CN113336728B - Carbon monoxide fluorescent micelle probe and application - Google Patents

Carbon monoxide fluorescent micelle probe and application Download PDF

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CN113336728B
CN113336728B CN202110390194.0A CN202110390194A CN113336728B CN 113336728 B CN113336728 B CN 113336728B CN 202110390194 A CN202110390194 A CN 202110390194A CN 113336728 B CN113336728 B CN 113336728B
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肖鹏
陶风波
刘建军
郭东亮
杨立恒
袁光宇
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Electric Power Research Institute of State Grid Jiangsu Electric Power Co Ltd
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Abstract

A carbon monoxide fluorescent micelle probe and application thereof belong to the research field of preparation process of carbon monoxide detection test paper. According to the carbon monoxide fluorescent micelle probe, probe molecules are placed in the micelle, positive charges on the surface of the cationic micelle can be mutually repelled, so that the cationic micelle can be favorably dispersed on test paper, the cross-linked micelle provides a stable probe molecule environment, and the probe molecule environment cannot be changed after the cross-linked micelle is contacted with a carrier. The carbon monoxide has higher solubility in the fluoro-solvent compared with other solvents, and the carbon monoxide probe in the fluoro-micelle has higher detection sensitivity. The fluorescent micelle probe can be used for safety early warning of the lithium ion battery, has the advantage of high sensitivity provided by the colorimetric fluorescent probe, and provides a reliable method for quick early warning of the battery.

Description

Carbon monoxide fluorescent micelle probe and application
Technical Field
The invention relates to a carbon monoxide fluorescent micelle probe and application thereof, belonging to the field of research on preparation processes of carbon monoxide detection test paper.
Background
The electrochemical energy storage technology represented by the lithium ion battery has the advantages of high energy density, long cycle life, environmental protection and the like, and has multiple functions of peak regulation, frequency modulation, standby, black start, emergency and the like in a power grid. In recent years, the installed capacity of a power grid side energy storage system is increased year by year, and energy storage is one of important technologies for promoting the development of a future smart power grid. As an electrochemical device with high energy density, the operation state of a lithium ion battery has important influence on the safety and stability of power grid equipment. Therefore, the method has great significance for the development and application of large-scale energy storage systems by effectively monitoring the state of the lithium ion battery.
Currently, the electrolyte mainly used in the lithium ion battery is ethylene carbonate or dimethyl carbonate. In the initial stage of thermal runaway of a battery, an organic electrolyte is decomposed inside the battery to generate carbon monoxide (CO) gas (other gases such as nitric oxide and hydrogen sulfide are also generated at the same time), and the organic electrolyte can diffuse into the environment before a battery safety valve is opened. Therefore, the characteristic gases such as CO and the like are monitored in real time, an early warning signal can be sent out at the first time when the battery is abnormal, corresponding measures are taken, and the safe operation of a battery system is ensured.
At present, classical detection methods exist for CO, such as a methylene spectrophotometer method, a gas chromatography method, a liquid chromatography method and the like for CO, wherein the gas chromatography method is the most conventional detection method, however, the method has complicated operation steps and cannot realize real-time synchronous detection. Commercial electrochemical gas sensors have low detection limit and are available in commercial portable equipment, but the problems of large influence of humidity, poor selectivity, long response time and the like exist in the practical application process. In recent years, a catalytic luminescence technology using a luminescence phenomenon generated when a solid material is catalytically oxidized by gas molecules as a raw material has the advantages of quick response, good selectivity, no influence of humidity and the like, makes up for the defects of an electrochemical gas sensor, but has high sensing temperature and poor catalyst temperature. Many inventions and patents of electric quantity type gas sensors (CN 201811131211.3; CN 201811036417.8; CN 201711248169.9; CN 201711045582.5; CN 201710575099.1; CN 201780038652.6) represented by impedance type gas sensors and electrochemical gas sensors are concentrated in solid electrolytes, and the problems of large humidity influence, poor selectivity, long response time and the like are still not solved. The optical gas sensor includes a spectral absorption type and a fluorescence type. The spectrum type comprises an infrared absorption type and an ultraviolet absorption type, and is realized by the intrinsic absorption of gas molecules in principle, for example, CO has absorption peaks at 4.65 mu m in a middle and far infrared region (2.5-1000 mu m) and 1567 nm in a near infrared region (0.76-2.5 mu m). In the middle and far infrared region, the absorption of CO is mainly fundamental frequency absorption, and the absorption at the position of 4.65 mu m is particularly strong, which is shown as a strong absorption peak on an infrared absorption spectrogram, but is easily interfered by the outside, brings great uncertainty to a measurement result, and has higher requirement on a light source; CO in a near infrared region is mainly frequency doubling absorption, and the absorption is weak. The method has the disadvantages of difficult miniaturization of instruments, great difficulty in developing handheld detectors and poor interference resistance. (Sens. activators, B: chem.2013, 184, 33; Sens. activators, B: chem.2008, 131, 306; Inorg. chem.2013, 52, 5924; Appl. Phys. Lett. 2011, 98, 223504)
