CN105505376A - Hg<2+> fluorescence probe containing rhodamine with double-carbon-sulfur-bond structure as well as preparation method and application of Hg<2+> fluorescence probe - Google Patents
Hg<2+> fluorescence probe containing rhodamine with double-carbon-sulfur-bond structure as well as preparation method and application of Hg<2+> fluorescence probe Download PDFInfo
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Abstract
The invention discloses an Hg<2+> fluorescence probe based on rhodamine with a double-carbon-sulfur-bond structure as well as a preparation method and an application of the Hg<2+> fluorescence probe. Recognition characteristics of a probe HgP1 in a CH3OH-H2O solution for metal ions are researched by an ultraviolet-visible spectrophotometer and a fluorescence spectrophotometer. A result indicates that the probe HgP1 has efficient and exclusive selectivity for Hg<2+>, has higher metal cation and anion interference resistance, and can realize naked-eye recognition for mercury ions through color change of the solution. The lowest detection limit of the probe on the mercury ions is 0.256 mu g/kg, so that the method can meet the limitation requirement of the national standard on the mercury ions, and the probe has higher actual application value.
Description
Technical field
The present invention relates to a kind of mercury ion (Hg
2+) detection agent, be specifically related to a kind of based on based on the Hg containing two carbon-sulfur bond structure rhodamine
2+the preparation method of fluorescent probe.
Background technology
Mercury is one of pollutent common in organism and environment, and mercury exists at normal temperatures in liquid form, possesses stronger volatility, brings larger harm to the ecosystem.Mercury mainly enters in organism with the form of inorganic mercury and methyl mercury, and enrichment in vivo.Mercury ion possesses stronger thiophilic property, and excessive mercury ion and organism include the protein of S or enzyme reacts, thus cause a series of disease.Great injury is caused to the neural system of organism and normal metabolic activity, as excessively in mercury ion can cause the symptoms such as irreversible DNA damage, myocardial infarction, CNS disorders and polytype autism.Just because of the hypertoxicity of mercury ion, strict requirement has all been done, as EPA (EPA) must not more than 2ppb with regard to the mercury ion content of strict regulation in tap water to mercury ion drinking the content in ArsenazoⅢ by multiple country and related tissue in the world.In recent years, the mercury ion content in Real-Time Monitoring organism and environment becomes an important field of research.Fluorescent probe is the advantage such as cost is lower, operating instrument is simple, detectability is low, Real-Time Monitoring owing to having, and fluorescence probe method detects metal ion and is subject to extensive concern in recent years.
Fluorescent sensing material based on " turn-on " mechanism can reduce detection mistake, it is more accurate to detect complex system, and by mechanism, it is divided into fluorescence chemical sensor (fluorescentchemsensor) and fluorescence chemical quantimeter (fluorescentchemodosimeter) two type.Wherein, fluorescence chemical quantimeter, owing to can there is irreversible chemical reaction with target analytes, shows highly selective to analyte, highlights its advantage in detection of heavy metal ion gradually.Mercury ion fluorescent chemical dosimeter mainly utilizes mercury ion and thiocarbonyl group generation desulphurization reaction and reacts with end-group alkyne or alkene generation oxymercuration and realizes mercury ion detecting.Oxymercuration reacts because reactive behavior is lower, usually needs higher temperature of reaction or longer reaction times, limits its application.Mercury ion fluorescent chemical dosimeter based on desulphurization reaction has fast response time, often with features such as colorimetric analysiss, more and more receives the concern of people.
Summary of the invention
The object of the invention is to propose a kind of Hg based on containing two carbon-sulfur bond structure rhodamine
2+the preparation method of fluorescent probe.
