A tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probes, their preparation methods and applications

Abstract

The present disclosure provides a tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe, preparation method and application thereof. A tetraphenylethylene derivative ion complex / Fe 3+ Preparation method of complex fluorescent probe, comprising: dissolving a tetraphenylethylene derivative ion complex in ethanol to obtain a stock solution I; dissolving FeCl3·6H2O in deionized water to obtain a stock solution II; mixing the stock solution I and the stock solution II, and diluting with deionized water to obtain a tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe. Tetraphenylethylene derivative ion complex / Fe 3+ Application of complex fluorescent probe in detection of F ‑ ions. The tetraphenylethylene ion complex / Fe 3+ complex of the present disclosure can realize detection of F ‑ “open type” fluorescence detection.

Description

Technical Field

[0001] This disclosure relates to the field of fluorescent probe technology, and more particularly to a tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probes, their preparation methods, and applications. Background Technology

[0002] In recent years, anions have played a crucial role in chemical, environmental, and biochemical processes, particularly in the development of sensors to identify anions in environmental and biological systems, which has attracted widespread attention. Among the many anions, fluoride ions (F...)... - Fluoride is a crucial trace element in the human body, and adequate fluoride levels play a vital role in preventing tooth decay and treating osteoporosis. However, excessive fluoride intake can lead to fluorosis of teeth and bones, and may even cause neurological disorders, damaging the kidneys, brain, and immune system. These health risks underscore the need to develop accurate, effective, highly selective, and highly sensitive fluoride ion detection materials to achieve quantitative detection of fluoride ions, ensure their safe concentration in the human body, and provide a scientific basis for fluoride pollution control. Researching novel fluoride ion detection materials not only has significant scientific importance but also holds broad practical application prospects.

[0003] To date, various analytical methods have been developed for fluoride ion detection, including ion-selective electrodes, ion chromatography, and colorimetry. While these techniques demonstrate some effectiveness in fluoride ion detection, they are typically limited by complex sample preparation, expensive equipment requirements, and time-consuming operations. In contrast, fluorescence-based detection methods have attracted significant attention due to their simplicity, low cost, high sensitivity, and real-time monitoring capabilities, making them an ideal choice for fluoride ion detection. Fluorescence-based detection methods offer high sensitivity and specificity, leading to substantial research focus on developing fluorescent sensors for fluoride ion detection. However, traditional fluorescence sensors largely rely on a "closed" fluorescence quenching mode, making them susceptible to interference from quenching agents or photobleaching, affecting detection accuracy. Furthermore, fluorescence sensors based on traditional luminescent molecules typically have high detection limits, failing to meet the demands of high-sensitivity detection of trace fluoride ions in practical applications. Therefore, achieving a "closed" fluorescence detection effect and improving the sensitivity for trace fluoride ion detection has become a research hotspot in the field of fluorescence sensors. Summary of the Invention

[0004] This disclosure provides a tetraphenylethylene derivative ion complex / Fe 3+ The invention relates to complex fluorescent probes, their preparation methods, and applications, aiming to address at least one of the technical problems existing in the prior art.

[0005] According to a first aspect of this disclosure, a tetraphenylethylene derivative ion complex / Fe is provided. 3+ Methods for preparing complex fluorescent probes include,

[0006] The tetraphenylethylene derivative ionic complex was dissolved in ethanol to obtain stock solution I;

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

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

[0009] The structural formula of the tetraphenylethylene derivative ionic complex is as follows:

[0010]

[0011] In one embodiment, the concentration of the tetraphenylethylene derivative ion complex in the stock solution I is 1 × 10⁻⁶. -4 M; The concentration of FeCl3·6H2O in the stock solution II is 1×10 -4 M.

[0012] In one embodiment, 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 was 10 μM.

[0013] According to a second aspect of this disclosure, a tetraphenylethylene derivative ion complex / Fe is provided. 3+ The complex fluorescent probe is prepared by the method described above.

[0014] According to a third aspect of this disclosure, the aforementioned tetraphenylethylene derivative ionic complex / Fe is provided. 3+ Complex fluorescent probes for detecting F - Applications in ions.

[0015] In one possible embodiment, the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe for F - The limit of detection for ions is 9.40 × 10⁻⁶. -8 M.

[0016] In one possible embodiment, the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probes in response to F - During ion detection, it is not affected by SO4. 2- Cl - Ac - NO3 - HClO4 - I - ,Br - HSO4 - HSO3 - NO2 - Interference with L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, and L-proline.

