CN107501567A - It is a kind of to be used to detect metal-organic framework material of the dyestuff containing two-photon of physiological temp and preparation method thereof - Google Patents
It is a kind of to be used to detect metal-organic framework material of the dyestuff containing two-photon of physiological temp and preparation method thereof Download PDFInfo
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- CN107501567A CN107501567A CN201710737180.5A CN201710737180A CN107501567A CN 107501567 A CN107501567 A CN 107501567A CN 201710737180 A CN201710737180 A CN 201710737180A CN 107501567 A CN107501567 A CN 107501567A
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Abstract
The invention discloses a kind of metal-organic framework material for being used to detect the dyestuff containing two-photon of physiological temp, can be detected in all band biology transparent window fluorescence temperature, its chemical formula is [M (L)x(G)y]·(R)n, wherein M is metal ion, and L is the triangular symmetry organic ligand containing tricarboxylic acid groups, and G is solvent molecule, and R represents the dye molecule in duct.The material is prepared using the method for solvent heat, in the case where 1000~1064nm is excited, launches 650~700nm visible ray, and the two range of wavelengths in the second biological window and the first biological window, can effectively avoid water from absorbing problem respectively；And temperature sensitive, the good cycle that lights, it can effectively detect physiological temp.Dyestuff be loaded after quantum efficiency, heat endurance be significantly improved, and in water and PBS physiological buffers stability it is high, good biocompatibility.It is expected to be applied in biologic medical etc..
Description
Technical field
The present invention relates to metal-organic framework material of a kind of dyestuff containing two-photon and preparation method thereof, the material is 1000
~1064nm is excited down, launches 650~700nm visible ray, that is, is excited and launched all in biological transparent window, and can be with
For carrying out physiological temp detection.
Background technology
It is a very important basic physical parameters in chemistry, physics and biological field, temperature.Particularly in organism
In regulation and control, the minor alteration of temperature can all influence mutual from gene expression to protein-protein in cell biological tissue, cell
Multiple processes of effect.The temperature of some sick cell tissues is higher generally than normal cell tissue in biological tissue,
Therefore health tissues cell and diseased tissue cell can be classified using cell temperature difference, additionally by change cell
Temperature, which carrys out regulating cell process, very important effect to disease treatment.Fluorescence temperature sensing material because with it is non-contact,
High sensitivity and it is not easy, by advantages such as the strong interference of electromagnetic field, to receive extensive concern.
At present, the fluorophor applied to physiological temp detection mainly has small molecule organic dyestuff, fluorescin, quantum dot
With the material such as metal complex.For this kind of material there is relatively low in water stability, self structure is unstable, and bio-toxicity is high, ultraviolet
Light excites the limitation such as big to biological tissue's infringement.And biological tissue's penetrability is weak, can not completely show thin below skin
Born of the same parents' state, most light wave can highly be absorbed by water and hemoglobin.But some wave-length coverages are to penetrate tissue, and
Water is avoided to absorb problem, these wave-length coverages are called biological window.Light between 650~950 nanometers, that is, near-infrared
Feux rouges is regarded as a biological window, and the infrared light between 1000~1350 nanometers is then second biological window.It is double
Photon fluorescence material, its exciting light are that near infrared light make it that its detection process is small to biological tissue's damage, wears in biological tissues
It is thoroughly deep and without biological tissue's autofluorescence interference, there is unique advantage in physiological temp field of detecting, but report at present
The two-photon temperature sensing material crossed all is exciting light in the second biological window, that is to say, that exciting and launching can fall in biology
The metal-organic framework material of the dyestuff containing two-photon of window does not have also, therefore further research has highly important meaning
Justice.
Metal-organic framework material due to its is porous, various structures, be readily synthesized, bio-toxicity is low, heat endurance is high etc.
Advantage is widely studied.There are luminescent metal organic framework materials luminescence sites to enrich, and the advantages such as framework duct is adjustable are in temperature
Degree sensory field has good development potentiality.The cation in one-dimensional channels in anionic metal organic frame can by from
The method that son exchanges is come out by the non-linear dye exchange of cation.By anionic metal organic frame to dye of positive ion height
Degree is loaded so that molecular polarity is orientated, and shows excellent two-photon fluorescence performance, while also solve dye molecule water stability
It is relatively low, structural instability, the problems such as bio-toxicity is high.
