CN107739604B - Fluorescent sensing material based on rhodamine B and cyano diphenol and preparation and application thereof - Google Patents
Fluorescent sensing material based on rhodamine B and cyano diphenol and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a fluorescence sensing material based on rhodamine B and cyano diphenol, a preparation method and application thereof, belonging to the technical field of fluorescence chemical sensing materials and chemical analysis and detection; dissolving rhodamine acyl ethylenediamine and 3-formyl-4-hydroxy-4-biphenylyl cyanide in absolute ethyl alcohol, adding a proper amount of glacial acetic acid, stirring and refluxing in an oil bath kettle, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure to obtain a crude product, and recrystallizing in the ethyl alcohol to obtain the fluorescent sensing material; the fluorescent sensing material prepared by the invention is Zn2+，Al3+，Fe3+And Cr3+The four metal ions have multiple responsivities, can well realize effective detection of trace amounts of target metal ions in an environmental water sample through different presented fluorescent signals, and have the characteristics of readily available raw materials, simple preparation process, good product stability, high detection sensitivity and the like.
Description
Technical Field
The invention relates to a chemical fluorescence sensing material, in particular to a fluorescence sensing material based on rhodamine B and cyano diphenol, a preparation method and application thereof, and belongs to the technical field of fluorescence chemical sensing materials and chemical analysis and detection.
Background
With the rapid development of social economy, the problem of environmental pollution has been a focus of attention. The harm of heavy metal ions as one of the pollutants to the environment is extremely serious, which is mainly shown in that the heavy metal pollutants cannot be degraded by microorganisms in the natural environment and only can be subjected to morphological change, and the toxicity of the heavy metal pollutants is not eliminated in the process; the heavy metal ions in different forms can act on animals and plants in biological migration, enrichment and other ways and finally enter human bodies through food chains; although some metal ions are essential trace elements, when the intake amount of metal ions exceeds the maximum concentration allowed by the body, serious biological disorders are caused, and interaction with biomacromolecule substances is caused, so that the biomacromolecule is inactivated, and various diseases are caused. For example, common Alzheimer's disease, Parkinson's disease is caused by excessive intake of iron and aluminum ions; diabetes, cardiovascular and cerebrovascular diseases, tumors and abnormal hyperplasia are closely related to excessive intake of chromium ions; this accumulation in the body can lead to chronic poisoning, and this cumulative hazard is often not detectable in the short term.
Effective real-time monitoring is essential to reduce and avoid the harm of heavy metal ions to the ecological environment and human beings. The traditional detection technologies such as atomic absorption spectrophotometry, flame atomization, inductively coupled plasma atomic emission spectrometry and the like all need to carry out complex pretreatment on a sample before detection, the interference factors of a detection result are more, and in addition, a detection instrument is expensive and the operation is complex, so that the universal application of the detection instrument is limited. In comparison, the fluorescence detection method has the advantages of high sensitivity, strong selectivity, short response time, simple operation, small dosage, low cost and the like, can be used for trace and trace detection of ions, and is widely applied to a plurality of fields such as environmental monitoring, clinical medicine, biomolecule detection and the like. The fluorescence sensing material has unique optical properties, when the fluorescence sensing material is combined with target ions, the intrinsic photophysical characteristics of the material are influenced, the output form of a fluorescence signal is changed, and the rapid detection of the specific ions is realized by taking the fluorescence change of the sensor before and after the combination of the target ions as a response signal. In recent years, some research progress has been made on fluorescent sensing materials for metal ions. Most of the reported sensing materials are Schiff base materials based on fluorescent groups such as rhodamine B, coumarin, quinoline, anthraquinone and the like. But most of them correspond to a specific single target metal ion. Therefore, the ion fluorescent sensing material with multiple responses is a new field of research at present, and has more potential application values because different measurable output optical signal changes can be generated for different target metal ions in the process of identification and analysis.
Disclosure of Invention
The invention aims to overcome the limitation of the traditional detection technology and provides a fluorescent sensing material with multiple response properties based on rhodamine B and cyano diphenol, a preparation method and application thereof3+，Cr3+，Al3+And Zn2+The method has the characteristics of easily available raw materials, simple preparation process, good product stability, high detection sensitivity and the like.
