CN110128674A - It is a kind of for fluorescence detection sulfa antibiotics, the rare earth metal organic framework materials that water is stable and preparation method thereof - Google Patents
It is a kind of for fluorescence detection sulfa antibiotics, the rare earth metal organic framework materials that water is stable and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of for fluorescence detection sulfa antibiotics, rare earth metal organic framework materials that water is stable preparation method, with N, N '-two (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide is ligand, rare-earth europium ion is that metal center passes through the solvent structure rare earth metal organic framework materials.The preparation method for the rare earth metal organic framework materials that the present invention synthesizes is simple, with high purity, activity is good, after drying collection, can be used to detect, eliminates the cumbersome last handling process such as high temperature or vacuum activating.The rare earth metal organic framework materials water stability that the present invention synthesizes is good, impregnates frame structure after two weeks in water and remains unchanged, and is conducive to practical application.The rare earth metal organic framework materials that the present invention synthesizes have many advantages, such as quick, easy, selectivity good, high sensitivity, recyclable regenerative in terms of detecting sulfa antibiotics.
Description
Technical field
The invention belongs to metal-organic framework material fields, and in particular to a kind of rare earth metal organic frame material that water is stable
Material preparing and its detecting to the fluorescence sense of sulfa antibiotics in water.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Sulfa antibiotics (SAs) have has a broad antifungal spectrum, it is curative for effect, using easy and wide in variety, yield greatly, price
The advantages that low, convenient for long-term preservation, is widely used in medical clinical and animal husbandry.However, such drug has simultaneously
There is the deficiency of bio-refractory, it is easy to be discharged into water and soil in a manner of drug prototype or metabolin, cause ambient water
The slow poisonings such as microorganism, fish in body and bed mud finally will lead to allergy, drug resistance and be swashed after food chain enters human body
Phenomena such as plain diacrisis, occurs.Therefore, the detection technique for developing sulfa antibiotics in water, to preserving the ecological environment and ensure
Human health is of great significance.Currently, the detection method for sulfa antibiotics mainly has high performance liquid chromatography, liquid phase
Chromatographic tandem mass spectrography, electrochemical process, ultraviolet spectrophotometry etc., but there is pretreatment complexity in these methods, instrument is held high mostly
Expensive, the problems such as time-consuming, sensitivity is low.In contrast, fluorescence detection is changing using fluorescence signal (such as wavelength, intensity)
Become to achieve the purpose that analysis detection, has many advantages, such as easy to operate, fast response time, high sensitivity.Fluorescent instrument has been
Highly developed equipment, at present, the key of fluorescence detection are the new materials that exploitation has fluorescence detection function.
In recent years, metal-organic framework material (Metal-Organic Frameworks, MOFs) is due to its good object
Reason and chemical property receive significant attention.Such material is that a kind of utilize has made of metal ion and organic ligand self assembly
The novel porous crystalline material of grid-structure, have it is convieniently synthesized, stability is high, large specific surface area, pore size and
The features such as reconfigurable is a kind of ideal fluorescent sensing material.Rare earth MOFs material with Stokes shift, send out by big, feature
The features such as peak is narrow, fluorescence lifetime is long is penetrated, has important application prospect in fluorescence detection field.Zhou etc. once reports an example
The metal-organic framework material of terbium, zinc, fluorescence sense detection result of study show: the material is to furazolidone, furans west in water
The Nitrofuran metabolites such as woods, furantoin have good detection performance (referring to Zhou Z.H. etc.,
Inorg.Chem.2018,57,3833)；Han etc. once reports the metal-organic framework material of an example sodium, europium, fluorescence sense inspection
Result of study is surveyed to show: the material to Ornidazole in water etc. have good selective enumeration method ability (referring to Han M.L. etc.,
J.Mater.Chem.C,2017,5,8469).However, the rare earth metal organic frame material for detecting sulfa antibiotics in water
Material, yet there are no report.
