CN104845612A - Polystyrene mercury ion fluorescence recognition materials and preparation method thereof - Google Patents
Polystyrene mercury ion fluorescence recognition materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polystyrene mercury ion fluorescence recognition materials. The structural formula of the polystyrene mercury ion fluorescence recognition materials is as follows. The invention also discloses a preparation method of the functionalized polystyrene mercury ion fluorescence recognition materials. The preparation method comprises the following specific implementation steps of, preparing 5-amino-2-(4'-hydroxy-3'-(2-(2''-ethylsuleenyl ethyl) amino) phenyl-5-amino benzo [d] oxazole (VII), preparing aldehyde polystyrene microspheres (IX) and performing reaction preparation on the compounds (VII) and (IX) obtained through preparation to obtain the functionalized polystyrene mercury ion fluorescence recognition materials (X). The detection sensitivity of the polystyrene mercury ion fluorescence recognition materials is greatly improved due to the molecular wire effect of a polymer and the detection limit is 0.006 micromole every liter. The polystyrene mercury ion fluorescence recognition materials can enter cells and can be applied to the detection on mercury ions in the cells.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of polystyrene Hg
2+fluorescence identifying material, the invention still further relates to a kind of polystyrene Hg
2+the preparation method of fluorescence identifying material.
Background technology
Heavy metal ion can enter human body by approach such as food chains, constantly gathers and endanger greatly the healthy generation of people in human body.Particularly Hg
2+be a kind of carcinogenic substance, namely extremely low concentration can cause the organ lesion such as kidney, gi system, and therefore, the detection of counterweight gold ion and Environmental capacity, as Pb
2+, Cd
2+, Hg
2+, Cu
2+, Ag
+deng, be the focus of current research.Because detection technique of fluorescence is highly sensitive, selectivity is good, simple to operate, is applicable to living things system and has the advantage such as multi-functional to be widely used in chemical detection, bio-imaging, drug screening and antibody test.Therefore, the fluorescent small molecule that there is recognition capability strong to metal ion is synthesized most important.But fluorescent small molecule easily comes off in the application, can only carry out detection metal ion, cannot by separation of metal ions, can not recycle and reuse.By contrast, macromolecular material has good stability and film-forming properties, be easy to make various device, conjugated polymers is because it has the pi-conjugated electronics of delocalization simultaneously, under the exciting of photon, energy can along polymer backbone transmission, i.e. " molecular wire effect " (Molecular wire effect), can amplify fluorescent signal by the exciton migration route number improving conjugated backbone.That is, under the irradiation of exciting light, the exciton that molecular line absorb photons produces moves along the skeleton of molecular line, when molecular line and analyte effect, as long as some Locus Analysis in Shoots things and molecular line produce combination will make exciton inactivation, make the fluorescent quenching of whole molecular line, this is compared with small molecule fluorescent, become the amplification fluorescent signal of hundred million times, improve sensitivity.So there is the design of highly selective and highly sensitive novel fluorescent material, synthesis and application cause people's interest widely.
At present for Hg
2+the fluorescent probe overwhelming majority be fluorescent small molecule, can not by detection and separation and combination, simultaneously to trace Hg
2+respond not strong.Therefore prepare Hg
2+the fluorescence polymer that recognition capability is strong has great importance.
Summary of the invention
The object of this invention is to provide a kind of polystyrene Hg of functionalization
2+fluorescence identifying material, solves the fluorescence identifying material existed in prior art and can only detect and can not be separated; Test material can not reuse the problem of amplifying with fluorescent quenching signal.
Another object of the present invention is to provide a kind of polystyrene Hg of functionalization
2+the preparation method of fluorescence identifying material.
First technical scheme of the present invention is, a kind of polystyrene Hg of functionalization
2+fluorescence identifying material, its structural formula is X:
Second technical scheme of the present invention is, a kind of polystyrene Hg of functionalization
2+the preparation method of fluorescence identifying material, specifically implements according to following steps:
Step 1, prepare amino-2-(4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) are amino) phenyl-benzo [d] oxazole (BOS, VII), its concrete synthetic route as shown in the formula shown in 1-formula 4,
Step 2, prepare aldehyde radical polystyrene microsphere (Ⅸ), its reaction process such as formula shown in 5-formula 6,
Step 3, (Ⅸ) prepared in the compound (VII) and step 2 that prepare in step 1 is utilized to prepare the polystyrene Hg of functionalization
2+fluorescence identifying material, its reaction process as shown in Equation 7,
Feature of the present invention is also,
Preparation amino-2-in step 1 (4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) amino) phenyl-benzo [d] oxazole (BOS, VII), specifically implement according to following steps:
Step 1.1, preparation two (2-ethylthio-ethyl) amine (III); With diethanolamine (I) for starting raw material, prepare two-(2-chloro ethyl) amine hydrochlorates (II) in organic solvent; And under the protection of nitrogen, add sulfur alcohol and prepare two (2-ethylthio-ethyl) amine (III);
Step 1.2, preparation contain 2-(4 '-hydroxy phenyl) benzo [preparation of d] oxazole (V) of nitro;
Step 1.3, by two (2-ethylthio-ethyl) amine (III) with [d] oxazole (V) is obtained by reacting (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI) by Mannich containing 2-(4 '-hydroxy phenyl) benzo of nitro;
Step 1.4, the compound obtained in step 3 (VI) being carried out to chloromethylation, to obtain amidized (ethylthio-ethyl) amino) phenyl benzo [d] oxazole derivative (VII).
In step 1.1, the preparation of two-(2-ethylthio-ethyl) amine (III) is specially:
Join in chloroform by diethanolamine (I), at-5 DEG C-5 DEG C, slowly add thionyl chloride, wherein, diethanolamine is 1:500mol/ml-1:700mol/ml with the molecular volume ratio of chloroform; The mol ratio of diethanolamine and thionyl chloride is 1:3-1:5; After room temperature reaction 1.5h-2.5h, be warming up to back flow reaction 2.5h-3.5h, cooling, adds ethanol and removes excessive thionyl chloride in reaction solution; Solvent is removed in underpressure distillation, then chloroform and ether is added, diethanolamine and chloroform are 1mol:40ml:120ml-1mol:100mL:300ml with the molecular volume ratio of ether, adularescent solid produces, suction filtration, solid washed with ether several, vacuum-drying, obtain white solid, i.e. two-(2-chloro ethyl) amine hydrochlorates (II);
Under nitrogen protection, sodium is dissolved in ethanol, in above-mentioned solution, adds sulfur alcohol, be warming up to 65 DEG C-75 DEG C, compound (II) is dissolved in ethanol, wherein, sodium: the mass volume ratio of ethanol is 1.1:50g/mL-1.3:50g/mL; Compound (II) is 1:1500mol/mL-1:1800mol/mL with the molecular volume ratio of ethanol; Join in the reaction solution containing sodium by compound (II) and the mixture of ethanol, the mol ratio of two-(2-chloroethyl) amine hydrochlorate and sodium is 1:3-1:4; Two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sulfur alcohol is 1:2.4-1:3; Continue reaction 1.5h-2.5h; After slightly cold, removed under reduced pressure solvent, add water, with chloroform extraction 5 times, merge organic phase, with anhydrous sodium sulfate drying, then underpressure distillation obtains colourless liquid, i.e. two (2-ethylthio-ethyl) amine (III), wherein, anhydrous sodium sulphate: the mass volume ratio of chloroform is 1:20g/ml-1:25g/ml.
