CN106497549A - A kind of europium terbium is co-doped with luminescent material and preparation method thereof, application - Google Patents
A kind of europium terbium is co-doped with luminescent material and preparation method thereof, application Download PDFInfo
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- CN106497549A CN106497549A CN201610919939.7A CN201610919939A CN106497549A CN 106497549 A CN106497549 A CN 106497549A CN 201610919939 A CN201610919939 A CN 201610919939A CN 106497549 A CN106497549 A CN 106497549A
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- terbium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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"
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The invention provides a kind of europium terbium is co-doped with luminescent material, including one or more in the hydrate of compound and the solvated compoundses of compound shown in Formulas I shown in compound shown in formula I, Formulas I：Zn8(Adenine)4(BPDA)6O EuxTb1‑xI；Wherein 0.1 ＜ x ＜ 0.25；The Adenine is adenine, and BPDA is 4,4' biphenyl dicarboxylic acids.The present invention with the metallic organic framework with loose structure as carrier, by with europium terbium rare earth ion exchanged, obtain europium terbium and be co-doped with luminous porous material.This is co-doped with luminous porous material and efficient energy transmission of the terbium to europium can occur so that material has the change of ratio fluorescent to anthrax bacillus biomarker, reduces the measurement error that may be caused by single fluorescence intensity change；And this be co-doped with luminous porous material can also to environment in anthrax bacillus biomarker molecule be enriched with, improve its test limit.
Description
Technical field
The present invention relates to rare earth luminescent material technical field, be related to a kind of europium terbium be co-doped with luminescent material and preparation method thereof,
Apply, more particularly to a kind of europium terbium is co-doped with luminous porous material and preparation method thereof, is used for anthrax bacillus biomarker ratio
The application of fluoroscopic examination.
Background technology
Ratio fluorescent technology (Ratio-type detection technique of fluorescence) is an important technology in fluorescence analysiss.The technology is being given birth to
In thing stain, can be excited by ultraviolet or blue violet light (short-wavelength light) and launch the dyestuff of fluorescence, referred to as fluorescent dye (fluorescence
Pigment)；Can be excited by long wavelength light, these fluorochromes are frequently referred to fluorescent probe.Fluorescent probe be generally used for fixing organization and
The dyeing of cell, and or living cells in application, additionally include being applied to internal fluorescent probe.Probe by with analyte
After (such as biometal ions) are combined, fluorescent characteristic is caused to change, by determining excitation wavelength, the transmitted wave of fluorescence
Length, fluorescence intensity, peak position, fluorescence lifetime, fluorescence quantum yield and anisotropy etc., obtain relevant information.Fluorescent method is determined
In, after being combined with reactant is there is the probe for exciting or emission spectrum is shifted, is usable in two different wave lengths in fluorescent probe
The fluorescence intensity ratio of measure is measured, referred to as ratio measure.Because being become by the fluorescence intensity of two selective wavelength
Change and can be often referred in wave-length coverage have fluorescence intensity significantly to change as quantitative foundation.
Anthrax is a kind of sensing disease for having a strong impact on human life.Since anthrax bacillus attack is received from the calendar year 2001 U.S.,
Countries in the world are classified as anthrax bacillus as potential attack of terrorism reagent.At present, traditional biology of anthrax bacillus is detected
The technology such as method such as bacteriology, seroimmunity analysis and polymerase chain reaction needs long detection time, complicated equipment and specially
The personnel of industry are operated.These methods are not all suitable for quick on-line checking.Optical technology detection anthrax rapidly and efficiently
The biomarker dipicolinic acid (dipicolinic acid, abbreviation DPA) of bacillus spores is caused by anthrax bacillus to prevention
The attack of terrorism and infectious disease significant.
Although there is simple to operate, with low cost, detection based on surface enhanced raman spectroscopy and fluorescence spectrum detection technique
The advantages of speed is fast is widely studied.But these detection methods are all based on the fluorescence intensity of single wavelength and strengthen to realize,
The error that the fluorescence intensity change that different degrees of presence detection environmental change or instrument itself cause is produced, and sensor sheet
The defect of the poor anti jamming capability of body.And Ratio-type detection technique of fluorescence can effectively avoid different detection environment and instrument certainly
The error that the fluorescence intensity change that body causes is produced, improves the capacity of resisting disturbance of sensor.
