CN105505376B - A kind of Hg containing double carbon-sulfur bond structure rhodamines2+Fluorescence probe and preparation method and application - Google Patents
A kind of Hg containing double carbon-sulfur bond structure rhodamines2+Fluorescence probe and preparation method and application Download PDFInfo
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- CN105505376B CN105505376B CN201510892168.2A CN201510892168A CN105505376B CN 105505376 B CN105505376 B CN 105505376B CN 201510892168 A CN201510892168 A CN 201510892168A CN 105505376 B CN105505376 B CN 105505376B
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The invention discloses a kind of based on the Hg containing double carbon-sulfur bond structure rhodamines2+Fluorescence probe and preparation method and application.Probe HgP1 have studied in CH by ultraviolet-uisible spectrophotometer and sepectrophotofluorometer3OH‑H2With the evident characteristics of metal ion in O solution.Result shows:Probe HgP1 is to Hg2+With efficiently single-minded selectivity, with stronger anti-metal cation and anion interference performance, and the bore hole identification realized to mercury ion can be changed by solution colour.The probe is limited to 0.256 μ g/kg to the lowest detection of mercury ion, shows that this method can meet limitation requirement of the national standard to mercury ion, possesses stronger actual application value.
Description
Technical field
The present invention relates to a kind of mercury ion (Hg2+) detection agent, and in particular to one kind is based on containing double carbon-sulfur bond structure sieve
Red bright Hg2+The preparation method of fluorescence probe.
Background technology
Mercury is one of common pollutant in organism and environment, and mercury exists in liquid form at normal temperatures, possess compared with
Strong volatility, larger harm is brought to the ecosystem.Mercury is main to be entered in organism in the form of inorganic mercury and methyl mercury,
And be enriched with vivo.Mercury ion possesses stronger thiophilic property, excessive mercury ion and organism include S protein or
Enzyme reacts, so as to cause a series of disease.Nervous system and normal metabolic activity to organism cause greatly wound
Evil, such as mercury ion can excessively cause irreversible DNA damage, miocardial infarction, CNS disorders and it is polytype from
Close the symptoms such as disease.Just because of the hypertoxicity of mercury ion, in the world multiple countries and linked groups to mercury ion in drinking water
Strict requirements are done with the content in food, the mercury ion with regard to strict regulations in drinking water contains such as EPA (EPA)
Amount must not exceed 2ppb.In recent years, the mercury ion content in real-time monitoring organism and environment turns into an important research neck
Domain.Fluorescence probe due to having the advantages that cost is relatively low, operating instrument is simple, test limit is low, real-time monitoring, examine by fluorescence probe method
Metal ion is surveyed to receive significant attention in recent years.
Fluorescent sensing material based on " turn-on " mechanism can reduce detection mistake, more accurate to complex system detection, press
Mechanism it be divided into fluorescence chemical sensor (fluorescentchemsensor) and fluorescence chemical dosimeter
(fluorescentchemodosimeter) two types.Wherein, fluorescence chemical dosimeter with target analytes due to that can send out
The irreversible chemical reaction of life, high selectivity is shown to analyte, gradually highlights it excellent in detection of heavy metal ion
Gesture.Mercury ion fluorescent chemical dosimeter mainly use mercury ion and thiocarbonyl group occur desulphurization reaction and with end-group alkyne or alkene
The reaction of generation oxymercuration is realized to mercury ion detecting.Oxymercuration reaction is relatively low due to reactivity, it is often necessary to reaction higher
Temperature or reaction time more long, limit its application.Mercury ion fluorescent chemical dosimeter based on desulphurization reaction has sound
The features such as answering that speed is fast, be often accompanied by colorimetric analysis, is increasingly paid close attention to by people.
The content of the invention
The purpose of the present invention is to propose to a kind of based on the Hg containing double carbon-sulfur bond structure rhodamines2+The preparation side of fluorescence probe
Method.