The fluorescence method has the advantages of high sensitivity, high selectivity, simple and convenient operation, real-time imaging and the like, and is one of the most important methods in the current analysis method. Patent CN 110229105 a reports a CO gas molecular probe with chemical name 3-nitro-N- (2-aminoethyl) -4-methylphenyl-1-sulfonamide naphthalimide for detecting carbon monoxide in solution, cells or organisms, whose organelle localization groups allow the molecular probe to accumulate on the endoplasmic reticulum; patent CN 108864029A reports a high-sensitivity carbon monoxide colorimetric fluorescent probe, which is allyl carbonate compound and needs additional Pd2+Catalyzing the reaction of the probe CO and the probe molecule by the ions; patent CN 108467364A reports a rapid high-selectivity carbon monoxide ratio type fluorescent probe, which adopts allyl ether compound as probe and also needs Pd2+Can realize the detection of CO; patent CN 108558801A reports a long-wavelength ultrasensitive carbon monoxide colorimetric fluorescent probe, which is a cyanine compound; nile red and Pd are reported in patent CN 107141319B2+The fluorescence of the novel probe formed by ion complexation is very weak, the solution obtained by adding water or an organic solvent is blue, after the novel probe reacts with carbon monoxide, the color of the solution becomes light, and the fluorescence intensity at 657 nm is gradually enhanced, but the metal complex type molecules reported above have the problems of complex synthesis, low molecular stability and the like. In conclusion, the patents are all focused on the field of biomolecule probes, have application values on tumor molecule and cell biological imaging, but have no related patent report on the application purpose of safety early warning of a battery stack.
Disclosure of Invention
The invention aims to provide a carbon monoxide fluorescent micelle probe for safety early warning of a lithium ion battery, and develops a molecular probe system and a method for CO applied to safety early warning of the lithium ion battery, so that CO can be quickly detected at the initial stage of thermal runaway of the battery, and potential safety hazards caused by untimely treatment are avoided.
In order to achieve the purpose, the invention adopts the technical scheme that: a carbon monoxide fluorescent micelle probe adopts a nano micelle structure with a fluorescent probe inside and a micelle monomer outside;
the fluorescent probe has the following structural general formula:
Figure 100002_DEST_PATH_IMAGE002
wherein: r1、R2、R3、R4、R5Each independently selected from one of a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a sulfonic acid group, an ester group and a hydroxyl group;
the micelle monomer is cetyl trimethyl ammonium bromide, dodecyl tripropyl alkynyl ammonium bromide or fluoro dodecyl tripropyl alkynyl ammonium bromide.
When the micelle monomer is dodecyl tripropylene ammonium bromide or fluoro dodecyl tripropylene ammonium bromide, the outer layer of the micelle monomer of the fluorescent micelle probe is crosslinked by a crosslinking agent to form a crosslinked nano micelle;
the cross-linking agent has the following structural general formula:
Figure 100002_DEST_PATH_IMAGE004
wherein R is6Is composed of
Figure DEST_PATH_IMAGE006
Or
Figure DEST_PATH_IMAGE008
N is each independently an integer of 0 to 12, R7Each independently is
Figure DEST_PATH_IMAGE010
Or
Figure DEST_PATH_IMAGE012
。
The invention selects an organic micromolecule probe with strong economic applicability as a colorimetric type fluorescent probe molecule, selects filter paper or a polymer film as a probe carrier, and selects a nano micelle as a contact medium of the probe molecule and the carrier.
The molecular probe has a molecular environment different from that in the solution when being loaded on fiber test paper, a polymer film or silica gel, and the reaction efficiency of molecules loaded on the test paper or silica gel and a substance to be detected is different from that in the solution caused by solvent volatilization. Cetyl trimethyl ammonium bromide, dodecyl tripropylene ammonium bromide or fluoro dodecyl tripropylene ammonium bromide are used as micelle molecule monomers, and the coated probe molecules form the fluorescent micelle probe with a nano micelle structure, wherein a common micelle system is formed when the cetyl trimethyl ammonium bromide is used as the micelle monomer, a common micelle system can be formed when the dodecyl tripropylene ammonium bromide or the fluoro dodecyl tripropylene ammonium bromide is used as the micelle monomer, and cross-linked micelles can be formed, and the structures of the three micelle monomers are as follows:
Figure DEST_PATH_IMAGE014
when dodecyl tripropyl alkynyl ammonium bromide or fluoro dodecyl tripropyl alkynyl ammonium bromide is used as a micelle monomer to form a cross-linked micelle structure, a cross-linking agent containing double azido groups is used to realize micelle molecule cross-linking by using copper-catalyzed azide-alkynyl Husige cycloaddition reaction.
