A fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers, a preparation method and applications thereof

Abstract

This invention provides a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer, its preparation method, and its application, belonging to the field of probe preparation technology. The method involves first mixing an aqueous solution of glutathione and an aqueous solution of tetrachlorohydrin to obtain a gold nanocluster solution; then adding adenine and water to a 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid buffer solution and stirring until homogeneous, followed by the addition of a zinc chloride solution to obtain a zinc-based coordination polymer; finally, the gold nanocluster solution and the zinc-based coordination polymer solution are mixed homogeneously to obtain the fluorescence-enhanced composite probe based on gold nanoclusters anchored on the zinc-based coordination polymer. The probe of this invention can rapidly and sensitively recognize adenosine triphosphate (ATP). It can also be used to construct fluorescent hydrogels by mixing this material with κ-carrageenan; the hydrogels exhibit a sensitive response to ATP and good self-healing ability.

Description

Technical Field

[0001] This invention belongs to the field of probe preparation technology, specifically relating to a fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers, its preparation method, and its application. Background Technology

[0002] Adenosine triphosphate (ATP), as the main energy source in organisms, plays a crucial role in cell metabolism, proliferation, energy replenishment, and immunity. As an extracellular messenger, abnormal ATP concentrations are associated with many diseases, such as cardiovascular disease, hypoglycemia, Parkinson's disease, and malignant tumors. Therefore, accurately monitoring changes in ATP concentrations in bodily fluids is of paramount importance for monitoring and understanding the pathogenesis of related diseases.

[0003] To date, researchers have devoted considerable effort to developing numerous effective and reliable methods for detecting adenosine triphosphate (ATP), such as nuclear magnetic resonance spectroscopy, capillary electrophoresis, high-performance liquid chromatography (HPLC), colorimetry, electrochemistry, and aptamer-based optical sensing methods. Most detection strategies rely on the use of aptamers or biological enzymes, which require cumbersome procedures and stringent reaction conditions. Furthermore, these methods demand costly equipment and time-consuming analysis, making on-site nursing diagnosis a significant challenge. Therefore, developing novel, reliable, and sensitive ATP sensors is of paramount importance and significance.

[0004] In recent years, fluorescence methods have been widely used in the analysis and determination of disease biomarkers due to their advantages such as high sensitivity, good selectivity, simple operation, and low cost. Compared with inorganic quantum dots (QDs) and organic dyes, metal nanoclusters (MNCs) have attracted much attention from researchers due to their low toxicity, good biocompatibility, and large Stokes shift. However, most prepared gold nanoclusters (AuNCs) suffer from weak fluorescence intensity and low quantum yield, which limits their practical applications. Therefore, developing an AuNCs-based composite material with high fluorescence performance is an urgent problem to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer, its preparation method, and its application. This composite material, as an adenosine triphosphate (ATP) sensing probe, can rapidly and sensitively identify ATP. It can also be used to construct fluorescent hydrogels by mixing the material with κ-carrageenan. The hydrogels exhibit a sensitive response to ATP and good self-healing ability.

[0006] This invention first provides a method for preparing a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer, comprising the following steps:

[0007] Step 1: Under oil bath conditions, mix glutathione aqueous solution and tetrachlorohydrin aqueous solution to obtain gold nanocluster solution;

[0008] Step 2: Add adenine and water to a 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES) buffer solution, stir until homogeneous, then add zinc chloride solution, stir the resulting mixture in a beaker, collect the precipitate, wash and dry to obtain zinc-based coordination polymer;

[0009] Step 3: Mix the gold nanocluster solution prepared in Step 1 and the zinc-based coordination polymer solution prepared in Step 2 evenly to obtain a fluorescence-enhanced composite probe based on gold nanoclusters anchored on the zinc-based coordination polymer.

[0010] Preferably, in step one, the molar ratio of glutathione to tetrachlorohydrin is 3:2.

[0011] Preferably, in step one, the heating temperature of the oil bath is 60-80℃, and the heating time is 20-28h.

[0012] Preferably, in step two, the molar ratio of adenine to zinc chloride is 1:1.5.

[0013] Preferably, in step two, the reaction temperature is room temperature and the reaction time is 1.5-2.5 hours.

[0014] Preferably, in step three, the volume ratio of the gold nanocluster solution to the zinc-based coordination polymer solution is 1:(0.25-7.5).

