CN109608382A - A kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application - Google Patents

A kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application Download PDF

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CN109608382A
CN109608382A CN201910072311.1A CN201910072311A CN109608382A CN 109608382 A CN109608382 A CN 109608382A CN 201910072311 A CN201910072311 A CN 201910072311A CN 109608382 A CN109608382 A CN 109608382A
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cyanide ion
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刘益江
潘华
刘书智
欧志鹏
陈红飙
黎华明
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Xiangtan University
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Abstract

Disclose a kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application.Probe of the invention it be using phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone as raw material, pass through Fischer react etc. synthesis N- ethyl -2,3,3- tri-methyl indole -5- potassium sulfonate；Condensing agent for synthesizing is reacted by Vilsmeier-Haack；Condensing agent and N- ethyl -2,3,3- tri-methyl indole -5- potassium sulfonate carry out Knoevenagel Condensation and reacts then to obtain with N- phenyl -3- carbazole boric acid by Suzuki coupling reaction again.Probe of the invention is near-infrared probe, which has the characteristics that highly selective, high sensitivity and quick response to cyanide ion and hypochlorous acid.

Description

A kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application
Technical field
The invention belongs to chemical analysis detection technique fields, and in particular to a kind of detection cyanide ion and hypochlorous fluorescence Probe and its methods for making and using same.
Background technique
Cyanide plays very important effect in the industrial production, is widely used in exploitation of gold deposit, plating, resin and fibre The fields such as dimension synthesis.However, cyanide is violent in toxicity, lethal dose 0.5-3.5mg/kg.Cyanide can pass through lung, skin Skin, contaminated food and the intake of contaminated drinking water are internal.Cyanide ion can inhibit the cellular respiration in mammal, and And by inhibiting central nervous system to lead to death.According to the World Health Organization (WHO), the highest cyaniding that allows in drinking water Object concentration is 1.9 μM.Therefore, cyanide ion detection is of great significance.
Hypochlorous acid is widely used as disinfectant, antibacterial agent and bleaching agent in daily life.Meanwhile hypochlorous acid is also a kind of Important active oxygen species (ROS), play an important role in various physiology and pathologic process.But excessive hypochlorous acid pair Human body is harmful, will lead to a variety of diseases, such as arthritis, nerve regression disease, cardiovascular disease and cancer.Therefore, secondary Chloric acid detection is of great significance.
So far, many detection cyanide ions and hypochlorous method are had been developed for.Including atomic absorption spectrum Method, electrochemical methods etc..But there is such as somewhat expensives for these methods, sample preparation is complicated, and testing time length etc. lacks Point.Organic fluorescence probe because have quickly detection, it is easy to operate and highly sensitive the advantages that and by vast researcher Concern.In recent years, various detection cyanide ions and hypochlorous fluorescence probe come into being, these probes face it is highly selective, The challenge of high sensitivity, quick response and good aqueous solubility.On the whole, it is directed to single cyanide ion and single hypochlorous acid at present Probe it is relatively more, but be the absence of one kind and can while fast and efficiently detect cyanide ion and hypochlorous probe.
Summary of the invention
It is an object of the invention to provide the chemiluminescence spies that a kind of easily prepared, inexpensive, quick detection, performance are stable Needle, and the synthetic method of the probe is provided, a kind of while highly selective and highly sensitive detection cyanogen is also developed on this basis Radical ion and hypochlorous method.
It is characteristic of the invention that using classical nir dye --- seven methine indoles cyanines derivatives be fluorophor with Recognition group devises the novel seven methines indoles cyanines of carbazole modification using the nucleophilicity and hypochlorous oxidisability of cyanide ion Derivative probe Cz-Cy7, the probe can rapidly and efficiently identify cyanide ion and hypochlorous acid simultaneously.
To achieve the above object, technical solution provided by the invention is as follows:
According to the first embodiment of the present invention, the compound with logical formula (I) is provided:
According to the second embodiment of the present invention, the preparation method of above compound is provided, which is characterized in that the preparation Method the following steps are included:
1) using phenylhydrazine -4- sulfonic acid, methyl isopropyl Ketone, bromoethane as raw material, pass through Fischer reaction and alkylated reaction The N- ethyl -2,3 with logical formula (II) is synthesized, 3- tri-methyl indole -5- potassium sulfonate is labeled as " indole derivatives "；Reaction is such as Under:
2) using cyclohexanone and phosphorus oxychloride as raw material, methylene chloride is solvent, and n,N-Dimethylformamide (DMF) is solvent And reaction reagent, there is the condensing agent of following general formula (III) by the synthesis of Vilsmeier-Haack formylation reaction:
3) indole derivatives with logical formula (II) for synthesizing step 1) lead to formula (III) with having for step 2) synthesis Condensing agent carries out Knoevenagel Condensation reaction, obtains the condensation product (M1) with following general formula (IV):
4) condensation product (M1) with logical formula (IV) for obtaining step 3) passes through with N- phenyl -3- carbazole boric acid (B) Suzuki coupling reaction has the target-probe compound of logical formula (I) to obtain:
Preferably, in the above preparation method, step 1) is done as follows:
Acetic acid, phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone are added in the reactor, carries out back flow reaction (preferably in inertia Back flow reaction 3-15 hours under the protection of gas)；Then be added potassium hydroxide Organic Alcohol saturated solution (such as isopropanol saturation Solution: potassium hydroxide is dissolved in saturation potassium hydroxide aqueous isopropanol made in isopropanol)；Add bromoethane and second Nitrile carries out back flow reaction (preferably back flow reaction 5-48 hours under the protection of inert gas)；After being cooled to room temperature, filters, wash It washs and (is preferably washed using ether), obtain N- ethyl -2,3 with logical formula (II), 3- after dry (preferably using vacuum drying) Tri-methyl indole -5- potassium sulfonate is labeled as " indole derivatives ".
Preferably, the molar ratio of phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone be 1:2-5, preferably 1:3-4, it is more excellent It is selected as 1:3.5-3.8；.