The carbon monoxide colorimetric fluorescent probe adopted by the invention is a cyanine compound. Preferably, the colorimetric fluorescent probe of the present invention is:
Figure DEST_PATH_IMAGE016
the invention provides two methods for preparing a carbon monoxide colorimetric fluorescent probe into a fluorescent micelle probe with a nano micelle structure. The method comprises the steps of preparing a fluorescent micelle probe with a common nano micelle structure by using the preferred probe and cetyl trimethyl ammonium bromide, dodecyl tripropyl alkynyl ammonium bromide or fluoro dodecyl tripropyl alkynyl ammonium bromide, and preparing a fluorescent micelle probe with a cross-linked nano micelle structure by using the preferred probe, the dodecyl tripropyl alkynyl ammonium bromide or fluoro dodecyl tripropyl alkynyl ammonium bromide and a cross-linking reagent.
The invention also provides a method for detecting the concentration of carbon monoxide in a sample, which comprises the step of contacting the fluorescent micelle probe with a sample to be detected.
The carbon monoxide fluorescent micelle probe provided by the invention acts with carbon monoxide to generate changes of fluorescence spectrum and color, so that the quantitative detection of carbon monoxide is realized.
The preparation method of the carbon monoxide colorimetric fluorescent probe comprises the following steps:
1) a process for the preparation of the precursor of a molecular probe, i.e. 2- (3-cyano-4, 5, 5-trimethylfuran-2 (5H) -methylene) malononitrile:
Figure DEST_PATH_IMAGE018
a) adding 3-hydroxy-3-methyl-2-butanone and malononitrile into an ethanol solution, and then adding sodium ethoxide, wherein the ratio of the 3-hydroxy-3-methyl-2-butanone to the malononitrile is 0.4-0.5, and the ratio of the 3-hydroxy-3-methyl-2-butanone to the sodium ethoxide is 5-6.5. Heating and stirring to react at 60-70 deg.c for 1-5 hr until the reactant is consumed completely.
b) And (3) separating and purifying the product: after cooling the reaction solution, a solid was separated by filtration. To increase the reaction yield, the filtrate may be concentrated to half the volume and then re-filtered.
2) The preparation method of the carbon monoxide colorimetric fluorescent probe, namely the cyanine fluorescent probe in the claims comprises the following steps:
Figure DEST_PATH_IMAGE020
a) dissolving 2- (3-cyano-4, 5, 5-trimethyl furan-2 (5H) -methylene) malononitrile and 4-nitrobenzophenone compounds in ethanol, adding a catalytic amount of piperazine, and heating for reaction until reactants are completely consumed. The ratio of 2- (3-cyano-4, 5, 5-trimethylfuran-2 (5H) -methylene) malononitrile to 4-nitrobenzophenones is between 0.9 and 1. The ratio of 2- (3-cyano-4, 5, 5-trimethylfuran-2 (5H) -methylene) malononitrile to piperazine is between 100 and 200. The reaction temperature is 25-60 deg.C, and the reaction time is 8-12 hr.
b) And (3) separating and purifying products: the reaction mixture was evaporated under reduced pressure to remove the solvent, and the dried solid was subjected to silica gel column chromatography with a eluent of dichloromethane/methanol (V/V =5: 1).
The preparation method of the micelle monomer dodecyl tripropyl alkynyl ammonium bromide or fluoro dodecyl tripropyl alkynyl ammonium bromide comprises the following steps:
1) firstly, dodecyl trifluoromethanesulfonate was synthesized:
Figure DEST_PATH_IMAGE022
a) dissolving dodecyl alcohol and trifluoromethanesulfonic anhydride in anhydrous dichloromethane, adding anhydrous pyridine as catalyst, and reacting until reactants are consumed. The molar ratio of the dodecyl alcohol to the trifluoromethanesulfonic anhydride is between 1 and 1.2; the molar ratio of the dodecyl alcohol to the pyridine is between 0.9 and 1.2. The reaction temperature is-25 to-5 ℃, and the reaction time is 3 to 12 hours.
b) And (3) separating and purifying products: after the reaction was complete, water was added, the organic phase was separated, washed twice with water and the aqueous phase was washed once with dichloromethane. The combined organic layers were washed with Na2SO4Drying, filtration and evaporation of the solvent gave the corresponding alkyl triflate as an oil, which was used without further purification.