[0017] According to a fourth aspect of this disclosure, a tetraphenylethylene derivative ion complex fluorescent probe is provided for the detection of Fe. 3+ Applications in ions, wherein the structural formula of the tetraphenylethylene derivative ionic complex is:

[0018]

[0019] In one embodiment, the tetraphenylethylene derivative ion complex fluorescent probe is used in Fe... 3+ Under the influence of ions, the fluorescence intensity decreases to quenching, affecting Fe. 3+ The limit of detection for ions is 8.76 × 10⁻⁶. -8 M.

[0020] In one embodiment, the tetraphenylethylene derivative ion complex fluorescent probe targets Fe. 3+ The detection of ions is not affected by Cd 2+ 、Sr 2+ Na + Cu 2+ Ba 2+ Co 2+ Pb 2+ K + Ca 2+ Zn 2+ Mg 2+ Ag + Sn 2+ Mo 2+ Cs + Interference from cations.

[0021] Compared with the prior art, the advantages of this application are: 1) The tetraphenylethylene derivative ion complex of the present invention has a significant aggregation-induced emission effect and excellent luminescence performance. In aqueous solution, the tetraphenylethylene ion complex achieves the effect of luminescence on Fe... 3+The "closed" fluorescence detection, and the resulting tetraphenylethylene ion complex / Fe 3+ Complexes can achieve the effect of F - "Open-type" fluorescence detection.

[0022] 2) The tetraphenylethylene derivative ion complex fluorescent probe and the tetraphenylethylene derivative ion complex / Fe of the present invention 3+ The preparation method of complex fluorescent probes is simple and the reaction conditions are mild, which is beneficial to environmental protection and meets the characteristics of green chemistry.

[0023] 3) The tetraphenylethylene derivative ion complex fluorescent probe and the tetraphenylethylene derivative ion complex / Fe prepared in this invention 3+ The complex fluorescent probe possesses excellent chemical stability, high sensitivity, and good anti-interference ability, and can pass through Fe... 3+ and F - Achieve rapid and efficient "off / on" fluorescence response.

[0024] It should be understood that the description in this section is not intended to identify key or essential features of the embodiments of this disclosure, nor is it intended to limit the scope of this disclosure. Other features of this disclosure will become readily apparent from the following description. Attached Figure Description

[0025] The above and other objects, features, and advantages of this disclosure will become readily apparent from the following detailed description of exemplary embodiments, taken in conjunction with the accompanying drawings. Several embodiments of this disclosure are illustrated in the drawings by way of example and not limitation, in which:

[0026] In the accompanying drawings, the same or corresponding reference numerals indicate the same or corresponding parts.

[0027] Figure 1 The TPE-DHAB of this disclosure embodiment is shown in the 1H NMR spectrum.

[0028] Figure 2 The carbon spectrum of TPE-DHAB according to an embodiment of this disclosure is shown;

[0029] Figure 3 The infrared spectrum of TPE-DHAB according to an embodiment of this disclosure is shown;

[0030] Figure 4 A high-resolution mass spectrum of TPE-DHAB according to an embodiment of this disclosure is shown;

[0031] Figure 5 The fluorescence spectrum of TPE-DHAB in deionized aqueous solution according to an embodiment of the present disclosure is shown.

[0032] Figure 6The following is a line graph showing the water content and I / I0 fluorescence intensity of TPE-DHAB in deionized aqueous solution according to an embodiment of the present disclosure;

[0033] Figure 7 The UV-absorbing spectrum of TPE-DHAB in deionized aqueous solution according to an embodiment of the present disclosure is shown.

[0034] Figure 8 The TPE-DHAB of this disclosure embodiment is shown in Fe 3+ Fluorescence spectra in aqueous solutions with concentrations ranging from 0 to 40 μM;

[0035] Figure 9 Fe, an embodiment of this disclosure, is shown. 3+ Fluorescence images of TPE-DHAB under UV irradiation at concentrations of 0 μM and 30 μM;

[0036] Figure 10 The columnar soil samples showing the fluorescence intensity of TPE-DHAB under different interfering substances according to embodiments of this disclosure are illustrated.

