CN113004206A - Naphthalene derivative fluorescent probe and preparation method and application thereof - Google Patents
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Abstract
A naphthalene derivative fluorescent probe and a preparation method and application thereof relate to a fluorescent detection probe and a preparation method and application thereof. It aims to solve the problem that the relay fluorescence detection of Hg in aqueous solution is not available at present2+And I–And the probe is susceptible to Au3+、Fe2+And Fe3+The technical problem of influence is that the naphthalene derivative fluorescent probe is 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride, and the structural formula is as follows:
it is prepared by N-alkylation, amidation and quaternization reactions. The fluorescent probe is utilized to pass through the fluorescent probe and Hg2+Hg detection by fluorescence enhancement through formation of stable complexes2+(ii) a The detection can be carried out within the pH value of 7.0-11.0, and the detection limit reaches 9.7 multiplied by 10– 8mol/L. Complex N-Hg2+Can also be added with I–Achievement of post-fluorescence recovery pair I–The detection of (2) can be used in the fields of environmental science, analytical chemistry, life science and medicine.
Description
Technical Field
The invention relates to a fluorescent detection probe and a preparation method and application thereof.
Background
Due to industrial and agricultural developments, a large amount of heavy metal ions enter the human ecological environment, thereby causing a series of health and environmental problems. In the 50 s of the 20 th century, a japanese outbreak-water preferentially suffering "since which pollution by mercury ions began to receive worldwide attention. The mercury ions are biologically accumulated under the action of a food chain, finally enter a human body through food, water and other ways, and after being absorbed by the human body, the central nervous system and the endocrine system of the human body are damaged, so that various diseases are caused. Meanwhile, iodide ions are also an indispensable trace element in human bodies, but ingestion of too much iodide ions may increase the incidence of thyroid cancer. Therefore, how to detect Hg in an aqueous solution2+And I–The content of (b) becomes an important task for scientific research.
The development of new probes capable of selectively recognizing toxic and harmful heavy metal ions and anions has been receiving increasing attention. Identification of Hg reported at present2+Most of the probes are also detected in a solvent, have low selectivity and are easy to be subjected to Au3+、Fe2+And Fe3+The influence of (c). For example, Ceren Canturk et al, Royal Council of chemistry, England journal of the Royal college of chemistry (RSC Advances)2015, No. 5, No. 30522, No. 30525, article for identifying Hg2+And Au3+The BODIPY-based fluorescent Probe (ABODIPY-based fluorescent Probe for the differential recognition of Hg (II) and Au (III) ions) of2+And Au3+(ii) a An article by Kaushik Ghosh et al (European Journal of Inorganic Chemistry)2015 at 311-317 of phase 2 (application of a simple naphthylamine fluorescent probe to selectively detect Hg in mixed solution media in Living cells and logic Gate)2+、Fe2+And Fe3+》(A Simple Fluorescent Probe Derived from Naphthylamine for Selective Detection of HgII,FeII and FeIIIIons in Mixed Aqueous Media Applications in Living Cells and Logic Gates) published fluorescent probes for detection of Hg2+、Fe2+And Fe3+None of the above probes can specifically detect Hg2+(ii) a Yutao Yang et al, at 204, 402 and 406 of sensor and driver B, 2014, A Highly selective recognition of hydrogen sulfide and mercury (II) by a commercially available fluorescence chemical sensor and its use in bioimaging, discloses a fluorescence probe for Hg in a mixed solution of dimethyl sulfoxide and water2+And HS–Relay fluorescence detection; an article "high-potency Hg based on triazole-bridged anthracenes and quinolines at 251, 729 and 738 in Ramesh C.Gupta et al (Sensors and Actuators B)2017, pp 251, 7292+The system selectively detects cyanide (An efficient Hg) in solution and living cells through response of a fluorescent switch2+An intense based on a three bridged anthracene and quinoline system for a selective detection of a nitrile fluorine turn-off-on-response in solution and live cell) the above published fluorescent probes were in tetrahydrofuranPara Hg in mixed solution of pyran and water2+And CN–Relay fluorescence detection; muthu Vengaian et al, Sensors and Actuators B2016, 232, 240, phenothiazine-Diaminomalonyl Hg2+And S2-Colorimetric and fluorometric "on-off" sensors (Phenothiazine-diamminemalononitrile based colorimetric and fluorometric-Turn-off-on "sensing of Hg2+and S2–) The published fluorescent probe is to Hg in a mixed solution of ethanol and water2+And S2–Relay fluorescence detection. At present, no method for treating Hg in aqueous solution is available2+And I–Fluorescent probes for simultaneous detection.
