A non-contact phosphorescent ion sensing material and a method for preparing and using the same

Abstract

The application provides a design, preparation and application method of a non-contact phosphorescent ion sensing material. The material is composed of an absorption type indicator with a response to ion concentration change and a long-life phosphorescent dye, wherein the absorption spectrum of the absorption type ion indicator and the emission spectrum of the phosphorescent dye have obvious spectral overlap, when the two are loaded on a matrix carrier, due to the spatial proximity of the two, obvious energy transfer occurs between the two, thereby converting the absorption spectrum signal with a response to ion concentration change into a change signal of phosphorescent lifetime, and accurate measurement of ion concentration is realized through a simple and available phase-resolved phosphorescent lifetime measurement technology. The material is simple to construct, has wide application range, good stability, can be used for long-term detection, and has reliable results, solves the problems of poor stability, low measurement accuracy and large error of existing fluorescent ion sensing materials, and breaks through the bottleneck problem of the small number of types of high-performance ion sensing materials.

Description

Technical Field

[0001] This invention belongs to the field of phosphorescent detection technology for ion concentration, specifically relating to a highly stable, non-contact phosphorescent ion sensing material based on phosphorescent lifetime measurement and its preparation and application methods. Background Technology

[0002] Ion detection plays a vital role in scientific research, health monitoring, biomedicine, agriculture, aquaculture, water quality protection, food and beverage, metallurgy, electroplating, and geological exploration. Ion-selective electrodes are a widely used, simple, rapid, and automated continuous ion detection and analysis tool. Currently, they are used for pH and F... - Cl - ,Br - I - NO3 - The ion-selective electrode method has become a standard detection method in national standards. However, in practical applications, ion-selective electrodes also have a series of problems: First, coexisting ions can cause interference. Although the addition of masking agents, oxidants, reducing agents, ionic strength calibration buffers, and pH adjustment can effectively reduce or even eliminate interference, it undoubtedly increases the complexity and difficulty of sample pretreatment. Second, although ion-selective electrodes are developing towards miniaturization and micro-miniaturization, there are still many problems to be solved in their practical application in closed systems, especially in emerging application scenarios such as cell therapy and biomedicine. Due to the small solution volume and the need for sealed sterilization, the installation, sterilization, and prevention of contamination of ion-selective electrodes become difficult. Third, ion-selective electrodes need to be calibrated before use, which increases the detection steps. In a sealed sterilization system, it is difficult to achieve timely calibration of the electrodes. Fourth, ion-selective electrodes are easily contaminated. The contaminated electrode surface will generate various redox signals, leading to a significant decrease in measurement selectivity, sensitivity, and accuracy.

[0003] Fluorescent ion sensors, based on changes in fluorescence signals, have attracted widespread attention due to their advantages such as high sensitivity, good selectivity, continuous measurement capability, and insensitivity to electrode surface characteristics. The greatest advantage of fluorescent ion sensors lies in their non-contact detection mode. The fluorescent sensing film can be fixed to the wall of a transparent, sealed container or to an optical window of the sealed container. After sterilization, the excitation light and generated fluorescence are transmitted to the measuring device via optical fiber, enabling non-contact measurement of ion concentration within the sealed container. There are three main measurement methods for fluorescent ion sensors: single-wavelength fluorescence intensity detection, dual-wavelength fluorescence intensity ratio detection, and fluorescence lifetime detection. However, single-wavelength fluorescence intensity detection is related to dye concentration and is easily affected by fluctuations caused by factors such as the light source and instrument. Furthermore, photobleaching leads to a decreasing trend in fluorescence intensity. Therefore, this method cannot accurately obtain fluorescence intensity information of fluorescent molecules, and consequently, it is difficult to obtain accurate concentration information of the analyte. Measurements based on the dual-wavelength fluorescence intensity ratio method can effectively eliminate the influence of uneven fluorescent dye concentration distribution, and perturbations caused by the light source and instrument can also be calibrated. However, dual-wavelength ratio-based detection based on two molecules is affected by differences in molecular photobleaching rates and the different fluorescence absorption characteristics of the loading materials, leading to a significant decrease in measurement stability, accuracy, and reliability. Fluorescence lifetime detection is independent of dye concentration and is not affected by factors such as light source, instrument, and photobleaching. It is only related to the microenvironment in which the dye exists, thus exhibiting good photostability and accuracy. It is a reliable analytical method for long-term detection and is increasingly favored by researchers.

[0004] Currently, the luminescent materials used for ion detection are mainly organic small molecule fluorescent probes. However, small molecule fluorescent probes have certain limitations: First, they have relatively poor photostability and are prone to photobleaching during measurement, which weakens the signal. Second, background fluorescence within cells can interfere with the measurement, thus affecting the sensitivity of the detection. Therefore, probes in the near-infrared region have received more attention. Third, the luminescence characteristics of fluorescent molecules are greatly affected by the microenvironment in which the molecules are located. To achieve accurate measurement, it is necessary to ensure that the fluorescent molecules are in a uniform and stable microenvironment. Studies have shown that loading small molecule fluorescent probes onto a support to construct nanoluminescent materials can improve the photostability of small organic molecules (Peng, J., He, X., Wang, K., Tan, W., Wang, Y., Liu, Y. (2007). Noninvasive Monitoring of Intracellular pH Change Induced by Drug Stimulation Using Silica Nanoparticle Sensors. Anal Bioanal Chem, 388(3), 645-54.). Secondly, by assembling and regulating nanoluminescent materials, they can have a longer fluorescence lifetime, which is different from the nanosecond-level background fluorescence in cells, thus improving the sensitivity of detection. Thirdly, nanoluminescent materials connect fluorescent molecules to nanomaterials to prevent the leakage of fluorescent molecules. At the same time, the analyte binds to the probe through diffusion to respond, so that the fluorescent molecules are in a relatively uniform microenvironment, which has the same response performance as small organic molecule fluorescent probes. Moreover, the detection based on fluorescence lifetime is not affected by the concentration of fluorescent probes or nanomaterials. Fourthly, nanoluminescent materials can be coupled with multiple fluorescent probes to achieve multi-parameter measurement.