2) Preparation of ammonium dodecyl tripropylene bromide:
Figure DEST_PATH_IMAGE024
a) and dissolving dodecyl trifluoromethanesulfonate in anhydrous tetrahydrofuran, adding propargylamine tripropargylamine, reacting until reactants are consumed, and observing the reaction progress by adopting a phosphomolybdic acid color developing agent. The molar ratio of dodecyl trifluoromethanesulfonate to propargylamine is between 1 and 1.2. The reaction temperature is-20 to-10 ℃, and the reaction time is 5 to 12 hours.
b) And (3) separating and purifying products: the reaction mixture was concentrated in vacuo and the residue was purified by column chromatography on silica gel using a dichloromethane/methanol mixture (15: 1 to 10: 1) as eluent to give the product as a white powder.
c) A white powdery solid was dissolved in methanol and a saturated NaBr solution (volume ratio = 1: 1) the ion exchange is carried out, and then the separation is carried out by adopting the following steps: the column was first eluted with NaBr/methanol (12%) until Br was present-Efflux (with silver nitrate AgNO)3Detection, white solid precipitated) and then dichloromethane was used until the column became clear. Then using dichloro-benzeneAnd (3) separating the methane and the methanol by using a chromatographic column with the volume ratio of 15: 1.
The preparation method of the fluorinated dodecyl tripropyl alkynyl ammonium bromide is the same as that of the dodecyl tripropyl alkynyl ammonium bromide.
The preparation method of the fluorescent micelle probe with the common nano micelle structure adopts the following steps:
a) dissolving a fluorescent probe in a methanol, acetonitrile, acetone or DMSO solution to prepare a solution of 5-25 mM;
b) dissolving micelle monomers of dodecyl tripropyl alkynyl ammonium bromide, fluoro dodecyl tripropyl alkynyl ammonium bromide or hexadecyl trimethyl ammonium bromide in water, and treating for 5-20 minutes under strong ultrasound;
c) and (c) adding the methanol, acetonitrile, acetone or DMSO solution of the probe molecules prepared in the step (a) into the micelle monomer solution in the step (b), and continuing to perform ultrasonic treatment for 5-20 minutes to enable the probe molecules to enter the micelle.
The preparation method of the fluorescent micelle probe with the cross-linked nano micelle structure adopts the following steps:
a) dissolving a fluorescent probe in a methanol, acetonitrile, acetone or DMSO solution to prepare a solution of 5-25 mM;
b) dissolving micelle monomer dodecyl tripropyl alkynyl ammonium bromide or fluoro dodecyl tripropyl alkynyl ammonium bromide in water, and treating for 5-20 minutes under strong ultrasound;
c) and (b) adding the methanol, acetonitrile, acetone or DMSO solution of the fluorescent probe prepared in the step (a) into the micelle monomer solution in the step (b), continuing to perform ultrasonic treatment for 5-20 minutes to enable probe molecules to enter the micelle, adding a cross-linking agent with the same molar weight as the micelle monomer, a catalytic amount of copper chloride and sodium ascorbate, reacting for 12-20 hours, and dialyzing by adopting a PVDF (polyvinylidene fluoride) membrane of 0.22 um to obtain the fluorescent micelle probe with a cross-linked micelle structure.
The application of the carbon monoxide fluorescent micelle probe comprises the following steps: the carbon monoxide fluorescent micelle probe is absorbed on filter paper or a polymer film to prepare detection test paper. The detection test paper is used for detecting the concentration of CO released by the lithium ion battery, and a convenient detection mode is provided for safety early warning of the lithium ion battery.
The preparation method of the detection test paper comprises the following steps: shearing a piece of filter paper or polymer film, placing the filter paper or polymer film in a solution (10 mM-25 mM) containing a common micelle fluorescent probe or a cross-linked micelle fluorescent probe, soaking for 5-20 minutes, taking out the filter paper or polymer film, and placing the filter paper or polymer film in a fume hood for air drying.
The technical scheme of the invention has the following beneficial effects:
1. the small organic molecular probe is dissolved in an aqueous solution or an organic solvent and then volatilizes to form a local concentration difference, and the volatilization at the solution boundary causes the molecular concentration at the edge of the solution to be higher, so that the condition that the probe is spotted on the fiber filter paper occurs. This does not take advantage of the fabrication and subsequent use of the fiber pilot. The invention arranges the probe molecules in the micelle, the positive charges on the surface of the cation micelle can be mutually repelled, thereby being beneficial to the dispersion of the cation micelle on the test paper, the cross-linked micelle provides a stable probe molecule environment, and the probe molecule environment can not be changed after the cross-linked micelle is contacted with the carrier.
2. The carbon monoxide has higher solubility in the fluoro-solvent compared with other solvents, and the carbon monoxide probe in the fluoro-micelle has higher detection sensitivity.
3. The fluorescent micelle probe can be used for safety early warning of the lithium ion battery, has the advantage of high sensitivity provided by the colorimetric fluorescent probe, and provides a reliable method for quick early warning of the battery.
Drawings
FIG. 1 is a structural diagram of a carbon monoxide fluorescent micelle probe. Wherein, the left figure is a dynamic micelle probe, and the right figure is a cross-linked micelle probe.
