CN115340542A - Fluorescent probe for detecting phosgene, and preparation method and use method thereof - Google Patents
Fluorescent probe for detecting phosgene, and preparation method and use method thereof Download PDFInfo
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N2021/6443—Fluorimetric titration
Abstract
The invention discloses a fluorescent probe for detecting phosgene, and a preparation method and a use method thereof. The cyanine as an excellent traditional fluorescent parent group has a unique D-pi-A conjugated system, and can generate an intramolecular charge transfer process from an electron donor to an electron acceptor under the excitation of light, so that the traditional cyanine dye has the characteristics of large molar extinction coefficient, large Stokes shift and the like. Therefore, the invention constructs a classical Intramolecular Charge Transfer (ICT) system based on the improved hemicyanine fluorescent mother. The probe has a strong ICT effect, so that the probe does not have fluorescence, but under the condition of existence of phosgene, phosgene and hydroxyl and amino on the probe molecule are subjected to a cyclization reaction, the ICT effect of the molecule is further reduced, the probe molecule emits strong yellow green fluorescence, and through the scheme, an open-type fluorescence response is obtained, and high-sensitivity and specific detection on the phosgene is realized.
Description
Technical Field
The invention belongs to the field of organic small-molecule fluorescent probes, and particularly relates to a preparation method and a use method of (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate serving as a phosgene fluorescent probe.
Background
Phosgene (COCl) 2 ) Phosgene, a highly toxic gas molecule with rotten grass odor, is the first toThe next world war was used for the first time as a chemical warfare agent. The carbonyl in phosgene has very high activity and can react with important functional groups such as sulfydryl, hydroxyl and the like in lung tissue protein, thereby influencing the normal metabolism and the function of lung cells. Therefore, phosgene has high toxicity and can cause serious damage to human lungs, and after phosgene is inhaled, physiological phenomena such as dyspnea, chest pain, blood pressure reduction and the like occur slightly, and coma and death occur seriously. However, phosgene is also an important industrial raw material and is widely used in the industries of plastics, pharmacy, dyes, pesticides and the like. Due to the wide range of applications of phosgene, phosgene leakage can pose a significant threat to public health and safety during production, storage and transportation. Therefore, a rapid, sensitive and highly selective phosgene detection method is urgently needed in the case of potential safety threats such as industrial accidents and chemical terrorist attacks.
Fluorescence detection methods have received much attention from researchers because of their excellent detection sensitivity and selectivity, and the ability to perform real-time, on-line detection of a sample to be detected.
The small-molecule fluorescent probe for detecting phosgene which has been developed at present is designed mainly based on the specific binding force between phosgene and nucleophilic atoms by adjusting the Photo-induced Electron Transfer (PET) or Intramolecular Charge Transfer (ICT) effect of a group. With the development of fluorescence analysis, more and more probes are used for detecting phosgene, and the probes published today can be roughly divided into the following categories: 1) Identifying phosgene by two nucleophilic substitutions with an amine; 2) Some reducing groups (e.g., oximes, amides, etc.) undergo specific oxidative rearrangement reactions with phosgene.
However, some of the reported probes have the defects of not fast reaction speed, not good enough selectivity and the like. For example, an ethylenediamine-based fluorescent probe (see reviews Zhijiang Xu; yabin Luo 1 Yu hong Zhang; shuang-Xi Gu; jun Yin. Spectrochi Acta Part A: molecular and Biomolecular Spectroscopy,2021,269, 120789.) affects the ability of the probe to detect phosgene in real time because the reaction time of the probe with the phosgene is relatively slow due to insufficient activity of the imine.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an open type fluorescent probe (BCy 428) for quantitatively detecting phosgene. The invention can be used for quantitatively detecting the trace phosgene in the sample.
The cyanine as an excellent traditional fluorescent parent group has a unique D-pi-A conjugated system, and can generate an intramolecular charge transfer process from an electron donor to an electron acceptor under the excitation of light, so that the traditional cyanine dye has the characteristics of large molar extinction coefficient, large Stokes shift and the like. Therefore, based on the improved hemicyanine fluorescent mother, a classical Intramolecular Charge Transfer (ICT) system is constructed. The probe has no fluorescence due to the strong ICT effect, but under the condition of existence of phosgene, phosgene and hydroxyl and amino on the probe molecule are subjected to cyclization reaction, so that the ICT effect of the molecule is inhibited, the probe molecule emits strong yellow green fluorescence, and through the scheme, an open-type fluorescence response is obtained, and the high-sensitivity and specific detection of phosgene is realized.