[0005] Currently, ion detection methods based on the measurement of luminescence lifetime of luminescent materials still have some problems, mainly including:

[0006] 1) The lifetimes of small molecule fluorescent substances are mostly in the nanosecond range, which makes them susceptible to severe interference from biological autofluorescence and requires high-frequency, expensive excitation light sources and expensive single-photon counting instruments to collect signals; 2) The phosphorescence lifetime of metal complexes is relatively long, but they generally do not have metal ion response behavior; modifying the structure of the complex to make it have a hydrogen ion response not only increases the difficulty of dye preparation, but also makes the response range of the prepared probe uncontrollable, and the response concentration range is difficult to predict through theoretical models, requiring a large number of synthesis and testing experiments for verification and confirmation. The following are some of the reported metal complex combinations with hydrogen ion concentration response based on lifetime detection: Clarke et al. used a modified polymer as a carrier to combine with a ruthenium complex, but the resulting sensor response range was only 3-5 (Clarke, Y., Xu, W., Demas, JN, DeGraff, BA (2000). Lifetime-Based pH Sensor System Based on a Polymer-Supported Ruthenium(II) Complex. Analytical Chemistry, 72(15), 3468-3475.). Others modified the carboxyl groups on the ligands of ruthenium complexes to make them pH responsive, but the response range was only 2-5 ( ). HMR, Maule, CD, Jorge, PAS, Esteves da Silva, JCG (2008). FiberOptic Lifetime pH Sensing Based on Ruthenium(II) Complexes with Dicarboxybipyridine. Analytica Chimica Acta, 626(1), 62-70.); Poehler et al. and Meier et al. coupled luciferin molecules to ligands of ruthenium and europium complexes, respectively. Although the pH detection range was improved (5-9.5 and 3-8, respectively), the synthesis and construction of such fluorescent molecules were relatively complex, and the photostability of the synthesized materials was poor (Poehler, E., Pfeiffer, SA, Herm, M., Gaebler, M., Busse, B., Nagl, S. (2016). Microchamber Arrays with an Integrated Long Luminescence Lifetime pH Sensor. Analytical and Bioanalytical Chemistry,408(11),2927-2935. & Meier, RJ; Simbürger, JMB; Soukka, T.; M., (2015). A FRET Based pH Probe with a Broad Working Range Applicable to Referenced Ratiometric Dual Wavelength and Luminescence Lifetime Read Out. Chemical Communications, 51(28), 6145-6148.); 3) Commercially available phosphorescent materials for ion detection remain classified, and their types and quantities are quite limited. Therefore, developing novel and simple phosphorescence lifetime-based ion sensors has significant application value. Summary of the Invention

[0007] The main objective of this invention is to provide a highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement, as well as its preparation and application methods. The core idea of ​​this invention is to combine an absorption indicator that responds to ion concentration with a phosphorescent dye whose emission spectrum overlaps with the absorption spectrum of the absorption indicator, exhibits good photostability, and has a long phosphorescence lifetime, on a matrix carrier to prepare a phosphorescent ion sensing material.

[0008] This invention provides a novel optical ion sensing material based on phosphorescence lifetime measurement. It combines an absorption indicator that responds to changes in ion concentration with a long-lifetime phosphorescent dye. The absorption spectrum of the absorption indicator and the emission spectrum of the phosphorescent dye exhibit significant spectral overlap. When both are loaded onto a matrix support, significant energy transfer occurs between them due to their spatial proximity. This transforms the absorption spectral signal, which responds to changes in ion concentration, into a phosphorescence lifetime change signal. Accurate ion concentration measurement is achieved using a simple and readily available phase-resolved phosphorescence lifetime measurement technique. Specifically:

[0009] First, this invention discloses a non-contact phosphorescent ion sensing material, which includes an absorptive indicator and a phosphorescent dye, as well as a loading material for loading the absorptive indicator and the phosphorescent dye. The absorption spectrum of the absorptive indicator and the emission spectrum of the phosphorescent dye overlap, thereby converting the absorption spectrum change signal of the absorptive indicator into the phosphorescence lifetime change signal of the phosphorescent dye. The phosphorescence lifetime change signal can be accurately measured by time-resolved or phase-resolved measurement techniques, and the concentration data of the ion to be measured can be obtained by calculation.

[0010] in:

[0011] The absorption indicator is an ion-responsive indicator, and the responsive ions include, but are not limited to, hydrogen ions, sodium ions, magnesium ions, aluminum ions, chloride ions, potassium ions, calcium ions, cobalt ions, copper ions, zinc ions, or lead ions.

[0012] The phosphorescent dyes mentioned include, but are not limited to, metal element complexes of ruthenium, iridium, platinum, palladium, or europium.

[0013] The combination of non-contact phosphorescent ion sensing materials involves combining indicators such as hydrogen ions, sodium ions, potassium ions, calcium ions, magnesium ions, aluminum ions, cobalt ions, copper ions, lead ions, zinc ions, and chloride ions with complexes such as ruthenium, iridium, platinum, palladium, and europium according to the principle of spectral overlap (i.e., the absorption spectrum of the former partially overlaps with the emission spectrum of the latter).

