CN102899028A - Metering type fluorinion fluorescence probe and preparation method - Google Patents
Metering type fluorinion fluorescence probe and preparation method Download PDFInfo
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Abstract
The invention relates to the organic chemistry field, which solves the requirement for a fluorescence probe used for determining the fluorinion with high selectivity and high sensitivity. The invention provides a metering type fluorinion fluorescence probe and a preparation method. The method comprises the following steps: in a container, adding alcohol with a luminescence group, then under the protection of inert gas, adding a solvent and triethylamine, adding a dichlorosilane compound, completing the droping in 15-30 minutes, reacting for 8-18 hours to obtain a metering type fluorinion fluorescence probe crude product, then performing pumping filtration on the obtained crude product according to a conventional method, and purifying to obtain a metering type fluorinion fluorescence probe pure product. The probe has good selectivity and sensitivity on the fluorinion, and can be used for detecting the fluorinion in a water phase system and cells; the preparation method of the probe is simple, and the equipment requirement is low, and the method of the invention is easy to be industrialized.
Description
Technical field
The present invention relates to organic chemistry filed, relate in particular to a kind of ratio metering response type fluorion fluorescent probe.
Background technology
Fluorion is a kind of important negatively charged ion, is one of trace element of needed by human.Fluorine is the indispensable element of bone and tooth, and a small amount of fluorine can effectively prevent carious tooth and osteoporotic generation.A large amount of fluorine is present in occurring in nature with the form of fluorion, takes in a large amount of fluorions and is easy to cause fluorosis, and fluorosis is a kind of chronic systemic disease.Such as: after excessive fluorine enters human body, can form dental fluorosis, cause tooth to be tawny or chocolate, gradually damaged coming off; Occur that ankylosis, lower limb are crooked, textured bone, even the symptom such as paralysis; Affect the normal development of children's intelligence and can larger infringement be arranged to the physiological system of human body, therefore, to the detection of fluorion seem particularly important (Coord. Chem. Rev., 2006,250,3094; Chem. Soc. Rev., 2010,39,3746; Chem. Commun., 2011,47,82).
In recent decades, the fluorion fluorescent probe technique is owing to having convenient and swift, highly sensitive and the characteristics such as selectivity is good, and the design of fluorion fluorescent probe and having prepared develops rapidly.The method that the conduct of reporting in the document at present detects fluorion mainly contains: (1) can form hydrogen bond by the effect of hydrogen bond with fluorion such as hydrogen-bond donor (pyrroles, acid amides etc.); (2) interaction between Lewis acid is such as the strong avidity of fluorion to the boron atom.This class fluorescent probe represents good sensing capabilities usually in organic solvent, but is subject to the impact of hydrogen bond or other negatively charged ion of water in aqueous phase system, and immunity from interference is relatively poor; Respond the drawbacks such as slower, waiting time length, seriously restricted its range of application (Chem. Soc. Rev., 2010,39,3936; Coord. Chem. Rev., 2006,250,3081).
The fluorion fluorescent probe can be divided into fluorescence according to different working mechanisms and strengthen (weakening) type probe and ratio metering type probe.The former in conjunction with fluorion after fluorescence intensity change, the utilization of ratio metering type fluorescent probe is combined rear wavelength of fluorescence and is changed with fluorion, can realize detection by quantitative to fluorion by the ratio variation of measuring two emission peaks that fluorion induces.Because the quantum yield of fluorescent probe is easily affected by environment, fluorescence strengthens the quantitative assay that (weakening) type probe is difficult to realize fluorinion concentration in the body.And ratio metering type probe can be avoided the impact of testing environment, realization is to the detection by quantitative of fluorion dynamic changing process, just because of this advantage of ratio metering type probe, the research work of this class probe has become the focus of present fluorion fluorescent probe research.
Fluorescent probe based on response type in the ratio metering type probe is to utilize the variation of the special irreversible chemical reaction front and back fluorescent signal that produces between probe molecule and the identification object that analytic target is detected, this class probe has specificity and non-reversibility, and does not affect detection sensitivity in aqueous phase system.The report of relevant ratio metering type fluorion probe based on response type is considerably less, so people are seeking a kind of quantitative highly selective and the fluorescent probe of highly sensitive mensuration fluorion always but at present.
Application number is that 201010179147.3 Chinese patent discloses a kind of fluorescent probe of identifying fluorion and its production and use, this disclosure of the invention probe compound and the test paper of a kind of spectral detection in conjunction with bore hole identification fluorion, this invention is particularly useful for the detection of fluorion in the water surrounding.But this invention can't be finished the detection to the fluorion in the cell.
