Composite fluorine ion sensing device

Abstract

The utility model discloses a combined type fluorine ion sensing device which comprises a laser beam emitting light source, a collimating lens is arranged on the side face of the laser beam emitting light source, and the emitting path of the laser beam emitting light source is arranged right opposite to the input end of the collimating lens, so that laser beams emitted by the laser beam emitting light source can enter the collimating lens smoothly and accurately. The end part of the collimating lens is connected with an evanescent wave optical fiber spherical sensor through a transmission optical fiber, and a shell of the transmission optical fiber is connected with composite detection test paper through a wire. According to the device, the functions of high fluorine ion selectivity, short detection time, high accuracy and low cost are realized.

Description

Technical Field

[0001] The utility model relates to the technical field of ion detection, and specifically to a composite fluorine ion sensor device. Background Art

[0002] Water pollution poses a significant threat to both the environment and human health, with fluoride pollution being a widespread problem. Fluoride is an important and essential element for human health and social development. An appropriate amount of fluoride ions in drinking water is believed to help reduce tooth decay. However, when the fluoride ion concentration exceeds the WHO drinking water safety value of 1.5 ppm, excessive fluoride can lead to bone and thyroid dysfunction, causing irreversible damage to the human body or even death. Therefore, it is particularly important to develop highly sensitive and selective fluoride ion sensors with qualitative and quantitative detection capabilities.

[0003] Commonly used technologies for detecting fluoride ion concentration in water include ion-selective electrodes, chemical colorimetry, spectrophotometry, etc. Among them, chemical colorimetry and optical sensing technology have become common technologies for detecting and analyzing various pollutants in water in recent years. In recent years, coumarin has been widely used in the preparation of chemical sensors due to its good biocompatibility and significant structural flexibility. The C=C bond fixed in the cis conformation helps to prevent the trans-cis transition in vinyl compounds, thereby making coumarin have good photostability. Since some coumarin derivatives have weak fluorescent groups, the quenching effect is suppressed in the quenching process such as photoinduced electron transfer and isomerization, and the fluorescence is restored after interaction with the analyte.

[0004] The advantages of fiber optic sensors include simple operation and the ability to detect various pollutants such as microbial agents, organic pollutants and heavy metals. In recent years, different researchers have improved the structure of sensors to improve the accuracy of optical sensors. These modified structural shapes include S-shaped, U-shaped and conical structures. Among them, U-shaped probe sensors have been shown to be 10 times more sensitive than straight sensors. U-shaped sensors have received widespread attention due to their sensitivity and reliability. Compared with other geometric shapes, other advantages of U-shaped probes are their simpler manufacturing process, longer active area, robustness and repeatability.

[0005] Nowadays, chemical and optical fluoride ion detection sensor technologies still have the following defects: the sensor is not very selective for fluoride ions, the sensor detection reaction time is long, the fluoride ion concentration detection accuracy is low, and the sensor preparation cost is high and the operation is complicated.

[0006] Therefore, the problem that the inventors want to solve is to design a device with strong selectivity for fluoride ions, short detection time, high accuracy and low cost. Utility Model Content

[0007] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a composite fluoride ion sensor device that can achieve the functions of strong selectivity for fluoride ions, short detection time, high accuracy and low cost.

[0008] The technical solution adopted by the device of the present utility model is: a composite fluoride ion sensing device, which includes a laser beam emitting light source, a collimating lens is arranged on the side of the laser beam emitting light source, the end of the collimating lens is connected to an evanescent wave fiber optic spherical sensor via a transmission optical fiber, and the outer shell of the transmission optical fiber is connected to a composite detection test paper via a wire, the evanescent wave fiber optic spherical sensor is connected to a signal receiver via the transmission optical fiber, the signal receiver is connected to a data processor via a data cable, and the data processor is connected to a computer via a data cable.