[0014] The absorption-type indicator selectively responds to changes in ion concentration, including: hydrogen ion indicator such as thymol blue; sodium ion indicator such as 12-crown-4 derivative; magnesium ion indicator such as acid chrome blue K; aluminum ion indicator such as xylenol orange; chloride ion indicator such as mercuric thiocyanate; potassium ion indicator such as 15-crown-5 derivative; calcium ion indicator such as azoarsine III; cobalt ion indicator such as xylenol orange; copper ion indicator such as dicyclohexanone oxalyl dihydrazone; zinc ion indicator such as dithizone; and lead ion indicator such as tetra-(3,5-dibromo-4-hydroxybenzene)porphyrin.

[0015] Preferably, the ruthenium complex comprises any combination of one or more of the following:

[0016]

[0017] Preferably, the platinum / palladium complex comprises any combination of one or more of the following:

[0018]

[0019] Preferably, the europium complex comprises any combination of one or more of the following:

[0020]

[0021] Preferably, the iridium complex comprises one or more of the following combinations:

[0022]

[0023] Preferably, the phosphorescent dye has a phosphorescence lifetime greater than 200 ns.

[0024] Preferably, the supporting material includes organic polymer materials and inorganic materials. More preferably, the supporting material includes polyesters, polyhydrocarbon organic polymers with surface-modifying groups, and inorganic nanomaterials and micromaterials. More preferably, the supporting material includes polyurethane, cellulose, and silica nanoparticles.

[0025] Preferably, the absorptive indicator and the phosphorescent dye are loaded in a supporting material, and the absorptive indicator and the phosphorescent dye are spatially close, thereby enabling energy transfer between the phosphorescent dye and the absorptive indicator. More preferably, the absorptive indicator and the phosphorescent dye are combined on a single supporting material or on different supporting nanoparticles, and are loaded through physical dissolution. Even more preferably, the loading method involves the phosphorescent dye being encapsulated inside the supporting material to protect the luminescent properties of the phosphorescent material from changes in external environmental factors, and the absorptive indicator being covalently linked to the supporting material.

[0026] A preferred hydrogen ion sensing material, wherein the pH indicator is thymol blue and the phosphorescent dye is a ruthenium complex, and the absorption spectrum of the pH indicator overlaps with the emission spectrum of the phosphorescent dye: the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 600 nm ± 100 nm and 575 nm ± 50 nm, respectively.

[0027] A preferred sodium ion sensing material, wherein the sodium ion indicator is a 12-crown-4 derivative, the phosphorescent dye is an iridium complex, and the absorption spectrum of the sodium ion indicator overlaps with the emission spectrum of the phosphorescent dye: the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 525nm±15nm and 525nm±50nm, respectively.

[0028] A preferred magnesium ion sensing material, wherein the magnesium ion indicator is acid chrome blue K, the phosphorescent dye is an iridium complex, the absorption spectrum of the magnesium ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 540nm±40nm and 525nm±50nm, respectively.

[0029] A preferred aluminum ion sensing material, wherein the aluminum ion indicator is xylenol orange and the phosphorescent dye is a ruthenium complex, the absorption spectrum of the aluminum ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 550nm±50nm and 575nm±50nm, respectively.

[0030] A preferred chloride ion sensing material, wherein the chloride ion indicator is mercuric thiocyanate, the phosphorescent dye is an iridium complex, the absorption spectrum of the chloride ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 460nm±30nm and 480nm±20nm, respectively.

[0031] A preferred potassium ion sensing material, wherein the potassium ion indicator is a 15-crown-5 derivative, the phosphorescent dye is an iridium complex, the absorption spectrum of the potassium ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 525nm±15nm and 525nm±50nm, respectively.

[0032] A preferred calcium ion sensing material, wherein the calcium ion indicator is azoarsine III and the phosphorescent dye is a platinum / palladium complex, the absorption spectrum of the calcium ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 630nm±30nm and 650nm±25nm, respectively.

[0033] A preferred cobalt ion sensing material, wherein the cobalt ion indicator is xylenol orange and the phosphorescent dye is a ruthenium complex, the absorption spectrum of the cobalt ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 550nm±50nm and 575nm±50nm, respectively.

[0034] A preferred copper ion sensing material, wherein the copper ion indicator is dicyclohexanone oxalyl dihydrazone, the phosphorescent dye is a europium complex, the absorption spectrum of the copper ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 600nm±100nm and 615nm±5nm, respectively.

[0035] A preferred zinc ion sensing material, wherein the zinc ion indicator is dithizone and the phosphorescent dye is an iridium complex, the absorption spectrum of the zinc ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectral range of the former and the maximum emission spectral range of the latter are 540nm±30nm and 525nm±50nm, respectively.

[0036] A preferred lead ion sensing material, wherein the lead ion indicator is tetra-(3,5-dibromo-4-hydroxybenzene)porphyrin, the phosphorescent dye is an iridium complex, the absorption spectrum of the lead ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 475nm±50nm and 480nm±20nm, respectively.

[0037] Secondly, the present invention also provides a method for preparing a non-contact phosphorescent ion sensing material, comprising the following steps:

[0038] S1. Selection of sensing materials: Select an absorption indicator that can respond to changes in ion concentration; select a phosphorescent dye whose emission spectrum overlaps with the absorption spectrum of the absorption indicator, has good photostability, and a phosphorescence lifetime greater than 200 ns; select an optically transparent and stable loading material.

[0039] S2. Adjustment of the detection range of the sensing material: By selecting absorbent indicators with different response performances and combining them with phosphorescent dyes, the detection range of ion concentration can be controlled; the detection range can be flexibly adjusted by selecting existing pH indicators and metal ion indicators with different responses.

[0040] S3. Construction of sensing materials: The absorbent indicator and phosphorescent dye are loaded onto a loading material. Preferably, the loading method can be to bind them onto a single nanoparticle, or to load them onto different nanoparticles through physical encapsulation or covalent modification.