Summary of the invention
For solving present people to a kind of quantitative highly selective and the fluorescent probe demand of highly sensitive mensuration fluorion, the present invention proposes a kind of metering type fluorion fluorescent probe probe of the present invention has good selectivity and sensitivity to fluorion, and the fluorion that can be used in aqueous phase system and the cell detects;
Another object of the present invention provides the preparation method of metering type fluorion fluorescent probe, and the preparation method of metering type fluorion fluorescent probe of the present invention is simple, low for equipment requirements, is easy to industrialization.
The present invention realizes by following steps: a kind of metering type fluorion fluorescent probe, and described metering type fluorion fluorescent probe contains following structural formula (A),
（A）
Wherein, m=1 ~ 4, n=1 ~ 4, R is selected from the luminophore that contains the conjugation aromatic nucleus, and as preferably, R is selected from boron two pyrroles's methylene radical, naphthyl, pyrenyl, anthryl, the porphyrin group a kind of.
A kind of preparation method of metering type fluorion fluorescent probe is following steps:
(1) in container, adds first the alcohol with conjugation aromatic nucleus luminophore, then under protection of inert gas, add solvent and triethylamine, then in 15 ~ 30 minutes, splash into the dichlorosilane compounds, reacted 8 ~ 18 hours, obtain metering type fluorion fluorescent probe crude product; As preferably, solvent is selected from tetrahydrofuran (THF) or ether, conjugation aromatic nucleus luminophore is selected from boron two pyrroles's methylene radical, naphthyl, pyrenyl, anthryl, the porphyrin group a kind of, described dichlorosilane compounds is selected from 1,1, a kind of in 2,2-tetramethyl-dichloro disilane, dimethyldichlorosilane(DMCS), the positive tetrasilane of prestox dichloro.
(2) crude product that step (1) is obtained carries out suction filtration, purifies, and obtains metering type fluorion fluorescent probe pure products.
Wherein, the dichlorosilane compounds, be 1:1.8 ~ 3:2 ~ 10 with the alcohol of conjugation aromatic nucleus luminophore and the mol ratio of triethylamine, the volume ratio 1:20 of triethylamine and solvent ~ 50.
A kind of metering type fluorion fluorescent probe is in the application that detects on the fluorion.Utilize Siliciumatom and fluorion specific binding in the metering type fluorion fluorescent probe, make the siloxane bond fracture.
The present invention utilizes between Siliciumatom and fluorine atom strong affinity interaction, and the aggregate of fluorophore and the luminous variation of monomer, prepared a series ofly based on chemically reactive ratio metering type fluorion fluorescent probe, this class probe has all been showed excellent selectivity and susceptibility in aqueous phase system and cell.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the selected reagent of metering type fluorion fluorescent probe of the present invention is common agents, and synthesis step is simple, and reaction conditions is gentle, and low for equipment requirements, the target product productive rate is high, is easy to separate be adapted to a large amount of synthesizing, and is easy to industrialization.
(2) metering type fluorion fluorescent probe of the present invention has water-soluble preferably.
(3) metering type fluorion fluorescent probe method of design of the present invention is novel, and selectivity is good, can ratio Measuring and testing fluorion.
(4) the present invention can also observe by cell imaging the variation of fluorescence, is easy to observe.
Description of drawings
Fig. 1 is the photophysical property test pattern of fluorescent probe;
Fig. 2 is for using the irradiation figure of 365 nm luminescent lamps;
Fig. 3 is the fluorescence spectrophotometer test pattern;
Fig. 4 is fluorescent probe response diagram to fluorion in viable cell.
Embodiment
Below by embodiment the present invention is described in further detail, raw materials used all commercially available among the embodiment.
Embodiment 1
In (200 a mL) round-bottomed flask, add pyrene methyl alcohol (2 g, 8.6 mmol); under nitrogen protection; add 90 milliliters of tetrahydrofuran (THF)s and triethylamine (2.64 mL, 18.9 mmol), dropwise add 1 again; 1; 2,2-tetramethyl-dichloro disilane (810 μ L, 4.3 mmol); approximately 20 minutes, be added dropwise to complete rear maintenance reaction 10 hours.Then directly suction filtration is removed precipitation, filtrate is used dichloromethane extraction three times, wash three times, use anhydrous sodium sulfate drying, separate the pure products 1 that can obtain white solid with chromatography column (sherwood oil is as eluent), be that structural formula is the metering type fluorion fluorescent probe 1 (1.92 g) of (A1), productive rate 77.3%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.15-8.04(m,?10?H),?8.01-7.93(m,?6?H),?7.85(d,?2?H),?5.42(s,?4?H),?0.37?(s,?12?H)
HR-MS:?Calcd.?for?C
38H
34O
2Si
2?[M
+]?578.8464.?Found?578.8468.