The content of the invention
It can be contaminated it is an object of the invention to provide a kind of what all band biology transparent window fluorescence temperature detected containing two-photon
The metal-organic framework material and preparation method of material.
The metal-organic framework material for being used to detect the dyestuff containing two-photon of physiological temp of the present invention, has long-range order
Crystal structure and rule duct, its chemical formula is [M (L)x(G)y]·(R)n, wherein M is metal ion,
Including In, Zn, Cu, Cr, Co, Cd or Zr；L is the triangular symmetry organic ligand containing tricarboxylic acid groups, including
1,3,5- tri- (4- carboxyl phenyls) benzene, the benzoic acid of 4,4', 4'- tri-, 4,4', 4'- phenalgins tricarboxylic acid, 4,4', 4 "-(benzene 1,3,5-
Three (oxygen)) three benzoic acid or 4,4', 4 "-((2,4,6- trimethylbenzenes -1,3,5) three (oxygen) benzenetricarboxylic acid, x=1~3；G represent with
Metallic ion coordination or the solvent molecule in crystal duct, be water, DMF, DMA or
Person's N, N- diethylformamide；Y=0~60, R represent the cyanine type dye molecule of cationic pyridinium half in duct, including 4- (4-
(diphenyl amino) styryl) -1- alkyl pyridines, 1- ethyls -4- (4- (methyl (phenyl) amino) styryl) pyridine, 4-
(4- (dimethylamino) styryl) -1- ethylpyridines, 4- (4- (diphenyl amino) phenyl) azo -1- ethylpyridines or 4-
(4- (lignocaine) styryl) -1- ethylpyridines, n=1~50.
The preparation method for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp of the present invention, bag
Include following steps：
Metal nitrate is added into deionized water together with the triangular symmetry organic ligand containing tricarboxylic acid groups and had
In solvent, mixed solution is obtained, 50~300 μ L acid is added, obtained solution is put into reactor inner bag, 120~
160 DEG C of heating responses 1~3 day, centrifugation, washing, obtain metal-organic framework material；Gained metal-organic framework material is soaked
In the organic solution of the cyanines class two-photon dyestuff of cationic pyridinium half, it is placed in 40~60 DEG C of baking ovens after being incubated 2~7 days and is used
In the metal-organic framework material of the dyestuff containing two-photon of detection physiological temp.
In the present invention, metal nitrate is indium nitrate, zinc nitrate, copper nitrate, chromic nitrate, cobalt nitrate, cadmium nitrate or nitric acid
Zirconium.
In the present invention, the triangular symmetry organic ligand containing tricarboxylic acid groups is (a) 1,3,5- tri- (4- carboxyl phenyls)
Benzene；Or the benzoic acid of (b) 4,4', 4'- tri-；Or (c) 4,4', 4'- phenalgin tricarboxylic acid；Or (d) 4,4', 4 "-(benzene 1,3,5- tri-
(oxygen)) three benzoic acid；Or (e) 4,4', 4 "-((2,4,6- trimethylbenzenes -1,3,5) three (oxygen) benzenetricarboxylic acid.Structural formula is respectively such as
Under：
In the present invention, the cyanines class two-photon Dyes structural formulae of cationic pyridinium half is as follows：(a) 4- (4- (diphenyl amino) benzene
Vinyl) -1- alkyl pyridines；(b) 1- ethyls -4- (4- (methyl (phenyl) amino) styryl) pyridine；(c) 4- (4- (diformazans
Amino) styryl) -1- ethylpyridines；(d) 4- (4- (diphenyl amino) phenyl) azo -1- ethylpyridines；Or (e) 4- (4-
(lignocaine) styryl) -1- ethylpyridines.
In the present invention, organic solvent used is Isosorbide-5-Nitrae-dioxane and DMF, N, N- dimethyl second
Any one in acid amides or N, N- diethylformamide.
In the present invention, metal ion is 1~3 with the triangular symmetry organic ligand mol ratio containing tricarboxylic acid groups.
In the present invention, the volume ratio of organic solvent and deionized water is 5~10.