The technical scheme adopted by the invention is as follows:
the invention firstly provides a multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol, wherein the material is a yellow orange powdery solid, the material is dissolved in a methanol/HEPES buffer solution (v/v =9:1, pH =7.4) system, the solution is yellow, and no obvious fluorescence emission is generated under 365nm ultraviolet light irradiation.
The invention also provides a preparation method of the multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol, which is characterized by comprising the following steps:
s1 synthesis of rhodamine acyl ethylenediamine:
references Dong L, Zeng X, Mu L, et al, The synthesis of a rhodomine B schiff-base chemosensor and reproduction properties for Fe3+ in neutral ethanol aqueous solution[J]Sensors and activators B Chemical, 2010, 145(1): 433-437.
Putting rhodamine B into a 100mL round-bottom flask, completely dissolving the rhodamine B with absolute ethyl alcohol, dropwise adding ethylenediamine while stirring, and putting the rhodamine B into an oil bath kettle to stir and reflux. And after the reaction is finished, cooling the reaction product to room temperature, decompressing and removing the solvent to obtain a crude rhodamine acyl ethylenediamine product, and recrystallizing and purifying the crude rhodamine acyl ethylenediamine product by using absolute ethyl alcohol to obtain a light pink solid.
In the synthesis method, 1 ~ 2.4.4 g (2 ~ 5mmol) of rhodamine B, ethylenediamine and absolute ethyl alcohol, 0.18 ~ 0.36.36 g (3 ~ 6 mmol) of anhydrous ethyl alcohol, and 20 ~ 40mL are adopted, the reflux reaction temperature is 60-70 ℃, and the reaction time is 8-12 h.
S2.preparation of 3-formyl-4-hydroxy-4-biphenylcarbonitrile:
reference is made to Alici O, Erdemir S. A cyanodiphenyl conjugation fluorescence "turn on" sensor for Al3+ ion in CH 3CN–water [J]Preparation was carried out by Sensors and activators B Chemical 2015, 208: 159-.
Paracyanobiphenol and urotropin were dissolved in glacial acetic acid and placed in a 100mL round bottom flask in an oil bath with stirring under reflux. After the reaction is finished, cooling to room temperature, adding 10M hydrochloric acid solution, stirring at room temperature, acidifying for 1h, extracting with dichloromethane, collecting an organic layer, washing with distilled water for 3 times, saturating with saline water for 1 time, drying with anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure to obtain a light yellow solid.
The dosage ratio of the 4-hydroxy-4-biphenylyl cyanide, the urotropine, the glacial acetic acid and the hydrochloric acid solution in the synthesis method is 0.39-0.78 g (2 ~ 4mmol), 1.41 ~ 2.82.82 g (10 ~ 20mmol), 30-70 mL and 80-120 mL, the reflux reaction temperature is 90-110 ℃, and the reaction time is 8-12 h.
S3. synthesis of multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol:
dissolving rhodamine acyl ethylenediamine and 3-formyl-4-hydroxy-4-biphenylyl cyanide in absolute ethyl alcohol, adding a proper amount of glacial acetic acid, stirring and refluxing in an oil bath kettle, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure to obtain a crude product, and recrystallizing in the ethyl alcohol to obtain the fluorescent sensing material.
The dosage ratio of the rhodamine ethylenediamine, the 3-formyl-4-hydroxy-4-biphenylyl cyanide, the absolute ethyl alcohol and the glacial acetic acid in the step S3 is 0.52-1.56 g (1 ~ 3mmol), 0.22-0.67 g (1 ~ 3mmol), 20-40 mL and 1 ~ 3 drops, the reflux reaction temperature is 65-75 ℃, and the reaction time is 8-12 hours.
The multiple response type fluorescent sensing material based on rhodamine B and cyano diphenol is used for Zn in an environmental water sample2+、Al3+、Fe3+Or Cr3+And (4) trace analysis and detection of four metal ions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol, a preparation method and application thereof. Rhodamine B as a fluorescent dye has a unique lactam ring structure, the fluorescence and the color of a solution system of the rhodamine B can be changed due to the opening of the lactam ring, and the rhodamine B has good optical properties. An aromatic ring conjugated system is also arranged in the structure of the p-cyanobiphenol, and the aldehyde group is easily modified at the ortho position of the phenolic hydroxyl group in the structure. The ethylene diamine is used as a connecting bridge to combine the ethylene diamine and the diamine to form a compound with double fluorescent groups, and the prepared material has a stable structure and cannot be decomposed after being placed for a long time. Because the lactam ring of the rhodamine B derivative group in the compound material is in a closed state, the fluorescence of the p-cyano o-phenol group part is not emitted, and the whole system does not show fluorescence. This also provides a precondition for realizing a switch-type fluorescent probe. In addition, the carbonyl oxygen atom, the hydroxyl oxygen atom and the nitrogen atom on the C = N group in the compound structure can provide electrons as binding sites of metal ions, and compared with a common small-molecule metal fluorescent sensing material, the material has more binding sites and stronger binding capacity with target metal ions.