Disclosure of Invention
The invention aims to solve the problem that the relay fluorescence detection of Hg in aqueous solution is not carried out at present2+And I–And the probe is susceptible to Au3+、Fe2+And Fe3+The technical problem of influence is solved, and the naphthalene derivative fluorescent probe, the preparation method and the application thereof are provided, and the probe can detect Hg in aqueous solution by high-selectivity relay fluorescence2+And I–。
The naphthalene derivative fluorescent probe is 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride, and the structural formula of the naphthalene derivative fluorescent probe is as follows:
The preparation method of the naphthalene derivative fluorescent probe comprises the following steps:
firstly, preparing 1-benzyl benzimidazole:
(1) taking benzimidazole, benzyl bromide, N-dimethylformamide and potassium hydroxide, wherein the molar ratio of the benzimidazole to the benzyl bromide is 1: 1-2, wherein the molar ratio of benzimidazole to sodium hydroxide is 1: 1-2; the ratio of the mole number of the benzimidazole to the volume of the N, N-dimethylformamide is 1 mmol: 3-5 mL;
(2) adding the benzimidazole and the potassium hydroxide weighed in the step (1) into a three-necked bottle provided with a stirring device, adding three fourths of the N, N-dimethylformamide weighed in the step (1) into the three-necked bottle, and introducing nitrogen for protection; stirring at room temperature until the mixture is dissolved; then mixing the benzyl bromide weighed in the step (1) with the rest N, N-dimethylformamide, dropwise adding the mixture into a three-necked bottle at a constant speed through a constant-pressure dropping funnel, controlling the temperature to be 60-65 ℃ during dropwise adding to react for 13-15 hours after dropwise adding is finished for 1 hour;
(3) after the reaction is finished, performing suction filtration, adding deionized water into the filtrate, adding dichloromethane for extraction, combining dichloromethane layers, extracting the dichloromethane layers with deionized water, finally adding anhydrous sodium sulfate into the dichloromethane layers for drying, filtering to remove sodium sulfate solids, and evaporating the solution to dryness to obtain 1-benzyl benzimidazole;
II, preparing 1-chloroacetamidonaphthalene:
(1) weighing 1-naphthylamine, chloroacetyl chloride, dichloromethane and pyridine, wherein the molar ratio of the 1-naphthylamine to the chloroacetyl chloride is 1: the molar ratio of 1-2, 1-naphthylamine to pyridine is 1: 1-2; the volume ratio of the mole number of the 1-naphthylamine to the dichloromethane is 1 mmol: 3-5 mL;
(2) adding the 1-naphthylamine and pyridine weighed in the step (1) into a three-necked bottle provided with a stirring device, adding three fourths of dichloromethane weighed in the step (1) into the three-necked bottle, and placing the three-necked bottle under the condition of ice-water bath and under the protection of nitrogen; stirring to dissolve; then mixing the chloroacetyl chloride weighed in the step (1) with the rest dichloromethane, dropwise adding the mixture into a three-necked bottle at a constant speed through a constant-pressure dropping funnel, after dropwise adding is finished for 2 hours, continuing to react for 4-5 hours, and stopping the reaction;
(3) removing dichloromethane using a rotary evaporator; cooling to room temperature, adding deionized water, precipitating solid, filtering, adding ethanol, and recrystallizing to obtain 1-chloroacetylaminonaphthalene;
thirdly, preparing 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride:
(1) taking the 1-benzyl benzimidazole prepared in the step one and the 1-chloroacetylaminonaphthalene prepared in the step two, and adding the mixture into a three-necked bottle provided with a condensation reflux device and a thermometerWherein the molar ratio of 1-benzylbenzimidazole to 1-chloroacetamidonaphthalene is 1: 1-2; acetonitrile (CH) is then added3CN) as a solvent, and stirring until the CN is dissolved;
(2) heating to 75-80 ℃, and reacting for 5-6 h;
(3) cooling the reaction liquid to room temperature, separating out white solid, and filtering to obtain a crude product; and recrystallizing the crude product by using acetonitrile and ethyl acetate to obtain the naphthalene derivative fluorescent probe, namely 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride.