In step 1.2, containing 2-(4 '-hydroxy phenyl) benzo of nitro, [preparation of d] oxazole (V) is specially: add containing the Ortho-Aminophenol of nitro, ammonium meta-vanadate and ethanol in the there-necked flask that induction stirring, reflux condensing tube, thermometer and dropping funnel are housed, wherein, be 5:1-7:1 containing the Ortho-Aminophenol of nitro and the mol ratio of ammonium meta-vanadate; Containing the Ortho-Aminophenol of nitro and the molecular volume ratio of ethanol be: 6:12-6:13; Control temperature slowly drips 4-hydroxy benzaldehyde and ethanolic soln at 5 DEG C-15 DEG C, wherein, is 3:2-1:1 containing the Ortho-Aminophenol of nitro and the mol ratio of 4-hydroxy benzaldehyde; The molecular volume ratio of 4-hydroxy benzaldehyde and ethanolic soln is: 1:1; 55 DEG C-65 DEG C reactions are warming up to after dripping, react rear concentrating under reduced pressure, cooling, add appropriate water fully to stir, suction filtration, water washing, obtains 2-(4 '-hydroxy phenyl) benzo [the d] oxazole (V) of target compound containing nitro by re-crystallizing in ethyl acetate after vacuum-drying.
Prepare in step 1.3 (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI) is specially: add successively in the round-bottomed flask that induction stirring is housed above-mentioned obtained compound V, two-(2-ethylthio-ethyl) amine (III), poly polyoxymethylene and ethanol, wherein, compound V, two-(2-ethylthio-ethyl) amine (III) is 5:5:6 with the mol ratio of poly polyoxymethylene; Compound V is 1:5-1:7 with the molecular volume ratio of ethanol; Load onto reflux condensing tube, after raw material all dissolves, be slowly heated to backflow, follow the tracks of reaction 24h-28h with TLC, after question response is complete, removed under reduced pressure solvent, then adds 100mL water, after fully stirring, uses CHCl
3extract, each 100ml, extracts three times; By organic over anhydrous MgSO
4drying, wherein, CHCl
3: MgSO
4volume mass than for 20ml:1g; After precipitation, residue silica gel column chromatography is separated to obtain light yellow solid Compound (VI), i.e. the amidized phenyl benzo of ethylthio-ethyl [d] oxazole derivative (VI).
Amidized (ethylthio-ethyl) is prepared amino in step 1.4) [d] oxazole derivative (VII) is specially phenyl benzo: in autoclave, add above-mentioned obtained compound (VI), Raney-Ni, methyl alcohol, wherein, compound (VI): Raney-Ni: the mass volume ratio of methyl alcohol is 12g:1.0g:200mL-15g:1.0g:300ml; With the air in the abundant replacement reaction kettle of nitrogen, be then slowly warming up to 35 DEG C-45 DEG C, start to pass into hydrogen, be warming up to 75 DEG C-85 DEG C again, pressure is 2.0Mpa-2.5Mpa, reacts 7h-9h with this understanding, after reacting completely, use nitrogen replacement hydrogen, heat filtering, the methanol wash of filter residue heat, merging filtrate, puts into refrigerator and continues cooling precipitation solid after being cooled to room temperature, filter, cold methanol washs, and vacuum-drying obtains white solid, is compound (VII).
Prepare aldehyde radical polystyrene microsphere (Ⅸ) in step 2 specifically to implement according to following steps:
Step 2.1, p-poly-phenyl ethene carry out chloromethylation, prepare chloromethylated polystyrene (VIII), be specially: in the four-hole boiling flask that electric stirring and thermometer are housed, add polystyrene and methylene dichloride that mass volume ratio (g/ml) is 1:10-1:15; Fully swelling through 15h-18h, then add the catalyst S nCl of 13ml Isosorbide-5-Nitrae-dichloro methyl butyl ether and 1.5mL
4, wherein, Isosorbide-5-Nitrae-dichloro methyl butyl ether: the volume mass of polystyrene is than being 1g:4mL-1g:5mL; Isosorbide-5-Nitrae-dichloro methyl butyl ether: SnCl
4volume ratio be 8:1-10:1; In room temperature reaction 8h-12h; After reaction terminates, with 0.8-1.2mol/L dilute hydrochloric acid process product mixtures, suction filtration, with Isosorbide-5-Nitrae-dioxane washing, be then washed with distilled water to filtrate and exist without chlorion, namely vacuum-drying obtain chlorine ball, chloromethylated polystyrene (VIII);
Step 2.2, aldehyde radical is carried out to chloromethylated polystyrene, prepare aldehyde radical polystyrene microsphere (Ⅸ), be specially: in the four-hole boiling flask that electric stirring is housed, add above-mentioned obtained chloromethylated polystyrene (VIII) and DMSO, after making the swelling 20-26h of chlorine ball, add NaHCO
3and KI, wherein, the mass volume ratio of chloromethylated polystyrene (VIII): DMSO is 1g:15mL-1g:25mL; Chloromethylated polystyrene (VIII): NaHCO
3mass ratio be 1:1.5-1:3; The mass ratio of chloromethylated polystyrene (VIII): KI is 1g:1.5g-1g:3.0g; After logical nitrogen removes the air in bottle, be warming up to 105 DEG C-115 DEG C and react 5h-7h in nitrogen atmosphere, cooling, suction filtration, with distilled water repetitive scrubbing product, vacuum-drying, to constant weight, obtains aldehyde radical polystyrene microsphere (Ⅸ).
The polystyrene Hg of functionalization in step 3
2+the preparation of fluorescence identifying material is specially and N,N-dimethylacetamide is mixed with compound (Ⅸ), then adds compound (VII), reacts 3 hours within the scope of 75-85 DEG C; Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material (Ⅹ).
The polystyrene Hg of functionalization in step 3
2+the preparation of fluorescence identifying material (X) is specially: in the four-hole boiling flask that electric stirring, reflux condensing tube and thermometer are housed, add N, N-N,N-DIMETHYLACETAMIDE and aldehyde radical polystyrene microsphere (Ⅸ), wherein, N,N-dimethylacetamide: the volume mass of aldehyde radical polystyrene microsphere (Ⅸ) is than being 15mL:3g – 25mL:3g; After aldehyde radical polystyrene microsphere (Ⅸ) is fully dissolved, add BOS wherein, wherein, the mass ratio of aldehyde radical polystyrene microsphere (Ⅸ): BOS is 3:1.5-3:2.5; 2-4 hour is reacted within the scope of 75-85 DEG C; Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material (X).
The invention has the beneficial effects as follows: will to Hg
2+fluorescent small molecule two-(2-ethylthio-ethyl) amine with Selective recognition replaces benzo [d] oxazole and is incorporated on macromolecular material, and one is maintain the ability of this material to the fluorescence selectivity identification of Hg2+, and 50 times to Hg
2+the Na of concentration
+, K
+, Mg
2+, Ca
2+, Mn
2+, Fe
2+, Fe
3+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+under existence, to Hg
2+detection noiseless.Two is that this fluorescent material can identify and isolates Hg from solution
2+.This material with in conjunction with Hg
2+after, can by solid-liquid separation by Hg
2+separate from solution, its loading capacity is 5.2mg/g.And through wash-out Hg
2+after can also reuse, reuse 10 times, its loading capacity only declines 2.2%.Three is that its detection sensitivity improves greatly due to high molecular " molecular wire effect ", and detectability is 0.006 μm of ol/L (be single molecular fluorescence, its detectability is 0.08 μm of ol/L).Four is that this material can enter cell, may be used for Hg in cell
2+detection.