It is proposed by the present invention a kind of based on the Hg containing double carbon-sulfur bond structure rhodamines2+The preparation method of fluorescence probe, first
Condensation acylation reaction is carried out by the rhodamine B and Mercaptamine of commercialization, a kind of rhodamine B-Cysteamine derivatives are obtained
(RhB-SH);Rhodamine B-the Cysteamine derivatives (RhB-SH) obtain the intermediate containing carbon-sulfur bond by lawesson reagent vulcanization
(S-RhB-SH);The intermediate (S-RhB-SH) containing carbon-sulfur bond carries out acyl chloride reaction and obtains one kind containing with m-phthaloyl chloride
The compound of double carbon-sulfur bond structure rhodamines, the compound can be used as Hg in methanol-water solution2+High selectivity fluorescence visit
Pin.
It is proposed by the present invention a kind of based on the Hg containing double carbon-sulfur bond structure rhodamines2+The preparation method of fluorescence probe, its tool
Body synthetic route is as follows:
(1) rhodamine B is dissolved in anhydrous 1,2- dichloroethanes, a certain amount of POCl3 is added dropwise under condition of ice bath,
Reacted 1 hour under ice bath, be changed to back flow reaction 3 hours, decompression removal solvent obtains rhodamine acyl chlorides RhB-Cl.By rhodamine
Acyl chlorides RhB-Cl is dissolved in anhydrous acetonitrile, and the acetonitrile solution dropwise of excessive Mercaptamine enters above-mentioned system under condition of ice bath
In, reaction system is warming up to room temperature after question response is complete, removal of solvent under reduced pressure is dissolved again with ethyl acetate, with pure water and
Saturated nacl aqueous solution is washed, organic phase anhydrous sodium sulfate drying, and filtering, removal of solvent under reduced pressure, silica gel column chromatography is separated
To intermediate product RhB-SH.
(2) intermediate RhB-SH and lawesson reagent are dissolved in dry toluene, are heated to reflux to reaction completely, vacuum distillation is dense
Contracting removes toluene, concentrate CH2Cl2Dissolving, saturated common salt water washing, organic phase anhydrous sodium sulfate drying, after filtering and concentrating
The isolated intermediate S-RhB-SH of silica gel column chromatography.
(3) intermediate S-RhB-SH and triethylamine are mixed in dichloromethane solution, isophthalic is added dropwise under condition of ice bath
The dichloromethane solution of dimethyl chloride, should be room temperature reaction after completion of dropping, after reaction completely, saturated nacl aqueous solution washing,
Organic phase anhydrous sodium sulfate drying, filtering, removal of solvent under reduced pressure, with dichloromethane and methyl alcohol as detergent, through silicagel column
Chromatography obtains product HgP1.
In the step (1), the ratio between amount of material of rhodamine B and POCl3 is 1:3-8, the condition of ice bath temperature
It it is less than 0 DEG C, back flow reaction temperature is 80-90 DEG C, the reaction time is 4-7 hours, rhodamine acyl chlorides RhB-Cl and cysteamine salt
The ratio between amount of material of hydrochlorate is 1:3-5, the reaction time is 5-8 hours, and yield is 60-80%.
In the step (1), the eluent of silica gel post separation is CH2Cl2And CH3OH, the CH2Cl2With CH3The volume of OH
Than being 20-30:1.
In the step (2), the ratio between amount of material of intermediate RhB-SH and lawesson reagent is 1:2-5, toluene used is needed
Through Non-aqueous processing, the heating reflux reaction temperature is 105-120 DEG C, and the reaction time is 10-15 hours, and silica gel post separation is washed
De- liquid is CH2Cl2And CH3OH, the CH2Cl2With CH3The volume ratio of OH is 8-20:1, yield is 15-30%.
In the step (3), the eluent of silica gel post separation is CH2Cl2And CH3OH, the CH2Cl2With CH3The volume of OH
Than being 10-25:1, yield is 70-90%.