Summary of the invention
To solve the above-mentioned problems, the object of the present invention is to provide a kind of metal organic frame new materials of europium that water is stable
And preparation method thereof, and successfully detect the fluorescence sense that the material is used for sulfa antibiotics in water.It is provided by the invention dilute
Earth metal organic framework materials preparation method is simple, purity is high, and activity is good, and water stability is strong；In the detection of sulfa antibiotics
Aspect has many advantages, such as quick, easy, selectivity good, high sensitivity, recyclable regenerative.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
It is a kind of for fluorescence detection sulfa antibiotics, rare earth metal organic framework materials that water is stable, the rare earth
The chemical formula of metal-organic framework material are as follows: [Eu2(L)3(H2O)2]n, n is the natural number of non-zero, in formula: H2L is N, N '-two
(4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide ligand, structural formula are as follows:
The application research discovery: rare-earth europium and N, N '-two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimide ligand
The special space structure formed makes metal-organic framework material be easier to send out to the electronics transfer between SNT (electron acceptor)
It is raw, to obtain higher fluorescent quenching efficiency；Meanwhile the metal-organic framework material also has stronger water stability, because
This can satisfy the testing requirements of trace sulfa antibiotics in Complex Water Environment.
In some embodiments, the sulfa antibiotics are sulfanitran (SNT), sulphathiazole (STZ), sulphadiazine
(SDZ), sulfamethoxazole (SMX), daimeton (SMM) or sulfadimidine (SMZ).
In the specific embodiment of the application, the sulfa antibiotics are preferably sulfanitran SNT.
The present invention also provides a kind of for fluorescence detection sulfa antibiotics, rare earth metal organic frame that water is stable
The preparation method of material, with N, N '-two (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide is ligand, rare-earth europium ion is
Metal center synthesizing rare-earth metal-organic framework material.Material after collection can be used to detect, and eliminate high temperature or vacuum
The cumbersome last handling processes such as activation show that experiment synthetic material activity is good.
The application research discovery: due to N, carboxylic in N '-two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimide ligand
Polymerization of olefin using catalyst oxygen atom can form strong europium oxygen key with the rare-earth europium (III) of oxyphie；And the hydrophobic methyl connected on the ligand
Group has spatial masking effect to hydrone, further protects europium oxygen key, therefore, the metal-organic framework material of preparation exists
Water stability is stronger, impregnates frame structure after two weeks in water and remains unchanged, and is conducive to practical application, as shown in Figure 2.
Metal ion and organic ligand have conclusive effect to the final structure of metal organic framework compound.It is different
Metal ion and organic ligand the gold of different topology structure can be obtained due to the difference of coordinationization environment, ligancy, coordination site
Belong to organic frame compound.Therefore, in some embodiments, the europium salt is europium nitrate (III) hexahydrate, to obtain expection
The metal-organic framework material of structure.
The difference of the molar ratio of metal ion and ligand can cause the change of metallic ion coordination number and coordination configuration, thus
Obtain the structure of monokaryon, double-core and multicore.Therefore, in some embodiments, europium salt and the (4- carboxyl -2- methylbenzene of N, N '-two
Base)-Isosorbide-5-Nitrae-aphthalimide molar ratio is 1~3:3, to effectively improve the selectivity, sensitive of metal-organic framework material
Degree and water stability.
Do not make special restriction in the application to the synthetic method of metal-organic framework material, can be common diffusion
Method (including the diffusion of gas phase diffusion, liquid phase and gel diffusion), volatility process and hydrothermal/solvent heat, are also possible to ultrasonic,
Ionic liquid method, solid reaction process, the new methods such as sublimed method, microwave process for synthesizing and two-phase synthetic method.In some embodiments, institute
Stating synthetic method is solvent-thermal method, and actual conditions are crystallization 48~72 hours at 100~130 DEG C.
Solvent has very big influence to the formation of crystal, while influencing ligand solubility, may also participate in coordination.Cause
This, in some embodiments, the solvent of solvent-thermal method is the mixed liquor of n,N-Dimethylformamide, distilled water, the volume of the two
Than promoting crystal nucleation for 1:1~2 to improve reaction efficiency.
The present invention also provides any above-mentioned method preparation for fluorescence detection sulfa antibiotics, water it is stable
Rare earth metal organic framework materials.
The present invention also provides a kind of methods of sulfa antibiotics in detection water, comprising:
Any above-mentioned rare earth metal organic framework materials are dispersed in water, its emission spectrum is measured, certain is then added
One sulfa antibiotics solution carries out fluorescence titration, records fluorescence intensity change, carries out with the fluorescence intensity of respective standard sample
It compares, determines the content of the sulfa antibiotics.
The present invention also provides a kind of fluorescent optical sensors of sulfa antibiotics in detection water, including any above-mentioned rare earth
Metal-organic framework material.
The beneficial effects of the present invention are:
(1) preparation method for the rare earth metal organic framework materials that the present invention synthesizes is simple, with high purity, activity is good, through drying in the air
After dry collection, it can be used to detect, eliminate the cumbersome last handling process such as high temperature or vacuum activating.