[0041] Third, this invention also provides a method for applying non-contact phosphorescent ion sensing materials. This method utilizes a phosphorescence lifetime measurement / imaging system to detect / image ion concentration. The phosphorescence lifetime can be obtained through time-correlated single-photon counting (TCSPC) and phase change measurement or phosphorescence lifetime microscopy (PLIM), thereby obtaining the concentration data of the ion to be measured. Furthermore, this detection method is non-contact, i.e., it uses a phosphorescence lifetime measurement / imaging system to detect / image ion concentration. The phosphorescence signal is transmitted through optical fibers, etc., and the signal is collected by a detector or imaging system, enabling remote, online monitoring.

[0042] In summary, the present invention has the following beneficial effects:

[0043] (1) There are many types of absorption indicators, the detection range can be easily and selectively adjusted, the ion selectivity is good, it is not affected by photobleaching, the stability is good, and the preparation process is mature and the cost is low. The ion detection range can be flexibly adjusted by selecting existing pH indicators, metal ion indicators (absorption indicators) with different response performances, etc., without the need to design and synthesize new or complex dyes with ion response.

[0044] (2) Phosphorescent dyes do not need to have ion response. Most complexes of metal elements such as ruthenium, iridium, platinum, palladium, and europium meet the requirement of having a long phosphorescence lifetime.

[0045] (3) The combination method is simple and diverse. There are many kinds of ion indicators such as pH indicators and metal ion indicators that have ion concentration response. The preparation process is mature and the cost is low. Therefore, there are many combinations with phosphorescent dyes. It can be used not only for the detection of different ions, but also to adjust the sensitivity of ion response. The applicable ion types and concentration detection ranges are also diverse and variable. It is only necessary to meet the requirement that the absorption spectrum of the absorption ion indicator and the emission spectrum of the phosphorescent dye have obvious spectral overlap. This method is not only suitable for the detection of different ions, but also for the detection of ions of different concentrations.

[0046] (4) The sensing material has the advantages of high sensitivity, good selectivity and non-contact detection. It can be used for long-term detection and the results are reliable. The detection method is based on phosphorescence lifetime and converts the absorption signal into phosphorescence signal. It has good photostability and is not affected by factors such as light source, instrument, photobleaching, dye concentration, etc. It has good stability and is suitable for long-term detection.

[0047] In summary, this material possesses advantages such as simple construction, wide application range, good stability, suitability for long-term detection, and reliable results. It solves the problems of poor stability, low measurement accuracy, and large errors in existing fluorescent ion sensing materials, and overcomes the bottleneck of the scarcity of high-performance ion sensing materials. High-stability, non-contact phosphorescent ion sensing materials based on phosphorescence lifetime measurement are excellent analytical tools for ion detection. Currently, there are numerous commercially available ion indicators such as pH indicators and metal ion indicators, with mature and low-cost preparation technologies. Combining these with long-lifetime phosphorescent dyes to prepare high-stability, non-contact phosphorescent ion sensing materials based on phosphorescence lifetime measurement is of great significance. Attached Figure Description

[0048] Figure 1 Schematic diagram of phosphorescent pH sensing material based on silicon oxide.

[0049] Figure 2 Transmission electron microscope image of a phosphorescent pH sensing material based on silicon oxide.

[0050] Figure 3 Phosphorescence spectra of a silica-based phosphorescent pH sensing film at different pH values.

[0051] Figure 4 Photostability diagram of phosphorescent pH sensing film based on silica material

[0052] Figure 5 Phosphorescence lifetime calibration curves of a silica-based phosphorescence pH sensing film at different pH values.

[0053] Figure 6 FLIM imaging of a phosphorescent pH sensing film based on silica material.

[0054] Figure 7 UV-Vis absorption spectra and pH calibration curves of bromothymol blue under different pH conditions.

[0055] Figure 8 UV-Vis absorption spectra and pH calibration curves of thymol blue under different pH conditions.

[0056] Figure 9 UV-Vis absorption spectra and pH calibration curves of phenol red under different pH conditions Detailed Implementation

[0057] To further illustrate the purpose, specific solutions, and advantages of this invention, the embodiments of this invention are described in detail and completely below. The examples described below are not all embodiments of this patent, but only some embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0058] Preferred combinations of absorbent indicators and phosphorescent dyes in embodiments of the present invention are shown in Table 1:

[0059] Table 1 Combinations of Absorption Indicators and Phosphorescent Dyes The chemical formulas of phosphorescent dye metal complexes that can be used for the above purposes are shown in Table 1 below:

[0060]

[0061] Example 1

[0062] This embodiment uses ruthenium complexes with long phosphorescence lifetimes as phosphorescent dyes, thymol blue dyes as pH indicators and silica nanoparticles as loading materials to construct a phosphorescent pH sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0063] The ruthenium complex was dissolved in deionized water to prepare a 5 mM solution A;

[0064] 38 mL of cyclohexane, 9 mL of 1-hexanol, and 9 mL of Triton X-100 were stirred evenly with a magnetic rotor in a round-bottom flask. 1.9 mL of deionized water and 0.5 mL of solution A were then added to obtain mixture B.

[0065] Add 0.5 mL of 28% ammonia and 0.5 mL of ethyl silicate to mixture B to obtain mixture C, and stir at room temperature for 24 hours.

[0066] Acetone was added to mixture C to break the emulsion, and the mixture was transferred to a 50 mL centrifuge tube. The tube was then washed with 95% ethanol by centrifugation, and the nanoparticles were redispersed in 95% ethanol to obtain 10 mg / mL. -1 The mixture D.

[0067] A pH indicator—thymol blue dye—is covalently attached to the nanomaterials in mixture D to form mixture E.

[0068] 5.0 g of polyurethane material was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution F.

