CN115403778B - Fluorescence enhanced coordination polymer for detecting erythromycin in water and application thereof - Google Patents
Fluorescence enhanced coordination polymer for detecting erythromycin in water and application thereof Download PDFInfo
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Abstract
A fluorescence-enhanced coordination polymer for detecting erythromycin in water, the complex having the formula: [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]The method comprises the steps of carrying out a first treatment on the surface of the Wherein 4-bmnpd is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide and HCPG is 3- (4-chlorophenyl) glutarate. Use of a fluorescence-enhanced coordination polymer for detecting erythromycin in water in the detection of erythromycin. The advantages are that: the synthesis method is simple, the synthesis raw materials are easy to obtain, the cost is low, and the synthesis yield is high; after erythromycin treatment, the synthesized cobalt coordination polymer has obviously enhanced fluorescence intensity and good molecular recognition effect on erythromycin.
Description
Technical Field
The invention belongs to the field of fluorescent material synthesis, and particularly relates to a fluorescence enhanced coordination polymer for detecting erythromycin in water and application thereof.
Background
Erythromycin is one of the most widely used and important macrolide antibiotics, can effectively inhibit the activities of gram-positive bacteria and gram-negative bacteria, and is therefore the first medicament widely used in clinic in the compounds, however, due to excessive use and improper discharge and treatment by people, erythromycin can be excessively deposited in a water channel, and although erythromycin has good pharmacological action, the problem of medicament residue in the water channel can cause serious damage to a life system and an ecological system. Therefore, the search for a simple, efficient and reliable method for detecting erythromycin in water has important significance for human health and protection of the ecosystem.
Currently, methods for identifying erythromycin include high performance liquid chromatography, near infrared reflectance spectroscopy, ultraviolet, electrochemical, liquid/mass spectrometry, gas/mass spectrometry, and the like. These conventional methods, although highly sensitive, have the disadvantages of being time consuming, laborious, expensive, difficult to operate in situ analysis, etc. In contrast, in recent years, fluorescence detection methods have received attention from many researchers because of their low cost, easy sample preparation, fast response time, and wide application range. In particular in the detection of antibiotics, it is considered to be the most promising and cheapest method. Thus, a suitable material for detecting erythromycin is sought.
Disclosure of Invention
The invention aims to solve the technical problem of providing the fluorescence enhanced coordination polymer for detecting erythromycin in water, which has the advantages of simple synthesis method, short synthesis time and low cost of synthesis raw materials, and the application thereof, and can be used for selectively identifying and detecting the erythromycin in water through fluorescence detection.
The technical scheme of the invention is as follows:
a fluorescence-enhanced coordination polymer for detecting erythromycin in water, the coordination polymer having the formula:
[Co(4-bmnpd)(HCPG) 2 (H 2 O) 2 ]；
wherein 4-bmnpd is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide and HCPG is 3- (4-chlorophenyl) glutarate.
A synthesis method of fluorescence enhancement coordination polymer for detecting erythromycin in water comprises the following specific steps: co is to be 2+ Adding deionized water, a semi-rigid bipyridine bisamide ligand, 3- (4-chlorophenyl) glutaric acid and sodium hydroxide, stirring for 20-30 min at room temperature to form a suspension mixture, wherein the semi-rigid bipyridine bisamide ligand is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalene bisamide, and the molar ratio of the semi-rigid bipyridine bisamide ligand to the 3- (4-chlorophenyl) glutaric acid is 12, the semi-rigid bipyridine bisamide ligand and Co 2+ The molar ratio of the nitrate of the semi-rigid bipyridine bisamide ligand to the sodium hydroxide is 1:2, the mixture is poured into a high-pressure reaction kettle, the temperature is raised to 120 ℃, the heat is preserved for 72 to 96 hours under the hydrothermal condition, the mixture is cooled to room temperature to obtain pink blocky crystals, and the mixture is naturally dried at room temperature to obtain the cobalt coordination polymer based on the semi-rigid bipyridine bisamide organic ligand and the 3- (4-chlorophenyl) glutaric acid.