(2) the rare earth metal organic framework materials water stability that the present invention synthesizes is high, impregnates frame knot after two weeks in water
Structure remains unchanged, and is conducive to practical application.
(3) the rare earth metal organic framework materials that the present invention synthesizes have quick, letter in terms of detecting sulfa antibiotics
Just, the advantages that selectivity good, high sensitivity, recyclable regenerative.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the tomograph of rare earth metal organic framework materials synthesized by embodiment 1.
Fig. 2 is rare earth metal organic framework materials synthesized by embodiment 1 and single crystal data simulation and is immersed in distillation
X-ray powder diffraction figure in water after two weeks.
Fig. 3 is fluorogram of the rare earth metal organic framework materials synthesized by embodiment 1 to various concentration SNT solution.
Fig. 4 is rare earth metal organic framework materials fluorescence intensity I of the SNT concentration to embodiment 10The curve graph of/I, illustration
It is SNT concentration to the rare earth metal organic framework materials fluorescence intensity I of embodiment 10The Stern-Volmer linear graph of/I
([SNT]≤7.4μmol/L)。
Fig. 5 is circular regeneration detection curve of the rare earth metal organic framework materials synthesized by embodiment 1 to SNT.
Fig. 6 is rare earth metal organic framework materials synthesized by embodiment 1 to different sulfa antibiotics fluorescence response columns
Shape comparison diagram.
Fig. 7 is rare earth metal organic framework materials fluorescent quenching efficiency synthesized by embodiment 1 with being alternately added other sulphurs
The line chart of amine antibiotic and SNT volume change.
Fig. 8 is the HOMO and lumo energy figure of sulfa antibiotics.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used in this application have logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
In the examples where no specific technique or condition is specified, according to the literature in the art described technology or conditions or
Person carries out according to product description.Reagents or instruments used without specified manufacturer, being can be by the normal of commercially available acquisition
Advise product.
As background technique is introduced, have for the rare earth metal for lacking fluorescence detection sulfa antibiotics in water at present
The problem of machine frame.Therefore, the present invention proposes a kind of rare earth metal organic frame new material for detecting sulfa antibiotics in water
And preparation method thereof.
The first aspect of the invention provides a kind of rare earth metal organic frame green wood for detecting sulfa antibiotics in water
Material, the three-dimensional structure of crystal are as shown in Figure 1.
Preferably, the antibiotic includes but is not limited to sulfanitran (SNT), sulphathiazole (STZ), sulphadiazine
(SDZ), sulfamethoxazole (SMX), daimeton (SMM) or sulfadimidine (SMZ)；
Most preferably, the antibiotic is sulfanitran (SNT).
The second aspect of the invention provides the rare earth metal organic framework materials of sulfa antibiotics in above-mentioned detection water
Preparation method, the material uses solvent by europium salt and (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide of N, N '-two
Thermal method is prepared.
Preferably, the europium salt is europium nitrate (III) hexahydrate.
Preferably, the europium salt and (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide dosage of N, N '-two press metal
Ion and organic ligand molar ratio are 1~3:3.
Preferably, the reaction condition of the solvent-thermal method are as follows: at 100~130 DEG C, crystallization 48~72 hours.
Preferably, the solvent is the mixed solvent of n,N-Dimethylformamide, distilled water, and volume ratio is 1:1~2.
It is specific the preparation method is as follows:
S1. europium salt and N, N '-two (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide are dissolved in solvent, by crystalline substance
After changing reaction, colorless and transparent bulk crystals are obtained；
S2. product in step S1 is filtered, is washed with distilled water, dries at room temperature, collected, obtaining rare earth metal has machine frame
Frame material.Material after collection can be used to detect, and eliminate the cumbersome last handling process such as high temperature or vacuum activating, table
Bright experiment synthetic material activity is good.
In still another embodiment of the invention, in the step S1, europium salt is europium nitrate (III) hexahydrate；It is molten
Agent is the mixed solvent of N,N-dimethylformamide, distilled water.
In still another embodiment of the invention, in the step S1, europium nitrate (III) hexahydrate and organic ligand
Molar ratio be 2:3, solvent is the mixed solvent of n,N-Dimethylformamide, distilled water, volume ratio 1:1.5, and reaction is warm
Degree is 120 DEG C, and the reaction time is 72 hours.
The third aspect of the invention provides the rare earth metal organic framework materials that the above method is prepared.
