CN109370572B - Ratiometric fluorescent nano probe for visually detecting hypochlorite and preparation and application thereof - Google Patents
Ratiometric fluorescent nano probe for visually detecting hypochlorite and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a ratiometric fluorescent nano probe for visually detecting hypochlorite and preparation and application thereof, wherein the fluorescent nano probe is a novel ratiometric fluorescent nano probe prepared by taking polyethylene oxide-co-polystyrene, 4- (1,2, 2-triphenylethylene) acetophenone and 5-nitro salicylaldehyde prepared according to the prior art as raw materials. The fluorescent nano probe can realize high-selectivity and high-sensitivity rapid ratio detection of hypochlorite in a pure water solution. Compared with the existing fluorescence detection technology, the fluorescent nanoprobe obtained by the invention has the advantages of high selectivity ratio quick response and visual detection to hypochlorite, capability of effectively avoiding aggregation-induced fluorescence quenching phenomenon, excellent biocompatibility and water dispersibility, low input cost, simple synthetic route and the like, is suitable for amplified synthesis and practical production application, and has huge application prospect in the technical fields of analytical chemistry, life science, environmental science and the like.
Description
Technical Field
Technical Field
The invention belongs to the technical field of chemical material preparation and analysis detection, and particularly relates to a ratiometric fluorescence nanoprobe for visually detecting hypochlorite, and preparation and application thereof.
Background
Hypochlorite is a very important active oxygen species widely existing in biological cells and plays an important role in the oxidative stress process of a biological system, but because of the characteristics of high activity, low content, uneven distribution and the like, the research on the functions of hypochlorite in organisms becomes particularly important. In addition, hypochlorite is also widely used in the disinfection treatment of domestic water, such as tap water disinfection, swimming pool water disinfection, and the like. The united nations health organization states that for the treatment of these domestic waters, the effective free chlorine concentration cannot be less than 0.2 mg/L (5.6 μ M) because of the strong oxidizing and bleaching properties of hypochlorite, which can adversely affect the organisms on long term exposure. Therefore, it is very important to develop a fluorescent nanoprobe for visually detecting hypochlorite, and to apply the fluorescent nanoprobe to the visual detection of hypochlorite in an actual sample.
At present, many methods for detecting hypochlorite are developed, but mainly small molecular probes are used. However, with respect to small molecule probes, above all small molecule probes mostly work in pure organic solvents or mixed solvents, because their applicability is limited by the biotoxicity of organic solvents; secondly, the small molecule fluorescent probes developed at present have aggregation induced fluorescence quenching (ACQ) due to pi-pi interaction with each other, which further limits the applicability, and also leads to the reduced feasibility of the application of such probes in practical detection. Although some ratiometric fluorescent nanoprobes for detecting hypochlorous acid (such as chinese patent CN201610689409.8, CN 201610834650.5) have been developed, these fluorescent nanoprobes still do not solve the defects of ACQ, and cannot effectively detect the hypochlorite existing in alkaline environment. In recent years, fluorescent nanoprobes based on aggregation-induced emission (AIE) effect have received more and more attention due to their excellent water solubility, ability to effectively avoid ACQ, low cytotoxicity, no organic solvent residue, strong designability, high sensitivity, high selectivity and other advantages, and have shown extremely broad application prospects in the research fields of chemistry, medicine, environmental science and the like. In response to the above problems, AIE-based fluorescent nanoprobes (CN 201810983228.5) have been reported, in this work, only for hypochlorous acid response in acidic environments. However, the water environment in daily life is a neutral environment with a pH value of about 7, which results in great limitation on the detection application in environment and daily life. Therefore, the invention is a simple, low-cost, excellent water-solubility, low-biotoxicity, effective ACQ avoidance, high-efficiency and rapid visualization detection technology in neutral environment, and has important practical significance and application prospect.
The present invention has been made in view of this situation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ratiometric fluorescent nanoprobe for visually detecting hypochlorite as well as preparation and application thereof, wherein the ratiometric fluorescent nanoprobe is prepared by taking polyethylene oxide-co-polystyrene (CN 201810983228.5) and 4- (1,2, 2-triphenylvinyl) acetophenone (J. org. chem., 2006, 71(26), 9873-asarone 9876) prepared according to the prior art as raw materials. Further application research shows that the fluorescent nano probe can realize high-sensitivity and high-selectivity rapid ratio detection and visual detection on hypochlorite.