Further, the Co 2+ Nitrate of (2) is Co (NO) 3 ) 2 ·6H 2 O。
Further, when the temperature is raised to 120 ℃, the temperature raising rate is 5 ℃/h to 10 ℃/h; when the temperature is reduced to the room temperature, the temperature reduction rate is 5 ℃/h to 10 ℃/h.
Further, the addition amount of the deionized water is 30-50% of the volume of the high-pressure reaction kettle.
The fluorescence enhancement coordination polymer for detecting erythromycin in water is applied to detection of erythromycin.
The detection steps are as follows:
(1) Grinding a cobalt coordination polymer based on a semi-rigid bipyridine bisamide organic ligand and 3- (4-chlorophenyl) glutaric acid to obtain coordination polymer powder;
(2) Dispersing coordination polymer powder into water, wherein the mass volume ratio of the coordination polymer to the conference is 0.1g/L, and carrying out ultrasonic treatment at room temperature for 20-30 min to obtain suspension;
(3) And (3) mixing the water sample to be detected and the suspension for 30 seconds according to the mass ratio of 1:6, and then carrying out fluorescence spectrum detection, wherein the fluorescence intensity is obviously enhanced, and the water sample to be detected contains the antibiotic erythromycin, otherwise, does not contain the antibiotic erythromycin.
Further, cobalt coordination polymer based on semi-rigid bipyridine bisamide organic ligand and 3- (4-chlorophenyl) glutaric acid has a linear corresponding relation to erythromycin at erythromycin concentration ranging from 0mM to 0.02mM, and sensitivity of 3.58X10 4 M -1 The correlation coefficient is 0.999, and the detection limit is 4.51X10 -6 M。
The invention takes cobalt nitrate as transition metal, takes 3- (4-chlorphenyl) glutaric acid as carboxylic acid ligand, takes N, N' -bis (3-methylpyridine-3-yl) -2, 6-naphthalene diamide as neutral organic amine ligand, and synthesizes a coordination polymer based on cobalt through hydrothermal synthesis; improving the coordination capacity of the ligand by introducing a bisamide functional group into the pyridine group; adjusting flexibility of the organic amine ligand by introducing naphthalene groups as a lattice, wherein ten atoms on the naphthalene group ring are in the same plane; the selection of the transition metal cobalt can also increase the hydrophilic fluorescence performance of the coordination polymer, so that the cobalt coordination polymer has good fluorescence characteristics; 1 transition metal cobalt coordination polymer with three-dimensional supermolecular skeleton structure is synthesized. Wherein, the semi-rigid bipyridine bisamide organic ligand 4-bmnpd adopts a bidentate coordination mode, and utilizes the nitrogen atoms of two pyridine groups to coordinate with cobalt; 3- (4-chlorophenyl) glutaric acid adopts a bidentate coordination mode; the oxygen atoms of 2 carboxylic acid groups are used to coordinate cobalt. The beneficial effects are as follows:
(1) The synthesis method is simple, the synthesis raw materials are easy to obtain, the cost is low, and the synthesis yield is high; the semi-rigid bipyridine bisamide ligand N, N' -bis (3-methylpyridine-3-yl) -2, 6-naphthalene bisamide is adopted as a neutral organic amine ligand, not only is pyridine nitrogen atom coordinated with metal ions, but also amide oxygen atom is a potential coordination point, and the hydrophilicity of the ligand is increased due to the introduction of amide groups, so that the crystallization process in the process of synthesizing the transition metal coordination polymer is accelerated, the synthesis period is shortened, the constant temperature time is shortened, and the power consumption is reduced;
(2) The synthesized cobalt coordination polymer has obvious solid state fluorescence emission characteristic at room temperature; the cobalt coordination polymer synthesized under the hydrothermal condition is insoluble in water and common organic solvents, is easy to separate, and prevents secondary pollution to the environment; the synthesized cobalt coordination polymer shows stable fluorescence intensity except pH=14 after being treated by water solutions with different pH values, and has excellent stability;
(3) After erythromycin treatment, the synthesized cobalt coordination polymer has obviously enhanced fluorescence intensity and good molecular recognition effect on erythromycin; after erythromycin treatment, a stable peak value can be reached in a short time, and a quick response time is shown for erythromycin; interferents (N) in menstrual Watera + ，Mg 2+ ，Cl - ，CO 3 2- Etc.), the fluorescence intensity change is not obvious, and the method has excellent anti-interference capability for detecting erythromycin in water; after the treatment of the water solution containing erythromycin with different concentrations, the fluorescence intensity and the erythromycin content in the solution form a linear relationship in low concentration, and the method can be applied to detecting the erythromycin content in water.
