CN109596593A - A kind of method of Nitrofuran antibiotics or quinolone antibiotics in detection drinking water - Google Patents
A kind of method of Nitrofuran antibiotics or quinolone antibiotics in detection drinking water Download PDFInfo
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- CN109596593A CN109596593A CN201910107634.XA CN201910107634A CN109596593A CN 109596593 A CN109596593 A CN 109596593A CN 201910107634 A CN201910107634 A CN 201910107634A CN 109596593 A CN109596593 A CN 109596593A
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- dcpcpt
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- drinking water
- dispersion liquid
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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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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"
- G01N2021/6432—Quenching
Abstract
A kind of method of Nitrofuran antibiotics or quinolone antibiotics in detection drinking water, the method for being related to detecting antibiotic in drinking water.There is the unstability to excitation wavelength dependence for existing lanthanide series metal-organic backbone in the present invention, and the method for existing measurement antibiotic, in the presence of special instrument is needed, pre-treatment is cumbersome, the high problem of operating cost.Detection method: one, Tb-dcpcpt crystal is prepared；Two, RhB@Tb-dcpcpt composite material is prepared；Three, RhB@Tb-dcpcpt dispersion liquid is prepared；Four, fluorescence detection.The present invention is for detecting Nitrofuran antibiotics or quinolone antibiotics in drinking water.
Description
Technical field
The present invention relates to the methods of antibiotic in detection drinking water.
Background technique
Lanthanide series metal-organic backbone (Ln-MOFs) is to pass through coordinate bond by the inorganic node of multiple tooth key and rare earth ion certainly
The lenticular organic/inorganic hybridization material with characteristic luminescence performance assembled.In Ln-MOFs, by adjusting ligand
To the energy transmission (antenna effect) of lanthanide ion, multi-emitting characteristic can be easily obtained, thus shining for Ln-MOFs
A sensitive platform is provided in terms of color and intensity.On the other hand, the sensibility of coordination environment results in Ln-MOFs hair again
The unstability of light.Using its unstability, Ln-MOFs can be used as the sensing of the environmental factors such as temperature, pH value, solvent effect
Device, this sensor are used as sensitive thermometer, pH indicator and solvent probe by wide coverage.However, to excitation wave
The unstability of long dependence is seldom resolved and utilizes.
Porosity is a determinant attribute of Ln-MOFs, facilitates the fluorogen encapsulated, and especially has excitation wave
The luminescent dye molecule of long unrelated performance, to construct ground state atom by ion exchange process and/or space restriction effect.It is logical
Cross and fluorescent dye be introduced into porous Ln-MOFs, double uniform multi-emitting dyestuff Ln-MOF composite materials, this be only design with
The unrelated luminescent material of excitation wavelength provides a new approach, and is total by the electronics transfer and fluorescence of photon induced
Vibration energy transmission obtains durable and sensitive sensor and provides chance.Difference analysis to each component part of multi-emitting sensor
The disturbance of object may change the luminescent color and emissive porwer ratio of element, to provide an easy and convenient ground distinguishing sequence group
The active platform of component in conjunction.By considering shine-to change colour simultaneously and opening/closing process, can be easily carried out more
Selection, which shines, to be sensed.But the multi-selection material or composite material seldom quilt of the influence of the wavelength that is not stimulated based on Ln-MOFs
Report, meanwhile, the network analysis to sensor mechanism is still a very big challenge to the development of such sensor.
In addition, antibiotic is the important drugs for preventing and treating certain diseases, especially to bacterium infection in water environment
Drug resistance.However, there are more antibiotic in grain, animal body even drinking water due to the extensive use of antibiotic
Residual.Taking in these contaminated foods for a long time may cause serious disease, and such as immunity degradation, allergic reaction, heredity is lost
Pass defect and various types of cancers.Currently, having developed various costly and complicated methods to measure antibiotic, such as chromatography
Technology, optical sensor, electrochemical sensor and biosensor.Although these technologies have very in terms of sensitivity and selectivity
Big advantage, but these technologies are necessarily required to special instrument, and pre-treatment is cumbersome, and operating cost is high.Therefore, as luminous sensing
Device, dyestuff@Ln-MOF can provide a kind of easy, high sensitivity antibiotic detection method.In addition, resisting in real world
The mixture of raw element is frequently present of.Therefore, the luminous sensing of the multi-selection of antibiotic has great importance and chooses in aqueous solution
War property.
Summary of the invention
The present invention exists to solve existing lanthanide series metal-organic backbone to the unstable of excitation wavelength dependence, and existing
Special instrument is needed with the presence of the method for measurement antibiotic, pre-treatment is cumbersome, and the high problem of operating cost provides a kind of detection
The method of Nitrofuran antibiotics or quinolone antibiotics in drinking water.
In a kind of detection drinking water the method for Nitrofuran antibiotics or quinolone antibiotics according to the following steps into
Row:
One, Tb-dcpcpt crystal is prepared:
1., by Tb (NO3)3·6H2O, three nitrogen of 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4-
Azoles, N, N '-dimethyl formamide and H2O mixing, obtains mixture, mixture is placed in pyroreaction kettle, is 150 in temperature
DEG C~200 DEG C under conditions of, sealing for 24 hours~72h carry out solvent thermal reaction, obtain crystal prototype；
3- (3,5- dicarboxyphenyi) -5- (4- the carboxyl phenyl) -1- hydrogen -1,2,4- triazole and Tb (NO3)3·
6H2The molar ratio of O is 1:(0.5~2)；3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4-
Triazole mole and N, the volume ratio of N '-dimethyl formamide be 0.1mmol:(5~10) mL；The N, N '-dimethyl
Formamide and H2The volume ratio of O is 1:(0.1~2)；
2., crystal prototype N, N '-dimethyl formamide and ethyl alcohol washed 3 times~5 times respectively, obtain Tb-dcpcpt
Crystal；
Two, RhB@Tb-dcpcpt composite material is prepared:
It is 10 that Tb-dcpcpt crystal, which is impregnated in concentration,-4Mol/L~10-5In the rhodamine B aqueous solution of mol/L, keep
12h~48h obtains pink crystal, pink crystal is rinsed, and dried in air with deionized water, obtains RhB Tb-
Dcpcpt composite material；
Three, RhB@Tb-dcpcpt dispersion liquid is prepared:
Under agitation, RhB@Tb-dcpcpt composite material is dispersed in water, obtains RhB@Tb-dcpcpt dispersion
Liquid；
The concentration of the RhB@Tb-dcpcpt dispersion liquid is 0.1g/L~10g/L；
Four, fluorescence detection:
Drinking water is mixed with RhB Tb-dcpcpt dispersion liquid, obtains drinking water to be detected, drinking water to be detected is used
Wavelength is the ultraviolet light of 300nm~390nm, observes solution colour；
The volume ratio of the drinking water and RhB@Tb-dcpcpt dispersion liquid is 1:(0.5~2)；
Contain Nitrofuran antibiotics or quinolone antibiotics in the drinking water；
When containing Nitrofuran antibiotics in the drinking water, and in drinking water Nitrofuran antibiotics concentration
When higher than 0.502 μm of ol/L, by yellow light fluorescent quenching occurs for solution colour；
When containing quinolone antibiotics in the drinking water, and the concentration of quinolone antibiotics is higher than in drinking water
When 0.448 μm of ol/L, solution colour is first become white from yellow, then becomes blue.