In the step (3), compound S-RhB-SH is 2-4 equivalents, and m-phthaloyl chloride is 1 equivalent, and triethylamine is 2-4
Equivalent, the condition of ice bath temperature is less than 0 DEG C, and the room temperature reaction time is 8-15 hours.
Hg containing double carbon-sulfur bond structure rhodamines2+Fluorescent probe molecule is in detection Hg2+In application.
The beneficial effects of the invention are as follows:Probe HgP1 is in CH3OH-H2To Hg in O (9/1, v/v) system2+With efficient spirit
Quick single-minded detectability.By experimental results such as above ultraviolet and fluorescence spectrum researchs, thus it is speculated that go out HgP1 identifications Hg2+Possibility
Mechanism is as shown in Figure 6:Hg is added in probe solution2+, due to Hg2+Thiophilic property, Hg2+With the S in ' C=S ' in molecular structure
Atom is combined, and generates and slough the HgS of two molecules, and causes the acyl spirolactone ring in rhodamine structure to be opened, and discharges fluorescence
Signal, product HgP1-Hg of the generation with fluorescence.The structure of product HgP1-Hg is confirmed (accompanying drawing 7) by HR-MS.
Test result indicate that, HgP1-Hg calculated values are shown as 484.2298 for 484.2417, HR-MS results.The data confirm
The mechanism of action shown in accompanying drawing 6.
Brief description of the drawings
Fig. 1 is the ultraviolet selective figures of fluorescence probe HgP1 of the invention, and illustration is solution colour variation diagram;
Fig. 2 is fluorescence probe HgP1 fluorescence selectivity figures of the invention, excitation wavelength 520nm;
Fig. 3 is that fluorescence probe HgP1 of the invention recognizes Hg2+Anti-metal Cation Interferences figure, excitation wavelength 520nm,
Launch wavelength 583nm;
Fig. 4 is that fluorescence probe HgP1 of the invention recognizes Hg2+Anti- anion interference figure, excitation wavelength 520nm, transmitting
Wavelength 583nm;
Fig. 5 is fluorescence probe HgP1 fluorescence titration figures of the invention, and illustration is LDL figure, excitation wavelength 520nm;
Fig. 6 is fluorescence probe HgP1 recognition mechanism figures of the invention;
Fig. 7 is that fluorescence probe HgP1 recognition mechanisms of the invention verify High-Resolution Map.
Specific embodiment
The Ah such as chemical reagent, solvent, metal ion for being used during fluorescence probe HgP1 is prepared in the present invention
Latin Reagent Company.Bruke companies DTX-400 type nuclear magnetic resonance is used in the confirmation and performance test process of fluorescence probe HgP1
Spectrometer, solvent is deuterochloroform, and proton nmr spectra and carbon spectrum are recorded by internal standard of TMS.Using the Q- of Thermo companies
ExactiveHR-MS mass spectrographs record high resolution mass spectrum data.Record glimmering using HIT's F-7000 XRFs
Light spectrum.
1st, the preparation of intermediate RhB-SH
In 100mL round-bottomed flasks, 2.18g (4.5mmol) rhodamine B is dissolved in anhydrous 1, the 2- dichloroethanes of 30mL, ice
The POCl3 of 1.5mL (16.4mmol) is added dropwise under the conditions of bath, (0 DEG C) is reacted 1 hour under ice bath, is changed to 85 DEG C of back flow reactions
3 hours, decompression removal solvent obtained rhodamine acyl chlorides RhB-Cl;Rhodamine acyl chlorides RhB-Cl is dissolved in 30mL anhydrous acetonitriles,
The anhydrous acetonitrile (15mL) of 0.51g (4.5mmol) Mercaptamine is added dropwise under the conditions of ice bath (0 DEG C), ice bath reaction 6 is small
When, reaction system is warming up to room temperature, removal of solvent under reduced pressure is dissolved again with ethyl acetate (35mL), with pure water (40mL × 2)
With saturated nacl aqueous solution (40mL × 2) washing, organic phase anhydrous sodium sulfate drying, filtering, removal of solvent under reduced pressure, through silica gel
(eluent is CH to column chromatography for separation2Cl2:CH3OH=20:1, volume ratio) intermediate product RhB-SH is obtained, yield is 69%.