Therefore, how to obtain a kind of luminescent material is used in Ratio-type detection technique of fluorescence, and the DPA of anthrax bacillus is carried out
Detection, it has also become the focus of many forward position researcher extensive concerns in the industry.
Content of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of europium terbium is co-doped with luminescent material and its preparation side
Method, application, the application being particularly used in anthrax bacillus biomarker DPA ratio fluorescent detection techniques, present invention design are closed
Into europium terbium be co-doped with luminous porous material, in Ratio-type fluorescence detection method, anthrax bacillus biomarker DPA can be entered
Row detection, but also can to environment in anthrax bacillus biomarker molecule be enriched with, improve its test limit.
The invention provides a kind of europium terbium is co-doped with luminescent material, including compound shown in compound shown in formula I, Formulas I
Hydrate and the solvated compoundses of compound shown in Formulas I in one or more：
Zn8(Adenine)4(BPDA)6O EuxTb1-xI；
Wherein 0.1 ＜ x ＜ 0.25；
The Adenine is adenine, and BPDA is 4,4'- biphenyl dicarboxylic acids.
Preferably, the specific surface area that the europium terbium is co-doped with luminescent material is 745～1025m2/g；
0.15≤x≤0.2.
The invention provides a kind of europium terbium is co-doped with the preparation method of luminescent material, comprise the following steps：
A) after by adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc, strong acid and solvent hybrid reaction, centre is obtained
Product；
B, after the intermediate products and terbium source europium source solution for) obtaining above-mentioned steps mix standing again, obtain europium terbium and be co-doped with sending out
Luminescent material.
Preferably, the strong acid includes one or more in nitric acid, hydrochloric acid and sulphuric acid；
The solvent is included in N,N-dimethylformamide, water, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone
One or more；
The adenine is (0.2～0.7) with the mol ratio of the 4,4'- biphenyl dicarboxylic acids：1；
The two acetate hydrates zinc is (1.5～3.5) with the adenine mol ratio：1；
The strong acid is (5～10) with the adenine mol ratio：1；
The solvent is (300～1000) with the mol ratio of the adenine：1.
Preferably, the terbium source includes one or more in halogenation terbium, Terbium nitrate (Tb(NO3)3) and oxalic acid terbium；
The europium source includes one or more in europium halide, europium nitrate and oxalic acid europium；
The solvent of terbium source europium source solution includes N, N-dimethylformamide, water, methanol, ethanol, Methanamide and N- methyl
One or more in ketopyrrolidine.
Preferably, in the solution of the terbium source europium source, the mol ratio of the terbium ion and the europium ion is (3～9)：1；
In the solution of the terbium source europium source, the terbium europium ion sum is (10～24) with the mol ratio of the adenine：1；
Terbium source europium source solution is terbium source saturated solution and europium source saturated solution, or is terbium source europium source saturated solution.
Preferably, step A) it is specially：
A1) after by adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc and solvent hybrid reaction, mixed liquor is obtained；
A2, after) mixed liquor for obtaining above-mentioned steps is reacted with strong acid, post processing obtains intermediate products.
Preferably, the time of the mixing is 10～60 minutes；
The temperature of the reaction is 85～150 DEG C；
The time of the reaction is 24～96 hours.
Preferably, the post processing include cooling down, be filtered, washed and dried in one or more；The temperature of the drying
Spend for 100～150 DEG C；
The time of the standing is more than or equal to 10 hours；Also include filtering and drying steps after the standing；The drying
Temperature be 100～150 DEG C.
Present invention also offers the europium terbium described in above-mentioned technical proposal any one is co-doped with luminescent material or above-mentioned technical side
Europium terbium prepared by case any one is co-doped with luminescent material answering in terms of Ratio-type fluoroscopic examination anthrax bacillus biomarker
With.
