CN103242827B - Florescent ion probe reagent for zinc ion detection and preparation method thereof - Google Patents
Florescent ion probe reagent for zinc ion detection and preparation method thereof Download PDFInfo
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- CN103242827B CN103242827B CN201310210999.8A CN201310210999A CN103242827B CN 103242827 B CN103242827 B CN 103242827B CN 201310210999 A CN201310210999 A CN 201310210999A CN 103242827 B CN103242827 B CN 103242827B
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Abstract
The invention discloses a florescent ion probe reagent for zinc ion detection, which contains triazole phenanthroline bridge type bis(beta-cyclodextrin), adopts phenanthroline as a probe molecule and takes the nitrogen atom on the phenanthroline ring and the nitrogen atom on the triazole ring as bonding sites of bivalent zinc ions. A preparation method comprises the following steps of: firstly synthesizing a 2,9-dipropargyl-1,10-phenanthroline intermediate from 2,9-dihydroxymethyl-1,10-phenanthroline, 3-propargyl bromide and the like; and then synthesizing a target product from the intermediate, uni-6-deoxy-6-azido-beta-cyclodextrin, sodium ascorbate and the like. As a water-soluble zinc ion florescent probe, the synthesis path of the cyclodextrin derivative is simple, the production cost is low, and the florescent ion probe reagent is suitable for amplification synthesis and practical production application; the zinc ion identifying operation is simple and practical and has high sensitivity, and the zinc ion is displayed by a fluorescence spectrum; and as a zinc ion florescent probe, the florescent ion probe reagent disclosed by the invention can effectively detect zinc ions in cells and has broad application prospects.
Description
Technical field
The present invention relates to the fluorescent ion probe field of metal ion detection, particularly a kind of fluorescent ion probe reagent detecting for zine ion and preparation method thereof.
Background technology
Zine ion is important metal ion in human body, it in vivo content be only second to iron ion and come second, in becoming human body, the content of zinc is about 2-3g.Zinc plays very important effect in vivo, and many biological procedureses for example brain function, pathology, gene transfection, metalloenzyme adjusting, immunologic function and the transmission of nervus centralis signal etc. all be unable to do without the participation of zine ion.Therefore in detection, the especially active somatic cell of zine ion and tissue, the mensuration of zinc is the field that biochemist pays special attention in recent years.But due to zine ion 3d
104s
0electron structure, himself is without measurable spectrum and nuclear magnetic signal, conventional UV spectrum, circular dichroism spectrum, nucleus magnetic resonance, electron paramagnetic resonance and Mossbauer spectrometer are all unsuitable for the mensuration to zine ion, and only having fluorescence spectrum is to detect one of effective means of zine ion.
Fluorescent ion probe converts molecular/ionic combining information to easily detected fluorescent signal, and then can identify ion.The features such as method is simple owing to having for fluorescent ion probe, highly selective, high sensitivity and transient response, and fluorescent measurement right and wrong are invasive, not disruptive to sample, be therefore the method for zinc ion content in a kind of effective detection of biological body.Cyclodextrin is by α-1 by the D-Glucopyranose of different quantities, the large ring host compound that 4 glycosidic links join end to end and form, in former report, cyclodextrin is because its inner chamber feature hydrophobic and that outer wall is hydrophilic is widely used in fluorescent probe and molecular recognition field.Many probes that can detect zine ion are in the news, but are seldom water miscible and are not subject to the interference of cadmium ion.
Summary of the invention
The object of the invention is for above-mentioned existing problems, a kind of fluorescent ion probe reagent detecting for zine ion and preparation method thereof is provided, this probe reagent has special selectivity and highly sensitive to zine ion, and its preparation method is simple and practical, is suitable for amplifying synthetic and production application.