It is a kind of based on the Hg containing two carbon-sulfur bond structure rhodamine that the present invention proposes
2+the preparation method of fluorescent probe, first carries out condensation acylation reaction by commercial rhodamine B and Mercaptamine, obtains a kind of rhodamine B-Cysteamine derivatives (RhB-SH); This rhodamine B-Cysteamine derivatives (RhB-SH) obtains the intermediate (S-RhB-SH) containing carbon-sulfur bond through lawesson reagent sulfuration; Should carry out acyl chloride reaction containing the intermediate (S-RhB-SH) of carbon-sulfur bond and m-phthaloyl chloride and obtain a kind of compound containing two carbon-sulfur bond structure rhodamine, this compound can be used as Hg in methanol-water solution
2+highly selective fluorescent probe.
It is a kind of based on the Hg containing two carbon-sulfur bond structure rhodamine that the present invention proposes
2+the preparation method of fluorescent probe, its concrete synthetic route is as follows:
(1) be dissolved in by rhodamine B in anhydrous 1,2-ethylene dichloride, be added dropwise to a certain amount of phosphorus oxychloride under condition of ice bath, react 1 hour, change back flow reaction into 3 hours under ice bath, solvent is removed in decompression, obtains rhodamine acyl chlorides RhB-Cl.Rhodamine acyl chlorides RhB-Cl is dissolved in anhydrous acetonitrile, under condition of ice bath, the acetonitrile solution dropwise of excessive Mercaptamine enters in above-mentioned system, reaction system is made to be warming up to room temperature after question response is complete, removal of solvent under reduced pressure, dissolves again by ethyl acetate, with pure water and saturated nacl aqueous solution washing, organic phase anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure, silica gel column chromatography is separated and obtains intermediate product RhB-SH.
(2) intermediate RhB-SH and lawesson reagent are dissolved in dry toluene, reflux is to reacting completely, and underpressure distillation is concentrated removes toluene, enriched material CH
2cl
2dissolve, saturated common salt water washing, organic phase anhydrous sodium sulfate drying, after filtering and concentrating, silica gel column chromatography is separated and obtains intermediate S-RhB-SH.
(3) intermediate S-RhB-SH and triethylamine are mixed in dichloromethane solution, the dichloromethane solution of m-phthaloyl chloride is added dropwise under condition of ice bath, it should be room temperature reaction after dropwising, after reacting completely, saturated nacl aqueous solution washs, organic phase anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure, with methylene dichloride and methyl alcohol as washing composition, is separated through silica gel column chromatography and obtains product HgP1.
In described step (1), rhodamine B is 1:3-8 with the ratio of the amount of substance of phosphorus oxychloride, described condition of ice bath temperature is less than 0 DEG C, back flow reaction temperature is 80-90 DEG C, reaction times is 4-7 hour, rhodamine acyl chlorides RhB-Cl is 1:3-5 with the ratio of the amount of substance of Mercaptamine, and the reaction times is 5-8 hour, and productive rate is 60-80%.
In described step (1), the elutriant that silicagel column is separated is CH
2cl
2and CH
3oH, described CH
2cl
2with CH
3the volume ratio of OH is 20-30:1.
In described step (2), intermediate RhB-SH is 1:2-5 with the ratio of the amount of substance of lawesson reagent, and toluene used need through Non-aqueous processing, and described heating reflux reaction temperature is 105-120 DEG C, reaction times is 10-15 hour, and the elutriant that silicagel column is separated is CH
2cl
2and CH
3oH, described CH
2cl
2with CH
3the volume ratio of OH is 8-20:1, and productive rate is 15-30%.
In described step (3), the elutriant that silicagel column is separated is CH
2cl
2and CH
3oH, described CH
2cl
2with CH
3the volume ratio of OH is 10-25:1, and productive rate is 70-90%.
In described step (3), compound S-RhB-SH is 2-4 equivalent, and m-phthaloyl chloride is 1 equivalent, and triethylamine is 2-4 equivalent, and described condition of ice bath temperature is less than 0 DEG C, and the room temperature reaction time is 8-15 hour.
Containing the Hg of two carbon-sulfur bond structure rhodamine
2+fluorescent probe molecule is at detection Hg
2+in application.
