl phenyl)-1,3,5-triazines and 0.9mmol is molten
In the N,N-dimethylacetamide (DMA) of 36mL, the deionized water of the methanol and 1.8mL that separately take 7.2mL is added thereto, and is made into
Mixed solution, then puts into mixed solution in airtight vial, is stirred vigorously lower reaction 45 minutes, Jing Guoli at 105 DEG C
The heart, washing, obtain the rare earth organic framework materials [Eu of micro/nano-scale0.41Tb0.59L(DMA)(H2O)]·(DMA)3(Fig. 1), chi
Very little at about 1000nm, productivity is 47.1%.
Can be obtained by single-crystal X-ray diffraction analysis, [Eu0.41Tb0.59L(DMA)(H2O)]·(DMA)3There is long-range order
Crystal structure and rule one-dimensional channels, pore size isUnder ultraviolet excitation, it has rare earth simultaneously
The characteristic luminescence peak of europium and terbium ion, their the strongest glow peak lays respectively at 613nm and 544nm, and their intensity all can be with
The change of temperature and change.In the range of 20-80 DEG C, the ratio of two glow peaks of this pair of rare earth organic framework materials and temperature
Become good exponential relationship can be fitted by equation below:
Wherein T is thermodynamic temperature (in units of K), kBFor Boltzmann constant, I is luminous intensity.
According to formulaWherein Δ=I544/I613, can be calculated, have when 25 DEG C the highest relative
Sensitivity is 3.97% K-1.Its glow color can be from green to redness along with the rising of temperature, and the change of color is the brightest
Aobvious, with the naked eye just it is observed that or use CCD camera record, thus can obtain temperature by the method for colorimetric.
We demonstrate its temperature imaging performance in cellular environment.The rare earth organic frame material of micro/nano-scale that will obtain
Material is dispersed in cellular environment, shoots its fluorescence photo in different temperatures, it appeared that when 20 DEG C, its glow color is green
Color, and when temperature is increased to 40 DEG C, its glow color is orange (see Fig. 2), it changes highly significant with the color of temperature, non-
Often it is suitable as sensing the material of imaging for biological tissue and cell interior fluorescence temperature, it was demonstrated that it has in bio-medical field
There is the highest practical value.
Newly synthesized [Eu0.41Tb0.59L(DMA)(H2O)]·(DMA)3X-ray diffractogram of powder spectrum can be with its monocrystalline mould
Intend X ray diffracting spectrum can extraordinary coincide, it was demonstrated that this material has the crystal structure of long-range order and crystallinity is preferable.
[the Eu detected0.41Tb0.59L(DMA)(H2O)]·(DMA)3X-ray diffractogram of powder spectrum still can with its monocrystalline simulate X
X ray diffraction collection of illustrative plates can extraordinary coincide, it was demonstrated that it still can keep the complete of structure in detection process, and
[Eu0.41Tb0.59L(DMA)(H2O)]·(DMA)3The constant rate at its two peak can be kept in the thermal cycle of 20 times always,
Prove that the credibility of its temperature-measuring results is higher, additionally it is possible to be recycled.By [Eu0.41Tb0.59L(DMA)(H2O)]·(DMA)3
After being immersed in the water 8 hours, its x-ray diffractogram of powder spectrum still can be good to simulate X ray diffracting spectrum with its monocrystalline
Preferably it coincide, it was demonstrated that it can be used the temperature sensing in biotic environment and imaging.[Eu0.41Tb0.59L(DMA)(H2O)]·
(DMA)3Bio-toxicity less, by itself and cell co-culture, when its concentration reaches 100 μ g/mL, the survival condition of cell
Still very well (Fig. 3), it was demonstrated that [Eu0.41Tb0.59L(DMA)(H2O)]·(DMA)3Temperature spy is carried out in can being used in tissue
Survey and imaging.