[0015] Preferably, the mixing time in step three is 1-35 minutes.

[0016] The present invention also provides a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer obtained by the above preparation method.

[0017] The present invention also provides the application of the above-mentioned fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers in the fluorescence detection of adenosine triphosphate.

[0018] The present invention also provides the application of the above-mentioned fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers in hydrogel construction.

[0019] Beneficial effects of the present invention

[0020] (1) It can significantly improve the fluorescence properties (fluorescence intensity and quantum yield) of gold nanoclusters.

[0021] The fluorescent probe of the present invention can effectively improve the fluorescence intensity and quantum yield of gold nanoclusters by anchoring gold nanoclusters on zinc-based coordination polymers and suppressing their non-radiative motion based on the aggregation-induced emission enhancement effect of coordination polymers on gold nanoclusters.

[0022] (2) It can sensitively and accurately detect the concentration of adenosine triphosphate.

[0023] The fluorescent probe of the present invention can utilize the strong interaction between adenosine triphosphate and zinc-based coordination polymers to suppress the aggregation-induced enhanced emission effect of gold nanoclusters by coordination polymers, thereby significantly reducing fluorescence intensity.

[0024] (3) Simple preparation, rapid response, and high sensitivity

[0025] The fluorescent probe of the present invention has the advantages of simple preparation, mild conditions, rapid response and high sensitivity, and can accurately detect changes in adenosine triphosphate concentration.

[0026] (4) It can be used for the construction of fluorescent hydrogels.

[0027] The fluorescently enhanced composite material of the present invention, by combining it with κ-carrageenan, prepared a fluorescent hydrogel that is sensitive to adenosine triphosphate (ATP). This hydrogel exhibits a sensitive response to ATP and good self-healing ability. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 The fluorescence emission spectra of the fluorescence-enhanced composite probes based on gold nanoclusters anchored on zinc-based coordination polymers prepared in Comparative Example 1 and Examples 1-8 are optimized for concentration.

[0030] Figure 2 The fluorescence emission spectra of the fluorescence-enhanced composite probes based on gold nanoclusters anchored on zinc-based coordination polymers prepared in Examples 9-16 are time-optimized.

[0031] Figure 3 The fluorescence emission spectra of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer and individual AuNCs prepared in Example 14 are shown.

[0032] Figure 4This is a hydration kinetics diameter diagram of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14;

[0033] Figure 5 This is the N2 adsorption-desorption isotherm of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14;

[0034] Figure 6 The fluorescence spectrum of the salt stability of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14 is shown.

[0035] Figure 7 This is the fluorescence spectrum of the UV radiation stability of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14.

[0036] Figure 8 The fluorescence spectrum of the pH stability of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14 is shown.

[0037] Figure 9 This is the fluorescence spectrum of the storage stability of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14;

[0038] Figure 10 This is a radar diagram of the response of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer prepared in Example 14 to adenosine triphosphate.

[0039] Figure 11 The fluorescence spectra of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer prepared in Example 14 and different concentrations of adenosine triphosphate are shown.

[0040] Figure 12 The images show actual images of fluorescent hydrogels with different contents prepared in Example 14, which are based on a fluorescence-enhanced composite probe anchored to a zinc-based coordination polymer with gold nanoclusters and combined with κ-carrageenan.

[0041] Figure 13 This is a sensitivity response diagram of adenosine triphosphate to a fluorescent hydrogel prepared by combining a gold nanocluster anchored on a zinc-based coordination polymer with κ-carrageenan, as described in Example 14.

[0042] Figure 14 This is a diagram illustrating the excellent self-healing ability of the fluorescent hydrogel prepared in Example 14, which is based on a fluorescently enhanced composite probe anchored to a zinc-based coordination polymer with gold nanoclusters and combined with κ-carrageenan. Detailed Implementation

[0043] This invention first provides a method for preparing a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer, comprising the following steps:

[0044] Step 1: Dissolve glutathione and tetrachloroalloy acid in water respectively. Mix the glutathione aqueous solution and the tetrachloroalloy acid aqueous solution under oil bath conditions of 60-80℃ and stir continuously for a preferred stirring time of 20-28h, more preferably 24h, to obtain a gold nanocluster solution; the molar ratio of glutathione to tetrachloroalloy acid is preferably 3:2.

