A molecular sensor and its application in detecting metal ions

Abstract

The present invention relates to the technical field of functional material metal ion detection, and in particular to a molecular sensor and its application in detecting metal ions. The molecular sensor is easy to prepare and has good sensitivity to Cu 2+ 、Al 3+ and Fe 3+ With different fluorescence "on-off or off-on" and accurate UV absorption double peak ratio detection signal, it can realize the detection of Cu in PVC basketball material. 2+ 、Al 3+ and Fe 3+ Fast and sensitive detection.

Description

Technical Field

[0001] The invention relates to the technical field of functional material metal ion detection, and in particular to a molecular sensor and application thereof in detecting metal ions. Background Art

[0002] Basketball can not only promote physical health, but also improve mental health and social skills. It is an all-round sports activity. According to its composition materials, basketballs mainly include polyurethane (PU) basketballs, polyvinyl chloride (PVC) basketballs, etc.; although PVC basketballs are slightly inferior to PU balls in terms of elasticity, feel and wear resistance, they are better than PU synthetic leather in waterproofing, mildew resistance and salt-alkali resistance. They are also more cost-effective and are the most common basketballs today. Usually, PVC basketballs undergo processes such as hot melting of plastic particles, coating, foaming in a furnace, surface dyeing, embossing, and grinding during the manufacturing process. A certain amount of heavy metal ions will inevitably be introduced into the above production process. Once the metal ion content exceeds the standard, it will not only reduce the service life of the basketball, but also because people touch it during basketball play, metal ions can easily enter the human body with food; especially for children and adolescents, basketball is one of their main forms of exercise during their growth. After the activity, sometimes they don’t have time to wash their hands before eating, and metal ions may enter the body and cause a series of diseases. For example, when copper accumulates to a certain extent in the body, it can lead to metabolic disorders, liver cirrhosis, liver ascites, or even worse; excessive iron ions can cause abnormal liver function, diabetes, and tumors; aluminum accumulation in the brain can cause brain nerve degeneration, memory loss, and even senile dementia, etc. Therefore, it is of great significance to develop a fast and sensitive method for detecting heavy metal ions in PVC basketball materials.

[0003] Among the many methods for detecting metal ions, molecular sensors have received increasing attention. Molecular sensors perform real-time detection at the molecular level, and the results are accurate and sensitive. However, most molecular sensors currently only show sensitive detection functions for a specific metal ion. Compared with single-function molecular sensors that detect one by one, molecular sensors with multiple detection performances are time-saving and economical; however, because multifunctional molecular sensors often involve complex preparation processes, high costs, and low yields, the current number of research and development is small, making it difficult to meet the growing market demand. The carbazole group has a high degree of conjugation and a large range of π-electron systems. It is a good light source signal group in the construction of molecular sensors; the dual receptor site formed by the condensation of aminocarbazole and salicylaldehyde compounds not only has a strong complexing ability for metal ions, but also shows sensitive spectroscopic signal changes. However, the current fluorescence detection method based on carbazole is used for Cu in basketball PVC materials. 2+ 、Al 3+ and Fe 3+ There are few reports on ion analysis. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides a molecular sensor and its application in detecting metal ions. The molecular sensor is easy to prepare and has good sensitivity to Cu 2+ 、Al 3+ and Fe 3+ With different fluorescence "on-off or off-on" and accurate UV absorption double peak ratio detection signal, it can realize the detection of Cu in PVC basketball material. 2+ 、Al 3+ and Fe 3+ Fast and sensitive detection.

[0005] In order to achieve the above technical objectives, the present invention adopts the following technical solutions:

[0006] The first object of the present invention is to provide the molecular sensor, which is a carbazole-juronidine molecule with the structural formula:

[0007]

[0008] The present invention also provides a method for preparing the molecular sensor, comprising the following steps:

[0009] 1,1,7,7-Tetramethyl-8-hydroxy-juronidin aldehyde and 3-amino-9-ethylcarbazole were placed in a round-bottom flask containing a mixed solvent of dichloromethane and anhydrous ethanol (1:1), and glacial acetic acid was added. The temperature was raised to reflux for reaction for 3-5 hours. The reaction mixture was filtered, washed with anhydrous ethanol, and dried to obtain a reddish-brown target molecule sensor.