The phosgene fluorescent probe is named as (E) -8- (3-hydroxyl-4-amido) -10, 10-dimethyl-10H-pyridine [1,2-a ]]Indolium perchlorate of the formula C 22 H 21 ClN 2O5 The structural formula is shown as the formula (I):
the preparation method of the fluorescent probe comprises the following steps: dissolving a certain amount of dicyclo hemicyanine perchlorate (1), 3-hydroxy-4-nitrobenzaldehyde (2) and piperidine (3) in absolute ethyl alcohol, reacting for a certain time, performing column chromatography after spin-drying to obtain a compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate (4). Adding a certain amount of (4) and stannous chloride (5) into absolute ethyl alcohol, and reacting for a period of time at a certain temperature. After the reaction is completed, the orange red solid compound (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate (6) is obtained by spin-drying and column chromatography, namely: BCy428.
The reaction formula for preparing the probe is as follows:
the phosgene fluorescent probe is used as follows:
step 1: adding the compound shown in the formula (I) with the same concentration into acetonitrile solutions of phosgene with different concentrations to prepare at least 5 standard solutions containing the compound shown in the formula (I) with different phosgene contents;
the concentration of the compound shown in the formula (I) in the standard solution is 1 nM-10 μ M;
the content of phosgene in the standard solution is 0.1 nM-1 mM;
step 2: respectively measuring the fluorescence emission spectra of the standard solutions, wherein the excitation wavelength is 403nm, the phosgene concentration is used as the abscissa, and I is used 526 Establishing a standard curve for the ordinate;
I 526 representing the fluorescence emission peak intensity value of the standard solution at the wavelength of 526 nm;
and step 3: adding a compound shown in a formula (I) into a sample to be detected, and controlling the concentration of the compound to be detected to be equal to the concentration of the compound shown in the formula (I) in the standard solution; and (3) measuring the fluorescence emission spectrum of the sample under the excitation light with the excitation wavelength of 403nm, namely calculating the phosgene content of the sample to be detected according to the standard curve.
Preferably, the mol ratio of the cyclo-hemicyanine perchlorate to the 3-hydroxy-4-nitrobenzaldehyde to the piperidine is 0.1-1: 1:1; the mass volume ratio of the piperidine to the absolute ethyl alcohol is 1:1 to 100; the reaction temperature is 30-80 ℃, and the reaction time is 1-24 hours;
the molar ratio of (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate to stannous chloride is 0.1-1: 1, the mass volume ratio of the stannous chloride to the absolute ethyl alcohol is 1: 1-100 parts of; the reaction temperature is 30-80 ℃ and the reaction time is 1-24 hours.
A method for preparing a fluorescent probe for detecting phosgene comprises the following steps:
i) The mol ratio of the dicyclo hemicyanine perchlorate (1), the 3-hydroxy-4-nitrobenzaldehyde (2) and the piperidine (3) is 1:1.1:1.1; the mass-volume ratio of the substances of the piperidine to the absolute ethyl alcohol is 1.1:8; the reaction temperature is 80 ℃, and the reaction time is 3 hours;
ii the molar ratio of (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) to stannous chloride (5) is 1:5; the mass-volume ratio of the stannous chloride to the absolute ethyl alcohol is 1:15; the reaction temperature was 80 ℃ and the reaction time was 5 hours.
The invention has the following characteristics:
1) The fluorescent probe provided by the invention is orange red solid powder and has good optical stability.
2) The solution of the fluorescent probe provided by the invention is sensitive to the concentration of phosgene, and the fluorescence of the aqueous solution is observed to be changed from no fluorescence to yellow green under an ultraviolet lamp along with the increase of the concentration of phosgene.