[0069] Mixture E and solution F are dropped onto a clean polyester film in a 1 / 4 ratio (adjustable), and dried to obtain a highly stable, non-contact phosphorescence sensing material G based on phosphorescence lifetime measurement.

[0070] Sensing material G was placed in a cuvette, and buffer solutions of different pH values ​​were added. The phosphorescence lifetime was tested using a steady-state and transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0071] The pH-responsive nanosensor in mixture E can be used for non-contact measurements at the cell scale. The specific procedure is as follows: After centrifugation, the nanoparticles in mixture E are washed at least twice with cell culture medium, then dispersed in sterile culture medium. The cells are then co-cultured in this medium, and the nanosensor can enter the cell via endocytosis. The cell culture dish incubating the nanosensor is placed on a microscope stage. The excitation light from a fluorescence microscope can directly illuminate the nanosensor within the cell. The fluorescence emitted by the nanosensor passes through a lens and enters a phosphorescence lifetime measurement system, thus achieving non-contact intracellular pH measurement.

[0072] As attached Figure 1 As shown, the hydrogen ion sensing material uses silica as a carrier, with a phosphorescent dye—Ru complex—loaded inside the nanoparticles, and an absorption-type pH indicator—thymol blue probe—loaded on the surface of the nanoparticles, thus forming nanoparticles with a core-shell structure (see attached diagram). Figure 2 This structure has significant advantages: 1. The close proximity of the phosphorescent dye and the absorption indicator allows for energy transfer, thus converting the absorption signal into a phosphorescent signal; 2. The pH indicator is located on the surface of the nanoparticles, facilitating sufficient contact with the analyte ion—hydrogen ions—reducing response time and improving detection accuracy.

[0073] The performance of the constructed hydrogen ion sensing material was tested. The results showed that: 1. The sensing material successfully converted the absorption signal into a phosphorescence signal and exhibited a significant pH response, with a detection range of 3-9 (see appendix). Figure 3 2. The sensing material exhibits good photostability; after 1 hour of continuous illumination, the phosphorescence signal decreases by 11% (see attached image). Figure 4 3. The sensing material has a phosphorescence lifetime in the microsecond range, and the phosphorescence lifetime detection signal has a good pH response (see appendix). Figure 54. Using phosphorescence lifetime as the detection signal is beneficial because it is unaffected by factors such as dye concentration and light source. Compared with fluorescence intensity as the detection signal, ion sensing materials exhibit better photostability and are suitable for long-term stable detection and imaging. (Appendix) Figure 6 ).

[0074] The constructed hydrogen ion sensing material has a flexible and adjustable pH detection range. Firstly, thymol blue-based pH indicators come in different types, each with a different color change range and suitable pH range for detection; for example, bromothymol blue (UV-Vis absorption spectrum as shown in the attached image). Figure 7 The pH range of color change for thymol blue (pKa 8.1) is smaller than that for thymol blue (UV-Vis absorption spectrum as shown in the attached image). Figure 8 Both have a pKa of 9.2, but their absorption spectra overlap well with those of the Ru complex, enabling energy transfer; therefore, hydrogen ion sensing materials with different pH detection ranges can be constructed. Secondly, there are many types of pH indicators, and thymol blue dyes can be replaced with other types of indicators; for example, phenol red, whose color-changing pH range is smaller than that of thymol blue (UV-Vis absorption spectra are attached). Figure 9 (pKa is 7.8), and the absorption spectrum has good overlap with the Ru complex, which can be used to construct hydrogen ion sensing materials with different pH detection ranges; finally, by constructing combinations of other pH indicators and phosphorescent dyes, such as methyl red and iridium complexes, hydrogen ion sensing materials applicable to the entire pH range can be constructed.

[0075] Example 2

[0076] This embodiment uses an iridium complex with a long phosphorescence lifetime as the phosphorescent dye, a sodium ion indicator—a 12-crown-4 derivative—as the absorption indicator, and polyurethane material as the loading material to construct a phosphorescent copper ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0077] A new polymer material A is formed by covalently attaching a sodium ion indicator—a 12-crown-4 derivative—to a polyurethane material.

[0078] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0079] An ethanol solution (100 μM) C of an iridium complex was prepared. Solutions B and C were mixed in a 4 / 1 ratio (adjustable) and dropped onto a clean polyester film. After drying, a highly stable, non-contact phosphorescence sensing material D based on phosphorescence lifetime measurement was obtained.

[0080] Sensing material D was placed in a cuvette, and buffer solutions with different sodium ion concentrations were added. The phosphorescence lifetime was tested using a steady-state and transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0081] The back of the phosphorescent sensing material D can be attached to the transparent light window of the cell culture bag or the transparent glass light window of the bioreactor using double-sided adhesive. After the cell culture bag or bioreactor is sterilized and sealed, the excitation light emitted by the measuring device can be guided through an optical fiber to the outer wall of the transparent light window of the cell culture bag or bioreactor, exciting the phosphorescent material D to emit light. The emitted light then returns to the detection device through the same optical fiber, thereby realizing non-contact detection of sodium ions in the sealed cell culture bag or bioreactor.

[0082] Example 3

[0083] This embodiment uses an iridium complex with a long phosphorescence lifetime as the phosphorescent dye, Acid Chrome Blue K as the magnesium ion indicator, and polyurethane material as the loading material to construct a phosphorescent zinc ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0084] A new polyurethane material A is formed by covalently bonding a magnesium ion indicator, Acid Chrome Blue K, to a polyurethane material.

[0085] 5.0 g of polyurethane was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0086] An ethanol solution (100 μM) C of an iridium complex was prepared. Solutions B and C were mixed in a 4 / 1 ratio (adjustable) and dropped onto a clean polyester film. After drying, a highly stable, non-contact phosphorescence sensing material D based on phosphorescence lifetime measurement was obtained.

