A water-based sprayable polymer for mustard gas fluorescence detection and labeling and its preparation method

Abstract

The present invention discloses a water-based sprayable polymer for mustard gas fluorescence detection and labeling and a preparation method thereof. The preparation method comprises the following steps: taking polymer A and adding it to a solvent to dissolve it to obtain a polymer A solution, wherein 100 to 200 mL of solvent is added for every 1 g of polymer A; adding a fluorescent probe for mustard gas detection to the polymer A solution, wherein 1 to 5 mg of the fluorescent probe is added for every 15 mL of polymer A solution; then gradually adding water under stirring to precipitate the polymer A loaded with the fluorescent probe; adding the polymer A loaded with the fluorescent probe in step 1) to an aqueous solution of polymer B and stirring evenly to obtain a polymer B solution; wherein the mass concentration of polymer B in the aqueous solution of polymer B is 5 to 20 mg.mL ‑1 Each 1 mL of polymer B aqueous solution dissolves 20-100 mg of fluorescent probe-loaded compound A. This water-based polymer can fluorescently label surfaces contaminated with mustard gas and can be used to mark contaminated areas before decontamination and evaluate decontamination effectiveness.

Description

Technical Field

[0001] The present invention relates to the technical field of mustard gas surface detection marking, and in particular to a water-based sprayable polymer for mustard gas fluorescence detection and marking and a preparation method thereof. Background Art

[0002] Mustard gas (β,β'-dichlorodiethyl sulfide or 2,2'-dichlorodiethyl sulfide) is a corrosive agent that primarily destroys body cells, with skin and mucous membrane erosion as its primary toxicity. With a boiling point of 217°C, mustard gas can kill people in both liquid and gaseous forms, causing poisoning upon contact with splashed liquid droplets or surfaces contaminated with mustard gas.

[0003] Currently, there are two main types of fluorescent probes reported in the literature for mustard gas detection: one based on the spirocyclic ring opening of rhodamine or fluorescein derivatives; the other based on direct sulfanylation of fluorescent "turn-on" probes. Both types of probes share the common feature of using the sulfur element in thioketone as the reaction site for the fluorescent probe with mustard gas.

[0004] Existing fluorescent probes for mustard gas detection are typically dissolved in organic solvents for detection. These solvents can contaminate or damage surfaces contaminated with mustard gas, particularly bioactive sites, causing irreversible damage. Furthermore, existing mustard gas detection methods typically require sampling and testing, making in-situ detection impossible. Summary of the Invention

[0005] The object of the present invention is to provide a method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling, so as to solve the problem that the existing mustard gas surface contamination detection cannot be carried out in situ.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is:

[0007] A method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling comprises the following steps:

[0008] 1) dissolving polymer A in a solvent to obtain a polymer A solution, with 100-200 mL of solvent added for every 1 g of polymer A; adding a fluorescent probe for mustard gas detection to the polymer A solution, with 1-5 mg of the fluorescent probe added for every 15 mL of the polymer A solution; and then gradually adding water while stirring to precipitate the polymer A loaded with the fluorescent probe;

[0009] 2) Add the polymer A loaded with fluorescent probe in step 1) to the aqueous solution of polymer B and stir evenly to obtain the polymer B; the mass concentration of polymer B in the aqueous solution of polymer B is 5 to 20 mg.mL -1 ; Every 1 mL of polymer B aqueous solution dissolves 20 to 100 mg of polymer A loaded with fluorescent probe.

[0010] Furthermore, the polymer A is one or more of polyacrylonitrile, polystyrene, poly(vinylidene chloride-co-acrylonitrile), and polyvinyl pyrrolidone, and the polymer B is one or more of polyacrylonitrile, polystyrene, poly(vinylidene chloride-co-acrylonitrile), and polyvinyl pyrrolidone.

[0011] Furthermore, the solvent is one of N,N-dimethylformamide, ethanol, and dimethyl sulfoxide.

[0012] Furthermore, the fluorescent probe is a thioanthraquinone structure probe.

[0013] Further, the fluorescent probe is 3,6-bispiperidinyl-9H-xanthene-9-thione (DPXT), OxSM-1, OxSM-2, OxSM-3, Probe1, wherein 3,6-bis(piperidin-1-yl)-9H-xanthene-9-thione is a prior art Turn-On Fluorescent Probe for Detection of Sub-ppm Levels of a Sulfur Mustard Simulant with High Selectivity (Anal. Chem. 2018, 90, 5481, Yuanlin Zhang, Yanlin Lv, Xuefei Wang, Aidong Peng, Kaiquan Zhang, Xiaoke Jie, Jijun Huang, and Zhiyuan Tian, ​​A Turn-On Fluorescent Probe for Detection of Sub-ppm Levels of a Sulfur Mustard Simulant with High Selectivity Selectivity), OxSM-1, OxSM-2, OxSM-3, and Probe1 are four fluorescent probes disclosed in Development of a Series of Fluorescent Probes for the Early Diagnostic Imaging of Sulfur Mustard Poisoning (Wenqi Meng, Mingxue Sun, Qingqiang Xu, Jinfeng Cen, Yongbing Cao, Zhenjiang Li, Kai Xiao; ACS Sensors, 4.10 (2019): 2794-2801) in the prior art.

