WO2026007754A1 - 基于CeO2增强荧光探针及其在硫离子或硫酸盐还原菌检测中的应用 - Google Patents

基于CeO2增强荧光探针及其在硫离子或硫酸盐还原菌检测中的应用

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WO2026007754A1
WO2026007754A1 PCT/CN2025/103148 CN2025103148W WO2026007754A1 WO 2026007754 A1 WO2026007754 A1 WO 2026007754A1 CN 2025103148 W CN2025103148 W CN 2025103148W WO 2026007754 A1 WO2026007754 A1 WO 2026007754A1
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ceo2
fluorescent probe
concentration
sulfate
fluorescence
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French (fr)
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李广芳
徐桂婵
代嘉伟
张天遂
刘宏芳
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Definitions

  • This invention belongs to the field of fluorescence sensing technology, specifically relating to CeO2- enhanced fluorescent probes and their application in the detection of sulfide or sulfate-reducing bacteria.
  • Fluorescence detection is a multifunctional spectroscopic detection method characterized by short response time, high sensitivity, simple technology, and wide applicability. It can be widely used in real-time and field detection.
  • fluorescence sensing is mostly used for foodborne microorganism detection, with very few reports on environmental microorganisms, especially SRB. Therefore, it is urgent to establish a rapid and efficient S2 ⁇ fluorescence analysis method to detect sulfate-reducing bacteria for monitoring and protecting aquatic environments.
  • current fluorescent probes for sulfur ion detection still have shortcomings such as insufficient intensity and limited linear range, making it impossible to accurately quantify the large bacterial content in aquatic environments. Therefore, achieving fluorescence enhancement to expand the linear range and sensitivity is of great significance.
  • this invention provides an enhanced fluorescent probe capable of detecting sulfide ions and sulfate-reducing bacteria (SRB).
  • CeO2 particles are loaded onto metal-organic frameworks (MOFs) with cobalt or copper as metal sites, and then modified with the fluorescent dye sodium riboflavin monophosphate (FMN-Na) via electrostatic adsorption and precipitation reactions to obtain the enhanced fluorescent probe (MOFs@ CeO2 @FMN-Na).
  • MOFs metal-organic frameworks
  • FMN-Na fluorescent dye sodium riboflavin monophosphate
  • the enhanced fluorescent probe prepared by this invention achieves high sensitivity and a wide linear range for the detection of sulfide ions or sulfate-reducing bacteria by enhancing the fluorescence signal, thereby solving the technical problems of insufficient fluorescent probe intensity and narrow linear range in existing technologies for detecting sulfide ions or sulfate-reducing bacteria.
  • a method for preparing a CeO2- enhanced fluorescent probe comprising the following steps:
  • the dispersion of the organic framework material is injected into the cerium source solution, a complexing precipitant is added, and then the mixture is heated. After the precipitate is separated, a metal-organic framework loaded with cerium dioxide particles is obtained; wherein the organic framework material is an organic framework material containing cobalt or an organic framework material containing copper.
  • step (2) Add riboflavin monophosphate solution to the metal-organic framework loaded with cerium dioxide particles obtained in step (1), wherein the riboflavin monophosphate is attached to the cerium dioxide particles to obtain a CeO2- enhanced fluorescent probe.
  • the ligands of the organic framework materials include at least one of aminoterephthalic acid, hydroxyterephthalic acid, and 2,6-bis(2-pyrazinyl)-4,4′-bipyridine.
  • a CeO2 -based fluorescent probe prepared by any one of the methods is provided.
  • the application of the CeO2- enhanced fluorescent probe for the detection of sulfide ions is provided.
  • the application specifically includes the following steps:
  • the CeO2 -based fluorescent probe was added to a salt solution containing sulfur ions with a gradient concentration, and then fluorescence detection was performed to establish a curve showing the relationship between the fluorescence intensity at the peak and the concentration of sulfur ions.
  • the application specifically includes the following steps:
  • the CeO2 -based fluorescent probe was added to a salt solution containing sulfur ions with gradient concentrations, and then fluorescence detection was performed to establish a curve showing the relationship between the ratio of fluorescence intensity at two peaks and the concentration of sulfur ions.
  • the application of the CeO2- enhanced fluorescent probe for detecting the concentration of sulfate-reducing bacteria is provided.
  • the application specifically includes the following steps:
  • the CeO2 -based fluorescent probe was added to the bacterial culture of sulfate-reducing bacteria with gradient concentrations, and then fluorescence detection was performed to establish the relationship curve between the fluorescence intensity at the peak and the concentration of sulfate-reducing bacteria.
  • the application specifically includes the following steps:
  • the CeO2 -based fluorescent probe was added to the bacterial solution of sulfate-reducing bacteria with gradient concentrations, and then fluorescence detection was performed to establish the relationship curve between the ratio of fluorescence intensity at two peaks and the concentration of sulfate-reducing bacteria.
  • the present invention provides a method for preparing a fluorescent dye composite material by loading CeO2 onto MOFs.
  • the fluorescent dye sodium riboflavin monophosphate (FMN-Na) is linked. This not only solves the problems of FMN-Na being easily quenched by solvent molecules and easily photodegraded and oxidized, but also achieves nearly 30 times fluorescence enhancement in aqueous solution, increasing the maximum detection concentration (from 10-50 ⁇ M to 270 ⁇ M). At the same time, it ensures that the detection limit is sufficient for practical detection, and the overall linear range is expanded, making it more suitable for the detection of sulfate-reducing bacteria in water environments.