[0087] Sensing material D was placed in a petri dish, and alkaline buffer solutions (pH 10) with different magnesium ion concentrations were added. The phosphorescence lifetime was tested using a steady-state transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0088] Example 4

[0089] This embodiment uses a ruthenium complex with a long phosphorescence lifetime as the phosphorescent dye, xylenol orange (an aluminum ion indicator) as the absorption indicator, and polyurethane material as the loading material to construct a phosphorescent aluminum ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0090] A new polymer material A is formed by covalently bonding the aluminum ion indicator, xylenol orange, to a polyurethane material.

[0091] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0092] Prepare an aqueous solution (100 μM) C of ruthenium complex. Mix solutions B and C in a 4 / 1 ratio (adjustable) and drop the mixture onto a clean polyester film. After drying, obtain a highly stable, non-contact phosphorescent sensing material D based on phosphorescence lifetime measurement.

[0093] Sensing material D was placed in a cuvette, and acidic buffer solutions (pH 3.0) with different aluminum ion concentrations were added. The phosphorescence lifetime was tested using a steady-state and transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0094] Example 5

[0095] This embodiment uses iridium complex II with a long phosphorescence lifetime as the phosphorescent dye, mercuric thiocyanate as the chloride ion indicator, and polyurethane as the loading material to construct a phosphorescent chloride ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0096] A new polymer material A is formed by covalently bonding a chloride ion indicator—mercuric thiocyanate—to a polyurethane material.

[0097] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0098] Prepare an ethanol solution (100 μM) B of the iridium complex. Mix solution B and solution C in a 4 / 1 ratio (adjustable) and drop the mixture onto a clean polyester film. After drying, obtain a highly stable, non-contact phosphorescent sensing material D based on phosphorescence lifetime measurement.

[0099] Sensing material D was placed in a petri dish, and buffer solutions with different chloride ion concentrations were added. The phosphorescence lifetime was tested using a steady-state and transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0100] Example 6

[0101] This embodiment uses an iridium complex with a long phosphorescence lifetime as the phosphorescent dye, a potassium ion indicator—a 15-crown-5 derivative—as the absorption indicator, and polyurethane material as the loading material to construct a phosphorescent copper ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0102] A new polymer material A is formed by covalently attaching a potassium ion indicator—a 15-crown-5 derivative—to a polyurethane material.

[0103] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0104] An ethanol solution (100 μM) C of an iridium complex was prepared. Solutions B and C were mixed in a 4 / 1 ratio (adjustable) and dropped onto a clean polyester film. After drying, a highly stable, non-contact phosphorescence sensing material D based on phosphorescence lifetime measurement was obtained.

[0105] Sensing material D was placed in a cuvette, and buffer solutions with different potassium ion concentrations were added. The phosphorescence lifetime was tested using a steady-state and transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0106] Example 7

[0107] This embodiment uses a platinum / palladium complex with a long phosphorescence lifetime as the phosphorescent dye, azoarsine III as the calcium ion indicator, and polyurethane as the loading material to construct a phosphorescent calcium ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0108] A new polymer material A is formed by covalently bonding a calcium ion indicator, azoarsine III, to a polyurethane material.

[0109] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0110] Prepare an ethanol solution (100 μM) C of platinum / palladium complex. Mix solutions B and C in a 4 / 1 ratio (adjustable) and drop the mixture onto a clean polyester film. After drying, obtain a highly stable, non-contact phosphorescent sensing material D based on phosphorescence lifetime measurement.

[0111] Sensing material D was placed in a cuvette, and neutral or slightly alkaline buffer solutions (pH 7.0) with different calcium ion concentrations were added. The phosphorescence lifetime was tested using a steady-state transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0112] Example 8

[0113] This embodiment uses a ruthenium complex with a long phosphorescence lifetime as the phosphorescent dye, xylenol orange as the cobalt ion indicator, and polyurethane as the loading material to construct a phosphorescent cobalt ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0114] A new polymer material A is formed by covalently bonding a cobalt ion indicator, xylenol orange, to a polyurethane material.

[0115] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0116] Prepare an aqueous solution (100 μM) C of ruthenium complex. Mix solutions B and C in a 4 / 1 ratio (adjustable) and drop the mixture onto a clean polyester film. After drying, obtain a highly stable, non-contact phosphorescent sensing material D based on phosphorescence lifetime measurement.

[0117] Sensing material D was placed in a cuvette, and acidic buffer solutions (pH 5.5) with different cobalt ion concentrations were added. The phosphorescence lifetime was tested using a steady-state transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0118] Example 9

[0119] This embodiment uses europium complexes with long phosphorescence lifetimes as phosphorescent dyes, dicyclohexanone oxalyl dihydrazone as an absorption indicator, and polyurethane material as a loading material to construct a phosphorescent copper ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0120] A new polymer material A is formed by covalently linking the copper ion indicator, dicyclohexanone oxaloyl dihydrazone, to a polyurethane material.

[0121] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0122] A 100 μM dimethyl sulfoxide solution C containing europium complex was prepared. Solutions B and C were mixed in a 4 / 1 ratio (adjustable) and dropped onto a clean polyester film. After drying, a highly stable, non-contact phosphorescence sensing material D based on phosphorescence lifetime measurement was obtained.

[0123] Sensing material D was placed in a cuvette, and alkaline buffer solutions (pH 8.5-9.5) with different copper ion concentrations were added. The phosphorescence lifetime was tested using a steady-state transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0124] Example 10

[0125] This embodiment uses an iridium complex with a long phosphorescence lifetime as the phosphorescent dye, dithizone as the zinc ion indicator, and cellulose material as the loading material to construct a phosphorescent zinc ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0126] A new cellulose material A is formed by covalently attaching the zinc ion indicator, dithizone, to the cellulose material.