In order to solve the technical problems, the invention adopts the technical scheme that:
the ratiometric fluorescent nanoprobe for visually detecting hypochlorite is formed by coprecipitation of a product 1 and polyethylene oxide-co-polystyrene in water, wherein the structural formula of the product 1 is as follows:
wherein R is NO2And H.
The structural formula of the polyethylene oxide-co-polystyrene prepared according to patent CN201810983228.5 is:
wherein n/x is 113-10: 40.
the preparation method of the ratiometric fluorescent nanoprobe for visually detecting hypochlorite comprises the following steps:
step 1, dissolving a certain amount of 4- (1,2, 2-triphenylethylene) acetophenone and 5-nitro salicylaldehyde in acetonitrile, adding a certain amount of piperidine, and placing in N2Carrying out reflux reaction for a certain time under the conditions of protection and light protection, and removing 85-95% of solvent by rotary evaporation after the reaction is finishedSeparating and purifying the product by a column, and drying in vacuum to obtain a product 1;
and 2, preparing the product 1 into a tetrahydrofuran solution A with a certain concentration, preparing polyethylene oxide-co-polystyrene prepared by the prior art into a tetrahydrofuran solution B with a certain concentration, and preparing the required nanoprobe according to a coprecipitation technology reported in a patent CN 201610689409.8. The method comprises the following specific steps: respectively mixing a certain amount of A and B, adding into 10 mL of water under an ultrasonic condition, continuing to perform ultrasonic treatment for 10 min after finishing dripping, then removing tetrahydrofuran under reduced pressure at room temperature, and metering to 10 mL to obtain the required fluorescent nano probe, namely the ratiometric fluorescent nano probe for visually detecting hypochlorite.
Further, in the step (1), the molar ratio of 4- (1,2, 2-triphenylvinyl) acetophenone to 5-nitrosalicylaldehyde is 1-1: 5, preferably 1-1: 2, and the concentration of 4- (1,2, 2-triphenylvinyl) acetophenone in acetonitrile is 1-20 mg/mL, preferably 2-8 mg/mL; in the step (2), the mass ratio of the product 2 to the polyethylene oxide-co-polystyrene is 1: 5-50, preferably 1: 3-50, and the concentration of the polyethylene oxide-co-polystyrene in water is 0.05-0.5 mg/mL, preferably 0.1-0.3 mg/mL.
The structural formula of the polyethylene oxide-co-polystyrene is:
the target molecule (product 1) prepared according to the above preparation method has the following specific reaction process:
the fluorescent nano probe prepared by the preparation method is applied to visual and ratio detection of hypochlorite.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
The required ratiometric fluorescent nano-probe is prepared by taking polyethylene oxide-co-polystyrene, 4- (1,2, 2-triphenylvinyl) acetophenone and 5-nitrosalicylaldehyde, which are prepared by reversible addition-fragmentation chain transfer polymerization in the prior art, as raw materials, and the fluorescent nano-probe can generate a weak fluorescence enhancement phenomenon along with the increase of hypochlorite concentration at 467 nm and an obvious fluorescence reduction phenomenon along with the increase of hypochlorite concentration at 563 nm after being diluted by a buffer solution with the pH of 7.4 in the presence of hypochlorite, thereby further showing an obvious ratiometric detection effect. And as the hypochlorite concentration increases, under ultraviolet light, the solution gradually changes from bright orange-red fluorescence to bright cyan fluorescence. And the fluorescent nano probe has obvious high-selectivity quick response and visual detection on the detection of hypochlorite and can achieve the effect of high-sensitivity detection. Compared with the existing detection technologies, the fluorescent probe has the advantages of low cost investment, simple synthetic route and convenient post-treatment, can directly realize specific identification and visual detection on hypochlorite, and has important significance for the detection of domestic water such as tap water and the like.
The invention provides a fluorescent nano probe for detecting hypochlorite by visual ratio and application thereof, and the fluorescent nano probe is simple to prepare, high in sensitivity and expected to be widely applied in the fields of analytical chemistry and environmental detection science.
The invention has the beneficial effects and innovations that:
(1) the invention adopts the product synthesized by the mature technology, further utilizes the existing mature technology to successfully prepare the fluorescence nanoprobe for visually detecting hypochlorite, and the fluorescence nanoprobe has stable dispersity and smaller grain diameter (about 60 nm).
(2) The AIE dye molecule prepared by the invention shows double-color fluorescence emission in a single molecule, can well realize ratio fluorescence detection effect, and compared with a dual-wavelength ratio detection probe with different molecular combinations, the probe prepared by the invention has simpler preparation process under the condition of ensuring high precision in detection, is less influenced by environmental factors, and cannot cause ratio change due to the change of the proportion between a reference fluorophore and a detection fluorescence image.