The application of the naphthalene derivative fluorescent probe is to utilize the naphthalene derivative fluorescent probe to perform relay fluorescence detection on Hg in an aqueous solution2+And I–. The specific detection method is as follows:
firstly, preparing a probe solution by using a naphthalene derivative fluorescent probe as a solute and using a HEPES (high efficiency particulate exchange) buffer solution with the pH value of 7.4 as a solvent; wherein the concentration of the naphthalene derivative fluorescent probe in the probe solution is 1.0 × 10–5mol/L；
Secondly, adding a sample I to be detected into the probe solution to obtain a solution I to be detected;
measuring fluorescence emission spectra of the probe solution and the solution I to be detected, and recording the fluorescence intensity of the solution I to be detected at the position with the wavelength of 428nm as F428 ⅠThe fluorescence intensity at 342nm is denoted as F342 ⅠAnd calculating the fluorescence ratio A1＝F428 Ⅰ/F342 Ⅰ(ii) a The fluorescence intensity of the probe solution at a wavelength of 428nm was recorded as F428 0The fluorescence intensity at 342nm is denoted as F342 0And calculating the fluorescence ratio A0＝F428 0/F342 0(ii) a Then the fluorescence ratio A of the solution I to be detected is measured1Fluorescence ratio to probe solution A0In contrast, if A1/A0When the Hg content is 5 to 10, Hg is contained in the sample I to be measured2+The complex [ N-Hg ] is formed2+]A solution;
tetra-directional complex [ N-Hg [ ]2+]Adding a sample II to be detected into the solution to obtain a solution II to be detected;
fifthly, measuring the fluorescence emission spectrum of the solution II to be measured, and if the fluorescence intensity B of the solution II to be measured at the position with the wavelength of 428nm3Fluorescence intensity B of the sample solution I at 428nm2In contrast, B2/B31-3, the sample II contains I–Completing Hg2+And I–Relay fluorescence detection.
The naphthalene derivative fluorescent probe can be used for high-selectively and singly detecting Hg in a water system2+Independent of other metal ions in the aqueous solution, e.g. Al3+、Zn2+、Ag+、Ca2+、Mg2+、Fe3+、Pb2+、Na+、Ba2+、Ni2+、K+、Cu2+、Cr3+、Cd2+、Co2+The interference of (2) has stronger anti-interference capability. N-Hg at a pH of 7.0 to 11.02+The complex generates obvious fluorescence enhancement phenomenon at 428nm, and the probe can be used for Hg2+Detection of (3). Detection limit of 9.7 × 10–8mol/L. Using N-Hg2+Complex pair I–Identification, I–With N-Hg2+The complex is combined to generate a three-component composition, the chemical environment of the three-component composition is changed to cause the spectral change of the three-component composition, the fluorescence of the probe molecule is recovered, and the relay fluorescence detection I in the aqueous solution can be realized–. The naphthalene derivative fluorescent probe realizes the aim of the detection of Hg in an aqueous solution2+And I–The relay fluorescence detection has extremely high application value. Meanwhile, the fluorescent probe is used for detection, the technical phenomenon change is obvious, and the operation is simple and quick, so that the method is an environment-friendly detection method and can be used in the fields of environmental science, analytical chemistry, life science, medicine and the like.
Drawings
FIG. 1 is a graph showing fluorescence emission spectra of 1-benzyl-3- (1-naphthylamineacetyl) benzimidazole chloride [ N ] fluorescent probe for different cations in example 1.
FIG. 2 shows 1-benzyl-3- (1-naphthylamineacetyl) benzimidazolium chloride [ N ] in example 1]At different Hg2+Fluorescence spectrum change pattern at concentration.
FIG. 3 is the 1-benzyl-3- (1-naphthylamineacetyl) benzimidazole chloride [ N ] of example 1]Ratio of fluorescence intensities of fluorescent probe solutions (F)428/F342) With Hg2+Linear dependence of concentration.
FIG. 4 shows other common metal ions and Hg in example 12+In competition, 1-benzyl-3- (1-naphthylamineacetyl) benzimidazolium chloride [ N [ ]]Fluorescence change pattern of (2).
FIG. 5 is a graph showing the change of fluorescence intensity with pH of a 1-benzyl-3- (1-naphthylamineacetyl) benzimidazolium chloride [ N ] fluorescent probe solution in example 1.