Preferably, the molar ratio of phenylhydrazine -4- sulfonic acid and bromoethane be 1:1-3, preferably 1:1.2-2.5, more preferably 1:1.5-2。
Preferably, in the above preparation method, step 1) is done as follows:
Acetic acid, phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone are added in the reactor, is returned under the protection of inert gas It flows (such as 3-15 hours)；Reaction mixture is cooling, then it is added drop-wise to poor solvent or precipitating solvent (such as acetic acid second Ester) in, there is pink solid precipitation；Then reaction mixture is filtered, solids is washed with solvent (such as ether), is done It is dry；Pink powder organic solvent (such as methanol or ethyl alcohol) dissolution after drying is obtained to the solution (example of compound (A) Such as the methanol solution or ethanol solution of compound (A)), the Organic Alcohol of potassium hydroxide is then added dropwise into the solution of compound (A) Saturated solution (such as isopropanol saturated solution: potassium hydroxide is dissolved in saturation potassium hydroxide isopropanol made in isopropanol Solution), yellow solid, centrifuge separation is precipitated, and washed and dried with solvent (such as ether), obtains corresponding sylvite；So Above-mentioned sylvite, organic solvent (such as acetonitrile) and bromoethane is added in another reactor afterwards, in inert gas (such as nitrogen Gas) the lower reflux of protection (such as 10-40 hours, such as 24 hours), there is red solids to be precipitated；After being cooled to room temperature, reaction is mixed Object is closed to be filtered, solids is washed with solvent (such as ether), and it is dry, obtain the compound of logical formula (II).
It is further preferred that step 1) is done as follows: into single port bottle, sequentially adding acetic acid, phenylhydrazine -4- sulfonic acid and first Base nezukone, reflux (such as 3-12 hours, such as 8 hours) under inert gas (such as nitrogen) protection, solution becomes at this time Kermesinus；After being cooled to room temperature, reaction solution is slowly dropped into ethyl acetate, there is pink solid precipitation in solution；Then it takes out Filter, and washed repeatedly with ether, finally it is dried in vacuo；Pink powder after above-mentioned drying is dissolved with methanol, by hydroxide Potassium, which is dissolved in isopropanol, is made saturated solution, and the isopropanol saturated solution of potassium hydroxide is then added dropwise into methanol solution, obtains Yellow solid, centrifuge separation, and washed (such as 3-4 times) with ether, it is dried in vacuo；A single port bottle separately is taken, successively into bottle Above-mentioned yellow solid, acetonitrile and bromoethane is added, flow back under inert gas (such as nitrogen) protection (such as 10-40 hours, such as 24 hours), there is red solid to be precipitated；It after being cooled to room temperature, filters, and washed with ether, is dried in vacuo, obtain logical formula (II) Compound.
Preferably, in the above preparation method, wherein step 2) is done as follows:
DMF is added into reactor, phosphorus oxychloride and dichloromethane are added under cooling (such as under the cooling of 0 DEG C of ice bath) Alkane, reaction (are preferably reacted 0.2-6 hours) at room temperature, and cyclohexanone, back flow reaction (preferably heating reflux reaction 1- is added 12 hours)；After reacting cooling (after being preferably cooled to room temperature), reaction mixture is instilled in ice water, stirring (is preferably stirred Mix 6-48 hours), it filters, it is dry (being preferably dried in vacuo), obtain the condensing agent with logical formula (III).
Preferably, cyclohexanone: phosphorus oxychloride: the molar ratio of DMF is 1:1-5:2-8, preferably 1:1.5-4.5:2.5- 7, more preferably 1:2-4:3-6.
Preferably, in the above preparation method, wherein step 2) is done as follows:
Organic solvent (such as DMF) is added in the reactor, slowly drips under cooling (such as under the cooling of 0 DEG C of ice bath) Add the mixed solution of phosphorus oxychloride and methylene chloride, then (example will be reacted after mixed solution heating (such as being warmed to room temperature) Such as 0.5-3 hours, such as 1 or 2 hour), then cyclohexanone is slowly added dropwise into mixed solution；After cyclohexanone drips, heat back It flowing (such as 2-6 hours), mixed solution becomes orange red at this time, after reaction mixture cooling (such as being cooled to room temperature), Mixed solution is added drop-wise in trash ice, is stirred (such as being stirred overnight), is filtered, it is dry (such as vacuum drying), obtain general formula (III) condensing agent.
Preferably, step 2) is done as follows: DMF being added into there-necked flask, trichlorine is slowly added dropwise under 0 DEG C of ice bath The mixed solution of oxygen phosphorus and methylene chloride；Remove ice bath, mixed solution reacts that (such as 0.5-3 hours, such as 1 or 2 is small at room temperature When), then cyclohexanone is slowly added dropwise into mixed solution；After dripping, mixture be heated to reflux (such as be heated to 40 DEG C, such as Reflux 2-6 hours, such as 4 hours), solution becomes orange red at this time；After reaction mixture is cooled to room temperature, mixed liquor is instilled It in ice, overnight, filters, is dried in vacuo (such as 24 hours), obtain the condensing agent of logical formula (III).
Preferably, in the above preparation method, wherein step 3) is done as follows:
The indole derivatives with logical formula (II) of addition step 1) synthesis, having for step 2) synthesis are led in the reactor Condensing agent, sodium acetate and the acetic anhydride of formula (III), back flow reaction (preferably back flow reaction 6-24 hours under nitrogen protection)； Cooling (being preferably cooled to room temperature), separation (preferably use and settle in ether and purify through column chromatography for separation), had The condensation product (M1) of following general formula (IV).
Preferably, step 1) synthesis has general formula with the indole derivatives and rapid 2) synthesis for leading to formula (II) (III) molar ratio of condensing agent is 1-10:1, preferably 2-8:1, more preferably 3-5:1.