The invention has the beneficial effects as follows: probe HgP1 is at CH
3oH-H
2to Hg in O (9/1, v/v) system
2+there is the single-minded detectivity of efficient and sensible.By experimental results such as above ultraviolet and fluorescence spectrum researchs, infer that HgP1 identifies Hg
2+possible mechanism as shown in Figure 6: add Hg in probe solution
2+, due to Hg
2+thiophilic property, Hg
2+s atom in molecular structure in ' C=S ' is combined, and generates and sloughs bimolecular HgS, and causes the acyl spironolactone ring in rhodamine structure to be opened, and discharges fluorescent signal, generates the product HgP1-Hg with fluorescence.Carry out confirming (accompanying drawing 7) to the structure of product HgP1-Hg by HR-MS.Experimental result shows, HgP1-Hg calculated value is that 484.2417, HR-MS result is shown as 484.2298.The mechanism of action shown in this data confirm accompanying drawing 6.
Accompanying drawing explanation
Fig. 1 is fluorescent probe HgP1 ultraviolet selectivity diagram of the present invention, and illustration is solution colour variation diagram;
Fig. 2 is fluorescent probe HgP1 fluorescence selectivity figure, excitation wavelength 520nm of the present invention;
Fig. 3 is that fluorescent probe HgP1 of the present invention identifies Hg
2+anti-metal Cation Interferences figure, excitation wavelength 520nm, emission wavelength 583nm;
Fig. 4 is that fluorescent probe HgP1 of the present invention identifies Hg
2+anti-negatively charged ion interference figure, excitation wavelength 520nm, emission wavelength 583nm;
Fig. 5 is fluorescent probe HgP1 fluorometric titration figure of the present invention, and illustration is lowest detectable limit figure, excitation wavelength 520nm;
Fig. 6 is fluorescent probe HgP1 recognition mechanism figure of the present invention;
Fig. 7 is fluorescent probe HgP1 recognition mechanism of the present invention checking High-Resolution Map.
Embodiment
Prepare in the present invention use in the process of fluorescent probe HgP1 chemical reagent, solvent, metal ion Deng Jun Aladdin Reagent Company.At confirmation and the performance test process employing Bruke company DTX-400 type nuclear magnetic resonance spectrometer of fluorescent probe HgP1, solvent is deuterochloroform, take TMS as internal labeling record proton nmr spectra and carbon spectrum.Adopt the Q-ExactiveHR-MS mass spectrograph record high resolution mass spectrum data of Thermo company.Adopt HIT F-7000 fluorescence spectrophotometer record fluorescence spectrum.
1, the preparation of intermediate RhB-SH
In 100mL round-bottomed flask, 2.18g (4.5mmol) rhodamine B is dissolved in 30mL anhydrous 1, in 2-ethylene dichloride, the phosphorus oxychloride of 1.5mL (16.4mmol) is added dropwise under condition of ice bath, (0 DEG C) reaction 1 hour under ice bath, change 85 DEG C of back flow reaction 3 hours into, solvent is removed in decompression, obtains rhodamine acyl chlorides RhB-Cl; Rhodamine acyl chlorides RhB-Cl is dissolved in 30mL anhydrous acetonitrile, the anhydrous acetonitrile (15mL) of 0.51g (4.5mmol) Mercaptamine is dripped under ice bath (0 DEG C) condition, ice bath reacts 6 hours, reaction system is made to be warming up to room temperature, removal of solvent under reduced pressure, again dissolve by ethyl acetate (35mL), with pure water (40mL × 2) and saturated nacl aqueous solution (40mL × 2) washing, organic phase anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure, through silica gel column chromatography separation, (elutriant is CH
2cl
2: CH
3oH=20:1, volume ratio) obtain intermediate product RhB-SH, productive rate is 69%.