[0010] The carbazole-juronidine molecular sensor preparation reaction formula is:

[0011]

[0012] Preferably, the molar ratio of the 1,1,7,7-tetramethyl-8-hydroxy-juradol aldehyde to 3-amino-9-ethylcarbazole is 1:1, and every 1 mmol of 1,1,7,7-tetramethyl-8-hydroxy-juradol aldehyde corresponds to 8 mL of a mixed solvent of dichloromethane-anhydrous ethanol (1:1), and every 1 mmol of 1,1,7,7-tetramethyl-8-hydroxy-juradol aldehyde corresponds to 100 µL of glacial acetic acid.

[0013] The present invention also provides the molecular sensor in Cu 2+ Application in detection.

[0014] Preferably, in the fluorescence emission spectrum, the carbazole-julolidine molecular sensor has a maximum fluorescence emission peak at 520 nm; adding Cu 2+After that, the fluorescence emission of the carbazole-julolidine molecular sensor weakened, and the intensity decreased by 90%, accompanied by the disappearance of the maximum fluorescence emission peak at 520 nm and the enhancement of fluorescence emission at 460 nm.

[0015] In the ultraviolet absorption spectrum, the molecular sensor has a maximum absorption peak near 415 nm. 2+ After that, the maximum absorption peak at 415 nm disappeared, and strong double absorption shoulder peaks appeared at 455 and 481 nm. The double peak ratio signal changed A 455 / A 415 From 0.70 to 2.9, A 481 / A 415 From 0.4 to 2.7, that is, the carbazole-juronidine molecular sensor is sensitive to Cu 2+ It presents dual-channel detection performance of fluorescence "on-off" and precise absorption ratio signal.

[0016] The present invention also provides the molecular sensor in Fe 3+ Application in detection.

[0017] Preferably, in the ultraviolet absorption spectrum, the molecular sensor has a maximum absorption peak near 415 nm. 3+ After that, the maximum absorption of the molecular sensor at 415 nm disappears, and a broad absorption without structural features appears in the range of 300-500 nm.

[0018] In the fluorescence emission spectrum, the carbazole-julolidine molecular sensor has a maximum fluorescence emission peak at 520 nm; adding Fe 3+ After that, the maximum fluorescence emission peak red-shifted to around 540 nm, and the fluorescence emission intensity decreased.

[0019] The present invention also provides the molecular sensor in Al 3+ Application in detection.

[0020] Preferably, in the ultraviolet absorption spectrum, the molecular sensor has a maximum absorption peak near 415 nm. 3+ After that, the maximum absorption of the molecular sensor red-shifted to 420 nm.

[0021] The present invention also provides the carbazole-juronidine molecular sensor for multiple analysis and detection of Fe 3+ 、Al 3+ Application in.

[0022] Preferably, in the fluorescence emission spectrum, the carbazole-julolidine molecular sensor has a maximum fluorescence emission peak at 520 nm; adding Cu 2+After that, the fluorescence emission of the carbazole-julolidine molecular sensor weakened, and the intensity decreased by 90%, accompanied by the disappearance of the maximum fluorescence emission peak at 520 nm and the enhancement of fluorescence emission at 460 nm.

[0023] Carbazole-julonidine-Cu 2+ Adding Fe to the binary system 3+ After the ionization, the intensity of the fluorescence emission peak at 460 nm increased by 4.4 times and red-shifted to 540 nm, that is, carbazole-juronidine-Cu 2+ Binary system for Fe 3+ Ions have fluorescence "off-on" detection performance;

[0024] Carbazole-juronidine-Cu 2+ Adding Al to the binary system 3+ After that, the intensity of the fluorescence emission peak at 460 nm increased by 7.7 times, and strong double emission appeared at 440 and 540 nm, namely, carbazole-juronidine-Cu 2+ Binary system for Al 3+ With fluorescence "off-on" detection performance.

[0025] In the ultraviolet absorption spectrum, the molecular sensor has a maximum absorption peak near 415 nm. 2+ After that, the maximum absorption peak at 415 nm disappeared, and strong double absorption peaks appeared at 455 and 481 nm.

[0026] Carbazole-julonidine-Cu 2+ Adding Fe to the binary system 3+ ions, carbazole-juronidine-Cu 2+ The two strong absorption shoulder peaks of the binary system at 455 and 481 nm gradually disappeared, the absorbance decreased, and a broad structureless characteristic absorption appeared in the range of 300-500 nm; that is, carbazole-juronidine-Cu 2+ Binary system with UV absorption detection of Fe 3+ performance;

[0027] Carbazole-juronidine-Cu 2+ Adding Al to the binary system 3+ After that, the maximum absorption peak appears at 398 nm, and the double peak ratio signal A 398 / A 455 From 0.23 to 1.5, A 398 / A 481 From 0.25 to 2.4, i.e., carbazole-juronidine-Cu 2+ Binary system for Al 3+ It has the performance of ultraviolet absorption double peak ratio signal detection.