The fourth aspect of the invention provides the detection side that above-mentioned rare earth metal organic framework materials have good water stability
Method, comprising: above-mentioned material is impregnated after two weeks in distilled water, is tested through X-ray powder diffraction.The result shows that X-ray
Significant change does not occur for the peak position that powder diagram is shown.
The fifth aspect of the invention provides above-mentioned rare earth metal organic framework materials sulfa antibiotics in detection water
Application.
In still another embodiment of the invention, a kind of rare earth metal organic frame prepared using above method is provided
Material.The material has good detection performance to sulfa antibiotics.
Preferably, the application method are as follows: above-mentioned rare earth metal organic framework materials are dispersed in water, its transmitting is measured
Then spectrum is added a certain sulfa antibiotics solution and carries out fluorescence titration, fluorescence intensity change recorded, with respective standard sample
Fluorescence intensity be compared, determine the content of the sulfa antibiotics.
The sixth aspect of the invention provides the recovery method of above-mentioned rare earth metal organic framework materials, comprising: will test
Rare earth metal organic framework materials distilled water immersion after sulfa antibiotics after ultrasonic cleaning 3 times, dries, recycling is stand-by.
Specific step is as follows:
Firstly, taking rare earth metal organic framework materials after the recovery, disperse it in distilled water again, it is initial glimmering to survey it
Then SNT is added in luminous intensity, then survey its fluorescence intensity, discovery recycling after material initial fluorescent intensity and be added SNT after it is glimmering
Luminous intensity and the fluorescence intensity after the initial fluorescent intensity and addition SNT of freshly prepd rare earth metal organic framework materials are almost complete
It is exactly the same, it repeats the above experiment process 5 times, does not find significant change.Therefore, rare earth metal organic frame provided by the invention
Material is a kind of material that recyclable regenerative utilizes.
The seventh aspect of the invention provides above-mentioned rare earth metal organic framework materials SNT in highly selective detection water
Application.
Preferably, the application method are as follows: the rare earth metal organic framework materials for weighing 0.5mg are scattered in 1ml steaming
In distilled water, its emission spectrum is measured；Then with microsyringe be added 20 μ L (point 2 times, every time 10 μ L) STZ solution (1.0 ×
10-4Mol/L) in Yu Shangshu dispersion liquid, then be added into the dispersion liquid 20 μ L (point 2 times, every time 10 μ L) SNT solution (1.0 ×
10-4Mol/L), STZ and SNT solution is successively alternately added according to above-mentioned steps, until accumulation addition each 60 μ L of STZ and SNT is
Only.By above-mentioned experimental program, replace STZ with SDZ, SMX, SMM, SMZ respectively, obtain the fluorescent quenching efficiency of synthesized material with
It is alternately added the line chart of other sulfa antibiotics and SNT volume change.SNT is added compared to the other sulfamido antibiosis of addition
Element, great changes have taken place for slope, it was demonstrated that material of the present invention has highly selective fluorescence sense detection performance to SNT.
It is described below by way of scheme of the specific embodiment to the application.
Embodiment 1
Synthesizing rare-earth metal-organic framework material: 29.7mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixed of 1ml N,N-dimethylformamide and 1.5ml distilled water
In bonding solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 120 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 80%.The three-dimensional structure of crystal is as shown in Figure 1.Material after collection eliminates height that is, for detecting
The cumbersome last handling process such as temperature or vacuum activating shows that experiment synthetic material activity is good.As shown in Fig. 2, the material experiment
It is almost the same with the peak position of the X-ray powder diffraction of simulation, show to test synthesized crystalline material purity higher.By the material
Material impregnates after two weeks in distilled water, shows the peak position that its X-ray powder diffraction figure is shown through X-ray powder diffraction test
Significant change does not occur, illustrates that the frame structure of the material remains unchanged, therefore, the rare earth metal organic frame that the present invention synthesizes
Material water stability with higher.
Embodiment 2
Synthesizing rare-earth metal-organic framework material: 14.9mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixed of 1ml N,N-dimethylformamide and 1.5ml distilled water
In bonding solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 120 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 61%.
Embodiment 3
Synthesizing rare-earth metal-organic framework material: 44.6mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixed of 1ml N,N-dimethylformamide and 1.5ml distilled water
In bonding solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 120 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 73%.
Embodiment 4
Synthesizing rare-earth metal-organic framework material: 29.7mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixing of 1ml N,N-dimethylformamide and 1ml distilled water
In solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 120 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 59%.
Embodiment 5
Synthesizing rare-earth metal-organic framework material: 29.7mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixing of 1ml N,N-dimethylformamide and 2ml distilled water
In solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 120 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 63%.