Accompanying drawing explanation
Fig. 1 is PSBOS of the present invention fluorescence response to different metal ion in Tris-HCl buffer system;
Fig. 2 is Hg of the present invention
2+on the impact of PSBOS fluorescence;
Fig. 3 is that the present invention is adding PSBOS, Hg in HeLa cell in Tris-HCl buffered soln
2+front and back imaging, wherein, A-1:HeLa cell, A-2:HeLa cell+PSBOS, B-1:HeLa cell+Hg
2+, B-2:HeLa cell+Hg
2++ PSBOS.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The invention provides a kind of polystyrene Hg of functionalization
2+the preparation method of fluorescence identifying material, specifically implements according to following steps:
Step 1, prepare amino-2-(4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) are amino) [d] oxazole (BOS, VII), its concrete synthetic route is as shown in the formula shown in 1-formula 4 for phenyl-benzo
Specifically implement according to following step:
The preparation of step 1.1, two-(2-ethylthio-ethyl) amine (III)
Join in chloroform by diethanolamine (chemical compounds I), at-5 DEG C-5 DEG C, slowly add thionyl chloride, wherein, diethanolamine is 1:500-1:700 with the molecular volume ratio (mol/ml) of chloroform; The mol ratio of diethanolamine and thionyl chloride is 1:3-1:5; After room temperature reaction 1.5h-2.5h, be warming up to back flow reaction 2.5h-3.5h, cooling, adds ethanol and removes excessive thionyl chloride in reaction solution.Solvent is removed in underpressure distillation, then chloroform and ether is added, diethanolamine and chloroform are 1:40:120-1:100:300 with the molecular volume ratio (mol/mL/mL) of ether, adularescent solid produces, suction filtration, solid washed with ether several, vacuum-drying, obtain white solid, i.e. two-(2-chloro ethyl) amine hydrochlorates (II);
Under nitrogen protection, sodium is dissolved in ethanol, in above-mentioned solution, adds sulfur alcohol, be warming up to 65 DEG C-75 DEG C, compound (II) is dissolved in ethanol, wherein, sodium: the mass volume ratio (g/mL) of ethanol is 1.1:50-1.3:50; Compound (II) is 1:1500-1:1800 with the molecular volume ratio (mol/mL) of ethanol; Compound (II) and the mixture of ethanol are joined in the reaction solution containing sodium, two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sodium is 1:3-1:4; Two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sulfur alcohol is 1:2.4-1:3; Continue reaction 1.5h-2.5h; After slightly cold, removed under reduced pressure solvent, add water, with chloroform extraction 5 times, merge organic phase, with anhydrous sodium sulfate drying, then underpressure distillation obtains colourless liquid, i.e. two (2-ethylthio-ethyl) amine (III), wherein, anhydrous sodium sulphate: the mass volume ratio (g/mL) of chloroform is 1:20-1:25;
Step 1.2,2-(4 '-hydroxy phenyl) benzo [preparation (V) of d] oxazole containing nitro;
Add containing the Ortho-Aminophenol (IV) of nitro, ammonium meta-vanadate and ethanol in the there-necked flask that induction stirring, reflux condensing tube, thermometer and dropping funnel are housed, wherein, be 5:1-7:1 containing the Ortho-Aminophenol of nitro and the mol ratio of ammonium meta-vanadate; Containing the Ortho-Aminophenol of nitro and the molecular volume ratio of ethanol be: 6:12-6:13; Control temperature slowly drips 4-hydroxy benzaldehyde and ethanolic soln at 5 DEG C-15 DEG C, wherein, is 3:2-1:1 containing the Ortho-Aminophenol of nitro and the mol ratio of 4-hydroxy benzaldehyde; The molecular volume ratio of 4-hydroxy benzaldehyde and ethanolic soln is: 1:1; 55 DEG C-65 DEG C reactions are warming up to after dripping, react rear concentrating under reduced pressure, cooling, add appropriate water fully to stir, suction filtration, water washing, obtains target compound by re-crystallizing in ethyl acetate after vacuum-drying, is 2-(4 '-hydroxy phenyl) benzo [the d] oxazole (V) containing nitro.
Step 1.3, preparation (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI);
Add successively in the round-bottomed flask that induction stirring is housed above-mentioned obtained compound V, two-(2-ethylthio-ethyl) amine (III), poly polyoxymethylene and ethanol, wherein, compound V, two-(2-ethylthio-ethyl) amine (III) is 5:5:6 with the mol ratio of poly polyoxymethylene; Compound V is 1:5-1:7 with the molecular volume ratio of ethanol; Load onto reflux condensing tube, after raw material all dissolves, be slowly heated to backflow, follow the tracks of reaction 24h-28h with TLC, after question response is complete, removed under reduced pressure solvent, then adds 100mL water, after fully stirring, uses CHCl
3(3 × 100ml) extracts, by organic over anhydrous MgSO
4drying, wherein, CHCl
3: MgSO
4volume mass ratio (ml/g) be 20:1; After precipitation, residue silica gel column chromatography is separated to obtain light yellow solid Compound (VI), i.e. the amidized phenyl benzo of ethylthio-ethyl [d] oxazole derivative (VI);
Step 1.4, to prepare amidized (ethylthio-ethyl) amino) phenyl benzo [d] oxazole derivative (VII);
Above-mentioned obtained compound (VI) is added, Raney-Ni, methyl alcohol in autoclave, wherein, compound (VI): Raney-Ni: the mass volume ratio (g/g/mL) of methyl alcohol is 12:1.0:200-15:1.0:300; With the air in the abundant replacement reaction kettle of nitrogen, be then slowly warming up to 35 DEG C-45 DEG C, start to pass into hydrogen, be warming up to 75 DEG C-85 DEG C again, pressure is 2.0Mpa-2.5Mpa, reacts 7h-9h with this understanding, after reacting completely, use nitrogen replacement hydrogen, heat filtering, the methanol wash of filter residue heat, merging filtrate, puts into refrigerator and continues cooling precipitation solid after being cooled to room temperature, filter, cold methanol washs, and vacuum-drying obtains white solid, is compound (VII).
The preparation of step 2, aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ), its concrete synthetic route is as shown in the formula shown in 5-formula 6:
Specifically implement according to following steps:
Step 2.1, to prepare chloromethylated polystyrene (CM-PS) (VIII);
Concrete steps are: in the four-hole boiling flask that electric stirring and thermometer are housed, and add polystyrene and methylene dichloride that mass volume ratio (g/mL) is 1:10-1:15; Fully swelling through 15h-18h, then add 13mL Isosorbide-5-Nitrae-dichloro methyl butyl ether and 1.5mL catalyst S nCl
4, wherein, Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB): the volume mass of polystyrene is than being 1g:4mL-1g:5mL; Isosorbide-5-Nitrae-dichloro methyl butyl ether: SnCl
4volume ratio be 8:1-10:1; In room temperature reaction 8h-12h.After reaction terminates, with 0.8 – 1.2mol/L dilute hydrochloric acid process product mixtures, suction filtration, with Isosorbide-5-Nitrae-dioxane washing, be then washed with distilled water to filtrate and exist without chlorion, namely vacuum-drying obtain chlorine ball, chloromethylated polystyrene (CM-PS) (VIII);
Preparation (AL-PS) (Ⅸ) of step 2.2, aldehyde radical polystyrene microsphere;
In the four-hole boiling flask that electric stirring is housed, add above-mentioned obtained chloromethylated polystyrene (VIII) and DMSO, after making the swelling 20-26h of chlorine ball, add NaHCO
3and KI, wherein, the mass volume ratio (g/mL) of chloromethylated polystyrene (VIII): DMSO is 1:15 – 1:25; Chloromethylated polystyrene (VIII): NaHCO
3mass ratio be 1:1.5-1:3; The mass ratio of chloromethylated polystyrene (VIII): KI is 1:1.5 – 1:3.0; After logical nitrogen removes the air in bottle, be warming up to 105 DEG C-115 DEG C and react 5h-7h in nitrogen atmosphere, cooling, suction filtration, with distilled water repetitive scrubbing product, vacuum-drying, to constant weight, obtains aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ).
The polystyrene Hg of step 3, functionalization
2+the preparation of fluorescence identifying material (X); Its concrete synthetic route is as shown in the formula shown in 7:
Specifically implement according to following steps:
In the four-hole boiling flask that electric stirring, reflux condensing tube and thermometer are housed, add N, N-N,N-DIMETHYLACETAMIDE (DMAC) and aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ), wherein, N,N-dimethylacetamide: the volume mass of aldehyde radical polystyrene microsphere (Ⅸ) is than being 15mL:3g – 25mL:3g; After aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ) is fully dissolved, add BOS wherein, wherein, the mass ratio of aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ): BOS is 3:1.5 – 3:2.5.2-4 hour is reacted within the scope of 75-85 DEG C.Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material, PS-BOS (X).