Drawings
FIG. 1 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the present invention 2 (H 2 O) 2 ]Powder diffraction pattern;
FIG. 2 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]Is a infrared spectrogram of (2);
FIG. 3 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]Is a coordination environment diagram of (1);
FIG. 4 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]Is a one-dimensional chain map of (2);
FIG. 5 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]A two-dimensional network map of ab axis direction;
FIG. 6 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]A two-dimensional network map of ac axis direction;
FIG. 7 is a schematic illustration of the invention [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]Is a three-dimensional network map of (2);
FIG. 8 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]Solid state fluorescence excitation and emission spectrograms;
FIG. 9 is a schematic diagram of [ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]And a solid state fluorescence emission spectrum of the semi-rigid bipyridine bisamide ligand 4-bmnpd;
FIG. 10 is a graph of [ Co (4-bmnpd) (HCPG) with and without addition of different interfering substances and erythromycin 2 (H 2 O) 2 ]A histogram of fluorescence emission peak intensity variation of (a);
FIG. 11 is a sample of [ Co (4-bmnpd) (HCPG) after treatment with an aqueous erythromycin solution 2 (H 2 O) 2 ]The fluorescence emission spectrum of (2) is shown in the figure with low concentration [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]Is a detection line graph of (1);
FIG. 12 is a graph of [ Co (4-bmnpd) (HCPG) after treatment with aqueous solutions of different pH 2 (H 2 O) 2 ]Is a fluorescent emission spectrum of (2);
FIG. 13 is a graph of [ Co (4-bmnpd) (HCPG) after treatment with aqueous solutions of different pH 2 (H 2 O) 2 ]A fluorescence emission intensity plot of (2);
FIG. 14 is a sample of [ Co (4-bmnpd) (HCPG) after treatment with an aqueous erythromycin solution 2 (H 2 O) 2 ]A plot of fluorescence intensity versus response time;
FIG. 15 is a sample of [ Co (4-bmnpd) (HCPG) after treatment with aqueous erythromycin solution 2 (H 2 O) 2 ]A graph of fluorescence intensity versus cycle number;
Detailed Description
EXAMPLE 1 Synthesis of [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]Wherein 4-bmnpd is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide and HCPG is 3- (4-chlorophenyl) glutarate 0.2mmol Co (NO) 3 ) 2 ·6H 2 O, 0.10mmol of N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide, 0.20mmol of 3- (4-chlorophenyl) glutaric acid, 0.20mmol of NaOH and 9.0mL of H 2 Adding O into a beaker in sequence, stirring at room temperature for 20min, pouring into a 25mL high-pressure reaction kettle, heating to 120 ℃ at a heating rate of 5 ℃/h, preserving heat for 72h under a hydrothermal condition, cooling to room temperature at a cooling rate of 5 ℃/h to obtain pink blocky crystals, and naturally airing at room temperature to obtain [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]The yield is 25%, the coordination environment diagram is shown in fig. 3, the two-dimensional network diagrams are shown in fig. 5 and 6, and the three-dimensional skeleton structure diagram is shown in fig. 7.
EXAMPLE 2 Synthesis of [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]Wherein 4-bmnpd is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide and HCPG is 3- (4-chlorophenyl) glutarate 0.2mmol Co (NO) 3 ) 2 ·6H 2 O, 0.10mmol of N, N' -bis (3-methylpyridine-3-)Phenyl) -2, 6-naphthalenediamide, 0.20 mmole 3- (4-chlorophenyl) glutaric acid, 0.20 mmole NaOH and 9.0mL H 2 Adding O into a beaker in sequence, stirring at room temperature for 30min, pouring into a 25mL high-pressure reaction kettle, heating to 120 ℃ at a heating rate of 5 ℃/h, preserving heat for 72h under a hydrothermal condition, cooling to room temperature at a cooling rate of 5 ℃/h to obtain pink blocky crystals, and naturally airing at room temperature to obtain [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]The yield is 27%, the coordination environment diagram is shown in fig. 3, the two-dimensional network diagrams are shown in fig. 5 and 6, and the three-dimensional skeleton structure diagram is shown in fig. 7.