  • the fluorescent probe of the present invention can achieve fluorescence enhancement, thereby improving detection sensitivity; the synthesis method is simple and low-cost, and it has a very significant fluorescence response to sulfide ions and sulfate-reducing bacteria (SRB) metabolic fluids.
  • the enhanced fluorescent probe of the present invention can also be designed as a double-quenched fluorescent probe, which refers to a fluorescent probe that measures the intensity of the emission spectrum at two wavelengths and corrects the error caused by local environmental changes by plotting the fluorescence ratio at the two wavelengths against the working curve of the analyte. This achieves high sensitivity and wide linear range detection of sulfide ions, and has the advantages of high selectivity, rapid detection, and strong practicality, providing potential application prospects for the rapid detection of harmful microorganisms in the aquatic environment.
  • this invention designs a fluorescent probe with a quenching mechanism that uses energy competition absorption between sulfide precipitates and fluorescent dyes.
  • the fluorescence emission peak only changes significantly when S2- is present.
  • Other common anions in water quality do not bind as well to cobalt or copper ions as sulfur ions.
  • the precipitates formed by a few interfering ions do not have strong energy competition absorption with fluorescent dyes. Therefore, this fluorescent probe has good anti-interference effect and good specificity, and has good application prospects in water quality detection.
  • Figure 1 shows the fluorescence spectra of MOFs@ CeO2 @FMN-Na at different S2- concentrations (0-300 ⁇ M).
  • Figure 2 shows the correlation curve between fluorescence intensity F533 and S2- concentration.
  • Figure 3 shows the fluorescence spectra corresponding to the probe selectivity experiment and anti-interference experiment of S 2- .
  • Figure 4 shows the relative fluorescence intensities corresponding to the probe selectivity experiment and anti-interference experiment of S 2- .
  • Figure 5 shows the fluorescence spectra of MOFs@ CeO2 @FMN-Na at different SRB bacterial concentrations (0-5.9* 104 cells/mL).
  • Figure 6 shows the correlation curve between fluorescence intensity F533 and SRB bacterial concentration.
  • Figure 7 shows the fluorescence spectra of MOFs@ CeO2 @FMN-Na at different S2- concentrations (0-2.6mM).
  • Figure 8 shows the correlation curves between the fluorescence intensity ratio F531/F431 and the S2- concentration.
  • Figure 9 shows the fluorescence spectra of probes prepared from different materials.
  • This invention provides a fluorescence-enhanced probe for detecting sulfide ions and sulfate-reducing bacteria (SRB). It involves loading CeO2 particles onto metal-organic frameworks (MOFs) with cobalt or copper as metal sites, followed by electrostatic adsorption and precipitation to modify the fluorescent dye FMN-Na, resulting in an enhanced fluorescence probe (MOFs@ CeO2 @FMN-Na). The degree of fluorescence enhancement can be altered by adjusting the loading of MOFs and cerium dioxide, thus achieving an enhanced fluorescence probe for monitoring sulfide ions and SRB.
  • the method includes the following steps:
  • a dispersion of metal-organic framework materials (MOFs) with cobalt or copper as metal sites is injected into a cerium source solution, a complexing precipitant is added, and the mixture is reacted at a certain temperature. The product is then separated and washed to obtain the corresponding metal-organic frameworks (MOFs)@ CeO2 loaded with cerium dioxide particles.
  • MOFs metal-organic framework materials
  • step (2) Add the MOFs@CeO 2 obtained in step (1) to riboflavin monophosphate sodium FMN-Na, stir at room temperature overnight to obtain enhanced fluorescent probe MOFs@CeO 2 @FMN-Na.
  • the preparation of metal-organic framework materials specifically involves: rapidly mixing a metal salt (cobalt salt or copper salt) solution with a ligand solution at a certain temperature (preferably 50-80°C), stirring for a certain time, separating the product, and washing it to obtain the corresponding metal-organic framework materials (MOFs);
  • the metal salt is one of cobalt nitrate, copper nitrate, cobalt chloride, copper sulfate, and cobalt sulfate, and its molar ratio with the ligand is 5:1 to 1:5.
  • the ligand is at least one selected from 2-methylimidazole, bipyridine, terephthalic acid, tricarboxylic acid, and naphthalic acid.
  • the ligand includes at least one of aminoterephthalic acid, hydroxyterephthalic acid, and 2,6-bis(2-pyrazinyl)-4,4′-bipyridine.
  • the solvent used for the ligand is ethanol, water, DMF, triethylamine, or a mixture of any proportions.
  • the solvent of the MOFs dispersion is one of water, ethanol, DMF, or a mixture of any proportion; the volume of the dispersion is 0.5-3.5 mL.
  • the cerium source is one of cerium nitrate and cerium sulfate, and the concentration of cerium nitrate is 1-8 g/L.
  • the complexing precipitant is one of arginine, citric acid, sodium hydroxide, or ammonia.
  • the molar ratio of cerium nitrate to complexing precipitant is 2.5:1 to 1:2.5.
  • the reaction temperature is 75-90°C and the reaction time is 2.5-4h.
  • the concentration of riboflavin monophosphate sodium is 1-3 mM.
  • the present invention provides the application of the fluorescence-enhancing probe prepared by the above preparation method for detecting sulfur ions or for detecting sulfate-reducing bacteria (SRB).