In the present invention, acid used can be nitric acid, hydrochloric acid, sulfuric acid, acetic acid.
In the present invention, during ion exchange process, the organic solution of dyestuff, wherein solvent can be N, N- dimethyl formyls
Any one in amine, DMA or N, N- diethylformamide.
It is used for the detection method of the two-photon luminescent metal organic framework materials of physiological temp detection, exciting light in the present invention
Wavelength is located near infrared region, biological second window (1000~1350nm), and two photon emission wavelength is located at biological first window
(650~950nm), it can be applied to the detection of 20~60 DEG C of scope physiological temps.
Specific beneficial effect of the invention is：
1st, method of the invention is used for detection of the metal-organic framework material of the dyestuff containing two-photon to physiological temp, lights
Intensity is linear related to temperature in Physiological temperatures range.Excite and be all located at biological transparent window, wherein skin with launch wavelength
The scattering and absorption of skin, tissue and blood to light are minimum, and this is still found for the first time in metal-organic framework material.
2nd, bio-toxicity is the major criterion that can a kind of material of evaluation be applied to biomedical sector, and of the invention contains
The metal-organic framework material bio-toxicity of two-photon dyestuff is low.And compared with simple dye toxicity, being loaded into metal has
After machine frame, toxicity significantly reduces.
3rd, compared with inorganic compound, complex or organic molecule, metal-organic framework material is a kind of with micro- in order
The crystalline material in hole, there is the crystal structure of long-range order and the duct of rule.Dye molecule can be evenly dispersed in framework
It is interior, fluorescent quenching caused by molecule is reunited is avoided, so as to improve luminous efficiency.
4th, two-photon dyestuff is due to easily dissolving, and heat endurance is poor, it is difficult to apply in biological tissues, it is organic by metal
Frame material can improve the heat endurance of dyestuff after loading, expand its application.
5th, the metal-organic framework material of the dyestuff containing two-photon of the invention can reuse, in multiple temperature cycles
Still keep recoverable luminescent properties.
6th, the metal-organic framework material of the dyestuff containing two-photon of the invention can keep prolonged structure steady in water
It is fixed.And structure also still remains intact after being soaked in biosimulation solution PBS, its answering in bio-science field ensure that
With.
Brief description of the drawings
Fig. 1 is the metal-organic framework material maximum emission intensity (at 650nm) and temperature of the dyestuff containing two-photon of the present invention
The relation of degree；
Fig. 2 is maximum of the metal-organic framework material of the dyestuff containing two-photon of the present invention in three temperature cycling cycles
Emissive porwer variation with temperature；
Fig. 3 is the metal-organic framework material of the dyestuff containing two-photon and the cytotoxicity experiment result of dyestuff of the present invention.
Embodiment
Below in conjunction with the example content that the present invention is furture elucidated, but these examples are not intended to limit the protection model of the present invention
Enclose, on the basis of technical scheme, those skilled in the art need not pay creative work can make it is each
Kind modification is deformed still within protection scope of the present invention.
Embodiment 1：
Using indium nitrate and 1,3,5- tri- (4- carboxyl phenyls) benzene, metal organic frame material is synthesized by solvent thermal process
Material, its specific synthetic route are as follows：
2.4mmol indium nitrate and 1.2mmol 1,3,5- tri- (4- carboxyl phenyls) benzene is dissolved in 36mL DMF, 24mL
1,4- dioxane and 4mL H2O in the mixed solvents, then add the dense HNO of 0.25mL3(mass fraction 62%).Solution is encapsulated
In 100mL ptfe autoclaves, it is placed in 120 DEG C of baking ovens and reacts 24h.Room temperature is cooled to, is washed 3 times, obtained with DMF
Colourless needles metal-organic framework material [In3(L)4(Me2NH2)3]·12DMF·22H2O.By 100mg, the crystal is put into
0.05mol L-1The DMF solution of dye of positive ion 4- (4- (diphenyl amino) styryl) -1- alkyl pyridines.Mixture is filled
Enter to put in 15mL vials reacted 7 days in 60 DEG C of baking ovens after take out, filter off except dye solution, washed 3 times with DMF, use ethanol
Washing 3 times, is put into 60 DEG C of drying, obtains the metal-organic framework material of the dyestuff containing two-photon, dye content 29.82wt%.