[0028] The present invention also provides the carbazole-juronidine molecular sensor for detecting Cu in PVC basketball material. 2+ The molecular sensor is used to detect Cu 2+ The fluorescence "on-off" and UV absorption ratio dual-channel detection signals presented are used to detect Cu in PVC basketball materials. 2+ The concentration was tested, with a reproducibility of 100.5% to 101% and a relative standard deviation of 0.5 to 1%.

[0029] The present invention also provides the carbazole-juronidine-Cu 2+ Effect of binary system on Fe content in PVC basketball material 3+ The molecular sensor is used to detect Fe 3+ The fluorescence "off-on" and ultraviolet absorption dual signal characteristics are shown for Fe in PVC basketball materials. 3+ The concentration was tested, with a reproducibility of 100.5% to 102% and a relative standard deviation of 0.5 to 2%.

[0030] The present invention also provides the carbazole-juronidine-Cu 2+ Effect of binary system on Al content in PVC basketball material 3+ The molecular sensor is used to detect Al 3+ The fluorescence "off-on" and absorption ratio signal dual-channel detection signals are presented to detect Al in PVC basketball materials. 3+ The concentration was tested, with a reproducibility of 98% to 102% and a relative standard deviation of 1 to 2%.

[0031] Compared with the prior art, the present invention has the following technical effects: the carbazole-juronidine molecular material contains three complexing sites of fatty amine, imine and ortho-phenolic hydroxyl at the same time, and the three act synergistically to make it bind to Cu 2+ 、Al 3+ and Fe 3+ The signal changes after the action of ions are different; the intramolecular imine and the enol tautomerism of the o-phenol hydroxyl group and the double-site synergy have a strong coordination ability for metal ions, making the carbazole-juronidine molecular sensor sensitive to Cu 2+ It shows sensitive fluorescence "on-off" and precise absorption ratio signal (A 455 / A 415 , A 481 / A 415 ) Dual-channel detection performance; Based on the replacement reaction between metal ions, carbazole-juronidine and Cu 2+ Binary system for Fe 3+It has significant fluorescence "on-off" and UV absorption dual signal detection performance; based on the three-site synergistic complexation, carbazole-juronidine and Cu 2+ Binary system for Al 3+ It has unique fluorescence "on-off" and precise absorption double peak ratio signal (A 398 / A 455 , A 398 / A 481 ) detection performance; multifunctional detection is accurate and fast, and has high application value; the invention provides a method for detecting Cu in PVC basketball material 2+ 、Al 3+ , Fe 3+ The material preparation process with sensitive and accurate detection function has the advantages of simple preparation process, mild reaction conditions, high yield, etc., which is suitable for industrial implementation and creates favorable conditions for the promotion and application of this detection material. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] FIG1 is a mass spectrum of the molecular sensor obtained in Example 1-2.

[0033] Figure 2 This is a graph showing the fluorescence detection performance of the carbazole-juronidine molecular sensor when different metal ions are added.

[0034] Figure 3 This is a graph showing the ultraviolet absorption detection performance of the carbazole-juronidine molecular sensor when different metal ions are added.

[0035] Figure 4 The carbazole-juronidin molecular sensor was used to detect the concentration of Cu 2+ Action fluorescence performance diagram.

[0036] Figure 5 The carbazole-juronidin molecular sensor was used to detect the concentration of Cu 2+ Graph showing UV absorption performance.

[0037] Figure 6 Cu 2+ Schematic diagram of the effect of concentration changes on absorbance.

[0038] Figure 7 Cu in the carbazole-juronidin molecular sensor 2+ Fluorescence performance diagram of coexistence with other metal ions.

[0039] Figure 8 Cu in carbazole-juronidin molecular sensor 2+ Ultraviolet absorption performance diagram of coexistence with other metal ions.

[0040] Fig. 9 Carbazole-juronidine-Cu 2+Binary system for Fe 3+ Fluorescence detection performance diagram.

[0041] Fig.10 Carbazole-juronidine-Cu 2+ Binary system for Fe 3+ UV absorption detection performance diagram.

[0042] Fig.11 Carbazole-juronidine-Cu 2+ Binary system for Al 3+ Fluorescence detection performance diagram.