The invention provides a kind of europium terbium is co-doped with luminescent material, including compound shown in compound shown in formula I, Formulas I
Hydrate and the solvated compoundses of compound shown in Formulas I in one or more：Zn8(Adenine)4(BPDA)6O
EuxTb1-xI；Wherein 0.1 ＜ x ＜ 0.25；The Adenine is adenine, and BPDA is 4,4'- biphenyl dicarboxylic acids.With existing skill
Art is compared, and the present invention is for existing surface enhanced raman spectroscopy and fluorescence spectrum detection technique in detection Bacillus anthracis spore
During biomarker dipicolinic acid (DPA), the fluorescence that different degrees of presence detection environmental change or instrument itself cause is strong
The error that degree change is produced, and the defect of the poor anti jamming capability of sensor itself, are kept away using Ratio-type detection technique of fluorescence
Exempt from the error of the fluorescence intensity change generation that different detection environment and instrument itself cause, improve the capacity of resisting disturbance of sensor,
And then a kind of luminous accordingly porous material is found for Ratio-type fluoroscopic examination DPA.What the present invention was provided is co-doped with luminous porous
Material, with the metallic organic framework with loose structure as carrier, by with europium terbium rare earth ion exchanged, obtain europium terbium be co-doped with send out
Light porous material.The europium terbium that the present invention is provided is co-doped with luminous porous material and efficient energy transmission of the terbium to europium can occur, and makes
Obtain material has the change of ratio fluorescent to anthrax bacillus biomarker, reduces the survey that may be caused by single fluorescence intensity change
Amount error；And the europium terbium of the present invention be co-doped with luminous porous material can to environment in anthrax bacillus biomarker molecule enter
Row enrichment, improves its test limit, so as to effectively solve the existing method complex operation for anthrax bacillus detection, equipment
Expensive；The Ratio-type detection technique of fluorescence that develops can effectively avoid the fluorescence that different detection environment and instrument itself cause
The error that Strength Changes are produced, improves the capacity of resisting disturbance of sensor.
Test result indicate that, the europium terbium that the present invention is provided is co-doped with luminous porous material and there is to DPA preferable ratio fluorescent
Response, the luminous of europium gradually weaken, and the luminous of terbium gradually strengthens, for the detection to DPA.
Description of the drawings
It is 3 that Fig. 1 is terbium europium mol ratio prepared by the embodiment of the present invention 1:It is dense to difference that 1 europium terbium is co-doped with luminous porous material
The fluorescence response figure of the DPA of degree；
It is 6 that Fig. 2 is terbium europium mol ratio prepared by the embodiment of the present invention 2:It is dense to difference that 1 europium terbium is co-doped with luminous porous material
The fluorescence response figure of the DPA of degree；
It is 9 that Fig. 3 is terbium europium mol ratio prepared by the embodiment of the present invention 3:It is dense to difference that 1 europium terbium is co-doped with luminous porous material
The fluorescence response figure of the DPA of degree；
Fig. 4 is the X-ray diffractogram of luminous porous material prepared by the embodiment of the present invention.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention rather than to patent requirements of the present invention
Limit.
The all raw materials of the present invention, originate to which and are not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
The all raw materials of the present invention, are not particularly limited to its purity, present invention preferably employs the pure or rear-earth-doped material of analysis
The conventional purity in material field.
The invention provides a kind of europium terbium is co-doped with luminescent material, including compound shown in compound shown in formula I, Formulas I
Hydrate and the solvated compoundses of compound shown in Formulas I in one or more：
Zn8(Adenine)4(BPDA)6O EuxTb1-xI；
Wherein 0.1 ＜ x ＜ 0.25；
The Adenine is adenine, and BPDA is 4,4'- biphenyl dicarboxylic acids.
In the present invention, the europium terbium is co-doped with luminescent material is included with formula Zn8(Adenine)4(BPDA)6O
EuxTb1-xCompound, the present invention is not particularly limited to the definition of the formula I and written form, with people in the art
The definition of formula and written form known to member, it is also possible to which Formulas I is defined as atomic ratio；The formula I can also be written as
Zn8(Adenine)4(BPDA)6O:EuxTb1-x.Europium terbium of the present invention is co-doped with luminescent material also includes Zn8(Adenine)4
(BPDA)6O EuxTb1-xHydrate, the present invention concrete structure of the hydrate is not particularly limited, people in the art
Member can be selected according to practical situations, raw material condition and product requirement and be adjusted, and hydrate of the present invention is excellent
Elect ten monohydrates, i.e. Zn as8(Adenine)4(BPDA)6O:EuxTb1-x·11H2O；Europium terbium of the present invention is co-doped with luminous material
Material also includes Zn8(Adenine)4(BPDA)6O EuxTb1-xSolvated compoundses, i.e. solvated compoundses based on formula I, this
The bright concrete structure to the solvated compoundses is not particularly limited, those skilled in the art can according to practical situations,
Raw material condition and product requirement are selected and are adjusted, such as Zn8(Adenine)4(BPDA)6O:EuxTb1-x, 8DMF, or Zn8
(Adenine)4(BPDA)6O:EuxTb1-x, 8DMF, 11H2O etc..