[0037] Figure 11 The TPE-DHAB / Fe embodiment of this disclosure is shown. 3+ In F - Fluorescence spectra in aqueous solutions with concentrations of 0-30 μM;

[0038] Figure 12 The TPE-DHAB / Fe embodiment of this disclosure is shown. 3+ fluorescence intensity and F - Correlation linearity plot for concentrations in the 0-30 μM range;

[0039] Figure 13 The TPE-DHAB / Fe embodiment of this disclosure is shown. 3+ Fluorescence intensity of columnar soil under different interfering substances;

[0040] Figure 14 TPE-DHAB and TPE-DHAB / Fe, embodiments of this disclosure are shown. 3+ A line graph showing the relationship between pH and I / I0 fluorescence intensity;

[0041] Figure 15 An initial particle size distribution of TPE-DHAB according to an embodiment of this disclosure is shown;

[0042] Figure 16 The TPE-DHAB with Fe added according to an embodiment of this disclosure is shown. 3+ The particle size distribution afterward;

[0043] Figure 17 The TPE-DHAB with Fe added according to an embodiment of this disclosure is shown.3+ F - The particle size distribution afterward;

[0044] Figure 18 An initial Zeta potential diagram of the TPE-DHAB according to an embodiment of this disclosure is shown;

[0045] Figure 19 The TPE-DHAB with Fe added according to an embodiment of this disclosure is shown. 3+ The subsequent Zeta potential diagram;

[0046] Figure 20 The TPE-DHAB with Fe added according to an embodiment of this disclosure is shown. 3+ F - The subsequent Zeta potential diagram. Detailed Implementation

[0047] To make the objectives, features, and advantages of this disclosure more apparent and understandable, the technical solutions in the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this disclosure, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without creative effort are within the scope of protection of this disclosure.

[0048] According to one embodiment of this disclosure, in a first aspect, the present invention provides a tetraphenylethylene derivative ion complex / Fe 3+ Methods for preparing complex fluorescent probes include,

[0049] The tetraphenylethylene derivative ionic complex was dissolved in ethanol to obtain stock solution I;

[0050] FeCl3·6H2O was dissolved in deionized water to obtain stock solution II;

[0051] Stock solution I and stock solution II were mixed and diluted with deionized water to obtain the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe;

[0052] The structural formula of the tetraphenylethylene derivative ionic complex is as follows:

[0053]

[0054] This application contains tetraphenylethylene derivative ion complexes / Fe 3+ The preparation method of complex fluorescent probes is simple and the reaction conditions are mild, which is beneficial to environmental protection and meets the characteristics of green chemistry.

[0055] In some embodiments, the concentration of the tetraphenylethylene derivative ion complex in the stock solution I is 1 × 10⁻⁶. - 4 M; The concentration of FeCl3·6H2O in the stock solution II is 1×10 -4 M.

[0056] 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 fluorescent probe was 10 μM. Exemplarily, 0.5 ml of stock solution I and 1.5 ml of stock solution II were mixed (volume ratio 1:3) and diluted with deionized water to 5 ml 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 fluorescent probe was 10 μM, and the Fe content was... 3+ The concentration is 30 μM.

[0057] According to a second aspect of this disclosure, the present invention provides a tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probe is prepared by the method described above.

[0058] According to a third aspect of this disclosure, the present invention also provides a tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probes for detecting F - Applications in ions. This application relates to tetraphenylethylene ion complexes / Fe 3+ Complexes can achieve the effect of F - "Open-type" fluorescence detection. Tetraphenylethylene derivative ion complex / Fe 3+ The complex fluorescent probes possess excellent chemical stability, high sensitivity, and good anti-interference ability, and can be detected by F... - Achieve rapid and efficient "on" fluorescence response.

[0059] In some embodiments, the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe for F - The detection limit for ions is 9.40 × 10⁻⁸ M.

[0060] In some embodiments, the tetraphenylethylene derivative ion complex / Fe3+ complex fluorescent probe is unaffected by the anion SO42- when detecting F- ions.2- Cl - Ac - NO3 - HClO4 - I - ,Br - HSO4 - HSO3 - NO2 - Interference with L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, and L-proline.

[0061] According to a fourth aspect of this disclosure, the present invention also provides a tetraphenylethylene derivative ion complex fluorescent probe for detecting Fe. 3+ In its application, the tetraphenylethylene derivative ion complex fluorescent probe has the following structural formula:

[0062] This application provides three different tetraphenylethylene derivative ionic complexes, wherein when R is C 14 H 29 When the tetraphenylethylene derivative ion complex is obtained, it is abbreviated as "TPE-DDAB"; when R is C 16 H 33 The resulting tetraphenylethylene derivative ion complex is abbreviated as "TPE-DHAB"; R is C 18 H 37 The resulting tetraphenylethylene derivative ion complex, abbreviated as "TPE-DOAB", was obtained. We found that all three tetraphenylethylene derivative ion complex fluorescent probes could target Fe... 3+ The ions are detected efficiently and rapidly, and the tetraphenylethylene ion complex / Fe is formed. 3+ Complexes can also efficiently detect F. - .