Embodiment 2:
Utilize acetic acid europium and acetic acid terbium and 2,4,6-tri-(3-carboxyl phenyl)-1,3,5-triazines, closed by solvent thermal process
Becoming the rare earth organic framework materials of micro/nano-scale, its concrete synthetic route is as follows:
By acetic acid europium and acetic acid terbium (mol ratio Eu of 0.1485mmol of 0.0015mmol3+:Tb3+=1:99),
The 2 of 0.075mmol, in the dodecanamide propyl decil of 4,6-tri-(3-carboxyl phenyl)-1,3,5-triazines and 0.9mmol
Ester is dissolved in the DMF (DMF) of 36mL, and the deionized water of the methanol and 1.8mL that separately take 7.2mL is added thereto,
It is made into mixed solution, then mixed solution is put in airtight vial, be stirred vigorously lower reaction 120 minutes at 40 DEG C,
Rare earth organic framework materials [Eu to micro/nano-scale0.01Tb0.99L2(DMF)(H2O)] (DMF), size at about 1000nm,
Productivity is 47.1%.
Can be obtained by single-crystal X-ray diffraction analysis, [Eu0.01Tb0.99L2(DMF)(H2O)] (DMF) has long-range order
Crystal structure and rule one-dimensional channels, pore size isUnder ultraviolet excitation, it has rare earth simultaneously
The characteristic luminescence peak of europium and terbium ion, their the strongest glow peak lays respectively at 613 and 544nm, and their intensity all can be along with
The change of temperature and change.In the range of 20-80 DEG C, the ratio of these two glow peaks of rare earth organic framework materials becomes very with temperature
Good exponential relationship.And its glow color along with temperature rising can from green to redness, the change of color clearly,
With the naked eye just it is observed that or use CCD camera record, thus can obtain temperature by the method for colorimetric.
Double rare earth organic framework materials of micro/nano-scale are dispersed in cellular environment, shoot its fluorescence in different temperatures
Photo, it appeared that when 20 DEG C, its glow color is green, and when temperature is increased to 40 DEG C, its glow color is orange,
It changes highly significant with the color of temperature, it was demonstrated that it has the highest practical value in bio-medical field.
[the Eu detected0.01Tb0.99L2(DMF)(H2O)] the x-ray diffractogram of powder spectrum of (DMF) still can be single with it
Brilliant simulation X ray diffracting spectrum can extraordinary coincide, it was demonstrated that it still can keep the complete of structure in detection process, and
[Eu0.01Tb0.99L2(DMF)(H2O)] (DMF) can keep the constant rate at its two peak in thermal cycle repeatedly, it was demonstrated that its
The credibility of temperature-measuring results is higher, and can be recycled.By [Eu0.01Tb0.99L2(DMF)(H2O)] (DMF) immerses
In water after 8 hours, its x-ray diffractogram of powder spectrum still can be good at can be preferable with its monocrystalline simulation X ray diffracting spectrum
It coincide, it was demonstrated that it can be used in the temperature sensing in biotic environment and imaging.[Eu0.01Tb0.99L2(DMF)(H2O)]·(DMF)
Bio-toxicity less so that it is with cell time altogether long cell can keep higher survival rate, it was demonstrated that [Eu0.01Tb0.99L2(DMF)
(H2O) temperature sensing and imaging are carried out in] (DMF) can be used in tissue.
Embodiment 3:
Utilizing europium nitrate and Terbium nitrate (Tb(NO3)3) and 2,4,6-tri-(3,5-dicarboxyphenyi)-1,3,5-triazines, by solvent thermal side
The rare earth organic framework materials of method synthesis micro/nano-scale, its concrete synthetic route is as follows:
By europium nitrate and Terbium nitrate (Tb(NO3)3) (mol ratio Eu of 0.075mmol of 0.075mmol3+:Tb3+=1:1), 0.075mmol
2,4,6-tri-(3,5-dicarboxyphenyi)-1,3,5-triazines and the lauryl alcohol phosphate ester potassium of 0.9mmol be dissolved in 36mL's
In N,N-dimethylacetamide, the deionized water of the methanol and 1.8mL that separately take 7.2mL is added thereto, and is made into mixed solution, then
Put in airtight vial, be stirred vigorously lower reaction 20 minutes at 140 DEG C, obtain the rare earth organic framework materials of micro/nano-scale
[Eu0.5Tb0.5L3(DMA)(H2O)]·(DMA)4, size is at about 1000nm, and productivity is 47.1%.
Can be obtained by single-crystal X-ray diffraction analysis, [Eu0.5Tb0.5L3(DMA)(H2O)]·(DMA)4There is long-range order
Crystal structure and the one-dimensional channels of rule, pore size isUnder ultraviolet excitation, it has rare-earth europium simultaneously
With the characteristic luminescence peak of terbium ion, their the strongest glow peak lays respectively at 613 and 544nm.In the range of 20-80 DEG C, this is dilute
The ratio of soil two glow peaks of organic framework materials becomes good exponential relationship with temperature.And its glow color is along with temperature
Raise can from green to redness, the change of color clearly, with the naked eye just it is observed that or use CCD camera record,
Thus can obtain temperature by the method for colorimetric.
