CN112409430A - Fluorescent probe capable of detecting viscosity and hydrogen sulfide, preparation and application thereof - Google Patents
Fluorescent probe capable of detecting viscosity and hydrogen sulfide, preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorescent probe capable of detecting viscosity and hydrogen sulfide, and preparation and application thereof. The fluorescent probe can detect viscosity change with high sensitivity, and can realize high selectivity and high sensitivity rapid ratio detection of hydrogen sulfide under a certain viscosity condition. Compared with the existing fluorescence detection technology, the fluorescent probe obtained by the invention has the advantages of simple preparation, mature synthetic route, dual detection functions, good selectivity, strong anti-interference capability, suitability for amplification synthesis and practical production application, and huge application prospect in the technical fields of analytical chemistry, life science, environmental science and the like.
Description
Technical Field
The invention relates to the fields of analytical chemistry, life science, environmental science and the like, in particular to preparation of a fluorescent probe with dual detection functions of viscosity and hydrogen sulfide and application of the fluorescent probe to viscosity and hydrogen sulfide detection.
Background
The viscosity is an important index for reflecting the viscosity degree of the solution, mainly depends on the diffusion speed of substances in the solution, has very important application value in the macroscopic and microscopic fields, and plays a crucial role in the whole life system in the viscosity level of the internal environment of the biological system. When the blood plasma viscosity of human body is gradually increased, various diseases, such as hypertension, hyperlipemia, cerebral infarction, heart disease, etc., can be induced, thus endangering the safety of people.
Hydrogen sulfide molecule (H2S) plays a very important role in regulating human physiological functions as one of important signal molecules in the body, and hydrogen sulfide can participate in hemoglobin modification, promote the reduction of nitroso compounds in the body, and regulate the functions of various enzymes in the body. And the hydrogen sulfide molecules in vivo have been shown to be closely related to many serious diseases, such as: hydrogen sulfide molecules can regulate the microvascular circulation in the normal liver and in the liver cirrhosis; and the heart muscle contraction force can be effectively adjusted, the blood vessels can be dilated, and the blood pressure can be stably and bidirectionally adjusted.
Currently, many methods have been developed for detecting viscosity and hydrogen sulfide. However, most detection methods have high cost investment and complicated detection process, and these factors severely restrict the application of some methods in practical detection. Fluorescent probes have become a major detection tool in life and environmental sciences due to their high sensitivity, good selectivity, easy synthesis, low cost, and good biological applications. Small-molecule fluorescent probes (CN106634968A, CN109053549A, CN106986782A) for detecting viscosity, small-molecule hydrogen sulfide fluorescent probes (CN108558875A, CN109134483A, CN109422721A), and the like are also reported in some patents. However, some fluorescent probe molecules can only detect viscosity or hydrogen sulfide, and can not realize detection of multiple response modes of one probe. Therefore, the simple, efficient and multi-response detection technology has quite 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 provides a fluorescent probe capable of detecting viscosity and hydrogen sulfide and preparation and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the preparation of fluorescent probe capable of detecting viscosity and hydrogen sulfide includes the following steps:
(1) dissolving the product 11,1' - (9H-carbazole-3, 6-diyl) bis (ethan-1-one) and potassium hydroxide in ethanol, heating at 70 ℃ for 6H, then evaporating the solvent and drying to obtain an intermediate product which is a yellowish brown solid, and using the intermediate product in the next step without further purification;
(2) dissolving the intermediate product synthesized in the step (1) in dimethyl sulfoxide, dropwise adding 3-bromopropyne, stirring at room temperature for 6h, dissolving the crude product in dichloromethane, washing with water, drying the organic layer with anhydrous sodium sulfate, concentrating, separating and purifying by using a silica gel chromatographic column, and drying in vacuum to obtain a corresponding product 2;