[0045] Step 2: Add adenine and water to a 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES) buffer solution and stir until homogeneous, preferably for 5 minutes. Then add zinc chloride solution and stir the resulting mixture in a beaker for 1.5-2.5 hours, more preferably 2 hours. Collect the precipitate, wash three times with HEPES buffer solution, and dry at 50°C for 8-12 hours to obtain a zinc-based coordination polymer; the molar ratio of adenine to zinc chloride is preferably 1:1.5.

[0046] Step 3: Mix the gold nanocluster solution prepared in Step 1 and the zinc-based coordination polymer solution prepared in Step 2 evenly. The mixing time is preferably 1-35 min, more preferably 10 min, to obtain a fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer. The volume ratio of gold nanocluster solution to zinc-based coordination polymer solution is preferably 1:(0.25-7.5).

[0047] The present invention also provides a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer obtained by the above preparation method.

[0048] This invention also provides the application of the above-mentioned fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers in the fluorescence detection of adenosine triphosphate (ATP). It includes the following steps:

[0049] In a centrifuge tube, add 200 μL of Tris-HCl buffer (pH=7) and 600 μL of adenosine triphosphate at different concentrations. Then, add 200 μL of the above-mentioned fluorescence-enhanced composite probe, dilute the mixture to 2.5 mL with ultrapure water, shake vigorously for 5 min, and then measure the fluorescence.

[0050] This invention also provides the application of the above-mentioned fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers in hydrogel construction. It includes the following steps:

[0051] Add 1 mL of fluorescence-enhanced composite probe to 2 mL of κ-carrageenan solution, heat the mixture to 80 °C and stir continuously for 30 min. Then transfer the hydrogel mixture to the corresponding mold and cool to room temperature to obtain a hydrogel with orange fluorescence.

[0052] The present invention will be further described in detail below with reference to specific embodiments. All raw materials involved in the embodiments were commercially available.

[0053] Example 1

[0054] A method for preparing a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer

[0055] Step 1: Preparation of gold nanoclusters

[0056] Glutathione and tetrachloroalkanic acid were dissolved in water, and the aqueous solutions of glutathione (100 mM, 150 μL) and tetrachloroalkanic acid (20 mM, 500 μL) were mixed and stirred continuously at 70 °C for 24 h to obtain a gold nanocluster solution.

[0057] Step 2: Preparation of Zinc-Based Coordination Polymers

[0058] Adenine (30 mM, 500 μL) and water (900 μL) were added to a 3 mL buffer solution of 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES) and stirred for 5 min. Zinc chloride solution (45 mM, 500 μL) was then added, and the resulting mixture was stirred in a beaker at room temperature for 2 h. The precipitate was collected, washed three times with HEPES buffer solution, and dried at 50 °C for 10 h to obtain the zinc-based coordination polymer.

[0059] Step 3: Preparation of fluorescence-enhanced composite probes based on gold nanoclusters anchored on zinc-based coordination polymers

[0060] 200 μL of the gold nanocluster solution prepared in step one and 50 μL of the zinc-based coordination polymer solution prepared in step two were mixed (1:0.25). The mixture was stirred at room temperature for 10 min to obtain a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer.

[0061] Comparative Example 1

[0062] The preparation and conditions were the same as in Example 1, except that in step three, the volume ratio of the gold nanocluster solution to the zinc-based coordination polymer solution was 1:0.

[0063] Examples 2-8

[0064] The preparation and conditions were the same as in Example 1, except that in step three, the gold nanocluster solution and zinc-based coordination polymer solution were mixed at volume ratios of 1:1, 1:2, 1:3, 1:4, 1:5, 1:6.25, and 1:7.5, respectively, and the changes at different concentrations were investigated. Figure 1 As shown, Figure 1 This indicates that the composite probe prepared with a volume ratio of gold nanocluster solution to zinc-based coordination polymer solution of 1:3 exhibits the strongest fluorescence.

[0065] Example 9

[0066] Step 1: Preparation of gold nanoclusters

[0067] Glutathione and tetrachloroalkanic acid were dissolved in water, and the aqueous solutions of glutathione (100 mM, 150 μL) and tetrachloroalkanic acid (20 mM, 500 μL) were mixed and stirred continuously at 70 °C for 24 h to obtain a gold nanocluster solution.