Preferably, in the above preparation method, wherein step 3) is done as follows:
Compound N-ethyl -2,3,3- the tri-methyl indole-of the logical formula (II) obtained in step 1) is added in the reactor Condensing agent, sodium acetate and the acetic anhydride for the logical formula (III) that 5- potassium sulfonate, step 2) obtain, flow back (example under inert gas protection 80 DEG C of reflux are such as heated to, such as are flowed back 4-20 hours, such as 12 hours), solution colour is rendered as green at this time；By reaction solution After cooling (such as being cooled to room temperature), acetic anhydride is removed under reduced pressure, and gained residue is dissolved with solvent (such as methanol or ethyl alcohol), Acquired solution is instilled in poor solvent or precipitating solvent (such as ether) again, is filtered, and with solvent (such as a large amount of ether) Washing, it is dry；Gained green crude product is purified (such as using column chromatography purification), obtains consolidating for green band metallic luster Body, i.e., the condensation product (M1) of logical formula (IV).
Preferably, into single port bottle, compound N-ethyl -2,3 of the logical formula (II) obtained in step 1) is sequentially added, Condensing agent, sodium acetate and the acetic anhydride for the logical formula (III) that 3- tri-methyl indole -5- potassium sulfonate, step 2) obtain, in inert gas The lower reflux of (such as nitrogen) protection (such as 80 DEG C of reflux are heated to, and it flows back 4-20 hours, such as 12 hours), solution colour is at this time It is now green；After being cooled to room temperature, acetic anhydride is removed under reduced pressure, is dissolved with methanol, then is instilled in ether, filters, and with greatly Measure ether washing, vacuum drying；Gained green crude product uses column chromatography purification, is with chloroform/methanol (such as 4:1, v/v) Eluant, eluent, collects the colour band of green, and solvent evaporated finally obtains the solid of green band metallic luster, i.e., the condensation of logical formula (IV) Product (M1).
Preferably, in the above preparation method, wherein step 4) is done as follows:
Condensation product (M1), the N- phenyl -3- carbazole boric acid of the logical formula (IV) that step 3) obtains are added into reactor (B), palladium catalyst, potassium carbonate and solvent, (preferably 78 DEG C reflux, preferably reaction 12-48 is small under nitrogen protection for back flow reaction When)；Cooling (being preferably cooled to room temperature), removes mixed solvent and the target for purifying to obtain logical formula (I) through column chromatography for separation is visited Needle compound.
Preferably, the condensation product (M1) of logical formula (IV) and the rubbing for N- phenyl -3- carbazole boric acid (B) of step 3) acquisition You are than being 1:0.8-5, preferably 1:1-4, more preferably 1:1.2-3.
Preferably, the solvent is the mixed liquor of second alcohol and water, preferably, the volume ratio of ethyl alcohol and water is 2-10: 1, preferably 3-8:1, more preferably 4-6:1.
Preferably, the palladium catalyst is Pd (PPh3)4Or Pd (OAc)2Or PdCl2Or Pd (dba)2.Palladium catalyst is excellent It is selected as Pd (PPh3)4。
Preferably, the dosage of palladium catalyst is 0.1-2%, the preferably 0.5-1.5% of condensation product M1 mass, more preferably 0.6-1.2%.
Preferably, in the above preparation method, wherein step 4) is done as follows:
Be added in the reactor the condensation product (M1) of logical formula (IV) obtained in step 3), N- phenyl -3- carbazole boric acid, Pd(PPh3)4, potassium carbonate and ethanol/water mixed solvent (such as 5:1 ratio, v/v), protected at inert gas (such as nitrogen) Lower reflux (such as reflux temperature is 78 DEG C, is flowed back 10-30 hours, such as 20 hours)；(such as room is cooled to for reactant is cooling Temperature) after, mixed solvent is removed under reduced pressure, is then dissolved with solvent (such as methanol), then acquired solution is instilled into poor solvent or is sunk It forms sediment in solvent (such as ether), filters, and washed with solvent (such as ether), it is dry；Gained green crude product is purified (such as using column chromatography purification) obtains the solid of green band metallic luster, i.e., the compound of logical formula (I).
Preferably, step 4) is done as follows: into single port bottle, sequentially adding the logical formula (IV) of step 3) acquisition Condensation product (M1), N- phenyl -3- carbazole boric acid, Pd (PPh3)4, potassium carbonate and ethanol/water mixed solvent (such as 5:1, v/v), Reflux (such as reflux temperature is 78 DEG C, is flowed back 10-30 hours, such as 20 hours) under inert gas (such as nitrogen) protection；It will After reactant cooling (such as being cooled to room temperature), mixed solvent is removed under reduced pressure, is then dissolved with methanol, then acquired solution is instilled It in ether, filters, and washed with ether, is dried in vacuo；Gained green crude product uses column chromatography purification, with ethyl acetate/ Methanol (such as 5:1, v/v) is eluant, eluent, collects dirty-green colour band, and solvent evaporated finally obtains consolidating for green band metallic luster Body, i.e., the compound of logical formula (I).
Preferably, having the compound of logical formula (I) to have following characteristics prepared by the present invention:1H NMR(400MHz, DMSO-d6) δ (ppm): 8.31-8.29 (d, J=8Hz, 2H), 8.20-8.19 (d, J=4.0Hz, 2H), 7.79 (s, 1H), 7.77-7.62 (t, 2H), 7.744-7.741 (d, J=1.2Hz, 1H), 7.57-7.54 (t, 2H), 7.51-7.50 (d, J= 4.0Hz, 4H), 7.497-7.495 (d, J=0.8Hz, 1H), 7.48-7.47 (d, J=4Hz, 1H), 7.29-7.28 (t, 1H), 7.264-7.260 (d, J=1.6Hz, 1H), 7.21 (s, 1H), 7.23 (s, 1H), 6.24-6.21 (d, J=12Hz, CH), 4.13-4.10(m,4H),2.75-2.74(t,4H),2.02-1.99(t,2H),1.25-1.15(t,6H),1.07-0.97(s, 12H).13C NMR(100MHz,DMSO-d6)δ(ppm):171.34,163.03,148.09,145.36,142.16,141.36, 140.42,137.24,132.08,130.93,128.50,128.07,127.4,127.2,126.55,123.41,122.81, 122.29,121.27,120.86,120.23,110.16.100.43,48.63,27.28,24.81,21.43, 12.42.MALDI-TOF MS(C52H51BrN3O6S2)m/z:calcd.958.01,found:878.93[Cz-Cy7-Br]+。
According to the third embodiment the present invention, the compound of above-mentioned logical formula (I) is provided or by above-mentioned preparation method institute Purposes of the compound of preparation as detection cyanide ion and/or hypochlorous fluorescence probe.