3) The fluorescent probe provided by the invention has the emission wavelengths of 526nm respectively, is a fluorescent 'on' type response, and the fluorescent intensity is increased by about 600 times after reaction, so that the influence of detection condition difference on the result during detection can be greatly eliminated, and the detection sensitivity is improved.
4) The fluorescent probe provided by the invention has a linear relation to the concentration of phosgene, and can be used for accurately measuring phosgene.
The open-type phosgene probe based on the parallel-ring hemicyanine dye has good response to phosgene solution, can realize sensitive quantitative detection of phosgene in a sample, and has the advantages of simple and convenient operation, low cost, sensitive response, easy popularization and application and the like.
Drawings
FIG. 1: nuclear magnetic resonance hydrogen spectrum of fluorescent probe BCy428.
FIG. 2: color response graph of fluorescent probe BCy428 to phosgene acetonitrile solution.
FIG. 3: fluorescence response graph of fluorescent probe BCy428 to phosgene acetonitrile solution.
FIG. 4 is a schematic view of: ultraviolet titration curve of fluorescent probe BCy428 in acetonitrile with probe concentration of 10.0. Mu.M.
FIG. 5: fluorescence titration curve of fluorescent probe BCy428 in acetonitrile liquid with excitation wavelength of 403nm and probe concentration of 10.0. Mu.M.
FIG. 6: and (3) a fluorescence response diagram of the fluorescent probe BCy428 to common volatile acyl chloride micromolecules, wherein the excitation wavelength is 403nm, the probe concentration is 10.0 mu M, and the concentration of the substance to be detected is 10.0 mu M.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The compound numbers in the examples correspond to those in the above-mentioned compounds.
Example 1, synthesis of compound BCy428.
Synthesis of Compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4).
400mg (1.29 mmol) of bicyclo hemicyanine perchlorate (1), 237mg (1.42 mmol) of 3-hydroxy-4-nitrobenzaldehyde (2), was dissolved in 8mL of anhydrous ethanol, 0.14mL of piperidine (3) (1.42 mmol) was added, and the reaction was carried out at 80 ℃ for 3 hours, followed by spin-drying and column chromatography to give 402mg of compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) in 68% yield.
1 H NMR(400MHz,DMSO-d 6 )δ9.81(d,J＝6.6Hz,1H),8.83(d,J＝1.7Hz,1H),8.40(ddd,J＝7.3,6.8,2.1Hz,2H),8.17–8.04(m,2H),7.99–7.93(m,1H),7.80–7.67(m,3H),7.42(d,J＝7.8Hz,2H),1.76(s,6H).
Synthesis of Compound (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (6).
200mg (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) (0.44 mmol) and 414mg stannous chloride (5) (2.18 mmol) were dissolved in 15mL of absolute ethanol and reacted under reflux conditions for 5 hours before spin column chromatography gave 70mg of the compound (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (6), i.e.: BCy428, yield 38%. The NMR spectrum is shown in FIG. 1.
1 H NMR(400MHz,Methanol-d 4 )δ9.26(d,J＝6.8Hz,1H),8.40(d,J＝1.8Hz,1H),8.18–8.11(m,1H),8.07(dd,J＝6.8,1.9Hz,1H),7.95(d,J＝15.9Hz,1H),7.87–7.80(m,1H),7.72–7.68(m,2H),7.52(dd,J＝8.8,6.9Hz,1H),7.43–7.36(m,2H),7.17(d,J＝2.0Hz,3H),6.77(d,J＝8.5Hz,1H),1.80(s,6H).
Example 2, synthesis of compound BCy428.
Synthesis of the compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4).
44mg (0.142 mmol) of bicyclo hemicyanine perchlorate (1), 237mg (1.42 mmol) of 3-hydroxy-4-nitrobenzaldehyde (2) were dissolved in 3mL of absolute ethanol, 0.14mL (1.42 mmol) of piperidine (3) was added, and the mixture was reacted at 30 ℃ for 1 hour, followed by spin-drying and column chromatography to obtain 35mg of compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4);
100mg (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) (0.22 mmol) and 414mg stannous chloride (5) (2.18 mmol) were dissolved in 15mL of absolute ethanol and reacted under reflux conditions for 2 hours before spin column chromatography gave 40mg of the compound (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (6), i.e.: BCy428.