(3) adding the product 2 synthesized in the step (2) and 4- (diethylamino) salicylaldehyde into methanesulfonic acid, stirring for 12h at 90 ℃, cooling to room temperature, adding the mixture into an ice water solution, adding 70% perchloric acid, extracting the obtained mixture with dichloromethane, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, separating and purifying with a silica gel chromatographic column, and drying under vacuum to obtain a corresponding product 3;
(4) taking a product 4 synthesized by a corresponding product 4(2R, 3R, 4S, 5S, 6R) -2-azido-6- (hydroxymethyl) tetrahydro-2H-pyran-3, 4, 5-triol, a product 3 synthesized in the step (3), beta-sodium ascorbate and copper sulfate pentahydrate, sealing a tube with 10mL, adding a tetrahydrofuran-water (3:2(v/v)) mixed solvent, filling nitrogen and discharging oxygen, reacting for 24H at room temperature, performing reduced pressure spin-drying, washing and drying with dichloromethane for multiple times, washing with distilled water for multiple times to obtain a black solid, and performing vacuum drying to obtain the required fluorescent probe, namely the fluorescent probe with viscosity and hydrogen sulfide detection function, wherein the structural formula is as follows:
further, in the step (1), the molar ratio of the product 1 to the potassium hydroxide is 1: 1-1.5, preferably 1: 1.2; in the step (2), the molar ratio of the intermediate product to the 3-bromopropyne is 1: 5-20, preferably 1: 10; in the step (3), the molar ratio of the product 2 to the 4- (diethylamino) salicylaldehyde is 1: 2-5, preferably 1:3, the reaction temperature is 60-80 ℃, preferably 75 ℃, the reaction time is 3-7 hours, preferably 5 hours, and the concentration of the product 2 in the methane sulfonic acid is 0.1-0.5 mol/L, preferably 0.2 mol/L; in the step (4), the molar ratio of the product 3 to the product 4 is 1: 2-5, preferably 1:3mol, and the volume ratio of the solvent water to the tetrahydrofuran is 1: 1-3, preferably 1: 1.5.
The specific reaction process of the fluorescent probe molecule prepared by the preparation method is as follows:
in the above reaction process, product 1 was synthesized according to the known literature (Dyes and Pigments 133(2016) 238-247); product 4 was synthesized according to the known patent CN 106543251A.
A fluorescent probe prepared according to the preparation method.
The fluorescent probe prepared by the preparation method is applied to the rapid detection of viscosity and hydrogen sulfide.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
The required fluorescent probe is prepared by reacting carbazole, 4- (diethylamino) salicylaldehyde and tetraacetyl-alpha-D-bromogalactose, and on one hand, the fluorescent intensity of the probe is obviously enhanced at 630nm along with the increase of viscosity. On the other hand, under the condition of certain viscosity, the fluorescent probe has H2S, when present, will follow H at 560nm2The increase in S concentration shows a significant fluorescence enhancement, whereas at 630nm, with H2The increase of the S concentration shows an obvious fluorescence reduction phenomenon, and further shows an obvious ratio detection effect. The fluorescent sensor has obvious high-selectivity quick response to the detection of viscosity and hydrogen sulfide, and can achieve the effect of high-sensitivity detection. Compared with the existing detection technologies, the fluorescent chemical probe has the advantages of low cost investment, simple synthetic route, convenient post-treatment, capability of directly realizing rapid specific identification on viscosity and hydrogen sulfide, and suitability for scale-up production and practical application. Especially, the application to the internal environment of organisms such as mitochondria and the like is of great significance.
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 nuclear magnetic diagram of the prepared fluorescent probe.
FIG. 2 is a schematic diagram showing the identification of viscosity and hydrogen sulfide by the prepared fluorescent probe.
FIG. 3 is a graph showing the change in fluorescence emission spectrum of a fluorescent probe at different viscosity concentrations (excitation wavelength: 470nm, to which a hydrogen sulfide scavenger has been added).
FIG. 4 is a graph showing a function of a fitted curve corresponding to a change value of fluorescence intensity of a fluorescent probe with respect to a change in viscosity and a curve corresponding to the fitted curve.
FIG. 5 is a graph showing the change of fluorescence emission spectrum of a fluorescent probe (λ ex 470nm) at different hydrogen sulfide concentrations under a constant viscosity condition, [ H ]2S]＝0(a)，2.0×10-6mol/L(b)，4.0×10-6mol/L(c)，6.0×10-6mol/L(d)，8×10-6mol/L(e)，1.0×10-5mol/L(f)，1.2×10-5mol/L(g)，1.4×10-5mol/L(h)，1.6×10- 5mol/L(i)，2.0×10-5mol/L(j)，2.4×10-5mol/L(k)，2.8×10-5mol/L(l)，3.2×10-5mol/L(m)，3.6×10-5mol/L(n)，4.0×10-5mol/L(o)，4.4×10-5mol/L(p)，4.8×10-5mol/L(q)，5.2×10-5mol/L(r)，5.6×10-5mol/L(s)，6.0×10-5mol/L(t)，6.4×10-5mol/L(u)，6.8×10- 5mol/L (v) (Note: the fluorescent probe concentration is 5. mu.M).