2, the preparation of intermediate S-RhB-SH
In 100mL round-bottomed flask, by intermediate RhB-SH (501mg, 1mmol) with lawesson reagent (809mg, 2mmol) be dissolved in 40mL dry toluene, reflux (110 DEG C) is to react completely (15 hours), underpressure distillation concentrated removing toluene, enriched material 50mLCH
2cl
2dissolve, saturated nacl aqueous solution (40mL × 2) washs, organic phase anhydrous sodium sulfate drying, and after filtering and concentrating, through silica gel column chromatography separation, (elutriant is CH
2cl
2: CH
3oH=18:1, volume ratio) obtain intermediate S-RhB-SH, productive rate is 21%.
3, the preparation of probe HgP1
In 100mL round-bottomed flask, by intermediate S-RhB-SH (1.29g, 2.5mmol) with triethylamine (252mg, 2.5mmol) be mixed in anhydrous methylene chloride (40mL) solution, m-phthaloyl chloride (0.2g is added dropwise under ice bath (0 DEG C) condition, anhydrous methylene chloride solution (15mL) 1mmol), it should be room temperature reaction after dropwising, react completely after (10 hours), saturated nacl aqueous solution (40mL × 2) washs, organic phase anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure, through silica gel column chromatography separation, (elutriant is CH
2cl
2: CH
3oH=22:1, volume ratio) obtain product HgP1, productive rate is 81%.Nuclear magnetic resonance measuring:
1hNMR (CDCl
3, 400MHz) and δ 1.14 (t, J=6.0Hz, 24H), 3.30 (m, 16H), 3.49 (d, J=4Hz, 4H), 3.83 (q, J=7.6Hz, 4H), 5.99 (q, J=2.3Hz, 2H), 6.17 (s, 6H), 6.46 (d, J=8Hz, 4H), 6.82 (m, 2H), 7.09 (t, J=4Hz, 2H), 7.49 (m, 4H), 7.60 (m, 2H), 8.15 (t, J=6Hz, 2H).
13CNMR(CDCl
3，100MHz)δ190.6，162.5，153.4，153.2，151.5，151.2，149.2，133.7，132.0，131.9，130.6，128.8，128.6，128.5，123.8，128.3，128.5，128.3，125.0，124.8，123.4，123.3，113.9，113.8，108.2，107.9，107.7，103.6，103.1，98.5，73.2，55.3，44.3，38.6，12.6。High resolution mass spectrum measures: HR-ESI-MScalcdforC68H73N6O4S4+:1165.4576, found1165.4329 [M+H+]; 1203.4063 [M+K+].
4, the application example of derivative HgP1 as Hg2+ fluorescent probe of two rhodamine is contained.
The preparation of solution:
Metal inorganic salt: lead nitrate, Silver Nitrate, cadmium nitrate, other are muriate (K
+, Na
+, Ca
2+, Mg
2+, Ba
2+, Zn
2+, Fe
2+, Fe
3+, Mn
2+, Cu
2+, Co
2+, Ni
2+, Hg
2+) and producer is Aladdin Reagent Company or Tianjin Ke Miou Reagent Company.Precise respective metal salt, is dissolved in high purity water the solution for standby preparing 10mM.
The probe solution preparation of 1mM: precise correspondent probe (HgP1), HgP1 is dissolved in methanol solution the solution for standby preparing 1mM.
Selectivity is tested:
Whether efficiently single-minded selectivity weighs fluorescent probe molecule major criterion.First, its metalloform-selective has been investigated with ultraviolet spectrometer.As shown in Figure 1, independent probe molecule is at CH
3oH-H
2almost there is no uv-absorbing in more than 450nm scope in O (9/1, v/v) solution, showing that it mainly exists, when adding the various common metal ion (K of 10 equivalents with the form of lactone ring five membered closed loop
+, Na
+, Ca
2+, Mg
2+, Ba
2+, Zn
2+, Fe
2+, Mn
2+, Pb
2+, Cu
2+, Co
2+, Fe
3+, Cr
3+, Ag
+, Ni
2+, Cd
2+, Hg
2+) after, only have make it obviously strengthen in the uv-absorbing at 560nm place adding of mercury ion, other metal ions add the only probe molecule uv-absorbing of rear effect merchandiser unanimously, show that it is to Hg
2+possesses good single-minded recognition capability.Meanwhile, independent probe molecule is observed at CH
3oH-H
2be colourless in O (9/1, v/v) solution, after other metal ions add, system color does not change, and only has Hg
2+add and make its color become pink, illustrate that probe HgP1 can reach bore hole recognition effect to the selection of mercury ion.