FIG. 6 is N-Hg in example 12+Fluorescence emission spectra of the fluorescent probe for different anions.
FIG. 7 is N-Hg in example 12+Fluorescent probes at different I-Fluorescence spectrum change pattern at concentration.
FIG. 8 shows the other common anions and I in example 1–In competition, N-Hg2+Fluorescence change pattern of (2).
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: the preparation method of the naphthalene derivative fluorescent probe of the embodiment is carried out according to the following steps:
firstly, preparing 1-benzyl benzimidazole:
(1) taking benzimidazole, benzyl bromide, N-dimethylformamide and potassium hydroxide, wherein the molar ratio of the benzimidazole to the benzyl bromide is 1: 1.2, the molar ratio of benzimidazole to sodium hydroxide is 1: 1.2; the ratio of the mole number of the benzimidazole to the volume of the N, N-dimethylformamide is 1 mmol: 4 mL;
(2) adding the benzimidazole and the potassium hydroxide weighed in the step (1) into a three-necked bottle provided with a stirring device, adding three fourths of the N, N-dimethylformamide weighed in the step (1) into the three-necked bottle, and introducing nitrogen for protection; stirring at room temperature until the mixture is dissolved; then mixing the benzyl bromide weighed in the step (1) with the rest N, N-dimethylformamide, dropwise adding into a three-necked bottle at a constant speed through a constant-pressure dropping funnel, controlling the temperature to react at 60 ℃ in the dropwise adding process after 1h, tracking the reaction progress degree by TLC, completing the reaction after 13h, and finishing the reaction;
(3) after the reaction is finished, performing suction filtration, adding deionized water into the filtrate, adding dichloromethane for extraction for 3 times, combining dichloromethane layers, extracting the dichloromethane layer for 10 times by using deionized water, finally adding anhydrous sodium sulfate into the dichloromethane layer for drying, filtering to remove sodium sulfate solids, and evaporating the solution to dryness to obtain 1-benzyl benzimidazole;
II, preparing 1-chloroacetamidonaphthalene:
(1) weighing 1-naphthylamine, chloroacetyl chloride, dichloromethane and pyridine, wherein the molar ratio of the 1-naphthylamine to the chloroacetyl chloride is 1: 1.2, 1-naphthylamine to pyridine molar ratio of 1: 1.2; the volume ratio of the mole number of the 1-naphthylamine to the dichloromethane is 1 mmol: 4 mL;
(2) adding the 1-naphthylamine and pyridine weighed in the step (1) into a three-necked bottle provided with a stirring device, adding three fourths of dichloromethane weighed in the step (1) into the three-necked bottle, and placing the three-necked bottle under the condition of ice-water bath and under the protection of nitrogen; stirring to dissolve; then mixing the chloroacetyl chloride weighed in the step (1) with the rest dichloromethane, dropwise adding into a three-necked bottle at a constant speed through a constant-pressure dropping funnel, after finishing dropwise adding for 2 hours, continuing to react, monitoring the reaction process by adopting a TLC (thin layer chromatography) method, after reacting for 4 hours, finishing the reaction, and stopping the reaction;
(3) removing dichloromethane using a rotary evaporator; cooling to room temperature, adding deionized water, precipitating solid, filtering, adding ethanol, and recrystallizing to obtain 1-chloroacetylaminonaphthalene;
thirdly, preparing 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride:
(1) 0.4830g (2.2mmol) of 1-benzylbenzimidazole prepared in the first step and 0.4160g (2.0mmol) of 1-chloroacetamidonaphthalene prepared in the second step were taken and charged into a three-necked flask equipped with a condensing reflux unit and a thermometer, and 20mL of acetonitrile (CH) was added3CN) as a solvent, and stirring until the CN is dissolved;
(2) heating to 76-78 ℃, reacting, tracking the reaction process by TLC, and finishing the reaction after 5 h;
(3) cooling the reaction liquid to room temperature, separating out white solid, and filtering to obtain a crude product; the crude product was recrystallized from acetonitrile and ethyl acetate, and dried in an oven at 40 ℃ to constant weight, yielding 0.6050g of a white powdery solid, namely naphthalene derivative fluorescent probe 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride, in 73.1% yield.