Embodiment 6
Synthesizing rare-earth metal-organic framework material: 29.7mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixed of 1ml N,N-dimethylformamide and 1.5ml distilled water
In bonding solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 120 DEG C
48h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 46%.
Embodiment 7
Synthesizing rare-earth metal-organic framework material: 29.7mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixed of 1ml N,N-dimethylformamide and 1.5ml distilled water
In bonding solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 100 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 45%.
Embodiment 8
Synthesizing rare-earth metal-organic framework material: 29.7mg europium nitrate (III) hexahydrate and 48.2mg N, N '-are weighed
Two (4- carboxyl -2- aminomethyl phenyl) -1,4- aphthalimides are dissolved in the mixed of 1ml N,N-dimethylformamide and 1.5ml distilled water
In bonding solvent, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene after ultrasonic dissolution, the isothermal reaction at 130 DEG C
72h is at the uniform velocity cooled to room temperature with 5 DEG C/h, obtains transparent cake crystal.Product is filtered, and is washed with distilled water, is dried in the air at room temperature
It is dry, it collects, yield is about 55%.
Embodiment 9
The rare earth metal organic framework materials for weighing the preparation of 0.5mg embodiment 1 are scattered in 1ml distilled water, measure its hair
Penetrate spectrum.Then with microsyringe successively accumulate addition 10,20,30,40,50,60,70,80,90,100,120,140,
160,180,200 μ L SNT solution (1.0 × 10-4Mol/L), its fluorescence emission spectrum is surveyed respectively.As shown in figure 3, embodiment 1
The maximum emission wavelength of rare earth metal organic framework materials in water be 615nm, fluorescence intensity with the increase of SNT concentration and
It is gradually reduced.When SNT concentration reaches 16.7 μm of ol/L, quenching degree is 94%.As shown in the illustration of Fig. 4, I0/ I is in [Q]
Good linear relationship, and obtaining its Stern-Volmer quenching constant is 5.7 × 105L/mol (Stern-Volmer equation:
I0/ I=1+KSV[Q], wherein I0For the initial fluorescent intensity of rare earth metal organic framework materials, rare earth gold in the presence of I is SNT
Belong to the fluorescence intensity of organic framework materials, [Q] is the concentration of SNT, KSVFor Stern-Volmer quenching constant).In identical reality
Under the conditions of testing, the fluorescence intensity I of rare earth metal organic framework materials in the presence of object to be detected need to be only measured, and calculates I0/ I,
The concentration [Q] of object SNT to be detected can be obtained according to standard curve.
Embodiment 10
After embodiment 9 is used to detect the material distilled water immersion of SNT, is cleaned by ultrasonic 3 times, dry, recycling is stand-by.It takes
Rare earth metal organic framework materials after the recovery, are scattered in distilled water, and successively accumulation be added 200 μ L SNT solution (1.0 ×
10-4Mol/L it) in Yu Shangshu dispersion liquid, finds the initial fluorescent intensity of the salvage material and the fluorescence intensity after SNT and new is added
The initial fluorescent intensity of the rare earth metal organic framework materials of preparation and the fluorescence intensity after addition SNT are nearly identical, weight
It multiple the above experimentation 5 times, does not find significant change (Fig. 5), it is reproducible, recyclable to show that material of the present invention has
The advantages of.
Embodiment 11
By experimental program described in embodiment 9, respectively to other sulfa antibiotics: STZ, SDZ, SMX, SMM, SMZ are carried out
Fluorescent quenching research, and be compared with the fluorescent quenching effect of SNT.Fig. 6 is that rare earth metal synthesized by embodiment 1 is organic
Frame material to different sulfa antibiotics fluorescence response cylindricality comparison diagrams, from fig. 6 it can be seen that material of the present invention to STZ,
The quenching effect of SDZ, SMX, SMM, SMZ can not show a candle to that SNT is obvious, and it is highly selective to illustrate that the material has the SNT in detection water.