The present invention is not particularly limited to the representative definition of each unit in the formula I, ripe with those skilled in the art
The usual definition that knows, Adenine of the present invention are adenine, and the BPDA is 4,4'- biphenyl dicarboxylic acids.The present invention is right
The adenine is not particularly limited, with adenine well known to those skilled in the art；The present invention is to the 4,4'- biphenyl
Dioctyl phthalate is not particularly limited, with 4,4'- biphenyl dicarboxylic acids well known to those skilled in the art, i.e. 4,4'- biphenyl dicarboxyls
Acid or 4,4'-Biphenyldicarboxylic acid.
The present invention is not particularly limited to the span of x in the formula I, and those skilled in the art can be according to reality
Applicable cases, raw material condition and product requirement are selected and are adjusted, and in formula I of the present invention, the span of x is preferred
For 0.1 ＜ x ＜ 0.25, more preferably 0.12≤x≤0.23, more preferably 0.15≤x≤0.20, most preferably 0.16≤x≤
0.19.
The present invention is not particularly limited to other characteristics that the europium terbium is co-doped with luminescent material, ripe with those skilled in the art
The characteristic of the rear-earth-doped luminous material that knows, those skilled in the art can according to practical situations, raw material condition with
And product requirement is selected and adjusted, europium terbium of the present invention is co-doped with the specific surface area preferably 45～1025m of luminescent material2/
G, more preferably 100～900m2/ g, more preferably 300～700m2/ g, most preferably 400～600m2/g.
The invention provides a kind of europium terbium is co-doped with the preparation method of luminescent material, comprise the following steps：
A) after by adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc, strong acid and solvent hybrid reaction, centre is obtained
Product；
B, after the intermediate products and terbium source europium source solution for) obtaining above-mentioned steps mix standing again, obtain europium terbium and be co-doped with sending out
Luminescent material.
After the present invention is first by adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc, strong acid and solvent hybrid reaction,
Obtain intermediate products.
The present invention is not particularly limited to the strong acid, with strong acid well known to those skilled in the art, this area skill
Art personnel can be selected according to practical situations, raw material condition and product requirement and be adjusted, strong acid of the present invention
Preferably inorganic acid, more preferably one or more in nitric acid, hydrochloric acid and sulphuric acid, more preferably nitric acid, hydrochloric acid or sulphuric acid,
Most preferably nitric acid.The present invention is not particularly limited to the solvent, with solvent well known to those skilled in the art, ability
Field technique personnel can be selected according to actual experiment situation, raw material condition and product requirement and be adjusted, of the present invention
Solvent be preferably N,N-dimethylformamide (DMF), water, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone in one kind or
Multiple, more preferably in DMF, water, N,N-dimethylacetamide and N-Methyl pyrrolidone two kinds or many
Plant, most preferably DMF and water.
The present invention is not particularly limited to the addition of 4, the 4'- biphenyl dicarboxylic acids, and those skilled in the art can be with root
Factually border experimental conditions, raw material condition and product requirement are selected and are adjusted, adenine of the present invention and described 4,4'-
The mol ratio of biphenyl dicarboxylic acid is preferably (0.2～0.7)：1, more preferably (0.3～0.6)：1, most preferably (0.4～0.5)：
1.
The present invention is not particularly limited to the addition of the two acetate hydrates zinc, and those skilled in the art can be according to reality
Border applicable cases, raw material condition and product requirement are selected and are adjusted, two acetate hydrates zinc of the present invention and the gland
Purine mol ratio is preferably (1.5～3.5)：1, more preferably (1.8～3.2)：1, most preferably (2.0～3.0)：1.
The present invention is not particularly limited to the addition of the strong acid, and those skilled in the art can be according to actual experiment feelings
Condition, raw material condition and product requirement are selected and are adjusted, and strong acid of the present invention is preferably with the adenine mol ratio
(5～10)：1, more preferably (6～9)：1, most preferably (7～8)：1.