The experiment of ultraviolet selectivity shows that it is to Hg
2+possess good single-minded selectivity, use fluorescence spectrophotometer to test its fluorescence selectivity at this.As shown in Figure 2, independent probe HgP1 (10 μMs) is at CH
3oH-H
2in O (9/1, v/v) solution, there is faint fluorescent emission intensity, when adding Hg
2+(10eq.) its fluorescent emission intensity obviously strengthens afterwards, but when adding other metal ion (100 μMs), its fluorescence intensity does not have considerable change.Above experimental result shows, this probe has good single-minded selectivity to mercury ion.
Fluorescence interference is tested:
In order to test probe molecule is to Hg
2+the immunity from interference detected, tests its metallic cation interference and negatively charged ion interference respectively in fluorescence emission spectrum.As shown in Figure 3, at HgP1 (10 μMs) at CH
3oH-H
2the various metallic cations (100 μMs) adding test in O (9/1, v/v) solution respectively test its fluorescent emission intensity (583nm), and then add the Hg of 100 μMs in the solution containing each metal ion species
2+solution, from accompanying drawing 3, add mercury ion when other metallic cations exist substantially identical with the fluorescence intensity (583nm) obtained when adding separately mercury ion, and this result shows that probe HgP1 is to Hg
2+detection there is stronger anti-metal Cation Interferences ability.Only have ferric ion, trivalent chromic ion to have certain quenching effect to Fluorescence Increasing due to its paramagnetism, but its quenching effect is not enough to affect HgP1 to Hg
2+identification.According to similar method, test it to Common Anions (Cl
-, Br
-, NO
3 -, NO
2 -, F
-, SO
4 2-) immunity from interference, as shown in Figure 4, probe HgP1 is to Hg
2+detection there is stronger anti-negatively charged ion interference performance.
Detectability:
Good detectability is inspection probe molecule whether one of standard with using value.Fluorescence spectrophotometer is adopted to measure it to Hg
2+detectability, at CH
3oH-H
2in O (9/1, v/v) solution, stationary probe HgP1 concentration is 10 μMs, measures its Hg to different concns
2+response intensity, along with Hg
2+the increase of concentration, system fluorescence intensity constantly strengthens (accompanying drawing 5), and research finds that solution fluorescence intensity level is at Hg
2+concentration is linearly (R between 0.01-0.1 μM
2=0.988) (3 σ/k) show that this probe molecule is to Hg, as calculated
2+detection be limited to 0.256 μ g/kg, this detectability can meet the limitation requirement of country to Mercury In Food ion content, shows that this probe molecule has larger using value in agricultural product quality and safety.