Qualitative detection and/or quantitative determination are carried out to cyanide ion and/or hypochlorous acid using the compound as probe.
Preferably, probe is 0.09 μM to the Monitoring lower-cut of cyanide ion concentration.
Preferably, probe is 0.014 μM to the Monitoring lower-cut of hypochlorous acid concentration.
It is preferred that probe dissolves in a solvent, to cyanide ion when being detected using UV absorption and fluorescence emission spectrometry And/or hypochlorous acid is detected.
Preferably, probe is dissolved in the first solvent, when detection cyanide ion using UV absorption and fluorescent emission Spectroscopic methodology detection cyanide ion.Preferably, the mixed solution that first solvent is water and DMF volume ratio is 3:7, first is molten Agent is more preferably the water for being added with pH buffer and DMF volume ratio is the mixed solution of 3:7.The pH buffer is slow for HEPES Rush solution.The pH of first solvent is 9-11.
Preferably, probe is dissolved in the second solvent, when detection hypochlorous acid using UV absorption and fluorescence emission Spectrometry detects hypochlorous acid.Preferably, the second solvent PBS buffer solution.Second solvent is more preferably the PBS containing acetonitrile Buffer solution, the volume content of acetonitrile are 40-60%.The pH of second solvent is 3-5.
Preferably, probe carries out colorimetric judgement to cyanide ion and/or hypochlorous detection under the conditions of daylight naked eye, Probe is either measured to cyanide ion and hypochlorous response by UV absorption and fluorescence emission spectrum.
Preferably, cyanide ion is added in the solution containing probe, solution colour becomes glassy yellow by blackish green, glimmering Light weakens.Hypochlorous acid is added in the solution containing probe, solution colour becomes khaki, fluorescent weakening by blackish green.
It is preferred that probe to the detection of cyanide ion there is no when fluorescence response, cyanide ion and probe in solution to be detected Molar ratio be 12:1.
It is preferred that probe acts on cyanide ion, there is no times when ultraviolet response to be no more than 5 minutes.
It is preferred that probe to hypochlorous detection there is no when fluorescence response, hypochlorous acid and probe rubs in solution to be detected You are than being 10:1
It is preferred that probe acts on hypochlorous acid, there is no times when ultraviolet response to be no more than 1 minute.
The above-mentioned synthesis process of the compound of the present invention (I) is as shown below:
In the present invention, it is based on seven methine indoles cyanines derivatives that cyanide ion and hypochlorous acid, which detect difunctional fluorescence probe, Compound (I), be labeled as fluorescence probe Cz-Cy7.
Another object of the present invention be to provide it is a kind of using the above method obtain fluorescence probe detection cyanide ion and time The application method of chloric acid, the probe both obtained using the above method carry out qualitative and quantitative determination to cyanide ion and hypochlorous acid.
Preferably, when being detected using UV absorption and fluorescence emission spectrometry, ingredient is the fluorescence probe of compound (I) It is dissolved in water and DMF (volume ratio 3:7) mixed solution, cyanide ion is detected.
Preferably, in the probe solution be added cyanide ion after solution colour rapidly gone to by original green it is bright orange Color, color change can also with the naked eye understand under fluorescent light to be differentiated.
Application of the fluorescence probe prepared by the present invention in cyanide ion detection.Probe is dissolved in water/DMF (volume Than being preferably added to HEPES buffer solution, pH=10 for 3:7) in the mixed solvent, preferably 5 μM of probe solution, cyanogen is then added Radical ion measures probe to the response of cyanide ion or the variation of directly observation solution colour by ultra-violet absorption spectrum.Cyanogen The addition of radical ion makes probe solution color become glassy yellow by blackish green, and absorption intensity reduces at 771nm.
Preferably, which is studied to the quantitative detection performance of cyanide ion using fluorescent spectrometry, acquisition probe adds Enter fluorescent emission intensity of the cyanide ion fore-and-aft architecture at 806nm；Experiment shows when to be added to probe molten for cyanide ion solution In liquid after 5 minutes, fluorescence intensity no longer extends with further variation with the time, illustrate the probe 5 minutes it The response to cyanide ion inside can be completed.Meanwhile fluorescence intensity increases with cyanide ion concentration and is reduced, when probe and cyanogen root When the concentration of ion is 1:12, fluorescent emission intensity of the system at 806nm reaches minimum, illustrates that probe and cyanide ion act on Completely, the variation of fluorescence probe intensity and cyanide ion concentration are linear, and Monitoring lower-cut is respectively 0.09 μM, much low In 1.9 μM of the safty of drinking water standard that the World Health Organization determines.
Preferably, other ten kinds of common anion of experimental selection detect probe, the results showed that probe Detection have not significant impact, illustrate the probe to cyanide ion detection have very excellent selectivity.
Fluorescence probe prepared by the present invention is applied in hypochlorous acid detection.Probe is dissolved in the buffering of the PBS containing acetonitrile In solution (pH=4 contains 50% acetonitrile), then the probe solution that preferred concentration is 5 μM is added hypochlorous acid, passes through UV absorption Spectroscopic assay probe observes the variation of solution colour to hypochlorous response or directly.Hypochlorous addition makes probe solution face Color becomes khaki by blackish green, and absorption intensity reduces at 762nm.