FIG. 6 shows fluorescence probe with H under certain viscosity condition2And a fitted curve corresponding to the fluorescence intensity change value with the change of the S concentration and a function graph corresponding to the curve.
FIG. 7 is a graph showing the selective comparison of the fluorescence ratio intensity of various ions to the fluorescent probe under a certain viscosity condition, wherein the concentration of the added ions is 6.0X 10-4mol/L, hydrogen sulfide concentration of 6.8X 10-5mol/L，I560And I630The fluorescence intensity change values of the fluorescent probes before and after the addition of each ion and peroxide at the excitation wavelength of 470nm and the emission wavelengths of 560nm and 630 nm.
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: preparation of a fluorescent probe with hydrogen sulfide and viscosity detection functions.
The method comprises the following steps:
(1) and (4) preparing an intermediate product.
A mixture of the product 11,1' - (9H-carbazole-3, 6-diyl) bis (ethan-1-one) (251.1mg, 1mmol) and potassium hydroxide (67.2mg, 1.2mmol) in ethanol (40mL) was heated at 70 ℃ for 6H. The solvent was then evaporated and dried to give the intermediate as a yellow-brown solid, which was used in the next step without further purification.
(2) Product 2 was synthesized using the intermediate product.
The intermediate synthesized in step (1) was completely dissolved in dimethyl sulfoxide, 3-bromopropyne (159.0mg, 10mmol) was added dropwise thereto, and stirred at room temperature for 6 hours, after which the crude product was dissolved in dichloromethane (60mL) and washed with water (105 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated, and the pure product was extracted on a column to give the corresponding product 2(143 mg).
(3) Product 3 was synthesized using product 2 and 4- (diethylamino) salicylaldehyde.
Product 2(86.7mg, 0.3mmol),4- (diethylamino) salicylaldehyde (173.7mg, 0.9mmol) was added to a 10mL round-bottom flask, which was then added to methanesulfonic acid (1mL) and stirred at 75 ℃ for 5 h. After cooling to room temperature, the mixture was added to an ice-water solution (30g), followed by 70% perchloric acid (1 mL). The resulting mixture was extracted with dichloromethane (120mL) in portions, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure, and the pure product was extracted on a column with dichloromethane: methanol (100: 1 by volume) was passed through the column to give the corresponding product 3(56.8 mg).
(4) The probe was synthesized using product 3 and product 4.
Taking the corresponding product 4(2R, 3R, 4S, 5S, 6R) -2-azido-6- (hydroxymethyl) tetrahydro-2H-pyran-3, 4, 5-triol (61.0mg,0.1mmol), the product 3(83.0mg,0.4mmol), the beta-sodium ascorbate (6.0mg, 0.03mmol) and the copper sulfate pentahydrate (4.0mg, 0.015mmol) to a 10mL sealed tube, adding 5mL of tetrahydrofuran-water (3:2) mixed solvent, charging nitrogen and discharging oxygen, reacting for 24H at room temperature, performing rotary drying under reduced pressure, washing and drying by using dichloromethane for multiple times, then washing by using distilled water for multiple times to obtain a black solid, and performing vacuum drying to obtain the required fluorescent probe, namely the fluorescent probe with hydrogen sulfide and viscosity recognition functions.
Example 2: and (5) viscosity detection experiment.
A test stock of dimethyl sulfoxide (DMSO) was prepared at a concentration of 0.5mM for the fluorescent probe obtained in example 1, and 50mg of hydrogen sulfide scavenger was added for use.
