Patent Application
20220178892
The measurement of analytes (e.g., fluoride, borate, carbonate, mercury, etc.) 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.
One embodiment provides a method for measuring an ion component of an aqueous sample using a photoreactive species, comprising: generating a metal organic framework by combining, in a reactive solution, at least one organic linker and at least one metal; impregnating the metal organic framework with the photoreactive species; introducing the impregnated metal organic framework into an aqueous sample; and measuring an analyte 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 component dissolving at least one of: the at least one organic linker and the at least one metal, and releasing the photoreactive species.
Another embodiment provides a measurement device for measuring an ion component of an aqueous sample using a photoreactive species, comprising: at least one chamber; a processor; and a memory device that stores instructions executable by the processor to: introduce an aqueous sample into a measurement device; generate a metal organic framework by combining, in a reactive solution, at least one organic linker and at least one metal; impregnate the metal organic framework with the photoreactive species; introduce the impregnated metal organic framework into an aqueous sample; and measure an analyte 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 component dissolving at least one of: the at least one organic linker and the at least one metal, and releasing the photoreactive species.
A further embodiment provides a product for measuring an ion component of an aqueous sample using a photoreactive species, comprising: a storage device having code stored therewith, the code being executable by the processor and comprising: code that introduces an aqueous sample into a measurement device; code that generates a metal organic framework by combining, in a reactive solution, at least one organic linker and at least one metal; code that impregnates the metal organic framework with the photoreactive species; code that introduces the impregnated metal organic framework into an aqueous sample; and code that measures an analyte 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 component dissolving at least one of: the at least one organic linker and the at least one metal, and releasing the photoreactive species.
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.
It will be readily understood that the components of the embodiments, as generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations in addition to the described example embodiments. Thus, the following more detailed description of the example embodiments, as represented in the figures, is not intended to limit the scope of the embodiments, as claimed, but is merely representative of example embodiments.
Reference throughout this specification to “one embodiment” or “an embodiment” (or the like) means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearance of the phrases “in one embodiment” or “in an embodiment” or the like in various places throughout this specification are not necessarily all referring to the same embodiment.
Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments. One skilled in the relevant art will recognize, however, that the various embodiments can be practiced without one or more of the specific details, or with other methods, components, materials, et cetera. In other instances, well known structures, materials, or operations are not shown or described in detail to avoid obfuscation.
Colorimetry, Henry's law, thermal conductivity and electrochemical sensors may be utilized for analysis of carbon dioxide dissolved in aqueous solutions. Electrochemical sensors may employ a carbon dioxide permeable membrane, that selectively allows carbon dioxide to enter the sensor. In the sensor, a constant voltage may be applied between anode and cathode, and the observed current is proportional to the partial pressure of carbon dioxide. In aqueous solutions, carbon dioxide may exist as an equilibrium between dissolved carbon dioxide, carbonic acid, carbonate anions and bicarbonate anions, whose relative concentrations may be calculated as a function of pH and temperature. Colorimetric methods may rely on the color change of an acid-base indicator molecule such as thymol blue in basic solution, in which carbon dioxide dissolves and forms carbonic acid that dissociates to decrease the pH, resulting in a color change. Henry's law describes the equilibrium between the concentration of a dissolved species and the partial pressure of that species in the gas phase by employing a characteristic Henry's constant, at a certain temperature. This thermodynamic relationship may be utilized by measuring the differential temperature and pressure of the gas above a given liquid solution with a known volume of headspace, from which the amount of dissolved carbon dioxide may be calculated. In another method that utilizes thermal conductivity, the dissolved carbon dioxide may be liberated into the headspace by acidifying the sample, and the thermal conductivity of the gas may be measured to yield the partial pressure of carbon dioxide, leading to quantifying the absolute amount of carbon dioxide present. Colorimetric and fluoride ion selective electrode methods are commonly used to measure fluoride levels. A common colorimetric method uses sulfanilic acid azochromotrope, 1,8-Dihydroxy-2-(4-sulfophenylazo)naphthalene-3,6-disulfonic acid trisodium salt, 2-(4-Sulfophenylazo)-1,8-dihydroxy-3,6-naphthalene disulfonic acid trisodium salt, 2-(4-Sulfophenylazo)chromotropic acid trisodium salt, or sodium 1-(parasulphophenylazo)-1,8-dihydroxy-3,6-naphthalene disulfate. These colorimetric methods are based upon the reaction between fluoride and a dark red zirconium dye to form a colorless complex anion. These methods result in a bleaching of the red color in an amount proportional to the fluoride concentration. For example, higher fluoride concentrations react with more of the zirconium-dye complex and the solution turns a lighter color. The resulting color from the colorimetric reaction may be determined photometrically, for example, using a spectrophotometer. The amount of fluoride may be determined by comparison to a similarly prepared blank vial. The absorbance of the sample reacted vial must be compared to the absorbance of the unreacted blank vial to determine the fluoride concentration of the sample reacted vial. Similar techniques, specifically the use of bleaching chemistries and comparison against blanks, are used for measuring other analytes (e.g., carbonate, mercury, borate, etc.).