[0014] Furthermore, after the polymer A loaded with fluorescent probes is precipitated in step 1), it is centrifuged, washed with water, and dried to obtain powdered polymer A loaded with fluorescent probes.

[0015] Furthermore, in step 2), before adding the aqueous solution of polymer B to the polymer A loaded with fluorescent probes, the powdered polymer A loaded with fluorescent probes is first moistened with an organic solvent.

[0016] A water-based sprayable polymer for mustard gas fluorescence detection and labeling, comprising a polymer A loaded with a fluorescent probe, water, and a polymer B; the mass concentration of the polymer A loaded with the fluorescent probe is 20 to 100 mg / mL -1; Mass concentration of polymer B 5~20mg.mL -1 .

[0017] Furthermore, the polymer A is one or more of polyacrylonitrile, polystyrene, poly(vinylidene chloride-co-acrylonitrile), and polyvinyl pyrrolidone, and the polymer B is one or more of polyacrylonitrile, polystyrene, poly(vinylidene chloride-co-acrylonitrile), and polyvinyl pyrrolidone.

[0018] The application of water-based sprayable polymers for mustard gas fluorescence detection and marking to detect and mark contamination on the surface of objects.

[0019] The method of the present invention has the following advantages:

[0020] The present invention provides a method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling. The method comprises the following steps: a fluorescent probe for mustard gas detection is dissolved in a mixture of polymer A and a solvent; water is then added to precipitate the polymer A loaded with the fluorescent probe; and an aqueous solution of polymer B is then used to disperse the polymer A loaded with the fluorescent probe to form a water-based system. The prepared water-based sprayable composition for mustard gas fluorescence detection and labeling does not contain an organic solvent and has a good detection effect on mustard gas.

[0021] The water-based sprayable polymer for mustard gas fluorescence detection and labeling of the present invention can realize colorimetric and fluorescence detection of mustard gas contaminated on the surface of an object at room temperature. The water-based sprayable polymer for mustard gas fluorescence detection and labeling exhibits an orange-yellow color under fluorescent light and exhibits no fluorescence under 365nm handheld ultraviolet light. When the water-soluble polymer containing the fluorescent probe is sprayed onto a metal paint sheet coated with mustard gas using a push-type sprayer, it exhibits bright fluorescence under the handheld ultraviolet light. The water-based sprayable polymer for mustard gas fluorescence detection and labeling has no effect on the selectivity of the fluorescent probe. In particular, it can realize visual detection and labeling of the surface of an object contaminated with mustard gas under sunlight. It can be used for marking contaminated areas before decontamination and evaluating decontamination effects, and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Graph showing the fluorescence intensity of the fluorescent probe at 570 nm and the concentration of mustard gas in Example 1;

[0023] Figure 2 is the reaction rate of the fluorescent probe and mustard gas in Example 1;

[0024] Figure 3 These are the fluorescence responses at 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, and 45 minutes after spraying the water-based sprayable composition for mustard gas fluorescence detection and labeling in Example 1. DETAILED DESCRIPTION

[0025] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. However, it should be understood by those skilled in the art that the embodiments described below are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work are within the scope of protection of the present invention.

[0026] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods. Unless otherwise specified, the materials, reagents, etc. used in the following examples are all commercially available.

[0027] Example 1

[0028] The method for preparing the water-based sprayable polymer for mustard gas fluorescence detection and labeling of this embodiment includes the following steps:

[0029] 150 mg of polyacrylonitrile was weighed and added to 15 mL of N,N-dimethylformamide at 55°C with stirring until the polyacrylonitrile was completely dissolved, yielding a polyacrylonitrile solution. 3 mg of a fluorescent probe for mustard gas detection was added to the polymer solution. 150 mL of water was then added dropwise with stirring to precipitate a pale yellow precipitate. The precipitate was separated by centrifugation, washed three times with water, and freeze-dried to yield a pale yellow powder, i.e., the fluorescent probe-loaded polyacrylonitrile. The fluorescent probe used to detect mustard gas is 3,6-dipiperidinyl-9H-xanthene-9-thione (DPXT), which is disclosed in the prior art A Turn-On Fluorescent Probe for Detection of Sub-ppm Levels of a Sulfur Mustard Simulant with High Selectivity (Anal. Chem. 2018, 90, 5481, Yuanlin Zhang, Yanlin Lv, Xuefei Wang, Aidong Peng, Kaiquan Zhang, Xiaoke Jie, Jijun Huang, and Zhiyuan Tian, ​​A Turn-On Fluorescent Probe for Detection of Sub-ppm Levels of a Sulfur Mustard Simulant with High Selectivity).