The material is under 1064nm laser excitations, and the peak value of resulting emission spectrum is located at 650nm, with temperature liter
Height, its intensity of emission spectra reduce, and its intensity of emission spectra has good linear relationship with temperature, can be intended with following formula
Close：
I=-0.01547T+1.285
Wherein I is maximum emission intensity.The metal-organic framework material of the dyestuff containing two-photon is when temperature is low, its fluorescence
Intensity is stronger, declines substantially with temperature rise, 1.52~3.39% can be reached by being computed the detectivity of the material
℃-1, resolution ratio can reach 0.013 DEG C, can be completely applied to bio-measurement.In order to verify the material in physiological temp section
Two-photon fluorescence thermometer sensor DS18B20 precision, the repetition varied with temperature we have studied two photon emission peak intensity can
Inverse property.As shown in Fig. 2 in the temperature cycles (20~60 DEG C) in three cycles, the two photon emission peak intensity of the material is with temperature
The change of degree is reversible, and this illustrates that the material may be reused.
The heat endurance of the material is characterized, is loaded into the Kong Zhonghou of metallo organic material, the thermostabilization of dyestuff
Property improves about 140 DEG C, thus expands the application of dyestuff.
From figure 3, it can be seen that the cytotoxicity of the metal-organic framework material for containing two-photon dyestuff is relatively low, when it contains
Amount reaches 250 μ gmL-1When, the survival rate of cell can also reach more than 80%, illustrate that the material has good biocompatibility,
It is expected to be applied to biomedical sector.In addition, dyestuff, after loading, bio-toxicity is more many than the reduction of pure dye molecule.Will
After material in water 2 days, its x-ray diffractogram of powder spectrum still can be good at that X-ray diffractogram can be simulated with its monocrystalline
Spectrum is preferably coincide, it was demonstrated that its water stability is preferable, can realize detection in the solution., should by the use of PBS solution as biosimulation solution
Material crystal structure after soaking two hours still keeps complete, illustrates that the material is adapted to biotic environment.
After being loaded, luminous quantum efficiency is significantly improved dyestuff, and composite wood is risen to by the 3.59% of simple dyestuff
25.76% in material, this also improves the sensitivity of material temperature detection to a certain extent.
Embodiment 2：
Using indium nitrate and 1,3,5- tri- (4- carboxyl phenyls) benzene, metal organic frame material is synthesized by solvent thermal process
Material, its specific synthetic route are as follows：
2.4mmol indium nitrate and 1.2mmol 1,3,5- tri- (4- carboxyl phenyls) benzene is dissolved in 36mL DMF, 24mL
1,4- dioxane and 4mL H2O in the mixed solvents, then add the dense HNO of 0.25mL3(62%).Solution is packaged in into 100mL to gather
In tetrafluoroethene reactor, it is placed in 120 DEG C of baking ovens and reacts 24h.Room temperature is cooled to, is washed 3 times with DMF, obtains colourless needles
Metal-organic framework material [In3(L)4(Me2NH2)3]·12DMF·22H2O.100mg crystal is put into 0.05mol L-1Sun from
The DMF solution of sub- dyestuff 4- (4- (dimethylamino) styryl) -1- ethylpyridines.Fill this blend into 15mL vials and put
Take out, filtered off except dye solution after being reacted 5 days in 60 DEG C of baking ovens, washed 3 times with DMF, washed 3 times with ethanol, be put into 60 DEG C
Drying.
The material is under 1064nm laser excitations, and the peak value of resulting emission spectrum is located at 650nm or so, with temperature
Rise, its intensity of emission spectra reduce, and its intensity of emission spectra has good linear relationship with temperature, and this contains two-photon dyestuff
For metal-organic framework material when temperature is low, its fluorescence intensity is stronger, declines substantially with temperature rise, is computed the spy of the material
Survey sensitivity is higher, and resolution ratio can reach the requirement of bio-measurement.In order to verify double light of the material in physiological temp section
The precision of sub- fluorescence temperature sensing characteristicses, we have studied the repetition invertibity that two photon emission peak intensity varies with temperature.