  • the application is specifically as follows:
  • the application is specifically as follows:
  • the ligand in the metal-organic framework material is a luminescent ligand, such as at least one of aminoterephthalic acid, hydroxyterephthalic acid, and 2,6-bis(2-pyrazinyl)-4,4′-bipyridine), then add different volumes of Na2S solution, shake well, and perform fluorescence detection after 2-4 min.
  • the excitation wavelength is 350nm
  • the scan rate is 600-2000nm/min
  • the slit width is 5nm
  • the emission spectrum at 370-800nm is recorded.
  • the application is specifically as follows:
  • the prepared enhanced fluorescent probe was diluted 10,000 times and then added to the treated SRB bacterial culture of different volumes. After shaking well, fluorescence detection was performed after 2-4 min. The excitation wavelength was 350 nm, the scan rate was 600-2000 nm/min, the slit width was 5 nm, and the emission spectrum of 370-800 nm was recorded.
  • step (3) Take 30 ⁇ L of the bacterial solution to be tested and perform the operation process described in step (1);
  • the application is specifically as follows:
  • the prepared enhanced fluorescent probe was diluted 10,000 times and then added to the treated SRB bacterial culture of different volumes. After shaking well, fluorescence detection was performed after 2-4 min. The excitation wavelength was 350 nm, the scan rate was 600-2000 nm/min, the slit width was 5 nm, and the emission spectrum of 370-800 nm was recorded.
  • step (3) Take 30 ⁇ L of the bacterial solution to be tested and perform the operation process described in step (1);
  • Cobalt nitrate solution and dimethylimidazole solution (1:1) were rapidly mixed at 50°C and stirred for 10 min.
  • the product was then separated and washed to obtain the corresponding metal-organic framework material Co-MOFs.
  • 1 mL of the Co-MOF dispersion was injected into cerium nitrate solution, sodium hydroxide was added, and the reaction was carried out at 85°C.
  • the product was then separated and washed to obtain the corresponding metal-organic framework Co-MOFs@ CeO2 loaded with cerium dioxide particles.
  • riboflavin monophosphate sodium FMN-Na was added, and the mixture was stirred at room temperature overnight to obtain the enhanced fluorescent probe MOFs@ CeO2 @FMN-Na.
  • the detection limit for S2 ⁇ was ultimately calculated to be 18.42 ⁇ M using 3N/S, with a maximum detection range of 270 ⁇ M. Therefore, this probe can be used for the quantitative detection of S2 ⁇ concentrations with a wide linear range.
  • a solution of common anions H2PO4 ⁇ , SCN ⁇ , Cl ⁇ , C2O42 ⁇ , SO32 ⁇ , S2O32 ⁇ , S2O82 ⁇ , S2 ⁇ ) at a concentration of 100 mM was prepared for use.
  • the enhanced fluorescent probe was diluted 10000 times, and 4.5 ⁇ L of the other seven anions ( excluding S2 ⁇ ) at a concentration of 10 mM was added.
  • fluorescence detection was performed after 2-4 min, with an excitation wavelength of 350 nm, a scan rate of 2000 nm/min, and a slit width of 5 nm. The emission spectra from 370 to 800 nm were recorded. Subsequently, 4.5 ⁇ L of S2 ⁇ at a concentration of 100 mM was added to the above solution, and after mixing, fluorescence detection was performed after 5 min.
  • the bacterial culture was filtered to obtain the SRB metabolic bacterial culture.
  • the enhanced fluorescent probe was diluted 10,000 times and then added to the SRB metabolic bacterial culture.
  • fluorescence detection was performed after 2-4 minutes.
  • the excitation wavelength was 350 nm
  • the scan rate was 2000 nm/min
  • the slit width was 5 nm.
  • the emission spectrum from 370 to 800 nm was recorded, as shown in Figure 5.
  • the arrows in the figure indicate the direction of increasing SRB metabolic bacterial culture concentration.
  • Cobalt nitrate solution was mixed with dimethylimidazole and aminoterephthalic acid solution (1:1:1) at 65°C and stirred for 12 h. The product was separated and washed to obtain the corresponding metal-organic framework material Co-MOFs. 1 mL of the Co-MOF dispersion was injected into cerium nitrate solution, sodium hydroxide was added, and the reaction was carried out at 80°C. The product was then separated and washed to obtain the corresponding metal-organic framework Co-MOFs@ CeO2 loaded with cerium dioxide particles. After dispersion in water, riboflavin monophosphate sodium FMN-Na was added, and the mixture was stirred at room temperature overnight to obtain the enhanced fluorescent probe MOFs@ CeO2 @FMN-Na.
  • Cobalt nitrate solution and dimethylimidazole solution (1:1) were rapidly mixed at 50°C and stirred for 10 min. The products were then separated and washed to obtain the corresponding metal-organic framework materials Co-MOFs.
  • the obtained Co-MOFs were diluted 10,000 times for fluorescence detection.
  • the excitation wavelength was 350 nm
  • the scan rate was 2000 nm/min
  • the slit width was 5 nm.
  • the emission spectrum from 370 to 800 nm was recorded as shown in Figure 9, with almost no fluorescence emission.
  • Cobalt nitrate solution and dimethylimidazole solution (1:1) were rapidly mixed at 50°C and stirred for 10 min.
  • the product was then separated and washed to obtain the corresponding metal-organic framework material Co-MOFs.
  • 1 mL of the Co-MOFs dispersion was injected into cerium nitrate solution, sodium hydroxide was added, and the mixture was reacted at 85°C.
  • the product was then separated and washed to obtain the corresponding metal-organic framework Co-MOFs@ CeO2 loaded with cerium dioxide particles.