[0068] Step 2: Preparation of Zinc-Based Coordination Polymers

[0069] Adenine (30 mM, 500 μL) and water (900 μL) were added to a 3 mL buffer solution of 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES) and stirred for 5 min. Zinc chloride solution (45 mM, 500 μL) was then added, and the resulting mixture was stirred in a beaker at room temperature for 2 h. The precipitate was collected, washed three times with HEPES buffer solution, and dried at 50 °C for 10 h to obtain the zinc-based coordination polymer.

[0070] Step 3: Preparation of fluorescence-enhanced composite probes based on gold nanoclusters anchored on zinc-based coordination polymers

[0071] 200 μL of the gold nanocluster solution prepared in step one and 600 μL of the zinc-based coordination polymer solution prepared in step two were mixed (1:3). The mixture was stirred at room temperature for 1 min to obtain a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer.

[0072] Examples 10-16

[0073] The preparation and conditions were the same as in Example 9, except that in step three, the mixture was stirred at room temperature for 2 min, 4 min, 6 min, 8 min, 10 min, 18 min, and 35 min, respectively, and the changes at different times were examined. Figure 2 As shown, Figure 2 This indicates that the composite probe prepared by reacting the gold nanocluster solution with the zinc-based coordination polymer for 10 min exhibits the strongest fluorescence.

[0074] The performance of the fluorescence-enhanced composite probe obtained in Example 14 above was tested:

[0075] 1) A fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer and fluorescence spectroscopy of individual gold nanoclusters. For example... Figure 3 As shown, Figure 3 This indicates that compared to standalone gold nanoclusters, anchoring them on zinc-based coordination polymers significantly enhances fluorescence intensity.

[0076] 2) A fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer for measuring the hydration kinetics diameter. For example... Figure 4 As shown, Figure 4 This indicates that the average particle size of the fluorescence-enhanced composite probe is 261.9 nm.

[0077] 3) An N2 adsorption-desorption isotherm test based on a fluorescence-enhanced composite probe of gold nanoclusters anchored on a zinc-based coordination polymer. For example... Figure 5 As shown, Figure 5 This indicates that the fluorescence-enhanced composite probe exhibits a type IV isotherm.

[0078] 4) Salt stability testing of a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer.

[0079] Add 500 μL of NaCl solution of different concentrations (0-150 mM) to 2000 μL of fluorescence-enhanced composite probe solution, shake for 10 min, and then test the corresponding fluorescence spectra. Figure 6 As shown, Figure 6 This indicates that the fluorescence-enhanced composite probe exhibits good stability even under high ionic strength.

[0080] 5) UV radiation stability testing of a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer.

[0081] 2000 μL of the fluorescence-enhanced composite probe solution was irradiated under a UV lamp for 0, 5, 10, 15, 20, 25, 30, 45, and 60 min, and the corresponding fluorescence spectra were measured. Figure 7 As shown, Figure 7 This indicates that the intensity of the fluorescence-enhanced composite probe decreased slightly even after 60 minutes of ultraviolet radiation, demonstrating its good photostability.

[0082] 6) pH stability test of a fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers

[0083] Add 500 μL of buffer solutions with different pH values ​​(4-9) to 2000 μL of fluorescence-enhanced composite probe solution, shake for 10 min, and then test the corresponding fluorescence spectra. Figure 8 As shown, Figure 8 This indicates that the fluorescence-enhanced composite probe has the highest fluorescence intensity at pH=7, demonstrating its broad application prospects in practical detection.

[0084] 7) Storage stability test of a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer.

[0085] The fluorescence spectra of the fluorescence-enhanced composite probes were tested at different storage times (1-15 days). Figure 9 As shown, Figure 9 This indicates that the fluorescence-enhanced composite probe has good storage stability.

[0086] 8) A fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers for testing the response of adenosine triphosphate (ATP).

[0087] In four centrifuge tubes, 200 μL of Tris-HCl buffer (pH=7) and 600 μL of adenosine triphosphate (ATP) at different concentrations were added, respectively. Then, 200 μL of the fluorescent composite probe was added. The mixture was diluted to 2.5 mL with ultrapure water, vigorously shaken for 5 min, and the fluorescence intensity change was measured using a fluorescence spectrometer. Figure 10 As shown, Figure 10 This indicates that the fluorescence-enhanced composite probe has a good response to adenosine triphosphate.