The building-up reactions equation is as follows:
（A1）
In (200 a mL) round-bottomed flask; add pyrene methyl alcohol (2 g; 8.6 mmol); under nitrogen protection, add 55 milliliters of tetrahydrofuran (THF)s and triethylamine (2.64 mL, 18.9 mmol); dropwise add again dimethyldichlorosilane(DMCS) (800 μ L; 4.3 mmol), approximately 30 minutes, be added dropwise to complete rear maintenance reaction 8 hours.Then directly suction filtration is removed a large amount of precipitations, and filtrate is used dichloromethane extraction three times, washes three times, uses anhydrous sodium sulfate drying, separates the pure products that can obtain white solid with chromatography column (sherwood oil is as eluent)
2, namely structural formula is the metering type fluorion fluorescent probe 2 (1.82g) of (A2), productive rate 81.2%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.15-8.05(m,?10?H),?8.05-7.98(m,?6?H),?7.89(d,?2?H),?5.40(s,?4?H),?0.39?(s,?6?H)
HR-MS:?Calcd.?for?C
36H
28O
2Si?[M
+]?520.6918.?Found?520.6919.
Structural formula is:
（A2）
Embodiment 3
In (200 a mL) round-bottomed flask; add pyrenyl normal-butyl alcohol 10 mmol; under argon shield, add 100 ml ether and triethylamine (3.07 mL, 22.5 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5 mmol; approximately 25 minutes; be added dropwise to complete rear maintenance reaction 10 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 3 of white solid; be that structural formula is the metering type fluorion fluorescent probe 3 (2.43 g) of (A3), productive rate 80.3%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.18-8.10(m,?10?H),?8.08-7.90(m,?6?H),?7.86(d,?2?H),?5.42(s,?4?H),?3.17?(t,?8?H),?1.60-1.90?(m,?8?H)?0.39?(s,?6?H)
HR-MS:?Calcd.?for?C
42H
40O
2Si?[M
+]?604.8513.?Found?604.8517.
Structural formula is:
（A3）
Embodiment 4
In (200 a mL) round-bottomed flask; add anthryl carbinol 10 mmol; under argon shield, add 100 ml ether and triethylamine (3.07 mL, 22.5 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5.1 mmol; approximately 18 minutes; be added dropwise to complete rear maintenance reaction 12 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 4 of white solid; be that structural formula is the metering type fluorion fluorescent probe 4 (1.92 g) of (A4), productive rate 81.2%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.51(s,?2?H),?8.37(m,?4?H),?8.03(m,?4?H),?7.46-7.60(m,?4?H),?6.24(s,?2?H),?0.33(s,?6?H)
HR-MS:?Calcd.?for?C
32H
28O
2Si?[M
+]?472.6490.?Found?472.6488.
Structural formula is:
（A4）
Embodiment 5
In (200 a mL) round-bottomed flask; add anthryl propyl carbinol 10 mmol; under nitrogen protection, add 150 ml tetrahydrofuran (THF)s and triethylamine (3.14 mL, 23.0 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5 mmol; approximately 15 minutes; be added dropwise to complete rear maintenance reaction 15 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 5 of white solid; be that structural formula is the metering type fluorion fluorescent probe 5 (2.25 g) of (A5), productive rate 80.8%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.50(s,?2?H),?8.37(m,?4?H),?8.06(m,?4?H),?7.46-7.62(m,?4?H),?6.23(t,?4?H),?3.11?(t,?8?H),?1.63-1.95?(m,?8?H),?0.34(s,?6?H)
HR-MS:?Calcd.?for?C
38H
40O
2Si?[M
+]?556.8085.?Found?556.8088.
Structural formula is:
（A5）
Embodiment 6
In (200 a mL) round-bottomed flask; add naphthalene methyl alcohol 10 mmol; under nitrogen protection, add 100 ml tetrahydrofuran (THF)s and triethylamine (1.28 mL, 10.0 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5 mmol; approximately 20 minutes; be added dropwise to complete rear maintenance reaction 10 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 6 of white solid; be that structural formula is the metering type fluorion fluorescent probe 6 (1.41g) of (A6), productive rate 78.5%.
