CN102899028B - 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: excessive fluorine enters after human body, can form dental fluorosis, causes tooth to be tawny or chocolate, gradually damaged coming off; There is ankylosis, lower limb bending, textured bone, even the symptom such as paralysis; Affect the normal development of children's intelligence and can have larger infringement 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 feature such as convenient and swift owing to having, the highly sensitive and selectivity of fluorion fluorescent probe technique is good, the design of fluorion fluorescent probe and having prepared develops rapidly.The method that the conduct of reporting in document at present detects fluorion mainly contains: (1) is by the effect of hydrogen bond, as hydrogen-bond donor (pyrroles, acid amides etc.) can form hydrogen bond with fluorion; (2) interaction between Lewis acid, as the strong avidity of fluorion to boron atom.This class fluorescent probe represents good sensing capabilities conventionally in organic solvent, but in aqueous phase system, is subject to the impact of hydrogen bond or other negatively charged ion of water, and immunity from interference is 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).
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, the ratio variation of the two emission peaks by measuring fluorion induction can realize the detection by quantitative to fluorion.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 body.And ratio metering type probe can be avoided the impact of testing environment, realize the detection by quantitative to 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 current fluorion fluorescent probe research.
Fluorescent probe based on response type in 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 identification object to detect analytic target, this class probe has specificity and non-reversibility, and does not affect detection sensitivity in aqueous phase system.But at present,, considerably less about the report of the ratio metering type fluorion probe based on response type, therefore people are seeking the fluorescent probe of a kind of quantitative highly selective and highly sensitive mensuration fluorion always.
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 water surrounding.But this invention cannot complete the detection to the fluorion in cell.
Summary of the invention
For solving the fluorescent probe demand of current people to a kind of quantitative highly selective and 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 can be used in aqueous phase system and cell detects;
Another object of the present invention is to provide 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 conjugation aromatic nucleus, and as preferably, R is selected from boron two pyrroles's methylene radical, naphthyl, pyrenyl, anthryl, porphyrin group a kind of.
A kind of preparation method of metering type fluorion fluorescent probe is following steps:
(1), in container, first add the alcohol with conjugation aromatic nucleus luminophore, then under protection of inert gas, add solvent and triethylamine, then in 15 ~ 30 minutes, splash into dichlorosilane compounds, react 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, 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 step (1) being obtained carries out suction filtration, purifies, and obtains metering type fluorion fluorescent probe pure products.
Wherein, dichlorosilane compounds, be 1:1.8 ~ 3:2 ~ 10 with the alcohol of conjugation aromatic nucleus luminophore and the mol ratio of triethylamine, volume ratio 1:20 ~ 50 of triethylamine and solvent.
A kind of metering type fluorion fluorescent probe is in the application detecting on fluorion.Utilize Siliciumatom and fluorion specific binding in metering type fluorion fluorescent probe, make 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 shown 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 gentleness is low for equipment requirements, and 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 novelty of the present invention, 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.
Brief description of the drawings
Fig. 1 is the photophysical property test pattern of fluorescent probe;
Fig. 2 is the irradiation figure that uses 365 nm luminescent lamps;
Fig. 3 is 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 in embodiment.
In (200 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), more dropwise add 1; 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, with 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 that (1.92 g), productive rate 77.3% for the metering type fluorion fluorescent probe 1 of (A1).
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.
Building-up reactions equation is as follows:
（A1）
In (200 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, with anhydrous sodium sulfate drying, separates the pure products that can obtain white solid with chromatography column (sherwood oil is as eluent)
2, 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）
In (200 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), more dropwise add 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 that (2.43 g), productive rate 80.3% for the metering type fluorion fluorescent probe 3 of (A3).
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 mL) round-bottomed flask; add anthryl carbinol 10 mmol; under argon shield, add 100 ml ether and triethylamine (3.07 mL, 22.5 mmol), more dropwise add 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 that (1.92 g), productive rate 81.2% for the metering type fluorion fluorescent probe 4 of (A4).
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 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), more dropwise add 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 that (2.25 g), productive rate 80.8% for the metering type fluorion fluorescent probe 5 of (A5).
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）
In (200 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), more dropwise add 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 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 that (1.74 g), productive rate 76.3% for the metering type fluorion fluorescent probe 7 of (A7).
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 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 that (2.34 g), productive rate 76.5% for the metering type fluorion fluorescent probe 8 of (A8).
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）
In (200 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 that (2.67 g), productive rate 76.8% for the metering type fluorion fluorescent probe 9 of (A9).
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 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), more dropwise add 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 that (5.26 g), productive rate 78.2% for the metering type fluorion fluorescent probe 10 of (A10).
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 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, structural formula is that (5.46 g), productive rate 76.4% for the metering type fluorion fluorescent probe 11 of (A11).