(2) The synthesis condition of the fluorescent sensing material is mild and easy to control, the post-treatment is simple and easy to implement by recrystallization purification, the preparation cost is low, and the feeding amount in the preparation process is the optimal reaction molar ratio determined based on a large amount of experimental research. The reaction temperature and time are determined based on the reaction rate and yield. Within the optimal parameter range, the synthesis yield can reach more than 75 percent.
(3) The fluorescent sensing material prepared by the invention has multiple responses, and Zn is added into a fluorescent sensing material solution system2+Then, strong blue fluorescence emission is observed under the irradiation of an ultraviolet lamp; adding Al3+Then, a yellow fluorescence emission is observed; adding Fe3+And Cr3+After that, the system will show red fluorescence. This is because the sensing material has two different fluorescence emitting groups, but not the sameTarget metal ion (Zn) of (1)2+, Al3+, Fe3+, Cr3+) When the metal ion complex is added, complex structures with different configurations can be formed due to different complexing modes, different fluorescence emissions are caused, multiple selectivity of metal ions can be realized by utilizing the difference of optical properties among the complexes, and compared with the traditional metal ion detection technology, the fluorescent molecule prepared by the method disclosed by the invention has the advantages that the Zn is subjected to multiple selectivity2+，Al3+，Fe3+And Cr3+Four metal ions are detected, the selectivity and the sensitivity are high, only a fluorescence spectrophotometer is needed for auxiliary detection, the change of a fluorescence signal under an ultraviolet lamp can be seen by naked eyes, the interference of other common metal ions is small, and the utilization value is greatly increased.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of the multiple response type fluorescent sensing material based on rhodamine B derivative and cyanobiphenol prepared in example 3;
FIG. 2 is a diagram of a fluorescent sensor material prepared in example 31H NMR, wherein the solvent is DMSO-D6。
FIG. 3 shows a fluorescent sensor material prepared in example 313C NMR chart in which the solvent is DMSO-D6。
FIG. 4 is a MS diagram of a fluorescent sensing material prepared in example 3;
FIG. 5 is a fluorescence spectrum of the fluorescence sensing material prepared in example 3 for different metal ions; in the figure, a is the fluorescence spectrum at an excitation wavelength of 360nm, and b is the fluorescence spectrum at an excitation wavelength of 520 nm.
FIG. 6 shows the different macroscopic fluorescence emissions of the fluorescence sensing material prepared in example 3 under the irradiation of an ultraviolet lamp after different metal ions are added; the fluorescence sensing material prepared by the invention is shown as 1 in the figure.
FIG. 7 shows the UV-VIS absorption spectra of the fluorescence sensing material prepared in example 3 for different metal ions.
FIG. 8 shows that the fluorescent sensing materials prepared in example 3 have different Zn concentrations2+(FIG. 8 a), Al3+(FIG. 8 b), Fe3+(drawing)8c) And Cr3+(FIG. 8 d) fluorescence spectra in the presence of four metal ions; wherein the insets are the respective degrees of fluorescence enhancement (I-I)0) And the concentration of metal ions.
FIG. 9 shows Zn identification of the fluorescent sensing material prepared in example 32+(FIG. 9 a), Al3+(FIG. 9 b), Fe3+(FIG. 9 c) and Cr3+(FIG. 9 d) a graph showing the experimental results of the interference of other common metal ions with target ions for four target metal ions; the fluorescence sensing material prepared by the invention is shown as 1 in the figure.
FIG. 10 shows that the fluorescent sensing material prepared in example 3 is used for Fe in an environmental water sample3+The detected fluorescence map of (1).