  • the obtained Co-MOFs@CeO 2 was diluted 10,000 times for fluorescence detection.
  • the excitation wavelength was 350 nm
  • the scan rate was 2000 nm/min
  • the slit width was 5 nm.
  • the emission spectrum from 370 to 800 nm was recorded as shown in Figure 9, with almost no fluorescence emission.
  • the obtained CeO2 @FMN-Na was diluted 10,000 times for fluorescence detection.
  • the excitation wavelength was 350 nm
  • the scan rate was 2000 nm/min
  • the slit width was 5 nm.
  • the emission spectrum from 370 to 800 nm was recorded as shown in Figure 9.
  • the obtained FMN-Na was diluted 10,000 times for fluorescence detection.
  • the excitation wavelength was 350 nm
  • the scan rate was 2000 nm/min
  • the slit width was 5 nm.
  • the emission spectrum from 370 to 800 nm was recorded as shown in Figure 9. The fluorescence emission was weak.
  • Comparative Examples 1, 2 and 4 all had lower fluorescence intensities than the fluorescent probe prepared in Example 1. Although Comparative Example 3 had higher fluorescence intensity than Example 1, it could not be used as a fluorescent material for detecting S 2- because it did not contain any substance (cobalt or copper) that could recognize S 2- .

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Abstract

本发明涉及基于CeO2增强荧光探针及其在硫离子或硫酸盐还原菌检测中的应用，属于荧光传感技术领域。本发明增强荧光探针由金属有机框架材料(MOFs)负载二氧化铈(CeO2)后再吸附荧光染料核黄素单磷酸钠(FMN-Na)得到，本发明的荧光探针能实现荧光增强，提高了检测灵敏度；合成方式简单且成本低，对硫离子(S2-)及硫酸盐还原菌(SRB)菌液有非常显著的荧光响应。该荧光增强探针还可以设计成双猝灭荧光探针，通过校正实现硫离子的高灵敏性、宽线性范围的检测，具有高选择性、快速检测、实用性强等优点，为水环境中有害微生物的快速检测提供潜在应用前景。

Description

基于CeO2增强荧光探针及其在硫离子或硫酸盐还原菌检测中的应用 【技术领域】
本发明属于荧光传感技术领域，具体涉及基于CeO2增强荧光探针及其在硫离子或硫酸盐还原菌检测中的应用。
【背景技术】
保护好长江流域是维护国家生态安全的重大需求，为了更好的进行防护，对水质进行在线监测是及其重要的一环。然而，受技术条件制约，只有极少数污染物可在线监测，对于有害微生物的监测，其检测的灵敏度、特异性仍未达到要求，水污染风险防范仍有漏洞，水质变化机理和碳排放研究已遇到技术瓶颈。因此，开展适应长江水环境的在线自动监测技术和设备研发，提升对水环境中有害微生物的监测能力和水质变化机理研究水平，是新时期长江大保护的迫切需求。
目前，长江经济带废水排放总量占全国的40％以上，近50％水源风险防控能力不足，部分河湖由碳库向碳源转变，黑臭水体大量存在；同时，研究显示湖泊甲烷排放量占全球排放量约25％。这些现象产生的“罪魁祸首”大部分来源于硫酸还原菌(SRB)。少量SRB代谢产生硫化物可极大地促进产甲烷菌产生大量甲烷，引发水体向碳源转变，而大量SRB则产生大量硫化氢，诱发黑臭水体。这些严重的环境问题都将加重温室效应，黑臭水体中的硫化氢则导致了生物疾病与对工业环境的严重腐蚀，导致经济损失甚至引发生命安全，开发高灵敏且便捷的SRB传感器迫在眉睫。因此，基于SRB的特征代谢产物硫离子，设计以增强荧光为核心技术的硫离子及SRB探针，具有灵敏度高、可视化效果好、特异性强以及便于现场监测的优势，以此更精准、全面、直观判断水质变化，为水环境中碳排放、黑臭水体形成、水污染等提供重要依据，从而保护美丽水环境。
传统SRB等微生物检测主要采用稀释培养技术法、PCR技术、ELISA等，灵敏度低，时间长，误差大，难以实现现场检测。因此，近年来运用电化学传感器检测硫离子及硫酸盐还原菌得到了极大的发展，但是在实现在线监测硫酸盐还原菌中仍然存在极大的技术瓶颈。