The rare earth organic framework materials of the micro/nano-scale obtained is dispersed in cellular environment, shoots it in different temperatures
Fluorescence photo, it appeared that when 20 DEG C, its glow color is green, and when temperature is increased to 40 DEG C, its glow color is
Orange, it changes highly significant with the color of temperature, it was demonstrated that it has the highest practical value in bio-medical field.
[the Eu detected0.5Tb0.5L3(DMA)(H2O)]·(DMA)4X-ray diffractogram of powder spectrum still can be single with it
Brilliant simulation X ray diffracting spectrum can extraordinary coincide, it was demonstrated that it still can keep the complete of structure in detection process, and
[Eu0.5Tb0.5L3(DMA)(H2O)]·(DMA)4The constant rate at its two peak can be kept in thermal cycle repeatedly, it was demonstrated that its
The credibility of temperature-measuring results is higher, and can be recycled.By [Eu0.5Tb0.5L3(DMA)(H2O)]·(DMA)4Immerse water
In after 8 hours, its x-ray diffractogram of powder spectrum still can be good at can with its monocrystalline simulation X ray diffracting spectrum preferably kiss
Close, it was demonstrated that it can be used in the temperature sensing in biotic environment and imaging.[Eu0.5Tb0.5L3(DMA)(H2O)]·(DMA)4Life
Thing toxicity is less so that it is time the longest with cell, cell can keep higher survival rate, it was demonstrated that [Eu0.5Tb0.5L3(DMA)(H2O)]·
(DMA)4Temperature sensing and imaging is carried out in can being used in tissue.
Embodiment 4:
Utilize Europium chloride and terbium chloride and 2,4,6-tri-(2-carboxyl phenyl)-1,3,5-triazines, closed by solvent thermal process
Becoming the rare earth organic framework materials of micro/nano-scale, its concrete synthetic route is as follows:
By Europium chloride and terbium chloride (mol ratio Eu of 0.1335mmol of 0.0165mmol3+:Tb3+=11:89),
The 2 of 0.075mmol, 4,6-tri-(2-carboxyl phenyl)-1,3,5-triazines and 0.9mmol cetyl trimethylammonium bromide are dissolved in
In 36mL N, N-diethylformamide (DEF), the deionized water of the methanol and 1.8mL that separately take 7.2mL is added thereto, and is made into mixed
Closing solution, be then placed in airtight vial, vigorous reaction 60 minutes under 80 DEG C of stirrings, the rare earth obtaining micro/nano-scale has
Machine frame material [Eu0.11Tb0.89L(DEF)(H2O)]·(DEF)2, size is at about 1000nm, and productivity is 47.1%.
Can be obtained by single-crystal X-ray diffraction analysis, [Eu0.11Tb0.89L(DEF)(H2O)]·(DEF)2There is long-range order
Crystal structure and rule one-dimensional channels, pore size isUnder ultraviolet excitation, it has rare earth simultaneously
The characteristic luminescence peak of europium and terbium ion, their the strongest glow peak lays respectively at 613 and 544nm.In the range of 20-80 DEG C, should
The ratio of two glow peaks of rare earth organic framework materials becomes good exponential relationship with temperature.And its glow color is along with temperature
Rising can from green to redness, the change of color clearly, with the naked eye just it is observed that or remember by CCD camera
Record, thus can obtain temperature by the method for colorimetric.
The rare earth organic framework materials of the micro/nano-scale obtained is dispersed in cellular environment, shoots it in different temperatures
Fluorescence photo, it appeared that when 20 DEG C, its glow color is green, and when temperature is increased to 40 DEG C, its glow color is
Orange, it changes highly significant with the color of temperature, it was demonstrated that it has the highest practical value in bio-medical field.