[0063] In some embodiments, the tetraphenylethylene derivative ion complex fluorescent probe in Fe 3+ Under the influence of ions, the fluorescence intensity decreases to quenching, affecting Fe. 3+ The limit of detection for ions is 8.76 × 10⁻⁶. -8 M.

[0064] In some embodiments, the tetraphenylethylene derivative ion complex fluorescent probe for Fe 3+ The detection of ions is not affected by Cd 2+ 、Sr 2+ Na + Cu 2+ Ba 2+ Co 2+ Pb2+ K + Ca 2+ Zn 2+ Mg 2+ Ag + Sn 2+ Mo 2+ Cs + Interference from cations.

[0065] The tetraphenylethylene derivative ionic complex of this invention exhibits significant aggregation-induced emission and excellent photophysical properties. In aqueous solution, the tetraphenylethylene derivative ionic complex achieves the effect of... 3+ The "closed" fluorescence detection, and the resulting tetraphenylethylene derivative ion complex / Fe 3+ Complexes can achieve the effect of F - "Open-type" fluorescence detection. The Fe of the tetraphenylethylene derivative ion complex of this invention. 3+ and F - The "off / on" fluorescent probe preparation method is simple, the reaction conditions are mild, which is beneficial to environmental protection and meets the characteristics of green chemistry. It can achieve the detection of Fe in complex pure water environments. 3+ and F - Rapid and efficient testing promises to enable industrialization and field applications.

[0066] The present application will be further described in detail below with reference to embodiments:

[0067] Example 1

[0068] The preparation method of tetraphenylethylene derivative ionic complex includes the following steps:

[0069] Step (1): Add 1.00 g (1.03 mmol) of compound (Ⅰ) and 0.24 g (4.29 mmol) of KOH to a 250 mL single-necked round-bottom flask and dissolve in 30 mL of deionized water to obtain TPE-4COO. - K + Solution, ready for use; the structural formula of compound (I) is,

[0070] Step (2), add 2.59 g (4.51 mmol) of (C) to another 250 mL single-necked round-bottom flask. 16 H 33 )2(CH3)2N + Br - Dissolve in a 60 mL mixture of ethanol and water (v / v = 1:2) and heat to 50 °C.

[0071] Step (3): Under stirring conditions at 50°C, TPE-4COO is added using a constant pressure dropping funnel. - K + The aqueous solution was slowly added dropwise to the solution containing (C) 16 H 33 )2(CH3)2N + Br - In an EtOH / H2O mixed solution, the dropping rate was 1 drop / min, and a precipitate was formed. The reaction was continued at 50℃ for 12 h. The mixture was filtered, and the precipitate was washed with a mixed solvent of ethanol and water in a volume ratio of 1:2. The mixture was then dried under vacuum to obtain a tetraphenylethylene derivative ion complex, abbreviated as "TPE-DHAB", with a yield of 88%.

[0072] The tetraphenylethylene derivative ion complex ( TPE-DHAB The reaction equation is:

[0073]

[0074] The chemical structure of the TPE-DHAB was characterized by 1H NMR, 1C NMR, IR spectroscopy, and high-resolution mass spectrometry. 1 H NMR(CDCl3,600MHz), 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 As shown.

[0075] 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, etc. Figure 2 As shown.

[0076] 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,as Figure 3 As shown.

[0077] MALDI-TOF-MS: calcd for C 194 H 328 N4O 12 :2908.4817.Found:2908.4817, as Figure 4 As shown, this proves that the TPE-DHAB of this application was successfully prepared.

[0078] Example 2

[0079] Photophysical properties determination of tetraphenylethylene derivative ion complex (TPE-DHAB)