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1:
s1 synthesis of rhodamine acyl ethylenediamine: 1g (2mmol) of rhodamine B is placed in a 100mL round-bottom flask, the rhodamine B is completely dissolved by 20mL of absolute ethanol, 0.18g (3mmol) of ethylenediamine is dropwise added while stirring, and the mixture is placed in a 60 ℃ oil bath and stirred and refluxed for 8 hours. And after the reaction is finished, cooling the reaction product to room temperature, decompressing and removing the solvent to obtain a crude rhodamine acyl ethylenediamine product, and recrystallizing and purifying the crude rhodamine acyl ethylenediamine product by using absolute ethyl alcohol to obtain a light pink product.
S2.preparation of 3-formyl-4-hydroxy-4-biphenylcarbonitrile: 0.39g (2mmol) of 4-hydroxy-4-biphenylcyanogen, 1.41g (10mmol) of urotropin was dissolved in 30mL of glacial acetic acid and placed in a 100mL round bottom flask in a 90 ℃ oil bath with stirring under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, 80mL of 10M hydrochloric acid solution was added thereto, and the mixture was acidified at room temperature for 1 hour with stirring, and then extracted with dichloromethane, and the organic layer was collected, washed with distilled water for 3 times, saturated brine for 1 time, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a pale yellow solid.
S3. synthesis of multiple response type fluorescence sensing material based on rhodamine B derivative and cyano diphenol: dissolving 0.52g (1 mmol) of rhodamine ethylenediamine and 0.23g (1 mmol) of 3-formyl-4-hydroxy-4-biphenylyl cyanide in 20mL of absolute ethyl alcohol, adding 1 drop of glacial acetic acid, stirring and refluxing in an oil bath kettle at 65 ℃ for 8 hours, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure to obtain a crude product, and recrystallizing in ethanol to obtain an orange solid with the yield of 78.2%.
Example 2:
s1 synthesis of rhodamine acyl ethylenediamine: 1.44g (3mmol) of rhodamine B is placed in a 100mL round bottom flask, completely dissolved by 30mL of absolute ethanol, 0.27g (4.5mmol) of ethylenediamine is added dropwise with stirring, and the mixture is placed in a 65 ℃ oil bath and stirred and refluxed for 10 hours. And after the reaction is finished, cooling the reaction product to room temperature, decompressing and removing the solvent to obtain a crude rhodamine acyl diamine product, and recrystallizing and purifying the crude rhodamine acyl diamine product by using absolute ethyl alcohol to obtain a light pink product.
S2.preparation of 3-formyl-4-hydroxy-4-biphenylcarbonitrile: 0.59g (3mmol) of 4-hydroxy-4-biphenylcyanogen and 2.11g (15mmol) of urotropin were dissolved in 50 mL of glacial acetic acid and placed in a 100mL round-bottomed flask in a 100 ℃ oil bath with stirring under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of 10M hydrochloric acid solution was added thereto, and the mixture was acidified at room temperature for 1 hour with stirring, and then extracted with dichloromethane, and the organic layer was collected, washed with distilled water for 3 times, saturated brine for 1 time, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a pale yellow solid.
S3. synthesis of multiple response type fluorescence sensing material based on rhodamine B derivative and cyano diphenol: dissolving 1.04g of rhodamine acyl ethylenediamine and 0.45g of 3-formyl-4-hydroxy-4-biphenylyl cyanide in 30mL of absolute ethanol, adding 2 drops of glacial acetic acid, stirring and refluxing in an oil bath kettle at 70 ℃ for 10 hours, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure to obtain a crude product, recrystallizing in ethanol to obtain an orange yellow solid, wherein the yield is 79.7%
Example 3:
s1 synthesis of rhodamine acyl ethylenediamine: 2.4g (5 mmol)) of rhodamine B is placed in a 100mL round-bottom flask, completely dissolved with 40mL of absolute ethanol, 0.36g (6 mmol) of ethylenediamine is added dropwise with stirring, and the mixture is placed in a 70 ℃ oil bath and stirred under reflux for 12 h. And after the reaction is finished, cooling the reaction product to room temperature, decompressing and removing the solvent to obtain a crude rhodamine acyl diamine product, and recrystallizing and purifying the crude rhodamine acyl diamine product by using absolute ethyl alcohol to obtain a light pink product.