Preferably, which is studied to hypochlorous quantitative detection performance using fluorescent spectrometry, acquisition probe is added Fluorescent emission intensity of the hypochlorous acid fore-and-aft architecture at 795nm；Experiment shows to be added to 1 in probe solution as hypochlorite solution After minute, fluorescence intensity no longer extends with further variation with the time, illustrates the probe within 1 minute It completes to hypochlorous response.Meanwhile fluorescence intensity increases with hypochlorous acid concentration and is reduced, when probe and hypochlorous concentration are When 1:10, fluorescent emission intensity of the system at 795nm reaches minimum, illustrates probe and hypochlorous acid effect completely, fluorescence probe The variation of intensity and hypochlorous acid concentration are linear, and Monitoring lower-cut is respectively 0.014 μM.
Fluorescence probe prepared by the present invention has highly selective, other common active oxygen species to hypochlorous acid detection (ONOO-,HO·,H2O2, TBHP and O2) detection of probe is had not significant impact.
Fluorescence probe prepared by the present invention can be used for cyanide ion and hypochlorous acid detection in the solid state, such as consolidate probe It is scheduled on filter paper, when cyanide ion and hypochlorous acid is added dropwise, color identical with solution state can be observed visually under natural light Variation.
In the present invention, hypochlorous acid and hypochlorite ion are general.
Beneficial effects of the present invention are as follows:
1, the fluorescence probe (compound for having general formula (1)) based on seven methine indoles cyanines derivatives that the present invention synthesizes Cyanide ion and hypochlorous acid can be detected simultaneously；
2, the present invention provides a kind of novel near-infrared probe, cyanide ion and time chlorine can be carried out in the presence of water Acid detection is expected to be applied to cyanide ion and hypochlorous fluorescent tracing and imaging in living biological cell；
3, probe of the invention has faster response speed, and cyanide ion detection can be completed in 5 minutes；Hypochlorous acid Detection can be completed in 1 minute, can be applied to cyanide ion and hypochlorous field quick detection and monitoring；
4, the fluorescence probe based on seven methine indoles cyanines derivatives that the present invention synthesizes has the characteristics that naked eyes identify；
5, probe of the invention reaches 0.09 μM to the Monitoring lower-cut of cyanide ion concentration, is more than many other types of cyanogen Radical ion probe, far below cyanide ion concentration in the safty of drinking water of World Health Organization's license；To hypochlorous Monitoring lower-cut Reach 0.014 μM, far below the hypochlorous acid probe based on indoles cyanines derivative reported at present；
6, probe of the invention has excellent selectivity and competitiveness, and when detecting cyanide ion and hypochlorous acid, other are normal The anion and active oxygen species seen do not generate interference.
Detailed description of the invention
Fig. 1 is the general structure of compound prepared by the present invention.
Fig. 2 is the synthetic route chart for having the compound of logical formula (I) prepared by the present invention.
Fig. 3 is probe to the ultraviolet-visible absorption spectroscopy response of cyanide ion, linear relationship curve and its under natural light Photo.
Fig. 4 is probe to the fluorescence spectrum response of cyanide ion, linear relationship curve.
Fig. 5 is kinetics relation curve of the probe to cyanide ion.
Fig. 6 detects cyanide ion for probe highly selective.
Fig. 7 be probe hypochlorous ultraviolet-visible absorption spectroscopy is responded, linear relationship curve and its under natural light Photo.
Fig. 8 be probe hypochlorous fluorescence spectrum is responded, linear relationship curve.
Fig. 9 is probe to hypochlorous kinetics relation curve.
Figure 10 detects hypochlorous acid for probe highly selective.
Figure 11 is the test paper (filter paper) based on probe to cyanide ion and hypochlorous portable inspectiont photo.
Specific embodiment
The present invention is described in further detail technical solution by following examples, but the present invention is not restricted to these implement Example.
Embodiment 1: the synthesis of target-probe Cz-Cy7
(1) synthesis (compound (II)) of N- ethyl -2,3,3- tri-methyl indole -5- potassium sulfonate
Into 50mL single port bottle, it is different to sequentially add 10mL acetic acid, phenylhydrazine -4- sulfonic acid (2.000g, 0.010mol) and methyl Propyl ketone 4.00mL (0.037mol) flows back 8 hours under nitrogen protection, and solution becomes kermesinus at this time.After being cooled to room temperature, Reaction solution is slowly dropped into ethyl acetate, there is pink solid precipitation in solution；It filters, and is washed repeatedly with ether, vacuum It is dry；Pink powder after above-mentioned drying is dissolved with proper amount of methanol, 0.561g potassium hydroxide is dissolved in isopropanol and is made Then the isopropanol saturated solution of potassium hydroxide is added dropwise into methanol solution, obtains yellow solid for saturated solution, be centrifuged, be used in combination Ether washs 3-4 times, vacuum drying.A 50mL single port bottle separately is taken, above-mentioned yellow solid, 20mL acetonitrile are sequentially added into bottle It with bromoethane 1.49mL (0.020mol), flows back 24 hours under nitrogen protection, there is red solid to be precipitated.It is cooled to room temperature Afterwards, it filters, and is washed (3 × 10mL) with ether, vacuum drying obtains compound (II).
(2) synthesis (compound (III)) of condensing agent
DMF 10mL (0.130mol) is added into 100mL there-necked flask, 10mL is slowly added dropwise under 0 DEG C of ice bath The mixed solution of (0.107mol) phosphorus oxychloride and 5mL methylene chloride.Ice bath is removed, is reacted 1 hour at room temperature, then to mixing 3.5mL (0.034mol) cyclohexanone is slowly added dropwise in solution.After dripping, it is heated to reflux 4 hours, solution becomes orange red at this time Color.After reacting and being cooled to room temperature, mixed liquor is instilled in ice, overnight, is filtered, vacuum drying obtains compound (III).
(3) compound (IV), the i.e. synthesis of condensation product M1
Into 25mL single port bottle, N- ethyl -2,3 is sequentially added, 3- tri-methyl indole -5- potassium sulfonate (0.843g, 2.2mmol), condensing agent (step 2 gained compound (III), 0.188g, 1.1mmol), sodium acetate (0.180g, 2.2mmol) and 10mL acetic anhydride flows back 12 hours under nitrogen protection, and solution colour is rendered as green at this time.After being cooled to room temperature, decompression is removed Acetic anhydride is removed, is dissolved with a small amount of methanol, then instilled in ether, is filtered, and washed with a large amount of ether, is dried in vacuo；Gained Green crude product uses column chromatography purification, with chloroform/methanol (4:1, v/v) for eluant, eluent, collects the colour band of green, is evaporated molten Agent finally obtains solid (M1) 0.664g of green band metallic luster, yield 64.4%.