10 sample bottles of 5mL were taken, and 3mL of solvents of glycerol and methanol in different ratios (glycerol: methanol 8.5:1.5, 8.0:2.0, 7.5:2.5, 7:3, 6.5:3.5, 6:4, 5:5, 4:6, 3:7, 2:8) were taken, i.e. viscosity was 453.17, 347.73, 263.93, 198.02, 146.75, 107.34, 35.01, 26.44, 11.8, 4.83pa.s, respectively. Then, the probe stock solution (final concentration: 5. mu.M) was added, and fluorescence scanning (excitation wavelength: 470nm) was performed to measure the relative fluorescence intensity in each system, as shown in FIG. 3. As can be seen from fig. 3, as the viscosity of the solvent increases, the relative fluorescence intensity becomes stronger, and a corresponding fitted relatively ideal function graph and a function graph corresponding to the function graph can be made according to the fluorescence intensity variation value of fig. 3, as shown in fig. 4.
Example 3: detection experiment of hydrogen sulfide.
A test mother liquor of dimethyl sulfoxide (DMSO) was prepared at a concentration of 0.5mM of the fluorescent probe obtained in example 1, and the viscosity of the mother liquor was fixed.
To 22 5mL sample bottles, 0.03mL of the mother liquor prepared with the fluorescent probe obtained in example 1 was added, and then glycerol: the volume ratio of methanol is 85: 15, 2.97mL, and then the concentrations were adjusted to [ H ]2S]＝0(a)，2.0×10- 3mol/L(b)，4.0×10-3mol/L(c)，6.0×10-3mol/L(d)，8×10-3mol/L(e)，1.0×10-2mol/L(f)，1.2×10-2mol/L(g)，1.4×10-2mol/L(h)，1.6×10-2mol/L(i)，2.0×10-2mol/L(j)，2.4×10-2mol/L(k)，2.8×10-2mol/L(l)，3.2×10-2mol/L(m)，3.6×10-2mol/L(n)，4.0×10-2mol/L(o)，4.4×10-2mol/L(p)，4.8×10-2mol/L(q)，5.2×10-2mol/L(r)，5.6×10-2mol/L(s)，6.0×10-2mol/L(t)，6.4×10-2mol/L(u)，6.8×10-2Adding 3 mu L of hydrogen sulfide solution of mol/L (v) into 22 sample bottles, stirring for 10min at normal temperature, and measuring the fluorescence intensity of the samples by taking 470nm as an excitation wavelength to obtain a fluorescence emission spectrum change diagram of the 22 samples, wherein the diagram is shown in figure 5. The measurement result shows that: under certain viscosity condition, the fluorescence intensity of the fluorescent probe at 560nm can follow H2The increase in S concentration shows a significant fluorescence enhancement, whereas at 630nm, with H2The increase of the S concentration shows a significant fluorescence decrease, and a corresponding fitted relatively ideal function curve graph and a function graph corresponding to the curve can be made according to the fluorescence intensity change value of fig. 5, as shown in fig. 6.
Example 4: comparative testing of other ionic and peroxide effects.
A test mother liquor of dimethyl sulfoxide (DMSO) was prepared at a concentration of 0.5mM of the fluorescent probe obtained in example 1, and the viscosity of the mother liquor was fixed.
25 5mL sample bottles were taken, 0.03mL of the mother solution prepared with the fluorescent probe obtained in example 1 was added, and then glycerol: the volume ratio of methanol is 85: 15.97 mL of each mixed solution, 0.1mol/L of Ca was added2+、Fe2+、Ni2+、Cu2+、Zn2+、Mg2+、Ca2+、H2O2、Na+、K+、NO3-、SO4 2-、Cl-、Ac-、H2PO4 2-TBHP (t-butyl peroxide), t-BuO (t-butyl peroxide radical), HO (hydroxyl radical), H2O218. mu.L of each of the (hydrogen peroxide) Hys, Cys and GSH solutions was added to 23 sample bottles, and 3. mu.L of each of the solutions was collected at a concentration of 6.8X 10-5mol/H of L2The S solution was added to sample No. 24 and sample No. 0 was blank. Then, fluorescence spectrum data of 25 samples under 470nm wavelength excitation were measured, respectively, to obtain the change values of the fluorescence ratio at 470nm and 630nm wavelength emission, and the results are shown in FIG. 7. The measurement result shows that: at a certain viscosity, except for H2S, the other ions and peroxides have no significant effect on the fluorescence ratio intensity of the prepared fluorescence transmission probe.