EXAMPLE 3 Synthesis of [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]Wherein 4-bmnpd is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide and HCPG is 3- (4-chlorophenyl) glutarate 0.2mmol Co (NO) 3 ) 2 ·6H 2 O, 0.10mmol of N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide, 0.20mmol of 3- (4-chlorophenyl) glutaric acid, 0.20mmol of NaOH and 11.0mL of H 2 Adding O into a beaker in sequence, stirring at room temperature for 20min, pouring into a 25mL high-pressure reaction kettle, heating to 120 ℃ at a heating rate of 5 ℃/h, preserving heat for 72h under a hydrothermal condition, cooling to room temperature at a cooling rate of 5 ℃/h to obtain pink blocky crystals, and naturally airing at room temperature to obtain [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]The yield is 30%, the coordination environment diagram is shown in fig. 3, the two-dimensional network diagrams are shown in fig. 5 and 6, and the three-dimensional skeleton structure diagram is shown in fig. 7.
EXAMPLE 4 Synthesis of [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]Wherein 4-bmnpd is N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide and HCPG is 3- (4-chlorophenyl) glutarate 0.2mmol Co (NO) 3 ) 2 ·6H 2 O, 0.10mmol of N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide, 0.20mmol of 3- (4-chlorophenyl) glutaric acid, 0.20mmol NaOH 11.0mL H 2 Adding O into a beaker in sequence, stirring at room temperature for 20min, pouring into a 25mL high-pressure reaction kettle, heating to 120 ℃ at a heating rate of 10 ℃/h, preserving heat for 96h under a hydrothermal condition, cooling to room temperature at a cooling rate of 5 ℃/h to obtain pink blocky crystals, and standing at room temperatureAir-dried to obtain [ Co (4-bmnpd) (HCPG) 2 (H 2 O) 2 ]The yield is 28%, the coordination environment diagram is shown in fig. 3, the two-dimensional network diagrams are shown in fig. 5 and 6, and the three-dimensional skeleton structure diagram is shown in fig. 7.
Characterization of cobalt coordination polymers based on semi-rigid bipyridine bisamide organic ligands and 3- (4-chlorophenyl) glutaric acid
(1) Characterization of phase purity by powder diffraction
The completed powder diffraction data were collected on a Rigaku Ultima IV powder X-ray diffractometer with an operating current of 40mA and a voltage of 40kV. Copper target X-rays were used. The scan was fixed, and the width of the receiving slit was 0.1mm. The density data collection uses a 2 theta/theta scan mode with a scan range of 5 deg. to 60 deg., a scan speed of 5 deg./s and a span of 0.02 deg./times. Data fitting uses the procedure of Cerius2 and single crystal structure powder diffraction spectrum simulated transformation uses Mercury 1.4.1.
Characterization of cobalt coordination polymers based on semi-rigid bipyridine bisamide organic ligands and 3- (4-chlorophenyl) glutaric acid
(1) Crystal structure determination
A single crystal of a suitable size was selected with a microscope, and a Bruker SMART APEX II diffractometer (graphite monochromator, mo-Ka,
) Diffraction data is collected. Scanning mode->
The diffraction data were corrected for absorbance using the sadbs procedure. Using ole 2, the structural problem is solved by the shelx structure solution program using the eigen phase and the structure is optimized using the SHELXL optimization package using least squares minimization. Coordination polymer 1[ Co (4-bmnpd) (HCPG) of the invention 2 (H 2 O) 2 ]The parameters of the crystallographic diffraction point data collection and structure refinement are shown in table 1:
TABLE 1
(2) Characterization of phase purity by powder diffraction
The completed powder diffraction data were collected on a Rigaku Ultima IV powder X-ray diffractometer with an operating current of 40mA and a voltage of 40kV. Copper target X-rays were used. The scan was fixed, and the width of the receiving slit was 0.1mm. The density data collection uses a 2 theta/theta scan mode with a scan range of 5 deg. to 60 deg., a scan speed of 5 deg./s and a span of 0.02 deg./times. Data fitting uses the procedure of Cerius2 and single crystal structure powder diffraction spectrum simulated transformation uses Mercury 1.4.1.