Example 3, synthesis of compound BCy428.
Synthesis of the compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4).
200mg (0.645 mmol) of bicyclo hemicyanine perchlorate (1), 237mg (1.42 mmol) of 3-hydroxy-4-nitrobenzaldehyde (2) were dissolved in 50mL of anhydrous ethanol, 0.14mL of piperidine (3) (1.42 mmol) was added, and the reaction was carried out at 80 ℃ for 20 hours, followed by spin-drying and column chromatography to give 255mg of compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) in 86% yield.
600mg (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) (1.32 mmol) and 414mg stannous chloride (5) (2.18 mmol) were dissolved in 80mL of absolute ethanol and reacted under reflux conditions for 20 hours before spin column chromatography afforded 360mg of the compound (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (6), i.e.: BCy428.
Example 4, color response of compound BCy428 to phosgene.
A test stock solution of dimethyl sulfoxide (DMSO) of the phosgene detecting fluorescent probe BCy428 of the invention with a concentration of 1mM was prepared for use. 100 mu L of the mother liquor is measured and dripped into the acetonitrile solution of phosgene with certain concentration, and the corresponding acetonitrile solution is used for fixing the volume to 10mL, so that the concentration of the probe in the test solution is 10.0 mu M, and the concentration of the phosgene is 10.0 mu M for color response test. As shown in FIGS. 2 and 3, after the phosgene solution was added, the color of the solution changed from orange to pale yellow as observed by naked eyes, and the fluorescence of the solution also changed from no fluorescence to yellow-green fluorescence, indicating that the probe BCy428 has an intuitive colorimetric response to phosgene.
Example 5 uv titration detection of compound BCy428 with different concentrations of phosgene.
A test stock solution of dimethyl sulfoxide (DMSO) of the phosgene detecting fluorescent probe BCy428 of the invention with a concentration of 1mM was prepared for use. 100 mu L of the mother solution is measured and respectively dripped into acetonitrile solutions of phosgene with different concentrations, and the corresponding acetonitrile solutions are used for fixing the volume to 10mL, so that the concentration of the probe in the test solution is 10.0 mu M, and the concentration of the phosgene is 0-30.0 mu M for absorption spectrum test. Obtaining an ultraviolet absorption curve in each system, and establishing a standard curve of absorbance and phosgene concentration. As shown in FIG. 4, as the concentration of phosgene increased, the absorbance gradually decreased at 485nm, and the absorbance gradually increased at 403nm, and A 403 /A 485 A good linear relationship with phosgene concentration (0-10.0. Mu.M).
Example 6 fluorescence titration detection of compound BCy428 with different concentrations of phosgene.
The invention is formulated at a concentration of 1mMThe phosgene detecting fluorescent probe BCy428 was in dimethyl sulfoxide (DMSO) in test stock solution for standby. 100 μ L of the mother solution was measured and added dropwise to acetonitrile solutions of phosgene of different concentrations, and the volume was adjusted to 10mL using the corresponding acetonitrile solutions, so that the concentration of the probe in the test solution was 10.0 μ M and the concentration of phosgene was 0-30.0 μ M for fluorescence detection (λ ex =403nm, λ em =526 nm). Obtaining the fluorescence intensity in each system, and establishing a standard curve of the fluorescence intensity and the phosgene concentration. As shown in FIG. 5, the fluorescence intensity of the system at 526nm gradually increased with the increase of the phosgene concentration, and the fluorescence intensity of the reaction system reached an equilibrium state when the phosgene concentration reached 10.0. Mu.M. Furthermore, at low concentrations, the fluorescence intensity (I) at 526nm 526 ) And the concentration of phosgene (0-2.0. Mu.M) showed a good linear relationship (R) 2 ＝0.99)。
Example 7, selectivity of compound BCy428 to different common acid chloride small molecules.