Step 1 of the present invention 1. described in 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4- three
Nitrogen azoles, English name be 3- (3,5-dicarboxylphenyl) -5- (4-carboxylphenyl) -1H-1,2,4-
Triazole, 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2 in the present invention, 4- triazole is abbreviated as
H3dcpcpt。
The molecular formula of 2. Tb-dcpcpt crystal that step 1 of the present invention is prepared is [(CH3)2NH2][Tb3(dcpcpt)3
(HCOO)]·DMF·15H2O is abbreviated as Tb-dcpcpt.
Beneficial effects of the present invention:
Select [(CH3)2NH2][Tb3(dcpcpt)3(HCOO)]·DMF·15H2The anion frame of O (Tb-dcpcpt)
RhB@Tb-dcpcpt composite material is prepared for the rhodamine B dye of positive ion (RhB).The composite material have Tb-dcpcpt and
The common of RhB shines, and lasting yellow emission is generated under the excitation of 300nm~390nm.It is shone to 14 kinds of antibiotic
Detection, either to the luminous intensity of Nitrofuran antibiotics, or to the luminescent color of quinolone antibiotics, all shows
Good distinguishing ability out.The sensing behavior has good sensitivity, selectivity and recuperability, by excitation wavelength
Influence very little.
Cationic RhB is fixed in the channel anion Ln-MOF by ion exchange, successfully synthesized it is a kind of with it is sharp
Send out the unrelated Yellow luminous composite material of wavelength.The composite material is with higher to Nitrofuran antibiotics (NZF and NFT)
Sensitivity and selective enumeration method ability.In addition, to quinolone antibiotics (CPFX and NFX), RhB@Tb-dcpcpt is also showed that
To the apparent-color change process that shines of blue from yellow to white.Influence very little of the excitation wavelength to sensing behavior.This is multiple
Condensation material detection limit is low, and (the detection limit to NZF and NFT is respectively 0.502 μm of ol/L and 0.448 μm of ol/L, to CPFX's and NFX
Detection limit is respectively 2.16 μm of ol/L and 0.63 μm of ol/L), stability is good, good, the recoverable of selectivity, is before one kind has very much
The furans and quinolone antibiotics sensor on way have potential practical value in terms of water quality monitoring.
Detailed description of the invention
Fig. 1 is X-ray powder diffraction spectrogram, and 1 is real for the RhB@Tb-dcpcpt composite material of one step 2 of embodiment preparation
X-ray powder diffraction curve is surveyed, 2 survey X-ray powder diffraction song for the Tb-dcpcpt crystal of one step 1 of embodiment preparation
Line, 3 are fitted X-ray powder diffraction curve for Tb-dcpcpt crystal；
Fig. 2 is that spectrogram is desorbed in nitrogen adsorption, and the 1 Tb-dcpcpt crystal prepared for one step 1 of embodiment, 2 be embodiment
The RhB@Tb-dcpcpt composite material of one step 2 preparation；
Fig. 3 is ultraviolet-visible absorption spectra figure, and the 1 Tb-dcpcpt crystal prepared for one step 1 of embodiment, 2 be rhodamine
B, 3 be the filtered RhB@Tb-dcpcpt composite material of aqueous solution；
Fig. 4 is the Tb-dcpcpt crystalline solid three-dimensional fluorescence spectrogram of one step 1 of embodiment preparation；
Fig. 5 is the RhB@Tb-dcpcpt composite material solid three-dimensional fluorogram of one step 2 of embodiment preparation；
Fig. 6 is the RhB@Tb-dcpcpt composite material and the filtered RhB@Tb- of aqueous solution of one step 2 of embodiment preparation
Dcpcpt composite material surveys X-ray powder diffraction spectrogram, and 1 is compound for the RhB@Tb-dcpcpt of one step 2 of embodiment preparation
Material, 2 be the filtered RhB@Tb-dcpcpt composite material of aqueous solution；
Fig. 7 is fluorogram under RhB@Tb-dcpcpt dispersion liquid difference excitation wavelength prepared by one step 3 of embodiment；
Fig. 8 is glimmering after the aqueous solution containing NZF is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Spectrogram, the 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment, the 2 RhB@prepared for one step 3 of embodiment
The aqueous solution containing NZF is added in Tb-dcpcpt dispersion liquid；
Fig. 9 is glimmering after the aqueous solution containing NFT is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Spectrogram, the 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment, the 2 RhB@prepared for one step 3 of embodiment
The aqueous solution containing NFT is added in Tb-dcpcpt dispersion liquid；
Figure 10 is after the aqueous solution containing CPFX is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram, the 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment, 2 be the preparation of one step 3 of embodiment
The aqueous solution containing CPFX is added in RhB@Tb-dcpcpt dispersion liquid；
Figure 11 is after the aqueous solution containing NFX is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram, the 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment, 2 be the preparation of one step 3 of embodiment
The aqueous solution containing NFX is added in RhB@Tb-dcpcpt dispersion liquid；
Figure 12 is that various concentration is added containing the water-soluble of NZF in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram after liquid；
Figure 13 is aqueous solution of the various concentration containing NZF 544nm at and the relationship comparison diagram of relative intensity of fluorescence；
Figure 14 is that various concentration is added containing the water-soluble of NFT in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram after liquid；
Figure 15 is aqueous solution of the various concentration containing NFT 544nm at and the relationship comparison diagram of relative intensity of fluorescence；
Figure 16 is the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation in the presence of other antibiotic, is added
Fluorescence peak intensity histogram at 544nm after aqueous solution of the various concentration containing NZF；
Figure 17 is the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation in the presence of other antibiotic, is added
Fluorescence peak intensity histogram at 544nm after aqueous solution of the various concentration containing NFT；
Figure 18 is that the water solution cycle containing NZF is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Spectrogram, 1 is RhB@Tb-dcpcpt dispersion liquid, and 2 are added the aqueous solution containing NZF for RhB@Tb-dcpcpt dispersion liquid；
Figure 19 is that the water solution cycle containing NFT is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Spectrogram, 1 is RhB@Tb-dcpcpt dispersion liquid, and 2 are added the aqueous solution containing NFT for RhB@Tb-dcpcpt dispersion liquid；
Figure 20 is that the aqueous solution containing different antibiotic is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Filtered X-ray powder diffraction figure, 1 is added for the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation containing NFX's
Aqueous solution, 2 are added the aqueous solution containing CPFX for the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation, and 3 be embodiment
The aqueous solution containing NFT is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 preparation, and 4 be the preparation of one step 3 of embodiment
The aqueous solution containing NZF is added in RhB@Tb-dcpcpt dispersion liquid, and 5 disperse for the RhB@Tb-dcpcpt of one step 3 of embodiment preparation
Liquid；
Figure 21 is the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation in the presence of ACL, be added containing CPFX or
Fluorescence CIE diagram after the aqueous solution of NFX, 1 is the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation and mixing for ACL