[0080] The prepared tetraphenylethylene derivative ionic complex was dissolved in DMF and prepared to a concentration of 1×10⁻⁶. -4 The solution of M is used as stock solution I; six 0.5 mL portions of stock solution I are taken, and 0, 1, 2, 3, 4, and 4.5 mL of deionized water are added respectively. The volume is then brought to 5 mL with DMF to prepare solutions with unsuitable solvent volume fractions of 0%, 20%, 40%, 60%, 80%, and 90% (water content f). w The solution was tested; the fluorescence and UV-absorption spectra of six solutions were measured, such as... Figure 5 and Figure 7 .from Figure 5 The fluorescence spectrum shows that as the water content (f) increases, the fluorescence intensity decreases. w With increasing water content, the absorbance of TPE-DHAB significantly increases due to aggregate formation. w Under conditions of less than 20% water content, the fluorescence emission of the TPE-DHAB solution reaches almost its minimum, exhibiting extremely weak luminescence. However, with increasing water content, the fluorescence emission intensity of the solution gradually increases, displaying typical AIE (aggregation-induced emission) characteristics. This fluorescence enhancement can be attributed to the increased intermolecular π-π stacking interactions within the TPE-DHAB aggregates and the restriction of intramolecular rotation. This restriction reduces non-radiative decay, thereby enhancing fluorescence emission. Figure 6It can be seen that the fluorescence intensity increased sharply as the moisture content increased from 20% to 40%, indicating that the aggregation efficiency of TPE-DHAB was significantly improved within this moisture content range. This enhanced aggregation further promoted the AIE effect. More significantly, at f w At 80% water content, the fluorescence intensity of TPE-DHAB was approximately 73 times higher than its emission intensity in pure DMF, highlighting the crucial role of water content in enhancing the AIE effect of TPE-DHAB. This significant fluorescence enhancement indicates that under high water content conditions, the intermolecular interactions of TPE-DHAB are maximized, resulting in more efficient luminescence performance. Furthermore, the UV-Vis absorption spectrum... Figure 7 A similar trend to fluorescence emission was also observed, further validating the aggregation-induced emission (AIE) properties of TPE-DHAB. This absorption trend demonstrates the structural state changes of TPE-DHAB molecules during aggregation and the further restriction of internal molecular rotation with increasing water content, enhancing 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 foundation for the future design and optimization of TPE-DHAB-like sensors.

[0081] Example 3

[0082] Tetraphenylethylene derivative ion complex fluorescent probe (i.e., fluorescent probe I) in different Fe 3+ Determination of fluorescence spectra under different concentrations:

[0083] The prepared tetraphenylethylene derivative ionic complex was dissolved in ethanol to prepare a solution with a concentration of 1×10⁻⁶. -4 The solution of M was used as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 The solution of M is used as stock solution II; 21 portions of stock solution I, each 0.5 mL in volume, are taken, and then 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, and 2 mL of stock solution II are added to 20 portions of stock solution I, respectively. Finally, the volume is brought up to 5 mL with deionized water to prepare Fe... 3+ Fluorescence spectra of aqueous solutions with concentrations ranging from 0 to 40 μM were measured, such as... Figure 8 As shown.

[0084] By analyzing different concentrations of Fe 3+ The fluorescence emission spectrum of TPE-DHAB in the presence of Fe indicates that... 3+With increasing concentration, the fluorescence intensity of TPE-DHAB gradually decreased, exhibiting a significant fluorescence quenching effect. In the absence of Fe... 3+ Under certain conditions, the TPE-DHAB solution showed a significant fluorescence signal, but with the gradual addition of Fe... 3+ Afterwards, the fluorescence emission gradually weakens until it disappears completely. When Fe 3+ When the concentration reaches or exceeds 30 μM, the fluorescence in the solution is almost undetectable, indicating that TPE-DHAB reacts with Fe at this concentration. 3 + The interaction has become saturated, leading to complete fluorescence quenching. Figure 9 This indicates that the fluorescence intensity of the TPE-DHAB fluorescent probe solution is related to Fe. 3+ The concentration exhibited a highly linear correlation (R² = 0.9987) in the range of 0–30 μM, indicating that the sensor (i.e., the fluorescent probe) can achieve Fe in this concentration range. 3+ Accurate quantitative detection.

[0085] Furthermore, the detection limit of this sensor was calculated to be 8.76 × 10⁻⁶. -8 M demonstrates its effectiveness against low concentrations of Fe. 3+ Its high sensitivity can effectively meet the requirements of low Fe content 3+ The need for testing. Figure 9 It showed 0 μM and 30 μM Fe 3+ Fluorescence images of TPE-DHAB under ultraviolet light irradiation under certain conditions visually demonstrate the differences in quenching at different concentrations: in the absence of Fe 3+ At 30 μM Fe, TPE-DHAB exhibits bright fluorescence, while at 30 μM Fe 3+ At this concentration, fluorescence almost completely disappears, highlighting the presence of Fe. 3+ Significant quenching effect on TPE-DHAB. These experimental results demonstrate the quenching effect of the tetraphenylethylene derivative ionic complex on Fe. 3+ It features highly sensitive "off-mode" fluorescence detection, based on the fluorescence quenching effect of Fe. 3+ It has potential applications in ion detection.