1, the fluorescent characteristic of this material
This material has highly selective and high sensitivity to mercury ion.As material X (pH=6 ~ 7.5, solvent can be ethanol/water/DMF/ ethyl acetate/dichloromethane) in Tris-HCl buffer system, in 428nm transmitted wave strong point, 1.0 μm of ol/L Hg
2+to the fluorescence of the PS-BOS of 20 μ g/g, there is cancellation effect, and, as shown in Figure 1, (pH=7.2 in Tris-HCl buffer system, solvent can be ethanol/water/DMF, v/v=2:6:1), PS-BOS (20 μ g/g) is to the fluorescence response of different metal ion (10 μm of ol/L), wherein, the fluorescence intensity of PS-BOS and Hg
2+concentration at 0.6 ~ 5.8 μm of ol/L, there is good linear relationship, its detectability is 0.06 μm of ol/L.Other ion, as: K
+, Na
+, Ca
2+, Mg
2+, Mn
2+, Fe
2+, Fe
3+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+the fluorescence of PS-BOS is not affected.Cu
2+a wee bit is had to affect on the fluorescence of PS-BOS.As shown in Figure 2, under the existence of each metal ion species (500 μm of ol/L), Hg
2+on the impact of PS-BOS (20 μ g/g) fluorescence, work as Hg
2+when existing, 50 times to Hg
2+the K of concentration
+, Na
+, Ca
2+, Mg
2+, Mn
2+, Fe
2+, Fe
3+, Co
2+, Ni
2+, Zn
2+, Cu
2+, Cd
2+, Pb
2+to the fluorescence intensity of PS-BOS X without change.
2, to mercury ion (Hg
2+) loading capacity and adsorption rate
The polystyrene of this functionalization, as X, optionally can adsorb Hg
2+, not by K
+, Na
+, Ca
2+, Mg
2+, Mn
2+, Fe
2+, Fe
3+, Co
2+, Ni
2+, Zn
2+, Cu
2+, Cd
2+, Pb
2+isoionic interference, reached adsorption equilibrium in 25 minutes, and its Static Adsorption capacity is 5.2mg/g.Absorption Hg
2+after, can filter and from solution, be separated this sorbing material and can reuse after wash-out, when repeating 10 times, its loading capacity only declines 2.2%.Illustrate that this material may be used for processing Hg
2+the waste water polluted.
3, the imaging of PS-BOS in cell
PS-BOS (X) (3 μ g/g) ethanolic soln is joined (pH 7.2 in the Tris-HCl buffered soln of cultured HeLa cell, ethanol/water/DMF, v/v=2:6:1), cultivate 50min in 37 DEG C in the medium, find that viable cell now has stronger blue fluorescence (Fig. 3 A-2).Then in the nutrient solution of above-mentioned cell, isopyknic Hg is added
2+(10 μm of ol/L), hatches 30min at 37 DEG C, finds the fluorescence almost completely dissolve (Fig. 3 B-2) of cell.Therefore, PS-BOS can realize Hg in HeLa viable cell
2+imaging.When this is poisoning to research mercury ion, distribution in vivo has potential using value.
Micro-Hg is can be used for by aforementioned this material known
2+fluorometric analysis detects and process Hg
2+the waste water polluted, its detectability is 0.06 μm of ol/L, and this material can be reused, and meanwhile, this material also can be applicable to Hg in cell
2+distribution research.
Embodiment 1
A kind of polystyrene Hg of functionalization
2+the preparation method of fluorescence identifying material, specifically implements according to following steps:
Step 1, preparation 5-amino-2-(4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) are amino) amino benzo [d] oxazole (BOS, VII) of phenyl-5-;
A. the preparation of two-(2-ethylthio-ethyl) amine (III)
5.25g (0.05mol) two-ethanolamine compound 1 is joined in 30mL chloroform, at 0 DEG C, slowly add 23.8g thionyl chloride, after room temperature reaction 2.0h, be warming up to back flow reaction 3h, cooling, adds ethanol and removes excessive thionyl chloride in reaction solution.Solvent is removed in underpressure distillation, then adds a small amount of chloroform and ether, and adularescent solid produces, suction filtration, and for several times, vacuum-drying, obtains 8.4g white solid to solid washed with ether, i.e. two-(2-chloro ethyl) amine hydrochlorates, and yield is 95.2%.
Under nitrogen protection, 1.18g sodium is dissolved in 50mL ethanol, in above-mentioned solution, adds 1.88g sulfur alcohol, be warming up to 70 DEG C, compound 2 is dissolved in 25mL ethanol, is slowly added drop-wise in reaction solution, continue reaction 2h.After slightly cold, removed under reduced pressure solvent, adds water, with chloroform extraction 5 times, merges organic phase, uses anhydrous sodium sulfate drying.Then underpressure distillation obtains colourless liquid 1.55g, b.p.147-150/15torr., i.e. compound (III), and two (2-ethylthio-ethyl) amine, yield is 80.0%.
1H NMR(300MHz,CDCl
3)，δ(ppm):2.81(t，4H，NCH
2)，2.68(t，4H，SCH
2)，2.53(q，4H，SCH
2CH
3)，1.68(s，1H，NH)，1.26(t，6H，CH
3)。
B.2-(4 '-hydroxyl-3 ' preparation of-amino benzo [d] oxazole (V) of (two-(2 "-ethylthio-ethyl) are amino) phenyl-5-
1., 5-nitro-2-(4 '-hydroxy phenyl) benzo [preparation of d] oxazole
1.85g (12mmol) 4-nitro-Ortho-Aminophenol (i.e. R is added in the there-necked flask that induction stirring, reflux condensing tube, thermometer and dropping funnel are housed
1, R
2=H), the ammonium meta-vanadate of 0.234g (2mmol) and 25mL ethanol, control temperature slowly drips the 10mL ethanolic soln of the 4-hydroxy benzaldehyde of 1.22g (10mmol) at about 10 DEG C, 60 DEG C of reactions are warming up to after dripping, react rear concentrating under reduced pressure, cooling, add appropriate water fully to stir, suction filtration, water washing, target compound (V) is obtained by re-crystallizing in ethyl acetate after vacuum-drying, 5-nitro-2-(4 '-hydroxy phenyl) benzo [d] oxazole, yield 62.3%.
Compound 5
1h NMR (CDCl
3, 300MHz) and δ (ppm): 5.16 (s, 2H), 6.73 ~ 6.76 (d, 2H), 7.58 ~ 7.63 (m, 1H), 7.96 ~ 8.03 (m, 2H), 8.23 ~ 8.36 (m, 2H); IR (KBr) ν (cm
-1): 3386,3037,2983,1625,1583,1467,1278,1221,822,753.Ms (EI, m/z): 256 (M+1,52%).
2., 5-nitro-2-(4 '-hydroxyl-3 ' the preparation of-amino benzo of (two-(2 "-ethylthio-ethyl) are amino) phenyl-5-also [d] oxazole
1.28g (5mmol) 5-nitro-2-(4 '-hydroxy phenyl) benzo [d] oxazole, 0.97g (5mmol) two-(2-ethylthio-ethyl) amine, the poly polyoxymethylene of 0.18g (6mmol) and the ethanol of 30mL is added successively in the round-bottomed flask that induction stirring is housed, load onto reflux condensing tube, after raw material all dissolves, slowly be heated to backflow, reaction is followed the tracks of with TLC, after question response is complete, removed under reduced pressure solvent, then 100mL water is added, after abundant stirring, use CHCl
3(3 × 100mL) extracts, by organic over anhydrous MgSO
4dry, after precipitation, residue silica gel column chromatography is separated to obtain light yellow solid Compound 6, namely 5-nitro-2-(4 '-hydroxyl-3 '-amino the benzo of (two-(2 "-ethylthio-ethyl) are amino) phenyl-5-also [d] oxazole; 1.06g, yield is 46%.