1H?NMR?(CDCl
3)?δ:?8.14-8.17?(dd,?2?H).?7.83-7.93?(m,?4?H)，7.45-7.59?(m,?8?H)，5.17?(s,?4H),?0.34?(bs,?6?H)
HR-MS:?Calcd.?for?C
23H
22O
2Si?[M
+]?358.1389.?Found?358.1391.
Structural formula is:
（A6）
Embodiment 7
In (200 a mL) round-bottomed flask; add naphthyl propyl carbinol 10 mmol; under nitrogen protection, add 100 ml tetrahydrofuran (THF)s and triethylamine (3.28 mL, 24.0 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5.3 mmol; approximately 30 minutes; be added dropwise to complete rear maintenance reaction 10 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 7 of white solid; be that structural formula is the metering type fluorion fluorescent probe 7 (1.74 g) of (A7), productive rate 76.3%.
1H?NMR?(CDCl
3)?δ:?8.14-8.17?(dd,?2?H).?7.83-7.93?(m,?4?H)，7.45-7.59?(m,?8?H)，5.17?(s,?4H),?3.72?(t,?8?H),?1.55-1.80?(m,?8?H),?0.34?(bs,?6?H)
HR-MS:?Calcd.?for?C
30H
36O
2Si?[M
+]?456.6911.?Found?456.6914.
Structural formula is:
（A7）
Embodiment 8
In (200 a mL) round-bottomed flask; add boron two pyrroles's methylene radical methyl alcohol 10 mmol; under nitrogen protection, add 120 ml ether and triethylamine (3.17 mL, 23.2 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5.1mmol; approximately 25 minutes; be added dropwise to complete rear maintenance reaction 11 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 8 of white solid; be that structural formula is the metering type fluorion fluorescent probe 8 (2.34 g) of (A8), productive rate 76.5%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?6.03?(s,?4H),?5.77(s,?4?H)?2.58?(s,?12H),?1.37?(s,?12?H),?0.33(s,?6?H)
HR-MS:?Calcd.?for?C
30H
38B
2F
4N
4O
2Si?[M
+]?612.2886.?Found?612.2884.
Structural formula is:
（A8）
Embodiment 9
In (200 a mL) round-bottomed flask; add boron two pyrroles's methylene radical butanols 10 mmol; under nitrogen protection, add 130 ml ether and triethylamine (3.17 mL, 23.2 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5.1mmol; approximately 18 minutes; be added dropwise to complete rear maintenance reaction 13 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 9 of white solid; be that structural formula is the metering type fluorion fluorescent probe 9 (2.67 g) of (A9), productive rate 76.8%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?6.03?(s,?4H),?5.77(s,?4?H),?4.10?(t,?8?H),?2.22-2.41?(m,?8?H),?2.58?(s,?12H),?1.37?(s,?12?H),?0.33(s,?6?H)
HR-MS:?Calcd.?for?C
36H
50B
2F
4N
4O
2Si?[M
+]?696.5089.?Found?696.5093.
Structural formula is:
（A9）
Embodiment 10
In (200 a mL) round-bottomed flask; add porphyrin methyl alcohol 10 mmol; under nitrogen protection, add 80ml tetrahydrofuran (THF) and triethylamine (3.28 mL, 24.0 mmol), dropwise add again dimethyldichlorosilane(DMCS) 5.4mmol; approximately 20 minutes; be added dropwise to complete rear maintenance reaction 11 hours, adopt the method for embodiment 1 to carry out suction filtration, purification, obtain the pure products 10 of white solid; be that structural formula is the metering type fluorion fluorescent probe 10 (5.26 g) of (A10), productive rate 78.2%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?8.86?(s,?16?H),?8.24-8.23?(m,?16?H),?7.82-7.75?(m,?22?H),?5.09?(s,?4?H),?0.33(s,?6?H),?-2.75?(s,?4?H)
HR-MS:?Calcd.?for?C
92H
68N
8O
2Si?[M
+]?1345.6622.?Found?1345.6625.
Structural formula is:
（A10）
Embodiment 11
In (200 a mL) round-bottomed flask; add porphyrin propyl carbinol 10 mmol; be filled with nitrogen; under nitrogen protection, add 100 ml tetrahydrofuran (THF)s and triethylamine (3.18 mL; 23.3 mmol); dropwise add again dimethyldichlorosilane(DMCS) 5.1 mmol; approximately 25 minutes; be added dropwise to complete rear maintenance reaction 10 hours; adopt the method for embodiment 1 to carry out suction filtration, purification; obtain the pure products 11 of white solid, namely structural formula is the metering type fluorion fluorescent probe 11 (5.46 g) of (A11), productive rate 76.4%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?8.84?(s,?16?H),?8.28-8.22?(m,?16?H),?7.79-7.70?(m,?22?H),?5.17?(s,?4?H),?4.12?(t,?8?H),?2.30-2.43?(m,?8?H),?0.40(s,?24?H),?-2.76?(s,?4?H)
HR-MS:?Calcd.?for?C
98H
80N
8O
2Si?[M
+]?1429.8217.?Found?1429.8216.