[0086] Example 4

[0087] Tetraphenylethylene derivative ion complex fluorescent probe (“Fluorescent Probe I”) for Fe 3+ Selectivity characterization of detection:

[0088] The prepared tetraphenylethylene derivative ionic complex was dissolved in ethanol to prepare a solution with a concentration of 1×10⁻⁶. -4 The solution of M was used as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4The solution of M is used as stock solution II.

[0089] Take 16 portions of stock solution I, each 0.5 mL in volume. Add 1.5 mL of stock solution II to one portion, and then add 1.5 mL of stock solution II (1×10⁻⁶) to the other 15 portions. -4 M aqueous solutions of CdCl2, SrCl2, NaCl, CuCl2, BaCl2, CoCl2, PbCl2, KCl, CaCl2, ZnCl2, MgCl2, AgNO3, SnCl2, and (NH4)6Mo7O 24 • 4H₂O aqueous solution and Cs₂CO₃ aqueous solution were used as interfering control groups. The final volume was made up to 5 mL with deionized water. The changes in fluorescence under UV light were observed, and fluorescence emission was measured to create a fluorescence intensity bar chart, as shown in the figure. Figure 10 As shown ( Figure 10 In this context, "counterion" refers to the aforementioned interfering factors. Figure 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. However, Cu... 2+ Fe 3+ and Ag + The fluorescence emission intensity of TPE-DHAB was significantly reduced, in which Fe 3+ The quenching effect on fluorescence emission was most significant, resulting in a relative emission intensity reduction to approximately 0.03, demonstrating the quenching effect of Fe. 3+ Strong interaction with TPE-DHAB. This difference is clearly visible under ultraviolet light, with significant fluorescence quenching, causing Fe... 3+ It can be visually distinguished from other cations.

[0090] Take 16 aliquots of stock solution I, each with a volume of 0.5 mL, and then add 1.5 mL of a 1×10⁻⁶ solution to each aliquot. -4 M aqueous solutions of CdCl2, SrCl2, NaCl, CuCl2, BaCl2, CoCl2, PbCl2, KCl, CaCl2, ZnCl2, MgCl2, AgNO3, SnCl2, and (NH4)6Mo7O 24 • Prepare 4H2O aqueous solution, Cs2CO3 aqueous solution, and stock solution II. Then, add 300 μL of stock solution II to each of the 16 stock solution I portions. Finally, top up all solutions with deionized water to a final volume of 5 mL. Observe the fluorescence changes of the solutions under a UV lamp and measure the fluorescence emission to plot a fluorescence intensity bar graph, as shown in the figure. Figure 10 As shown. (Through) Figure 10It can be seen that, in the presence of other interfering substances, the tetraphenylethylene derivative ionic complex affects Fe... 3+ The fluorescence response remained almost unchanged, indicating that the tetraphenylethylene derivative ion complex can effectively and specifically detect Fe even in the presence of other interfering substances. 3+ These results demonstrate that tetraphenylethylene derivative ion complexes can serve as a potential highly selective and drought-resistant fluorescent sensor (i.e., a fluorescent probe) for the detection of Fe. 3+ It also maintains good detection performance in complex environments.

[0091] Example 5

[0092] 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 detected:

[0093] The prepared tetraphenylethylene derivative ionic complex was dissolved in ethanol to prepare a solution with a concentration of 1×10⁻⁶. -4 The solution of M was used as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M was prepared as stock solution II; NaF was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 The solution of M is used as stock solution III; take 16 aliquots of stock solution I (0.5 mL each) and add 1.5 mL of stock solution II to each. 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, and 1.5 mL of stock solution III to each of the 16 aliquots respectively. Finally, bring the total volume to 5 mL with deionized water to prepare solution F. - Fluorescence spectra of aqueous solutions with ion concentrations of 0-30 μM were measured. (See attached image.) Figure 11 With F - As the concentration of the protons increases, the fluorescence intensity of the solution gradually increases. This gradual increasing trend is observed in F... - The effect was particularly pronounced at a concentration of 30 μM, where the fluorescence intensity was approximately 19 times greater than that of the blank control solution. This significant fluorescence response is attributed to the presence of TPE-DHAB on Fe... 3+ F in the presence of ions - Specific recognition and binding of ions. F - The addition triggered Fe 3+ Competitive substitution of ions alters the molecular structure of TPE-DHAB, restoring its fluorescence intensity. This process demonstrates that TPE-DHAB is susceptible to F... -Its high sensitivity and strong recognition ability demonstrate its role as an F - The enormous potential of “open-type” fluorescent sensors. Figure 12 It shows that TPE-DHAB / Fe 3+ The fluorescence intensity of the fluorescent probe solution and F - The concentrations showed a highly linear correlation (R0) in the range of 0-30 μM. 2 =0.9985), indicating that the sensor (i.e., the fluorescent probe) can achieve F in this concentration range. - Accurate quantitative detection is achieved. Furthermore, the detection limit of this sensor was calculated to be 9.40 × 10⁻⁶. -8 M demonstrated its effectiveness against low concentrations of F. - Its high sensitivity can effectively meet the requirements of low-content F - The need for testing. Figure 12 The illustrations also provide visual evidence showing the effects of ultraviolet light on TPE-DHAB / Fe 3+ Complex solutions with and without 30 μM F - The fluorescence showed a significant change at that time. Without the addition of F... - In the absence of [specific condition], the solution exhibits weak fluorescence, while with the addition of F [specific substance], [the fluorescence increases]. - Subsequently, the fluorescence intensity significantly increased, highlighting F. - There exists a relationship between TPE-DHAB / Fe 3+ The effect of the complex's fluorescence properties. These results clearly demonstrate the influence of TPE-DHAB / Fe... 3+ Coordination compounds as F - The sensor's high selectivity and high sensitivity enable it to operate in "on" environments under complex conditions. - It has promising applications in testing.