1H NMR(CDCl
3，300MHz)δ(ppm)：1.17(t，6H)，2.42(q，4H)，2.58(t，4H)，2.71(t，4H)，5.08(s，2H)，6.67～6.70(d，1H)，7.56～7.60(m，1H)，7.69～7.73(m，1H)，7.82～7.87(m，1H)，8.21～8.32(m，2H)；Ms(EI，m/z)：461(M
+，26％)。
3., 5-amino-2-(4 '-hydroxyl-3 ' preparation of-amino benzo [d] oxazole of (two-(2 "-ethylthio-ethyl) are amino) phenyl-5-
Above-mentioned obtained compound 6 (13.8g is added in autoclave, 0.03mol), Raney-Ni 1.0g, methyl alcohol 200g, with the air in the abundant replacement reaction kettle of nitrogen, then 40 DEG C are slowly warming up to, start to pass into hydrogen, be warming up to 78-80 DEG C again, pressure is 2.0-2.5Mpa, react 7-9h with this understanding, after reacting completely, use nitrogen replacement hydrogen, heat filtering, the methanol wash of filter residue heat, merging filtrate, put into refrigerator after being cooled to room temperature and continue cooling precipitation solid, filter, cold methanol washs, vacuum-drying obtains white solid 10.6g, yield 82%.
1H NMR(CDCl
3，300MHz)δ(ppm):1.16(t，6H)，2.40(q，4H)，2.57(t，4H)，2.69(t，4H)，4.98(s,2H)，6.61～6.63(d，2H)，6.49～6.51(m，1H)，6.74～6.75(m，1H)，7.18～7.20(m，1H)，7.73～7.75(m，2H).Ms(EI，m/z):431(M
+，18％)。
The preparation of step 2, aldehyde radical polystyrene microsphere
1., the chloromethylation of polystyrene
Concrete steps are: in the four-hole boiling flask that electric stirring and thermometer are housed, and add 3g polystyrene and 30mL methylene dichloride, fully swelling through 16h, then add the catalyst S nCl of 13mL Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB) and 1.5mL
4, in room temperature reaction 10h.After reaction terminates, with 1mol/L dilute hydrochloric acid process product mixtures, suction filtration, with Isosorbide-5-Nitrae-dioxane washing, be then washed with distilled water to filtrate and exist without chlorion, namely vacuum-drying obtain chloromethylated polystyrene (CMPS).Fo Erhadefa is adopted to measure the chlorinity of chlorine ball.Result shows, and the chlorine ball chlorinity of preparation is 13.6 (wt) %.KBr compressing tablet is adopted to measure infrared spectra.IR ν (cm
-1): 3102,3027,2923,1601,1583,1493,1421 (CH
2ν C-Cl in Cl), 1026,906,767,697,670 (CH
2δ C-H in Cl), 540.
2., the preparation of aldehyde radical polystyrene microsphere;
In the four-hole boiling flask that electric stirring is housed, add the above-mentioned obtained chlorine ball of 1g and 20mL DMSO, after making the swelling 24h of chlorine ball, add 2g NaHCO
3with 2.5g KI, after logical nitrogen removes the air in bottle, be warming up to 110 DEG C and react 6h in nitrogen atmosphere, cooling, suction filtration.With distilled water repetitive scrubbing product, vacuum-drying, to constant weight, obtains aldehyde radical polystyrene microsphere (AL-PS).KBr compressing tablet is adopted to measure infrared spectra.IR(KBr)ν(cm
-1)：3105，3028，2924，1673(CHO)，1602，1585，1495，1030，768，670。
The polystyrene Hg of step 3, functionalization
2+the preparation of fluorescence identifying material;
In the four-hole boiling flask that electric stirring, reflux condensing tube and thermometer are housed, add 50mL N, N-N,N-DIMETHYLACETAMIDE (DMAC) and 3g aldehyde radical polystyrene microsphere (AL-PS), after PS is fully dissolved, add 1.92g BOS wherein.React 3 hours within the scope of 75-85 DEG C.Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material, PS-BOS.IR(KBr，cm-1)ν：3356(-OH)，3029，2908，1639(C＝N)，1605，1579，1489，1028，907(＝C-H)，833，762。
Embodiment 2
Step 1, prepare amino-2-(4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) are amino) phenyl-benzo [d] oxazole (BOS, VII), specifically implement according to following step:
The preparation of step 1.1, two-(2-ethylthio-ethyl) amine (III), be specially: diethanolamine (chemical compounds I) is joined in chloroform, thionyl chloride is slowly added at-5 DEG C-5 DEG C, wherein, diethanolamine is 1:500 with the molecular volume ratio (mol/ml) of chloroform; The mol ratio of diethanolamine and thionyl chloride is 1:3; After room temperature reaction 2.5h, be warming up to back flow reaction 3.5h, cooling, adds ethanol and removes excessive thionyl chloride in reaction solution.Solvent is removed in underpressure distillation, then chloroform and ether is added, diethanolamine and chloroform are 1:40:120 with the molecular volume ratio (mol/mL/mL) of ether, adularescent solid produces, suction filtration, solid washed with ether several, vacuum-drying, obtain white solid, i.e. two-(2-chloro ethyl) amine hydrochlorates (II);
Under nitrogen protection, sodium is dissolved in ethanol, in above-mentioned solution, adds sulfur alcohol, be warming up to 65 DEG C, compound (II) is dissolved in ethanol, wherein, sodium: the mass volume ratio (g/mL) of ethanol is 1.3:50; Compound (II) is 1:1500 with the molecular volume ratio (mol/mL) of ethanol; Compound (II) and the mixture of ethanol are joined in the reaction solution containing sodium, two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sodium is 1:4; Two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sulfur alcohol is 1:2.4; Continue reaction 2.5h; After slightly cold, removed under reduced pressure solvent, add water, with chloroform extraction 5 times, merge organic phase, with anhydrous sodium sulfate drying, then underpressure distillation obtains colourless liquid, i.e. two (2-ethylthio-ethyl) amine (III), wherein, anhydrous sodium sulphate: the mass volume ratio (g/mL) of chloroform is 1:25;
Step 1.2,2-(4 '-hydroxy phenyl) benzo [preparation (V) of d] oxazole containing nitro; Adding in the there-necked flask that induction stirring, reflux condensing tube, thermometer and dropping funnel are housed containing the Ortho-Aminophenol of nitro, ammonium meta-vanadate and ethanol, wherein, is 5:1 containing the Ortho-Aminophenol of nitro and the mol ratio of ammonium meta-vanadate; Compare for 6:13 containing the Ortho-Aminophenol of nitro and the molecular volume of ethanol; Control temperature slowly drips 4-hydroxy benzaldehyde and ethanolic soln at 5 DEG C, wherein, is 1:1 containing the Ortho-Aminophenol of nitro and the mol ratio of 4-hydroxy benzaldehyde; The molecular volume of 4-hydroxy benzaldehyde and ethanolic soln is than being 1:1; 55 DEG C of reactions are warming up to after dripping, react rear concentrating under reduced pressure, cooling, add appropriate water fully to stir, suction filtration, water washing, obtains target compound by re-crystallizing in ethyl acetate after vacuum-drying, is 2-(4 '-hydroxy phenyl) benzo [the d] oxazole (V) containing nitro.