[0127] 5.0 g of cellulose was placed in a 100 mL reaction flask, and 95 g of a mixed solution of toluene and ethanol in a volume ratio of 3 / 2 was added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% cellulose solution B.

[0128] An ethanol solution (100 μM) C of an iridium complex was prepared. Solutions B and C were mixed in a 4 / 1 ratio (adjustable) and dropped onto a clean polyester film. After drying, a highly stable, non-contact phosphorescence sensing material D based on phosphorescence lifetime measurement was obtained.

[0129] Sensing material D was placed in a petri dish, and acidic buffer solutions (pH 4.0-5.5) with different zinc ion concentrations were added. The phosphorescence lifetime was tested using a steady-state transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0130] Example 11

[0131] This embodiment uses iridium complex II with a long phosphorescence lifetime as the phosphorescent dye, tetra-(3,5-dibromo-4-hydroxybenzene)porphyrin as the lead ion indicator and polyurethane material as the loading material to construct a phosphorescent lead ion sensor, further illustrating this highly stable, non-contact phosphorescent ion sensing material based on phosphorescence lifetime measurement. The specific implementation method is as follows:

[0132] A new polymer material A is formed by covalently linking the lead ion indicator tetra-(3,5-dibromo-4-hydroxybenzene)porphyrin to a polyurethane material.

[0133] 5.0 g of polymer material A was placed in a 100 mL reaction flask, and 90 mL of anhydrous ethanol and 10 mL of deionized water were added. The mixture was magnetically stirred at room temperature until completely dissolved to obtain a 5% polyurethane material solution B.

[0134] An ethanol solution (100 μM) C of an iridium complex was prepared. Solutions B and C were mixed in a 4 / 1 ratio (adjustable) and dropped onto a clean polyester film. After drying, a highly stable, non-contact phosphorescence sensing material D based on phosphorescence lifetime measurement was obtained.

[0135] Sensing material D was placed in a petri dish, and alkaline buffer solutions with different lead ion concentrations were added. The phosphorescence lifetime was tested using a steady-state and transient phosphorescence spectrometer, and phosphorescence lifetime images were obtained using a phosphorescence lifetime microscopic imaging system under a wide-field microscope.

[0136] In summary, this invention is applicable to the detection of various types of ions. It only requires combining the indicator of the ion to be detected with a phosphorescent dye, ensuring that the absorption spectrum of the former overlaps with the phosphorescence spectrum of the latter. This invention is also applicable to the detection of ions at different concentrations; simply adjusting the response range of the indicator or replacing it with a different indicator is sufficient, again requiring that the absorption spectrum of the indicator overlaps with the emission spectrum of the phosphorescent dye. Therefore, this invention has the advantages of being applicable to the detection of different types and concentrations of ions, and offering flexible and adjustable combination methods.

[0137] As a comparative example, in the prior art, Qiu et al. designed and synthesized a pH probe based on Ir complexes (Qiu, K., Huang, H., Liu, B., Liu, Y., Huang, Z., Chen, Y., Ji, L., Chao, H. (2016). Long-Term Lysosomes Tracking with a Water-Soluble Two-Photon Phosphorescent Iridium(III) Complex. ACS Appl Mater Interfaces, 8(20), 12702-10.). By selecting and modifying the ligands, the Ir complexes were made to have a pH response. This probe has good photostability under two-photon excitation; however, the pH detection range of this probe is limited (only 6-8), the photostability under single-photon excitation is poor, and the detection sensitivity is lower than that of the pH sensor in Example 1: as attached Figure 3As shown, the fluorescence intensity at pH 9 is one-third that at pH 3; the fluorescence intensity of the Ir complex at pH 8 is slightly greater than half that at pH 6. Therefore, compared with the comparative examples of existing technologies, the sensing material obtained by the technical solution provided by this invention exhibits a significant improvement in application performance.

[0138] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit it. Although the present patent has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention are included within the protection scope of the present invention.

Claims

1. A non-contact phosphorescent ionic sensing material, characterized by, The material includes an absorption indicator and a phosphorescent dye, as well as a loading material for loading the absorption indicator and the phosphorescent dye; the absorption spectrum of the absorption indicator and the emission spectrum of the phosphorescent dye overlap, thereby converting the absorption spectrum change signal of the absorption indicator into the phosphorescence lifetime change signal of the phosphorescent dye. in: The absorption indicator is an ion-responsive indicator, and the responsive ions include hydrogen ions, sodium ions, magnesium ions, aluminum ions, chloride ions, potassium ions, calcium ions, cobalt ions, copper ions, zinc ions, or lead ions. The phosphorescent dyes include metal element complexes of ruthenium, iridium, platinum, palladium, or europium; the phosphorescence lifetime of the phosphorescent dyes is greater than 200 ns. The absorbent indicator and phosphorescent dye are loaded onto a single nanoparticle; the loading method is that the phosphorescent dye is encapsulated inside the loading material to protect the luminescence properties of the phosphorescent material from changes in external environmental factors, and the absorbent indicator is covalently linked to the loading material; the absorbent indicator and phosphorescent dye are spatially close, thereby enabling energy transfer between the phosphorescent dye and the absorbent indicator.

2. A non-contact phosphorescent ionic sensing material as claimed in claim 1, wherein, The absorption-type indicators selectively respond to changes in ion concentration, including: the hydrogen ion indicator is thymol blue; the sodium ion indicator is a 12-crown-4 derivative indicator; the magnesium ion indicator is acid chrome blue K indicator; the aluminum ion indicator is xylenol orange indicator; the chloride ion indicator is mercuric thiocyanate indicator; the potassium ion indicator is a 15-crown-5 derivative indicator; the calcium ion indicator is azoarsine III indicator; the cobalt ion indicator is xylenol orange indicator; the copper ion indicator is dicyclohexanone oxalyl dihydrazone indicator; the zinc ion indicator is dithizone indicator; and the lead ion indicator is tetra-(3,5-dibromo-4-hydroxybenzene)porphyrin indicator.