Technical scheme of the present invention:
A kind of fluorescent ion probe reagent detecting for zine ion, for containing the two beta-cyclodextrins of triazole phenanthroline bridge-type, it adopts phenanthroline as probe molecule, usings nitrogen-atoms on phenanthroline ring and the nitrogen-atoms in triazole ring as the binding site of divalent zinc ion, and its chemical formula is C
104h
154n
8o
70, structural formula is
。
A preparation method for the described fluorescent ion probe reagent detecting for zine ion, step is as follows:
1) 2,9-dipropargyl-1,10-phenanthroline intermediate synthetic
By 2, 9-dihydroxymethyl-1, 10-phenanthroline joins anhydrous N, in N '-dimethyl formamide, ice bath is cooled to 0 ℃, add sodium hydride, under ice bath, react 30min, add 3-propargyl bromide under ice bath, to react 3 hours, obtain reaction solution, then in reaction solution, add sodium hydride, at 18-25 ℃, react 12 hours, under 0.1Pa, distillation obtains solid a except after desolventizing, gained solid a is dissolved in trichloromethane, water extraction three times, by organic phase with after anhydrous magnesium sulfate drying, under 0.1Pa, distill and concentrate, then the mixed solution of methylene dichloride and ethyl acetate of take is developping agent, with 200-300 order silicagel column, carry out separation and can make 2, 9-dipropargyl-1, 10-phenanthroline intermediate,
2) synthesizing containing the two beta-cyclodextrins of triazole phenanthroline bridge-type
Under nitrogen atmosphere, by above-mentioned 2,9-dipropargyl-1,10-phenanthroline intermediate, list-6-deoxidation-6-nitrine-beta-cyclodextrin, cupric sulfate pentahydrate and sodium ascorbate add in the mixed solution of tetrahydrofuran (THF) and water, 50
?under C, react 48 hours, remove by filter insolubles, filtrate is obtained to solid b through distillation under 0.1Pa after removing solvent, gained solid b is soluble in water to all dissolving and obtain solution, then under agitation this solution is splashed in acetone, after filtering, collect solid same soluble in water to all dissolving, again under agitation this solution is splashed in acetone, use twice of acetone repeated washing, after filtering, collect solid, finally with n-propyl alcohol, water and mass percent concentration are that 25% ammonia water mixture is developping agent, with 200-300 order silicagel column, carry out separation and can make crude product, it is pressed to the preparative column purification for 0.3MPa through post, the aqueous ethanolic solution of take makes containing the two beta-cyclodextrin sterlings of triazole phenanthroline bridge-type after eluent drip washing, be the fluorescent ion probe reagent detecting for zine ion.
Described 2,9-dipropargyl-1,10-phenanthroline and anhydrous N, the amount ratio of N '-dimethyl formamide solution is 0.1 mol/L; Described 2,9-dihydroxymethyl-1, the mol ratio of 10-phenanthroline, 3-propargyl bromide and sodium hydride is 2:4:5.
The amount ratio of described solid a and trichloromethane is 0.02mol/L.
In described methylene dichloride and ethyl acetate mixed solution, the volumetric ratio of methylene dichloride and ethyl acetate is 5:3.
Described 2,9-dipropargyl-1, the mol ratio of 10-phenanthroline intermediate, list-6-deoxidation-6-nitrine-beta-cyclodextrin, cupric sulfate pentahydrate and sodium ascorbate is 1:5:10:25; In the mixed solution of tetrahydrofuran (THF) and water, tetrahydrofuran (THF) and water capacity are than being 2:7; The amount ratio of the mixed solution of list-6-deoxidation-6-nitrine-beta-cyclodextrin and tetrahydrofuran (THF) and water is 0.03 mol/L.
The aqueous solution of described solid b and the volumetric ratio of acetone are 1:30.
In described developping agent, n-propyl alcohol, water and mass percent concentration are that the volumetric ratio of 25% ammoniacal liquor is 6:3:2.
In described eluent, the volumetric ratio of second alcohol and water is 3:17.
Advantage of the present invention is: as water-soluble zinc ion fluorescent reagent, the present invention prepared containing the two beta-cyclodextrins of triazole phenanthroline bridge-type, synthetic route is simple, reaction conditions is gentle, aftertreatment is simple and convenient, is suitable for amplifying synthetic and production application; The identifying operation of the zine ion playing an important role for organism is simple and practical, have high sensitivity, not disruptive to sample, and recognition result shows and is easy to monitoring with fluorescence spectrum; As zinc ion fluorescent, can effectively detect the zine ion in viable cell, have broad application prospects.
[accompanying drawing explanation]
Fig. 1 is the synthetic route schematic diagram of this fluorescent ion probe reagent.