Step 1.3, preparation (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI); Add successively in the round-bottomed flask that induction stirring is housed above-mentioned obtained compound V, two-(2-ethylthio-ethyl) amine (III), poly polyoxymethylene and ethanol, wherein, compound V, two-(2-ethylthio-ethyl) amine (III) is 5:5:6 with the mol ratio of poly polyoxymethylene; Compound V is 1:5 with the molecular volume ratio of ethanol; Load onto reflux condensing tube, after raw material all dissolves, be slowly heated to backflow, follow the tracks of reaction 24h with TLC, after question response is complete, removed under reduced pressure solvent, then adds 100mL water, after fully stirring, uses CHCl
3(3 × 100mL) extracts, by organic over anhydrous MgSO
4drying, wherein, CHCl
3: MgSO
4volume mass ratio (mL/g) be 20:1; After precipitation, residue silica gel column chromatography is separated to obtain light yellow solid Compound (VI), i.e. the amidized phenyl benzo of ethylthio-ethyl [d] oxazole derivative (VI);
Step 1.4, to prepare amidized (ethylthio-ethyl) amino) phenyl benzo [d] oxazole derivative (VII); Above-mentioned obtained compound (VI) is added, Raney-Ni, methyl alcohol in autoclave, wherein, compound (VI): Raney-Ni: the mass volume ratio (g/g/mL) of methyl alcohol is 15:1.0:300; With the air in the abundant replacement reaction kettle of nitrogen, be then slowly warming up to 45 DEG C, start to pass into hydrogen, be warming up to 75 DEG C again, pressure is 2.5Mpa, reacts 7h with this understanding, after reacting completely, use nitrogen replacement hydrogen, heat filtering, the methanol wash of filter residue heat, merging filtrate, puts into refrigerator and continues cooling precipitation solid after being cooled to room temperature, filter, cold methanol washs, and vacuum-drying obtains white solid, is compound (VII).
The preparation of step 2, aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ), specifically implement according to following steps:
Step 2.1, to prepare chloromethylated polystyrene (CM-PS) (VIII); Concrete steps are: in the four-hole boiling flask that electric stirring and thermometer are housed, and add polystyrene and methylene dichloride that mass volume ratio (g/mL) is 1:15; Fully swelling through 15h, then add the catalyst S nCl of 13mL Isosorbide-5-Nitrae-dichloro methyl butyl ether and 1.5mL
4, wherein, Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB): the volume mass of polystyrene is than being 1g:4mL; Isosorbide-5-Nitrae-dichloro methyl butyl ether: SnCl
4volume ratio be 10:1; In room temperature reaction 8h.After reaction terminates, with 0.8mol/L dilute hydrochloric acid process product mixtures, suction filtration, with Isosorbide-5-Nitrae-dioxane washing, be then washed with distilled water to filtrate and exist without chlorion, namely vacuum-drying obtain chlorine ball, chloromethylated polystyrene (CM-PS) (VIII);
Preparation (AL-PS) (Ⅸ) of step 2.2, aldehyde radical polystyrene microsphere; Concrete steps are: in the four-hole boiling flask that electric stirring is housed, add above-mentioned obtained chloromethylated polystyrene (VIII) and DMSO, after making the swelling 20-26h of chlorine ball, add NaHCO
3and KI, wherein, the mass volume ratio (g/mL) of chloromethylated polystyrene (VIII): DMSO is 1:25; Chloromethylated polystyrene (VIII): NaHCO
3mass ratio be 1:1.5; The mass ratio of chloromethylated polystyrene (VIII): KI is 1:3.0; After logical nitrogen removes the air in bottle, be warming up to 105 DEG C and react 7h in nitrogen atmosphere, cooling, suction filtration, with distilled water repetitive scrubbing product, vacuum-drying, to constant weight, obtains aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ).
The polystyrene Hg of step 3, functionalization
2+the preparation of fluorescence identifying material (X); Specifically implement according to following steps: in the four-hole boiling flask that electric stirring, reflux condensing tube and thermometer are housed, add N, N-N,N-DIMETHYLACETAMIDE (DMAC) and aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ), wherein, N,N-dimethylacetamide: the volume mass of aldehyde radical polystyrene microsphere (Ⅸ) is than being 15mL:3g; After aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ) is fully dissolved, add BOS wherein, wherein, the mass ratio of aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ): BOS is 3:1.5.2-4 hour is reacted within the scope of 75 DEG C.Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material, PS-BOS (X).
Embodiment 3
Step 1, prepare amino-2-(4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) are amino) phenyl-benzo [d] oxazole (BOS, VII), specifically implement according to following step:
The preparation of step 1.1, two-(2-ethylthio-ethyl) amine (III), be specially: diethanolamine (chemical compounds I) is joined in chloroform, thionyl chloride is slowly added at-5 DEG C-5 DEG C, wherein, diethanolamine is 1:700 with the molecular volume ratio (mol/ml) of chloroform; The mol ratio of diethanolamine and thionyl chloride is 1:5; After room temperature reaction 1.5h, be warming up to back flow reaction 2.5h, cooling, adds ethanol and removes excessive thionyl chloride in reaction solution.Solvent is removed in underpressure distillation, then chloroform and ether is added, diethanolamine and chloroform are 1:100:300 with the molecular volume ratio (mol/mL/mL) of ether, adularescent solid produces, suction filtration, solid washed with ether several, vacuum-drying, obtain white solid, i.e. two-(2-chloro ethyl) amine hydrochlorates (II);
Under nitrogen protection, sodium is dissolved in ethanol, in above-mentioned solution, adds sulfur alcohol, be warming up to 75 DEG C, compound (II) is dissolved in ethanol, wherein, sodium: the mass volume ratio (g/mL) of ethanol is 1.1:50; Compound (II) is 1:1800 with the molecular volume ratio (mol/mL) of ethanol; Compound (II) and the mixture of ethanol are joined in the reaction solution containing sodium, two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sodium is 1:4; Two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sulfur alcohol is 1:3; Continue reaction 1.5h; After slightly cold, removed under reduced pressure solvent, add water, with chloroform extraction 5 times, merge organic phase, with anhydrous sodium sulfate drying, then underpressure distillation obtains colourless liquid, i.e. two (2-ethylthio-ethyl) amine (III), wherein, anhydrous sodium sulphate: the mass volume ratio (g/mL) of chloroform is 1:20;
Step 1.2,2-(4 '-hydroxy phenyl) benzo [preparation (V) of d] oxazole containing nitro; Adding in the there-necked flask that induction stirring, reflux condensing tube, thermometer and dropping funnel are housed containing the Ortho-Aminophenol of nitro, ammonium meta-vanadate and ethanol, wherein, is 7:1 containing the Ortho-Aminophenol of nitro and the mol ratio of ammonium meta-vanadate; Containing the Ortho-Aminophenol of nitro and the molecular volume ratio of ethanol be: 6:12; Control temperature slowly drips 4-hydroxy benzaldehyde and ethanolic soln at 15 DEG C, wherein, is 3:2 containing the Ortho-Aminophenol of nitro and the mol ratio of 4-hydroxy benzaldehyde; The molecular volume of 4-hydroxy benzaldehyde and ethanolic soln is than being 1:1; 65 DEG C of reactions are warming up to after dripping, react rear concentrating under reduced pressure, cooling, add appropriate water fully to stir, suction filtration, water washing, obtains target compound by re-crystallizing in ethyl acetate after vacuum-drying, is 2-(4 '-hydroxy phenyl) benzo [the d] oxazole (V) containing nitro.