2nd, the preparation of intermediate S-RhB-SH
It is in 100mL round-bottomed flasks, intermediate RhB-SH (501mg, 1mmol) and lawesson reagent (809mg, 2mmol) is molten
In 40mL dry toluenes, (110 DEG C) are heated to reflux to reacting completely (15 hours), vacuum distillation concentration removes toluene, concentration
Thing 50mLCH2Cl2Dissolving, saturated nacl aqueous solution (40mL × 2) washing, organic phase anhydrous sodium sulfate drying, filtering and concentrating
By silica gel column chromatography separation, (eluent is CH2Cl2:CH3OH=18:1, volume ratio) intermediate S-RhB-SH is obtained, yield is
21%.
3rd, the preparation of probe HgP1
In 100mL round-bottomed flasks, by intermediate S-RhB-SH (1.29g, 2.5mmol) and triethylamine (252mg,
2.5mmol) it is mixed in anhydrous methylene chloride (40mL) solution, m-phthaloyl chloride is added dropwise under the conditions of ice bath (0 DEG C)
The anhydrous methylene chloride solution (15mL) of (0.2g, 1mmol), should be room temperature reaction after completion of dropping, and reaction is completely (10 hours)
Afterwards, saturated nacl aqueous solution (40mL × 2) washing, organic phase anhydrous sodium sulfate drying, filtering, removal of solvent under reduced pressure, through silicon
(eluent is CH for plastic column chromatography separation2Cl2:CH3OH=22:1, volume ratio) product HgP1 is obtained, yield is 81%.Nuclear-magnetism is total to
Shake measure:1HNMR(CDCl3, 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(CDCl3,
100MHz) δ 190.6,162.5,153.4,153.2,151.5,151.2,149.2,133.7,132.0,131.9,130.6,
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
Determine:HR-ESI-MScalcdforC68H73N6O4S4+:1165.4576, found1165.4329 [M+H+];1203.4063
[M+K+]。
4th, the derivative HgP1 containing double rhodamines as Hg2+ fluorescence probes application example.
The preparation of solution:
Metal inorganic salt:Plumbi nitras, silver nitrate, cadmium nitrate, other are chloride (K+, Na+, Ca2+, Mg2+, Ba2+, Zn2 +, Fe2+, Fe3+, Mn2+, Cu2+, Co2+, Ni2+, Hg2+) and producer is Aladdin Reagent Company or Tianjin Ke Miou reagents are public
Department.Precise respective metal salt, is dissolved in the solution for standby of preparation 10mM in high purity water.
The probe solution of 1mM is prepared:Precise correspondent probe (HgP1), HgP1 prepares 1mM in being dissolved in methanol solution
Solution for standby.
Selectivity experiment:
Whether single-minded selectivity is to weigh the efficient major criterion of fluorescent probe molecule.First, examined with ultraviolet spectrometer
Its metalloform-selective is examined.As shown in Figure 1, single probe molecule is in CH3OH-H2In O (9/1, v/v) solution
450nm range above shows its main presence in the form of lactone ring five membered closed loop almost without UV absorption, works as when adding 10
Various common metal ion (the K of amount+, Na+, Ca2+, Mg2+, Ba2+, Zn2+, Fe2+, Mn2+, Pb2+, Cu2+, Co2+, Fe3+, Cr3+, Ag+, Ni2+, Cd2+, Hg2+) after, the addition of only mercury ion is remarkably reinforced its UV absorption at 560nm, other metals from
The only probe molecule UV absorption of effect merchandiser is consistent after son is added, and shows it to Hg2+Possesses preferable single-minded recognition capability.Together
When, it was observed that individually probe molecule is in CH3OH-H2It is colourless in O (9/1, v/v) solution, after the addition of other metal ions,
System color is not changed in, only Hg2+Addition make its color be changed into pink, illustrate that selections of the probe HgP1 to mercury ion can
To reach bore hole recognition effect.