S2.preparation of 3-formyl-4-hydroxy-4-biphenylcarbonitrile: 0.78g (4mmol) of 4-hydroxy-4-biphenylnitrile, 2.82g (20mmol) of urotropin were dissolved in 70 mL of glacial acetic acid and placed in a 100mL round-bottomed flask in a 110 ℃ oil bath with stirring under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, 120mL of a 10M hydrochloric acid solution was added thereto, and the mixture was acidified at room temperature for 1 hour with stirring, then extracted with dichloromethane, and the organic layer was collected, washed with distilled water for 3 times, saturated brine for 1 time, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a pale yellow solid.
S3. synthesis of multiple response type fluorescence sensing material based on rhodamine B derivative and cyano diphenol: dissolving 1.56g (3mmol) of rhodamine ethylene diamine and 0.67g (3mmol) of 3-formyl-4-hydroxy-4-biphenylyl cyanide in 40mL of absolute ethanol, adding 3 drops of glacial acetic acid, stirring and refluxing in an oil bath kettle at 75 ℃ for 12 hours, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure to obtain a crude product, recrystallizing in ethanol to obtain an orange yellow solid with the yield of 81.5 percent
FIG. 1 is a schematic diagram of a synthetic process of a multiple-response fluorescent sensing material based on rhodamine B derivatives and cyano diphenol.
The multiple response type fluorescent sensing material based on rhodamine B derivative and cyano diphenol is shown in figure 21H NMR chart in which the solvent is CDCl3. Spectrum analysis: 1H NMR (400MHz CDCl3) 8.15(1H, s), 7.94(1H, dd), 7.71(2H, d), 7.71(2H, d), 7.62(2H, d), 7.53(1H, dd), 7.47(2H, dd) 7.39(1H, d), 7.11(1H, dd), 7.02(1H, d), 6.44(4H, t), 6.28 (1H, d), 6.25(1H, d),3.51(2H, dd), 3.44(2H, m), 3.34(8H, dd), 1.18(12H, t); based on rhodamine B derivatives as shown in FIG. 3And cyano diphenol multiple response type fluorescent sensing material13C NMR chart in which the solvent is CDCl3. Spectrum analysis:13C NMR (101 MHz, CDCl3) δ 168.40 (s, 1H), 165.65 (s, 1H), 162.15 (s, 1H), 153.47 (d, J = 17.7 Hz, 4H), 148.89 (s, 3H), 144.85 (s, 1H), 132.58 (d, J =7.3 Hz, 9H), 130.98 (s, 2H), 130.78 (s, 2H), 129.86 (s, 2H), 129.18 (s, 2H),128.84 (s, 5H), 128.10 (s, 4H), 126.87 (s, 5H), 123.84 (s, 5H), 122.88 (s,3H), 119.01 (s, 3H), 118.11 (s, 3H), 110.14 (s, 2H), 108.17 (s, 7H), 105.49(s, 5H), 97.87 (s, 8H), 77.36 (s, 35H), 77.04 (s, 33H), 76.73 (s, 34H), 65.00 (s, 5H), 56.98 (s, 6H), 44.35 (s, 12H), 40.86 (s, 9H), 12.62 (s, 13H).
the molecular structure of the prepared and synthesized fluorescent sensing material can be confirmed to be consistent with the expected structure in the figure 1 through nuclear magnetic spectrum analysis.
FIG. 4 shows a fluorescent sensing material (C)44H43N5O3Mn =689), wherein 712.13 is [ M + Na]The molecular weight of the corresponding fluorescent sensing material.
Example 4: the fluorescent sensing material prepared by the invention is Zn2+, Al3+, Fe3+And Cr3+Specificity verification of detection
6.89 mg of the fluorescent sensor material prepared in example 3 was weighed out and dissolved in methanol to 10mL to prepare a 10mM stock solution. 0.1mL of the above stock solution was removed and made up to 100mL of a fluorescent sensing material solution prepared at 10. mu.M (methanol/HEPES buffer solution, v/v:9:1, pH = 7.2) to be used. Transferring 4mL of the above 10 μ M solution to be used, and adding 10 equivalents of different common metal ions (Ni)2+, Ca2+, Co2+, Zn2+, Cr3+, Al3+, Fe3+, Na+, Cd2+, K+, Mg2+, Li+, Fe2+, Cu2+, Mn2+, Sr2+, Cs2+, Pb2+And Hg2+) And respectively measuring the respective fluorescence spectra by using a fluorescence spectrometer.