[the Eu detected0.11Tb0.89L(DEF)(H2O)]·(DEF)2X-ray diffractogram of powder spectrum still can be single with it
Brilliant simulation X ray diffracting spectrum can extraordinary coincide, it was demonstrated that it still can keep the complete of structure in detection process, and
[Eu0.11Tb0.89L(DEF)(H2O)]·(DEF)2The constant rate at its two peak can be kept in thermal cycle repeatedly, it was demonstrated that its
The credibility of temperature-measuring results is higher, and can be recycled.By [Eu0.11Tb0.89L(DEF)(H2O)]·(DEF)2Immerse
In water after 8 hours, its x-ray diffractogram of powder spectrum still can be good at can be preferable with its monocrystalline simulation X ray diffracting spectrum
It coincide, it was demonstrated that it can be used in the temperature sensing in biotic environment and imaging.[Eu0.11Tb0.89L(DEF)(H2O)]·(DEF)2
Bio-toxicity less so that it is with cell time altogether long cell can keep higher survival rate, it was demonstrated that [Eu0.11Tb0.89L(DEF)
(H2O)]·(DEF)2Temperature sensing and imaging is carried out in can being used in tissue.
Claims (5)
1., for biological tissue and a rare earth organic framework materials for cell interior fluorescence temperature sensing imaging, it is characterized in that tool
Having the crystal structure of long-range order and the duct of rule, its molecular formula is [LnLx(G)(H2O)]·(G)n, wherein Ln is rare earth
Eu or Tb；L be 2,4,6-tri-(4-carboxyl phenyl)-1,3,5-triazines, 2,4,6-tri-(3-carboxyl phenyl)-1,3,5-triazines, 2,
4,6-tri-(2-carboxyl phenyl)-1,3,5-triazines or 2,4,6-tri-(3,5-dicarboxyphenyi)-1,3,5-triazines；G represent with
Rare-earth ion coordination or the solvent molecule in crystal duct, for DMF, N,N-dimethylacetamide or
N, N-diethylformamide；X=1～3；N=1～4.
2. the rare earth organic frame sensing imaging for biological tissue and cell interior fluorescence temperature described in preparation claim 1
The method of material, comprises the following steps:
By rare-earth europium salt and rare earth terbium salt europium in molar ratio: the mixing of terbium=1:99～1:1, then with contain simultaneously benzene carboxylic acid group and
The organic ligand of triazine group and surfactant are dissolved in organic solvent together, mole total amount of two of which rare-earth salts,
The mol ratio simultaneously containing benzene carboxylic acid group and the organic ligand of triazine group and surfactant is 2:1:12, is subsequently adding
Deionized water and methanol, the volume ratio of deionized water, methanol and organic solvent is 1:4:20, obtains mixed solution, will mix molten
Liquid is put in airtight vial, in 40 DEG C-140 DEG C stirring reactions 20-120 minute, centrifugal, washing, obtains for biological group
Knit and the rare earth organic framework materials of cell interior fluorescence temperature sensing imaging.
The rare earth organic frame sensing imaging for biological tissue and cell interior fluorescence temperature the most according to claim 2
The preparation method of material, it is characterised in that described rare-earth europium salt is europium nitrate, Europium chloride or acetic acid europium；Described rare earth terbium salt
For Terbium nitrate (Tb(NO3)3), terbium chloride or acetic acid terbium.