Object is closed, 2 be the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation in the presence of ACL, is added containing the water-soluble of CPFX
Liquid, 3 be the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation in the presence of ACL, and the aqueous solution containing NFT is added；
Figure 22 is that various concentration is added containing the water-soluble of CPFX in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram after liquid；
Figure 23 is that various concentration is added containing the water-soluble of CPFX in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorescence CIE diagram after liquid, 1 be one step 3 of embodiment preparation RhB Tb-dcpcpt dispersion liquid be added concentration be 0mmol/L
Aqueous solution containing CPFX, 2 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 1mmol/L contains
The aqueous solution of CPFX, 3 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 2mmol/L contains
The aqueous solution of CPFX, 4 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 3mmol/L contains
The aqueous solution of CPFX, 5 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 4mmol/L contains
The aqueous solution of CPFX, 6 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 5mmol/L contains
The aqueous solution of CPFX, 7 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 6mmol/L contains
The aqueous solution of CPFX, 8 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 7mmol/L contains
The aqueous solution of CPFX, 9 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 8mmol/L contains
The aqueous solution of CPFX；
Figure 24 is that various concentration is added containing CPFX or NFX in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Aqueous solution after fluorescence color variation, it is different dense that a is that the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation is added
The aqueous solution containing CPFX is spent, b is that various concentration is added containing NFX in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Aqueous solution；
Figure 25 is that various concentration is added containing the water-soluble of NFX in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram after liquid；
Figure 26 is that various concentration is added containing the water-soluble of NFX in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorescence CIE diagram after liquid, 1 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be that 0mmol/L contains
The aqueous solution of NFX, 2 be that concentration is added is 1mmol/L containing NFX for the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Aqueous solution, 3 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be water of the 2mmol/L containing NFX
Solution, 4 be one step 3 of embodiment preparation RhB@Tb-dcpcpt dispersion liquid be added concentration be 3mmol/L containing the water-soluble of NFX
Liquid, 5 be that concentration is added is aqueous solution of the 4mmol/L containing NFX for the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation, 6
RhB@Tb-dcpcpt dispersion liquid addition concentration for the preparation of one step 3 of embodiment is aqueous solution of the 5mmol/L containing NFX, and 7 be real
It is aqueous solution of the 6mmol/L containing NFX that concentration, which is added, in the RhB@Tb-dcpcpt dispersion liquid for applying the preparation of one step 3 of example, and 8 be embodiment
It is aqueous solution of the 7mmol/L containing NFX that concentration, which is added, in the RhB@Tb-dcpcpt dispersion liquid of one step 3 preparation, and 9 be one step of embodiment
It is aqueous solution of the 8mmol/L containing NFX that concentration, which is added, in the RhB@Tb-dcpcpt dispersion liquid of rapid three preparation；
Figure 27 is the fluorescence swarming figure of the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation；
Figure 28 is glimmering after aqueous solution of the RhB@Tb-dcpcpt dispersion liquid addition containing CPFX of one step 3 of embodiment preparation
Light swarming；
Figure 29 is glimmering after aqueous solution of the RhB@Tb-dcpcpt dispersion liquid addition containing NFX of one step 3 of embodiment preparation
Light swarming；
Figure 30 is the fluorogram of the Tb-dcpcpt crystal of one step 1 of embodiment preparation, CPFX solid and NFX solid, and 1 is
The Tb-dcpcpt crystal of one step 1 of embodiment preparation, 2 be NFX solid, and 3 be CPFX solid.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: Nitrofuran antibiotics or quinolones are anti-in a kind of detection drinking water of present embodiment
The method of raw element follows the steps below:
One, Tb-dcpcpt crystal is prepared:
1., by Tb (NO3)3·6H2O, three nitrogen of 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4-
Azoles, N, N '-dimethyl formamide and H2O mixing, obtains mixture, mixture is placed in pyroreaction kettle, is 150 in temperature
DEG C~200 DEG C under conditions of, sealing for 24 hours~72h carry out solvent thermal reaction, obtain crystal prototype；
3- (3,5- dicarboxyphenyi) -5- (4- the carboxyl phenyl) -1- hydrogen -1,2,4- triazole and Tb (NO3)3·
6H2The molar ratio of O is 1:(0.5~2)；3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4-
Triazole mole and N, the volume ratio of N '-dimethyl formamide be 0.1mmol:(5~10) mL；The N, N '-dimethyl
Formamide and H2The volume ratio of O is 1:(0.1~2)；
2., crystal prototype N, N '-dimethyl formamide and ethyl alcohol washed 3 times~5 times respectively, obtain Tb-dcpcpt
Crystal；Two, RhB@Tb-dcpcpt composite material is prepared:
It is 10 that Tb-dcpcpt crystal, which is impregnated in concentration,-4Mol/L~10-5In the rhodamine B aqueous solution of mol/L, keep
12h~48h obtains pink crystal, pink crystal is rinsed, and dried in air with deionized water, obtains RhB Tb-
Dcpcpt composite material；
Three, RhB@Tb-dcpcpt dispersion liquid is prepared:
Under agitation, RhB@Tb-dcpcpt composite material is dispersed in water, obtains RhB@Tb-dcpcpt dispersion
Liquid；
The concentration of the RhB@Tb-dcpcpt dispersion liquid is 0.1g/L~10g/L；
Four, fluorescence detection:
Drinking water is mixed with RhB Tb-dcpcpt dispersion liquid, obtains drinking water to be detected, drinking water to be detected is used
Wavelength is the ultraviolet light of 300nm~390nm, observes solution colour；
The volume ratio of the drinking water and RhB@Tb-dcpcpt dispersion liquid is 1:(0.5~2)；
Contain Nitrofuran antibiotics or quinolone antibiotics in the drinking water；
When containing Nitrofuran antibiotics in the drinking water, and in drinking water Nitrofuran antibiotics concentration
When higher than 0.502 μm of ol/L, by yellow light fluorescent quenching occurs for solution colour；
When containing quinolone antibiotics in the drinking water, and the concentration of quinolone antibiotics is higher than in drinking water
When 0.448 μm of ol/L, solution colour is first become white from yellow, then becomes blue.
Nitrofuran antibiotics are not existed simultaneously with quinolone antibiotics in drinking water in present embodiment.
Present embodiment the utility model has the advantages that
Select [(CH3)2NH2][Tb3(dcpcpt)3(HCOO)]·DMF·15H2The anion frame of O (Tb-dcpcpt)
RhB@Tb-dcpcpt composite material is prepared for the rhodamine B dye of positive ion (RhB).The composite material have Tb-dcpcpt and
The common of RhB shines, and lasting yellow emission is generated under the excitation of 300nm~390nm.It is shone to 14 kinds of antibiotic
Detection, either to the luminous intensity of Nitrofuran antibiotics, or to the luminescent color of quinolone antibiotics, all shows
Good distinguishing ability out.The sensing behavior has good sensitivity, selectivity and recuperability, by excitation wavelength
Influence very little.