(4) synthesis (compound (I)) of target product Cz-Cy7
Into 100mL single port bottle, condensation product M1 (1.220g, 2.00mmol) (step 3 gained compound is sequentially added (IV)), N- phenyl -3- carbazole boric acid (1.040g, 3.60mmol), Pd (PPh3)4(0.230g, 0.20mmol), potassium carbonate 0.280g, 2.00mmol) and 50mL ethanol/water (5:1, v/v), it flows back 20 hours under nitrogen protection.After being cooled to room temperature, subtract Pressure removes mixed solvent, is then dissolved with a small amount of methanol, then instilled in ether, filters, and washed with ether, and vacuum is dry It is dry.Gained green crude product uses column chromatography purification, with ethyl acetate/methanol (5:1, v/v) for eluant, eluent, collects dirty-green Colour band, solvent evaporated finally obtain the solid 1.197g of green band metallic luster.
Probe characterization:1H NMR (400MHz, DMSO-d6) δ (ppm): 8.31-8.29 (d, J=8Hz, 2H), 8.20- 8.19 (d, J=4.0Hz, 2H), 7.79 (s, 1H), 7.77-7.62 (t, 2H), 7.744-7.741 (d, J=1.2Hz, 1H), 7.57-7.54 (t, 2H), 7.51-7.50 (d, J=4.0Hz, 4H), 7.497-7.495 (d, J=0.8Hz, 1H), 7.48-7.47 (d, J=4Hz, 1H), 7.29-7.28 (t, 1H), 7.264-7.260 (d, J=1.6Hz, 1H), 7.21 (s, 1H), 7.23 (s, 1H), 6.24-6.21 (d, J=12Hz), 4.13-4.10 (m, 4H), 2.75-2.74 (t, 4H), 2.02-1.99 (t, 2H), 1.25-1.15(t,6H),1.07-0.97(s,12H).13CNMR(100MHz,DMSO-d6)δ(ppm):171.34,163.03, 148.09,145.36,142.16,141.36,140.42,137.24,132.08,130.93,128.50,128.07,127.4, 127.2,126.55,123.41,122.81,122.29,121.27,120.86,120.23,110.16.100.43,48.63, 27.28,24.81,21.43,12.42.MALDI-TOF MS(C52H51BrN3O6S2)m/z:calcd.958.01,found: 878.93[Cz-Cy7-Br]+。
Embodiment 2: titration experiments of the cyanide ion to probe
In the in the mixed solvent of water and DMF (volume ratio 3:7 is preferably added to HEPES buffer solution, pH=10), prepare The probe solution that concentration is 5 μM.Then respectively be added dropwise various concentration cyanide ion (0 μM, 5 μM, 10 μM, 15 μM, 20 μM, 25 μ M, 30 μM, 35 μM, 40 μM, 45 μM, 50 μM, 55 μM, 60 μM), after 5min, passes through ultraviolet-visible absorption spectroscopy and fluorescence spectrum is surveyed Try the absorption and fluorescent emission response of mixed system.
From the figure 3, it may be seen that absorption peak strength of the probe at 771nm increases with cyanide ion concentration and is reduced, solution colour Become glassy yellow from blackish green.
As shown in Figure 4, emission peak intensity of the probe at 806nm increases with cyanide ion concentration and is reduced, probe and 12 Equivalent cyanide ion fully reacting, emission peak intensity and cyanide ion concentration are linear, illustrate that this probe can be examined quantitatively Survey cyanide ion.
Embodiment 3: probe tests the kinetics of cyanide ion
At room temperature, (water/DMF, volume ratio 3:7 are preferably added to HEPES buffering to the probe solution that compound concentration is 5 μM Solution, pH=10), cyanide ion then is added with micro syringe and records ultraviolet suction of the different time sample at 771nm Receive intensity.
As shown in Figure 5, as the time increases, absorption intensity of the probe at 771nm is reduced, after five minutes, system it is ultraviolet Absorption intensity no longer extends at any time and is further change in, and illustrates that the probe can be completed within 5 minutes to cyanide ion Detection.
Embodiment 4: the selectivity test of probe in detecting cyanide ion
At room temperature, probe solution (water/DMF, volume ratio 3:7, HEPES buffer solution, pH that compound concentration is 5 μM =10) and various anion solutions (Na2CO3, KSCN, Na2SO4, KF, NaCl, NaBr, KI, NaNO2, NaHCO3, NaOAc), it will Various anion and cyanide ion are separately added into probe solution, shake up placement after five minutes, probe is measured in Fluorescence Spectrometer Fluorescent emission intensity.
It will be appreciated from fig. 6 that common anion does not significantly interfere with probe in detecting, illustrate that probe detects tool to cyanide ion There is good selectivity.
Embodiment 5: titration experiments of the hypochlorous acid to probe
The probe solution that (pH=4 contains 50% acetonitrile), compound concentration was 5 μM in PBS buffer solution.Then it is added dropwise respectively The hypochlorous acid (0 μM, 5 μM, 10 μM, 15 μM, 20 μM, 25 μM, 30 μM, 35 μM, 40 μM, 45 μM, 50 μM) of various concentration, 1 minute Afterwards, the absorption of mixed system is tested by ultraviolet-visible absorption spectroscopy and fluorescence spectrum and fluorescent emission responds.
As shown in Figure 7, absorption peak strength of the probe at 762nm with hypochlorous acid concentration increase and reduce, solution colour by It is blackish green to become khaki.
As shown in Figure 8, emission peak intensity of the probe at 795nm increases with hypochlorous acid concentration and is reduced, and probe is worked as with 10 Hypochlorous acid fully reacting is measured, emission peak intensity is linear with hypochlorous acid concentration, illustrates that this probe can be with quantitative detection time chlorine Acid.