荧光检测是一种具有响应周期短、灵敏度高、技术简单、适用性广等特点的多功能光谱检测方法，可广泛应用于实时和现场检测，然而目前荧光传感大多用于食源性微生物检测，对环境微生物尤其是SRB报道极少，因此，建立快速、高效的S2-荧光分析方法，从而检测硫酸盐还原菌，以对水质环境加以监测与保护刻不容缓。然而目前针对硫离子检测的荧光探针仍然存在强度不够，线性范围不够大的缺点，对于水环境中存在大量的细菌含量不能够准确定量，因此实现荧光增强从而扩大线性范围及灵敏度具有重要意义。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明提供了一种能检测硫离子及硫酸盐还原菌SRB的增强荧光探针，将钴或铜为金属位点的金属有机框架材料MOFs负载CeO2颗粒，再通过静电吸附及沉淀反应修饰荧光染料核黄素单磷酸钠FMN-Na，得到增强荧光探针(MOFs@CeO2@FMN-Na)。本发明制备得到的增强荧光探针通过增强荧光信号实现硫离子或硫酸盐还原菌的高灵敏度、宽线性范围的检测，从而解决现有技术中硫离子或硫酸盐还原菌检测的荧光探针强度不够，线性范围窄的技术问题。
根据本发明第一方面，提供了一种基于CeO2增强荧光探针的制备方法，包括以下步骤：
(1)将有机框架材料的分散液注入铈源溶液中，再加入络合沉淀剂，然后进行加热，将生成的沉淀分离后，得到负载有二氧化铈颗粒的金属有机框架；其中，所述有机框架材料为含有金属钴元素的有机框架材料或者含有金属铜元素的有机框架材料；
(2)向步骤(1)得到的负载有二氧化铈颗粒的金属有机框架中加入核黄素单磷酸钠溶液，所述核黄素单磷酸钠连接到二氧化铈颗粒上，即得到基于CeO2增强荧光探针。
优选地，所述有机框架材料的配体为二甲基咪唑、联吡啶、对苯二甲酸、苯三甲酸、萘二酸中的至少一种。
优选地，所述有机框架材料MOFs的配体包括氨基对苯二甲酸、羟基对苯二甲酸、2,6-双(2-吡嗪基)-4,4′-联吡啶中的至少一种。
根据本发明另一方面，提供了任意一项方法制备得到的基于CeO2增强荧光探针。
根据本发明另一方面，提供了所述的基于CeO2增强荧光探针用于检测硫离子的应用。
优选地，所述应用具体包括以下步骤：
(1)将所述基于CeO2增强荧光探针加入到梯度浓度的含有硫离子的盐溶液中，然后进行荧光检测，建立峰值处的荧光强度与硫离子浓度的关系曲线；
(2)将所述基于CeO2增强荧光探针加入到待测溶液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测溶液中的硫离子的浓度。
优选地，所述应用具体包括以下步骤：
(1)将所述基于CeO2增强荧光探针加入到梯度浓度的含有硫离子的盐溶液中，然后进行荧光检测，建立两个峰值处的荧光强度的比值与硫离子浓度的关系曲线；
(2)将所述基于CeO2增强荧光探针加入到待测溶液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测溶液中的硫离子的浓度。
根据本发明另一方面，提供了所述的基于CeO2增强荧光探针用于检测硫酸盐还原菌浓度的应用。
优选地，所述应用具体包括以下步骤：
(1)将所述基于CeO2增强荧光探针加入到梯度浓度的硫酸盐还原菌的菌液中，然后进行荧光检测，建立峰值处的荧光强度与硫酸盐还原菌浓度的关系曲线；
(2)将所述基于CeO2增强荧光探针加入到待测菌液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测菌液中的硫酸盐还原菌的浓度。
优选地，所述应用具体包括以下步骤：
(1)将所述基于CeO2增强荧光探针加入到梯度浓度的硫酸盐还原菌的菌液中，然后进行荧光检测，建立两个峰值处的荧光强度的比值与硫酸盐还原菌浓度的关系曲线；
(2)将所述基于CeO2增强荧光探针加入到待测菌液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测菌液中的硫酸盐还原菌的浓度。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，主要具备以下的技术优点：
(1)本发明通过MOFs负载CeO2连接荧光染料复合材料的制备方法，通过CeO2对磷酸盐的强烈作用连接荧光染料核黄素单磷酸钠FMN-Na，不仅解决了FMN-Na易被溶剂分子猝灭，容易光降解氧化等难以利用的问题，还实现其在水溶液中的将近30倍的荧光增强，提高了最高检测浓度(由10～50μM提高到270μM)，同时也保证检测限足够应用于实际检测，整体扩大了线性范围，更适合应用于水质环境中硫酸盐还原菌的检测。
(2)长期以来都聚焦于对贵金属材料增强荧光的效应研究，而对半导体的研究相对较少，半导体(尤其是金属氧化物)在地壳中丰度高、成本低，在工业化应用中更有优势和潜力。利用CeO2与带有磷酸盐的荧光团强烈相互作用，使得荧光染料FMN-Na在聚集态下因分子内基团运动受限而发出明亮的荧光；另外，近年来的研究显示，一些简并掺杂的半导体具有显著的表面等离激元效应，CeO2作为含有丰富的氧空位的半导体材料，通过调控CeO2的合成，可以使得CeO2对荧光染料有类等离激元增强荧光的作用，构建半导体增强荧光的模型可以为生物传感器的设计提供理论价值参考。
(3)本发明的荧光探针能实现荧光增强，提高了检测灵敏度；合成方式简单且成本低，对硫离子及硫酸盐还原菌(SRB)代谢菌液有非常显著的荧光响应。本发明优选地，该增强荧光探针还可以设计成双猝灭荧光探针，指的是在两个波长处测量发射光谱的强度，通过做两个波长处的荧光比值与待测物的工作曲线来校正因局域环境变化而导致的误差的一种荧光探针，从而实现硫离子的高灵敏性、宽线性范围的检测，具有高选择性、快速检测、实用性强等优点，为水环境中有害微生物的快速检测提供潜在应用前景。