Step 1.3, preparation (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI); Add successively in the round-bottomed flask that induction stirring is housed above-mentioned obtained compound V, two-(2-ethylthio-ethyl) amine (III), poly polyoxymethylene and ethanol, wherein, compound V, two-(2-ethylthio-ethyl) amine (III) is 5:5:6 with the mol ratio of poly polyoxymethylene; Compound V is 1:7 with the molecular volume ratio of ethanol; Load onto reflux condensing tube, after raw material all dissolves, be slowly heated to backflow, follow the tracks of reaction 28h with TLC, after question response is complete, removed under reduced pressure solvent, then adds 100mL water, after fully stirring, uses CHCl
3(3 × 100mL) extracts, by organic over anhydrous MgSO
4drying, wherein, CHCl
3: MgSO
4volume mass ratio (mL/g) be 20:1; After precipitation, residue silica gel column chromatography light yellow solid Compound (VI) discretely, the i.e. amidized phenyl benzo of ethylthio-ethyl [d] oxazole derivative (VI);
Step 1.4, to prepare amidized (ethylthio-ethyl) amino) phenyl benzo [d] oxazole derivative (VII); Above-mentioned obtained compound (VI) is added, Raney-Ni, methyl alcohol in autoclave, wherein, compound (VI): Raney-Ni: the mass volume ratio (g/g/ml) of methyl alcohol is 12:1.0:200; With the air in the abundant replacement reaction kettle of nitrogen, be then slowly warming up to 35 DEG C-45 DEG C, start to pass into hydrogen, be warming up to 85 DEG C again, pressure is 2.0Mpa-2.5Mpa, reacts 7h-9h with this understanding, after reacting completely, use nitrogen replacement hydrogen, heat filtering, the methanol wash of filter residue heat, merging filtrate, puts into refrigerator and continues cooling precipitation solid after being cooled to room temperature, filter, cold methanol washs, and vacuum-drying obtains white solid, is compound (VII).
The preparation of step 2, aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ), specifically implement according to following steps:
Step 2.1, to prepare chloromethylated polystyrene (CM-PS) (VIII); Concrete steps are: in the four-hole boiling flask that electric stirring and thermometer are housed, and add polystyrene and methylene dichloride that mass volume ratio (g/ml) is 1:10; Fully swelling through 15h, then add the catalyst S nCl of 13mL Isosorbide-5-Nitrae-dichloro methyl butyl ether and 1.5mL
4, wherein, Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB): the volume mass of polystyrene is than being 1g:5mL; Isosorbide-5-Nitrae-dichloro methyl butyl ether: SnCl
4volume ratio be 8:1; In room temperature reaction 12h.After reaction terminates, with 1.2mol/L dilute hydrochloric acid process product mixtures, suction filtration, with Isosorbide-5-Nitrae-dioxane washing, be then washed with distilled water to filtrate and exist without chlorion, namely vacuum-drying obtain chlorine ball, chloromethylated polystyrene (CM-PS) (VIII);
Preparation (AL-PS) (Ⅸ) of step 2.2, aldehyde radical polystyrene microsphere; Concrete steps are: in the four-hole boiling flask that electric stirring is housed, add above-mentioned obtained chloromethylated polystyrene (VIII) and DMSO, after making the swelling 20-26h of chlorine ball, add NaHCO
3and KI, wherein, the mass volume ratio (g/ml) of chloromethylated polystyrene (VIII): DMSO is 1:15; Chloromethylated polystyrene (VIII): NaHCO
3mass ratio be 1:3; The mass ratio of chloromethylated polystyrene (VIII): KI is 1:1.5; After logical nitrogen removes the air in bottle, be warming up to 115 DEG C and react 5h in nitrogen atmosphere, cooling, suction filtration, with distilled water repetitive scrubbing product, vacuum-drying, to constant weight, obtains aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ).
The polystyrene Hg of step 3, functionalization
2+the preparation of fluorescence identifying material (X); Specifically implement according to following steps: in the four-hole boiling flask that electric stirring, reflux condensing tube and thermometer are housed, add N, N-N,N-DIMETHYLACETAMIDE (DMAC) and aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ), wherein, N,N-dimethylacetamide: the volume mass of aldehyde radical polystyrene microsphere (Ⅸ) is than being 25mL:3g; After aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ) is fully dissolved, add BOS wherein, wherein, the mass ratio of aldehyde radical polystyrene microsphere (AL-PS) (Ⅸ): BOS is 3:2.5.2-4 hour is reacted within the scope of 75-85 DEG C.Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material, PS-BOS (X).
Claims (10)
1. the polystyrene Hg of a functionalization
2+fluorescence identifying material, is characterized in that, its structural formula is X:
2. the polystyrene Hg of a functionalization
2+the preparation method of fluorescence identifying material, is characterized in that, specifically implements according to following steps:
Step 1, prepare amino-2-(4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) are amino) phenyl-benzo [d] oxazole (BOS, VII), its concrete synthetic route as shown in the formula shown in 1-formula 4,
Step 2, prepare aldehyde radical polystyrene microsphere (Ⅸ), its reaction process such as formula shown in 5-formula 6,
Step 3, the polystyrene Hg of functionalization prepared by (Ⅸ) that prepare in the compound prepared in step 1 (VII) and step 2
2+fluorescence identifying material, its reaction process as shown in Equation 7,
3. the polystyrene Hg of functionalization according to claim 1
2+the preparation method of fluorescence identifying material, it is characterized in that, preparation amino-2-in described step 1 (4 '-hydroxyl-3 '-(two-(2 "-ethylthio-ethyl) amino) phenyl-benzo [d] oxazole (VII), specifically implement according to following steps:
Step 1.1, preparation two (2-ethylthio-ethyl) amine (III); With diethanolamine (I) for starting raw material, prepare two-(2-chloro ethyl) amine hydrochlorates (II) in organic solvent; And under the protection of nitrogen, add sulfur alcohol and prepare two (2-ethylthio-ethyl) amine (III);
Step 1.2, preparation contain 2-(4 '-hydroxy phenyl) benzo [preparation of d] oxazole (V) of nitro;
Step 1.3, by two (2-ethylthio-ethyl) amine (III) with [d] oxazole (V) is obtained by reacting (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI) by Mannich containing 2-(4 '-hydroxy phenyl) benzo of nitro;
Step 1.4, the compound obtained in step 3 (VI) being carried out to chloromethylation, to obtain amidized (ethylthio-ethyl) amino) phenyl benzo [d] oxazole derivative (VII).
4. the polystyrene Hg of functionalization according to claim 3
2+the preparation method of fluorescence identifying material, is characterized in that, in described step 1.1, the preparation of two-(2-ethylthio-ethyl) amine (III) is specially:
Join in chloroform by diethanolamine (I), at-5 DEG C-5 DEG C, slowly add thionyl chloride, wherein, diethanolamine is 1:500mol/ml-1:700mol/ml with the molecular volume ratio of chloroform; The mol ratio (mol/mol) of diethanolamine and thionyl chloride is 1:3-1:5; After room temperature reaction 1.5h-2.5h, be warming up to back flow reaction 2.5h-3.5h, cooling, adds ethanol and removes excessive thionyl chloride in reaction solution; Solvent is removed in underpressure distillation, then chloroform and ether is added, diethanolamine and chloroform are 1mol:40ml:120ml-1mol:100mL:300ml with the molecular volume ratio of ether, adularescent solid produces, suction filtration, solid washed with ether several, vacuum-drying, obtain white solid, i.e. two-(2-chloro ethyl) amine hydrochlorates (II);
Under nitrogen protection, sodium is dissolved in ethanol, in above-mentioned solution, adds sulfur alcohol, be warming up to 65 DEG C-75 DEG C, compound (II) is dissolved in ethanol, wherein, sodium: the mass volume ratio of ethanol is 1.1:50g/ml-1.3:50g/ml; Compound (II) is 1:1500mol/mL-1:1800mol/ml with the molecular volume ratio of ethanol; Join in the reaction solution containing sodium by compound (II) and the mixture of ethanol, the mol ratio of two-(2-chloroethyl) amine hydrochlorate and sodium is 1:3-1:4; Two-(2-chloroethyl) amine hydrochlorates: the mol ratio of sulfur alcohol is 1:2.4-1:3; Continue reaction 1.5h-2.5h; After slightly cold, removed under reduced pressure solvent, add water, with chloroform extraction 5 times, merge organic phase, with anhydrous sodium sulfate drying, then underpressure distillation obtains colourless liquid, i.e. two (2-ethylthio-ethyl) amine (III), wherein, anhydrous sodium sulphate: the mass volume ratio of chloroform is 1:20g/ml-1:25g/ml.