The naphthalene derivative fluorescent probe obtained in the embodiment is subjected to Fourier infrared spectroscopy and mass spectrometry, and the results are as follows:
IR(KBr),ν/cm-1:3400,3115,2960,1688,1596,1548,1484,1354,977,870,744,690；
H-NMR:(600MHz,DMSO-d6)H:10.97(s,1H,NH),10.08～10.10(d,J＝14.4,1H,CH),8.30～8.31(d,J＝7.8,1H,ArH),8.18～8.19(d,J＝7.8,1H,ArH),8.01～8.03(d,J＝8.4,1H,ArH),7.96～7.98(d,J＝7.8,1H,ArH),7.81～7.82(d,J＝7.8,1H,ArH),7.71～7.73(d,J＝7.2,2H,ArH),7.67～7.69(t,J＝7.8,1H,ArH),7.57～7.61(m,2H,ArH),7.51～7.57(m,3H,ArH),7.42～7.44(t,J＝7.2,2H,ArH),7.38～7.40(t,J＝7.2,1H,ArH),2.89(s,2H,CH2—N+),5.81～5.85(m,J＝12.6,2H,CH2—N)；ESI-MS for N(C26H22ClN3O),m/z calcd.([M-Cl-]+),392.1757,found,392.1756。
the fourier infrared spectroscopy and mass spectrometry tests show that the naphthalene derivative fluorescent probe prepared in the embodiment has the structural formula:
the naphthalene derivative fluorescent probe [ N]And (4) showing.
The naphthalene derivative fluorescent probe [ N ] prepared in example 1 was used as a solvent in HEPES buffer solution having a pH of 7.4]As solute, the concentration is 1.0X 10–5mol/L probe solution. 16 kinds of cations were added to the probe solutions so that the concentrations of the cations were 1.0X 10–5mol/L, 16 cations are Al3+、Zn2+、Ag+、Ca2+、Mg2+、Fe3+、Hg2+、Pb2+、Na+、Ba2 +、Ni2+、K+、Cu2+、Cr3+、Cd2+、Co2+The fluorescence spectra of the test probe solution and the solution after addition of cations, as shown in FIG. 1, are only 1.0X 10 as seen in FIG. 1–5mol/L Hg2+After addition, Hg2+And N are combined to form an excimer, so that the fluorescence emission peak at 342nm is reduced to 175a.u., and the fluorescence emission peak at 428nm is enhanced to 496a.u., namely only Hg2+The fluorescence of N is obviously enhanced, and the fluorescence emission peak intensity at 428nm is recorded as F428 Ⅰ，F428 Ⅰ496 a.u.; the fluorescence emission peak intensity at 342nm is denoted F342 Ⅰ，F342 Ⅰ175 a.u.; calculating the fluorescence ratio A1＝F428 Ⅰ/F342 Ⅰ2.83; while the fluorescence emission peak intensity of the probe solution at 428nm is denoted as F428 0，F428 080a.u., the fluorescence emission peak intensity at 342nm is recorded as F342 0，F342 0248a.u., fluorescence ratio a0＝F428 0/F342 0When the value is 0.32, a can be calculated1/A0＝8.84。
And the fluorescence spectrum of the metal ion is not obviously changed after other metal ions are added. This is due to the addition of Hg to the HEPES system of the probe2+Thereafter, two probe compounds N and Hg2+And (3) interacting to ensure that one fluorophore (naphthalene group) is excited and the other fluorophore (naphthalene group) in a ground state form an excimer through pi-pi stacking, so that the monomer emission peak at 342nm is weakened, and the excimer emission peak at 428nm is strengthened. FIG. 1 also shows that the fluorescent probes prepared in this example are N vs Hg2+Has the characteristic of single-selection fluorescence detection. In fig. 1: the ordinate represents the fluorescence intensity and the abscissa represents the fluorescence wavelength.