(4)本发明基于钴或铜离子与硫离子能够特异性结合生成沉淀的反应，设计了以硫化物沉淀与荧光染料产生能量竞争吸收为猝灭机制的荧光探针，只有当S2-存在时，荧光发射峰才发生显著变化。其他水质中常见的阴离子与钴或铜离子的结合能力不如硫离子，另外，少数干扰离子形成的沉淀对与荧光染料没有强烈能量竞争吸收，因此该荧光探针具有较好的抗干扰效果，特异性较好，在水质检测中具有较好的应用前景。
【附图说明】
图1是MOFs@CeO2@FMN-Na在不同S2-浓度(0-300μM)下的荧光光谱。
图2是荧光强度F533与S2-浓度的相关曲线。
图3是S2-的探针选择性实验和抗干扰实验对应荧光光谱。
图4是S2-的探针选择性实验和抗干扰实验对应相对荧光强度。
图5是MOFs@CeO2@FMN-Na在不同SRB菌液浓度(0-5.9*104cells/mL)下的荧光光谱。
图6是荧光强度F533与SRB菌液浓度的相关曲线。
图7是MOFs@CeO2@FMN-Na在不同S2-浓度(0-2.6mM)下的荧光光谱。
图8是荧光强度比F531/F431与S2-浓度的相关曲线。
图9是不同材料制备的探针所得的荧光光谱。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明提供了一种能检测硫离子及硫酸盐还原菌SRB的荧光增强探针，将钴或铜为金属位点的金属有机框架材料MOFs负载CeO2颗粒，再通过静电吸附及沉淀反应修饰荧光染料FMN-Na得到增强荧光探针(MOFs@CeO2@FMN-Na)，通过调节MOFs以及二氧化铈的负载情况可以改变荧光增强的程度，从而实现对硫离子及SRB监测的增强荧光探针，可包括以下步骤：
(1)将将钴或铜为金属位点的金属有机框架材料MOFs分散液注入铈源溶液，加入络合沉淀剂后在一定温度下反应，然后将产物分离、清洗后得到相应的负载有二氧化铈颗粒的金属有机框架MOFs@CeO2。
(2)将所述步骤(1)得到的MOFs@CeO2加入核黄素单磷酸钠FMN-Na，室温搅拌一夜后得到增强荧光探针MOFs@CeO2@FMN-Na。
一些实施例中，金属有机框架材料MOFs的制备具体为：将金属盐(钴盐或铜盐)溶液与配体溶液在一定温度(优选为50-80℃)下迅速混合，搅拌一定时间将产物分离、清洗得到相应的金属有机框架材料MOFs；
作为本发明的进一步优选，所述金属盐为硝酸钴、硝酸铜、氯化钴、硫酸铜、硫酸钴中的一种，其与配体的摩尔比为5:1-1:5。
作为本发明的进一步优选，配体为2-甲基咪唑、联吡啶、对苯二甲酸、苯三甲酸、萘二酸中的至少一种。
优选地，配体包括氨基对苯二甲酸、羟基对苯二甲酸、2,6-双(2-吡嗪基)-4,4′-联吡啶中的至少一种。
作为本发明的进一步优选，配体所用溶剂为乙醇、水、DMF、三乙胺或者任意比例混合溶液。
作为本发明的进一步优选，所述步骤(1)中，所述MOFs分散液的溶剂为水、乙醇、DMF、或任意比例混合中的一种；该分散液体积为0.5-3.5mL。
作为本发明的进一步优选，所述步骤(1)中，铈源为硝酸铈、硫酸铈中的一种，所述硝酸铈浓度为1-8g/L。
作为本发明的进一步优选，所述步骤(1)中，络合沉淀剂为精氨酸、柠檬酸、氢氧化钠、氨水中的一种。
作为本发明的进一步优选，所述步骤(1)中，硝酸铈与络合沉淀剂的摩尔比为2.5：1-1：2.5。
作为本发明的进一步优选，所述步骤(1)中，所述反应的一定温度为75-90℃，反应时间为2.5-4h。
作为本发明的进一步优选，所述步骤(2)中，所述核黄素单磷酸钠浓度为1-3mM。
按照本发明的另一方面，本发明提供了上述制备方法制得的荧光增强探针用于检测硫离子的应用或检测硫酸盐还原菌SRB中的应用。
一些实施例中，该应用具体为：
(1)配制好100mM的Na2S溶液，将增强荧光探针稀释10000倍，随后加入不同体积的Na2S溶液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速600-2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱；
(2)建立荧光发射强度F533与S2-的关系曲线(建立峰值处的荧光强度与S2-的关系曲线)；
(3)取待测溶液30μL进行步骤(1)所述的操作过程；
(4)根据步骤(2)荧光发射强度F533得到的S2-浓度关系曲线，得到待测溶液的S2-浓度值。
一些实施例中，该应用具体为：
(1)配制好100mM的Na2S溶液，将制备的双猝灭荧光探针稀释10000倍(金属有机框架材料中的配体为能发光的配体，如：包括氨基对苯二甲酸、羟基对苯二甲酸、2,6-双(2-吡嗪基)-4,4′-联吡啶中的至少一种)，随后加入不同体积的Na2S溶液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速600-2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱；
(2)建立荧光发射强度比F531/F413(两个峰值处的荧光强度比与S2-的关系曲线)与S2-的关系曲线；
(3)取待测溶液30μL进行步骤(1)所述的操作过程；
(4)根据步骤(2)荧光发射强度比F531/F413得到的S2-关系曲线，得到待测溶液的S2-浓度值。
一些实施例中，该应用具体为：
(1)将培养一周的SRB菌液用滤膜过滤后，将制备的增强荧光探针稀释10000倍，随后加入的处理好不同体积的SRB菌液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速600-2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱；
(2)建立荧光发射强度F533与SRB菌液浓度的关系曲线；