Cationic RhB is fixed in the channel anion Ln-MOF by ion exchange, successfully synthesized it is a kind of with it is sharp
Send out the unrelated Yellow luminous composite material of wavelength.The composite material is with higher to Nitrofuran antibiotics (NZF and NFT)
Sensitivity and selective enumeration method ability.In addition, to quinolone antibiotics (CPFX and NFX), RhB@Tb-dcpcpt is also showed that
To the apparent-color change process that shines of blue from yellow to white.Influence very little of the excitation wavelength to sensing behavior.This is multiple
Condensation material detection limit is low, and (the detection limit to NZF and NFT is respectively 0.502 μm of ol/L and 0.448 μm of ol/L, to CPFX's and NFX
Detection limit is respectively 2.16 μm of ol/L and 0.63 μm of ol/L), stability is good, good, the recoverable of selectivity, is before one kind has very much
The furans and quinolone antibiotics sensor on way have potential practical value in terms of water quality monitoring.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: step 1 1. described in 3-
(3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4- triazole and Tb (NO3)3·6H2The molar ratio of O is 1:
(0.5~1).It is other same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one or two: step 1 1. in
Described 3- (3,5- dicarboxyphenyi) -5- (4- the carboxyl phenyl) -1- hydrogen -1,2,4- triazole mole and N, N '-dimethyl
The volume ratio of formamide is 0.1mmol:(8~10) mL.It is other identical as one of specific embodiment one or two.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: step 1 1. in
The N, N '-dimethyl formamide and H2The volume ratio of O is 1:(0.25~2).It is other with specific embodiment one to three it
One is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: will in step 2
It is 10 that Tb-dcpcpt crystal, which is impregnated in concentration,-5In the rhodamine B aqueous solution of mol/L, for 24 hours~48h is kept, pink crystal is obtained,
Pink crystal is rinsed with deionized water, and is dried in air, RhB Tb-dcpcpt composite material is obtained.It is other with it is specific
One of embodiment one to four is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: will in step 2
It is 10 that Tb-dcpcpt crystal, which is impregnated in concentration,-5In the rhodamine B aqueous solution of mol/L, holding 12h~for 24 hours, pink crystal is obtained,
Pink crystal is rinsed with deionized water, and is dried in air, RhB Tb-dcpcpt composite material is obtained.It is other with it is specific
One of embodiment one to five is identical.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: institute in step 3
The concentration for the RhB@Tb-dcpcpt dispersion liquid stated is 1g/L~10g/L.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: institute in step 3
The concentration for the RhB@Tb-dcpcpt dispersion liquid stated is 0.1g/L~1g/L.It is other identical as one of specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: institute in step 4
The volume ratio of the drinking water and RhB@Tb-dcpcpt dispersion liquid stated is 1:(1~2).It is other with specific embodiment one to eight it
One is identical.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: institute in step 4
The volume ratio of the drinking water and RhB@Tb-dcpcpt dispersion liquid stated is 1:(0.5~1).Other and specific embodiment one to nine
One of it is identical.
Using following experimental verifications effect of the present invention:
Embodiment one:
One, Tb-dcpcpt crystal is prepared:
1., by 0.1mmol Tb (NO3)3·6H2O, 0.1mmol 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -
1- hydrogen -1,2,4- triazole, 8mL N, N '-dimethyl formamide and 2mL H2O mixing, obtains mixture, mixture is placed in
In pyroreaction kettle, under conditions of temperature is 160 DEG C, sealing 72h carries out solvent thermal reaction, obtains crystal prototype；
2., crystal prototype N, N '-dimethyl formamide and ethyl alcohol washed 3 times respectively, obtain Tb-dcpcpt crystal；
Two, RhB@Tb-dcpcpt composite material is prepared:
It is 10 that 1.6mg Tb-dcpcpt crystal, which is impregnated in 8mL concentration,-5In the rhodamine B aqueous solution of mol/L, keep
For 24 hours, pink crystal is obtained, pink crystal is rinsed with deionized water, and dries in air, it is multiple to obtain RhB Tb-dcpcpt
Condensation material；
Three, RhB@Tb-dcpcpt dispersion liquid is prepared:
Under agitation, RhB@Tb-dcpcpt composite material is dispersed in water, obtains RhB@Tb-dcpcpt dispersion
Liquid；
The concentration of the RhB@Tb-dcpcpt dispersion liquid is 1g/L；
Four, fluorescence detection:
Drinking water is mixed with RhB Tb-dcpcpt dispersion liquid, obtains drinking water to be detected, drinking water to be detected is used
Wavelength is the ultraviolet light of 300nm~390nm, observes solution colour；
The volume ratio of the drinking water and RhB@Tb-dcpcpt dispersion liquid is 1:1；
Contain Nitrofuran antibiotics or quinolone antibiotics in the drinking water；
When containing Nitrofuran antibiotics in the drinking water, and in drinking water Nitrofuran antibiotics concentration
When higher than 0.502 μm of ol/L, by yellow light fluorescent quenching occurs for solution colour；
When containing quinolone antibiotics in the drinking water, and the concentration of quinolone antibiotics is higher than in drinking water
When 0.448 μm of ol/L, solution colour is first become white from yellow, then becomes blue.
The present embodiment material and instrument: the present embodiment step 1 1. described in 3- (3,5- dicarboxyphenyi) -5- (4- carboxylic
Base phenyl) -1- hydrogen -1,2,4- triazole is the production of Jinan Heng Hua Science and Technology Ltd., product number 130811AS, English name
Referred to as 3- (3,5-dicarboxylphenyl) -5- (4-carboxylphenyl) -1H-1,2,4-triazole, the present embodiment
Middle 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4- triazole is abbreviated as H3dcpcpt。
Tb2O3Tb (NO is made with nitric acid reaction3)3·6H2O.Other chemicals are bought from commercial company, not purified
And it uses.The production firm of all antibiotic is strong Science and Technology Ltd..
Ultraviolet (UV) spectrum is acquired on 35 spectrometer of Perkin-Elmer Lambda.In Perkin-Elmer
Elemental analysis has been carried out to C, H, O and N on 2400 analyzers.With Edinburg FLS920 fluorescence spectrophotometer measurement luminescence generated by light
(PL) spectrum, the spectrum after correction are that the calibration curve provided by instrument obtains.
The Tb-dcpcpt crystal yield prepared in the present embodiment step 1: 1.6mg (2.02wt%).
Theoretical calculation carbon (C) is in compound C57H67N11O36Tb3In the mass ratio that occupies be 34.94%；Hydrogen (H) is in chemical combination
Object C57H67N11O36Tb3In the mass ratio that occupies be 3.45%, oxygen (O) is in compound C57H67N11O36Tb3In the mass ratio that occupies
It is 29.40%, nitrogen (N) is in compound C57H67N11O36Tb3In the mass ratio that occupies be 7.86%.
Analyze and test via actual element: carbon (C) accounts for 34.68% in Tb-dcpcpt crystal；Hydrogen (H) is in Tb-dcpcpt crystalline substance
Body accounts for 3.48%, and oxygen (O) accounts for 29.44% in Tb-dcpcpt crystal, and nitrogen (N) accounts for 8.03% in Tb-dcpcpt crystal.
Fig. 1 is X-ray powder diffraction spectrogram, and 1 is real for the RhB@Tb-dcpcpt composite material of one step 2 of embodiment preparation
X-ray powder diffraction curve is surveyed, 2 survey X-ray powder diffraction song for the Tb-dcpcpt crystal of one step 1 of embodiment preparation
Line, 3 are fitted X-ray powder diffraction curve for Tb-dcpcpt crystal.The present embodiment has synthesized Tb- according to previous document report
Dcpcpt crystal, Tb-dcpcpt crystal are by rigid ligand H3Dcpcpt and Tb (NO3)3·6H2O is generated under the conditions of solvent heat
's.Resulting Tb-dcpcpt crystal has consistent PXRD spectrogram with the mono-crystalline structures that are previously reported, it was confirmed that Tb-dcpcpt
Successful synthesis (Fig. 1).It is worth noting that, Tb-dcpcpt crystal not only has permanent porosity (specific surface area 801m2/
g；One-dimensional channel dimensions arePorosity be 49.8%), and have anion structure, therefore, utilize it make
For the carrier for encapsulating the dye of positive ion.