Embodiment 6: probe tests hypochlorous kinetics
At room temperature, the probe solution (in PBS buffer solution, pH=4 contains 50% acetonitrile) that compound concentration is 5 μM, then Hypochlorous acid is added with micro syringe and records UV absorption intensity of the different time sample at 762nm.
As shown in Figure 9, as the time increases, absorption peak strength of the probe at 762nm is reduced, after 1 minute, the purple of system Outer absorption intensity no longer extends at any time and is further change in, and illustrates that the probe can be completed within 1 minute to hypochlorous Detection.
Embodiment 7: the hypochlorous selectivity test of probe in detecting
At room temperature, compound concentration be 5 μM probe solution (in PBS buffer solution, pH=4, contain 50% acetonitrile) and respectively Kind active oxygen species (HO, H2O2,ONOO-,·O2, TBHP), it is molten that various active oxygen species and hypochlorous acid are separately added into probe In liquid, after shaking up placement 1 minute, the fluorescent emission intensity of probe is measured in Fluorescence Spectrometer.
As shown in Figure 10, common active oxygen species do not significantly interfere with probe in detecting hypochlorous acid, illustrate probe to secondary Chloric acid detection has selectivity well.
Embodiment 8: portable probe (probe is fixed on filter paper) is applied in cyanide ion and hypochlorous acid detection
Certain density probe solution is prepared, the filter paper cut is immersed after probe sufficiently adsorbs, room temperature is true Sky is dry.
It is subsequent:
(1) cyanide ion and the hypochlorite solution of various concentration is added dropwise respectively on filter paper, uses number after room temperature in vacuo is dry Code camera shooting (see attached drawing 11a).Wherein: the concentration of cyanide ion is followed successively by 3eq, 6eq, 9eq, 12eq from left to right；Secondary chlorine The concentration of acid ion is followed successively by 2.5eq, 5eq, 7.5eq, 10eq from left to right.
(2) several representative anion (AcO are added dropwise respectively on filter paper-,SO4 2-,CO3 2-,HCO3 -,NO2 -) and Active oxygen (HO, H2O2,ONOO-,TBHP,·O2), (see attached drawing 11b) is shot with digital camera after room temperature in vacuo is dry.Its In: that detects cyanide ion is successively added dropwise AcO from left to right-、SO4 2-、CO3 2-、HCO3 -、NO2 -；Detect it is hypochlorous from left to right HO, H is successively added dropwise2O2、ONOO-、TBHP,·O2。
As shown in Figure 11, on portable test paper, probe generation and identical color change in solution, i.e., with cyanide ion Concentration increases, and test paper gradually becomes glassy yellow by blackish green；As hypochlorous acid concentration increases, test paper gradually becomes soil by blackish green Yellow；Other interfering ions and active specy do not interfere probe to cyanide ion and hypochlorous detection.Illustrate design of the present invention The probe of synthesis can be used to portable, quick, efficient detection cyanide ion and hypochlorous acid.

Claims (10)

1. the compound with logical formula (I):
2. the preparation method of compound according to claim 1, which is characterized in that the preparation method the following steps are included:
1) it using phenylhydrazine -4- sulfonic acid, methyl isopropyl Ketone, bromoethane as raw material, is synthesized by Fischer reaction and alkylated reaction N- ethyl -2,3 with logical formula (II), 3- tri-methyl indole -5- potassium sulfonate are labeled as " indole derivatives "；It reacts as follows:
2) using cyclohexanone and phosphorus oxychloride as raw material, methylene chloride is solvent, and n,N-Dimethylformamide (DMF) is for solvent and instead Reagent is answered, there is the condensing agent of following general formula (III) by the synthesis of Vilsmeier-Haack formylation reaction:
3) by the indole derivatives with logical formula (II) of step 1) synthesis and the condensation with logical formula (III) of step 2) synthesis Agent carries out Knoevenagel Condensation reaction, obtains the condensation product (M1) with following general formula (IV):
4) condensation product (M1) and N- phenyl -3- carbazole boric acid (B) for the logical formula (IV) for obtaining step 3) pass through Suzuki idol Connection reaction has the target-probe compound for leading to formula (I) to obtain:
3. according to the method described in claim 2, wherein step 1) is done as follows:
Acetic acid, phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone are added in the reactor, carries out back flow reaction (preferably in inert gas Protection under back flow reaction 3-15 hours)；Then be added potassium hydroxide Organic Alcohol saturated solution (such as isopropanol saturation it is molten Liquid: potassium hydroxide is dissolved in saturation potassium hydroxide aqueous isopropanol made in isopropanol)；Bromoethane and acetonitrile are added, It carries out back flow reaction (preferably back flow reaction 5-48 hours under the protection of inert gas)；It after being cooled to room temperature, filters, washing (preferably being washed using ether) obtains N- ethyl -2,3 with logical formula (II), 3- tri- after dry (preferably using vacuum drying) Methyl indol -5- potassium sulfonate is labeled as " indole derivatives "；
Preferably, the molar ratio of phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone is 1:2-5, preferably 1:3-4, more preferably 1: 3.5-3.8；The molar ratio of phenylhydrazine -4- sulfonic acid and bromoethane is 1:1-3, preferably 1:1.2-2.5, more preferably 1:1.5-2.
4. according to the method in claim 2 or 3, wherein step 2) is done as follows:
DMF is added into reactor, phosphorus oxychloride and methylene chloride are added under cooling (such as under the cooling of 0 DEG C of ice bath), Reaction (is preferably reacted 0.2-6 hours) at room temperature, and cyclohexanone, back flow reaction (preferably heating reflux reaction 1-12 is added Hour)；After reacting cooling (after being preferably cooled to room temperature), reaction mixture is instilled in ice water, stirring (is preferably stirred 6-48 hours), it filters, it is dry (being preferably dried in vacuo), obtain the condensing agent with logical formula (III)；
Preferably, cyclohexanone: phosphorus oxychloride: the molar ratio of DMF be 1:1-5:2-8, preferably 1:1.5-4.5:2.5-7, more Preferably 1:2-4:3-6.