(3)取待测菌液30μL进行步骤(1)所述的操作过程；
(4)根据步骤(2)荧光发射强度F533得到的SRB菌液的浓度关系曲线，得到待测溶液的SRB菌液浓度值。
一些实施例中，该应用具体为：
(1)将培养一周的SRB菌液用滤膜过滤后，将制备的增强荧光探针稀释10000倍，随后加入的处理好不同体积的SRB菌液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速600-2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱；
(2)建立荧光发射强度比F531/F413(两个峰值处的荧光强度比与S2-的关系曲线)与SRB菌液浓度的关系曲线；
(3)取待测菌液30μL进行步骤(1)所述的操作过程；
(4)根据步骤(2)荧光发射强度比F531/F413(两个峰值处的荧光强度比与S2-的关系曲线)与SRB菌液浓度的关系曲线，得到待测菌液的浓度。以下为具体实施例：
实施例1
荧光探针MOFs@CeO2@FMN-Na的合成：
将硝酸钴溶液与二甲基咪唑溶液(1：1)在50℃下迅速混合，搅拌10min将产物分离、清洗得到相应的金属有机框架材料Co-MOFs；将Co-MOFs分散液1mL注入硝酸铈溶液，加入氢氧化钠后在85℃反应，然后将产物分离、清洗后得到相应的负载有二氧化铈颗粒的金属有机框架Co-MOFs@CeO2，用水分散后加入核黄素单磷酸钠FMN-Na，室温搅拌一夜后得到增强荧光探针MOFs@CeO2@FMN-Na。
荧光探针MOFs@CeO2@FMN-Na对不同浓度S2-的荧光响应：
配制好100mM的Na2S溶液，将增强荧光探针稀释10000倍，随后加入不同体积的Na2S溶液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图1所示，图中箭头方向即S2-浓度增大方向。进一步发现，F533在S2-浓度为0-150μM与150-270μM时有较好的线性关系，分别为：F533＝-4356.14*[S2-]+5.6E6(R2＝0.95)、F533＝-16542.80*[S2-]+7.39E6(R2＝0.99)，如图2所示，最终通过3N/S计算得到S2-检测限为18.42μM，最高检测范围为270μM。因此，该探针可用于线性范围宽的S2-浓度的定量检测。
实施例2
采用实施例1中制备得到的荧光探针MOFs@CeO2@FMN-Na对不同阴离子的选择性和干扰性：
为了排除水相中可能存在的其它阴离子对S2-检测的影响，配制了浓度为100mM的常见阴离子(H2PO4 -，SCN-，Cl-，C2O4 2-，SO3 2-，S2O3 2-，S2O8 2-，S2-)待用。将增强荧光探针稀释10000倍，加入4.5μL浓度为10mM除S2-的其他7种阴离子，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱；随后，在上述溶液基础上再加入4.5μL浓度为100mM的S2-，摇匀，5min后进行荧光检测。
如图3所示，只有当S2-存在时，533nm处荧光发射峰才发生显著变化。如图4所示，当这些干扰物质与S2-共存时，S2-与在增强荧光探针作用的相对荧光强度变化最大。这些结果说明MOFs@CeO2@FMN-Na对S2-具有较好的特异性。
实施例3
采用实施例1中制备得到的荧光探针MOFs@CeO2@FMN-Na对不同浓度SRB菌液的荧光响应：
培养SRB一周后，将菌液过滤取其SRB代谢菌液；增强荧光探针稀释10000倍，随后加入SRB代谢菌液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图5所示，图中箭头方向即SRB代谢菌液浓度增大方向。进一步发现，F533在SRB代谢菌液浓度为0-5.9*104cells/mL时有较好的线性关系：F533＝-11.69*[CSRB]+1.18E6(R2＝0.99)，如图6所示，最终通过3N/S计算得到SRB代谢菌液检测限为840cells/mL。因此，该探针可用于SRB浓度的定量检测。
实施例4
为了实现信号校正，还制备了双猝灭荧光探针MOFs@CeO2@FMN-Na，其合成过程如下：
将硝酸钴溶液与二甲基咪唑、氨基对苯二甲酸溶液(1：1：1)在65℃下混合，搅拌12h，将产物分离、清洗得到相应的金属有机框架材料Co-MOFs；将Co-MOFs分散液1mL注入硝酸铈溶液，加入氢氧化钠后在80℃反应，然后将产物分离、清洗后得到相应的负载有二氧化铈颗粒的金属有机框架Co-MOFs@CeO2，用水分散后加入核黄素单磷酸钠FMN-Na，室温搅拌一夜后得到增强荧光探针MOFs@CeO2@FMN-Na。
双猝灭荧光探针MOFs@CeO2@FMN-Na对不同浓度S2-的荧光响应：
配制好100mM的Na2S溶液，将增强荧光探针稀释10000倍，随后加入Na2S溶液，摇匀，2-4min后进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图7所示，图中箭头方向即S2-浓度增大方向，随着S2-浓度的增加，体系中MOFs@CeO2@FMN-Na在发射波长为413nm与531nm处的荧光强度逐渐减弱，当体系中S2-浓度达到12.17mM时，荧光猝灭率超过90％。进一步发现，F531/F413在S2-浓度为150-720μM与720-1230μM时有较好的线性关系，分别为：F531/F413＝-0.011*[S2-]+18.65(R2＝0.99)、F531/F413＝-0.014*[S2-]+20.67(R2＝0.99)，如图8所示。因此，该探针可用于S2-浓度的定量检测。
对比例1