(3) The fluorescent nano probe prepared by the invention has excellent light stability, long-term stability, selectivity and anti-interference performance, and can visually detect hypochlorite, so the fluorescent nano probe has very important application prospect in the fields of environment and the like.
(4) Compared with the reported fluorescent nanoprobe (ZL 201610071721.0; ZL 201610834650.5; ZL 201610689409.8; CN 201810983228.5) based on the nanoparticles and capable of detecting hypochlorous acid in an acidic environment, the AIE dye adopted by the invention not only can effectively avoid the ACQ effect, but also can effectively visually detect the hypochlorite in a neutral environment, and has more advantages in practical environment detection application.
(5) Compared with the reported alpha, beta-unsaturated carbonyl compounds (org, Lett, 2017, 19, 82-85; ACS chem, biol, 2015, 10, 864, 874; org, Lett, 2015, 17, 5978, 5981) for detecting the macromolecule reductive biological thiol (cysteine, glutathione and the like), the core-shell structure provided by the polymer can effectively avoid the problem of poor water solubility, can also effectively avoid the interference of the macromolecule thiol, and can better improve the accuracy and precision of detection.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention to its proper form. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a particle size diagram of the fluorescent nanoprobe of the present invention.
FIG. 2 is a schematic diagram of hypochlorite identification by the fluorescent nanoprobe of the present invention.
FIG. 3 is a drawing showingDifferent hypochlorite (ClO)-) At concentration, the fluorescence emission spectrum change pattern of the fluorescent nanoprobe (excitation wavelength: 365 nm) [ ClO ]-] = 0 (a)，0.5×10-6 mol/L (b）, 1.0×10-6 mol/L (c), 2.0×10-6mol/L(d)，4×10-6 mol/L (e), 6.0×10-6mol/L(f), 8×10-6mol/L (g), 1×10-5 mol/L (h), 1.5×10-5 mol/L (i), 2.0×10-5 mol/L (j), 3.0×10-5 mol/L (k), 4.0×10-5mol/L (l), 6.0×10-5 mol/L (m), 8.0×10-5 mol/L (n), 1.0×10-4 mol/L (o)。
FIG. 4 is a graph of data showing the selective comparison of the fluorescence ratio intensity of various ions to the fluorescent nanoprobe, wherein the concentration of the added ions is 2X 10-4mol/L, hypochlorite concentration of 2.0X 10-5 mol/L，I467And I563The fluorescence intensity change values of the fluorescent nanoprobes before and after the addition of each ion and peroxide at the excitation wavelength of 365 nm and the emission wavelengths of 467 nm and 563 nm.
FIG. 5 is a photograph of fluorescence photographs of nanoparticles loaded on filter paper and then placed in hypochlorite solutions of different concentrations for 2 min.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1: the preparation method of the ratiometric fluorescent nanoprobe for visually detecting hypochlorite comprises the following specific steps:
(1) 4- (1,2, 2-triphenylvinyl) acetophenone (0.267 mmol) and 5-nitro salicylaldehyde (0.401 mmol) were dissolved in 20 mL of acetonitrileSeveral drops of piperidine are added and placed in N2Carrying out reflux reaction for 12 hours under the conditions of protection and light protection, carrying out rotary evaporation to remove 85-95% of solvent after the reaction is finished, carrying out column separation and purification on the product, and carrying out vacuum drying to obtain a product 1;
(2) preparing a product 1 synthesized in the step (1) into a Tetrahydrofuran (THF) solution A of 0.02 mg/mL, preparing polyethylene oxide-co-polystyrene prepared according to patent CN201810983228.5 into a Tetrahydrofuran (THF) solution B of 2 mg/mL, mixing 1 mL of A and B respectively, adding into 10 mL of water under ultrasonic conditions, continuing to perform ultrasonic treatment for 10 min after dropwise addition is completed, then removing tetrahydrofuran under reduced pressure at room temperature, and fixing the volume to 10 mL to obtain the required fluorescent nano probe, namely the ratiometric fluorescent nano probe for visually detecting hypochlorite. The fluorescent nanoprobe exists in the form of nanoparticles, and the particle size data thereof are shown in fig. 1.