The rare earth organic frame sensing imaging for biological tissue and cell interior fluorescence temperature the most according to claim 2
The preparation method of material, it is characterised in that while described, the organic ligand containing benzene carboxylic acid group and triazine group is structural formula
For the 2 of (a), 4,6-tri-(4-carboxyl phenyl)-1,3,5-triazines, structural formula are the 2 of (b), 4,6-tri-(3-carboxyl phenyl)-1,3,
5-triazine, structural formula are the 2 of (c), and 4,6-tri-(2-carboxyl phenyl)-1,3,5-triazines or structural formula are the 2 of (d), 4,6-tri-
(3,5-dicarboxyphenyi)-1,3,5-triazines；
The rare earth organic frame sensing imaging for biological tissue and cell interior fluorescence temperature the most according to claim 2
The preparation method of material, it is characterised in that described surfactant is cetyl trimethylammonium bromide, dodecanamide propyl
Decil lactone or lauryl alcohol phosphate ester potassium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168091.9A CN105732678B (en) | 2016-03-23 | 2016-03-23 | Rare earth organic framework materials for biological tissue and the sensing imaging of cell interior fluorescence temperature and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168091.9A CN105732678B (en) | 2016-03-23 | 2016-03-23 | Rare earth organic framework materials for biological tissue and the sensing imaging of cell interior fluorescence temperature and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732678A true CN105732678A (en) | 2016-07-06 |
| CN105732678B CN105732678B (en) | 2017-10-13 |
Family
ID=56250995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610168091.9A Active CN105732678B (en) | 2016-03-23 | 2016-03-23 | Rare earth organic framework materials for biological tissue and the sensing imaging of cell interior fluorescence temperature and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732678B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106768406A (en) * | 2016-11-24 | 2017-05-31 | 哈尔滨工业大学 | A kind of cell temperature measuring system |
| CN108279077A (en) * | 2018-03-20 | 2018-07-13 | 广东工业大学 | A kind of hot-quenching of luminescent material is gone out application of the behavior in temperature indicator and lamps and lanterns |
| CN108912337A (en) * | 2018-06-01 | 2018-11-30 | 中山大学 | A kind of rare earth metal organic framework materials of high quantum production rate and preparation method thereof |
| CN109374143A (en) * | 2018-10-30 | 2019-02-22 | 国网江苏省电力有限公司镇江供电分公司 | The contactless internal temp measuring method of dry-type transformer |
| CN110170059A (en) * | 2019-06-04 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method of the internal targeting ovarian cancer cell imaging nano material of multifunctional macromolecule and metal organic framework composition |
| CN112485420A (en) * | 2020-11-19 | 2021-03-12 | 海卫特(广州)医疗科技有限公司 | Fluorescence immunochromatography kit for detecting feline pancreatitis and preparation method thereof |
| CN114133924A (en) * | 2021-10-27 | 2022-03-04 | 天津大学 | Material for measuring microscopic hot spots in microwave field, application and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011545A2 (en) * | 2007-07-16 | 2009-01-22 | Insilicotech Co., Ltd. | Compound or solvate thereof with mesoporous metal-organic framework |
| CN104031638A (en) * | 2014-06-24 | 2014-09-10 | 浙江大学 | Dye/rare earth organic framework composite material for physiological temperature detection and preparation method of composite material |
| CN104045659A (en) * | 2014-06-11 | 2014-09-17 | 浙江大学 | Dual-rare earth organic frame material with biotemperature and pH multi-detection property |
-
2016
- 2016-03-23 CN CN201610168091.9A patent/CN105732678B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011545A2 (en) * | 2007-07-16 | 2009-01-22 | Insilicotech Co., Ltd. | Compound or solvate thereof with mesoporous metal-organic framework |
| CN104045659A (en) * | 2014-06-11 | 2014-09-17 | 浙江大学 | Dual-rare earth organic frame material with biotemperature and pH multi-detection property |
| CN104031638A (en) * | 2014-06-24 | 2014-09-10 | 浙江大学 | Dye/rare earth organic framework composite material for physiological temperature detection and preparation method of composite material |
Non-Patent Citations (2)
| Title |
|---|
| DORINA F. SAVA GALLIS ET AL: "Efficient Photoluminescence via Metal−Ligand Alteration in a New MOFs Family", 《CHEM. MATER.》 * |
| YOUNG KWAN PARK ET AL: "Crystal Structure and Guest Uptake of a Mesoporous Metal–Organic Framework Containing Cages of 3.9 and 4.7nm in Diameter", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106768406A (en) * | 2016-11-24 | 2017-05-31 | 哈尔滨工业大学 | A kind of cell temperature measuring system |
| CN106768406B (en) * | 2016-11-24 | 2019-03-26 | 哈尔滨工业大学 | A kind of cell temperature measuring system |
| CN108279077A (en) * | 2018-03-20 | 2018-07-13 | 广东工业大学 | A kind of hot-quenching of luminescent material is gone out application of the behavior in temperature indicator and lamps and lanterns |