5. the polystyrene Hg of functionalization according to claim 4
2+the preparation method of fluorescence identifying material, it is characterized in that, in described step 1.2, containing 2-(4 '-hydroxy phenyl) benzo of nitro, [preparation of d] oxazole (V) is specially: add containing the Ortho-Aminophenol of nitro, ammonium meta-vanadate and ethanol in the there-necked flask that induction stirring, reflux condensing tube, thermometer and dropping funnel are housed, wherein, be 5:1-7:1 containing the Ortho-Aminophenol of nitro and the mol ratio of ammonium meta-vanadate; Containing the Ortho-Aminophenol of nitro and the molecular volume ratio (mol/L) of ethanol be: 6:12-6:13; Control temperature slowly drips 4-hydroxy benzaldehyde and ethanolic soln at 5 DEG C-15 DEG C, wherein, is 3:2-1:1 containing the Ortho-Aminophenol of nitro and the mol ratio of 4-hydroxy benzaldehyde; The molecular volume ratio of 4-hydroxy benzaldehyde and ethanolic soln is: 1:1; 55 DEG C-65 DEG C reactions are warming up to after dripping, react rear concentrating under reduced pressure, cooling, add appropriate water fully to stir, suction filtration, water washing, obtains target compound by re-crystallizing in ethyl acetate after vacuum-drying, is 2-(4 '-hydroxy phenyl) benzo [the d] oxazole (V) containing nitro.
6. the polystyrene Hg of functionalization according to claim 5
2+the preparation method of fluorescence identifying material, it is characterized in that, prepare in described step 1.3 (ethylthio-ethyl) amidized phenyl benzo [d] oxazole derivative (VI) is specially: add successively in the round-bottomed flask that induction stirring is housed above-mentioned obtained compound V, two-(2-ethylthio-ethyl) amine (III), poly polyoxymethylene and ethanol, wherein, compound (V), two-(2-ethylthio-ethyl) amine (III) are 5:5:6 with the mol ratio of poly polyoxymethylene; Compound (V) is 1:5-1:7 with the molecular volume ratio (mol/L) of ethanol; Load onto reflux condensing tube, after raw material all dissolves, be slowly heated to backflow, follow the tracks of reaction 24h-28h with TLC, after question response is complete, removed under reduced pressure solvent, then adds 100ml water, after fully stirring, uses CHCl
3extract, each 100ml, extracts three times; By organic over anhydrous MgSO
4drying, wherein, CHCl
3: MgSO
4volume mass than for 20:1ml/g; After precipitation, residue silica gel column chromatography is separated to obtain light yellow solid Compound (VI), i.e. the amidized phenyl benzo of ethylthio-ethyl [d] oxazole derivative (VI).
7. the polystyrene Hg of functionalization according to claim 6
2+the preparation method of fluorescence identifying material, it is characterized in that, amidized (ethylthio-ethyl) is prepared amino in described step 1.4) [d] oxazole derivative (VII) is specially phenyl benzo: in autoclave, add above-mentioned obtained compound (VI), Raney-Ni, methyl alcohol, wherein, compound (VI): Raney-Ni: the mass volume ratio of methyl alcohol is 12g:1.0g:200ml-15g:1.0g:300ml; With the air in the abundant replacement reaction kettle of nitrogen, then 35 DEG C-45 DEG C are slowly warming up to, start to pass into hydrogen, be warming up to 75 DEG C-85 DEG C again, pressure is 2.0Mpa-2.5Mpa, react 7h-9h with this understanding, after reacting completely, use nitrogen replacement hydrogen, heat filtering, the methanol wash of filter residue heat, merging filtrate, puts into refrigerator and continues cooling precipitation solid after being cooled to room temperature, filter, cold methanol washs, and vacuum-drying obtains white solid, is amidized (ethylthio-ethyl) amino) phenyl benzo [d] oxazole derivative (VII).
8. the polystyrene Hg of functionalization according to claim 7
2+the preparation method of fluorescence identifying material, is characterized in that, prepares aldehyde radical polystyrene microsphere (Ⅸ) and specifically implement according to following steps in described step 2:
Step 2.1, p-poly-phenyl ethene carry out chloromethylation, prepare chloromethylated polystyrene (VIII), be specially: in the four-hole boiling flask that electric stirring and thermometer are housed, add polystyrene and methylene dichloride that mass volume ratio (g/ml) is 1:10-1:15; Fully swelling through 15h-18h, then add the catalyst S nCl4 of 13ml Isosorbide-5-Nitrae-dichloro methyl butyl ether and 1.5ml, wherein, Isosorbide-5-Nitrae-dichloro methyl butyl ether: the volume mass of polystyrene is than being 1g:4ml-1g:5ml; Isosorbide-5-Nitrae-dichloro methyl butyl ether: SnCl
4volume ratio be 8:1-10:1; In room temperature reaction 8h-12h; After reaction terminates, with 0.8-1.2mol/L dilute hydrochloric acid process product mixtures, suction filtration, with Isosorbide-5-Nitrae-dioxane washing, be then washed with distilled water to filtrate and exist without chlorion, namely vacuum-drying obtain chlorine ball, chloromethylated polystyrene (VIII);
Step 2.2, aldehyde radical is carried out to chloromethylated polystyrene, prepare aldehyde radical polystyrene microsphere (Ⅸ), be specially: in the four-hole boiling flask that electric stirring is housed, add above-mentioned obtained chloromethylated polystyrene (VIII) and DMSO, after making the swelling 20-26h of chlorine ball, add NaHCO
3and KI, wherein, the mass volume ratio of chloromethylated polystyrene (VIII): DMSO is 1g:15mL-1g:25mL; Chloromethylated polystyrene (VIII): NaHCO
3mass ratio be 1:1.5-1:3; The mass ratio of chloromethylated polystyrene (VIII): KI is 1g:1.5g-1g:3.0g; After logical nitrogen removes the air in bottle, be warming up to 105 DEG C-115 DEG C and react 5h-7h in nitrogen atmosphere, cooling, suction filtration, with distilled water repetitive scrubbing product, vacuum-drying, to constant weight, obtains aldehyde radical polystyrene microsphere (Ⅸ).
9. the polystyrene Hg of functionalization according to claim 8
2+the preparation method of fluorescence identifying material, is characterized in that, the polystyrene Hg of functionalization in described step 3
2+the preparation of fluorescence identifying material is specially and N,N-dimethylacetamide is mixed with compound (Ⅸ), then adds compound (VII), reacts 3 hours within the scope of 75-85 DEG C; Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material (Ⅹ).
10. the polystyrene Hg of functionalization according to claim 9
2+the preparation method of fluorescence identifying material, is characterized in that, the polystyrene Hg of functionalization in described step 3
2+the preparation of fluorescence identifying material (X) is specially: in the four-hole boiling flask that electric stirring, reflux condensing tube and thermometer are housed, add N, N-N,N-DIMETHYLACETAMIDE and aldehyde radical polystyrene microsphere (Ⅸ), wherein, N,N-dimethylacetamide: the volume mass of aldehyde radical polystyrene microsphere (Ⅸ) is than being 15ml:3g – 25ml:3g; After aldehyde radical polystyrene microsphere (Ⅸ) is fully dissolved, add BOS wherein, wherein, the mass ratio of aldehyde radical polystyrene microsphere (Ⅸ): BOS is 3:1.5 – 3:2.5; 2-4 hour is reacted within the scope of 75-85 DEG C; Then cool, be that product settles out by precipitation agent with ethanol, again with the alternately washing of ethanol and distilled water, vacuum-drying, to constant weight, obtains 3 '-the polystyrene Hg of (two-(2 "-ethylthio-ethyl) are amino) Ben base benzoxazole derivative functionalization
2+fluorescence identifying material (X).
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