As shown in fig. 1, the powder X-ray diffraction pattern of the cobalt coordination polymer of 3- (4-chlorophenyl) glutaric acid was substantially identical to the fitted XRD pattern, indicating that the coordination polymers were all pure phases.
Fluorescence property test of cobalt coordination Polymer based on semi-rigid bipyridine bisamide organic ligand and 3- (4-chlorophenyl) glutaric acid
Co (4-bmnpd) (HCPG) synthesized in examples 1 to 4 2 (H 2 O) 2 ]The solid state fluorescence spectrum of the (coordination polymer 1) and the semi-rigid bipyridine bisamide organic ligand N, N' -bis (3-methylpyridine-3-yl) -2, 6-naphthalene bisamide at room temperature is measured, and the result shows that the coordination polymer 1 has strong fluorescence emission characteristics and can be applied to fluorescent materials.
The solid state excitation and emission spectrum experiment of the coordination polymer 1 at the temperature comprises the following specific steps:
30mg of the coordination polymer 1 was ground into a uniform powder in an agate mortar, and subjected to solid-state excitation and fluorescence emission spectrometry. As shown in FIG. 8, the maximum emission wavelength of the coordination polymer 1 was 381nm in the solid state using light having a wavelength of 358nm as excitation light. When light with a wavelength of 381nm is used as the emission light in the solid state, the maximum excitation wavelength of 358nm of the coordination polymer 1, and the experimental result shows that the excitation wavelength of 358nm of the coordination polymer 1 and the emission wavelength of 381nm.
The solid state fluorescence spectrum experiment of coordination polymer 1 and semi-rigid bipyridine bisamide organic ligand N, N' -bis (3-methylpyridin-3-yl) -2, 6-naphthalene bisamide at room temperature comprises the following specific steps:
30mg of coordination polymer 1 was ground into a uniform powder in an agate mortar, subjected to solid state fluorescence spectroscopy, and a semi-rigid bipyridine bisamide organic ligand of the same quality was taken as a control experiment. As shown in fig. 9, the semi-rigid bipyridine bisamide organic ligand 4-bmnpd has fluorescence emission characteristic under the solid state with light with the wavelength of 358nm, and the maximum emission wavelength is 370nm, and the emission peak can be attributed to pi- & gt pi or n- & gt pi electron transfer in the ligand. When the ligand is coordinated with cobalt ions to form a coordination polymer, the solid fluorescent property of the coordination polymer 1 is changed. The maximum emission wavelength of coordination polymer 1 was 381nm, a certain red shift occurred with respect to the 4-bmnpd ligand, and the fluorescence intensity was significantly increased due to the result of the charge transfer from ligand to metal (LMCT) after formation of coordination polymer. Experimental results show that the cobalt coordination polymer has good fluorescence emission property and can be used as a fluorescent material.
The selective fluorescence experiment of the coordination polymer 1 on different ions and antibiotics comprises the following specific steps:
30mg of the powder of coordination polymer 1 was dispersed in 3mL of an aqueous solution, sonicated at room temperature for 30 minutes, then filled into a cuvette, and fluorescence emission spectra were measured and recorded, and 0.5mL of a 0.01mol/L ion to be measured (Na + ，Ca 2+ ，Mg 2+ ，K + ，Cl - ，CO 3 2- ，HCO 3 - ) And antibiotics (sulfadiazine TAP, thiamphenicol SDZ), respectively adding into a cuvette, testing fluorescence emission spectra, and recording, respectively adding 1mL erythromycin with concentration of 0.005mol/L based on the above detection, as shown in FIG. 10, the xy axis represents the selectivity of coordination polymer to erythromycin, and origin represents the original fluorescence intensity of coordination polymer, when different antibiotics and ionic aqueous solutions are added, the corresponding fluorescence intensity is not greatly different from the original fluorescence intensity, when erythromycin aqueous solution is added, coordination polymerThe ratio of the fluorescence intensity of (C) to the original fluorescence intensity is obviously enhanced, which shows that the fluorescent dye has good fluorescence selectivity recognition effect on erythromycin in water.