[0043] Fig.12 Carbazole-juronidine-Cu 2+ Binary system for Al 3+ UV absorption detection performance diagram. DETAILED DESCRIPTION

[0044] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0045] The invention discloses a method for treating Cu in basketball PVC material. 2+ 、Al 3+ , Fe 3+ The molecular sensor with sensitive detection function has the following molecular structure:

[0046] ;

[0047] The molecular sensor is prepared by using 1,1,7,7-tetramethyl-8-hydroxy-juronidin aldehyde and 3-amino-9-ethylcarbazole as raw materials through a one-step nucleophilic addition elimination reaction, and the preparation reaction formula is:

[0048] .

[0049] Example 1

[0050] 1 mmol of 1,1,7,7-tetramethyl-8-hydroxy-juronidin aldehyde and 1 mmol of 3-amino-9-ethylcarbazole were placed in a round-bottom flask containing 8 mL of a mixed solvent of dichloromethane and anhydrous ethanol (1:1), and 100 µL of glacial acetic acid was added, followed by heating to reflux for 3 hours. The reaction mixture was filtered, washed with anhydrous ethanol, and dried to obtain a reddish-brown material A, 381 mg, with a yield of 82%.

[0051] Example 2

[0052] 1 mmol of 1,1,7,7-tetramethyl-8-hydroxy-juronidin aldehyde and 1 mmol of 3-amino-9-ethylcarbazole were placed in a round-bottom flask containing 8 mL of a mixed solvent of dichloromethane and anhydrous ethanol (1:1), and 100 µL of glacial acetic acid was added, followed by heating to reflux for 5 hours. The reaction mixture was filtered, washed with anhydrous ethanol, and dried to obtain a reddish-brown material B, 390 mg, with a yield of 84%.

[0053] The molecular sensor materials A and B obtained in Examples 1-2 were analyzed and measured. The mass spectra of the two Figure 1 To, see Figure 1 , the data are as follows: MS (MALDI-TOP) data are as follows: the isotope cluster peak is located at m / z 465.42 [theoretical value 465.28]; elemental analysis C 31 H 35 Theoretical value of N3O: C, 79.96; H, 7.58; N, 9.02. Measured value: C, 79.87; H, 7.42; N, 9.32, which is basically consistent with the theoretical value of carbazole-amino salicylic acid molecular compound. It can be confirmed that the molecular structure of compound A and B is:

[0054] , i.e. the carbazole-juronidine molecule.

[0055] Example 3

[0056] Fluorescence detection performance of carbazole-juronidine molecular sensor for different metal ions: in 70% DMF aqueous solution, concentration of 1.0×10 -5 mol / L carbazole-hydroxyl-julonidine compound, 10 times the molar amount of Li + 、Na + , K + Mg 2 + , Ca 2+ , Ba 2+ 、Zn 2+ , Mn 2+ 、Cd 2+ , Pb 2+ , Hg 2+ 、Co 2+ 、Ni 2+ , Cu 2+ , Fe 3+ 、Al 3+ When the two are mixed, their fluorescence emission spectra are as follows: Figure 2 As shown: the carbazole-julolidine molecular sensor has a maximum fluorescence emission peak at 520 nm; Fe 3+After addition, the maximum fluorescence emission peak of the detection material red-shifted to around 540 nm, and the fluorescence emission intensity decreased slightly. 2+ After addition of other metal ions, the fluorescence emission spectrum of the carbazole-hydroxyjulolidine compound changed little. For specific results, see Figure 2 ; It shows that the carbazole-julonidine molecular sensor is sensitive to Cu 2+ It has obvious fluorescence quenching response and has the potential for fluorescence "on-off" detection and recognition.

[0057] Example 4

[0058] UV detection performance of carbazole-juronidine molecular sensor for different metal ions: In 70% methanol aqueous solution, the concentration was 1×10 -5 mol / L carbazole-juronidine compound has a maximum absorption peak near 415nm; adding 10 times the equivalent of Cu 2+ After adding Fe 3+ After that, the maximum absorption of the compound at 415 nm disappeared, and a broad absorption without structural characteristics appeared in the range of 300-500 nm; Al 3+ After addition, the maximum absorption of the compound red-shifted to 420 nm; other metal ions such as Li + 、Na + , K + Mg 2+ , Ca 2+ , Ba 2+ 、Zn 2+ , Mn 2+ 、Cd 2+ , Pb 2+ , Hg 2+ 、Co 2+ 、Ni 2+ After addition, the UV absorption spectrum of the compound hardly changed. For specific results, see Figure 3 ; This indicates that the carbazole-juronidine molecular sensor is sensitive to Cu 2+ , Fe 3+ 、Al 3+ It has certain potential for ultraviolet absorption spectrum recognition.