[0009] Furthermore, a liquid container is provided outside the composite test paper and the evanescent wave optical fiber spherical sensor. The circumferential surface of the liquid container is provided with a scale and the liquid container is transparent.

[0010] Furthermore, the composite test paper is a coumarin-pyrazole composite test paper, and the coumarin-pyrazole composite test paper comprises glass fiber paper, and the coumarin-pyrazole complex is attached to the surface of the glass fiber paper.

[0011] Furthermore, the size of the composite test paper is 50 mm×20 mm.

[0012] Furthermore, the evanescent wave optical fiber spherical sensor is an evanescent wave optical fiber spherical sensor.

[0013] Furthermore, the emission path of the laser beam emitting light source is arranged directly facing the input end of the collimating lens.

[0014] Furthermore, a color chart is also included.

[0015] Furthermore, a fluoride ion solution is provided inside the liquid container, and the composite detection test paper and the evanescent wave optical fiber spherical sensor are in contact with the fluoride ion solution.

[0016] The beneficial effects of the device of the utility model are:

[0017] 1. The utility model adopts the composite detection test paper and the evanescent wave optical fiber spherical sensor to detect the liquid containing fluoride ions at the same time, achieving the functions of strong selectivity for fluoride ions, short detection time, high accuracy and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic structural diagram of the utility model.

[0019] Figure 2 This is a test result curve of the evanescent wave optical fiber spherical sensor of the utility model.

[0020] Figure 3 It is a histogram of the fluorescence intensity test results of the coumarin-pyrazole complex of the utility model in acetonitrile solution.

[0021] Explanation of the accompanying symbols: 1-laser beam emitting light source; 2-collimating lens; 3-transmission optical fiber; 4-composite detection test paper; 5-evanescent wave optical fiber spherical sensor; 6-signal receiver; 7-data processor; 8-computer. DETAILED DESCRIPTION

[0022] The present invention will be further described below with reference to specific embodiments. These embodiments are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. It should also be understood that after reading the teachings of the present invention, those skilled in the art may make various changes or modifications to the present invention, and that these equivalent forms also fall within the scope defined by the appended claims.

[0023] See also Figure 1 This is a schematic diagram of the structure of the utility model, a composite fluoride ion sensing device, which includes a laser beam emitting light source 1, a collimating lens 2 is arranged on the side of the laser beam emitting light source 1, and the emission path of the laser beam emitting light source 1 is arranged opposite to the input end of the collimating lens 2, so that the laser beam emitted by the laser beam emitting light source 1 can enter the collimating lens 2 smoothly and accurately, the end of the collimating lens 2 is connected to the evanescent wave fiber optic spherical sensor 5 through the transmission optical fiber 3, and the outer shell of the transmission optical fiber 3 is connected to the composite detection paper 4 through a line, the light passing through the collimating lens 2 passes through the evanescent wave fiber optic spherical sensor 5, and then the evanescent wave fiber optic spherical sensor 5 is connected to the signal receiver 6 through the transmission optical fiber 3. In this process, the evanescent wave fiber optic spherical sensor 5 collects data, and after transmitting the data signal to the signal receiver 6, the signal receiver 6 is connected to the data processor 7 through the data line and transmits the data to the data processor 7, which is processed by the data processor 7 and finally transmitted to the connected computer 8 through the data line by the data processor 7 and displayed on the computer 8.

[0024] A liquid container is provided on the outside of the composite test paper 4 and the evanescent wave optical fiber spherical sensor 5. A scale is provided on the circumferential surface of the liquid container and the liquid container is transparent. A fluoride ion solution is provided on the inside of the liquid container. The composite test paper 4 and the evanescent wave optical fiber spherical sensor 5 are in contact with the fluoride ion solution. A color comparison card is also included. By comparing the color on the composite test paper 4 with the color card, an initial judgment is made as to whether fluoride ions are contained.