Fig. 2 is the fluorescence co-focusing experimental result of Hela cell.
[embodiment]
Embodiment:
A preparation method for the fluorescent ion probe reagent detecting for zine ion, step is as follows:
1) 2,9-dipropargyl-1,10-phenanthroline intermediate synthetic
By 481mg(2mmol) 2, 9-dihydroxymethyl-1, 10-phenanthroline adds the anhydrous N of 20mL, in N '-dimethyl formamide, ice bath is cooled to 0 ℃, add 100mg (4.2mmol) sodium hydride, under ice bath, react 30min, add 500ul (4mmol) 3-propargyl bromide under ice bath, to react 3 hours, obtain reaction solution, then in reaction solution, add 20mg (0.8mmol) sodium hydride, at 18-25 ℃, react 12 hours, under 0.1Pa, distillation obtains solid a except after desolventizing, gained solid a is dissolved in 100ml trichloromethane, with 50ml water extraction three times, by organic phase with after anhydrous magnesium sulfate drying, under 0.1Pa, distill and concentrate, then the methylene dichloride that the volumetric ratio of take is 5:3 and ethyl acetate mixed solution are developping agent, with the separation of 200-300 order silicagel column, can make 2, 9-dipropargyl-1, 10-phenanthroline intermediate,
2) synthesizing containing the two beta-cyclodextrins of triazole phenanthroline bridge-type
Under nitrogen atmosphere, by 90mg (0.285mmol) above-mentioned 2,9-dipropargyl-1, it is in the tetrahydrofuran (THF) of 2:7 and the mixed solution of water, 50 that 10-phenanthroline intermediate, 1.65g (1.42mmol) list-6-deoxidation-6-nitrine-beta-cyclodextrin, 710mg (2.84mmol) cupric sulfate pentahydrate and 1.4g (7.10mmol) sodium ascorbate add 45ml volumetric ratio
?under C, react 48 hours, remove by filter insolubles, filtrate is obtained to solid b through distillation under 0.1Pa after removing solvent, gained solid b is soluble in water to all dissolving, then under agitation this solution is splashed in 300ml acetone, after filtering, collect solid same soluble in water to all dissolving, again under agitation this solution is splashed in acetone, use twice of acetone repeated washing, after filtering, collect solid, finally with n-propyl alcohol, water and mass percent concentration are that the mixed solution that the volumetric ratio of 25% ammoniacal liquor is 6:3:2 is developping agent, with 200-300 order silicagel column, carry out separation and can make crude product, it is pressed to the preparative column purification for 0.3MPa through post, the aqueous ethanolic solution that the volumetric ratio of second alcohol and water of take is 3:17 makes containing the two beta-cyclodextrin sterlings of triazole phenanthroline bridge-type after eluent drip washing, be the fluorescent ion probe reagent detecting for zine ion.
Detection display the present invention relates to 2,9-dipropargyl-1, the nuclear-magnetism of 10-phenanthroline intermediate, high resolution mass spectrum characterize as follows:
1h NMR (400 MHz, CDCl
3, ppm): δ=2.51 (s, 2H, CH ≡ C-), 4.38 (d, 4H ,-CH
2-), 5.16 (s, 4H ,-CH
2-), 7.79 (s, 2H, H of phenanthroline), 7.89 (d, 2H, H of phenanthroline), 8.29 (d, 2H, H of phenanthroline).HR-MS (ESI), calculated value C
20h
16n
2o
2: 339.1109 [M+Na]
+, measured value: 339.1108.
Nuclear-magnetism, ultimate analysis and the mass spectral characteristi of the two beta-cyclodextrins of the phenanthroline bridge-type containing triazole prepared by detection display the present invention are as follows:
1h NMR (400 MHz, D
2o, ppm): δ=3.27-3.98 (m, 84H, H of C-3, C-5, C-6, C-2, C-4 of β-CD), 4.83 (d, 4H ,-CH
2-), 4.89 (s, 4H ,-CH
2-), 4.97-5.10 (m, 14H, H of C-1 of β-CD), 7.72-7.75 (m, 4H, H of phenanthroline and triazole), 8.10 (s, 2H, H of phenanthroline), 8.31 (d, 2H, H of phenanthroline).Ultimate analysis C
104h
154n
8o
7019H
2o: calculated value: C, 41.94; H, 6.50; N, 3.76.Measured value: C, 41.85; H, 6.40; N, 4.10.MALDI-TOF MS: 2636.88 [M+H]
+, 2658.87 [M+Na]
+。
Fig. 1 is the synthetic route schematic diagram of this fluorescent ion probe reagent.
