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EP-3948264-B1 - NON-BLEACHING COLORIMETRIC AND FLUOROMETRIC ANALYTE DETECTION BY DEGRADATION OF SOLIDS

EP3948264B1EP 3948264 B1EP3948264 B1EP 3948264B1EP-3948264-B1

Inventors

  • MIERITZ, Daniel, Gustav
  • GREENAWALT, Angella, Nicholle

Dates

Publication Date
20260506
Application Date
20200328

Claims (3)

  1. A method for measuring an analyte ion component of an aqueous sample using a photoreactive species, comprising: generating (201) a metal organic framework by combining, in a reactive solution, at least one organic linker and at least one metal salt; wherein the analyte ion component is selected from the group consisting of: fluoride, carbonate, borate, and mercury; wherein the at least one linker is selected from the group consisting of: terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and trimesic acid; and wherein the at least one metal salt is selected from the group consisting of: aluminum nitrate nonahydrate, aluminum chloride hexahydrate, zirconyl chloride, and zirconium (IV) tetrachloride; impregnating (202) the metal organic framework with the photoreactive species; introducing (203) the impregnated metal organic framework into an aqueous sample, whereby the analyte ion component binds to the at least one metal salt and removes the metal from the metal organic framework to release the at least one linker and the photoreactive species into solution; measuring (204) an analyte ion component concentration of the aqueous sample, wherein the measuring comprises measuring a change in the aqueous sample, wherein the change is responsive to the analyte ion component dissolving the at least one metal salt, and releasing the at least one organic linker, thereby providing a colorimetric and/or fluorescent change to the aqueous sample; and wherein the measuring comprises measuring an absorbance or fluorescence at a given wavelength of the at least one linker.
  2. The method of claim 1, wherein the photoreactive species is a chromophore.
  3. The method of claim 1, wherein the photoreactive species is a fluorochrome.

Description

BACKGROUND The measurement of analytes (e.g., fluoride, borate, carbonate, mercury) in drinking water is an important task for water treatment facilities. With respect to fluoride, most municipal water facilities introduce a controlled amount of fluoride into drinking water. One benefit to this introduction of fluoride is that when the fluoride is ingested it slows the rate of tooth enamel demineralization and increases the rate of remineralization. This process reduces the incidence of tooth cavities in the population served by fluoridated water. However, high concentrations of fluoride can be detrimental. For example, if the fluoride concentration is too high, dental fluorosis may occur. Additionally, the facility is wasting resources by the addition of too much fluoride. On the other hand, if the fluoride concentration is too low, the prevention of tooth cavities suffers. Therefore, it is desired to closely monitor the level of fluoride in drinking water to achieve a desired concentration of fluoride, and to ensure compliance with regulations. Similarly, the concentrations of other analytes within drinking water are closely monitored in order to ensure compliance within a predetermined range or to ensure that the analyte is not present at all within the drinking water. There are a number of methods to measure fluoride in drinking water. These include the SPADNS and ion selective electrode techniques. SPADNS requires the preparation of a blank sample vial, and because the chemistry involves the bleaching of a dye, differing styles of measurement may lead to inaccurate results. The ion selective technique requires the addition of an ionic strength adjustment buffer, and the equilibrium time for low levels of fluoride that are not within a linear range may be sensitive to sample movement and temperature leading to inaccurate results. Similar techniques are conventional for measuring other analytes. Article HINTERHOLZINGER FLORIAN M ET AL; "Highly sensitive and selective fluoride detection in water through fluorophore release from a metal-organic framework", SCIENTIFIC REPORTS, vol. 3, 2562, 6 September 2013, pages 1-7, DOI: 10.1038/srep02562, describes the use of a porous crystalline framework for fluoride ion sensing, where the porous crystalline framework serves as a host for a fluorescent reporter molecule, whereby the detection is based on the decomposition of the host scaffold which induces the release of the fluorescent dye molecule. Article ZHAO XUDONG ET AL: "Fluorescent molecule incorporated metal-organic framework for fluoride sensing in aqueous solution", APPLIED SURFACE SCIENCE, ELSEVIER, NL, vol. 402, 11 January 2017, pages 129-135, ISSN: 0169-4332, DOI: 10.1016/J.APSUSC.2017.01.075 describes a method according to which a fluorescent molecule was incorporated in a zirconium-based MOF. Article GUO YUEXIN ET AL: "Tuning the Luminescence of Metal-Organic Frameworks for Detection of Energetic Heterocyclic Compounds", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 136, 17 October 2014, pages 15485-15488, DOI: 10.1021/ ja508962m describes a detection method for explosives using a Mg-, Ni- or Co-MOF which is not impregnated with a photoreactive species, as the detection is based on reassembling of the released linkers TABD-COOH to form emissive aggregates due to aggregation-induced emission. BRIEF SUMMARY The present invention provides a method for measuring an ion component of an aqueous sample using a photoreactive species, comprising the steps disclosed at claim 1. The dependent claims outline advantageous ways of carrying out the method. The foregoing is a summary and thus may contain simplifications, generalizations, and omissions of detail; consequently, those skilled in the art will appreciate that the summary is illustrative only and is not intended to be in any way limiting. For a better understanding of the embodiments, together with other and further features and advantages thereof, reference is made to the following description, taken in conjunction with the accompanying drawings. The scope of the invention will be pointed out in the appended claims. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS FIG. 1 illustrates an example of computer circuitry.FIG. 2 illustrates a flow diagram of an example analyte detection and measuring system.FIG. 3 illustrates a synthesis scheme of an example of analyte detection.FIG. 4 illustrates an example raw absorbance curve of a CO2 test of Al-NH2-TPA MOF.FIG. 5 illustrates the MOF dose response curve for the same test illustrated in FIG. 4, specifically a CO2 test of Al-NH2-TPA MOF.FIG. 6 illustrates the delta absorbance of the test illustrated in FIG. 4 and FIG. 5, specifically a CO2 test of Al-NH2-TPA MOF.FIG. 7 illustrates an example fluorescent response curve of NH2-UiO-66 to CO2. DETAILED DESCRIPTION Colorimetry, Henry's law, thermal conductivity and electrochemical sensors may be utilized for analysis of carbon dioxide dissolved in aqueous solu