[0059] Example 5

[0060] Carbazole-juronidin molecular sensor for different concentrations of Cu 2+ Fluorescence detection performance: at a concentration of 1×10-5 mol / L carbazole-juronidin molecular sensor was added with different concentrations of Cu in 70% DMF aqueous solution. 2+ The fluorescence emission spectrum is as follows: 2+ When the concentration increased from 0 to 0.8 times the molar amount, the emission intensity of the compound gradually weakened and decreased by 90%, the maximum fluorescence emission around 520 nm disappeared, and a weaker maximum emission peak appeared around 460 nm; then, the concentration of Cu continued to increase. 2+ When the concentration is from 0.8 to 10 times the molar amount, the fluorescence emission spectrum remains basically unchanged. For specific results, see Figure 4 , indicating that the carbazole-juronidine molecular sensor is sensitive to Cu 2+ It has the potential to sensitively identify fluorescent "on-off" signals.

[0061] Example 6

[0062] Carbazole-juronidin molecular sensor for different concentrations of Cu 2+ UV absorption detection performance: at a concentration of 1×10 - 5 mol / L carbazole-juronidin molecular sensor was added with different concentrations of Cu in 70% DMF aqueous solution. 2+ The ultraviolet absorption spectrum of Cu ions is as follows: the carbazole-juronidine molecular sensor has a maximum absorption peak near 415 nm. 2+ When the concentration increases from 0 to 0.8 times the molar equivalent, the maximum absorption peak near 415 nm disappears, and two strong absorptions appear at 455 and 481 nm, resulting in a double peak ratio signal change A. 455 / A 415 From 0.70 to 2.9, A 481 / A 415 From 0.4 to 2.7, see the specific results Figure 5 and Figure 6 ; It shows that the carbazole-juronidine molecular sensor is sensitive to Cu 2+ It has accurate double peak absorption ratio signal detection performance.

[0063] Example 7

[0064] Cu in Carbazole-Juronidine Molecular Sensor 2+ Competitive performance of fluorescence spectrum with other metal ions: at a concentration of 1×10 -5 mol / L carbazole-juronidin molecular sensor was simultaneously added with 10 times the equivalent of Cu 2+ and other different metal ions, the mixed system fluorescence emission spectrum study showed that: the carbazole-juronidine molecular sensor added 10 times the equivalent of Cu 2+After that, the maximum emission intensity at 520 nm decreased, and a weak maximum absorption peak appeared at 460 nm. + 、Na + , K + Mg 2+ , Ca 2+ , Ba 2+ 、Zn 2+ , Mn 2+ 、Cd 2+ , Pb 2+ , Hg 2+ 、Co 2+ 、Ni 2+ The metal ions are added to the carbazole-juronidine molecule-Cu 2+ After the system was established, the fluorescence emission spectrum of the binary system was almost unchanged; Fe 3+ Ion addition of carbazole-juronidine-Cu 2+ After the binary system, its weak fluorescence emission intensity increased by 4.4 times, and the maximum fluorescence emission peak position red-shifted from 460 nm to 540 nm, which was similar to that of carbazole-juronidine and Fe 3+ The spectra of the binary system are similar; carbazole-juronidine-Cu 2+ Adding Al to the binary system 3+ After addition, its weak fluorescence emission was significantly enhanced, increasing by 7.7 times, and strong dual emission appeared at 440 and 540 nm, but it was different from carbazole-juronidine and Al 3+ The different spectra of the binary system may be due to the coordinated complexation of the bimetallic ions by the three sites of carbazole-juronidine fatty amine, imine, and ortho-phenolic hydroxyl, resulting in the carbazole-juronidine-Cu 2+ -Al 3+ The unique spectral properties of the ternary system indicate that carbazole-juronidine-Cu 2+ Binary system for Fe 3+ 、Al 3+ With different fluorescence "off-on" detection potential, see Figure 7 .

[0065] Example 8

[0066] Cu in Carbazole-Juronidine Molecular Sensor 2+ UV spectrum competition performance with other metal ions: at a concentration of 1×10 -5 mol / L carbazole-juronidin molecular sensor was simultaneously added with 10 times the equivalent of Cu 2+ and other different metal ions, mixed system UV absorption spectroscopy studies show that: carbazole-juronidine molecular sensor added 10 times the equivalent of Cu 2+After that, the maximum absorption at 415 nm disappears, and two strong absorptions appear at 455 and 481 nm. + 、Na + , K + Mg 2+ , Ca 2+ , Ba 2+ 、Zn 2+ , Mn 2+ 、Cd 2+ , Pb 2+ , Hg 2+ 、Co 2+ 、Ni 2+ Metal ions such as Cu 2+ After adding carbazole-juronidine molecular materials at the same time, its ultraviolet spectrum absorption is similar to that of carbazole-juronidine-Cu 2+ The spectra of the binary system are close; Fe 3+ Ion addition of carbazole-juronidine-Cu 2+ After the binary system, its UV spectrum absorption is similar to that of carbazole-juronidine-Fe 3+ The mixed system is close to a broad structureless characteristic absorption in the range of 300-500nm; Al 3+ Ion addition of carbazole-juronidine-Cu 2+ After the binary system, its UV spectrum absorption is similar to that of carbazole-juronidine-Al 3+ The mixed system is different in that it absorbs at 398 nm; this indicates that carbazole-juronidine-Cu 2+ Binary system has UV recognition of Fe 3+ 、Al 3+ Potential, for specific results, see Figure 8 .

[0067] Example 9

[0068] Carbazole-Juronidine-Cu 2+ Binary system for Fe 3+ Fluorescence detection performance: at a concentration of 1×10 -5 mol / L carbazole-juronidin molecular sensor was simultaneously added with 10 times the equivalent of Cu 2+ and different concentrations of Fe 3+ The fluorescence spectrum of Fe 3+ When the concentration increases from 0 to 10 times the molar amount, carbazole-juronidine-Cu 2+ The fluorescence emission of the binary system gradually increased by 4.4 times, and the maximum fluorescence emission peak position red-shifted from 460 nm to 540 nm. 3+ concentration, the fluorescence of the mixed system basically did not change, indicating that carbazole-juronidine-Cu 2+Binary system with fluorescence “off-on” detection of Fe 3+ Potential, for specific results, see Fig. 9 .

[0069] Example 10

[0070] Carbazole-Juronidine-Cu 2+ System for Fe 3+ UV absorption detection performance: at a concentration of 1×10 -5 mol / L carbazole-juronidin molecular sensor was simultaneously added with 10 times the equivalent of Cu 2+ and different concentrations of Fe 3+ The fluorescence spectrum of Fe 3+ When the concentration increases from 0 to 10 times the molar amount, carbazole-juronidine-Cu 2+ The two strong absorption peaks of the binary system at 455 and 481 nm gradually disappeared and the absorbance decreased. At the same time, a structurally uncharacteristic absorption peak appeared in the range of 300-500 nm. 3+ When the concentration was increased to 20 times, the UV absorption spectrum of the mixed system basically did not change, indicating that carbazole-juronidine-Cu 2+ Binary system with UV detection of Fe 3+ Potential, for specific results, see Fig.10 .

[0071] Embodiment 11

[0072] Carbazole-Juronidine-Cu 2+ System for Al 3+ Fluorescence detection performance: at a concentration of 1×10 -5 mol / L carbazole-juronidin molecular sensor was simultaneously added with 10 times the equivalent of Cu 2+ and different concentrations of Al 3+ The fluorescence emission spectrum of the mixed system shows that: 3+ When the concentration increases from 0 to 10 times the molar amount, carbazole-juronidine-Cu 2+ The fluorescence emission of the binary system gradually increased, the emission intensity increased by 7.7 times, and strong double emission appeared at 440 and 540 nm. 3+ When the concentration was increased to 20 times, the fluorescence of the mixed system basically did not change, indicating that carbazole-juronidine-Cu 2+ Binary system has fluorescence "off-on" detection of Al 3+ Potential, for specific results, see Fig.11 .

[0073] Example 12

[0074] Carbazole-Juronidine-Cu 2+ System for Al3+ UV absorption detection performance: at a concentration of 1×10 -5 mol / L carbazole-juronidin molecular sensor was simultaneously added with 10 times the equivalent of Cu 2+ and different concentrations of Al 3+ The ultraviolet absorption spectrum of the mixed system shows that: with the increase of Al 3+ When the concentration increases from 0 to 10 times the molar amount, carbazole-juronidine-Cu 2+ The absorbance of the binary system at 455 and 481 nm double absorption peaks gradually decreases, and at the same time, a maximum absorption peak appears at 398 nm, resulting in a double peak ratio signal A. 398 / A 455 From 0.23 to 1.5, A 398 / A 481 From 0.25 to 2.4, it shows accurate proportional absorption signal detection performance. For specific results, see Fig.12 .

[0075] Embodiment 13

[0076] Carbazole-juronidine molecular sensor for Cu in PVC basketball material 2+ Actual detection performance of ions: Weigh a certain amount of PVC basketball raw materials, use microwave digestion, remove acid, and adjust the pH to neutral with alkaline solution. Based on inductively coupled plasma (ICP-MS), we determine that there is no Cu in the raw materials of the PVC basketball. 2+ ; Weigh a certain amount of basketball PVC raw material, add a certain amount of Cu 2+ A series of samples containing different concentrations of Cu were prepared by digestion, acid removal, pH adjustment to neutrality, and distilled water. 2+ Basketball PVC material solution, using carbazole-juronidine molecular sensor to detect Cu 2+ The results are shown in Table 1 below. The carbazole-juronidine detection material has a good effect on Cu 2+ The reproducibility of the results is 100.5%~101%, which is within the allowable error range. This indicates that the carbazole-juronidine detection material is effective for Cu in the raw materials of PVC basketballs. 2+ The analysis and detection has high accuracy and broad application prospects.

[0077] Table 1 Carbazole-juronidine detection materials for Cu in PVC basketball materials 2+ Actual Detection Performance of Ions

[0078]

[0079] a n = 3; b Add Mg 2+ , Ca 2+ , Li +、Na + and K + (10.00 μM) basketball PVC material; Test conditions: 10 μM carbazole-juronidine test material in DMF-water (7:3) mixed solvent.

[0080] Embodiment 14

[0081] Carbazole-Juronidine-Cu 2+ Effect of binary system on Fe content in PVC basketball material 3+ Actual detection performance of ions: Weigh a certain amount of PVC basketball raw materials, use microwave digestion, remove acid, and adjust the pH to neutral with alkaline solution. Based on inductively coupled plasma (ICP-MS), we determine that there is no Fe in the raw materials of the PVC basketball. 3+ ; Weigh a certain amount of basketball PVC raw material, add a certain amount of Fe 3 + A series of Fe 3+ Basketball PVC material solution, through carbazole-juronidine-Cu 2+ Binary system detection of Fe 3+ The results are shown in Table 2 below. 2+ Binary system for Fe 3+ The reproducibility of carbazole-juronidine-Cu 2 + Binary system for Fe content in raw materials of PVC basketball 3+ The analysis and detection has high accuracy and broad application prospects.

[0082] Table 2 Carbazole-juronidine-Cu 2+ Effect of binary system on Fe content in PVC basketball material 3+ Actual Detection Performance of Ions

[0083]

[0084] a n = 3; b Add Mg 2+ , Ca 2+ , Li + 、Na + and K + (10.00 μM) Basketball PVC material; Test conditions: 10 μM Carbazole-Juronidine-Cu 2+ (10 times molar equivalent) binary system materials in DMF-water (7:3) mixed solvent.

[0085] Embodiment 15

[0086] Carbazole-Juronidine-Cu 2+ Effect of binary system on Al content in PVC basketball material 3+ Actual detection performance of ions: Weigh a certain amount of PVC basketball raw materials, use microwave digestion, remove acid, and adjust the pH to neutral with alkaline solution. Based on inductively coupled plasma (ICP-MS), we determine that there is no Al in the raw materials of the PVC basketball. 3+ ; Weigh a certain amount of basketball PVC raw material, add a certain amount of Al 3 + A series of samples containing different concentrations of Al were prepared by digestion, acid removal, pH adjustment to neutrality, and distilled water to volume. 3+ Basketball PVC material solution, through carbazole-juronidine-Cu 2+ Binary system detection of Al 3+ The results are shown in the following table: Carbazole-Juronidine-Cu 2+ Binary system for Al 3+ The reproducibility of carbazole-juronidine-Cu 2+ Effect of binary system on Al content in raw materials of PVC basketball 3+ The analysis and detection has high accuracy and broad application prospects.

[0087] Table 3 Carbazole-juronidine-Cu 2+ Effect of binary system on Al content in PVC basketball material 3+ Actual Detection Performance of Ions

[0088]

[0089] a n = 3; b Add Mg 2+ , Ca 2+ , Li + 、Na + and K + (10.00 μM) Basketball PVC material; Test conditions: 10 μM Carbazole-Juronidine-Cu 2+ (10 times molar equivalent) binary system materials in DMF-water (7:3) mixed solvent.

Claims

1. A molecular sensor, characterized in that: The molecular sensor is a carbazole-juronidine molecule, and its structure is: 。 2. The molecular sensor according to claim 1, characterized in that: The method for preparing the molecular sensor comprises the following steps: 1,1,7,7-tetramethyl-8-hydroxy-juronidin aldehyde and 3-amino-9-ethylcarbazole were placed in a round-bottom flask containing a 1:1 dichloromethane-anhydrous ethanol mixed solvent, and glacial acetic acid was added, and the mixture was heated to reflux for reaction for 3-5 hours; the reaction mixture was filtered, washed with anhydrous ethanol, and dried to obtain a reddish-brown target molecule sensor; The carbazole-juronidine molecular sensor preparation reaction formula is: 。 3. A molecular sensor according to claim 1 in Cu 2+ The application in detection is characterized by: Carbazole-julonidine molecular sensor for Cu 2+ The fluorescence "on-off" and UV absorption ratio signals were detected. In the fluorescence emission spectrum analysis, the maximum fluorescence emission peak of the carbazole-julolidine molecular sensor was at 520 nm. 2+ When it is present, the fluorescence intensity decreases by 90%, and the fluorescence peak at 520 nm disappears, while the fluorescence emission at 460 nm is enhanced; In the UV absorption spectrum, the carbazole-julolidine molecular sensor showed a maximum absorption peak at 415 nm. 2+ When it exists, the absorption peak at 415nm disappears, while double absorption shoulders appear at 455nm and 481nm. The ratio signal of the double absorption shoulders changes significantly, the ratio of A455 / A415 increases from 0.70 to 2.9, and the ratio of A481 / A415 increases from 0.4 to 2.

7.

4. The molecular sensor according to claim 3 is in Cu 2+ The application in detection is characterized by: Detection of Cu in PVC basketball material using carbazole-julolidine molecular sensor 2+ .

5. A molecular sensor according to claim 1 in Fe 3+ The application in detection is characterized by: In the UV absorption spectrum, the carbazole-julolidine molecular sensor showed a maximum absorption peak at 415 nm. 3+ After that, the maximum absorption peak at 415 nm disappears, and a broad absorption without structural characteristics appears in the range of 300-500 nm; In the fluorescence emission spectrum, the carbazole-julolidine molecular sensor showed a maximum fluorescence emission peak at 520 nm; the addition of Fe 3+ After that, the maximum fluorescence emission peak red-shifted to around 540 nm, and the intensity decreased.

6. A molecular sensor according to claim 1 in Al 3+ The application in detection is characterized by: In the UV absorption spectrum, the carbazole-julolidine molecular sensor showed a maximum absorption peak at 415 nm. 3+ After that, the maximum absorption of carbazole-julolidine molecular sensor red-shifted to 420 nm.

7. A molecular sensor as claimed in claim 1 for detecting Fe in multiplex analysis 3+ The application is characterized by: Carbazole-julonidine-Cu 2+ Binary system for the analysis and detection of Fe 3+ , Carbazole-Juronidine-Cu 2+ Binary system for Fe 3+ It has fluorescence "off-on" and UV absorption dual signal detection performance, specifically: carbazole-juronidine-Cu 2+ Adding Fe to the binary system 3+ After ionization, the intensity of the fluorescence emission peak at 460 nm increased by 4.4 times and red-shifted to 540 nm; Carbazole-julonidine-Cu 2+ Adding Fe to the binary system 3+ ions, carbazole-juronidine-Cu 2+ The two strong absorption peaks of the binary system at 455 and 481 nm gradually disappeared, the absorbance decreased, and a broad structureless characteristic absorption appeared in the range of 300-500 nm.

8. The molecular sensor according to claim 7 is used for multiplex analysis of Fe 3+ The application is characterized by: Carbazole-juronidine-Cu 2+ Binary system to detect Fe in PVC basketball material 3+ .

9. A molecular sensor as claimed in claim 1 for detecting Al in multiple analysis 3+ The application is characterized by: Carbazole-julonidine-Cu 2+ Binary system for the analysis and detection of Al 3+ , Carbazole-Juronidine-Cu 2+ Binary system for Al 3+ It has dual-channel detection performance of fluorescence "off-on" and absorption ratio signal, specifically: Carbazole-juronidine-Cu 2+ Adding Al to the binary system 3+ After that, the intensity of the fluorescence emission peak at 460 nm increased by 7.7 times, and strong double emission appeared at 440 and 540 nm. Carbazole-juronidine-Cu 2+ Adding Al to the binary system 3+ After that, the maximum absorption peak appears at 398 nm, and the double peak ratio signal A 398 / A 455 From 0.23 to 1.5, A 398 / A 481 From 0.25 to 2.

4.

10. The molecular sensor according to claim 9 is used for multiplex analysis and detection of Al 3+ The application is characterized by: Carbazole-juronidine-Cu 2+ Binary system to detect Al in PVC basketball material 3+ .

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