Fluorescence transmitterThe sensing material solution itself has very weak fluorescence emission (excitation wavelength is 360 nm) at 465nm, and the fluorescence spectra when 10 equivalents of different metal ions are added are shown in FIG. 5, wherein the excitation wavelengths of FIG. 5a and FIG. 5b are 360nm and 520nm, respectively, and it can be seen from the figure that Zn2+, Al3+, Fe3+And Cr3+Respectively, cause different fluorescence spectra to change. When Zn2+When present, a strong fluorescence emission peak appears at 465 nm; al (Al)3+The existence of the fluorescent dye can cause fluorescence emission peaks at 490nm and 580 nm; fe3+And Cr3+The addition of (A) respectively initiates a strong fluorescence emission at 580 nm. FIG. 6 shows the different fluorescence signals visible to the naked eye under UV light. Fig. 7 shows the corresponding uv-vis absorption spectrum. From the spectrum and the fluorescence chart, the existence of other metal ions can be found out without causing the change of the fluorescence of the sensing material system. The result shows that the fluorescent sensing material prepared by the invention is used for Zn2+, Al3+, Fe3+And Cr3+Has multiple responsiveness and can realize Zn2+, Al3 +, Fe3+And Cr3+Selective identification detection.
Example 5: the fluorescent sensing material prepared by the invention is Zn2+， Al3+，Fe3+ And Cr3+Sensitivity verification of detection
10 μ M of the ready-to-use solution prepared in example 4 was pipetted off separately for Zn2+, Al3+, Fe3+And Cr3+Performing a fluorescence titration experiment, namely adding 0-10 equivalent of Zn respectively2+, Al3+, Fe3+And Cr3+Fluorescence spectrometry was performed. The metal ion concentrations used in this example were respectively: 0.05X 10-5M、0.1×10-5M、0.2×10-5M、0.3×10-5M、0.4×10- 5M、0.5×10-5M、0.6×10-5M、0.7×10-5M、0.8×10-5M、0.9×10-5M、1.0×10-5M、2.0×10-5M、3.0×10-5M、4.0×10-5M、6.0×10-5M、8.0×10-5M、10.0×10-5And M. Wherein for Zn2+And Al3+The excitation wavelength of the sample to be detected is 365nm, and for Fe3+And Cr3+The excitation wavelength of the sample to be measured is 520 nm.
The fluorescence emission spectrum of the fluorescence titration experiment is shown in fig. 8, and it can be seen from the graph that as the concentration of the metal increases, the corresponding fluorescence emission peak gradually increases, and the corresponding fluorescence intensity tends to stabilize and no longer increases after the metal ion is combined to reach a saturation state. It is also noteworthy that with Al3+The fluorescence spectrum corresponding to the increase in concentration not only shows an increase in fluorescence intensity, but also shows a red shift phenomenon in which one of the emission peaks gradually red-shifts from 460nm to 490nm with the increase in metal ion concentration the corresponding inset in FIG. 8 shows that at a certain concentration range (0 ~ 1X 10)-5M) corresponding degree of fluorescence enhancement (I-I)0) Exhibits a good linear relationship with the concentration of the metal ion. This shows that the fluorescent sensing material can perform quantitative detection on four target metal ions within a certain concentration range. The lowest detection limit was calculated to be as low as 1.61 × 10, respectively, based on the slope (slope) of the linear equation and the detection limit calculation formula LOD =3 σ/slope (where σ is 1.462 corresponding to the standard deviation of the blank sample for 20 times)-7 M (Zn2+), 8.94×10-8 M (Al3+), 8.61×10-8 M (Fe3+) And 8.42X 10-8 M (Cr3+). The result shows that the fluorescence sensing material has high sensitivity for detecting four target metal ions.