Structural formula is:
（A11）
Embodiment 12
In (200 a mL) round-bottomed flask; add pyrene methyl alcohol (2 g; 8.6 mmol); under nitrogen protection, add 90 milliliters of tetrahydrofuran (THF)s and triethylamine (2.64 mL; 18.9 mmol), dropwise add again the positive tetrasilane of prestox dichloro (823 μ L, 4.3 mmol); approximately 18 minutes, be added dropwise to complete rear maintenance reaction 14 hours.Then directly suction filtration is removed a large amount of precipitations, filtrate is used dichloromethane extraction three times, wash three times, use anhydrous sodium sulfate drying, can obtain white solid pure products 12 with chromatography column (sherwood oil is as eluent) separation, be that structural formula is the metering type fluorion fluorescent probe 12 (2.48 g) of (A12), productive rate 83.1%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.20-8.12(m,?10?H),?8.08-7.96(m,?6?H),?7.87(d,?2?H),?5.45(s,?4?H),?0.36?(s,?24?H)
HR-MS:?Calcd.?for?C
42H
46O
2Si
4?[M
+]?695.1554.?Found?695.1557.
Structural formula is:
（A12）
Embodiment 13
In (200 a mL) round-bottomed flask; add pyrenyl normal-butyl alcohol 10 mmol; under nitrogen protection, add 110 ml tetrahydrofuran (THF)s and triethylamine (3.10 mL; 22.2 mmol); dropwise add again positive tetrasilane 5.1 mmol of prestox dichloro; approximately 15 minutes, be added dropwise to complete rear maintenance reaction 14 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 13, and namely structural formula is the metering type fluorion fluorescent probe 13 (3.16 g) of (A13), productive rate 81.2%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.18-8.12(m,?10?H),?8.07-7.93(m,?6?H),?7.88(d,?2?H),?5.40(s,?4?H),?3.18(t,?8?H),?1.63-1.90?(m,?8?H)?0.35?(s,?24?H)
HR-MS:?Calcd.?for?C
48H
58O
2Si
4?[M
+]?779.3149.?Found?779.3146.
Structural formula is:
（A13）
Embodiment 14
In (200 a mL) round-bottomed flask, add anthryl carbinol 10 mmol, under nitrogen protection, add 100 ml milliliter tetrahydrofuran (THF)s and triethylamine (6.93 mL; 50 mmol); dropwise add again positive tetrasilane 5 mmol of prestox dichloro, approximately 30 minutes, be added dropwise to complete rear maintenance reaction 8 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 14, and namely structural formula is the metering type fluorion fluorescent probe 14 (2.50 g) of (A14), productive rate 77.3%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.50(s,?2?H),?8.37(m,?4?H),?8.04(m,?4?H),?7.46-7.61(m,?8?H),?6.22(s,?4?H),?0.39(s,?24?H)
HR-MS:?Calcd.?for?C
38H
46O
2Si
4?[M
+]?646.2578.?Found?646.2575.
Structural formula is:
（A14）
Embodiment 15
In (200 a mL) round-bottomed flask; add anthryl normal-butyl alcohol 10 mmol; under argon shield, add 120 ml milliliter tetrahydrofuran (THF)s and triethylamine (3.34 mL; 24.0 mmol); dropwise add again positive tetrasilane 5.3 mmol of prestox dichloro; approximately 25 minutes, be added dropwise to complete rear maintenance reaction 10 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 15, and namely structural formula is the metering type fluorion fluorescent probe 15 (2.80 g) of (A15), productive rate 76.5%.
1H?NMR?（400?MHz,?CDCl
3)?δ:?8.52(s,?2?H),?8.36(m,?4?H),?8.04(m,?4?H),?7.46-7.60(m,?8?H),?6.26(s,?4?H),?3.12?(t,?8?H),?1.60-1.88?(m,?8?H),?0.41(s,?24?H)
HR-MS:?Calcd.?for?C
44H
58O
2Si
4[M
+]?731.2721.?Found?731.2724.