Ultraviolet selectivity experiment shows it to Hg2+Possesses preferable single-minded selectivity, herein using XRF to it
Fluorescence selectivity is tested.As shown in Figure 2, single probe HgP1 (10 μM) is in CH3OH-H2O (9/1, v/v) solution
In have faint fluorescent emission intensity, when add Hg2+(10eq.) its fluorescent emission intensity is remarkably reinforced afterwards, but adds it
During its metal ion (100 μM), its fluorescence intensity does not have significant change.Above test result indicate that, the probe to mercury ion have
There is preferable single-minded selectivity.
Fluorescence interference is tested:
In order to test probe molecule to Hg2+The antijamming capability of detection, tests its gold respectively in fluorescence emission spectrum
Category Cation Interferences and anion interference.As shown in Figure 3, in HgP1 (10 μM) in CH3OH-H2O (9/1, v/v) solution
In be separately added into the various metal cations (100 μM) of test and test its fluorescent emission intensity (583nm), then again to containing each
100 μM of Hg is added in the solution of metal ion species2+Solution, from accompanying drawing 3, mercury is added in the presence of other metal cations
Ion is essentially identical with fluorescence intensity (583nm) resulting when being individually added into mercury ion, and the result shows probe HgP1 to Hg2+
Detection have stronger anti-metal Cation Interferences ability.Only ferric ion, trivalent chromic ion are due to its paramagnetism pair
Fluorescence Increasing has certain quenching effect, but its quenching effect is not enough to influence HgP1 to Hg2+Identification.According to similar side
Method, tests it to Common Anions (Cl-, Br-, NO3 -, NO2 -, F-, SO4 2-) antijamming capability, as shown in Figure 4, probe
HgP1 is to Hg2+Detection have stronger anti-anion interference performance.
Test limit:
Good test limit is to check whether a probe molecule has one of standard of application value.Using fluorescence spectrum
Instrument determines it to Hg2+Test limit, in CH3OH-H2In O (9/1, v/v) solution, fixed probe HgP1 concentration is 10 μM, is determined
Its Hg to various concentrations2+Response intensity, with Hg2+The increase of concentration, system fluorescence intensity constantly strengthens (accompanying drawing 5), grinds
Discovery solution fluorescence intensity level is studied carefully in Hg2+Concentration is linear (R between 0.01-0.1 μM2=0.988), it is computed (3 σ/k) and draws
The probe molecule is to Hg2+Detection be limited to 0.256 μ g/kg, the test limit can meet limit of the country to Mercury In Food ion concentration
Amount requirement, shows that the probe molecule has larger application value in terms of agricultural product quality and safety.