Fig. 2 is the fluorescence co-focusing imaging results of Hela cell, and as shown in the figure, (a), (b), (c) three figure only add fluorescent ion probe reagent containing the two beta-cyclodextrins of triazole phenanthroline bridge-type, to hatch three hours white light figure, fluorogram and stacking diagrams afterwards.(d), (e), (f) after three figure are respectively and use in advance zinc perchlorate solution-treated 1h, then hatch 3h white light figure, fluorogram and stacking diagram afterwards with fluorescent ion probe reagent.In figure, show: with the Hela cell of zinc perchlorate solution hatching, presented bright blue-fluorescence in advance, and with the pretreated Hela cell of zinc perchlorate solution, do not shown very weak fluorescence, show can effectively detect intracellular zine ion containing the two beta-cyclodextrins of triazole phenanthroline bridge-type.
Concrete application of the present invention and effect are as follows:
It is in 7.2 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) buffered soln that this reagent is dissolved in to pH value, make the probe reagent solution of 0.015 mM, then the zinc perchlorate solution that adds 2 equivalents, the fluorescence of fluorescent probe solution has occurred significantly to raise, this is due to the nitrogen-atoms on phenanthroline ring and the collaborative coordination zine ion of the nitrogen-atoms in triazole ring, has suppressed radiationless n in molecule
π* transition, detection display: containing the two beta-cyclodextrins of phenanthroline bridge-type and the Zn of triazole
2+bonding ratio be 1:1, bonding constant is 8.96 * 10
5m, detects and is limited to 4.92 * 10
-7m.After adding 2 equivalent divalent zinc ions, obviously there is movement to low place in the nuclear-magnetism peak that belongs to phenanthroline and triazole ring on the two beta-cyclodextrins of phenanthroline bridge-type containing triazole, and this is due to Zn
2+coordination, reduced phenanthroline base and triazolyl cloud density around.
Hela cell (human hela cell) is layered on to (every empty 2ml, 2 * 10 in 6 orifice plates of the DMEM substratum that contains 10% foetal calf serum
4individual cell/ml), under 37 ℃ and 4% carbon dioxide conditions, cultivate 24h, to it, add respectively 50ul, the zinc perchlorate solution of 4mM, 100ul, the two beta-cyclodextrin solution of the phenanthroline bridge-type containing triazole of 1mM, cultivate respectively 1h and 3h, and then to adding 50ul in the Hela cell culture medium by zinc perchlorate solution-treated in advance, 2mM containing the two beta-cyclodextrin solution cultured continuously 3h of the phenanthroline bridge-type of triazole, under fluorescence inverted microscope, observe two beta-cyclodextrin fluorescent ion probes of phenanthroline bridge-type containing triazole to cell in Zn
2+recognition capability.Result shows, as shown in Figure 2, with the Hela cell of zinc perchlorate solution hatching, presented bright blue-fluorescence in advance, and with the pretreated Hela cell of zinc perchlorate solution, do not shown very weak fluorescence, show can effectively detect intracellular zine ion containing the two beta-cyclodextrins of triazole phenanthroline bridge-type.