Structural formula is:
（A15）
Embodiment 16
In (200 a mL) round-bottomed flask, add naphthalene methyl alcohol 10 mmol, under nitrogen protection, add 150 ml milliliter ether and triethylamine (3.06 mL; 22.0 mmol); dropwise add again the positive tetrasilane 5.2mmol of prestox dichloro, approximately 25 minutes, be added dropwise to complete rear maintenance reaction 18 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 16, and namely structural formula is the metering type fluorion fluorescent probe 16 (2.06 g) of (A16), productive rate 75.6%.
1H?NMR?(CDCl
3)?δ:?8.12-8.18?(dd,?2?H).?7.80-7.90?(m,?4?H)，7.50-7.62?(m,?8?H)，5.18?(s,?4H)，0.41?(bs,?24?H)
HR-MS:?Calcd.?for?C
30H
42O
2Si
4?[M
+]?546.2262.?Found?546.2261.
Structural formula is:
（A16）
Embodiment 17
In (200 a mL) round-bottomed flask; add anthryl normal-butyl alcohol 10 mmol; under nitrogen protection, add 130 ml tetrahydrofuran (THF)s and triethylamine (3.27 mL; 23.5 mmol); dropwise add again positive tetrasilane 3.33 mmol of prestox dichloro; about 30 minutes, be added dropwise to complete rear maintenance reaction 8 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 17, and namely structural formula is the metering type fluorion fluorescent probe 17 (2.44 g) of (A17), productive rate 77.2%.
1H?NMR?(CDCl
3)?δ:?8.11-8.17?(dd,?2?H).?7.80-7.93?(m,?4?H)，7.52-7.62?(m,?8?H)，5.20?(s,?4H),?3.74?(t,?8?H),?1.59-1.84?(m,?8?H),?0.40?(bs,?24?H)
HR-MS:?Calcd.?for?C
36H
54O
2Si
4?[M
+]?631.1548.?Found?631.1541.
Structural formula is:
（A17）
Embodiment 18
In (200 a mL) round-bottomed flask; add boron two pyrroles's methylene radical methyl alcohol 10 mmol; under nitrogen protection, add 100 ml tetrahydrofuran (THF)s and triethylamine (3.20 mL; 23.0 mmol); dropwise add again positive tetrasilane 5 mmol of prestox dichloro; approximately 25 minutes, be added dropwise to complete rear maintenance reaction 10 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 18, and namely structural formula is the metering type fluorion fluorescent probe 18 (3.11 g) of (A18), productive rate 79.2%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?6.10?(s,?4H),?5.79(s,?4?H)?2.50?(s,?12H),?1.40?(s,?12?H),?0.43(s,?24?H)
HR-MS:?Calcd.?for?C
36H
56B
2F
4N
4O
2Si
4?[M
+]?786.3603.?Found?786.3600.
Structural formula is:
（A18）
Embodiment 19
In (200 a mL) round-bottomed flask; add boron two pyrroles's methylene radical normal-butyls alcohol 10 mmol; under nitrogen protection, add 90 ml tetrahydrofuran (THF)s and triethylamine (3.03 mL; 21.8 mmol); dropwise add again the positive tetrasilane 5.1mmol of prestox dichloro; approximately 20 minutes, be added dropwise to complete rear maintenance reaction 17 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 19, and namely structural formula is the metering type fluorion fluorescent probe 19 (3.42 g) of (A19), productive rate 78.6%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?6.10?(s,?4?H),?5.79(s,?4?H),?4.06?(t,?8?H),?2.27-2.45?(m,?8?H),?2.50?(s,?12?H),?1.40?(s,?12?H),?0.43(s,?24?H)
HR-MS:?Calcd.?for?C
42H
68B
2F
4N
4O
2Si
4?[M
+]?870.9725.?Found?870.9728.
Structural formula is:
（A19）
Embodiment 20
In (200 a mL) round-bottomed flask, add porphyrin methyl alcohol 10mmol, under nitrogen protection, add 100 ml tetrahydrofuran (THF)s and triethylamine (3.34 mL; 24.0 mmol); dropwise add again the positive tetrasilane 5mmol of prestox dichloro, approximately 30 minutes, be added dropwise to complete rear maintenance reaction 9 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 20, and namely structural formula is the metering type fluorion fluorescent probe 20 (5.65 g) of (A20), productive rate 74.3%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?8.88?(s,?16?H),?8.27-8.21?(m,?16?H),?7.80-7.66?(m,?22?H),?5.10?(s,?4?H),?0.39(s,?24?H),?-2.75?(s,?4?H)
HR-MS:?Calcd.?for?C
98H
86N
8O
2Si
4?[M
+]?1520.1258.?Found?1520.1260.