However, the current analyte testing methods have limitations which are overcome by the methods and techniques as described in more detail herein. One limitation of the current techniques is that they use a bleaching chemistry not favorable to some uses and measurement systems. Additionally, the traditional colorimetric methods require the preparation of a separate “blank” vial. The extra step of preparing a blank vial can introduce error to the measurement based upon individual human techniques in preparing the blank. Also, since the traditional colorimetric technique involves the bleaching of a dye, the time for preparation and time a measurement is taken, can introduce variability in the sample reading. Additionally, because the techniques include bleaching of a dye, difficulty may arise because there may not be the same volume of starting colorimetric dye in both the blank and sample vial, thereby introducing error into the determination of the amount of analyte found in the sample. This error may result in a false positive or false negative result.
The ion selective electrode may also have disadvantages. The ion selective electrode requires the addition of an ionic strength adjustment buffer. Measurements may be affected by the omission or addition of this buffer and it requires an additional preparation step. Also, the equilibrium time for low parts per billion (ppb) levels of fluoride and other analytes is long and sensitive to both sample movement and temperature, which can in turn, lead to inaccurate results.
Accordingly, an embodiment includes generation of a metal organic framework (MOF). The MOF may be generated in a reactive solution and may contain at least one organic linker and at least one metal. In an embodiment, the MOF may be impregnated with a photoreactive species. The photoreactive species may be a dye, a chromophore, a fluorochrome, or the like. In an embodiment, there may be multiple photoreactive species used to impregnate the MOF. The impregnated MOF may be introduced into an aqueous sample. In an embodiment, an analyte component concentration of an aqueous sample may be measured. In an embodiment, the analyte component may be fluoride, borate, carbonate, mercury, or the like.
Additionally, in an embodiment a photoreactive species or linker molecule (including more than one linker molecule) may be selected based upon the analyte to be measured. The analyte may be fluoride, carbonate, borate, phosphate, mercury, sulphite, chromate, oxoanions, carbonate, or the like. Thus, the photoreactive species or linker molecule that is selected may be specific to the analyte that is being measured. The impregnated MOF may contain at least one organic linker and at least one metal. In an embodiment, a metal may be selected based upon an interaction with a linker and/or the analyte to be measured. In an embodiment, the linker may be selected such that the linker is released into a solution in the presence of an analyte. The dissociation of the MOF and release of a photoreactive species may allow the dye to come into contact with the analyte in the aqueous sample. In an embodiment, the organic linker and/or the metal may be dissolved. In an embodiment, the dye may be a colorimetric dye, a fluorescent dye, the like, or a combination of dyes.
Some current fluoride or other analyte tests use a bleaching chemistry. In other words, the color dissipates over time in the presence of fluoride or another analyte, which may or may not become colorless. The impregnated MOF disclosed herein starts with a solution that does not exhibit a significant absorbance or fluorescence at the desired measurement wavelength. The absorbance or fluorescence at the desired measurement wavelength, or over a certain wavelength range, increases when fluoride is present in solution. Thus, the impregnated MOF discussed herein does not require the measurement of a “loss of color” or “loss of fluorescence” as in the bleaching chemistries and also does not require the preparation of a “blank”, thereby providing a system that provides more accurate measurements of the analyte than conventional systems.