5. wherein step 3) is done as follows according to method described in Claims 2 or 3 or 4:
What the indole derivatives with logical formula (II) of addition step 1) synthesis, step 2) synthesized in the reactor has general formula (III) condensing agent, sodium acetate and acetic anhydride, back flow reaction (preferably back flow reaction 6-24 hours under nitrogen protection)；It is cold But (be preferably cooled to room temperature), separation (preferably using in ether settle and purified through column chromatography for separation), obtain have with The condensation product (M1) of logical formula (IV) down；
Preferably, step 1) synthesis leads to formula (III) with the indole derivatives for leading to formula (II) and having for step 2) synthesis Condensing agent molar ratio be 1-10:1, preferably 2-8:1, more preferably 3-5:1..
6. the method according to any one of claim 2-5, wherein step 4) is done as follows:
Condensation product (M1), the N- phenyl -3- carbazole boric acid (B), palladium of the logical formula (IV) that step 3) obtains are added into reactor Catalyst, potassium carbonate and solvent, back flow reaction (are preferably reacted 12-48 hours) under nitrogen protection；It is cooling (preferably cooling To room temperature), it removes mixed solvent and purifies to obtain the target-probe compound of logical formula (I) through column chromatography for separation；
Preferably, the condensation product (M1) for the logical formula (IV) that step 3) obtains and the molar ratio of N- phenyl -3- carbazole boric acid (B) For 1:0.8-5, preferably 1:1-4, more preferably 1:1.2-3；Affiliated solvent is the mixed liquor of second alcohol and water, preferably, second The volume ratio of alcohol and water is 2-10:1, preferably 3-8:1, more preferably 4-6:1；The palladium catalyst is Pd (PPh3)4Or Pd (OAc)2Or PdCl2Or Pd (dba)2, palladium catalyst is preferably Pd (PPh3)4, the dosage of palladium catalyst is condensation product M1 mass 0.1-2%, preferably 0.5-1.5%, more preferable 0.6-1.2%.
7. the method according to any one of claim 2-6, it is characterised in that: the prepared chemical combination with logical formula (I) Object has following characteristics:1H NMR(400MHz,DMSO-d6) δ (ppm): 8.31-8.29 (d, J=8Hz, 2H), 8.20-8.19 (d, J=4.0Hz, 2H), 7.79 (s, 1H), 7.77-7.62 (t, 2H), 7.744-7.741 (d, J=1.2Hz, 1H), 7.57- 7.54 (t, 2H), 7.51-7.50 (d, J=4.0Hz, 4H), 7.497-7.495 (d, J=0.8Hz, 1H), 7.48-7.47 (d, J =4Hz, 1H), 7.29-7.28 (t, 1H), 7.264-7.260 (d, J=1.6Hz, 1H), 7.21 (s, 1H), 7.23 (s, 1H), 6.24-6.21 (d, J=12Hz, CH), 4.13-4.10 (m, 4H), 2.75-2.74 (t, 4H), 2.02-1.99 (t, 2H), 1.25- 1.15(t,6H),1.07-0.97(s,12H).13C NMR(100MHz,DMSO-d6)δ(ppm):171.34,163.03, 148.09,145.36,142.16,141.36,140.42,137.24,132.08,130.93,128.50,128.07,127.4, 127.2,126.55,123.41,122.81,122.29,121.27,120.86,120.23,110.16.100.43,48.63, 27.28,24.81,21.43,12.42.MALDI-TOF MS(C52H51BrN3O6S2)m/z:calcd.958.01,found: 878.93[Cz-Cy7-Br]+。
8. the compound of logical formula (I) or the compound of the preparation of the method as described in any one of claim 2-7 are as detection The purposes of cyanide ion and/or hypochlorous fluorescence probe, wherein using the compound as probe to cyanide ion and/or secondary Chloric acid carries out qualitative detection and/or quantitative determination；Preferably, probe is 0.09 μM to the Monitoring lower-cut of cyanide ion concentration, Probe is 0.014 μM to the Monitoring lower-cut of hypochlorous acid concentration.
9. purposes according to claim 8, which is characterized in that probe is dissolved in the first solvent, using UV absorption Cyanide ion is detected with fluorescence emission spectrometry；Preferably, the mixing that first solvent is water and DMF volume ratio is 3:7 Solution, the first solvent is more preferably the water for being added with pH buffer and DMF volume ratio is the mixed solution of 3:7；The pH buffering Agent is HEPES buffer solution, and the pH of the first solvent is 9-11；And/or
Probe is dissolved in the second solvent, hypochlorous acid is detected using UV absorption and fluorescence emission spectrometry；Preferably, institute Stating the second solvent is PBS buffer solution；Second solvent is more preferably the PBS buffer solution containing acetonitrile, the volume content of acetonitrile For 40-60%, the pH of the second solvent is 3-5；And/or
Probe carries out colorimetric judgement to cyanide ion and/or hypochlorous detection under the conditions of daylight naked eye, or passes through purple Outer absorption and fluorescence emission spectrum measurement probe are to cyanide ion and hypochlorous response；Preferably, containing the molten of probe Cyanide ion is added in liquid, solution colour becomes glassy yellow, fluorescent weakening by blackish green；It is added in the solution containing probe secondary Chloric acid, solution colour become khaki, fluorescent weakening by blackish green.
10. purposes according to claim 9, which is characterized in that there is no fluorescence responses for detection of the probe to cyanide ion When, the molar ratio of cyanide ion and probe is 12:1 in solution to be detected, and there is no ultraviolet responses to cyanide ion effect for probe When time be no more than 5 minutes；And/or
Probe is to hypochlorous detection there is no when fluorescence response, and the molar ratio of hypochlorous acid and probe is 10 in solution to be detected: 1, there is no times when ultraviolet response no more than 1 minute to hypochlorous acid effect for probe.
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