[0025] The composite test paper 4 is a coumarin-pyrazole composite test paper 4 , which comprises glass fiber paper with a coumarin-pyrazole complex attached to the surface of the glass fiber paper. The size of the composite test paper 4 is 50 mm×20 mm.

[0026] The evanescent wave optical fiber spherical sensor 5 is an evanescent wave optical fiber spherical sensor 5 .

[0027] Method for preparing coumarin-pyrazole composite test paper 4: using Vilsmeier-Haack reaction, 3-methylcoumarin is reacted with dimethylformamide and phosphorus oxychloride at 110 ° C for 20 hours, so that a formylation reaction occurs on the aromatic ring of coumarin to attach an aldehyde group, 3 mol of N (4) -pyrrolidine thiosemicarbazide is added to the product, and the mixture is dissolved in 40 mL of ethanol, and then 5 drops of acetic acid are added to the mixed solution and refluxed at 80 ° C for 10 hours. Finally, the reaction mixture is evaporated and the separated product is the coumarin-pyrazole complex. Take glass fiber paper, cut it into 50 mmX20 mm size, and place it on 1×10 -3 mol / L coumarin-pyrazole complex solution for 3 h, and then dried in air to obtain coumarin-pyrazole composite detection test paper 4.

[0028] Method for preparing evanescent wave optical fiber spherical sensor 5: A sensor probe is developed using multimode OMPF1000 polymer optical fiber, the optical fiber is heated at 90°C to 100°C, subjected to force and prepared into the desired shape, and the cladding in the sensor probe area is removed.

[0029] When the utility model detects the fluoride ion content of the aqueous solution to be tested, the coumarin-pyrazole composite test paper 4 first contacts the aqueous solution to be tested, and through the color reaction, quickly and qualitatively determines whether fluoride ions exist in the water. Subsequently, the colorimetric card obtained in the test can be used to preliminarily determine the fluoride ion concentration range.

[0030] After the coumarin-pyrazole composite test paper 4 qualitatively determines whether there is fluoride ion and its concentration, if further determination of the fluoride ion concentration is required, further detection is performed using the evanescent wave optical fiber spherical sensor 5 .

[0031] The fluoride ion concentration is detected by the evanescent wave fiber optic spherical sensor 5. First, a laser beam is emitted from a light source. After being focused by a collimating lens 2, the laser beam is transmitted through an optical fiber to the evanescent wave fiber optic spherical sensor 5 in contact with the sample solution. After part of the light is absorbed by the solution, the remaining light is captured by the signal receiver 6 on the other side of the optical fiber and the detection data is fed back. The obtained data is processed by a data processor 7 and the detection result is fed back.

[0032] The coumarin-pyrazole composite test paper 4 makes a quick qualitative judgment, and the evanescent wave optical fiber spherical sensor 5 accurately detects the concentration of fluoride ions. After the detection is completed, the evanescent wave optical fiber spherical sensor 5 needs to be washed with distilled water and dried with propanol before it can be reused.

[0033] Example 1: See Figure 2 This graph shows the test results of the evanescent wave fiber optic spherical sensor 5. To prepare the sample solution, dry sodium fluoride was dissolved in 1L of deionized water to create a 1000ppm fluoride ion stock solution. This stock solution was then diluted with deionized water to prepare standard fluoride ion solutions with concentrations of 1ppm, 2ppm, 3ppm, 4ppm, and 5ppm.

[0034] To fabricate an evanescent wave fiber spherical sensor 5, a sensor probe was developed using multimode OMPF1000 polymer optical fiber. The optical fiber was heated at 90°C to 100°C and subjected to force to form the desired spherical shape. The cladding in the sensor probe region was removed.

[0035] The test results curve of the utility model, the traditional conical sensor, the UV-visible spectrophotometer and the prepared sample solutions with different fluoride ion concentrations show the direct relationship between the absorption of light and the concentration of the fluoride solution, which shows that the sensitivity of the spherical sensor is improved compared with the traditional sensor.