The naphthalene derivative fluorescent probe prepared in example 1 was dissolved in HEPES buffer solution having a pH of 7.4 to prepare a solution having a concentration of 1.0X 10–5A probe solution of mol/L; then, the concentration of the mixture is varied (0 to 1X 10)-5mo/L) of Hg2+Added to the probe solution to test different concentrations of Hg2+The change in fluorescence emission spectra of the solutions, as shown in FIG. 2, can be seen from FIG. 2 as Hg2+The results that the monomer fluorescence emission peak of N at 342nm is gradually reduced and the association fluorescence emission peak at 428nm is gradually enhanced and equal emission points are formed at 370nm are shown by the continuous increase of the concentration, and the N is used as a ratio fluorescence probe for Hg2+Has higher sensitivity. In fig. 2: the ordinate represents the fluorescence intensity and the abscissa represents the fluorescence wavelength. With 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride [ N]Ratio of fluorescence intensities of fluorescent probe solutions (F)428/F342) As a longitudinal guide, in Hg2+The concentration is plotted on the abscissa, as shown in FIG. 3, from which in FIG. 3 it can be seen that Hg is2+The concentration is 1 to 9 x 10–6Fluorescence intensity vs. Hg at mol/L2+In a linear relation, the linear equation is that Y is 0.14318+2.93711X (linear correlation coefficient: R)20.99063); the blank was subjected to 20 replicates and the detection limit was calculated to be 9.7X 10 at 3. sigma/K (σ is the standard deviation of the blank and K is the slope of the regression equation)– 8mol/L. This result indicates that probe N can qualitatively detect Hg with high sensitivity2+。
The naphthalene derivative fluorescent probe N prepared in example 1 was dissolved in HEPES buffer solution having a pH of 7.4 to prepare a solution having a concentration of 1.0X 10–5A probe solution of mol/L; respectively adding 15 kinds of cation Al into the probe solution3+、Zn2+、Ag+、Ca2+、Mg2+、Fe3+、Pb2+、Na+、Ba2+、Ni2+、K+、Cu2+、Cr3+、Cd2+、Co2+The concentration of the cation is 2X 10- 5mol/L, shaking, standing for 5min, and adding Hg respectively2+To make Hg in the solution2+To a concentration of 1X 10-5And (5) shaking up to obtain a mixed solution. The fluorescence emission spectrum of the mixed solution was measured, as shown in FIG. 4, and it can be seen from FIG. 4 that the probe N dissolvedIn liquid according to a ratio of 2X 10-5The fluorescence intensity after adding the 15 cations at the mol/L concentration is close to that of the probe. When the 15 cations are mixed with Hg2+Coexisting and the cation concentration is Hg2+At 2 times the concentration, the probe N does not interfere with Hg2+The system still has obvious fluorescence enhancement response, which indicates that the probe N is applied to Hg2+The detection has excellent anti-interference performance and can be used for detecting Hg2+The fluorescence-enhanced probe of (1). In fig. 4: the ordinate represents the fluorescence intensity, and the abscissa represents the metal ion species.
The naphthalene derivative fluorescent probe N prepared in example 1 was dissolved in HEPES buffer solution having a pH of 7.4 to prepare a solution having a concentration of 1.0X 10–5A probe N solution of mol/L; hg is added into the probe N solution2+To make Hg2+Has a concentration of 1.0X 10–5mol/L to obtain Hg-containing2+Probe N solution of (1). Probe N solution and Hg-containing solution2+The pH value of the probe solution is adjusted by hydrochloric acid or sodium hydroxide solution, then the change situation of the fluorescence intensity of the solution along with the pH value is measured, as shown in figure 5, as can be seen from figure 5, two curves of the fluorescence intensity along with the change of the pH value show that when the pH value ranges from 7.0 to 11.0, Hg2+And a stable complex is formed with the probe N, so that the fluorescence of the solution is remarkably enhanced. The probe can be used for treating Hg in the pH range of 7.0-11.0, especially in the physiological environment of pH 7.35-7.452+The identification detection of (1).
After selective enhancement and identification, Hg is studied by fluorescence spectroscopy2+Stable complex N-Hg formed with probe N2+Relayed fluorescence detection capability of 18 anions in HEPES buffer solution with pH 7.4, wherein the 18 anions are F–、Cl–、Br–、I–、S2–、SCN–、HCO3 –、CO3 2–、SO3 2–、HSO3 –、SO4 2–、NO3 –、NO2 –、H2PO4 –、BrO3 –、SCN–、AcO–、PO4 3–. In the complex N-Hg2+The concentration is 1.0 × 10–5Adding the above 18 anions into the solution at mol/L to make the concentration of the anions reach 5 × 10-5mol/L, the fluorescence spectra of each solution were measured, as shown in FIG. 6, and as can be seen from FIG. 6, it was only 5X 10-5mol/L of I–The fluorescence intensity can be reduced compared to only small changes caused by other anions. N-Hg2+Complex pair I–Is due to the recognition of–With N-Hg2+The complex is combined to generate a three-component composition, so that the chemical environment of the three-component composition is changed to cause the spectrum of the three-component composition to change. Apparently, the complex N-Hg2+Can be used as a fluorescent probe in relay fluorescence detection and used for biological analysis. In fig. 6: the ordinate represents the fluorescence intensity and the abscissa represents the fluorescence wavelength.