FIG. 2 is a comparative view showing the state where the fluorescent probe A2 solution and the micellar probe C2 solution are dispersed on a fibrous filter paper. Wherein, the left figure is a dispersion and model diagram of probe molecules, and the right figure is a dispersion diagram of micelle probes on fiber filter paper.
FIG. 3 is a spectrum of a carbon monoxide colorimetric fluorescent probe A1 in CTAB solution with time, wherein A is an ultraviolet-visible absorption spectrum and B is a fluorescence spectrum.
FIG. 4 is a graph showing the change in fluorescence intensity of the carbon monoxide colorimetric fluorescent probe A1 in CTAB at different concentrations.
FIG. 5 is a graph showing the change in fluorescence intensity of the carbon monoxide colorimetric fluorescent probe A1 in 10 mM SDS.
FIG. 6 is a graph comparing the response intensity of test strips D1-D3 to CO.
Detailed Description
To further illustrate the invention, the following examples are set forth without limiting the scope of the invention as defined by the various appended claims.
Example 1
Preparation of carbon monoxide colorimetric fluorescent probe A1
Figure DEST_PATH_IMAGE026
Preparation of 2- (3-cyano-4, 5, 5-trimethylfuran-2 (5H) -methylene) malononitrile: 3-hydroxy-3-methyl-2-butanone (1 mL, 9.5 mmoL) and malononitrile (1.3 g, 20 mmoL) were dissolved in sequence in 8 mL absolute ethanol; sodium ethoxide (0.1 g, 1.5 mmol) was then added and the solution stirred at room temperature for 1.5 h, then refluxed at 60 ℃ for 1 h. Cooled to room temperature, filtered to give a precipitate, washed 3 times with cold ethanol, and dried in vacuo to give compound 1 (1.1 g, yield: 60%). 1H NMR (CDCl 3, 400 MHz): δ = 2.37 (s, 3H) and δ = 1.63 (s, 6H).
Preparing a carbon monoxide colorimetric fluorescent probe A1: 2- (3-cyano-4, 5, 5-trimethylfuran-2 (5H) -methylene) malononitrile (199 mg, 1 mmol) and 4-nitro-3-hydroxybenzaldehyde (167 mg, 1 mmol) were dissolved in 10 mL of ethanol, after which a piece of anhydrous piperidine was immediately added to the mixed solution, and stirred at room temperature for 8H. After waiting for the reaction to be complete, the solution was filtered to give the yellow solid compound probe NIR-CO (226 mg, 65%). 1H NMR (400 MHz, DMSO-d 6) δ (× 10-6): 1.81 (s, 6H), 7.27 (d, J = 20 Hz, 1H), 7.55 (t, J = 8 Hz, 1H), 7.85 (d, J = 16 Hz, 1H), 8.00 (d, J = 8 Hz, 1H), 11.24 (s, 1H).
Example 2
Preparation of carbon monoxide colorimetric fluorescent probe A2
Figure DEST_PATH_IMAGE028
2- (3-cyano-4, 5, 5-trimethylfuran-2 (5H) -methylene) malononitrile (199 mg, 1 mmol) and 4-nitro-3-acetate benzaldehyde (209 mg, 1 mmol) were dissolved in 10 mL of ethanol, after which a piece of anhydrous piperidine was immediately added to the mixed solution, and stirred at room temperature until the reaction was complete. After waiting for the reaction to be complete, the solution was filtered to give the yellow solid compound probe NIR-CO (125 mg, 32%). 1H NMR (500 MHz, Chloroform-d)1H NMR (500 MHz, Chloroform-d) δ 8.10 (d, J = 7.5 Hz, 1H), 7.57 (ddd, J = 7.5, 2.0, 1.1 Hz, 1H), 7.29 (dd, J = 2.0, 1.0 Hz, 1H), 7.15 (d, J = 15.0 Hz, 1H), 6.80 (dt, J = 15.1, 1.0 Hz, 1H), 2.67 (s, 3H), 1.53 (s, 6H).
Example 3
Preparation of carbon monoxide colorimetric fluorescent probe A3
Figure DEST_PATH_IMAGE030
The procedure is as in example 2 except that 4-nitro-3-sulfobenzaldehyde is used instead of 4-nitro-3-acetate benzaldehyde.
Example 4
Preparation of ammonium dodecyl tripropylene bromide:
trifluoromethanesulfonic anhydride (1.1 eq. 1.10 mmol 185.06 mmol) was dissolved in anhydrous dichloromethane (3.5 mL), cooled to-5 to 5 ℃ and dodecanol (1 eq. 1.0 mmol, 186.34 mg) and anhydrous pyridine (1.1 eq. 1.10 mmol 88.62 mmol) were added dropwise (1.74 mL) dissolved in anhydrous dichloromethane, maintaining the internal temperature below 5 ℃. The reaction mixture was stirred for 3 hours, then water (2.6 mL) was added. The organic phase was separated, washed twice with water and the aqueous phase once with dichloromethane. The combined organic layers were washed with Na2SO4Drying, filtering and evaporating the solvent to obtainThe corresponding alkyl triflate as an oil was used without further purification.