Example 2: the preparation method of the ratiometric fluorescent nanoprobe for visually detecting hypochlorite comprises the following specific steps:
(1) 4- (1,2, 2-Triphenylvinyl) acetophenone (0.267 mmol) and 5-nitrosalicylaldehyde (0.267 mmol) were dissolved in 10 mL acetonitrile, several drops of piperidine were added, and the mixture was placed in N2Carrying out reflux reaction for 8 hours under the conditions of protection and light protection, carrying out rotary evaporation to remove 85-95% of solvent after the reaction is finished, carrying out column separation and purification on the product, and carrying out vacuum drying to obtain a product 1;
(2) preparing a product 1 synthesized in the step (1) into a Tetrahydrofuran (THF) solution A of 0.02 mg/mL, preparing polyethylene oxide-co-polystyrene prepared according to patent CN201810983228.5 into a Tetrahydrofuran (THF) solution B of 1.5 mg/mL, mixing 1 mL of A and B respectively, adding into 10 mL of water under ultrasonic conditions, continuing to perform ultrasonic treatment for 10 min after the dropwise addition is completed, then removing the tetrahydrofuran under reduced pressure at room temperature, and fixing the volume to 10 mL to obtain the required fluorescent nano probe, namely the ratiometric fluorescent nano probe for visually detecting hypochlorite.
Example 3: the preparation method of the ratiometric fluorescent nanoprobe for visually detecting hypochlorite comprises the following specific steps:
(1) taking 4- (1,2, 2-triphenylethylene) acetophenone (0.2)67 mmol) and 5-Nitrosalicylaldehyde (0.534 mmol) were dissolved in 30 mL of acetonitrile, a few drops of piperidine were added, and the mixture was placed in N2Carrying out reflux reaction for 16 h under the conditions of protection and light protection, carrying out rotary evaporation to remove 85-95% of solvent after the reaction is finished, carrying out column separation and purification on the product, and carrying out vacuum drying to obtain a product 1;
(2) preparing a product 1 synthesized in the step (1) into a Tetrahydrofuran (THF) solution A of 0.02 mg/mL, preparing polyethylene oxide-co-polystyrene prepared according to patent CN201810983228.5 into a Tetrahydrofuran (THF) solution B of 2.5 mg/mL, mixing 1 mL of A and B respectively, adding into 10 mL of water under ultrasonic conditions, continuing to perform ultrasonic treatment for 10 min after the dropwise addition is completed, then removing the tetrahydrofuran under reduced pressure at room temperature, and fixing the volume to 10 mL to obtain the required fluorescent nano probe, namely the ratiometric fluorescent nano probe for visually detecting hypochlorite.
Example 4: detection experiment of hypochlorite.
0.3 mL of the fluorescent nanoprobe solution obtained in example 1 (the concentration of the original solution of the fluorescent nanoprobe was 0.204 mg/mL) was added to 14 5 mL sample bottles, 2.7 mL of a buffer solution having a pH of 7.4 was added in order, and the mixture was stirred for 3 min, followed by addition of [ ClO ] at a concentration of-] = 0 (a)，0.5×10-3 mol/L (b）, 1.0×10-3 mol/L (c), 2.0×10-3 mol/L(d)，4×10-3 mol/L (e), 6.0×10-3 mol/L(f), 8×10-3 mol/L (g), 1×10-2 mol/L (h), 1.5×10-2 mol/L (i), 2.0×10-2 mol/L (j), 3.0×10-2 mol/L (k), 4.0×10-2 mol/L (l), 6.0×10-2 mol/L (m), 8.0×10-2 mol/L (n), 1.0×10-1Adding 3 mu L of hypochlorite solution of mol/L (o) into 14 sample bottles, stirring for 2 min at normal temperature, and respectively measuring the fluorescence emission spectrum of each sample by taking 365 nm as an excitation wavelength to obtain a fluorescence emission spectrum change diagram of 14 samples, wherein the diagram is shown in FIG. 3. The measurement result shows that: the fluorescence intensity of the fluorescent nano probe at 467 nm slightly increases along with the gradual increase of the concentration of hypochlorite, and the fluorescence intensity at 563 nm obviously decreases.
Example 5: comparative testing of other ionic and peroxide effects.