In the temperature cycles (20~60 DEG C) in three cycles, the two photon emission peak intensity variation with temperature of the material is reversible
, this illustrates that the material may be reused.
The heat endurance of the material is characterized, is loaded into the Kong Zhonghou of metallo organic material, the thermostabilization of dyestuff
Property is improved significantly, and thus expands the application of dyestuff.
The cytotoxicity of the metal-organic framework material of the dyestuff containing two-photon is relatively low, has good biocompatibility, has
Prestige is applied to biomedical sector.In addition, dyestuff, after loading, bio-toxicity is more many than the reduction of pure dye molecule.By material
Material is immersed in the water after a few days, and its x-ray diffractogram of powder spectrum still can be good at that X ray diffracting spectrum can be simulated with its monocrystalline
Preferably it coincide, it was demonstrated that its water stability is preferable, can realize detection in the solution.Biosimulation solution, the material are used as by the use of PBS solution
Crystal structure still keeps complete to material after immersion for a period of time, illustrates that the material is adapted to biotic environment.
Dyestuff is after being loaded, and luminous quantum efficiency significantly improves, and this also improves material temperature to a certain extent
The sensitivity of detection.
Embodiment 3：
Using zinc nitrate and 4,4', 4 "-(benzene 1,3,5- tri- (oxygen)) three benzoic acid, synthesizing metal by solvent thermal process has
Machine frame frame material, its specific synthetic route are as follows：
By 2.4mmol zinc nitrate and 1.2mmol 4,4', 4 "-(benzene 1,3,5- tri- (oxygen)) three benzoic acid are dissolved in
36mL DMF, 24mL 1,4- dioxane and 4mL H2O in the mixed solvents, then add the dense HNO of 0.25mL3(62%).Will be molten
Fluid-tight is loaded in 100mL ptfe autoclaves, is placed in 120 DEG C of baking ovens and is reacted 24h.Room temperature is cooled to, 3 are washed with DMF
It is secondary, obtain metal-organic framework material [Zn (L)2]·15DMF·20H2O.100mg crystal is put into 0.05mol L-1Cation
The DMF solution of dyestuff 4- (4- (lignocaine) styryl) -1- ethylpyridines.Fill this blend into 15mL vials and put 60
Taken out after being reacted 7 days in DEG C baking oven, filter off except dye solution, washed 3 times with DMF, washed 3 times with ethanol, be put into 60 DEG C of bakings
It is dry.
The material is under 1064nm laser excitations, and the peak value of resulting emission spectrum is located at 650nm or so, with temperature
Rise, its intensity of emission spectra reduce, and its intensity of emission spectra has good linear relationship with temperature, and this contains two-photon dyestuff
For metal-organic framework material when temperature is low, its fluorescence intensity is stronger, declines substantially with temperature rise, is computed the spy of the material
Survey sensitivity is higher, and resolution ratio can reach the requirement of bio-measurement.In order to verify double light of the material in physiological temp section
The precision of sub- fluorescence temperature sensing characteristicses, we have studied the repetition invertibity that two photon emission peak intensity varies with temperature.
In the temperature cycles (20~60 DEG C) in three cycles, the two photon emission peak intensity variation with temperature of the material is reversible
, this illustrates that the material may be reused.
The heat endurance of the material is characterized, is loaded into the Kong Zhonghou of metallo organic material, the thermostabilization of dyestuff
Property is improved significantly, and thus expands the application of dyestuff.
The cytotoxicity of the metal-organic framework material of the dyestuff containing two-photon is relatively low, has good biocompatibility, has
Prestige is applied to biomedical sector.In addition, dyestuff, after loading, bio-toxicity is more many than the reduction of pure dye molecule.By material
Material is immersed in the water after a few days, and its x-ray diffractogram of powder spectrum still can be good at that X ray diffracting spectrum can be simulated with its monocrystalline
Preferably it coincide, it was demonstrated that its water stability is preferable, can realize detection in the solution.Biosimulation solution, the material are used as by the use of PBS solution
Crystal structure still keeps complete to material after immersion for a period of time, illustrates that the material is adapted to biotic environment.