Tripropargylamine (0.053 mL, 0.712 mmol) was added to a solution of compound 3 (0.2 g, 0.628 mmol) in dry THF (3.39 mL) at-20 deg.C, and the cold bath apparatus was removed. After 5 hours at room temperature, the reaction mixture was concentrated in vacuo and the residue was purified by column chromatography on silica gel using a dichloromethane/methanol mixture (15: 1 to 10: 1) as eluent to give the product as a white powder (0.188 g, 85%). 1H NMR (500 MHz, Chloroform-d) δ 4.58 (d, J = 2.5 Hz, 6H), 3.65-3.55 (m, 2H), 2.97 (d, J = 2.5 Hz, 3H), 1.91 (p, J = 7.4, 6.9 Hz, 2H), 1.39-1.21 (m, 20H), 0.88 (t, J = 6.8 Hz, 3H).
Example 4
Preparation of crosslinking agent B1:
Figure DEST_PATH_IMAGE032
2, 2' -Bioxaet ethane (0.5 mL, 6.45 mmol) was dissolved in 10 mL of water, followed by addition of sodium azide (2.52 g, 38.7 mmol) and reaction at 25 ℃ for 12 hours, and progress of the reaction was observed with phosphomolybdic acid developer. The reaction aqueous solution was extracted with ethyl acetate (3 '50 mL), and the organic phase was washed with brine (3' 20 mL), dried over anhydrous sodium sulfate, and vacuum-dried to obtain a colorless oily substance. 1H NMR (400 MHz, Chloroform-d) delta 3.77 (s, 1H), 3.84-3.70 (m, 1H), 3.47 (d, J = 5.5 Hz, 4H), 2.83 (s, 2H).
Example 6
Figure DEST_PATH_IMAGE034
Ethylene glycol diglycidyl ether (600.00 mg, 3.44mmol) was dissolved in 10 mL of water, followed by addition of sodium azide (862.10mg, 13.26mmol), reaction at 25 ℃ for 12 hours, and the progress of the reaction was observed with a phosphomolybdic acid developer. The reaction aqueous solution was extracted with ethyl acetate (3 '50 mL), and the organic phase was washed with brine (3' 20 mL), dried over anhydrous sodium sulfate, and vacuum-dried to obtain a colorless oily substance. 1H NMR (400 MHz, Chloroform-d) Δ 4.04-3.84 (m, 2H), 3.87-3.46 (m, 10H), 3.49-3.33 (m, 2H), 3.37-3.22 (m, 2H).
Example 7
Preparation of a cross-linked micelle fluorescent probe C1:
the prepared probe molecule A1 was first dissolved in DMSO to prepare a 25 mM solution. Perfluoroundecyltripropylammonium bromide trifluoromethanesulfonate (20.1 mg, 0.03 mmol) was weighed out and added to 3mL of distilled water, and the mixture was dissolved completely by sonication and dispersed uniformly in water. Then 50 μ L of probe molecule A1 (5.0X 10) was added-7mol) of DMSO. The resulting mixture was sonicated for an additional 20 min. The mixed solution was added with 0.04 mg of CuCl and 0.1 mg of crosslinking agent B (0.03 mmol) in this order2And 1.5 mg of sodium ascorbate, and stirring at room temperature for 12 hours to form stable cross-linked micelles, and then treating the mixed aqueous solution with a dialysis membrane for 12 hours to remove unreacted small molecules to obtain a cross-linked micelle fluorescent probe C1.
Example 8
Preparation of a cross-linked micelle fluorescent probe C2:
dodecyl tripropyl alkynyl ammonium bromide (11.4 mg, 0.03 mmol) was weighed and added to 3mL of distilled water, and the mixture was dissolved completely by sonication and dispersed uniformly in water. Then 50 μ L of probe molecule A1 (5.0X 10) was added-7mol) DMSO solution. The resulting mixture was sonicated for an additional 20 min. The mixed solution was added with 0.04 mg of CuCl and 0.1 mg of crosslinking agent B (0.03 mmol) in this order2And 1.5 mg of sodium ascorbate, and stirring at room temperature for 12 hours to form stable cross-linked micelles, and then treating the mixed aqueous solution with a dialysis membrane for 12 hours to remove unreacted small molecules to obtain a cross-linked micelle fluorescent probe C2.