In HEPES buffer solution with pH value of 7.4, different concentrations (0-5 × 10)-5mol/L) of I–Adding to a concentration of 1.0X 10–5mol/L of N-Hg2+In solution, the results of the change in fluorescence emission spectra at different concentrations were tested. As shown in FIG. 7, it can be seen from FIG. 7 that I is found to accompany I–Increase in concentration, N-Hg at 428nm2+Gradually decreases while the fluorescence intensity at 342nm remains substantially unchanged, N-Hg2+Complex pair I–Is based on I–With N-Hg2+The complex is combined to generate a three-component composition, so that the chemical environment of the three-component composition is changed to cause the spectrum of the three-component composition to change. This recognition pattern is different from the commonly reported I–Replacement of Hg2+Displacement method leading to its fluorescence recovery.
At a concentration of 1.0X 10–5mol/L of N-Hg2+Adding the solution into the solution at a concentration of 2 × 10-5mol/L of 17 anions (F)–、Cl–、Br–、S2–、HCO3 –、CO3 2–、SO3 2–、HSO3 –、SO4 2–、NO3 –、NO2 –、HPO4 2–、H2PO4 –、BrO3 –、SCN–、AcO–、PO4 3–) Shaking the solution, standing for 10min, and adding 1 × 10-5mol/L I–Shaking the solution evenly. The fluorescence spectrum of the test solution, as shown in FIG. 8, can be seen from FIG. 8, N-Hg2+Adding 2X 10 to the solution–5The fluorescence intensity of the 17 interfering ions and [ N-Hg ] in mol/L2+]The fluorescence intensity of (a) is close. When the 17 anions mentioned above are reacted with I–Co-exists at a concentration of I–At a concentration of 2 times, the [ N-Hg ] is not affected2+]To I–The detection shows that the system still has obvious fluorescence quenching phenomenon, which indicates that the system has N-Hg2+To I–The detection has excellent anti-interference performance.
Claims (7)
1. A naphthalene derivative fluorescent probe is characterized in that the probe is 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride, and the structural formula of the probe is as follows:
2. the method for preparing the naphthalene derivative fluorescent probe as claimed in claim 1, which is characterized by comprising the following steps:
firstly, preparing 1-benzyl benzimidazole:
(1) taking benzimidazole, benzyl bromide, N-dimethylformamide and potassium hydroxide;
(2) adding the benzimidazole and the potassium hydroxide weighed in the step (1) into a three-necked bottle provided with a stirring device, adding three fourths of the N, N-dimethylformamide weighed in the step (1) into the three-necked bottle, and introducing nitrogen for protection; stirring at room temperature until the mixture is dissolved; then mixing the benzyl bromide weighed in the step (1) with the rest N, N-dimethylformamide, dropwise adding the mixture into a three-necked bottle at a constant speed through a constant-pressure dropping funnel, controlling the temperature to be 60-65 ℃ during dropwise adding to react for 13-15 hours after dropwise adding is finished for 1 hour;
(3) after the reaction is finished, performing suction filtration, adding deionized water into the filtrate, adding dichloromethane for extraction, combining dichloromethane layers, extracting the dichloromethane layers with deionized water, finally adding anhydrous sodium sulfate into the dichloromethane layers for drying, filtering to remove sodium sulfate solids, and evaporating the solution to dryness to obtain 1-benzyl benzimidazole;
II, preparing 1-chloroacetamidonaphthalene:
(1) weighing 1-naphthylamine, chloroacetyl chloride, dichloromethane and pyridine;
(2) adding the 1-naphthylamine and pyridine weighed in the step (1) into a three-necked bottle provided with a stirring device, adding three fourths of dichloromethane weighed in the step (1) into the three-necked bottle, and placing the three-necked bottle under the condition of ice-water bath and under the protection of nitrogen; stirring to dissolve; then mixing the chloroacetyl chloride weighed in the step (1) with the rest dichloromethane, dropwise adding the mixture into a three-necked bottle at a constant speed through a constant-pressure dropping funnel, after dropwise adding is finished for 2 hours, continuing to react for 4-5 hours, and stopping the reaction;
(3) removing dichloromethane using a rotary evaporator; cooling to room temperature, adding deionized water, precipitating solid, filtering, adding ethanol, and recrystallizing to obtain 1-chloroacetylaminonaphthalene;
thirdly, preparing 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride:
(1) taking the 1-benzyl benzimidazole prepared in the step one and the 1-chloroacetylaminonaphthyl prepared in the step two, adding the mixture into a three-necked flask provided with a condensation reflux device and a thermometer, adding acetonitrile serving as a solvent, and stirring until the mixture is dissolved;
(2) heating to 75-80 ℃, and reacting for 5-6 h;
(3) cooling the reaction liquid to room temperature, separating out white solid, and filtering to obtain a crude product; and recrystallizing the crude product by using acetonitrile and ethyl acetate to obtain the naphthalene derivative fluorescent probe, namely 1-benzyl-3- (1-naphthylamine acetyl) benzimidazole chloride.