An embodiment in which the solution turns from colorless to exhibiting a color, or non-emitting to exhibiting fluorescence, has advantages. Accordingly, an embodiment is able to get an initial measurement because the measurement is colorless or does not exhibit a significant absorbance or fluorescence at the desired measurement wavelength, thereby eliminating the need for a “blank”. During the reaction, the sample turns a color or emits fluorescent light which can then be measured. In other words, an embodiment goes from colorless to some degree of color, for example, colorless to pink to red over time, thereby allowing for more accurate measurements than attempting to measure a colored sample going to a less colored sample as in the bleaching chemistries. In another embodiment, a sample that does not fluoresce may begin to emit blue fluorescent light upon excitation with a lower wavelength of light, thereby allowing for more accurate measurements than attempting to measure a brightly fluorescent sample going to a less fluorescent sample as in the bleaching chemistries. Further embodiments include the possibility of absorbing or emitting other colors such as yellow, green, or any other color measurable by laboratory apparatus. The absorbance can be translated to the concentration of fluoride, carbonate, or other target analyte in solution. In an embodiment, this relationship is 1:1 between the absorbance and a type of analyte to be measured, however the absorbance or fluorescence may be different for other photoreactive species. Therefore, the techniques and methods as described herein may be used with current technologies.
The illustrated example embodiments will be best understood by reference to the figures. The following description is intended only by way of example, and simply illustrates certain example embodiments.
While various other circuits, circuitry or components may be utilized in information handling devices, with regard to an instrument for analyte measurement according to any one of the various embodiments described herein, an example is illustrated in
There are power management chip(s) 103, e.g., a battery management unit, BMU, which manage power as supplied, for example, via a rechargeable battery 104, which may be recharged by a connection to a power source (not shown). In at least one design, a single chip, such as 101, is used to supply BIOS like functionality and DRAM memory.
System 100 typically includes one or more of a WWAN transceiver 105 and a WLAN transceiver 106 for connecting to various networks, such as telecommunications networks and wireless Internet devices, e.g., access points. Additionally, devices 102 are commonly included, e.g., a transmit and receive antenna, oscillators, RF amplifiers, PLLs, etc. System 100 includes input/output devices 107 for data input and display/rendering (e.g., a computing location located away from the single beam system that is easily accessible by a user). System 100 also typically includes various memory devices, for example flash memory 108 and SDRAM 109.
It can be appreciated from the foregoing that electronic components of one or more systems or devices may include, but are not limited to, at least one processing unit, a memory, and a communication bus or communication means that couples various components including the memory to the processing unit(s). A system or device may include or have access to a variety of device readable media. System memory may include device readable storage media in the form of volatile and/or nonvolatile memory such as read only memory (ROM) and/or random access memory (RAM). By way of example, and not limitation, system memory may also include an operating system, application programs, other program modules, and program data. The disclosed system may be used in an embodiment to perform analyte measurement of an aqueous sample.
Referring now to
At 201, in an embodiment a metal organic framework (MOF) may be generated. In an embodiment, the synthesis of the MOF itself performed by standard techniques. In an embodiment, the MOF may be added in excess to the preparation technique. An exemplar method of making a purified MOF is illustrated in
In an embodiment, aluminum or zirconium metal may be used in the generation of the MOF. In an embodiment, these metals may be dissolved by fluoride, carbonate, oxoanions, or the like. In an embodiment the metal may be a metal salt. The metal salt may have as the cation aluminum (Al3+), zirconium (Zr4+), or the like. Selection of the metal may be determined based upon the analyte to be measured. In an embodiment, the linker may be selected based upon the photosensitive species to be used. Alternatively, the linkers may be selected based upon their own signal created by an analyte presence. The linker may be terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, trimesic acid, or the like. In an embodiment, the organic linker and/or the metal may be dissolved.