Claims (1)
1. the preparation method of the fluorescent ion probe reagent detecting for zine ion, described fluorescent ion probe reagent is for containing the two beta-cyclodextrins of triazole phenanthroline bridge-type, it adopts phenanthroline as probe molecule, using nitrogen-atoms on phenanthroline ring and the nitrogen-atoms in triazole ring as the binding site of divalent zinc ion, and its chemical formula is C
104h
154n
8o
70, structural formula is
It is characterized in that preparation process is as follows:
1) 2,9-dipropargyl-1,10-phenanthroline intermediate synthetic
By 2, 9-dihydroxymethyl-1, 10-phenanthroline joins anhydrous N, in N '-dimethyl formamide, ice bath is cooled to 0 ° of C, add sodium hydride, under ice bath, react 30min, add 3-propargyl bromide under ice bath, to react 3 hours, obtain reaction solution, then in reaction solution, add sodium hydride, under 18-25 ° of C, react 12 hours, under 0.1Pa, distillation obtains solid a except after desolventizing, gained solid a is dissolved in trichloromethane, water extraction three times, by organic phase with after anhydrous magnesium sulfate drying, under 0.1Pa, distill and concentrate, then the mixed solution of methylene dichloride and ethyl acetate of take is developping agent, with 200-300 order silicagel column, carry out separation and can make 2, 9-dipropargyl-1, 10-phenanthroline intermediate,
2) synthesizing containing the two beta-cyclodextrins of triazole phenanthroline bridge-type
Under nitrogen atmosphere, by above-mentioned 2, 9-dipropargyl-1, 10-phenanthroline intermediate, list-6-deoxidation-6-nitrine-beta-cyclodextrin, cupric sulfate pentahydrate and sodium ascorbate add in the mixed solution of tetrahydrofuran (THF) and water, under 50 ° of C, react 48 hours, remove by filter insolubles, filtrate is obtained to solid b through distillation under 0.1Pa after removing solvent, gained solid b is soluble in water to all dissolving and obtain solution, then under agitation this solution is splashed in acetone, after filtering, collect solid same soluble in water to all dissolving, again under agitation this solution is splashed in acetone, use twice of acetone repeated washing, after filtering, collect solid, finally with n-propyl alcohol, water and mass percent concentration are that 25% ammonia water mixture is developping agent, with 200-300 order silicagel column, carry out separation and can make crude product, it is pressed to the preparative column purification for 0.3MPa through post, the aqueous ethanolic solution of take makes containing the two beta-cyclodextrin sterlings of triazole phenanthroline bridge-type after eluent drip washing,
Described 2,9-dipropargyl-1,10-phenanthroline and anhydrous N, the amount ratio of N '-dimethyl formamide solution is 0.1 mol/L; Described 2,9-dihydroxymethyl-1, the mol ratio of 10-phenanthroline, 3-propargyl bromide and sodium hydride is 2:4:5;
The amount ratio of described solid a and trichloromethane is 0.02mol/L;
In described methylene dichloride and ethyl acetate mixed solution, the volumetric ratio of methylene dichloride and ethyl acetate is 5:3;
Described 2,9-dipropargyl-1, the mol ratio of 10-phenanthroline intermediate, list-6-deoxidation-6-nitrine-beta-cyclodextrin, cupric sulfate pentahydrate and sodium ascorbate is 1:5:10:25; In the mixed solution of tetrahydrofuran (THF) and water, tetrahydrofuran (THF) and water capacity are than being 2:7; The amount ratio of the mixed solution of list-6-deoxidation-6-nitrine-beta-cyclodextrin and tetrahydrofuran (THF) and water is 0.03 mol/L;
The aqueous solution of described solid b and the volumetric ratio of acetone are 1:30;
In described developping agent, n-propyl alcohol, water and mass percent concentration are that the volumetric ratio of 25% ammoniacal liquor is 6:3:2;
In described eluent, the volumetric ratio of second alcohol and water is 3:17.
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| CN104151867B (en) * | 2014-05-09 | 2017-01-04 | 上海大学 | Temperature response type cyclodextrin probe double with pH and preparation method thereof |
| CN105820811B (en) * | 2016-04-28 | 2017-03-08 | 南京晓庄学院 | A kind of fluorescence probe and synthetic method and its application |
| CN108384027B (en) * | 2018-05-07 | 2021-03-26 | 江西省科学院应用化学研究所 | Zinc-organic framework with acetylacetone fluorescent response and preparation method thereof |
| CA3125554A1 (en) | 2019-01-03 | 2020-07-09 | Underdog Pharmaceuticals, Inc. | Cyclodextrin dimers, compositions thereof, and uses thereof |
| CN113278157B (en) * | 2021-05-21 | 2022-03-18 | 山西大学 | Cadmium coordination polymer and preparation method and application thereof |
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| CN101555296A (en) * | 2009-05-22 | 2009-10-14 | 南开大学 | Fluorescent ion probe reagent used in cadmium ion detection and preparation method thereof |
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