Structural formula is:
（A20）
Embodiment 21
In (200 a mL) round-bottomed flask; add boron two pyrroles's methylene radical normal-butyls alcohol 10 mmol; under nitrogen protection, add 110 ml tetrahydrofuran (THF)s and triethylamine (3.34 mL; 24.0 mmol); dropwise add again the positive tetrasilane 5.2mmol of prestox dichloro; about 25 minutes, be added dropwise to complete rear maintenance reaction 12 hours.Method suction filtration, purification according to embodiment 12 obtain white solid pure products 21, and namely structural formula is the metering type fluorion fluorescent probe 21 (6.02 g) of (A21), productive rate 75.1%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?8.86?(s,?16?H),?8.26-8.22?(m,?16?H),?7.82-7.70?(m,?24?H),?5.14?(s,?4?H),?4.10?(t,?8?H),?2.33-2.40?(m,?8?H),?0.41(s,?24?H),?-2.78?(s,?4?H)
HR-MS:?Calcd.?for?C
104H
98N
8O
2Si
4?[M
+]?1604.2853.?Found?1604.2858.
Structural formula is:
（A21）
Test case 1: the photophysical property test of fluorescent probe
The fluorescent probe of arbitrary preparation among above-described embodiment 1 ~ embodiment 21 is dissolved in the mixing solutions of tetrahydrofuran (THF) that volume ratio is 1:1 and water, makes the test soln that volumetric molar concentration is every liter of 0.01 mmole.
Respectively get respectively 1 milliliter of above-mentioned fluorescent probe test soln of having prepared, each adds 10 microlitre volumetric molar concentrations is the CO of every liter of 1 mmole
3 2-, NO
2 -, NO
3 -, Cl
-, Br
-, SCN
-, ClO
4 -, SO
4 2-, HPO
4 2-, H
2PO
4 -, F
-When with shorter excitation, relatively add respectively the fluorescence spectrum and the fluorescence spectrum that does not add the fluorescent probe of any negatively charged ion of the fluorescent probe of various negatively charged ion, find to add CO
3 2-, NO
2 -, NO
3 -, Cl
-, Br
-, I
-, SCN
-, ClO
4 -, SO
4 2-, HPO
4 2-, H
2PO
4 -The time fluorescence spectrum change hardly, and add F
-After, the fluorescence spectrum of system varies widely, long wavelength (470 nm) luminescent decay, and the luminous place that locates short wavelength (378 nm) strengthens gradually, mainly is the fracture of compound siloxane bond, and the luminescent decay of state of aggregation is until disappear.As shown in Figure 1, as can be seen from the figure this fluorescent probe to F
-Preferably selectivity is arranged.
Respectively get respectively the test soln of the fluorescent probe of having prepared in the test case 1, each adds 1 microlitre, 2 microlitres, and 3 microlitres, 4 microlitres, 5 microlitres, 6 microlitres, 7 microlitres, 8 microlitres, 9 microlitres, 10 microlitre concentration are the F of every liter of 1 mmole
-, each was placed 2 minutes, the variation of test fluorescence spectrum.As shown in Figure 2, under 365 nm fluorescent lamp, the fluorescence that adds fluorion solution is become light blue by blueness; As shown in Figure 3, find with the fluorescence spectrophotometer test, along with the increase of fluorion amount, the luminous intensity of shortwave strong point strengthens gradually, and the luminous intensity of long wave strong point weakens gradually, can realize the detection by quantitative to fluorion.
Test case 3: test fluorescent probe response to fluorion in viable cell
Fluorescent probe is entered in the HELA cell, as shown in Figure 4, find that the fluorescent emission wave spectrum is positioned at 440-600 nm place, the not emission at 410-440 nm place, but add 100 μ M fluorions at 37 ℃, finding after 2 hours has emission at 410-440 nm place, and 440-600 nm place peak intensity obviously weakens.This variation mainly is that the compound emission is got back to Monomer emission by state of aggregation because the adding of fluorion makes the siloxane bond fracture.Further verified also that by test this fluorescent probe limit of detection in viable cell is low.
Claims (8)
1. a metering type fluorion fluorescent probe is characterized in that, described metering type fluorion fluorescent probe has following structural formula (A),
（A）
Wherein, m=1 ~ 4, n=1 ~ 4, R is selected from the luminophore that contains the conjugation aromatic nucleus.