| CN108912337A (en) * | 2018-06-01 | 2018-11-30 | 中山大学 | A kind of rare earth metal organic framework materials of high quantum production rate and preparation method thereof |
| CN109374143A (en) * | 2018-10-30 | 2019-02-22 | 国网江苏省电力有限公司镇江供电分公司 | The contactless internal temp measuring method of dry-type transformer |
| CN110170059A (en) * | 2019-06-04 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method of the internal targeting ovarian cancer cell imaging nano material of multifunctional macromolecule and metal organic framework composition |
| CN112485420A (en) * | 2020-11-19 | 2021-03-12 | 海卫特(广州)医疗科技有限公司 | Fluorescence immunochromatography kit for detecting feline pancreatitis and preparation method thereof |
| CN114133924A (en) * | 2021-10-27 | 2022-03-04 | 天津大学 | Material for measuring microscopic hot spots in microwave field, application and method |
| CN114133924B (en) * | 2021-10-27 | 2023-12-29 | 天津大学 | Material for measuring microscopic hot spots in microwave field, application and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105732678B (en) | 2017-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732678A (en) | Rare-earth organic framework material for fluorescent temperature sensation imaging in biological tissue and cells and preparation method thereof | |
| Zhang et al. | Magnetic and optical properties of NaGdF 4: Nd 3+, Yb 3+, Tm 3+ nanocrystals with upconversion/downconversion luminescence from visible to the near-infrared second window | |
| Hu et al. | Efficient two-photon-sensitized luminescence of a novel europium (iii) β-diketonate complex and application in biological imaging | |
| Du et al. | Near-infrared light-triggered visible upconversion emissions in Er3+/Yb3+-codoped Y2Mo4O15 microparticles for simultaneous noncontact optical thermometry and solid-state lighting | |
| CN108998007A (en) | A kind of preparation method of rare earth metal organic framework materials | |
| CN105924388B (en) | Thermotropic and photochromic material based on iodine silver hydrochlorate hybrid and preparation method thereof | |
| Yue et al. | Ratiometric near infrared luminescent thermometer based on lanthanide metal-organic frameworks | |
| Xu et al. | Assembly, stabilities, and photophysical behaviors of highly efficient luminescent materials fabricated from a terbium complex doped silica/polymer hybrids | |
| Yu et al. | Acid and alkali-resistant Dy 4 coordination clusters: synthesis, structure and slow magnetic relaxation behaviors | |
| Salas-Juárez et al. | Visual temperature sensor and luminescent thermometer based on the complex Tb/Eu–TPTZ incorporated in transparent PMMA film | |
| Dissanayake et al. | Multicolor emission in chemically and structurally tunable Er: Yb: SrFX (X= Cl, Br) upconverting nanocrystals | |
| CN108148083A (en) | One kind is bis- based on o-carboxyl phenylacetic acid and 1,2-（3- pyridinylmethylenes）Cadmium complex of hydrazine ligand and preparation method thereof | |
| Huang et al. | High-temperature, high-pressure hydrothermal synthesis, crystal structure, and luminescence properties of Cs3EuSi6O15, a new europium (III) silicate with a three-dimensional framework structure | |
| Luo et al. | Magnetic regulation of the luminescence of hybrid lanthanide-doped nanoparticles | |
| Gusev et al. | Ln (III) complexes of a bis (5-(pyridine-2-yl)-1, 2, 4-triazol-3-yl) methane ligand: synthesis, structure and fluorescent properties | |
| CN106046388B (en) | A kind of furancarboxylic acid class rare earth neodymium metal-organic framework luminescent material and its synthetic method | |
| Kumar et al. | Slow magnetic relaxation in Nd (iii) and Sm (iii) complexes formed in three-dimensional lanthanide-dicyanidometallate (i) frameworks exhibiting luminescent properties | |
| Dai et al. | Effect of defect energy level on improving Cr3+-based near-infrared persistent luminescence by codoped lanthanide ions | |
| CN105949224B (en) | A kind of self calibration fluorescence temperature sensing material suitable for ultralow temperature | |
| CN110256687B (en) | Fluorescent material based on rare earth organic framework structure and preparation method and application thereof | |
| Sun et al. | Near-infrared emission sensitization of lanthanide cation based on Ag+ functionalized metal-organic frameworks | |
| Han et al. | Luminescent and magnetic bifunctional coordination complex based on a chiral tartaric acid derivative and europium | |
| Panda et al. | Sc 1− x Er x AlO 3 perovskites: high-pressure synthesis, photoluminescence properties, and in vitro bioimaging | |
| Zhou et al. | Photoluminescent carbon dots based on a rare 3D inorganic–organic hybrid cadmium borate crystal | |
| Zhang et al. | Syntheses, structures, photoluminescent and magnetic properties of pyrazine-2, 3-dicarboxylate-based cadmium-lanthanide/lanthanide coordination polymers tuned by CdII |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |