Tetraphenylethylene derivative ion complex / Fe < 3 + > complex fluorescent probe as well as preparation method and application thereof

Abstract

The invention provides a tetraphenylethylene derivative ion complex / Fe < 3 + > complex fluorescent probe as well as a preparation method and application thereof. A preparation method of a tetraphenylethylene derivative ion complex / Fe < 3 + > complex fluorescent probe comprises the following steps: dissolving a tetraphenylethylene derivative ion complex in ethanol to obtain a stock solution I; the preparation method comprises the following steps: dissolving FeCl3. 6H2O in deionized water to obtain a stock solution II; and mixing the stock solution I and the stock solution II, and diluting with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe < 3 + > complex fluorescent probe. The tetraphenylethylene derivative ion complex / Fe < 3 + > complex fluorescent probe is applied to detection of F <-> ions. The tetraphenyl ethylene ion complex / Fe < 3 + > complex provided by the invention can realize F <-> 'open-type 'fluorescence detection.

Description

Technical Field

[0001] The present invention relates to the technical field of fluorescent probes, and in particular to a tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe and preparation method and application thereof. Background Art

[0002] In recent years, anions play an extremely important role in chemical, environmental and biochemical processes, especially in the development of sensors for identifying anions in the environment and biological systems. Among the many anions, fluoride ions (F-) have attracted much attention due to their impact on human health and the ecological environment. Fluoride ions are one of the indispensable trace elements in the human body, and an appropriate amount of fluoride plays a key role in preventing dental caries and treating osteoporosis. However, excessive intake of fluoride can lead to fluorosis of teeth and bones, and may even cause neurological diseases, causing damage to the kidneys, brain and immune system. These health risks highlight the need to develop accurate, effective, highly selective and highly sensitive fluoride ion detection materials to achieve quantitative detection of fluoride ions, ensure that they are maintained at a safe dose in the human body, and provide a scientific basis for the prevention and control of fluoride pollution. Research on new fluoride ion detection materials is not only of great scientific significance, but also has broad practical application prospects.

[0003] To date, a variety of analytical methods have been developed for fluoride ion detection, including ion-selective electrodes, ion chromatography, and colorimetry. Although these techniques have certain effectiveness in fluoride ion detection, they are usually limited by complex sample preparation, expensive equipment requirements, and time-consuming operations. In contrast, fluorescence-based detection methods have attracted much attention due to their simplicity, low cost, high sensitivity, and real-time monitoring capabilities, making them ideal for detecting fluoride ions. Fluorescence-based detection methods have high sensitivity and high specificity, so a large number of studies have focused on the development of fluorescent sensors for fluoride ion detection. However, most traditional fluorescent sensors rely on the "off" mode of fluorescence quenching, which is easily interfered by factors such as quenchers or photobleaching, affecting the detection accuracy. In addition, fluorescent sensors based on traditional luminescent molecules usually have high detection limits and are difficult to meet the needs of high-sensitivity detection of trace fluoride ions in practical applications. Therefore, achieving an "on" type of fluorescence detection effect and improving the detection sensitivity of trace fluoride ions has become a research hotspot in the field of fluorescent sensors. Summary of the invention

[0004] The present invention discloses a tetraphenylethylene derivative ion complex / Fe 3+ The invention discloses a complex fluorescent probe and a preparation method and application thereof, so as to solve at least one of the technical problems existing in the prior art.

[0005] According to a first aspect of the present disclosure, there is provided a tetraphenylethylene derivative ion complex / Fe 3+ A method for preparing a complex fluorescent probe comprises:

[0006] The tetraphenylethylene derivative ion complex is dissolved in ethanol to obtain a stock solution I;

[0007] Dissolve FeCl3·6H2O in deionized water to obtain stock solution II;

[0008] The stock solution I and the stock solution II are mixed and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe;

[0009] Wherein, the structural formula of the tetraphenylethylene derivative ion complex is:

[0010] In one embodiment, the concentration of the tetraphenylethylene derivative ion complex in the stock solution I is 1×10 -4 M; the concentration of FeCl3·6H2O in the stock solution II is 1×10 -4 M.

[0011] In one embodiment, stock solution I and stock solution II are mixed in a volume ratio of 1:3-4, and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe, wherein the tetraphenylethylene derivative ion complex / Fe 3+ The concentration of the tetraphenylethylene derivative ion complex in the complex fluorescent probe is 10 μM.

[0012] According to a second aspect of the present disclosure, there is provided a tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is prepared by the preparation method described above.

[0013] According to the third aspect of the present disclosure, there is provided the tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is used to detect F - Application in ions.

[0014] In one embodiment, the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe F - The minimum detection limit of ions is 9.40×10 -8 M.

[0015] In one embodiment, the tetraphenylethylene derivative ion complex / Fe 3+The complex fluorescent probe is used for F - When ion detection is performed, it is not affected by SO4 2- , Cl - ,Ac - 、NO3 - 、HClO4 - ,I - Br - 、HSO4 - 、HSO3 - 、NO2 - 、F - and interference from L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, and L-proline.

[0016] According to a fourth aspect of the present disclosure, a tetraphenylethylene derivative ion complex fluorescent probe is provided for detecting Fe 3+ Ion application, wherein the structural formula of the tetraphenylethylene derivative ion complex is:

[0017]

[0018] In one embodiment, the tetraphenylethylene derivative ion complex fluorescent probe is 3+ Under the action of ions, the fluorescence intensity decreases to quenching. 3+ The minimum detection limit of ions is 8.76×10 -8 M.

[0019] In one embodiment, the tetraphenylethylene derivative ion complex fluorescent probe is 3+ The detection of ions is not affected by Cd 2+ , Sr 2+ 、Na + , Cu 2+ , Ba 2+ , Fe 3+ 、Co 2+ , Pb 2+ , K + , Ca 2+ 、Zn 2+ Mg 2+ 、Ag + Sn 2+ 、Mo 2+ , Cs + Cationic interference.

[0020] Compared with the prior art, the advantages of the present application are: 1) The tetraphenylethylene derivative ion complex of the present invention has obvious aggregation-induced luminescence effect and excellent luminescence performance. In aqueous solution, the tetraphenylethylene ion complex can achieve the effect of Fe 3+The "off" fluorescence detection of the tetraphenylethylene ion complex / Fe 3+ The complex can achieve F - “Turn-on” fluorescence detection.

[0021] 2) The tetraphenylethylene derivative ion complex fluorescent probe and the tetraphenylethylene derivative ion complex / Fe 3+ The preparation method of the complex fluorescent probe is simple and the reaction conditions are mild, which is beneficial to environmental protection and meets the characteristics of green chemistry.

[0022] 3) The tetraphenylethylene derivative ion complex fluorescent probe and tetraphenylethylene derivative ion complex / Fe prepared by the present invention 3+ The complex fluorescent probe has excellent chemical stability, high sensitivity and good anti-interference ability, and can be used to detect Fe 3+ and F - Achieve fast and efficient "off / on" fluorescence response.

[0023] It should be understood that the content described in this section is not intended to identify the key or important features of the embodiments of the present disclosure, nor is it intended to limit the scope of the present disclosure. Other features of the present disclosure will become easily understood through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The above and other objects, features and advantages of the exemplary embodiments of the present disclosure will become readily understood by reading the detailed description below with reference to the accompanying drawings. In the accompanying drawings, several embodiments of the present disclosure are shown in an exemplary and non-limiting manner, in which:

[0025] In the drawings, the same or corresponding reference numerals represent the same or corresponding parts.

[0026] Figure 1 The NMR hydrogen spectrum of TPE-DHAB of the embodiment of the present disclosure is shown;

[0027] Figure 2 The carbon spectrum of TPE-DHAB of the embodiment of the present disclosure is shown;

[0028] Figure 3 shows an infrared spectrum of TPE-DHAB of an embodiment of the present disclosure;

[0029] Figure 4 shows a high-resolution mass spectrum of TPE-DHAB according to an embodiment of the present disclosure;

[0030] Figure 5 The fluorescence spectrum of TPE-DHAB in a deionized water solution according to an embodiment of the present disclosure is shown;

[0031] Figure 6A line graph showing the water content and I / I0 fluorescence intensity of TPE-DHAB in a deionized water solution according to an embodiment of the present disclosure is shown;

[0032] Figure 7 The UV-absorption spectrum of TPE-DHAB in a deionized water solution of an embodiment of the present disclosure is shown;

[0033] Figure 8 It shows that the TPE-DHAB of the embodiment of the present disclosure is 3+ Fluorescence spectra in aqueous solution systems with concentrations of 0-40 μM;

[0034] Fig. 9 The Fe of the embodiment of the present disclosure is shown 3+ Fluorescence images of TPE-DHAB under UV irradiation at concentrations of 0 μM and 30 μM;

[0035] Fig.10 The fluorescence intensity columnar soil of TPE-DHAB of the disclosed embodiment under different interferents is shown;

[0036] Fig.11 The TPE-DHAB / Fe 3+ In F - Fluorescence spectra in aqueous solution systems with concentrations of 0-30 μM;

[0037] Fig.12 The TPE-DHAB / Fe 3+ The fluorescence intensity and F - Correlation linear plot in the concentration range of 0-30 μM;

[0038] Fig.13 The TPE-DHAB / Fe 3+ Fluorescence intensity columnar soil under different interferences;

[0039] Fig.14 The TPE-DHAB and TPE-DHAB / Fe 3+ pH and I / I0 fluorescence intensity line graph;

[0040] Fig.15 shows an initial particle size diagram of TPE-DHAB of an embodiment of the present disclosure;

[0041] Fig.16 The TPE-DHAB of the present disclosure embodiment is shown to have added Fe 3+ The particle size diagram after

[0042] Fig.17 The TPE-DHAB of the present disclosure embodiment is shown to have added Fe3+ 、F - The particle size diagram after

[0043] Fig.18 shows the initial Zeta potential diagram of TPE-DHAB of the embodiment of the present disclosure;

[0044] Fig.19 The TPE-DHAB of the present disclosure embodiment is shown to have added Fe 3+ Zeta potential diagram after

[0045] Fig. 20 The TPE-DHAB of the present disclosure embodiment is shown to have added Fe 3+ 、F - Zeta potential diagram after. DETAILED DESCRIPTION

[0046] In order to make the purpose, features, and advantages of the present disclosure more obvious and easy to understand, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings in the embodiments of the present disclosure. Obviously, the described embodiments are only part of the embodiments of the present disclosure, not all of the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present disclosure.

[0047] According to one embodiment of the present disclosure, in a first aspect, the present invention provides a tetraphenylethylene derivative ion complex / Fe 3+ A method for preparing a complex fluorescent probe comprises:

[0048] The tetraphenylethylene derivative ion complex is dissolved in ethanol to obtain a stock solution I;

[0049] Dissolve FeCl3·6H2O in deionized water to obtain stock solution II;

[0050] The stock solution I and the stock solution II are mixed and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe;

[0051] Wherein, the structural formula of the tetraphenylethylene derivative ion complex is:

[0052]

[0053] The present invention relates to tetraphenylethylene derivative ion complex / Fe 3+ The preparation method of the complex fluorescent probe is simple and the reaction conditions are mild, which is beneficial to environmental protection and meets the characteristics of green chemistry.

[0054] In some embodiments, the concentration of the tetraphenylethylene derivative ion complex in the stock solution I is 1×10 - 4 M; the concentration of FeCl3·6H2O in the stock solution II is 1×10 -4 M.

[0055] In some embodiments, stock solution I and stock solution II are mixed at a volume ratio of 1:3-4, and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe, wherein the tetraphenylethylene derivative ion complex / Fe 3+ The concentration of the tetraphenylethylene derivative ion complex in the complex fluorescent probe is 10 μM. For example, 0.5 ml of stock solution I and 1.5 ml of stock solution II are mixed (the volume ratio of the two is 1:3), and diluted to 5 ml with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe, wherein the tetraphenylethylene derivative ion complex / Fe 3+ The concentration of tetraphenylethylene derivative ion complex in the complex fluorescent probe is 10 μM, Fe 3+ The concentration is 30 μM.

[0056] According to a second aspect of the present disclosure, the present invention provides a tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is prepared by the preparation method described above.

[0057] According to the third aspect of the present disclosure, the present invention also provides a tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is used to detect F - Application in ions. The present invention relates to tetraphenylethylene ion complex / Fe 3+ The complex can achieve F - "Open" fluorescence detection. Tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe has excellent chemical stability, high sensitivity and good anti-interference ability. - Achieve fast and efficient "on" fluorescence response.

[0058] In some embodiments, the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe F - The lowest detection limit of the ion is 9.40×10-8M.

[0059] In some embodiments, the tetraphenylethylene derivative ion complex / Fe3+ complex fluorescent probe is not affected by anions SO4 when detecting F- ions.2- , Cl - ,Ac - 、NO3 - 、HClO4 - ,I - Br - 、HSO4 - 、HSO3 - 、NO2 - 、F - and interference from L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, and L-proline.

[0060] According to the fourth aspect of the present disclosure, the present invention also provides a tetraphenylethylene derivative ion complex fluorescent probe for detecting Fe 3+ The application of the invention, wherein the structural formula of the tetraphenylethylene derivative ion complex fluorescent probe is:

[0061] The present application provides three different tetraphenylethylene derivative ionic complexes, wherein when R is C 14 H 29 When R is C 16 H 33 When the tetraphenylethylene derivative ion complex is obtained, it is referred to as "TPE-DHAB"; R is C 18 H 37 When the tetraphenylethylene derivative ion complex was obtained, it was referred to as "TPE-DOAB". We found that these three tetraphenylethylene derivative ion complex fluorescent probes can detect Fe 3+ ions for efficient and rapid detection, the tetraphenylethylene ion complex / Fe 3+ The complex can also efficiently detect F - .

[0062] In some embodiments, the tetraphenylethylene derivative ion complex fluorescent probe is 3+ Under the action of ions, the fluorescence intensity decreases to quenching. 3+ The minimum detection limit of ions is 8.76×10 -8 M.

[0063] In some embodiments, the tetraphenylethylene derivative ion complex fluorescent probe is 3+ The detection of ions is not affected by Cd 2+ , Sr 2+ 、Na + , Cu 2+ , Ba 2+ , Fe 3+、Co 2+ , Pb 2+ , K + , Ca 2+ 、Zn 2+ Mg 2+ 、Ag + Sn 2+ 、Mo 2+ , Cs + Cationic interference.

[0064] The tetraphenylethylene derivative ion complex of the present invention has a significant aggregation-induced luminescence effect and excellent photophysical properties. In aqueous solution, the tetraphenylethylene derivative ion complex achieves 3+ The "off" fluorescence detection of the tetraphenylethylene derivative ion complex / Fe 3+ The complex can achieve F - "Open" fluorescence detection. The Fe of the tetraphenylethylene derivative ion complex of the present invention 3+ and F - The preparation method of the "off / on" fluorescent probe is simple and the reaction conditions are mild, which is beneficial to environmental protection and meets the characteristics of green chemistry. 3+ and F - Rapid and efficient detection is expected to be industrialized and applied on site.

[0065] The present application is further described in detail below with reference to the embodiments:

[0066] Example 1

[0067] The preparation method of tetraphenylethylene derivative ion complex comprises the following steps:

[0068] Step (1), 1.00 g (1.03 mmol) of compound (I) and 0.24 g (4.29 mmol) of KOH were added to a 250 mL single-mouth round-bottom flask and dissolved in 30 mL of deionized water to obtain TPE-4COO - K + solution for standby use; wherein the structural formula of compound (I) is,

[0069] Step (2), add 2.59 g (4.51 mmol) of (C 16 H 33 )2(CH3)2N + Br - The mixture was dissolved in 60 mL of a mixed solvent of ethanol / water (v / v=1:2) and heated to 50°C.

[0070] Step (3), under stirring at 50°C, use a constant pressure dropping funnel to add TPE-4COO - K + The aqueous solution was slowly added dropwise to the 16 H 33 )2(CH3)2N + Br - The mixture was added into a mixed solution of EtOH / H2O at a rate of 1 drop / min. A precipitate was generated. The reaction was continued at 50°C for 12 h. The precipitate was filtered and washed with a mixed solvent of ethanol and water in a volume ratio of 1:2. The precipitate was dried in vacuo to obtain a tetraphenylethylene derivative ion complex, referred to as "TPE-DHAB", with a yield of 88%.

[0071] The tetraphenylethylene derivative ion complex ( T The reaction equation of PE-DHAB) is:

[0072]

[0073] The chemical structure of TPE-DHAB was characterized by nuclear magnetic resonance hydrogen spectrum, carbon spectrum, infrared spectrum and high-resolution mass spectrum: 1 H NMR (CDC13,600MHz), δ (TMS,ppm): 8.05 (d,8H,Ar-H), 7.33 (d,8H,Ar-H), 6.90 (d,8H,Ar-H), 6.66 (d,8H,Ar-H), 4.99 (s ,8H,4OCH2),3.35(m,16H,8CH2),3.29(s,24H,8CH3),2.31(m,16H,8CH2),1.25(m,208H,104CH2),0.88(t,24H,8CH3),such as Figure 1 shown.

[0074] 13 C NMR (CDCl3, 600MHz), δ (TMS, ppm): 170.51, 156.16, 138.23, 137.55, 137.07, 135.92, 131.50, 128.61, 125.58, 112.90, 68.75, 62.46, 50.33, 30.91, 28.71, 28.67, 28.63, 28.50, 28.39, 28.36, 28.16, 25.19, 21.68, 21.63, 13.12, as Figure 2 shown.

[0075] FTIR(KBr,cm -1):718,763,784,829,837,852,858,896,920,954,1021,1035,1047,1107,1177,1243,1272,1295,1402,1470,1487,1511,1550,1594,1611,1659,2849,2917,2955, such as Figure 3 shown.

[0076] MALDI-TOF-MS:calcd for C 194 H 328 N4O 12 :2908.4817.Found:2908.4817, Figure 4 This proves that the TPE-DHAB of the present application was successfully prepared.

[0077] Example 2

[0078] Determination of Photophysical Properties of Tetraphenylethylene Derivative Ionic Complex (TPE-DHAB)

[0079] The prepared tetraphenylethylene derivative ion complex was dissolved in DMF to a concentration of 1×10 -4 M solution as stock solution I; take 6 portions of stock solution I with a volume of 0.5 mL, add 0, 1, 2, 3, 4, and 4.5 mL of deionized water, respectively, and make up to 5 mL with DMF to prepare poor solvent volume fractions of 0%, 20%, 40%, 60%, 80%, and 90% (water content f w ) solution; measuring the fluorescence spectrum and UV-absorption spectrum of 6 solutions, such as Figure 5 and Figure 7 .from Figure 5 It can be seen from the fluorescence spectrum that with the increase of water content (f w ) increases, the absorbance of TPE-DHAB increases significantly due to the formation of aggregates. w When the water content is less than 20%, the fluorescence emission of the TPE-DHAB solution almost reaches the minimum value, showing extremely weak luminescence. However, as the water content increases, the fluorescence emission intensity of the solution gradually increases, showing typical AIE (aggregation-induced emission) characteristics. This fluorescence enhancement phenomenon can be attributed to the increase in the π-π stacking effect between some molecules in the TPE-DHAB aggregates and the restriction of intramolecular rotation, which reduces non-radiative attenuation and thus enhances fluorescence emission. Figure 6It can be seen that the fluorescence intensity increases sharply when the water fraction increases from 20% to 40%, indicating that the aggregation efficiency of TPE-DHAB is significantly improved within this water fraction range. This intensification of aggregation further promotes the emergence of the AIE effect. More significantly, at f w When it reaches 80%, the fluorescence intensity of TPE-DHAB is about 73 times higher than its emission intensity in pure DMF, highlighting the key role of water content in enhancing the AIE effect of TPE-DHAB. This significant fluorescence enhancement effect indicates that under high water content conditions, the interaction between TPE-DHAB molecules is maximized, thereby achieving more efficient luminescence performance. In addition, in the UV-visible absorption spectrum Figure 7 A trend similar to that of fluorescence emission was also observed in the AIE material, further verifying the aggregation-induced emission characteristics of TPE-DHAB. This absorption trend proves the change in the structural state of TPE-DHAB molecules during aggregation, as well as the further restriction of the internal rotation of the molecule during the increase of water content, which strengthens its significant luminescence effect under high water content conditions. This phenomenon not only illustrates the role of water in promoting aggregation in AIE materials, but also provides a basis for the future design and optimization of TPE-DHAB sensors.

[0080] Example 3

[0081] The fluorescent probe of tetraphenylethylene derivative ion complex (i.e., fluorescent probe Ⅰ) was investigated on different Fe 3+ Determination of fluorescence spectrum under concentration:

[0082] The prepared tetraphenylethylene derivative ion complex was dissolved in ethanol to a concentration of 1×10 -4 M solution as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution II; take 21 portions of stock solution I with a volume of 0.5 mL, and add 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 mL of stock solution II to 20 portions of stock solution I, respectively, and finally make up to 5 mL with deionized water to prepare Fe 3+ The fluorescence spectrum of the aqueous solution system with a concentration of 0-40 μM is measured, such as Figure 8 shown.

[0083] By analyzing different concentrations of Fe 3+ The fluorescence emission spectrum of TPE-DHAB in the presence of Fe 3+With the increase of concentration, the fluorescence intensity of TPE-DHAB gradually decreased, showing a significant fluorescence quenching effect. 3+ In the case of the gradual addition of Fe 3+ After that, the fluorescence emission gradually weakened until it disappeared completely. 3+ When the concentration reached or exceeded 30 μM, the fluorescence in the solution was almost undetectable, indicating that the TPE-DHAB and Fe 3 + The interaction has reached saturation, resulting in complete fluorescence quenching. Fig. 9 It shows that the fluorescence intensity of TPE-DHAB fluorescent probe solution is related to Fe 3+ The concentration showed a highly linear correlation in the range of 0-30 μM (R 2 =0.9987), which indicates that the sensor (i.e., fluorescent probe) can achieve Fe 3+ Accurate quantitative detection.

[0084] In addition, the detection limit of the sensor was calculated to be 8.76×10 -8 M, showing its ability to resist low concentration Fe 3+ High sensitivity, can effectively meet the low content Fe 3+ The need for testing. Fig. 9 0 μM and 30 μM Fe are shown 3+ The fluorescence images of TPE-DHAB under UV irradiation under different conditions intuitively show the quenching differences at different concentrations: 3+ When 30 μM Fe 3+ At concentrations below 1.5, the fluorescence almost completely disappears, highlighting the Fe 3+ The experimental results show that the tetraphenylethylene derivative ion complex has a significant quenching effect on Fe 3+ With high sensitivity "off-mode" fluorescence detection, based on the fluorescence quenching effect of Fe 3+ It has potential application prospects in ion detection.

[0085] Example 4

[0086] Tetraphenylethylene derivative ion complex fluorescent probe ("fluorescent probe Ⅰ") for Fe 3+ Selectivity characterization of assays:

[0087] The prepared tetraphenylethylene derivative ion complex was dissolved in ethanol to a concentration of 1×10 -4 M solution as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare 1×10-4 M solution as stock solution II.

[0088] Take 16 portions of 0.5 mL of stock solution I, add 1.5 mL of stock solution II to one portion, and then add 1.5 mL of 1×10 -4 M of CdCl2 aqueous solution, SrCl2 aqueous solution, NaCl aqueous solution, CuCl2 aqueous solution, BaCl2 aqueous solution, CoCl2 aqueous solution, PbCl2 aqueous solution, KCl aqueous solution, CaCl2 aqueous solution, ZnCl2 aqueous solution, MgCl2 aqueous solution, AgNO3 aqueous solution, SnCl2 aqueous solution, (NH4)6Mo7O 24 4H2O aqueous solution and Cs2CO3 aqueous solution were used as interference control groups. Finally, they were filled up to 5mL with deionized water. The changes in the fluorescence of the solutions under ultraviolet light were observed, and their fluorescence emission was measured to draw a fluorescence intensity bar graph, as shown in the figure Fig.10 As shown ( Fig.10 In the above, counterion refers to the above-mentioned interferent). Fig.10 It can be seen that most cations have little effect on the fluorescence signal of TPE-DHAB, indicating that the interaction between these ions and the TPE-DHAB probe is limited or non-existent. 2+ , Fe 3+ and Ag + The fluorescence emission intensity of TPE-DHAB was significantly reduced, and Fe 3+ The quenching effect on fluorescence emission was the most significant, causing the relative emission intensity to drop to about 0.03, showing that Fe 3+ This difference is clearly visible under UV light, with a significant quenching of fluorescence, which makes Fe 3+ Visually distinguished from other cations.

[0089] Take 16 portions of 0.5 mL of stock solution I and add 1.5 mL of 1×10 -4 M of CdCl2 aqueous solution, SrCl2 aqueous solution, NaCl aqueous solution, CuCl2 aqueous solution, BaCl2 aqueous solution, CoCl2 aqueous solution, PbCl2 aqueous solution, KCl aqueous solution, CaCl2 aqueous solution, ZnCl2 aqueous solution, MgCl2 aqueous solution, AgNO3 aqueous solution, SnCl2 aqueous solution, (NH4)6Mo7O 24 ·4H2O aqueous solution, Cs2CO3 aqueous solution and stock solution II, then add 300μL of stock solution II to 16 parts of stock solution I, and finally make up all the solutions to 5mL with deionized water, observe the fluorescence changes of the solutions under ultraviolet light, and measure their fluorescence emission to draw a fluorescence intensity bar graph, as shown in the figure Fig.10 As shown. Fig.10 It can be seen that in the presence of other interfering substances, the tetraphenylethylene derivative ion complex has a strong affinity for Fe 3+ The fluorescence response of Fe was almost unchanged, indicating that the tetraphenylethylene derivative ion complex can effectively and specifically detect Fe even in the presence of other interferents. 3+ These results demonstrate that the tetraphenylethylene derivative ion complex can be used as a potential highly selective and anti-drying fluorescent sensor (i.e., fluorescent probe) for the detection of Fe 3+ , and still has good detection effect in complex environments.

[0090] Example 5

[0091] Tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe (TPE-DHAB / Fe 3+ , i.e. "fluorescent probe II") for F - Determination of the fluorescence spectrum of the detection:

[0092] The prepared tetraphenylethylene derivative ion complex was dissolved in ethanol to a concentration of 1×10 -4 M solution as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution II; NaF was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution III; take 16 portions of stock solution I with a volume of 0.5 mL, and add 1.5 mL of stock solution II to them, then add 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1, 1.1, 1.2, 1.3, 1.4, 1.5 mL of stock solution III to 15 of them respectively, and finally make up to 5 mL with deionized water to prepare F - The fluorescence spectrum of the aqueous solution system with ion concentration of 0-30μM is measured. Fig.11 With F - As the concentration of ions increases, the fluorescence intensity of the solution gradually increases. This gradual increase trend is - The fluorescence intensity was particularly significant when the concentration reached 30 μM, and the fluorescence intensity at this time was enhanced by about 19 times compared with the blank control solution. This significant fluorescence response is believed to be due to the 3+ In the presence of ions, F - Specific recognition and binding of ions. - The addition of Fe 3+ The competitive replacement of ions by TPE-DHAB changes the molecular structure of TPE-DHAB and restores its fluorescence intensity. This process shows that TPE-DHAB has a strong affinity for F -The high sensitivity and strong recognition ability of F - The great potential of “turn-on” fluorescence sensors. Fig.12 It shows that TPE-DHAB / Fe 3+ Fluorescence intensity of fluorescent probe solution and F - The concentration showed a highly linear correlation in the range of 0-30 μM (R 2 =0.9985), which indicates that the sensor (i.e., fluorescent probe) can achieve F - In addition, the detection limit of the sensor was calculated to be 9.40×10 -8 M, showing its ability to resist low concentrations of F - High sensitivity, can effectively meet the low content F - The need for testing. Fig.12 The inset also provides visual evidence showing that TPE-DHAB / Fe 3+ The complex solution was added with and without 30 μM F - When F - In the case of adding F - After that, the fluorescence intensity increased significantly, highlighting the F - There is a positive correlation between TPE-DHAB / Fe 3+ These results clearly show that TPE-DHAB / Fe 3+ Complex as F - The high selectivity and high sensitivity of the sensor make it an “open” F - It has good application prospects in detection.

[0093] Example 6

[0094] Tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe (TPE-DHAB / Fe 3+ , fluorescent probe II) for F - Selectivity characterization of assays:

[0095] The prepared tetraphenylethylene derivative ion complex was dissolved in ethanol to a concentration of 1×10 -4 M solution as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution II; NaF was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution III.

[0096] Take 18 portions of 0.5 mL of stock solution I, add 1.5 mL of stock solution II to each of the 18 portions of stock solution I, then add 1.5 mL of stock solution III to one of them, and then add 1.5 mL of 1×10 -4 M of Na2SO4 aqueous solution, NaCl aqueous solution, NaAc aqueous solution, Co(NO3)2 aqueous solution, tetrabutylammonium perchlorate aqueous solution, KI aqueous solution, tetrabutylammonium bromide aqueous solution, L-alanine aqueous solution, aspartic acid aqueous solution, glycine aqueous solution, L-threonine aqueous solution, L-histidine aqueous solution, L-serine aqueous solution, L-proline aqueous solution, NaHSO4 aqueous solution, NaHSO3 aqueous solution, NaNO2 aqueous solution were used as interference control groups, and finally deionized water was used to make up to 5mL. The changes in the fluorescence of the solutions under ultraviolet light were observed, and the fluorescence emission was measured to draw a fluorescence intensity bar graph, as shown in the figure. Fig.13 As shown. Fig.13 It can be seen that except for F - Other anions have a significant effect on TPE-DHAB / Fe 3+ The fluorescence intensity of TPE-DHAB / Fe 3+ The fluorescence intensity of F - In the presence of 3+ The fluorescence intensity of TPE-DHAB / Fe 3+ Fluorescent probe pair F - High selectivity, able to effectively distinguish F in aqueous solution - and other anions, showing their specificity as F - Application potential of fluorescent probes.

[0097] Take 18 portions of 0.5 mL of stock solution I, add 1.5 mL of stock solution II to each of the 18 portions of stock solution I, and add 1.5 mL of stock solution III to each of the 18 portions of stock solution I, and then add 1.5 mL of 1×10 -4 M of Na2SO4 aqueous solution, NaCl aqueous solution, NaAc aqueous solution, Co(NO3)2 aqueous solution, tetrabutylammonium perchlorate aqueous solution, KI aqueous solution, tetrabutylammonium bromide aqueous solution, L-alanine aqueous solution, aspartic acid aqueous solution, glycine aqueous solution, L-threonine aqueous solution, L-histidine aqueous solution, L-serine aqueous solution, L-proline aqueous solution, NaHSO4 aqueous solution, NaHSO3 aqueous solution, NaNO2 aqueous solution and stock solution III, observe the fluorescence changes of their solutions under ultraviolet light, measure their fluorescence emission and draw a fluorescence intensity bar graph, see Fig.13 .pass Fig.13It can be seen that in the presence of other interfering substances, the tetraphenylethylene derivative ion complex / Fe 3+ F - The fluorescence response of the tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe can also effectively and specifically recognize F - These results demonstrate that the tetraphenylethylene derivative ion complex / Fe 3+ It can be used as a potential highly selective and anti-drying fluorescent sensor for the detection of F - , and still has good detection effect in complex environments.

[0098] Example 7

[0099] Tetraphenylethylene derivative ion complex fluorescent probe for Fe 3+ Detection (fluorescent probe I) and tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe (TPE-DHAB / Fe 3+ )(Fluorescent probe II) - Characterization of the test at different pH values:

[0100] The prepared tetraphenylethylene derivative ion complex was dissolved in ethanol to a concentration of 1×10 -4 M solution as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution II; NaF was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution III.

[0101] Take 28 portions of 0.5 mL of stock solution I, add 1.5 mL of stock solution II to them, and fill 14 portions with blank solutions of pH 1-14 to 5 mL; and add 1.5 mL of stock solution III to the other 14 portions and then fill them with blank solutions of pH 1-14 to 5 mL, test their fluorescence emission and draw a line graph of I / I0 fluorescence intensity, as shown below: Fig.14 As shown. Fig.14 As shown, in the pH range of 2-12, the tetraphenylethylene derivative ion complex has a strong affinity for Fe 3+ The detection is almost unaffected by pH. In strong acid and strong base environments, probe I is somewhat disturbed, but the overall scope of application is not affected. The fluorescence intensity of the solution is basically unchanged. Tetraphenylethylene derivative ion complex / Fe 3+ (TPE-DHAB / Fe 3+ ) -The detection of Fe is almost unaffected in the entire pH range of 1-14, and basically does not affect the actual detection effect. It proves that the prepared fluorescent probes I and II have good acid-base stability and can still detect Fe in a wide pH range. 3+ and F - effective detection.

[0102] Example 8

[0103] Tetraphenylethylene derivative ion complex fluorescent probe for Fe 3+ Detection (Fluorescent Probe I) Tetraphenylethylene Derivative Ion Complex / Fe 3+ Complex fluorescent probe (TPE-DHAB / Fe 3+ )(Fluorescent probe II) - Determination of detection mechanism:

[0104] The prepared tetraphenylethylene derivative ion complex was dissolved in ethanol to a concentration of 1×10 -4 M solution as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution II; NaF was dissolved in deionized water to prepare 1×10 -4 M solution as stock solution III.

[0105] Take 3 portions of 0.5 mL of stock solution I, add 1.5 mL of stock solution II to one portion, add 1.5 mL of stock solution II and 1.5 mL of stock solution III to one portion, and add nothing to the other portion. Finally, fill up to 5 mL with pure water solution and test its particle size and Zeta potential. The results are as follows: Figure 15-Figure 20 As shown. Figure 15-20 It can be seen that the initial particle size and potential of the tetraphenylethylene derivative ion complex are 56.2nm and 10.6mV, respectively. 3+ The particle size and potential of the added F were 395.6 nm and 21.8 mV, respectively. Finally, 30 μM F - The addition of Fe resulted in a change in particle size and potential of 102.7 nm and 29.4 mV, respectively. We speculate that this may be due to the fact that the tetraphenylethylene derivative ion complex carries a certain charge. 3+ The addition of F leads to fluorescence quenching through electrostatic interaction, while - The electrostatic interaction is stronger and takes away Fe 3+ The fluorescence was restored. The change in Zeta potential proved that the tetraphenylethylene derivative ion complex with Fe 3+ and F - There is electrostatic interaction between them.

[0106] It should be understood that the various forms of processes shown above can be used to reorder, add or delete steps. For example, the steps recorded in this disclosure can be executed in parallel, sequentially or in different orders, as long as the desired results of the technical solutions disclosed in this disclosure can be achieved, and this document does not limit this.

[0107] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present disclosure, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0108] The above is only a specific embodiment of the present disclosure, but the protection scope of the present disclosure is not limited thereto. Any person skilled in the art who is familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present disclosure, which should be included in the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure should be based on the protection scope of the claims.

Claims

1. A tetraphenylethylene derivative ion complex / Fe 3+ The method for preparing a complex fluorescent probe is characterized by: include, The tetraphenylethylene derivative ion complex is dissolved in ethanol to obtain a stock solution I; Dissolve FeCl3·6H2O in deionized water to obtain stock solution II; The stock solution I and the stock solution II are mixed and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe; Wherein, the structural formula of the tetraphenylethylene derivative ion complex is:

2. The preparation method according to claim 1, characterized in that: The concentration of the tetraphenylethylene derivative ion complex in the stock solution I is 1×10 -4 M; the concentration of FeCl3·6H2O in the stock solution II is 1×10 -4 M.

3. The preparation method according to claim 2, characterized in that: The stock solution I and the stock solution II were mixed at a volume ratio of 1:3-4, and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe, wherein the tetraphenylethylene derivative ion complex / Fe 3+ The concentration of the tetraphenylethylene derivative ion complex in the complex fluorescent probe is 10 μM.

4. A tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is characterized by: It is prepared by the preparation method described in any one of claims 1 to 3.

5. The tetraphenylethylene derivative ion complex / Fe according to claim 4 3+ The complex fluorescent probe is used to detect F - Application in ions.

6. The use according to claim 5, characterized in that: The tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe F - The minimum detection limit of ions is 9.40×10 -8 M.

7. The use according to claim 5, characterized in that: The tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is used for F - When ion detection is performed, it is not affected by SO4 2- , Cl - ,Ac - 、NO3 - 、HClO4 - ,I - Br - 、HSO4 - 、HSO3 - 、NO2 - 、F - and interference from L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, and L-proline.

8. Tetraphenylethylene derivative ion complex fluorescent probe in the detection of Fe 3+ Ion application, wherein the structural formula of the tetraphenylethylene derivative ion complex is:

9. The use according to claim 8, characterized in that: The tetraphenylethylene derivative ion complex fluorescent probe is 3+ Under the action of ions, the fluorescence intensity decreases to quenching. 3+ The minimum detection limit of ions is 8.76×10 -8 M.

10. The use according to claim 8, characterized in that: The tetraphenylethylene derivative ion complex fluorescent probe is used for Fe 3+ The detection of ions is not affected by Cd 2+ , Sr 2+ 、Na + , Cu 2+ , Ba 2+ , Fe 3+ 、Co 2+ , Pb 2+ , K + , Ca 2+ 、Zn 2+ Mg 2+ 、Ag + Sn 2+ 、Mo 2+ , Cs + Cationic interference.

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