The present invention is not particularly limited to the addition of the solvent, and those skilled in the art can be according to actual experiment feelings
Condition, raw material condition and product requirement are selected and are adjusted, and solvent of the present invention with the mol ratio of the adenine is
(300～1000)：1, more preferably (400～900)：1, most preferably (500～800)：1.
The present invention is raising reaction effect, it is ensured that the uniform and stable of reaction is carried out, step A) it is particularly preferred as：
A1) after by the mixing of adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc and solvent, mixed liquor is obtained；
A2, after) mixed liquor for obtaining above-mentioned steps is reacted with strong acid, post processing obtains intermediate products.
The present invention was not particularly limited to the time of the mixing, with incorporation time well known to those skilled in the art,
Even mixing, those skilled in the art can be selected according to actual experiment situation, raw material condition and product requirement and
Adjustment, the time of mixing of the present invention are preferably 10～60 minutes, more preferably 20～55 minutes, most preferably 30～50 points
Clock.The present invention is not particularly limited to the condition of the reaction, with reaction condition well known to those skilled in the art, uniform mixing
, those skilled in the art can be selected according to actual experiment situation, raw material condition and product requirement and be adjusted, this
The temperature for inventing the reaction is preferably 85～150 DEG C, more preferably 100～140 DEG C, most preferably 110～130 DEG C；Described
The time of reaction is preferably 24～96 hours, more preferably 36～84 hours, most preferably 48～72 hours.
The present invention preferably also includes post processing for improving the performance of reaction effect and final products after the completion of the reaction
Step.
The present invention is not particularly limited to the design parameter of the post-processing step and operation, ripe with those skilled in the art
The design parameter of the post-processing step that knows and operation, those skilled in the art can be according to actual experiment situation, raw material feelings
Condition and product requirement are selected and are adjusted, post processing of the present invention includes cooling down, be filtered, washed and dried in one kind
Or multiple, more preferably include successively cooling down, be filtered, washed and dried in one or more, most preferably include successively cold
But, it is filtered, washed and dried.The present invention is not particularly limited to the actual conditions of above-mentioned detailed process, with people in the art
Cooling, the actual conditions being filtered, washed and dried known to member, those skilled in the art can be according to actual experiment feelings
Condition, raw material condition and product requirement are selected and are adjusted, and the temperature of drying of the present invention is preferably 100～150 DEG C, more
Preferably 110～140 DEG C, most preferably 120～130 DEG C；The mode of the drying is preferably and is vacuum dried；The cooling is preferably
To room temperature；Described filtration is preferably sucking filtration；The washing is preferably repeatedly washs, more preferably organic solvent washing, most preferably
It is repeatedly to be washed using DMF and dichloromethane.
After the intermediate products and terbium source europium source solution that above-mentioned steps are finally obtained by the present invention mix standing again, europium is obtained
Terbium is co-doped with luminescent material.
The present invention is not particularly limited to the terbium source, is used for preparing rare earth with liquid phase method well known to those skilled in the art
Can be wanted according to actual experiment situation, raw material condition and product in the terbium source of terbium doped compound, those skilled in the art
Ask and selected and adjusted, terbium source of the present invention is preferably included in the oxalates containing Tb ions, halogenide and nitrate
One or more, more preferably one or more in halogenation terbium, Terbium nitrate (Tb(NO3)3) and oxalic acid terbium, more preferably terbium chloride, Terbium nitrate (Tb(NO3)3)
Or oxalic acid terbium, most preferably Terbium nitrate (Tb(NO3)3).The present invention is not particularly limited to the europium source, with liquid well known to those skilled in the art
Phase method is used for the europium source for preparing rare-earth europium doped compound, and those skilled in the art can be according to actual experiment situation, original
Material situation and product requirement are selected and are adjusted, and europium source of the present invention preferably includes the oxalates containing Eu ions, halogen
One or more in one or more in compound and nitrate, more preferably europium halide, europium nitrate and oxalic acid europium, more preferably
For Europium chloride, europium nitrate or oxalic acid europium, most preferably europium nitrate.The present invention is not special to the solvent of terbium source europium source solution
Limit, with the solvent for rare earth well known to those skilled in the art, those skilled in the art can be according to actual experiment
Situation, raw material condition and product requirement are selected and are adjusted, and the solvent of terbium source europium source of the present invention solution is preferably included
One or more in DMF, water, methanol, ethanol, Methanamide and N-Methyl pyrrolidone, more preferably wraps
Include DMF, water, methanol, ethanol, Methanamide or N-Methyl pyrrolidone, most preferably N, N dimethyl formyl
Amine.