Example 6: the fluorescent sensing material prepared by the invention is Zn2+，Al3+，Fe3+ And Cr3+Verification of anti-interference performance of other metal ions during detection
10 μ M of the solution to be used prepared in example 4 was transferred, and 10 equivalents of Zn were added, respectively2+, Al3+, Fe3+And Cr3+Preparing multiple groups of parallel samples with metal ion solution, and adding 10 equivalents of other common metal ions (Ni) into each group of parallel samples after 10min2+, Ca2+, Co2+, Na+, Cd2+, K+, Mg2+, Li+, Fe2+, Cu2+, Mn2+, Sr2+, Cs2+, Pb2+And Hg2 +) And respectively measuring the respective fluorescence spectra by using a fluorescence spectrometer, wherein the fluorescence spectra contain Zn2+And Al3+The excitation wavelength of the sample to be detected is 365nm, and the sample contains Fe3+And Cr3+The excitation wavelength of the sample to be measured is 520 nm.
FIG. 9 shows that the sensing material system detects Zn in the presence of other metal ions2+, Al3+, Fe3+And Cr3+The interference situation of the time can be seen from the figure, except that the four target ions slightly interfere with each other, other coexisting metal ions identify and detect Zn for the sensing material2+，Al3+，Fe3+ And Cr3+Has almost no influence. Mutual interference among the four metal ions can be reduced and avoided by increasing the concentration of the fluorescent sensing material during detection.
Example 7: the fluorescent sensing material prepared by the invention can be used for Zn in water sample2+, Al3+, Fe3+And Cr3+Performed labeling experiments
Collecting actual environmental water samples (Yangtze river water and lake water) for Zn2+, Al3+, Fe3+And Cr3+The four target metal ions are subjected to a labeling experiment and are respectively prepared into Zn with the concentration of 0.5mM, 1mM and 2mM2+, Al3+, Fe3+And Cr3+And taking the water solution as a water sample to be detected. 5mL of the 10. mu.M solution for fluorescence sensing material prepared in example 4 was removed, and 50. mu.L of Zn prepared as described above and having different concentrations were added thereto2+, Al3+, Fe3+And Cr3+Water sample, and measuring the fluorescence spectrum of the system.
Fluorescence sensing material for Zn in actual water sample2+, Al3+, Fe3+And Cr3+The detection effect of (2) is shown in fig. 10, and the result shows that the fluorescence sensing material is applied to Zn in the actual water body2+, Al3+, Fe3+And Cr3+The identification and detection of (2) are also applicable, and still have high sensitivity and are applicable to different concentrationsZn2+, Al3+, Fe3+And Cr3+In other words, the detected fluorescence enhancement degree conforms to the linear relationship between the fluorescence enhancement degree and the metal ion concentration in example 5, which also indicates that the fluorescent sensing material prepared by the invention can realize qualitative and quantitative detection of the target metal ions in the water body.
Claims (7)
1. A multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol is characterized in that the material is a yellow orange powdery solid, the yellow powdery solid is dissolved in a methanol/HEPES buffer solution system, the solution is yellow, and no obvious fluorescence emission is generated under 365nm ultraviolet light irradiation, wherein the volume ratio of methanol to HEPES in the buffer solution is 9:1, and the pH of the buffer solution is = 7.4; the structural formula of the fluorescence sensing material is as follows:
。
2. the method for preparing the multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol as claimed in claim 1, characterized by comprising the following steps:
s1 synthesis of rhodamine acyl ethylenediamine:
s2.preparation of 3-formyl-4-hydroxy-4-biphenylcarbonitrile:
s3. synthesis of multiple response type fluorescence sensing material based on rhodamine B and cyano diphenol:
dissolving rhodamine acyl ethylenediamine and 3-formyl-4-hydroxy-4-biphenylyl cyanide in absolute ethyl alcohol, adding a proper amount of glacial acetic acid, stirring and refluxing in an oil bath kettle, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure to obtain a crude product, and recrystallizing in the ethyl alcohol to obtain the fluorescent sensing material.
3. The preparation method according to claim 2, wherein the mass ratio of rhodamine acyl ethylenediamine to the 3-formyl-4-hydroxy-4-biphenyl group is 0.52 to 1.56 g: 0.22g to 0.67 g.
4. The method according to claim 3, wherein the amount of the absolute ethanol used in step S3 is 20-40 mL.
5. The method according to claim 3, wherein the reflux reaction temperature is 65 to 75 ℃.
6. The preparation method according to claim 3, wherein the reflux reaction time is 8-12 h.
7. The multiple-response type fluorescence sensing material based on rhodamine B derivative and cyanobiphenol as claimed in claim 1, wherein Zn is contained in environmental water sample2+、Al3+、Fe3+Or Cr3+In trace detection.
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