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 (10)
1. A fluorescent probe capable of detecting viscosity and hydrogen sulfide is characterized by being prepared from carbazole, 4- (diethylamino) salicylaldehyde and tetraacetyl-alpha-D-bromogalactose serving as raw materials, wherein the chemical name of the fluorescent probe is 2,2' - (9- ((1- ((3R, 4S, 5S, 6R) -3,4, 5-trihydroxy-6- (hydroxymethyl) tetrahydro-2H-pyran-2-yl) -1H-1,2, 3-triazol-4-yl) methyl) -9H-carbazole-3, 6-diyl) bis (7- (diethylamino) pyran), and the structural formula of the fluorescent probe is as follows:
2. a preparation method of a fluorescent probe capable of detecting viscosity and hydrogen sulfide is characterized by comprising the following steps:
(1) dissolving the product 11,1' - (9H-carbazole-3, 6-diyl) bis (ethan-1-one) and potassium hydroxide in ethanol, heating at 70 ℃ for 6H, then evaporating the solvent and drying to obtain an intermediate product which is a yellowish brown solid, and using the intermediate product in the next step without further purification;
(2) dissolving the intermediate product synthesized in the step (1) in dimethyl sulfoxide, dropwise adding 3-bromopropyne, stirring at room temperature for 6h, dissolving the crude product in dichloromethane, washing with water, drying and concentrating the organic layer with anhydrous sodium sulfate, separating and purifying by using a silica gel chromatographic column, and drying in vacuum to obtain a corresponding product 2;
(3) adding the product 2 synthesized in the step (2) and 4- (diethylamino) salicylaldehyde into methanesulfonic acid, heating and stirring at 90 ℃ for 5 hours, cooling to room temperature, adding the mixture into an ice water solution, adding 70% perchloric acid, extracting the obtained mixture with dichloromethane, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, separating and purifying with a silica gel chromatographic column, and drying under vacuum to obtain a corresponding product 3;
(4) taking the corresponding product 4(2R, 3R, 4S, 5S, 6R) -2-azido-6- (hydroxymethyl) tetrahydro-2H-pyran-3, 4, 5-triol, adding the product 3 synthesized in the step (3), beta-sodium ascorbate and copper sulfate pentahydrate into a 10mL sealed tube, adding a tetrahydrofuran-water (3:2(v/v)) mixed solvent, filling nitrogen and discharging oxygen, reacting for 24H at room temperature, performing rotary drying under reduced pressure, washing and drying with dichloromethane for multiple times, washing with distilled water for multiple times to obtain a black solid, and performing vacuum drying to obtain a product 5 which is a fluorescent probe capable of detecting viscosity and hydrogen sulfide.
3. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (1), the molar ratio of the product 1 to the potassium hydroxide is 1: 1-1.5.
4. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (1), the molar ratio of the product 1 to the potassium hydroxide is 1: 1.2.
5. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (2), the molar ratio of the intermediate substance to the 3-bromopropyne is 1: 5-20.
6. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (2), the molar ratio of the intermediate substance to the 3-bromopropyne is 1: 10.
7. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (3), the molar ratio of the product 2 to the 4- (diethylamino) salicylaldehyde is 1: 2-5, the reaction temperature is 60-80 ℃, the reaction time is 3-7 hours, and the concentration of the product 2 in the methane sulfonic acid is 0.1-0.5 mol/L, preferably 0.2 mol/L.
8. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (3), the molar ratio of the product 2 to the 4- (diethylamino) salicylaldehyde is 1:3, the reaction temperature is 75 ℃, the reaction time is 5 hours, and the concentration of the product 2 in the methane sulfonic acid is 0.2 mol/L.
9. The method for preparing a fluorescent probe capable of detecting viscosity and hydrogen sulfide as claimed in claim 2, wherein: in the step (4), the molar ratio of the product 3 to the product 4 is 1: 2-5, preferably 1:3, and the volume ratio of the solvent water to the tetrahydrofuran is 1: 1-3, preferably 1: 1.5.
10. Use of a fluorescent probe according to claim 1 or prepared according to any one of claims 2 to 9 for the detection of viscosity and hydrogen sulfide.
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|---|---|---|---|---|
| CN114805262A (en) * | 2022-05-05 | 2022-07-29 | 曲阜师范大学 | Viscosity and polarity response type platform fluorescent probe, hydrogen sulfide detection fluorescent probe, synthesis process and application thereof |
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