3. The method for preparing a naphthalene derivative fluorescent probe according to claim 2, wherein the molar ratio of benzimidazole to benzyl bromide in step one (1) is 1: 1-2, wherein the molar ratio of benzimidazole to sodium hydroxide is 1: 1-2; the ratio of the mole number of the benzimidazole to the volume of the N, N-dimethylformamide is 1 mmol: 3-5 mL.
4. The method for preparing a naphthalene derivative fluorescent probe according to claim 2 or 3, wherein the molar ratio of 1-naphthylamine to chloroacetyl chloride in the step two (1) is 1: the molar ratio of 1-2, 1-naphthylamine to pyridine is 1: 1-2; the volume ratio of the mole number of the 1-naphthylamine to the dichloromethane is 1 mmol: 3-5 mL.
5. The method for preparing a naphthalene derivative fluorescent probe according to claim 2 or 3, wherein the molar ratio of 1-benzylbenzimidazole to 1-chloroacetamidonaphthalene in step three (1) is 1: 1 to 2.
6. The use of the naphthalene derivative fluorescent probe as claimed in claim 1, wherein the use is in the relay fluorescence detection of Hg in an aqueous solution2+And I–。
7. The use of the naphthalene derivative fluorescent probe as claimed in claim 6, wherein the naphthalene derivative fluorescent probe is used for relay fluorescence detection of Hg in an aqueous solution2+And I–The method specifically comprises the following steps:
firstly, preparing a probe solution by using a naphthalene derivative fluorescent probe as a solute and using a HEPES (high efficiency particulate exchange) buffer solution with the pH value of 7.4 as a solvent; wherein the concentration of the naphthalene derivative fluorescent probe in the probe solution is 1.0 × 10–5mol/L；
Secondly, adding a sample I to be detected into the probe solution to obtain a solution I to be detected;
measuring fluorescence emission spectra of the probe solution and the solution I to be detected, and recording the fluorescence intensity of the solution I to be detected at the position with the wavelength of 428nm as F428 ⅠThe fluorescence intensity at 342nm is denoted as F342 ⅠAnd calculating the fluorescence ratio A1＝F428 Ⅰ/F342 Ⅰ(ii) a The fluorescence intensity of the probe solution at a wavelength of 428nm was recorded as F428 0The fluorescence intensity at 342nm is denoted as F342 0And calculating the fluorescence ratio A0＝F428 0/F342 0(ii) a Then the fluorescence ratio A of the solution I to be detected is measured1Fluorescence ratio to probe solution A0In contrast, if A1/A0When the Hg content is 5 to 10, Hg is contained in the sample I to be measured2+The complex [ N-Hg ] is formed2+]A solution;
tetra-directional complex [ N-Hg [ ]2+]Adding a sample II to be detected into the solution to obtain a solution II to be detected;
fifthly, measuring the fluorescence emission spectrum of the solution II to be measured, if the fluorescence intensity B of the solution II to be measured at 428nm3Fluorescence intensity B at 428nm with solution I to be tested2In contrast, B2/B31-3, the sample II contains I–Completing Hg2+And I–Relay fluorescence detection.
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