Claims (7)
1. a kind of Hg containing double carbon-sulfur bond structure rhodamines2+Fluorescent probe molecule, it is characterised in that the fluorescence probe structural formula
It is as follows:
2. the Hg containing double carbon-sulfur bond structure rhodamines as described in right 1 is required2+The preparation method of fluorescent probe molecule, its feature
Be, it the step of it is as follows:
(1) rhodamine B is dissolved in anhydrous 1,2- dichloroethanes, POCl3 is added dropwise under condition of ice bath, 1 is reacted under ice bath small
When, then back flow reaction 3 hours, decompression removal solvent, obtain rhodamine acyl chlorides RhB-Cl;Rhodamine acyl chlorides RhB-Cl is dissolved in nothing
The acetonitrile solution of excessive Mercaptamine is added dropwise in water-acetonitrile, under condition of ice bath, reaction system is heated up after question response is complete
To room temperature, removal of solvent under reduced pressure is dissolved with ethyl acetate, is washed with pure water and saturated nacl aqueous solution, the anhydrous sulphur of organic phase
Sour sodium is dried, filtering, removal of solvent under reduced pressure, the isolated intermediate product RhB-SH of silica gel column chromatography;
(2) intermediate product RhB-SH and lawesson reagent are dissolved in dry toluene, are heated to reflux, vacuum distillation concentration complete to reaction
Remove toluene, concentrate CH2Cl2Dissolving, saturated common salt water washing, organic phase anhydrous sodium sulfate drying, silicon after filtering and concentrating
The isolated intermediate S-RhB-SH of plastic column chromatography;
(3) intermediate S-RhB-SH and triethylamine are mixed in dichloromethane solution, isophthalic diformazan is added dropwise under condition of ice bath
The dichloromethane solution of acyl chlorides, is changed to room temperature reaction after completion of dropping, after reaction completely, saturated nacl aqueous solution washing is organic
Anhydrous sodium sulfate drying is mutually used, is filtered, removal of solvent under reduced pressure is detergent with dichloromethane and methyl alcohol, through silica gel column chromatography point
From the Hg for obtaining containing double carbon-sulfur bond structure rhodamines2+Fluorescent probe molecule.
3. as claimed in claim 2 containing couple Hg of carbon-sulfur bond structure rhodamines2+The preparation method of fluorescent probe molecule, its feature
It is:In the step (1), the ratio between amount of material of rhodamine B and POCl3 is 1:3-8, the condition of ice bath temperature is 0
Below DEG C, back flow reaction temperature is 80-90 DEG C, and the reaction time is 4-7 hours, rhodamine acyl chlorides RhB-Cl and Mercaptamine
The ratio between the amount of material be 1:3-5, the reaction time is 5-8 hours, and yield is 60-80%.
4. as claimed in claim 2 containing couple Hg of carbon-sulfur bond structure rhodamines2+The preparation method of fluorescent probe molecule, its feature
It is:In the step (1), the eluent of silica gel post separation is CH2Cl2And CH3OH, the CH2Cl2With CH3The volume ratio of OH
It is 20-30:1.
5. as claimed in claim 2 containing couple Hg of carbon-sulfur bond structure rhodamines2+The preparation method of fluorescent probe molecule, its feature
It is:In the step (2), the ratio between amount of material of intermediate RhB-SH and lawesson reagent is 1:2-5, toluene used need to be through nothing
Water process, the heating reflux reaction temperature is 105-120 DEG C, and the reaction time is 10-15 hours, the eluent of silica gel post separation
It is CH2Cl2And CH3OH, the CH2Cl2With CH3The volume ratio of OH is 8-20:1, yield is 15-30%.
6. as claimed in claim 2 containing couple Hg of carbon-sulfur bond structure rhodamines2+The preparation method of fluorescent probe molecule, its feature
It is:In the step (3), the eluent of silica gel post separation is CH2Cl2And CH3OH, the CH2Cl2With CH3The volume ratio of OH
It is 10-25:1, yield is 70-90%.
7. as claimed in claim 2 containing couple Hg of carbon-sulfur bond structure rhodamines2+The preparation method of fluorescent probe molecule, its feature
It is:In the step (3), compound S-RhB-SH is 2-4 equivalents, and m-phthaloyl chloride is 1 equivalent, and triethylamine is worked as 2-4
Amount, the condition of ice bath temperature is less than 0 DEG C, and the room temperature reaction time is 8-15 hours.
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Dithiolane linked thiorhodamine dimer for Hg2+ recognition in living cells;Weimin Liu等;《Organic and Biomolecular Chemistry》;20090106;第7卷;第660-664页 * |
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