Example 9
Preparation of a common micelle fluorescent probe C3:
cetyl trimethylammonium bromide (10.9 mg, 0.03 mmol) was weighed into 3mL of distilled water, and dissolved completely by sonication, and dispersed uniformly in water. Then 50 μ L of probe molecule A1 (5.0X 10) was added-7mol) DMSO solution. The resulting mixture was sonicated for a further 20 min,the ordinary micelle fluorescent probe C3 was obtained.
Example 10
Preparation of a cross-linked micelle fluorescent probe C4:
perfluoroundecyltripropylammonium bromide trifluoromethanesulfonate (20.1 mg, 0.03 mmol) was weighed out and added to 3mL of distilled water, and the mixture was dissolved completely by sonication and dispersed uniformly in water. Then 50 μ L of probe molecule A1 (5.0X 10) was added-7mol) of methanol solution. The resulting mixture was sonicated for a further 15 min. The mixed solution was added with 0.04 mg of CuCl and 0.2 mg of crosslinking agent B (0.03 mmol) in this order2And 1.5 mg of sodium ascorbate, and stirring at room temperature for 16 hours to form stable cross-linked micelles, and then treating the mixed aqueous solution with a dialysis membrane for 12 hours to remove unreacted small molecules to obtain a cross-linked micelle fluorescent probe C4.
Example 11
Preparation of a cross-linked micelle fluorescent probe C5:
weighing dodecyl tripropyl alkynyl ammonium bromide (11.4 mg, 0.03 mmol) and adding 3mL distilled water, and ultrasonically dissolving and uniformly dispersing in water. Then 50 μ L of probe molecule A2 (5.0X 10) was added-7mol) acetonitrile solution. The resulting mixture was sonicated for 5 min. The mixed solution was added with 0.04 mg of CuCl and 0.2 mg of crosslinking agent B (0.03 mmol) in this order2And 1.5 mg of sodium ascorbate, and stirring at room temperature for 20 hours to form stable cross-linked micelles, and then treating the mixed aqueous solution with a dialysis membrane for 12 hours to remove unreacted small molecules to obtain a cross-linked micelle fluorescent probe C5.
Example 12
Preparation of a cross-linked micelle fluorescent probe C6:
weighing dodecyl tripropyl alkynyl ammonium bromide (11.4 mg, 0.03 mmol) and adding 3mL distilled water, and ultrasonically dissolving and uniformly dispersing in water. Then 50 μ L of probe molecule A3 (5.0X 10) was added-7mol) of DMSO. The resulting mixture was sonicated for 10 min. The mixed solution was added with 0.04 mg of CuCl and 0.1 mg of crosslinking agent B (0.03 mmol) in this order2And 1.5 mg of sodium ascorbate and stirred at room temperature for 18 hours to form stable crosslinked micelles, and then the mixed aqueous solution was dialyzedAnd (5) performing membrane treatment for 12 h, and removing unreacted small molecules to obtain the cross-linked micelle fluorescent probe C6.
Example 13
Preparing a cross-linked micelle fluorescent probe C1 into detection test paper D1: a piece of filter paper was cut out and placed in a 25 mM DMSO solution of the cross-linked micelle fluorescent probe C1, and after dipping for 5 minutes, the filter paper was taken out and placed in a fume hood to be air-dried.
Preparation of fluorescent probe A1 Dip-stained filter paper: a further piece of filter paper was cut out and immersed in a 25 mM DMSO solution of fluorescent probe A1 for 5 minutes and then placed in a fume hood for air drying.
The color uniformity of the filter paper after air drying is detected by comparing the test paper D1 and the fluorescent probe A1. As shown in fig. 2, the left graph is a dispersion and model graph of probe molecules on a fiber filter paper, and the right graph is a dispersion graph of micelle probes on the fiber filter paper, and it can be seen from the graph that for a filter paper impregnated with only probe molecules, the concentration of molecules at the edge of the solution is high due to volatilization at the boundary of the solution, so that a spot-shaped probe appears on the fiber filter paper, which reduces the detection sensitivity, and the prepared detection test paper cannot be used for subsequent detection of carbon monoxide. The detection test paper prepared by the fluorescent micelle probe or the cross-linked fluorescent micelle probe does not have the spot phenomenon, probe molecules are placed in the micelle, and positive charges on the surface of the cationic micelle can be mutually repelled, so that the uniform dispersion of the cationic micelle on the test paper is facilitated.
Example 14
Preparation of test paper D2: a piece of filter paper is cut and placed in a DMSO solution of a 25 mM cross-linked micelle fluorescent probe C2, and after dipping for 5 minutes, the filter paper is taken out and placed in a fume hood to be air-dried, so that the test paper D2 is obtained.
Example 15
Preparation of test paper D3: a piece of filter paper is cut and placed in a DMSO solution of a 25 mM common micelle fluorescent probe C3, and after dipping for 5 minutes, the filter paper is taken out and placed in a fume hood to be dried by air so as to obtain the test paper D3.