[0094] Example 6

[0095] Tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe (TPE-DHAB / Fe) 3+ Fluorescent probe II) for F - Selectivity characterization of detection:

[0096] The prepared tetraphenylethylene derivative ionic complex was dissolved in ethanol to prepare a solution with a concentration of 1×10⁻⁶. -4 The solution of M was used as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M was prepared as stock solution II; NaF was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M is used as stock solution III.

[0097] Take 18 portions of stock solution I, each with a volume of 0.5 mL. 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 the portions, and then add 1.5 mL of stock solution II (1×10⁻⁶) to the other 17 portions. -4 Aqueous solutions of Na₂SO₄, NaCl, NaAc, Co(NO₃)₂, tetrabutylammonium perchlorate, KI, tetrabutylammonium bromide, L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, L-proline, NaHSO₄, NaHSO₃, and NaNO₂ were used as interfering control groups. All solutions were then brought to a final volume of 5 mL with deionized water. The changes in fluorescence under UV light were observed, and fluorescence emission was measured to create a fluorescence intensity bar graph, as shown in Figure [Figure number missing]. Figure 13 As shown. From Figure 13 It can be seen that, except for F - Other anions besides TPE-DHAB / Fe 3+ The fluorescence intensity is minimally affected and cannot affect TPE-DHAB / Fe 3+ The fluorescence intensity recovered. This indicates that in F... - In the presence of TPE-DHAB / Fe 3+ The fluorescence intensity significantly recovered to its initial level. This strong fluorescence response validates the TPE-DHAB / Fe 3+ Fluorescent probe for F - Its high selectivity enables it to effectively distinguish F in aqueous solutions. - And other anions, showing its specific F - The application potential of fluorescent probes.

[0098] Take 18 portions of stock solution I, each with a volume of 0.5 mL. 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. Then add 1.5 mL of a 1×10⁻⁶ solution to each of the 18 portions of stock solution I. -4 The following solutions were used: 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. The fluorescence changes of these solutions were observed under ultraviolet light, and fluorescence intensity histograms were plotted. (See...) Figure 13 .pass Figure 13It can be seen that, in the presence of other interfering substances, the tetraphenylethylene derivative ion complex / Fe 3+ For F - The fluorescence response remained almost unchanged, indicating that even in the presence of other interfering substances, the tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probes can also effectively and specifically recognize F. - These results demonstrate that the tetraphenylethylene derivative ionic complex / Fe 3+ It can serve as a potential highly selective and drought-resistant fluorescence sensor for detecting F. - It also maintains good detection performance in complex environments.

[0099] Example 7

[0100] Tetraphenylethylene derivative ion complex fluorescent probe for Fe 3+ Detection of (fluorescent probe I) and tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probe (TPE-DHAB / Fe) 3+ (Fluorescent probe II) for F - Characterization under different pH levels:

[0101] The prepared tetraphenylethylene derivative ionic complex was dissolved in ethanol to prepare a solution with a concentration of 1×10⁻⁶. -4 The solution of M was used as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M was prepared as stock solution II; NaF was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M is used as stock solution III.