[0036] Example 2: Preparation of a coumarin-pyrazole complex. 3-Methylcoumarin was reacted with dimethylformamide and phosphorus oxychloride at 110°C for 20 hours using the Vilsmeier-Haack reaction, resulting in a formylation reaction on the aromatic ring of the coumarin, thereby attaching an aldehyde group. To the resulting product was added 3 mol of N(4)-pyrrolidinethiosemicarbazide, and the mixture was dissolved in 40 mL of ethanol. Five drops of acetic acid were then added to the mixed solution, which was then refluxed at 80°C for 10 hours. Finally, the reaction mixture was evaporated, and the resulting product, the coumarin-pyrazole complex, was isolated.

[0037] Fluorescence emission spectroscopy was used to detect the interaction strength between the coumarin-pyrazole complex and various anions in acetonitrile solution. The excitation wavelength was selected to be 372 nm based on the absorption wavelength of the sensor. The selected comparison anions included F − ,CN − ,Cl − ,Br − ,I − ,ClO4 − and OH − .

[0038] See also Figure 3 This is a bar graph showing the fluorescence intensity test results of the coumarin-pyrazole complex of the present invention in acetonitrile solution. When fluoride ions are added to the coumarin-pyrazole complex, fluorescence amplification is performed at 492 nm, while other anions fail to produce any significant fluorescence spectrum changes.

[0039] The above results indicate that the coumarin-pyrazole complex is selective for fluoride ions when reacting with common anions in aqueous solution, and has the advantages of accuracy and rapidity in qualitatively measuring the presence and concentration range of fluoride ions in water.

[0040] The utility model adopts the composite detection test paper 4 and the evanescent wave optical fiber spherical sensor 5 to simultaneously detect the liquid containing fluoride ions, thereby achieving the functions of strong selectivity for fluoride ions, short detection time, high accuracy and low cost.

Claims

1. A composite fluoride ion sensor device, characterized in that: The invention comprises a laser beam emitting light source (1), a collimating lens (2) is provided on the side of the laser beam emitting light source (1), an end of the collimating lens (2) is connected to an evanescent wave optical fiber spherical sensor (5) via a transmission optical fiber (3), and the outer shell of the transmission optical fiber (3) is connected to a composite detection test paper (4) via a wire, the evanescent wave optical fiber spherical sensor (5) is connected to a signal receiver (6) via the transmission optical fiber (3), the signal receiver (6) is connected to a data processor (7) via a data line, and the data processor (7) is connected to a computer (8) via a data line.

2. A composite fluoride ion sensor device according to claim 1, characterized in that: A liquid container is provided outside the composite test paper (4) and the evanescent wave optical fiber spherical sensor (5); a scale is provided on the circumferential surface of the liquid container, and the liquid container is transparent.

3. The composite fluoride ion sensor device according to claim 1, characterized in that: The composite test paper (4) is a coumarin-pyrazole composite test paper (4), and the coumarin-pyrazole composite test paper (4) comprises glass fiber paper, and the coumarin-pyrazole complex is attached to the surface of the glass fiber paper.

4. A composite fluoride ion sensor device according to claim 3, characterized in that: The size of the composite test paper (4) is 50 mm×20 mm.

5. The composite fluoride ion sensor device according to claim 1, characterized in that: The evanescent wave optical fiber spherical sensor (5) is an evanescent wave optical fiber spherical sensor (5).

6. The composite fluoride ion sensor device according to claim 1, characterized in that: The emission path of the laser beam emitting light source (1) is arranged directly opposite to the input end of the collimating lens (2).

7. The composite fluoride ion sensor device according to claim 1, characterized in that: Also includes a color chart.

8. The composite fluoride ion sensor device according to claim 2, characterized in that: A fluoride ion solution is provided inside the liquid container, and the composite detection test paper (4) and the evanescent wave optical fiber spherical sensor (5) are in contact with the fluoride ion solution.

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