将硝酸钴溶液与二甲基咪唑溶液(1：1)在50℃下迅速混合，搅拌10min将产物分离、清洗得到相应的金属有机框架材料Co-MOFs。
测试材料Co-MOFs的荧光响应：
将所得Co-MOFs稀释10000倍进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图9所示，几乎无荧光发射。
对比例2
将硝酸钴溶液与二甲基咪唑溶液(1：1)在50℃下迅速混合，搅拌10min将产物分离、清洗得到相应的金属有机框架材料Co-MOFs；将Co-MOFs分散液1mL注入硝酸铈溶液，加入氢氧化钠后在85℃反应，然后将产物分离、清洗后得到相应的负载有二氧化铈颗粒的金属有机框架Co-MOFs@CeO2。
测试材料Co-MOFs@CeO2的荧光响应：
将所得Co-MOFs@CeO2稀释10000倍进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图9所示，几乎无荧光发射。
对比例3
在硝酸铈溶液中加入氢氧化钠后在85℃反应，然后将产物分离、清洗后得到相应的二氧化铈颗粒CeO2；用水分散后加入核黄素单磷酸钠FMN-Na，室温搅拌一夜后得到材料CeO2@FMN-Na。
测试材料CeO2@FMN-Na的荧光响应：
将所得CeO2@FMN-Na稀释10000倍进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图9所示。
对比例4
在水中加入核黄素单磷酸钠FMN-Na，室温搅拌一夜后得到材料FMN-Na。
测试材料FMN-Na的荧光响应：
将所得FMN-Na稀释10000倍进行荧光检测，激发波长为350nm，扫速2000nm/min，狭缝宽度均为5nm，记录370-800nm的发射光谱如图9所示，荧光发射较弱。
对比例1、2和4制备得到的荧光探针均低于实施例1中所制得荧光探针的荧光强度，对比例3虽然高于实施例1，但是由于材料中没有能够识别S2-的物质(金属钴或铜)，因此不能用作检测S2-的荧光材料。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 基于CeO2增强荧光探针的制备方法，其特征在于，包括以下步骤：
    (1)将有机框架材料的分散液注入铈源溶液中，再加入络合沉淀剂，然后进行加热，将生成的沉淀分离后，得到负载有二氧化铈颗粒的金属有机框架；其中，所述有机框架材料为含有金属钴元素的有机框架材料或者含有金属铜元素的有机框架材料；
    (2)向步骤(1)得到的负载有二氧化铈颗粒的金属有机框架中加入核黄素单磷酸钠溶液，所述核黄素单磷酸钠连接到二氧化铈颗粒上，即得到基于CeO2增强荧光探针。
  2. 如权利要求1所述的基于CeO2增强荧光探针的制备方法，其特征在于，所述有机框架材料的配体为二甲基咪唑、联吡啶、对苯二甲酸、苯三甲酸、萘二酸中的至少一种。
  3. 如权利要求1或2所述的基于CeO2增强荧光探针的制备方法，其特征在于，所述有机框架材料的配体包括氨基对苯二甲酸、羟基对苯二甲酸、2,6-双(2-吡嗪基)-4,4′-联吡啶中的至少一种。
  4. 如权利要求1-3任意一项方法制备得到的基于CeO2增强荧光探针。
  5. 如权利要求4所述的基于CeO2增强荧光探针用于检测硫离子的应用。
  6. 如权利要求5所述的应用，其特征在于，所述应用具体包括以下步骤：
    (1)将所述基于CeO2增强荧光探针加入到梯度浓度的含有硫离子的盐溶液中，然后进行荧光检测，建立峰值处的荧光强度与硫离子浓度的关系曲线；
    (2)将所述基于CeO2增强荧光探针加入到待测溶液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测溶液中的硫离子的浓度。
  7. 如权利要求5所述的应用，其特征在于，所述应用具体包括以下步骤：
    (1)将所述基于CeO2增强荧光探针加入到梯度浓度的含有硫离子的盐溶液中，然后进行荧光检测，建立两个峰值处的荧光强度的比值与硫离子浓度的关系曲线；
    (2)将所述基于CeO2增强荧光探针加入到待测溶液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测溶液中的硫离子的浓度。
  8. 如权利要求4所述的基于CeO2增强荧光探针用于检测硫酸盐还原菌浓度的应用。
  9. 如权利要求8所述的应用，其特征在于，所述应用具体包括以下步骤：
    (1)将所述基于CeO2增强荧光探针加入到梯度浓度的硫酸盐还原菌的菌液中，然后进行荧光检测，建立峰值处的荧光强度与硫酸盐还原菌浓度的关系曲线；
    (2)将所述基于CeO2增强荧光探针加入到待测菌液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测菌液中的硫酸盐还原菌的浓度。
  10. 如权利要求8所述的应用，其特征在于，所述应用具体包括以下步骤：
    (1)将所述基于CeO2增强荧光探针加入到梯度浓度的硫酸盐还原菌的菌液中，然后进行荧光检测，建立两个峰值处的荧光强度的比值与硫酸盐还原菌浓度的关系曲线；
    (2)将所述基于CeO2增强荧光探针加入到待测菌液中，并在与步骤(1)中荧光检测相同激发波长的条件下进行荧光检测，然后根据步骤(1)所述关系曲线，得到所述待测菌液中的硫酸盐还原菌的浓度。
PCT/CN2025/103148 2024-07-05 2025-06-24 基于CeO2增强荧光探针及其在硫离子或硫酸盐还原菌检测中的应用 Pending WO2026007754A1 (zh)

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