The present invention is not particularly limited to the addition in the terbium source and europium source, with liquid phase well known to those skilled in the art
Method is used for the conventional addition for preparing rare-earth hybridized compound, and those skilled in the art can be according to actual experiment situation, original
Material situation and product requirement are selected and are adjusted, in the solution of terbium source europium source of the present invention, the terbium ion and the europium
The mol ratio of ion is preferably (3～9)：1, more preferably (4～8)：1, most preferably (5～7)：1；Terbium source europium source solution
In, the terbium europium ion sum is preferably (10～24) with the mol ratio of the adenine：1, more preferably (12～22)：1, more
Preferably (14～20)：1, most preferably (16～18)：1.The present invention is raising reaction effect and the performance of product, institute
State terbium source europium source solution and be preferably terbium source saturated solution, europium source saturated solution, or be terbium source europium source saturated solution, more excellent
Elect terbium source europium source saturated solution as.
The present invention is not particularly limited to the condition of the standing, and those skilled in the art can be according to actual experiment feelings
Condition, raw material condition and product requirement are selected and are adjusted, the preferably greater than or equal to 10 hours time of standing of the present invention,
More preferably 10～20 hours, more preferably 12～18 hours, most preferably 14～16 hours.
The present invention, also includes filtering and drying after the completion of the standing for improving the performance of reaction effect and final products
Step.
The present invention is not particularly limited to the design parameter and operation of the filtration and drying steps, with people in the art
The design parameter with drying steps and operation is filtered known to member, and those skilled in the art can be according to actual experiment feelings
Condition, raw material condition and product requirement are selected and are adjusted, and the temperature of drying of the present invention is preferably 100～150 DEG C, more
Preferably 110～140 DEG C, most preferably 120～130 DEG C；The mode of the drying is preferably and is vacuum dried；The cooling is preferably
To room temperature；Described filtration is preferably sucking filtration.
The present invention has prepared europium terbium through above-mentioned steps and has been co-doped with luminous porous material, with the metal with loose structure
Organic backbone is carrier, anthrax bacillus biomarker (DPA) is had by being prepared for the ion exchange of europium terbium blend solution
The europium terbium of ratio fluorescent response is co-doped with luminous porous material.
Present invention also offers the europium terbium described in above-mentioned technical proposal any one is co-doped with luminescent material or above-mentioned technical side
Europium terbium prepared by case any one is co-doped with luminescent material answering in terms of Ratio-type fluoroscopic examination anthrax bacillus biomarker
With.The present invention is not particularly limited to the definition of the Ratio-type fluoroscopic examination, with fluorescence ratio well known to those skilled in the art
Rate detection technique.
The europium terbium that the present invention is provided is co-doped with luminous porous material and efficient energy transmission of the terbium to europium can occur so that material
Material has the change of ratio fluorescent to anthrax bacillus biomarker, reduces and is missed by the measurement that single fluorescence intensity change may cause
Difference；And the europium terbium of the present invention be co-doped with luminous porous material can to environment in anthrax bacillus biomarker molecule carry out richness
Collection, improves its test limit, so as to effectively solve the existing method complex operation for anthrax bacillus detection, apparatus expensive
And the error that the different fluorescence intensity changes for detecting that environment and instrument itself cause are produced is greatly, sensor capacity of resisting disturbance is weak
Defect.Test result indicate that, the europium terbium that the present invention is provided is co-doped with luminous porous material and there is to DPA preferable ratio fluorescent to ring
Should, the luminous of europium gradually weakens, and the luminous of terbium gradually strengthens, for the detection to DPA.
In order to further illustrate the present invention, luminescent material is co-doped with to a kind of europium terbium that the present invention is provided with reference to embodiments
And preparation method thereof, application be described in detail, but it is to be understood that these embodiments are with technical solution of the present invention as front
Put and implemented, give detailed embodiment and specific operating process, simply for further illustrate the present invention spy
Seek peace advantage, rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
Step one：
Will be molten to adenine (0.25mmol), 4,4- diphenyl dicarboxylic acids (0.5mmol) and two acetate hydrate zinc (0.75mmol)
In the mixed liquor of DMF (27mL) and water (2mL), stir 60 minutes, be subsequently adding nitric acid (2mmol).Above-mentioned solution is shifted
To in 40mL reactors, heat 48 hours at 130 DEG C.Be cooled to room temperature, sucking filtration obtains the crystal of needle-like, by crystal with DMF and
Dichloromethane is washed for several times, in 120 DEG C of dried in vacuum overnight, obtains sample 1.