2. a kind of metering type fluorion fluorescent probe according to claim 1 is characterized in that, described R is selected from boron two pyrroles's methylene radical, naphthyl, pyrenyl, anthryl, the porphyrin group a kind of.
3. the preparation method of an a kind of metering type fluorion fluorescent probe as claimed in claim 1 or 2 is characterized in that, described preparation method is following steps:
(1) in container, adds first the alcohol with conjugation aromatic nucleus luminophore, then under protection of inert gas, add solvent and triethylamine, then in 15 ~ 30 minutes, splash into the dichlorosilane compounds, reacted 8 ~ 18 hours, obtain metering type fluorion fluorescent probe crude product; Wherein the dichlorosilane compounds, be 1:1.8 ~ 3:2 ~ 10 with the alcohol of conjugation aromatic nucleus luminophore and the mol ratio of triethylamine;
(2) crude product that step (1) is obtained carries out suction filtration, purifies, and obtains metering type fluorion fluorescent probe pure products.
4. the preparation method of a kind of metering type fluorion fluorescent probe according to claim 3 is characterized in that, solvent is selected from tetrahydrofuran (THF) or ether.
5. the preparation method of a kind of metering type fluorion fluorescent probe according to claim 3, it is characterized in that, described alcohol with conjugation aromatic nucleus luminophore, wherein conjugation aromatic nucleus luminophore is selected from boron two pyrroles's methylene radical, naphthyl, pyrenyl, anthryl, the porphyrin group a kind of.
6. the preparation method of a kind of metering type fluorion fluorescent probe according to claim 3, it is characterized in that, described dichlorosilane compounds is selected from 1,1, a kind of in 2,2-tetramethyl-dichloro disilane, dimethyldichlorosilane(DMCS), the positive tetrasilane of prestox dichloro.
7. according to claim 3 or the preparation method of 4 or 5 or 6 described a kind of metering type fluorion fluorescent probes, it is characterized in that the volume ratio 1:20 of triethylamine and solvent ~ 50.
8. an a kind of metering type fluorion fluorescent probe as claimed in claim 1 or 2 is in the application that detects on the fluorion.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845611A (en) * | 2015-04-28 | 2015-08-19 | 中国科学院理化技术研究所 | Novel fluorinion rate fluorescent probe and application |
| CN107699228A (en) * | 2017-09-12 | 2018-02-16 | 上海应用技术大学 | A kind of fluorine ion fluorescence probe of nano silicon load, preparation method and applications |
| CN109490283A (en) * | 2018-11-23 | 2019-03-19 | 西北师范大学 | Application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion |
| JP2020091192A (en) * | 2018-12-05 | 2020-06-11 | 学校法人北里研究所 | Compound and use thereof |
| CN114214059A (en) * | 2021-11-18 | 2022-03-22 | 淮阴工学院 | Fluorine ion fluorescent probe and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007821A (en) * | 2007-01-04 | 2007-08-01 | 山东师范大学 | Fluorescent probe for detecting fluorinion and its synthesis method and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101007821A (en) * | 2007-01-04 | 2007-08-01 | 山东师范大学 | Fluorescent probe for detecting fluorinion and its synthesis method and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104845611A (en) * | 2015-04-28 | 2015-08-19 | 中国科学院理化技术研究所 | Novel fluorinion rate fluorescent probe and application |
| CN107699228A (en) * | 2017-09-12 | 2018-02-16 | 上海应用技术大学 | A kind of fluorine ion fluorescence probe of nano silicon load, preparation method and applications |
| CN107699228B (en) * | 2017-09-12 | 2020-01-31 | 上海应用技术大学 | nanometer silicon dioxide loaded fluorine ion fluorescent probe, preparation method and application thereof |
| CN109490283A (en) * | 2018-11-23 | 2019-03-19 | 西北师范大学 | Application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion |
| CN109490283B (en) * | 2018-11-23 | 2021-07-16 | 西北师范大学 | Application of tetra (p-hydroxyphenyl) porphyrin-beta-CD supramolecules in detecting fluoride ions |
| JP2020091192A (en) * | 2018-12-05 | 2020-06-11 | 学校法人北里研究所 | Compound and use thereof |
| JP7193842B2 (en) | 2018-12-05 | 2022-12-21 | 学校法人北里研究所 | Compounds and uses thereof |
| CN114214059A (en) * | 2021-11-18 | 2022-03-22 | 淮阴工学院 | Fluorine ion fluorescent probe and preparation method and application thereof |
| CN114214059B (en) * | 2021-11-18 | 2024-03-12 | 淮阴工学院 | Fluorine ion fluorescent probe and preparation method and application thereof |
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