3. A non-contact phosphorescent ionic sensing material as claimed in claim 1, wherein, The ruthenium metal element complexes mentioned above include one or more of the following combinations: 。 4. A non-contact phosphorescent ionic sensing material as claimed in claim 1, wherein, The platinum / palladium metal element complexes include one or more of the following combinations: 。 5. A non-contact phosphorescent ionic sensing material as claimed in claim 1, wherein, The europium metal element complexes include one or more of the following combinations: 。 6. The non-contact phosphorescent ion sensing material as described in claim 1, characterized in that, The aforementioned iridium metallic element complexes include one or more of the following combinations: 。 7. The non-contact phosphorescent ion sensing material as described in claim 1, characterized in that, The loading materials include polyurethane, cellulose, and silica nanoparticles.

8. The non-contact phosphorescent ionization sensing material as described in claim 1, characterized in that: The ion sensing material is a hydrogen ion sensing material, wherein the pH indicator is thymol blue and the phosphorescent dye is a ruthenium metal element complex. The absorption spectrum of the pH indicator overlaps with the emission spectrum of the phosphorescent dye: the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 600 nm ± 100 nm and 575 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be a sodium ion sensing material, wherein the sodium ion indicator is a 12-crown-4 derivative, the phosphorescent dye is an iridium metal element complex, and the absorption spectrum of the sodium ion indicator overlaps with the emission spectrum of the phosphorescent dye: the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 525 nm ± 15 nm and 525 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be a magnesium ion sensing material, wherein the magnesium ion indicator is acid chrome blue K, the phosphorescent dye is an iridium metal element complex, the absorption spectrum of the magnesium ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 540 nm ± 40 nm and 525 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be an aluminum ion sensing material, wherein the aluminum ion indicator is xylenol orange, the phosphorescent dye is a ruthenium metal element complex, the absorption spectrum of the aluminum ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 550 nm ± 50 nm and 575 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be a chloride ion sensing material, wherein the chloride ion indicator is mercuric thiocyanate, the phosphorescent dye is an iridium metal element complex, the absorption spectrum of the chloride ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 460 nm±30 nm and 480 nm±20 nm, respectively. Alternatively, the ion sensing material may be a potassium ion sensing material, wherein the potassium ion indicator is a 15-crown-5 derivative, the phosphorescent dye is an iridium metal element complex, the absorption spectrum of the potassium ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 525 nm ± 15 nm and 525 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be a calcium ion sensing material, wherein the calcium ion indicator is azoarsine III, the phosphorescent dye is a platinum / palladium metal element complex, the absorption spectrum of the calcium ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 630 nm±30 nm and 650 nm±25 nm, respectively. Alternatively, the ion sensing material may be a cobalt ion sensing material, wherein the cobalt ion indicator is xylenol orange, the phosphorescent dye is a ruthenium metal element complex, the absorption spectrum of the cobalt ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 550 nm ± 50 nm and 575 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be a copper ion sensing material, wherein the copper ion indicator is dicyclohexanone oxalyl dihydrazone, and the phosphorescent dye is a europium metal element complex. The absorption spectrum of the copper ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 600 nm ± 100 nm and 615 nm ± 5 nm, respectively. Alternatively, the ion sensing material may be a zinc ion sensing material, wherein the zinc ion indicator is dithizone, the phosphorescent dye is an iridium metal element complex, the absorption spectrum of the zinc ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 540 nm ± 30 nm and 525 nm ± 50 nm, respectively. Alternatively, the ion sensing material may be a lead ion sensing material, wherein the lead ion indicator is tetra-(3,5-dibromo-4-hydroxybenzene)porphyrin, and the phosphorescent dye is an iridium metal element complex. The absorption spectrum of the lead ion indicator overlaps with the emission spectrum of the phosphorescent dye, and the maximum absorption spectrum range of the former and the maximum emission spectrum range of the latter are 475 nm ± 50 nm and 480 nm ± 20 nm, respectively.

9. A method for preparing a non-contact phosphorescent ionizing sensing material as described in any one of claims 1-8, characterized in that, Includes the following steps: S1. Selection of sensing materials: Select an absorption indicator that can respond to changes in ion concentration; select a phosphorescent dye whose emission spectrum overlaps with the absorption spectrum of the absorption indicator. S2. Adjustment of the detection range of the sensing material: By selecting absorbent indicators with different response performances and combining them with phosphorescent dyes, the detection range of ion concentration can be adjusted; the detection range can also be adjusted by selecting existing pH indicators and metal ion indicators with different responses. S3. Construction of sensing materials: Loading the absorbent indicator with the phosphorescent dye using a loading material.

10. A method for applying the non-contact phosphorescent ionization sensing material as described in any one of claims 1-8, characterized in that, Ion concentration can be detected / imaged using a phosphorescence lifetime measurement / imaging system. Phosphorescence lifetime can be measured by time-correlated single-photon counting (TCSPC) and phase change measurement or phosphorescence lifetime microscopic imaging (PLIM), thereby obtaining the concentration data of the ion to be measured.

11. The application method of the non-contact phosphorescent ion sensing material as described in claim 10, characterized in that, This detection method is non-contact, that is, it uses a phosphorescence lifetime measurement / imaging system to detect / image ion concentration. The phosphorescence signal is transmitted through optical fiber and collected by a detector or imaging system, which can be monitored remotely and online.

Images