Rhodamine B (RhB) is a kind of outstanding fluorescence carrier, is sensed for chemical/biological.However, polymerization initiation is sudden
It goes out and limits the extensive use of RhB.In the present embodiment, a kind of assembly strategy is more by capturing and inhibiting RhB molecule to enter
Hole on framework is realized.By the way that Tb-dcpcpt crystal to be immersed in RhB aqueous solution, dyestuff is introduced into the channel Tb-dcpcpt,
Obtain RhB@TB-dcpcpt composite material.After encapsulation, the crystal color under sunshine becomes pink from transparent, under ultraviolet light
Luminescent color becomes yellow from green.PXRD map before and after introducing RhB shows identical frame structure (Fig. 1).
Fig. 2 is that spectrogram is desorbed in nitrogen adsorption, and the 1 Tb-dcpcpt crystal prepared for one step 1 of embodiment, 2 be embodiment
The RhB@Tb-dcpcpt composite material of one step 2 preparation；N2Adsorption isotherm and ultraviolet-ray visible absorbing further demonstrate
The successful loading (Fig. 2 and 5) of RhB.
Several factors promote the realization of encapsulation: on the one hand, the aerodynamic size of RhBWith Tb-
The window size of dcpcpt is suitableTo provide a possibility that capturing RhB in hole.It is encapsulating
After RhB, the porous channel of frame is almost (Fig. 2) sealed.On the other hand, anion Tb-dcpcpt frame can attract RhB
Cation leads to ion exchange process.Quick encapsulating (1 day) and the lower RhB concentration (10 of soak-5Mol/L) further
Confirm that RhB is easily accessible in the duct Tb-dcpcpt.
The luminescence generated by light of Tb-dcpcpt crystal and RhB@Tb-dcpcpt composite material:
Have studied Tb-dcpcpt crystal, RhB and RhB@Tb-dcpcpt composite material be solid-state when luminescent spectrum.Fig. 4
For the Tb-dcpcpt crystalline solid three-dimensional fluorescence spectrogram of one step 1 of embodiment preparation；As shown in figure 4, Tb-dcpcpt crystal point
Tb is not shown at 489nm, 544nm, 581nm and 619nm3+Ion is corresponding with 5D4 → 7FJ (J=6,5,4 and 3) transition
Sharp features peak.
Fig. 5 is the RhB@Tb-dcpcpt composite material solid three-dimensional fluorogram of one step 2 of embodiment preparation；RhB can
To represent apparent red emission range from 600nm to 670nm, therefore RhB@Tb-dcpcpt composite material shows Tb3+With
The total of RhB shines (Fig. 5), and the strong transmitting of 489nm and the place 544nm belong to skeleton transmitting, another near 635nm emits by force category
In the transmitting of RhB.
Since synthesized RhB@Tb-dcpcpt composite material can detect antibiotic in aqueous solution, to RhB@
Tb-dcpcpt composite material stability in an aqueous medium and the characteristics of luminescence are detected.By stirring RhB@Tb-
Dcpcpt composite material is suspended in water, obtains RhB@Tb-dcpcpt dispersion liquid, then again by RhB@Tb-dcpcpt dispersion liquid
Middle RhB@Tb-dcpcpt composite material filters out, and obtains the filtered RhB@Tb-dcpcpt composite material of aqueous solution；
In RhB@Tb-dcpcpt composite material, fluorescence resonance energy from skeleton be transferred to RhB potentially contribute to skeleton and
The common of dyestuff shines.Fig. 3 is ultraviolet-visible absorption spectra figure, and the 1 Tb-dcpcpt crystal prepared for one step 1 of embodiment, 2 are
Rhodamine B, 3 be the filtered RhB@Tb-dcpcpt composite material of aqueous solution.As in Fig. 3 and shown in Fig. 4, the UV-Vis of RhB inhales
Spectrum is received mainly near 544nm, it is almost be overlapped with 5D4 → 7F2 transition band of Tb-dcpcpt.After cladding, Tb-dcpcpt
Luminous intensity at 544nm is substantially reduced, it was confirmed that the presence of effective fluorescence resonance energy transfer.
Fig. 6 is the RhB@Tb-dcpcpt composite material and the filtered RhB@Tb- of aqueous solution of one step 2 of embodiment preparation
Dcpcpt composite material surveys X-ray powder diffraction spectrogram, and 1 is compound for the RhB@Tb-dcpcpt of one step 2 of embodiment preparation
Material, 2 be the filtered RhB@Tb-dcpcpt composite material of aqueous solution；The RhB@Tb-dcpcpt's filtered out from suspension
PXRD map has almost no change, and illustrates that frame suspending is still complete (Fig. 6) afterwards in water.
It can detecte a small amount of RhB by ultraviolet-visible spectrum, illustrate that RhB is located in the channel of skeleton (Fig. 3).
These results indicate that the composite material is with good stability, while showing that nano pore assembles RhB and conciliating
From with certain restriction effect, the stability of composite material is substantially increased.Experimental result also demonstrates RhB@Tb-dcpcpt
Application in chemistry of aqueous solution/bio-sensing.
Fig. 7 is fluorogram under RhB@Tb-dcpcpt dispersion liquid difference excitation wavelength prepared by one step 3 of embodiment；
The yellow light that RhB@Tb-dcpcpt composite material luminescent color keeps stable within the scope of entire excitation wavelength 300nm~390nm is sent out
It penetrates.This contribution solves group of the lanthanides sensor instability problem related with excitation wavelength in luminous intensity and color.To the greatest extent
Pipe RhB@Tb-dcpcpt composite material has lasting yellow emission (Fig. 7) in aqueous solution, but the RhB's wrapped up is luminous
Become the 590nm in Fig. 7 from the 635nm in Fig. 5, this is because caused by the concentration effect of dye molecule.Importantly, passing through
Encapsulation RhB dyestuff is removed using porous network, these results confirm RhB molecule, and there is no aggregation inducing Quenchings.
The detection of Nitrofuran antibiotics:
It is 0.01mol/L containing anti-that concentration is added in the RhB@Tb-dcpcpt dispersion liquid prepared to one step 3 of embodiment
The aqueous solution of raw element, and use wavelength for the ultraviolet light of 320nm, micro antibiotic is detected to study RhB@Tb-dcpcpt
Ability, the volume ratio of the antibiotic aqueous solution and RhB@Tb-dcpcpt dispersion liquid is 1:1.Described contains antibiosis
Antibiotic is one of following 14 kinds of 6 class common antibiotics in the aqueous solution of element, such as beta-lactam antibiotic (penicillin
PCL, Amoxicillin ACL, Cefixime CFX, Cefradine CFD), (gentamicin GTM, to block that mould for aminoglycoside antibiotics
Plain KNM), macrolide antibiotics (roxithromycin ROX, azithromycin AZM), quinolone antibiotics (Ciprofloxacin CPFX,
Norfloxacin NFX), Nitrofuran antibiotics (furazolidone NZF, furantoin NFT) and other class antibiotic it is (mould through the ages
Plain VCC, lincomycin LCC).