[0102] Take 28 aliquots of stock solution I (0.5 mL each), add 1.5 mL of stock solution II to each, and bring 14 aliquots to a final volume of 5 mL with blank solution of pH 1-14. Add 1.5 mL of stock solution III to the remaining 14 aliquots, then bring the final volume to 5 mL with blank solution of pH 1-14. Measure the fluorescence emission and plot the I / I0 fluorescence intensity curve. Figure 14 As shown. Figure 14 As shown, in the pH range of 2-12, the tetraphenylethylene derivative ionic complex has a significant effect on Fe... 3+ The detection is almost unaffected by pH. Probe I is slightly interfered with in strongly acidic and alkaline environments, but its overall applicability remains unaffected. The fluorescence intensity of the solution remains essentially unchanged. Tetraphenylethylene derivative ion complex / Fe 3+ (TPE-DHAB / Fe 3+ ) for F -The detection is almost unaffected across the entire pH range of 1-14, and has virtually no impact on the actual detection results. This demonstrates that the prepared fluorescent probes I and II possess good acid-base stability and can still achieve detection of Fe over a wide pH range. 3+ and F - Effective detection.

[0103] Example 8

[0104] Tetraphenylethylene derivative ion complex fluorescent probe for Fe 3+ Detection of tetraphenylethylene derivative ion complex / Fe (fluorescent probe I) 3+ Complex fluorescent probe (TPE-DHAB / Fe) 3+ (Fluorescent probe II) for F - Determination of the detection mechanism:

[0105] The prepared tetraphenylethylene derivative ionic complex was dissolved in ethanol to prepare a solution with a concentration of 1×10⁻⁶. -4 The solution of M was used as stock solution I; FeCl3·6H2O was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M was prepared as stock solution II; NaF was dissolved in deionized water to prepare a solution of 1×10⁻⁶. -4 A solution of M is used as stock solution III.

[0106] Take three 0.5 mL aliquots of stock solution I. Add 1.5 mL of stock solution II to one aliquot, add 1.5 mL of stock solution II and 1.5 mL of stock solution III to another aliquot, and add nothing to the third aliquot. Finally, bring all aliquots to a total volume of 5 mL with pure aqueous solution. Test the particle size and zeta potential. The results are as follows: Figures 15-20 As shown. From Figure 15-20 It can be seen that the initial particle size and potential of the tetraphenylethylene derivative ionic complex were 56.2 nm and 10.6 mV, respectively. With the addition of 30 μM Fe... 3+ The added particle size and potential changed to 395.6 nm and 21.8 mV, respectively, and finally 30 μM F - The addition of [a substance] caused changes in particle size and potential of 102.7 nm and 29.4 mV, respectively. We speculate that this may be attributed to the fact that the tetraphenylethylene derivative ionic complex carries a certain charge, and with the addition of Fe [a substance]... 3+ The addition of leads to fluorescence quenching through electrostatic interactions, while with F - The electrostatic interaction was stronger, which took away Fe 3+ This restored the fluorescence. The change in Zeta potential demonstrated the interaction between the tetraphenylethylene derivative ionic complex and Fe. 3+ and F - There is an electrostatic interaction between them.

[0107] It should be understood that the various forms of processes shown above can be used to rearrange, add, or delete steps. For example, the steps described in this disclosure can be executed in parallel, sequentially, or in different orders, as long as the desired result of the technical solution disclosed in this disclosure can be achieved, and this is not limited herein.

[0108] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this disclosure, "a plurality of" means two or more, unless otherwise explicitly specified.

[0109] The above description is merely a specific embodiment of this disclosure, but the scope of protection of this disclosure is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this disclosure should be included within the scope of protection of this disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the claims.

Claims

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

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 1×10⁻⁶. -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: Stock solution I and 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 was 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 1-3.

5. The tetraphenylethylene derivative ion complex / Fe as described in claim 4 3+ Complex fluorescent probes for detecting F - Applications in ions.

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

7. The application according to claim 5, characterized in that: The tetraphenylethylene derivative ion complex / Fe 3+ Complex fluorescent probes in response to F - During ion detection, it is not affected by SO4. 2- Cl - Ac - NO3 - HClO4 - I - ,Br - HSO4 - HSO3 - NO2 - Interference with L-alanine, aspartic acid, glycine, L-threonine, L-histidine, L-serine, and L-proline.

8. Tetraphenylethylene derivative ion complex fluorescent probe for detecting Fe 3+ Applications in ions, wherein the structural formula of the tetraphenylethylene derivative ionic complex is:

9. The application according to claim 8, characterized in that: The tetraphenylethylene derivative ion complex fluorescent probe in Fe 3+ Under the influence of ions, the fluorescence intensity decreases to quenching, affecting Fe. 3+ The limit of detection for ions is 8.76 × 10⁻⁶. -8 M.

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

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