The coordination polymer 1 is subjected to an anti-interference experiment of erythromycin aqueous solution and ions and antibiotics in different waters, and the specific steps are as follows:
30mg of the powder of coordination polymer 1 was dispersed in 3mL of an aqueous solution, sonicated at room temperature for 30 minutes, and then placed in a cuvette to test fluorescence emission spectra and record, and 0.5mL of 0.01mol/L interfering substance (Na + ，Ca 2 + ，Mg 2+ ，K + ，Cl - ，CO 3 2- ，HCO 3 - Sulfadiazine TAP, thiamphenicol SDZ), 0.5mL of 0.01mol/L erythromycin was added, and fluorescence emission spectra were measured and recorded. As shown in FIG. 10, the yz axis shows the anti-interference ability of the coordination polymer in water, and the fluorescence intensity of the coordination polymer 1 after erythromycin is added in the presence of different antibiotics and ionic water solutions corresponding to the xy axis is obviously enhanced compared with that of the coordination polymer without erythromycin (only the anti-interference substance exists), which indicates that the coordination polymer can still effectively detect the presence of the interference substance and has good interference ability.
The specific steps of the fluorescence spectrum experiment of the coordination polymer 1 after being treated by erythromycin water solutions with different concentrations are as follows: 30mg of the powder of the coordination polymer 1 is dispersed into 3mL of water solution, ultrasonic treatment is carried out at room temperature for 30 minutes, the solution is filled into a cuvette for testing fluorescence emission spectrum, then a certain amount of 0.001mol/L erythromycin water solution is sucked by a 1-200 mu L pipette, and the cuvette is added for carrying out fluorescence emission spectrum testing on erythromycin water solutions with different concentrations. As shown in FIG. 11, with the increase of erythromycin concentration, the fluorescence intensity of the coordination polymer 1 gradually increases, and as shown in the inset, the fluorescence intensity of the erythromycin-coordination polymer 1 aqueous solution (x-axis of the inset of FIG. 11) with different concentrations in the low concentration range changes in a linear relationship, which shows that the coordination polymer 1 has application value in the quantitative detection of erythromycin.
The specific steps of the fluorescence spectrum experiment of the coordination polymer 1 subjected to the aqueous solution treatment with different pH values are as follows:
30mg of the powder of coordination polymer 1 was dispersed in 3mL of aqueous solutions of different pH (pH=1 to 14), sonicated at room temperature for 30 minutes, and then filled into a cuvette for fluorescence emission spectroscopy. As shown in fig. 12 and 13, the fluorescent intensity of the coordination polymer 1 of the aqueous solution of the rest pH was not greatly floated except for the aqueous solution of ph=14 and exhibited good fluorescent intensity, indicating that the coordination polymer 1 had excellent stability.
The specific procedure for the response time experiment of the fluorescence spectrum of coordination polymer 1 is as follows:
30mg of the powder of coordination polymer 1 was dispersed in 3mL of an aqueous solution, subjected to ultrasonic treatment at room temperature for 30 minutes, then placed in a cuvette for testing fluorescence emission spectra, 0.5mL of an aqueous solution of erythromycin at 0.008mol/L was added, and fluorescence emission spectra at different times were tested. As shown in FIG. 14, the fluorescence intensity after 28s tended to stabilize, indicating that the coordination polymer 1 had a shorter response time, facilitating rapid detection.
The specific steps of the cyclic fluorescence spectrum experiment of the coordination polymer 1 are as follows:
30mg of the powder of the coordination polymer 1 was dispersed in 3mL of an aqueous solution, after ultrasonic treatment for 30 minutes, the mixture was placed in a cuvette to test fluorescence emission spectrum, 1mL of an aqueous solution of erythromycin of 0.01mol/L was added to test fluorescence emission spectrum, ethanol was added to wash and centrifugation, and then the fluorescence emission spectrum was tested, thus 1 cycle was obtained. As shown in FIG. 15, the fluorescence intensity remained unchanged from the first one after 5 cycles, indicating that the coordination polymer 1 had a good cycle stability and was recyclable.