Fig. 8 is glimmering after the aqueous solution containing NZF is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Spectrogram；The 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment, the 2 RhB@prepared for one step 3 of embodiment
The aqueous solution containing NZF is added in Tb-dcpcpt dispersion liquid；Fig. 9 is the RhB@Tb-dcpcpt dispersion of one step 3 of embodiment preparation
The fluorogram after the aqueous solution containing NFT is added in liquid；The 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment,
2 be aqueous solution of the addition containing NFT in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation；Figure 10 is embodiment one
The fluorogram after the aqueous solution containing CPFX is added in the RhB@Tb-dcpcpt dispersion liquid of step 3 preparation；1 is one step of embodiment
The RhB@Tb-dcpcpt dispersion liquid of rapid three preparation, 2 be to add in the RhB@Tb-dcpcpt dispersion liquids of one step 3 of embodiment preparation
Enter the aqueous solution containing CPFX；Figure 11 is that the water containing NFX is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram after solution；The 1 RhB@Tb-dcpcpt dispersion liquid prepared for one step 3 of embodiment, 2 be one step 3 of embodiment
The aqueous solution containing NFX is added in the RhB@Tb-dcpcpt dispersion liquid of preparation；According to Fig. 8~Figure 11, RhB@Tb-dcpcpt is adding
It will appear high luminescence queenching when adding Nitrofuran antibiotics (such as NZF and NFT).
Figure 20 is that the aqueous solution containing different antibiotic is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Filtered X-ray powder diffraction figure, 1 is added for the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation containing NFX's
Aqueous solution, 2 are added the aqueous solution containing CPFX for the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation, and 3 be embodiment
The aqueous solution containing NFT is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 preparation, and 4 be the preparation of one step 3 of embodiment
The aqueous solution containing NZF is added in RhB@Tb-dcpcpt dispersion liquid, and 5 disperse for the RhB@Tb-dcpcpt of one step 3 of embodiment preparation
Liquid；It is confirmed through PXRD, after the sensing experiment to NZF and NFT, the structure of RhB@Tb-dcpcpt is intact (Figure 20).
The water containing Nitrofuran antibiotics is added in the RhB@Tb-dcpcpt dispersion liquid prepared to one step 3 of embodiment
Solution, and use wavelength for the ultraviolet light of 320nm, to study RhB@Tb-dcpcpt detection Nitrofuran antibiotics
The volume ratio of detection limit, the aqueous solution containing Nitrofuran antibiotics and RhB@Tb-dcpcpt dispersion liquid is 1:1.With
Stern-Volmer (SV) equation: I0/ I=1+KSV× [C], wherein KSVFor quenching constant (mol/L)-1If containing itrofurans
The concentration of Nitrofuran antibiotics is [C] in the aqueous solution of antibiotic, and the unit of [C] is mol/L, I0It is in nitre respectively with I
Luminous intensity when base furans antibiotic absence and presence, the Nitrofuran antibiotics be furazolidone NZF or
Furantoin NFT.
Figure 12 is that various concentration is added containing the water-soluble of NZF in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation
Fluorogram after liquid；The fluorescence intensity of curves different in Figure 12 is calculated and drawn with Stern-Volmer (SV) equation
Figure, obtains Figure 13, Figure 13 be aqueous solution of the various concentration containing NZF 544nm at the relationship comparison diagram of relative intensity of fluorescence, scheme
14 be the fluorescence after RhB@Tb-dcpcpt dispersion liquid addition aqueous solution of the various concentration containing NFT of one step 3 of embodiment preparation
Spectrogram is calculated and is drawn with Stern-Volmer (SV) equation to the fluorescence intensity of curves different in Figure 14, obtains Figure 15,
Figure 15 is aqueous solution of the various concentration containing NFT 544nm at and the relationship comparison diagram of relative intensity of fluorescence；The SV of NZF and NFT is bent
Line is in good linear relationship, K of the RhB@TB-dcppt to NZF and NFTSVValue is respectively 5.98 × 104(mol/L)-1With 6.69
×104(mol/L)-1(Figure 13 and Figure 15).Repeat the K of fluorescence measurement three times according to blank solutionSVValue and standard deviation (σ=
0.010), it is determined that RhB@Tb-dcpcpt limits (LOD=3 σ/K to the detection of NZF and NFTSV), calculated value is respectively 0.502 μ
Mol/L (99.47ppb) and 0.448 μm of ol/L (106.7ppb).The method sensitivity of the present embodiment is much better than most of reported
NZF and NFT fluorescence probe, the highest for meeting antibiotic in Environmental Protection Agency USA and World Health Organization's drinking water allows to contain
The standard of amount.
It is very high sudden that RhB@Tb-dcpcpt, which there are Nitrofuran antibiotics, to be shown to the excellent susceptibility of NZF and NFT
It goes out efficiency, but then insensitive to other kinds of antibiotic.On this basis, the present embodiment further has checked in other antibiosis
To the detecting and selecting property of Nitrofuran antibiotics in the presence of element.It is 1mmol/L containing antibiotic by concentration in control experiment
The aqueous solution of (PCL, ACL, CFX, CFD, GTM, KNM, ROX, AZM, CPFX, NFX, VCC or LCC) is added to one step of embodiment
Three preparation RhB@Tb-dcpcpt dispersion liquids in, then be added aqueous solution of the various concentration containing NZF or NFT, and use wavelength for
RhB@Tb-dcpcpt points of the ultraviolet light of 320nm, the antibiotic aqueous solution and the preparation of one step 3 of embodiment
The volume ratio of dispersion liquid is 1:1, the RhB@of aqueous solution of the various concentration containing NZF or NFT and the preparation of one step 3 of embodiment
The volume ratio of Tb-dcpcpt dispersion liquid is 1:1.
Figure 16 is the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation in the presence of other antibiotic, is added
Fluorescence peak intensity histogram at 544nm after aqueous solution of the various concentration containing NZF；Figure 17 is the RhB@of one step 3 of embodiment preparation
Tb-dcpcpt dispersion liquid is in the presence of other antibiotic, fluorescence peak intensity at 544nm after addition aqueous solution of the various concentration containing NFT
Histogram；In the excessive situation of other antibiotic (Figure 16 and 17), the luminous intensity of RhB Tb-dcpcpt is slightly changed.It will
After Nitrofuran antibiotics introduce the mixture of RhB@Tb-dcpcpt and other antibiotic, shines and significantly quenched, explanation
RhB@TB-dcpcpt quenching selectivity with higher to nitrofuran.
In addition, concentration is added into RhB@Tb-dcpcpt dispersion liquid prepared by one step 3 of embodiment for 1:1 by volume
For the aqueous solution containing NZF or NFT of 1mmol/L, and use wavelength for the ultraviolet light of 320nm, after use by centrifugation
It is washed several times with water, filtering retrieves RhB@Tb-dcpcpt, and then RhB@Tb-dcpcpt is distributed in water again, is obtained
The RhB@Tb-dcpcpt dispersion liquid for being 1g/L to concentration, and be by volume the RhB@Tb-dcpcpt that 1:1 is 1g/L to concentration
The aqueous solution containing NZF or NFT that concentration is 1mmol/L is rejoined in dispersion liquid, uses wavelength for the ultraviolet lighting of 320nm
It penetrates, is recycled with this, the cyclicity of research RhB@Tb-dcpcpt detection Nitrofuran antibiotics.Figure 18 is one step of embodiment
The water solution cycle spectrogram containing NZF is added in the RhB@Tb-dcpcpt dispersion liquid of three preparations, and 1 disperses for RhB@Tb-dcpcpt
Liquid, 2 are added the aqueous solution containing NZF for RhB@Tb-dcpcpt dispersion liquid；Figure 19 is the RhB@Tb- of one step 3 of embodiment preparation
The water solution cycle spectrogram containing NFT is added in dcpcpt dispersion liquid, and 1 is RhB@Tb-dcpcpt dispersion liquid, and 2 be RhB@Tb-
The aqueous solution containing NFT is added in dcpcpt dispersion liquid；It is good recyclable to illustrate that fluorescence detection has Nitrofuran antibiotics
Property, it can regenerate and use (Figure 18 and 19) with a large amount of circulating repetition.