A test stock solution of dimethyl sulfoxide (DMSO) of the phosgene detecting fluorescent probe BCy428 of the invention with a concentration of 1mM was prepared for use. Preparing solutions of various acyl chloride micromolecules to be detected with the concentration of 10mM for later use. 100 mu L of the mother liquor is measured and respectively added into acetonitrile solutions of different small molecules to be detected in a dropwise manner, and the volume is determined to be 10mL by using the corresponding acetonitrile solutions, so that the concentration of the probe in the test liquor is 10.0 mu M, and the concentration of the small molecules to be detected is 10.0 mu M, and fluorescence detection is carried out (lambda ex =403nm, lambda em =526 nm). Obtaining the fluorescence intensity in each system, and establishing the fluorescence intensity (I) 526 ) And a histogram of the relationship between each analyte. As shown in FIG. 6, other common acyl chloride small molecules to be detected have little influence on the fluorescence of the probe BCy428.
Claims (5)
1. A fluorescent probe for detecting phosgene is characterized in that: the molecular formula is C 22 H 21 ClN 2O5 BCy for short 428 The structural formula is shown as formula (I);
2. the method for preparing a fluorescent probe for detecting phosgene as claimed in claim 1, wherein the synthesis steps are as follows:
1) Dissolving the bicyclo hemicyanine perchlorate, 3-hydroxy-4-nitrobenzaldehyde and piperidine in absolute ethyl alcohol, and reacting for a certain time to obtain an intermediate compound (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate;
2) Adding the intermediate compound and stannous chloride into absolute ethyl alcohol to react for a period of time to obtain (E) -8- (3-hydroxy-4-amino) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate, namely: BCy428;
the reaction formula is as follows:
3. the use of the fluorescent probe for detecting phosgene according to claim 1; the method is characterized in that:
1) Adding the compound shown in the formula (I) with the same concentration into acetonitrile solutions of phosgene with different concentrations to prepare at least 5 standard solutions containing the compound shown in the formula (I) with different phosgene contents;
the concentration of the compound shown in the formula (I) in the standard solution is 1 nM-10 μ M;
the content of phosgene in the standard solution is 0.1 nM-1 mM;
2) Respectively measuring the fluorescence emission spectra of the standard solutions, wherein the excitation wavelength is 403nm, the phosgene concentration is used as the abscissa, and I is used 526 Establishing a standard curve for the ordinate;
I 526 representing the fluorescence emission peak intensity value of the standard solution at the wavelength of 526 nm;
3) Adding a compound shown in a formula (I) into a sample to be detected, and controlling the concentration of the compound to be detected to be equal to the concentration of the compound shown in the formula (I) in the standard solution; and (3) measuring the fluorescence emission spectrum of the sample under the excitation light with the excitation wavelength of 403nm, namely calculating the phosgene content of the sample to be detected according to the standard curve.
4. The method for preparing a fluorescent probe for detecting phosgene as claimed in claim 2, wherein:
the mol ratio of the 3-hydroxy-4-nitrobenzaldehyde to the piperidine of the cyclo-hemicyanine perchlorate in the step 1) is 0.1-1: 1:1; the mass-volume ratio of the substances of the piperidine to the absolute ethyl alcohol is 1:1 to 100; the reaction temperature is 30-80 ℃, and the reaction time is 1-24 hours;
the molar ratio of (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyridine [1,2-a ] indolium perchlorate to stannous chloride in the 2) is 0.1-1: 1, the mass volume ratio of the stannous chloride to the absolute ethyl alcohol is 1:1 to 100; the reaction temperature is 30-80 ℃ and the reaction time is 1-24 hours.
5. The method for preparing a fluorescent probe for detecting phosgene as claimed in claim 1, wherein:
i) The mol ratio of the dicyclo hemicyanine perchlorate (1), the 3-hydroxy-4-nitrobenzaldehyde (2) and the piperidine (3) is 1:1.1:1.1; the mass-volume ratio of the substances of the piperidine to the absolute ethyl alcohol is 1.1:8; the reaction temperature is 80 ℃, and the reaction time is 3 hours;
ii (E) -8- (3-hydroxy-4-nitro) -10, 10-dimethyl-10H-pyrido [1,2-a ] indolium perchlorate (4) and stannous chloride (5) in a molar ratio of 1:5; the mass-volume ratio of the stannous chloride to the absolute ethyl alcohol is 1:15; the reaction temperature was 80 ℃ and the reaction time was 5 hours.
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