The above is only a specific embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An application of fluorescence enhanced coordination polymer for detecting erythromycin in water in detection of erythromycin, which is characterized in that:
the molecular formula of the coordination polymer is as follows:
[Co(4-bmnpd)(HCPG) 2 (H 2 O) 2 ]；
wherein 4-bmnpd isN,N'-bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide, HCPG being 3- (4-chlorophenyl) glutarate.
2. Use of a fluorescence-enhanced coordination polymer for the detection of erythromycin in water according to claim 1, characterized in that:
the specific synthesis steps of the coordination polymer are as follows:
co is to be 2+ Adding deionized water into nitrate of the ligand, the ligand of the semi-rigid bipyridine bisamide, 3- (4-chlorophenyl) glutaric acid and sodium hydroxide, stirring for 20-30 min at room temperature to form a suspension mixture, wherein the ligand of the semi-rigid bipyridine bisamide isN,N'-bis (3-methylpyridin-3-yl) -2, 6-naphthalenediamide, the molar ratio of semi-rigid bipyridine bisamide ligand to 3- (4-chlorophenyl) glutaric acid being 1:2, the semi-rigid bipyridine bisamide ligand to Co 2+ The molar ratio of the nitrate of the semi-rigid bipyridine bisamide ligand to the sodium hydroxide is 1:2, the mixture is poured into a high-pressure reaction kettle, the temperature is raised to 120 ℃, the heat is preserved for 72 to 96 hours under the hydrothermal condition, the mixture is cooled to room temperature to obtain pink blocky crystals, and the mixture is naturally dried at room temperature to obtain the cobalt coordination polymer based on the semi-rigid bipyridine bisamide organic ligand and the 3- (4-chlorophenyl) glutaric acid.
3. Use of a fluorescence-enhanced coordination polymer for the detection of erythromycin in water according to claim 2, characterized in that: the Co is 2+ Nitrate of (2) is Co (NO) 3 ) 2 ·6H 2 O。
4. Use of a fluorescence-enhanced coordination polymer for the detection of erythromycin in water according to claim 2, characterized in that: when the temperature is raised to 120 ℃, the temperature raising rate is 5-10 ℃ per hour; when the temperature is reduced to the room temperature, the temperature reduction rate is 5 ℃/h to 10 ℃/h.
5. Use of a fluorescence-enhanced coordination polymer for the detection of erythromycin in water according to claim 2, characterized in that: the addition amount of the deionized water is 30% -50% of the volume of the high-pressure reaction kettle.
6. Use of a fluorescence-enhanced coordination polymer for the detection of erythromycin in water according to claim 1, characterized in that:
the detection steps are as follows:
(1) Grinding a cobalt coordination polymer based on a semi-rigid bipyridine bisamide organic ligand and 3- (4-chlorophenyl) glutaric acid to obtain coordination polymer powder;
(2) Dispersing coordination polymer powder into water, wherein the mass volume ratio of the coordination polymer to the water is 0.1g/L, and performing ultrasonic treatment at room temperature for 20-30 min to obtain suspension;
(3) And (3) mixing the water sample to be detected and the suspension for 30 seconds according to the mass ratio of 1:6, and then carrying out fluorescence spectrum detection, wherein the fluorescence intensity is obviously enhanced, and the water sample to be detected contains the antibiotic erythromycin, otherwise, does not contain the antibiotic erythromycin.
7. Use of a fluorescence-enhanced coordination polymer for the detection of erythromycin in water according to claim 1, characterized in that: cobalt coordination polymer based on semi-rigid bipyridine bisamide organic ligand and 3- (4-chlorophenyl) glutaric acid has linear corresponding relation to erythromycin at concentration range of erythromycin of 0mM-0.02mM, and sensitivity of 3.58×10 4 M −1 The correlation coefficient is 0.999, and the detection limit is 4.51X10 −6 M。
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