The mechanism of action of the RhB@TB-dcpcpt to NZF and NFT: firstly, being confirmed through PXRD, in the sensing to NZF and NFT
After experiment, the structure of RhB@Tb-dcpcpt is intact (Figure 20).Secondly, according to those skilled in the art's common knowledge, antibiotic
Ultraviolet-visible spectrum, NZF and NFT have stronger absorption at 300nm~400nm, since competition photonic absorption leads to RhB@
The luminescence queenching of Tb-dcpcpt.Lowest unoccupied molecular orbital (LUMO) energy of third, NZF and NFT are lower than other antibiosis
Element illustrates that the electronics transfer of photoinduction is a kind of mechanism for the luminescence queenching observed in such systems.The result shows that electronics
Shift and compete coexisting so that furfuran compound is shown good compared with other analysis substances having been found for photonic absorption
Good luminescence queenching effect.
The detection of quinolone antibiotics:
It is 0.01mol/L containing quinoline that concentration is added in the RhB@Tb-dcpcpt dispersion liquid prepared to one step 3 of embodiment
The aqueous solution of promise ketone antibiotic, and use wavelength for the ultraviolet light of 320nm, luminous coloration process is tested, it is described
The volume ratio of the RhB@Tb-dcpcpt dispersion liquid of aqueous solution and one step 3 of the embodiment preparation of quinolone containing class antibiotic is 1:
1。
Figure 27 is the fluorescence swarming figure of the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation；Figure 28 is to implement
The fluorescence swarming after the aqueous solution containing CPFX is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of example preparation；Figure 29 is to implement
The fluorescence swarming after the aqueous solution containing NFX is added in the RhB@Tb-dcpcpt dispersion liquid of one step 3 of example preparation；With CPFX and
The increase of NFX, ligand-centered emission generate deep mutagens colo(u)rimetric shift.This shows exist from RhB@Tb-dcpcpt to quinolone molecule
Radiation capture.Therefore, ligand-centered emission plays a leading role in emission spectrum, make luminescent color occur by yellow to white to
The variation of blue.
The water-soluble of quinolone containing class antibiotic is added in the RhB@Tb-dcpcpt dispersion liquid prepared to one step 3 of embodiment
Liquid, and use wavelength for the ultraviolet light of 320nm, the aqueous solution and RhB@Tb- of the quinolone containing class antibiotic
The volume ratio of dcpcpt dispersion liquid is 1:1.Figure 22 is that the RhB@Tb-dcpcpt dispersion liquid of one step 3 of embodiment preparation is added not
With the fluorogram after aqueous solution of the concentration containing CPFX；Figure 23 is the RhB@Tb-dcpcpt dispersion of one step 3 of embodiment preparation
The fluorescence CIE diagram after aqueous solution of the various concentration containing CPFX, the 1 RhB Tb- prepared for one step 3 of embodiment is added in liquid
It is aqueous solution of the 0mmol/L containing CPFX, the 2 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 1mmol/L containing CPFX, the 3 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 2mmol/L containing CPFX, the 4 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 3mmol/L containing CPFX, the 5 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 4mmol/L containing CPFX, the 6 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 5mmol/L containing CPFX, the 7 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 6mmol/L containing CPFX, the 8 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 7mmol/L containing CPFX, the 9 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 8mmol/L containing CPFX that concentration, which is added, in dcpcpt dispersion liquid；Figure 24 is the RhB@Tb- of one step 3 of embodiment preparation
The fluorescence color variation after aqueous solution of the various concentration containing CPFX or NFX is added in dcpcpt dispersion liquid, and a is one step 3 of embodiment
Aqueous solution of the various concentration containing CPFX is added in the RhB@Tb-dcpcpt dispersion liquid of preparation, and b is the preparation of one step 3 of embodiment
Aqueous solution of the various concentration containing NFX is added in RhB@Tb-dcpcpt dispersion liquid；Figure 25 is the RhB@of one step 3 of embodiment preparation
The fluorogram after aqueous solution of the various concentration containing NFX is added in Tb-dcpcpt dispersion liquid；Figure 26 is the preparation of one step 3 of embodiment
RhB@Tb-dcpcpt dispersion liquid be added aqueous solution of the various concentration containing NFX after fluorescence CIE diagram, 1 be one step 3 of embodiment
It is aqueous solution of the 0mmol/L containing NFX that concentration, which is added, in the RhB@Tb-dcpcpt dispersion liquid of preparation, and 2 prepare for one step 3 of embodiment
RhB@Tb-dcpcpt dispersion liquid be added concentration be aqueous solution of the 1mmol/L containing NFX, 3 for one step 3 of embodiment preparation
It is aqueous solution of the 2mmol/L containing NFX, the 4 RhB@prepared for one step 3 of embodiment that concentration, which is added, in RhB@Tb-dcpcpt dispersion liquid
It is aqueous solution of the 3mmol/L containing NFX, the 5 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in Tb-dcpcpt dispersion liquid
It is aqueous solution of the 4mmol/L containing NFX, the 6 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 5mmol/L containing NFX, the 7 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 6mmol/L containing NFX, the 8 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 7mmol/L containing NFX, the 9 RhB@Tb- prepared for one step 3 of embodiment that concentration, which is added, in dcpcpt dispersion liquid
It is aqueous solution of the 8mmol/L containing NFX that concentration, which is added, in dcpcpt dispersion liquid；2- Figure 26 according to fig. 2, the luminescent color of sample obviously by
Yellow becomes white, subsequently becomes blue.With the increase of CPFX and NFX concentration, Tb3+Decline rapidly with the intensity of RhB component,
But the component of NFX ligand still remains unchanged, and the ligand component of CPFX even increases (Figure 22 and Figure 25).Therefore, with CPFX and
NFX's is continuously added, and blue emission gradually occupies leading position, causes luminescent color from yellow to white to blue.According to figure
24, when CPFX or NFX concentration is 4mmol/L, the luminescent color of sample becomes white, and when 7mmol/L becomes blue, this is one
A relatively low vision-based detection limitation.Intensity monitor is carried out at 544nm, the detection limit to CPFX and NFX is respectively 2.16 μ
Mol/L (716ppb) and 0.63 μm of ol/L (201ppb).The result shows that RhB@Tb-dcpcpt has double and low vision-based detection
Limit, detection range are wide.