Further to prove material of the present invention to the highly selective of SNT, the rare earth metal for weighing the embodiment 1 of 0.5mg has
Machine frame frame material is scattered in 1ml distilled water, its emission spectrum is measured, and 20 μ L then are added with microsyringe and (divide 2
It is secondary, 10 μ L every time) STZ solution (1.0 × 10-4Mol/L) in Yu Shangshu dispersion liquid, then 20 μ L is added into the dispersion liquid and (divide 2
It is secondary, 10 μ L every time) SNT solution (1.0 × 10-4Mol/L), STZ and SNT solution is successively alternately added according to above-mentioned steps, until
Until each 60 μ L of STZ and SNT is added in accumulation.By above-mentioned experimental program, STZ is replaced with SDZ, SMX, SMM, SMZ respectively, obtains institute
The fluorescent quenching efficiency of synthetic material is with the line chart for being alternately added other sulfa antibiotics and SNT volume change.It can from Fig. 7
Know, SNT is added compared to other sulfa antibiotics are added, great changes have taken place for slope, further demonstrates material of the present invention to SNT
It is highly selective.
The application verifies above-mentioned experimental result also in terms of mechanism, and the nitryl group contained in SNT is strong
Electron-withdrawing group, so that SNT is more easily accepted by electronics than other sulfa antibiotics, and metal-organic framework material is typically good
Good electron donor, therefore, under illumination condition, it is easier to occur (electric from metal-organic framework material (electron donor) to SNT
Sub- receptor) between electronics transfer (PET effect), so as to cause the fluorescent quenching efficiency highest of SNT.In addition, general by density
Letter theory (DFT) calculates, it is found that the lumo energy sequence of sulfa antibiotics is SNT > STZ ≈ SDZ > SMX ≈ SMM ≈ SMZ
(Fig. 8), showing that SNT connects nucleophobic ability will be strong than the ability of other sulfa antibiotics molecules, this with test it is resulting
Fluorescent quenching efficiencies are almost the same.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (10)
1. a kind of for fluorescence detection sulfa antibiotics, rare earth metal organic framework materials that water is stable, which is characterized in that
The chemical formula of the rare earth metal organic framework materials are as follows: [Eu2(L)3(H2O)2]n, n is the natural number of non-zero, in formula: H2L is
N, N '-two (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide ligand, structural formula are as follows:
2. rare earth metal organic framework materials as described in claim 1, which is characterized in that the sulfa antibiotics are sulfanilamide (SN)
Nitre benzene SNT, sulphathiazole STZ, sulphadiazine SDZ, sulfamethoxazole SMX, daimeton SMM or sulfadimidine
SMZ。
3. it is a kind of for fluorescence detection sulfa antibiotics, rare earth metal organic framework materials that water is stable preparation method,
It is characterized in that, N '-two (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide is ligand, rare-earth europium ion is metal with N
Center synthesizing rare-earth metal-organic framework material.
4. rare earth metal organic frame material that be used for fluorescence detection sulfa antibiotics as claimed in claim 3, that water is stable
The preparation method of material, which is characterized in that europium salt and N, N '-two (4- carboxyl -2- aminomethyl phenyl)-Isosorbide-5-Nitrae-aphthalimide mole
Than for 1~3:3.
5. rare earth metal organic frame material that be used for fluorescence detection sulfa antibiotics as claimed in claim 4, that water is stable
The preparation method of material, which is characterized in that the europium salt is europium nitrate (III) hexahydrate.
6. rare earth metal organic frame material that be used for fluorescence detection sulfa antibiotics as claimed in claim 4, that water is stable
The preparation method of material, which is characterized in that the synthetic method is solvent-thermal method, and actual conditions are at 100~130 DEG C, and crystallization is anti-
It answers 48~72 hours.
7. rare earth metal organic frame material that be used for fluorescence detection sulfa antibiotics as claimed in claim 4, that water is stable
The preparation method of material, which is characterized in that the solvent of solvent-thermal method is the mixed liquor of n,N-Dimethylformamide, distilled water, the two
Volume ratio be 1:1~2.
8. claim 3-7 described in any item methods preparation for fluorescence detection sulfa antibiotics, that water is stable is dilute
Earth metal organic framework materials.
9. a kind of method of sulfa antibiotics in detection water characterized by comprising
Claim 1,2 or 8 described in any item rare earth metal organic framework materials are dispersed in water, it is measured and emits light
Then spectrum is added a certain sulfa antibiotics solution and carries out fluorescence titration, fluorescence intensity change recorded, with respective standard sample
Fluorescence intensity is compared, and determines the content of the sulfa antibiotics.
10. the fluorescent optical sensor of sulfa antibiotics in a kind of detection water, which is characterized in that any including claim 1,2 or 8
Rare earth metal organic framework materials described in.
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| CN116239783A (en) * | 2023-01-16 | 2023-06-09 | 福州大学 | Double-emission rare earth metal organic framework material for detecting heavy metal lead ions and sulfonamides |
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