Step 2：
The sample 1 prepared in step one is added to terbium europium molar ratio for 3:In the saturation DMF solution of 1 concentration, place
Overnight.Sucking filtration, is dried overnight at 120 DEG C, obtains final product europium terbium and is co-doped with luminous porous material.
It is co-doped with luminous porous material to detect to europium terbium prepared by above-mentioned steps of the present invention.
Referring to Fig. 1, it is 3 that Fig. 1 is terbium europium mol ratio prepared by the embodiment of the present invention 1:1 europium terbium is co-doped with luminous porous material
Fluorescence response figure to the DPA of variable concentrations.It can be seen that the material that is co-doped with of embodiment 1 has ratio fluorescent to DPA
Response, the luminous of europium gradually weaken, and the luminous of terbium gradually strengthens, and is limited to 35 micromoles to the detection of DPA.
Embodiment 2
Step one：With embodiment 1；
Step 2：
The sample 1 prepared in step one is added to terbium europium molar ratio for 6:In the saturation DMF solution of 1 concentration, place
Overnight.Sucking filtration, is dried overnight at 120 DEG C, obtains final product europium terbium and is co-doped with luminous porous material.
It is co-doped with luminous porous material to detect to europium terbium prepared by above-mentioned steps of the present invention.
Referring to Fig. 2, it is 6 that Fig. 2 is terbium europium mol ratio prepared by the embodiment of the present invention 2:1 europium terbium is co-doped with luminous porous material
Fluorescence response figure to the DPA of variable concentrations.It can be seen that the material that is co-doped with of embodiment 2 has ratio fluorescent to DPA
Response, europium luminous gradually weaken the luminous of terbium gradually strengthen, 15 micromoles are limited to the detection of DPA.
Embodiment 3
Step one：With embodiment 1；
Step 2：
The sample 1 prepared in step one is added to terbium europium molar ratio for 9:In the saturation DMF solution of 1 concentration, place
Overnight.Sucking filtration, is dried overnight at 120 degree, obtains final product europium terbium and is co-doped with luminous porous material.
It is co-doped with luminous porous material to detect to europium terbium prepared by above-mentioned steps of the present invention.
Referring to Fig. 3, it is 9 that Fig. 3 is terbium europium mol ratio prepared by the embodiment of the present invention 3:1 europium terbium is co-doped with luminous porous material
Fluorescence response figure to the DPA of variable concentrations.As can be seen from the figure the material that is co-doped with of embodiment 3 has ratio fluorescent to DPA
Response, europium luminous gradually weaken the luminous of terbium gradually strengthen, 25 micromoles are limited to the detection of DPA.
Referring to Fig. 4, Fig. 4 is the X-ray diffractogram of luminous porous material prepared by the embodiment of the present invention.Wherein, (a) it is root
According to the X-ray diffractogram that architecture computer is fitted, (b) X-ray diffractogram of the sample 1 prepared for embodiment 1, it is (c) enforcement
Europium terbium prepared by example 1 is co-doped with the X-ray diffractogram of luminous porous material, and (d) the europium terbium prepared for embodiment 2 is co-doped with luminous porous
The X-ray diffractogram of material, (e) the europium terbium prepared for embodiment 3 be co-doped with the X-ray diffractogram of luminous porous material.Can by Fig. 4
To find out, after the present invention carries out rare-earth europium terbium ion exchange again, the framing structure of porous material is not affected.
To sum up, the present invention is prepared for europium terbium and is co-doped with luminous porous material, be used in combination using effective and feasible experimental technique
In the detection of anthrax bacillus biomarker DPA, from test result it can be seen that material has extraordinary ratio fluorescent to DPA
Response, can be used for the detection to DPA.