Then detecting and selecting property of quinolone drugs in the presence of other antibiotic is studied.It is by concentration
The aqueous solution containing antibiotic (PCL, ACL, CFX, CFD, GTM, KNM, ROX, AZM, VCC or LCC) of 1mmol/L is added to implementation
In the RhB@Tb-dcpcpt dispersion liquid of one step 3 of example preparation, it is 0.01mol/L containing CPFX's or NFX that concentration, which is then added,
Aqueous solution, and use wavelength for the ultraviolet light of 320nm, the antibiotic aqueous solution and one step 3 system of embodiment
The volume ratio of standby RhB@Tb-dcpcpt dispersion liquid is 1:1, the aqueous solution containing CPFX or NFX and one step of embodiment
The volume ratio of the RhB@Tb-dcpcpt dispersion liquid of three preparations is 1:1.Figure 21 is the RhB@Tb- of one step 3 of embodiment preparation
Dcpcpt dispersion liquid in the presence of ACL, be added the aqueous solution containing CPFX or NFX after fluorescence CIE diagram, 1 be one step of embodiment
The mixture of RhB the@Tb-dcpcpt dispersion liquid and ACL of three preparations, the 2 RhB@Tb-dcpcpt prepared for one step 3 of embodiment
The aqueous solution containing CPFX is added in the presence of ACL in dispersion liquid, and 3 disperse for the RhB@Tb-dcpcpt of one step 3 of embodiment preparation
The aqueous solution containing NFT is added in the presence of ACL in liquid；The quinolones such as CPFX and NFX are being added in RhB@Tb-dcpcpt composite material
After class drug, fluorescence color is from yellow to the significant change process (Figure 21) of blue.In RhB@Tb-dcpcpt and other antibiotic
Mixture in introduce quinolone drugs after, luminescent color obviously becomes blue, it was demonstrated that RhB@Tb-dcpcpt is on luminescent color
To carbostyril compound selectivity with higher (Figure 21).
The mechanism of luminous coloration process: firstly, the PXRD for detecting front and back RhB@Tb-dcpcpt to quinolone antibiotics schemes
It composes almost the same, shows that fluorescence metachromatism is unrelated with structure change (Figure 20).Secondly, being sent out RhB@Tb-dcpcpt
Photo-peak analysis (Figure 27~29).With the increase of CPFX and NFX, ligand-centered emission generates deep mutagens colo(u)rimetric shift.This show from
There are radiation captures to quinolone molecule by [email protected], ligand-centered emission plays leading work in emission spectrum
With occurring that luminescent color by yellow to white to blue variation.Third, under the excitation of 320nm, carbostyril compound
It shines at 400nm~500nm with weak, with H3Shining for dcpcpt is similar, this is to keep blue light prevailing another
A reason (Figure 30), Figure 30 are the fluorescence of the Tb-dcpcpt crystal of one step 1 of embodiment preparation, CPFX solid and NFX solid
Figure, the 1 Tb-dcpcpt crystal prepared for one step 1 of embodiment, 2 be NFX solid, and 3 be CPFX solid.Therefore, RhB@Tb-
Dcpcpt to the luminous coloration process of carbostyril compound be due to analyte luminescence emissions and energy transmission interference co-existence
With caused by disturbance of the ligand to lanthanide ion energy transfer.
Claims (10)
1. a kind of method of Nitrofuran antibiotics or quinolone antibiotics in detection drinking water, it is characterised in that Yi Zhongjian
The method of Nitrofuran antibiotics or quinolone antibiotics in drinking water is surveyed to follow the steps below:
One, Tb-dcpcpt crystal is prepared:
1., by Tb (NO3)3·6H2O, 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4- triazole, N,
N '-dimethyl formamide and H2O mixing, obtain mixture, mixture be placed in pyroreaction kettle, temperature be 150 DEG C~
Under conditions of 200 DEG C, seals for 24 hours~72h and carry out solvent thermal reaction, obtain crystal prototype；
3- (3,5- dicarboxyphenyi) -5- (4- the carboxyl phenyl) -1- hydrogen -1,2,4- triazole and Tb (NO3)3·6H2O
Molar ratio be 1:(0.5~2)；Three nitrogen of 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4-
Azoles mole and N, the volume ratio of N '-dimethyl formamide be 0.1mmol:(5~10) mL；The N, N '-dimethyl formyl
Amine and H2The volume ratio of O is 1:(0.1~2)；
2., crystal prototype N, N '-dimethyl formamide and ethyl alcohol washed 3 times~5 times respectively, obtain Tb-dcpcpt crystal；
Two, RhB@Tb-dcpcpt composite material is prepared:
It is 10 that Tb-dcpcpt crystal, which is impregnated in concentration,-4Mol/L~10-5In the rhodamine B aqueous solution of mol/L, holding 12h~
48h obtains pink crystal, and pink crystal is rinsed with deionized water, and dries in air, and it is multiple to obtain RhB Tb-dcpcpt
Condensation material；
Three, RhB@Tb-dcpcpt dispersion liquid is prepared:
Under agitation, RhB@Tb-dcpcpt composite material is dispersed in water, obtains RhB@Tb-dcpcpt dispersion liquid；
The concentration of the RhB@Tb-dcpcpt dispersion liquid is 0.1g/L~10g/L；
Four, fluorescence detection:
Drinking water is mixed with RhB Tb-dcpcpt dispersion liquid, obtains drinking water to be detected, wavelength is used to drinking water to be detected
For the ultraviolet light of 300nm~390nm, solution colour is observed；
The volume ratio of the drinking water and RhB@Tb-dcpcpt dispersion liquid is 1:(0.5~2)；
Contain Nitrofuran antibiotics or quinolone antibiotics in the drinking water；
When containing Nitrofuran antibiotics in the drinking water, and the concentration of Nitrofuran antibiotics is higher than in drinking water
When 0.502 μm of ol/L, by yellow light fluorescent quenching occurs for solution colour；
When containing quinolone antibiotics in the drinking water, and the concentration of quinolone antibiotics is higher than in drinking water
When 0.448 μm of ol/L, solution colour is first become white from yellow, then becomes blue.
2. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that step 1 1. described in 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4- tri-
Nitrogen azoles and Tb (NO3)3·6H2The molar ratio of O is 1:(0.5~1).
3. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that step 1 1. described in 3- (3,5- dicarboxyphenyi) -5- (4- carboxyl phenyl) -1- hydrogen -1,2,4- tri-
Nitrogen azoles mole and N, the volume ratio of N '-dimethyl formamide be 0.1mmol:(8~10) mL.
4. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that step 1 1. described in N, N '-dimethyl formamide and H2The volume ratio of O is 1:(0.25~2).
5. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that it is 10 that Tb-dcpcpt crystal, which is impregnated in concentration, in step 2-5In the rhodamine B aqueous solution of mol/L, protect
For 24 hours~48h is held, pink crystal is obtained, pink crystal is rinsed, and dried in air with deionized water, obtains RhB Tb-
Dcpcpt composite material.
6. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that it is 10 that Tb-dcpcpt crystal, which is impregnated in concentration, in step 2-5In the rhodamine B aqueous solution of mol/L, protect
12h~for 24 hours is held, pink crystal is obtained, pink crystal is rinsed, and dried in air with deionized water, obtain RhB Tb-
Dcpcpt composite material.
7. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that the concentration of RhB@Tb-dcpcpt dispersion liquid described in step 3 is 1g/L~10g/L.
8. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that the concentration of RhB@Tb-dcpcpt dispersion liquid described in step 3 is 0.1g/L~1g/L.
9. the side of Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that the volume ratio of drinking water described in step 4 and RhB@Tb-dcpcpt dispersion liquid is 1:(1~2).
10. Nitrofuran antibiotics or quinolone antibiotics in a kind of detection drinking water according to claim 1
Method, it is characterised in that the volume ratio of drinking water described in step 4 and RhB@Tb-dcpcpt dispersion liquid is 1:(0.5~1).
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