Dyestuff is after being loaded, and luminous quantum efficiency significantly improves, and this also improves material temperature to a certain extent
The sensitivity of detection.
Embodiment 4：
Using indium nitrate and 4,4', the benzoic acid of 4'- tri-, metal-organic framework material is synthesized by solvent thermal process, it has
The synthetic route of body is as follows：
By 2.4mmol indium nitrate and 1.2mmol 4,4', the benzoic acid of 4'- tri- is dissolved in 36mL DMF, 24mL 1,4-
Dioxane and 4mL H2O in the mixed solvents, then add the dense HNO of 0.25mL3(62%).Solution is packaged in 100mL polytetrafluoros
In ethylene reaction kettle, it is placed in 120 DEG C of baking ovens and reacts 24h.Room temperature is cooled to, is washed 3 times with DMF, obtains metal organic frame
Material [In3(L)4(Me2NH2)3]·12DMF·22H2O.100mg crystal is put into 0.05mol L-1Dye of positive ion 4- (4-
(lignocaine) styryl) -1- ethylpyridines DMF solution.Fill this blend into 15mL vials and put in 60 DEG C of baking ovens
Reaction is taken out after 7 days, is filtered off except dye solution, is washed 3 times with DMF, washed 3 times with ethanol, is put into 60 DEG C of drying.
The material is under 1064nm laser excitations, and the peak value of resulting emission spectrum is located at 650nm or so, with temperature
Rise, its intensity of emission spectra reduce, and its intensity of emission spectra has good linear relationship with temperature, and this contains two-photon dyestuff
For metal-organic framework material when temperature is low, its fluorescence intensity is stronger, declines substantially with temperature rise, is computed the spy of the material
Survey sensitivity is higher, and resolution ratio can reach the requirement of bio-measurement.In order to verify double light of the material in physiological temp section
The precision of sub- fluorescence temperature sensing characteristicses, we have studied the repetition invertibity that two photon emission peak intensity varies with temperature.
In the temperature cycles (20~60 DEG C) in three cycles, the two photon emission peak intensity variation with temperature of the material is reversible
, this illustrates that the material may be reused.
The heat endurance of the material is characterized, is loaded into the Kong Zhonghou of metallo organic material, the thermostabilization of dyestuff
Property is improved significantly, and thus expands the application of dyestuff.
The cytotoxicity of the metal-organic framework material of the dyestuff containing two-photon is relatively low, has good biocompatibility, has
Prestige is applied to biomedical sector.In addition, dyestuff, after loading, bio-toxicity is more many than the reduction of pure dye molecule.By material
Material is immersed in the water after a few days, and its x-ray diffractogram of powder spectrum still can be good at that X ray diffracting spectrum can be simulated with its monocrystalline
Preferably it coincide, it was demonstrated that its water stability is preferable, can realize detection in the solution.Biosimulation solution, the material are used as by the use of PBS solution
Crystal structure still keeps complete to material after immersion for a period of time, illustrates that the material is adapted to biotic environment.
Dyestuff is after being loaded, and luminous quantum efficiency significantly improves, and this also improves material temperature to a certain extent
The sensitivity of detection.
Claims (10)
- A kind of 1. metal-organic framework material for being used to detect the dyestuff containing two-photon of physiological temp, it is characterised in that the material The duct of crystal structure and rule with long-range order, its chemical formula is [M (L)x(G)y]·(R)n, wherein M be metal from Son, including In, Zn, Cu, Cr, Co, Cd or Zr；L is the triangular symmetry organic ligand containing tricarboxylic acid groups, including 1,3, 5- tri- (4- carboxyl phenyls) benzene, the benzoic acid of 4,4', 4'- tri-, 4,4', 4'- phenalgins tricarboxylic acid, 4,4', 4 "-(benzene 1,3,5- tri- (oxygen)) three benzoic acid or 4,4', 4 "-((2,4,6- trimethylbenzenes -1,3,5) three (oxygen) benzenetricarboxylic acid, x=1~3；G is represented and gold Belong to ion coordination or the solvent molecule in crystal duct, be water, DMF, DMA or N, N- diethylformamide；Y=0~60, R represent the cyanine type dye molecule of cationic pyridinium half in duct, including 4- (4- (two Phenyl amino) styryl) -1- alkyl pyridines, 1- ethyls -4- (4- (methyl (phenyl) amino) styryl) pyridine, 4- (4- (dimethylamino) styryl) -1- ethylpyridines, 4- (4- (diphenyl amino) phenyl) azo -1- ethylpyridines or 4- (4- (lignocaine) styryl) -1- ethylpyridines, n=1~50.