Each of 12 5 mL sample bottles was filled with 0.3 mL of the fluorescent nanoprobe solution obtained in example 1 (the concentration of the fluorescent nanoprobe was 0.204 mg/mL), 2.7 mL of a buffer solution having a pH of 7.4 was sequentially added thereto, and after stirring for 3 min, Na was added at a concentration of 0.2 mol/L+、K+、Ni2+、Co2+、Ca2+、Zn2+、Fe2+、1O2(singlet oxygen), H2O2(Hydrogen peroxide), TBHP (tert-Butanol peroxide) solution and concentration of 2.0X 10-2Adding 3 mu L of the hypochlorite solution of mol/L into a sample bottle of No. 2-12, wherein the sample of No. 1 is a blank sample. Then, fluorescence spectrum data of 12 samples under 365 nm wavelength excitation were measured, respectively, to obtain the change values of the fluorescence ratio at 467 nm and 563 nm wavelength emissions, and the results are shown in FIG. 4. The measurement result shows that: the various ions and peroxides mentioned above have no significant effect on the fluorescence ratio intensity of the prepared fluorescent nanoprobe other than hypochlorite.
Example 6: and (3) an experiment for detecting hypochlorite in an actual aqueous solution by using test paper as a carrier.
Taking filter paper, cutting into small discs with the diameter of 1 cm, then taking dispersed liquid to drop on the filter paper for drying, and repeating the operation for 5 times to obtain the test strip. Then preparing an actual sample with the hypochlorous acid heel concentration of 0 muM, 5 muM, 10 muM, 30 muM, 60 muM and 100 muM, and sequentially placing the prepared test strip in a solution for 2 min. Then, the film was taken out, dried and photographed under an ultraviolet lamp of 365 nm, and the result was shown in FIG. 5. The measurement result shows that: the test paper prepared by the nano particles can well visually detect hypochlorite in an aqueous solution by fluorescence.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The ratiometric fluorescent nano probe for visually detecting hypochlorite is characterized in that a probe molecule product 1 has a structural formula as follows:
wherein R is NO2。
2. The preparation method of the ratiometric fluorescent nanoprobe for visually detecting hypochlorite according to claim 1, which comprises the following steps:
step 1, dissolving a certain amount of 4- (1,2, 2-triphenylethylene) acetophenone and 5-nitro salicylaldehyde in acetonitrile, adding a certain amount of piperidine, and placing in N2Carrying out reflux reaction for a certain time under the conditions of protection and light resistance, carrying out rotary evaporation to remove 85-95% of solvent after the reaction is finished, carrying out column separation and purification on the product, and carrying out vacuum drying to obtain a product 1;
step 2, preparing the product 1 into a tetrahydrofuran solution A with a certain concentration, preparing polyethylene oxide-co-polystyrene prepared according to the technology into a tetrahydrofuran solution B with a certain concentration, respectively mixing a certain amount of A, B, adding into water under the ultrasonic condition, continuing to perform ultrasonic treatment for 10 min after the dropwise addition is completed, then removing the tetrahydrofuran under reduced pressure at room temperature, and performing constant volume to obtain a required fluorescent nano probe, namely a ratiometric fluorescent nano probe for visually detecting hypochlorite;
the structural formula of the polyethylene oxide-co-polystyrene is:
3. the method for preparing the ratiometric fluorescent nanoprobe for visually detecting hypochlorite according to claim 2, wherein in the step 1, the molar ratio of 4- (1,2, 2-triphenylvinyl) acetophenone to 5-nitrosalicylaldehyde is 1-1: 5, and the concentration of 4- (1,2, 2-triphenylvinyl) acetophenone in acetonitrile is 1-20 mg/mL.
4. The method for preparing the ratiometric fluorescent nanoprobe for visually detecting hypochlorite according to claim 2, wherein in the step 1, the molar ratio of 4- (1,2, 2-triphenylvinyl) acetophenone to 5-nitrosalicylaldehyde is 1-1: 2, and the concentration of 4- (1,2, 2-triphenylvinyl) acetophenone in acetonitrile is 2-8 mg/mL.
5. The method for preparing the ratiometric fluorescent nanoprobe for visually detecting hypochlorite according to claim 2, wherein in the step 2, the mass ratio of the product 1 to the polyethylene oxide-co-polystyrene is 1: 5-50, and the concentration of the polyethylene oxide-co-polystyrene in water is 0.05-0.5 mg/mL.
6. The method for preparing the ratiometric fluorescent nanoprobe for visually detecting hypochlorite according to claim 2, wherein in the step 2, the mass ratio of the product 1 to the polyethylene oxide-co-polystyrene is 1: 3-50, and the concentration of the polyethylene oxide-co-polystyrene in water is 0.1-0.3 mg/mL.
7. Use of the ratiometric fluorescent nanoprobe of claim 1 for the visual detection of hypochlorite in the visual and ratiometric detection of hypochlorite.
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