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 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), more dropwise add 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, with anhydrous sodium sulfate drying, separate and can obtain white solid pure products 12 with chromatography column (sherwood oil is as eluent), be that structural formula is that (2.48 g), productive rate 83.1% for the metering type fluorion fluorescent probe 12 of (A12).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 13, structural formula is that (3.16 g), productive rate 81.2% for the metering type fluorion fluorescent probe 13 of (A13).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 14, structural formula is that (2.50 g), productive rate 77.3% for the metering type fluorion fluorescent probe 14 of (A14).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 15, structural formula is that (2.80 g), productive rate 76.5% for the metering type fluorion fluorescent probe 15 of (A15).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 16, structural formula is that (2.06 g), productive rate 75.6% for the metering type fluorion fluorescent probe 16 of (A16).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 17, structural formula is that (2.44 g), productive rate 77.2% for the metering type fluorion fluorescent probe 17 of (A17).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 18, structural formula is that (3.11 g), productive rate 79.2% for the metering type fluorion fluorescent probe 18 of (A18).
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 mL) round-bottomed flask; add boron two pyrroles's methylene radical normal-butyl 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 19, structural formula is that (3.42 g), productive rate 78.6% for the metering type fluorion fluorescent probe 19 of (A19).
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 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 20, structural formula is that (5.65 g), productive rate 74.3% for the metering type fluorion fluorescent probe 20 of (A20).
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 mL) round-bottomed flask; add boron two pyrroles's methylene radical normal-butyl 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.According to method suction filtration, the purification of embodiment 12, obtain white solid pure products 21, structural formula is that (6.02 g), productive rate 75.1% for the metering type fluorion fluorescent probe 21 of (A21).
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
It is in the tetrahydrofuran (THF) of 1:1 and the mixing solutions of water that the fluorescent probe of arbitrary preparation in above-described embodiment 1 ~ embodiment 21 is dissolved in to volume ratio, 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, respectively adding 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
-.In the time of excitation with shorter, relatively add respectively the fluorescence spectrum and the fluorescence spectrum of fluorescent probe that does not add 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 -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 locating short wavelength (378 nm) strengthens gradually, is mainly the fracture of compound siloxane bond, and the luminescent decay of state of aggregation, until disappear.As shown in Figure 1, as can be seen from the figure this fluorescent probe to F
-there is good selectivity.
The test soln of respectively getting respectively the fluorescent probe of having prepared in test case 1, respectively 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
-, respectively place the variation of test fluorescence spectrum 2 minutes.As shown in Figure 2, under 365 nm fluorescent lamp, add the fluorescence of fluorion solution to be become light blue from blueness; As shown in Figure 3, find with 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
Make fluorescent probe enter in HELA cell taking PLA nanoparticle as carrier, as shown in Figure 4, find that fluorescent emission wave spectrum is positioned at 440-600 nm place, the not transmitting at 410-440 nm place, but add 100 μ M fluorions at 37 DEG C, after 2 hours, finding has transmitting at 410-440 nm place, and 440-600 nm place peak intensity obviously weakens.This variation is mainly that compound transmitting is got back to Monomer emission by state of aggregation owing to making siloxane bond fracture adding of fluorion.Also further verified that by test this fluorescent probe limit of detection in viable cell is low.
Claims (5)
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 conjugation aromatic nucleus,
The preparation method of described a kind of metering type fluorion fluorescent probe is following steps:
(1), in container, first add the alcohol with conjugation aromatic nucleus luminophore, then under protection of inert gas, add solvent and triethylamine, then in 15 ~ 30 minutes, splash into dichlorosilane compounds, react 8 ~ 18 hours, obtain metering type fluorion fluorescent probe crude product; Wherein 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 step (1) being obtained carries out suction filtration, purifies, and obtains metering type fluorion fluorescent probe pure products;
Wherein, the described alcohol with conjugation aromatic nucleus luminophore, wherein conjugation aromatic nucleus luminophore is selected from boron two pyrroles's methylene radical, naphthyl, pyrenyl, anthryl, porphyrin group a kind of;
Dichlorosilane compounds is selected from 1,1,2,2-tetramethyl-dichloro disilane, dimethyldichlorosilane(DMCS), the positive tetrasilane of prestox dichloro a kind of.
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, porphyrin group a kind of.
3. a kind of metering type fluorion fluorescent probe according to claim 1, is characterized in that, solvent is selected from tetrahydrofuran (THF) or ether.
4. a kind of metering type fluorion fluorescent probe according to claim 1, is characterized in that, volume ratio 1:20 ~ 50 of triethylamine and solvent in preparation method's step (1).
5. an a kind of metering type fluorion fluorescent probe as claimed in claim 1 is in the application detecting on fluorion.
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