- 2. prepare the side for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp described in claim 1 Method, it is characterised in that comprise the following steps：Metal nitrate is added together with the triangular symmetry organic ligand containing tricarboxylic acid groups to deionized water and organic molten In agent, mixed solution is obtained, 50~300 μ L acid is added, obtained solution is put into reactor inner bag, at 120~160 DEG C Heating response 1~3 day, centrifugation, washing, obtains metal-organic framework material；Gained metal-organic framework material is immersed in sun In the organic solution of the cyanines class two-photon dyestuff of ion pyridine half, it is placed in 40~60 DEG C of baking ovens after being incubated 2~7 days and obtains being used to visit Survey the metal-organic framework material of the dyestuff containing two-photon of physiological temp.
- 3. the system according to claim 2 for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp Preparation Method, it is characterised in that described metal nitrate is indium nitrate, zinc nitrate, copper nitrate, chromic nitrate, cobalt nitrate, nitric acid Cadmium or zirconium nitrate.
- 4. the system according to claim 2 for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp Preparation Method, it is characterised in that the triangular symmetry organic ligand containing tricarboxylic acid groups is (a) 1,3,5- tri- (4- carboxylics Base phenyl) benzene；Or the benzoic acid of (b) 4,4', 4'- tri-；Or (c) 4,4', 4'- phenalgin tricarboxylic acid；Or (d) 4,4', 4 "-(benzene 1,3, 5- tri- (oxygen)) three benzoic acid；Or (e) 4,4', 4 "-((2,4,6- trimethylbenzenes -1,3,5) three (oxygen) benzenetricarboxylic acid；Structural formula is distinguished It is as follows：
- 5. the system according to claim 2 for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp Preparation Method, it is characterised in that the organic solution of the described cyanines class two-photon dyestuff of cationic pyridinium half, wherein cationic pyridinium half Cyanines class two-photon dyestuff is：(a) 4- (4- (diphenyl amino) styryl) -1- alkyl pyridines；Or (b) 1- ethyl -4- (4- (methyl (phenyl) amino) styryl) pyridine；Or (c) 4- (4- (dimethylamino) styryl) -1- ethylpyridines；Or (d) 4- (4- (diphenyl amino) phenyl) azo -1- ethylpyridines；Or (e) 4- (4- (lignocaine) styryl) -1- ethyl pyrroles Pyridine；Structural formula is as follows：
- 6. the system according to claim 2 for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp Preparation Method, it is characterised in that described organic solvent is Isosorbide-5-Nitrae-dioxane and DMF, N, N- dimethyl second Any one in acid amides or N, N- diethylformamide；And described organic solvent and the volume ratio of deionized water are 5~10.
- 7. the system according to claim 2 for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp Preparation Method, it is characterised in that the metal ion in described metal nitrate has with the triangular symmetry containing tricarboxylic acid groups Machine part mol ratio is 1~3.
- 8. the system according to claim 2 for being used to detect the metal-organic framework material of the dyestuff containing two-photon of physiological temp Preparation Method, it is characterised in that described acid is nitric acid, hydrochloric acid, sulfuric acid or acetic acid.
- 9. the purposes of the metal-organic framework material of a kind of dyestuff containing two-photon, it is characterised in that described material is such as right It is required that the material that the material described in 1 or the method as described in claim any one of 2-8 prepare, the material is used for 20~60 The detection of DEG C scope physiological temp.
- 10. the purposes of the metal-organic framework material of the dyestuff according to claim 9 containing two-photon, it is characterised in that should When material is used for physiological temp detection, excitation wavelength is located at biological second window (1000~1350nm) near infrared region；Double light Sub- launch wavelength is located at biological first window (650~950nm).
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| CN111205468B (en) * | 2020-01-10 | 2021-06-25 | 浙江大学 | Dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing and preparation method thereof |
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