[0088] 9) A fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers for the linear assay of adenosine triphosphate (ATP).

[0089] In a series of centrifuge tubes, 200 μL of Tris-HCl buffer (pH=7) and 600 μL of adenosine triphosphate (ATP) at different concentrations were added, respectively. Then, 200 μL of a fluorescent composite probe was added. The mixture was diluted to 2.5 mL with ultrapure water, shaken vigorously for 5 min, and the fluorescence intensity change was measured using a fluorescence spectrometer. Figure 11 As shown, Figure 11 This indicates that as adenosine triphosphate (ATP) is continuously added, the fluorescence intensity of the fluorescence-enhanced composite probe gradually decreases, and there is a good linear relationship between the fluorescence intensity of the probe and the concentration of ATP.

[0090] 10) Application of a fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers in the construction of fluorescent hydrogels.

[0091] 1 mL of the fluorescence-enhanced composite material was added to 2 mL of κ-carrageenan solution. The mixture was heated to 80 °C and stirred continuously for 30 min. The hydrogel mixture was then transferred to a mold and cooled to room temperature to obtain a hydrogel with orange fluorescence. Figure 12 As shown, Figure 12 A and 12B are photographs of hydrogels with different contents under sunlight and ultraviolet light, respectively, indicating that the luminescence intensity of the fluorescent hydrogel is closely related to the content of the composite material. Figure 13 The transition from A: sunlight (B: ultraviolet light) to C: sunlight (D: ultraviolet light) was achieved by adding equal amounts of adenosine triphosphate (ATP) to certain specific wells of a 96-well plate, quenching the fluorescence intensity in those wells and thus allowing the abbreviation "JLU" of Jilin University to be seen under ultraviolet light, demonstrating the sensitive response of the fluorescent hydrogel to ATP. Furthermore, from... Figure 14 From A (intact) to 14B (damaged) and then to 14C (restored), it can be seen that the fluorescent hydrogel has good self-healing ability.

Claims

1. A preparation method of a fluorescence-enhanced composite probe based on gold nanoclusters anchored on a zinc-based coordination polymer, characterized in that, The method comprises the following steps: Step 1: mixing glutathione aqueous solution and tetrachloroauric acid aqueous solution under oil bath condition to obtain gold nanocluster solution; Step 2: adding adenine and water into 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid buffer solution, stirring uniformly, then adding zinc chloride solution, stirring the obtained mixture in a beaker, collecting the precipitate, washing and drying to obtain zinc-based coordination polymer; Step 3: mixing the gold nanocluster solution prepared in step 1 and the zinc-based coordination polymer solution prepared in step 2 uniformly to obtain fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer.

2. The preparation method of the fluorescence enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers according to claim 1, characterized in that, In step 1, the molar ratio of glutathione and tetrachloroauric acid is 3:

2.

3. The preparation method of the fluorescence enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers according to claim 1, characterized in that, In step 1, the heating temperature of the oil bath is 60-80℃, and the heating time is 20-28h.

4. The preparation method of the fluorescence enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymers according to claim 1, characterized in that, In step 2, the molar ratio of adenine and zinc chloride is 1:1.

5.

5. The preparation method of the fluorescence enhanced composite probe based on gold nanoclusters anchored in zinc-based coordination polymers according to claim 1, characterized in that, In step 2, the reaction temperature is room temperature, and the reaction time is 1.5-2.5h.

6. The preparation method of the fluorescence enhanced composite probe based on gold nanoclusters anchored in zinc-based coordination polymers according to claim 1, characterized in that, In step 3, the volume ratio of gold nanocluster solution and zinc-based coordination polymer solution is 1:(0.25-7.5).

7. The preparation method of the fluorescence enhanced composite probe based on gold nanoclusters anchored in zinc-based coordination polymers according to claim 1, characterized in that, The mixing time in step 3 is 1-35min.

8. The fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer obtained by the preparation method of claim 1.

9. The application of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer of claim 8 in fluorescence detection of adenosine triphosphate.

10. The application of the fluorescence-enhanced composite probe based on gold nanoclusters anchored on zinc-based coordination polymer of claim 8 in construction of hydrogel.

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