Example 16
The test strips D1-D3 prepared in examples 13-15 were subjected to carbon monoxide gas detection: test paper D1-D3 was placed in a conical flask, nitrogen gas containing CO at various concentrations was introduced into the flask, and the CO gas concentration was determined by measuring the change in color with time. As shown in fig. 6, the three test strips can produce a sensitive colorimetric change on carbon monoxide, so as to detect carbon monoxide. The test paper D3 prepared by the carbon monoxide cross-linked micelle probe in the fluoro micelle has higher detection sensitivity.
Example 17
FIG. 1 is a structural diagram of a carbon monoxide fluorescent micelle probe. As can be seen from the figure, the fluorescent probe molecules are wrapped in micelles formed by micelle monomers, and the micelle molecules in the dynamic micelles (shown in the left figure) are rapidly exchanged in a solution environment and a micelle system and have dynamic property; while the cross-linked micelles (as shown in the right) provide a more stable nanostructure.
Example 18
The UV absorption and fluorescence intensity vs. time spectra of a probe solution containing carbon monoxide probe A1 at a concentration of 10. mu.M, cetyltrimethylammonium bromide at a concentration of 5 mM, and CO at a concentration of 500 ppm were determined. As shown in FIG. 3, the maximum absorption peak and fluorescence intensity of probe A1 increased significantly with time.
Example 19
The amount of carbon monoxide introduced was fixed, and the fluorescence intensity change pattern of the carbon monoxide colorimetric fluorescent probe A1 in CTAB at different concentrations was measured. As shown in FIG. 4, in the concentration range of 1-10 mM, the fluorescence intensity increased with increasing CTAB concentration, reaching a maximum at 10 mM. This is because the NIR-CO is encapsulated into the CTAB, which alters the reaction behavior of the NIR-CO with CO. Since CTAB micelles provide a basic and non-polar microenvironment, the reaction in CTAB-PBS is greatly accelerated.
Example 20
FIG. 5 is a graph showing the change in fluorescence intensity of the carbon monoxide colorimetric fluorescent probe A1 in 10 mM SDS. As shown, fluorescent probe a1 did not substantially react with carbon monoxide in SDS micelles, had no distinct peak and did not change in intensity, although SDS may also provide a nonpolar microenvironment, whereas the probe did not change in fluorescence intensity in SDS-PBS, demonstrating that the charge characteristics of the surfactant play a critical role in this reaction.
Although the present invention has been described in the above-mentioned embodiments, it is to be understood that the present invention may be further modified and changed without departing from the spirit of the present invention, and that such modifications and changes are within the scope of the present invention.

Claims (3)

1. A carbon monoxide fluorescent micelle probe is characterized in that the fluorescent micelle probe adopts a nano micelle structure with the fluorescent probe inside and micelle monomers outside;
the fluorescent probe has the following structure:
Figure DEST_PATH_IMAGE002
the micelle monomer is cetyl trimethyl ammonium bromide and dodecyl tripropyl alkynyl ammonium bromide;
the outer layer of the micelle monomer of the fluorescent micelle probe is crosslinked by a crosslinking agent to form a crosslinked nano micelle;
the cross-linking agent has the following structure:
Figure DEST_PATH_IMAGE004
。
2. the method for preparing the carbon monoxide fluorescent micelle probe according to claim 1, which is characterized by comprising the following steps:
a) dissolving a fluorescent probe in a DMSO solution to prepare a solution with the concentration of 5-25 mM;
b) dissolving micelle monomer dodecyl tripropyl alkynyl ammonium bromide or hexadecyl trimethyl ammonium bromide in water, and treating for 5-20 minutes under ultrasound;
c) and (b) adding the DMSO solution of the fluorescent probe prepared in the step (a) into the micelle monomer solution in the step (b), continuing ultrasonic treatment for 5-20 minutes to enable probe molecules to enter the micelle, adding a cross-linking agent with the same molar quantity as the micelle monomer, a catalytic amount of copper chloride and sodium ascorbate, reacting for 12-20 hours, and dialyzing by adopting a PVDF (polyvinylidene fluoride) membrane of 0.22 um to obtain the fluorescent micelle probe with a cross-linked micelle structure.
3. A test paper for detecting carbon monoxide, which is prepared by adsorbing the carbon monoxide fluorescent micelle probe prepared according to claim 2 on filter paper or a polymer film.
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DMABN在表面活性剂胶束水溶液中的荧光性质;林翠英等;《物理化学学报》;20080915(第09期);第1709-1713页 *
一种新型的荧光探针及其在表面活性剂溶液胶束形成过程中的应用;姜永才，汪鹏飞，吴世康;《感光科学与光化学》;19940823;第12卷(第03期);第273-277页 *
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