At 202, the MOF may be impregnated with a dye or photoreactive species. For ease of reading, the example of a dye may be described herein. A MOF may be a microporous material and soaked in a dye solution. This soaking of the MOF in a dye may be referring to as impregnating the MOF. The resulting dye and MOF product may be referred to as an impregnated MOF or a dye-impregnated MOF. The MOF may be impregnated by soaking in a dye solution overnight. Other soak times may be used to achieve proper soaking of a dye. In an embodiment, two hours may be sufficient for the impregnating step. The soaking solution may use a mechanical means such as stirring for proper impregnation of the dye into the MOF. In an embodiment, ethanol solution may be used during the soaking. After soaking, there may be a washing or rinsing step. The washing may remove excess dye. The washing may ensure that any dye present in the impregnated MOF is within the matrix or pores of the MOF. The impregnated MOF may be filtered. The impregnated MOF may be centrifuged for separation of excess dye. In an embodiment at least one cycle of washing and centrifugation may be performed. The MOF may deteriorate in the presence of an analyte, and may, therefore, release the dye into an aqueous solution.
The dye may be selected based upon metal linker and dye interaction. For example, a linker that is stable with a dye may be used to maintain the dye within the MOF until an analyte to be measured is present. The absorbance of the dye may be proportional to the analyte to be measured. In an embodiment, the measured absorbance may be dependent on the amount of dye in a MOF matrix or micropores. A MOF may be selected based upon a metal organic framework pore size as compared to a dye size. For example, a MOF may be selected such that a dye may fit inside the matrix or pores of the MOF. In an embodiment, a dye may not be chemically immobilized.
At 203, in an embodiment, an analyte may be measured using an impregnated MOF. The analyte (e.g., fluoride, oxoanions, dichromate, mercury, borate, carbonate, etc.) may be an ion in an aqueous sample. When the MOF is introduced to the aqueous sample, the analyte may bind to the metal and remove the metal from the framework to release the linkers and the dye into solution. The concentration of linker and/or photoreactive species may then be directly measured. Alternatively, the free linker and/or photoreactive species may interact with the analyte in the aqueous solution, thereby providing a colorimetric and/or fluorescent change to the aqueous sample. Thus, the colorimetric and/or fluorescent change may be detected and measured by appropriate measurement devices.
In an embodiment, the impregnated MOF may be introduced into a chamber, vessel, or the like containing an aqueous sample for analyte measurement. Alternatively, the aqueous sample may be introduced to the impregnated MOF. The combination of the aqueous sample and the impregnated MOF may occur in the same or in a different chamber in which an absorption measurement occurs. In an embodiment, pumps, valves, and piping may control and direct the flow of reagents. In an embodiment, these systems may be automated or controlled by a processor.
Additionally or alternatively at 203, in an embodiment, absorbance of a linker may be measured. Absorbance measurement of a linker may be independent or in conjunction with absorbance measurement of a dye. For example, an absorbance scan in the range of 250-800 nm may measure two distinct peaks or signal. For example, a linker may show up at 300 nm and a dye at 500 nm. In an embodiment, both the absorbance value of the linker and/or the dye may be measured. The absorbance of the linker may be proportional to the analyte to be measured. Colorimetric or fluorescent methods may be used to measure a linker's absorbance or fluorescence. In an embodiment, a fluorescent method may be more sensitive.
At 204 an analyte concentration may be determined. In an embodiment the presence of an analyte in an aqueous solution may cause a shift in the absorption of a dye. Examples of this shift in absorbance and dose response curves for various dyes, MOFs, and conditions may be illustrated in Figures attached herewith in the Appendix.
At 205, a measurement of analyte concentration may be provided. The change in absorption may be measured using a spectrophotometer. Spectrophotometry is a measurement of reflection or transmission properties of a sample measured at a wavelength. Spectrophotometry may be a quantitative measure of how much light is absorbed by a material. Additionally or alternatively, the change in fluorescence may be measured using a spectrofluorometer. Spectrofluorometry is measurement of emission and/or transmission properties of a sample measured at a wavelength. Spectrofluorometry may be a quantitative measure of how much light is emitted by a material after absorbing light. This material may be linkers or photoreactive species released from an impregnated MOF sensitive to fluoride in an aqueous sample. The absorbance or fluorescence wavelength may be in a visible or ultraviolet wavelength, as chromophores, fluorochromes, or the like may be used. The change in absorption or fluorescence may also be measured using other colorimetric or fluorometric measurement devices.