Above to the present invention provide a kind of europium terbium be co-doped with luminescent material and preparation method thereof, in Ratio-type fluoroscopic examination
Application be described in detail, specific case used herein is explained to the principle of the present invention and embodiment
State, the explanation of above example is only intended to help and understands the method for the present invention and its core concept, including best mode, and
Also so that any person skilled in the art can put into practice the present invention, including manufacturing and using any device or system and real
The method for applying any combination.It should be pointed out that for those skilled in the art, without departing from the principle of the invention
On the premise of, some improvement and modification can also be carried out to the present invention, these improvement and modification also fall into the claims in the present invention
Protection domain in.The scope of patent protection of the present invention is defined by the claims, and may include those skilled in the art's energy
The other embodiment that enough expects.If there is these other embodiments the structure for being not different from claim character express to want
Element, or if they include the equivalent structural elements with the character express of claim without essence difference, then these other
Embodiment should also include within the scope of the claims.
Claims (10)
1. a kind of europium terbium is co-doped with luminescent material, it is characterised in that including the water of compound shown in compound shown in formula I, Formulas I
One or more in the solvated compoundses of compound shown in compound and Formulas I：
Zn8(Adenine)4(BPDA)6O EuxTb1-xI；
Wherein 0.1 ＜ x ＜ 0.25；
The Adenine is adenine, and BPDA is 4,4'- biphenyl dicarboxylic acids.
2. europium terbium according to claim 1 is co-doped with luminous porous material, it is characterised in that the europium terbium is co-doped with luminescent material
Specific surface area be 745～1025m2/g；
0.15≤x≤0.2.
3. a kind of europium terbium is co-doped with the preparation method of luminescent material, it is characterised in that comprise the following steps：
A) after by adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc, strong acid and solvent hybrid reaction, middle product is obtained
Product；
B, after the intermediate products and terbium source europium source solution for) obtaining above-mentioned steps mix standing again, obtain europium terbium and be co-doped with luminous material
Material.
4. preparation method according to claim 3, it is characterised in that the strong acid is included in nitric acid, hydrochloric acid and sulphuric acid
One or more；
The solvent includes the one kind in N,N-dimethylformamide, water, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone
Or it is multiple；
The adenine is (0.2～0.7) with the mol ratio of the 4,4'- biphenyl dicarboxylic acids：1；
The two acetate hydrates zinc is (1.5～3.5) with the adenine mol ratio：1；
The strong acid is (5～10) with the adenine mol ratio：1；
The solvent is (300～1000) with the mol ratio of the adenine：1.
5. preparation method according to claim 3, it is characterised in that the terbium source includes halogenation terbium, Terbium nitrate (Tb(NO3)3) and oxalic acid
One or more in terbium；
The europium source includes one or more in europium halide, europium nitrate and oxalic acid europium；
The solvent of terbium source europium source solution includes N, N-dimethylformamide, water, methanol, ethanol, Methanamide and N- methylpyrroles
One or more in alkanone.
6. preparation method according to claim 3, it is characterised in that in the solution of the terbium source europium source, the terbium ion and
The mol ratio of the europium ion is (3～9)：1；
In the solution of the terbium source europium source, the terbium europium ion sum is (10～24) with the mol ratio of the adenine：1；
Terbium source europium source solution is terbium source saturated solution and europium source saturated solution, or is terbium source europium source saturated solution.
7. the preparation method according to claim 1～6 any one, it is characterised in that step A) it is specially：
A1) after by the mixing of adenine, 4,4'- biphenyl dicarboxylic acids, two acetate hydrate zinc and solvent, mixed liquor is obtained；
A2, after) mixed liquor for obtaining above-mentioned steps is reacted with strong acid, post processing obtains intermediate products.
8. preparation method according to claim 7, it is characterised in that the time of the mixing is 10～60 minutes；
The temperature of the reaction is 85～150 DEG C；
The time of the reaction is 24～96 hours.
9. preparation method according to claim 8, it is characterised in that the post processing includes cooling down, filter, wash and doing
One or more in dry；The temperature of the drying is 100～150 DEG C；
The time of the standing is more than or equal to 10 hours；Also include filtering and drying steps after the standing；The temperature of the drying
Spend for 100～150 DEG C.
10. the europium terbium described in claim 1～2 any one is co-doped with prepared by luminescent material or claim 3～9 any one
Europium terbium be co-doped with application of the luminescent material in terms of Ratio-type fluoroscopic examination anthrax bacillus biomarker.
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