[0030] 2) Take 15 mg of the powdered fluorescent probe-loaded polyacrylonitrile obtained in step 1), rinse with anhydrous ethanol, and then add 1 mL of polyvinyl pyrrolidone aqueous solution and stir evenly to obtain the obtained product; the mass concentration of polyvinyl pyrrolidone in the aqueous solution is 20 mg / mL -1 .

[0031] The water-based sprayable polymer for mustard gas fluorescence detection and marking of this embodiment is prepared by the preparation method of the water-based sprayable polymer for mustard gas fluorescence detection and marking of this embodiment.

[0032] The use of the water-based sprayable polymer for mustard gas fluorescence detection and marking to detect and mark contaminated surfaces of objects in this embodiment includes the following steps: adding the water-based sprayable polymer for mustard gas fluorescence detection and marking to a spray bottle, spraying it onto the surface of a paint flake contaminated with mustard gas, and recording the fluorescence response of the water-based sprayable polymer for mustard gas fluorescence detection and marking at 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, and 45 minutes after irradiation with a 365 nm ultraviolet lamp. Figure 3 As shown, Figure 3 1, 2, 3, 4, 5, and 6 are fluorescence response graphs obtained 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, and 45 minutes after spraying the water-based sprayable composition for mustard gas fluorescence detection and labeling, respectively. There is a significant fluorescence contrast between the contaminated area and the uncontaminated area.

[0033] Test example

[0034] Determination of the detection limit and detection rate of DPXT for mustard gas

[0035] 1. Determination of the detection limit of DPXT for mustard gas

[0036] DPXT was synthesized and the detection limit of the probe for mustard gas was tested in a solution of acetonitrile: water = 30:70 (v / v). Figure 1 As shown, the detection limit was 1.1 μM and R2 = 0.9826.

[0037] 2. Determine the detection rate of DPXT for mustard gas

[0038] The concentration of the fluorescent probe was 10 μM, the concentration of mustard gas was 100 times the equivalent, and the reaction rate of the fluorescent probe and mustard gas was detected in acetonitrile: water = 30:70 (v / v). Mustard gas was added at 300 s and the excitation wavelength was 570 nm. The results are shown in Figure 2. Figure 2 shown.

[0039] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made thereto. Therefore, such modifications and improvements, without departing from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling, characterized in that: The following steps are involved: 1) Polymer A is dissolved in a solvent to obtain a polymer A solution, with 100 to 200 mL of solvent added for every 1 g of polymer A; a fluorescent probe for detecting mustard gas is added to the polymer A solution, with 1 to 5 mg of the fluorescent probe added for every 15 mL of polymer A solution; and water is gradually added under stirring to precipitate the polymer A loaded with the fluorescent probe; the polymer A is polyacrylonitrile; the polymer B is polyvinylpyrrolidone; and the fluorescent probe is 3,6-bispiperidinyl-9H-xanthene-9-thione; 2) Add the polymer A loaded with the fluorescent probe in step 1) to the aqueous solution of polymer B and stir evenly to obtain the polymer B; the mass concentration of polymer B in the aqueous solution of polymer B is 5 to 20 mg. mL -1 ; Dissolve 20-100 mg of polymer A loaded with fluorescent probe in every 1 mL of polymer B aqueous solution.

2. The method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling according to claim 1, characterized in that: The solvent is N,N-dimethylformamide.

3. The method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling according to claim 1, characterized in that: In step 1), after the polymer A loaded with the fluorescent probe is precipitated, it is centrifuged and washed with water to obtain a powdered polymer A loaded with the fluorescent probe.

4. The method for preparing a water-based sprayable polymer for mustard gas fluorescence detection and labeling according to claim 3, characterized in that: In step 2), before adding the aqueous solution of polymer B to the polymer A loaded with fluorescent probes, the powdered polymer A loaded with fluorescent probes is first wetted.

5. The water-based sprayable polymer for mustard gas fluorescence detection and labeling prepared by the preparation method of claim 1, characterized in that: The method comprises polymer A loaded with a fluorescent probe, water, and polymer B; the mass concentration of polymer A loaded with a fluorescent probe is 20 to 100 mg / mL. -1 ; Mass concentration of polymer B 5~20 mg. mL -1 .

6. Use of the water-based sprayable polymer according to claim 5 for mustard gas fluorescence detection and labeling.

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