Alternatively or additionally, fluoride and/or carbonate concentration measurement may be at periodic intervals set by the user or preprogrammed frequencies in the device. Measurement of fluoride and/or carbonate by a device allows for real time data with very little human involvement in the measurement process. Cleaning of the colorimetric and/or fluorometric chamber may be required at an unspecified time interval. A programmed calibration curve may be entered into the device.
A chamber, vessel, cell, chamber, or the like may contain an aqueous sample, at least one MOF that may be impregnated with photoreactive species, and associated reagents. A device may contain one or more bottles of reagents which contain necessary reagents such as, but not limited to, at least one impregnated MOF, buffers, or any reagent that may not be premixed before the measuring process. The reagents contained in the one or more bottles may be pump fed or gravity fed. The flow of the reagents may be metered to ensure proper volume delivery to the measurement cell. The aqueous sample may be fed through a pressured inlet, a vessel, or the like. The aqueous sample may be introduced into the measurement chamber by a pump or gravity fed. The sampling device may be in series or parallel to an aqueous flow. The device may have a system to ensure proper mixing of the aqueous sample, impregnated MOF, and related reagents.
The analyte or fluoride measurement may be an output upon a device in the form of a display, printing, storage, audio, haptic feedback, or the like. Alternatively or additionally, the output may be sent to another device through wired, wireless, fiber optic, Bluetooth®, near field communication, or the like. An embodiment may use an alarm to warn of an analyte measurement or concentration outside acceptable levels. An embodiment may use a system to shut down water output or shunt water from sources with unacceptable levels of an analyte. For example, an analyte measuring device may use a relay coupled to an electrically actuated valve, or the like.
As will be appreciated by one skilled in the art, various aspects may be embodied as a system, method or device program product. Accordingly, aspects may take the form of an entirely hardware embodiment or an embodiment including software that may all generally be referred to herein as a “circuit,” “module” or “system.” Furthermore, aspects may take the form of a device program product embodied in one or more device readable medium(s) having device readable program code embodied therewith.
It should be noted that the various functions described herein may be implemented using instructions stored on a device readable storage medium such as a non-signal storage device, where the instructions are executed by a processor. In the context of this document, a storage device is not a signal and “non-transitory” includes all media except signal media.
Program code for carrying out operations may be written in any combination of one or more programming languages. The program code may execute entirely on a single device, partly on a single device, as a stand-alone software package, partly on single device and partly on another device, or entirely on the other device. In some cases, the devices may be connected through any type of connection or network, including a local area network (LAN) or a wide area network (WAN), or the connection may be made through other devices (for example, through the Internet using an Internet Service Provider), through wireless connections, e.g., near-field communication, or through a hard wire connection, such as over a USB connection.
Example embodiments are described herein with reference to the figures, which illustrate example methods, devices and products according to various example embodiments. It will be understood that the actions and functionality may be implemented at least in part by program instructions. These program instructions may be provided to a processor of a device, e.g., a hand-held measurement device such as illustrated in
It is noted that the values provided herein are to be construed to include equivalent values as indicated by use of the term “about.” The equivalent values will be evident to those having ordinary skill in the art, but at the least include values obtained by ordinary rounding of the last significant digit.
This disclosure has been presented for purposes of illustration and description but is not intended to be exhaustive or limiting. Many modifications and variations will be apparent to those of ordinary skill in the art. The example embodiments were chosen and described in order to explain principles and practical application, and to enable others of ordinary skill in the art to understand the disclosure for various embodiments with various modifications as are suited to the particular use contemplated.
Thus, although illustrative example embodiments have been described herein with reference to the accompanying figures, it is to be understood that this description is not limiting and that various other changes and modifications may be affected therein by one skilled in the art without departing from the scope or spirit of the disclosure.
This application claims priority to U.S. Provisional Application No. 62/825,472 filed on Mar. 28, 2019, entitled “NON-BLEACHING COLORIMETRIC AND FLUOROMETRIC ANALYTE DETECTION BY DEGRADATION OF SOLIDS,” which is incorporated by reference herein in its entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/025588 | 3/28/2020 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62825472 | Mar 2019 | US |