Claims (8)
1. the Hg containing two carbon-sulfur bond structure rhodamine
2+fluorescent probe molecule, is characterized in that, described fluorescent probe structural formula is as follows:
2. as right 1 require as described in the Hg containing two carbon-sulfur bond structure rhodamine
2+the preparation method of fluorescent probe molecule, is characterized in that, its step is as follows:
(1) rhodamine B is dissolved in anhydrous 1,2-ethylene dichloride, under condition of ice bath, is added dropwise to phosphorus oxychloride, react 1 hour under ice bath, then back flow reaction 3 hours, solvent is removed in decompression, obtains rhodamine acyl chlorides RhB-Cl; Rhodamine acyl chlorides RhB-Cl is dissolved in anhydrous acetonitrile, the acetonitrile solution of excessive Mercaptamine is dripped under condition of ice bath, reaction system is made to be warming up to room temperature after question response is complete, removal of solvent under reduced pressure, with acetic acid ethyl dissolution, with pure water and saturated nacl aqueous solution washing, organic phase anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure, silica gel column chromatography is separated and obtains intermediate product RhB-SH;
(2) intermediate product RhB-SH and lawesson reagent are dissolved in dry toluene, reflux is to reacting completely, and underpressure distillation is concentrated removes toluene, enriched material CH
2cl
2dissolve, saturated common salt water washing, organic phase anhydrous sodium sulfate drying, after filtering and concentrating, silica gel column chromatography is separated and obtains intermediate S-RhB-SH;
(3) intermediate S-RhB-SH and triethylamine are mixed in dichloromethane solution, the dichloromethane solution of m-phthaloyl chloride is added dropwise under condition of ice bath, it should be room temperature reaction after dropwising, after reacting completely, saturated nacl aqueous solution washs, organic phase anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure is washing composition with methylene dichloride and methyl alcohol, is separated the Hg obtained containing two carbon-sulfur bond structure rhodamine through silica gel column chromatography
2+fluorescent probe molecule.
3. the Hg containing two carbon-sulfur bond structure rhodamine as claimed in claim 2
2+the preparation method of fluorescent probe molecule, it is characterized in that: in described step (1), rhodamine B is 1:3-8 with the ratio of the amount of substance of phosphorus oxychloride, described condition of ice bath temperature is less than 0 DEG C, back flow reaction temperature is 80-90 DEG C, and the reaction times is 4-7 hour, and rhodamine acyl chlorides RhB-Cl is 1:3-5 with the ratio of the amount of substance of Mercaptamine, reaction times is 5-8 hour, and productive rate is 60-80%.
4. the Hg containing two carbon-sulfur bond structure rhodamine as claimed in claim 2
2+the preparation method of fluorescent probe molecule, is characterized in that: in described step (1), and the elutriant that silicagel column is separated is CH
2cl
2and CH
3oH, described CH
2cl
2with CH
3the volume ratio of OH is 20-30:1.
5. the Hg containing two carbon-sulfur bond structure rhodamine as claimed in claim 2
2+the preparation method of fluorescent probe molecule, it is characterized in that: in described step (2), intermediate RhB-SH is 1:2-5 with the ratio of the amount of substance of lawesson reagent, toluene used need through Non-aqueous processing, described heating reflux reaction temperature is 105-120 DEG C, reaction times is 10-15 hour, and the elutriant that silicagel column is separated is CH
2cl
2and CH
3oH, described CH
2cl
2with CH
3the volume ratio of OH is 8-20:1, and productive rate is 15-30%.
6. the Hg containing two carbon-sulfur bond structure rhodamine as claimed in claim 2
2+the preparation method of fluorescent probe molecule, is characterized in that: in described step (3), and the elutriant that silicagel column is separated is CH
2cl
2and CH
3oH, described CH
2cl
2with CH
3the volume ratio of OH is 10-25:1, and productive rate is 70-90%.
7. the Hg containing two carbon-sulfur bond structure rhodamine as claimed in claim 2
2+the preparation method of fluorescent probe molecule, is characterized in that: in described step (3), and compound S-RhB-SH is 2-4 equivalent, m-phthaloyl chloride is 1 equivalent, triethylamine is 2-4 equivalent, and described condition of ice bath temperature is less than 0 DEG C, and the room temperature reaction time is 8-15 hour.
8. containing the Hg of two carbon-sulfur bond structure rhodamine
2+fluorescent probe molecule is at detection Hg
2+in application.
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| CN108896523A (en) * | 2018-08-31 | 2018-11-27 | 河南省农业科学院农业质量标准与检测技术研究所 | A kind of methods and applications of fluorescence enhancement type detection hypochlorite |
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