CN105131935B - Quick high-selectivity fluorine ion colorimetric probe and preparation method thereof - Google Patents
Quick high-selectivity fluorine ion colorimetric probe and preparation method thereof Download PDFInfo
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- CN105131935B CN105131935B CN201510534709.4A CN201510534709A CN105131935B CN 105131935 B CN105131935 B CN 105131935B CN 201510534709 A CN201510534709 A CN 201510534709A CN 105131935 B CN105131935 B CN 105131935B
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- fluorine ion
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- 0 *Cc1nc2ccccc2[s]1 Chemical compound *Cc1nc2ccccc2[s]1 0.000 description 2
- LAIMFYUZBFPGFS-YYDJUVGSSA-N CC(C)(C)[Si](c1ccccc1)(c1ccccc1)Oc1ccc(/C=C(/c2nc(cccc3)c3[s]2)\C#N)cc1 Chemical compound CC(C)(C)[Si](c1ccccc1)(c1ccccc1)Oc1ccc(/C=C(/c2nc(cccc3)c3[s]2)\C#N)cc1 LAIMFYUZBFPGFS-YYDJUVGSSA-N 0.000 description 1
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Abstract
The present invention relates to quick high-selectivity fluorine ion colorimetric probe and preparation method thereof.This kind of probe can not only with high selectivity recognize fluorine ion and the mode that can be observed with the naked eye qualitatively and quantitatively is analyzed fluorine ion.This kind of probe quickly can be realized responding to fluorine ion, it is possible to achieve the instant detection to fluorine ion.This kind of probe is stable in properties, can for a long time preserve and use.Additionally, this kind of probe can also carry out quantitative analysis to fluorine ion using absorption spectrometry, and with stronger antijamming capability.The synthesis of this kind of probe uses room temperature procedure, only needs single step reaction, and synthesis is simple.
Description
Technical field
The present invention relates to as fluorine ion colorimetric probe, its preparation method and its quick high-selectivity identification to fluorine ion
Application.
Background technology
In environmental and biological materials, anion is ubiquitous, and it is present in empty gas and water and soil in environment,
It is present in organ, the cell of human body, even in cell liquid, it plays extremely important angle in environment and the ecosystem
Color.And be the indispensable element of biological life activity as fluorine ion minimum in anion, dredged in teeth caring and treatment sclerotin
The aspect important role such as loose disease.In order to contain enough fluorine ions in human body, people are using it as a kind of important
Additive, is usually used in toothpaste, medicine and drinking water.However, the fluorine of excess is not only to aquatile and the toxic effect of plant,
Will also result in serious human health problems.The sodium fluoride (NaF) of such as higher concentration can disturb normal cell metabolism.It is anxious
Property intake is heavy dose of or fluorine of long-term intake low dosage, acute stomach trouble and kidney disorder, tooth and bone can be caused chronic
Poisoning, lithiasis, serious even can cause death.At present, the whole world still has many people drinking the water containing fluorine high
Source, this health to the mankind generates threat.
In consideration of it, research is a kind of can to detect that fluorine ion has the method with content, no matter treatment, guarantor in clinical disease
Retaining ring border or academic research aspect suffer from extremely important effect.Have much although detecting the method for fluorine ion, it is unfortunate
Be that capillary electrophoresis sensitivity is low, the poor reproducibility of fluoride ion selective electrode, the high cost of fluorine ion nuclear magnetic resonance, sternly
Its application is limited again and is developed.It is with low cost because colorimetric probe is simple to operate, it might even be possible to by the conversion of molecular recognition signal
Into the change of color, it is not necessary to expensive instrument directly can with naked eye, therefore, colorimetric probe is compared with other recognition methods
With significant advantage.
The content of the invention
It is badly in need of one kind and prepares simple quick high-selectivity fluorine ion colorimetric probe in this area such that it is able to effective detection fluorine
Ion.Therefore, the present invention has synthesized the novel fluorine ion colorimetric probe of a class, its synthesis is simple, stability is high, and/or selection
Property is high, and/or can quickly recognize fluorine ion.
Specifically, the invention provides a kind of fluorine ion colorimetric probe, it is 4- tert-butyl diphenyl siloxy benzene second
Vinyl compound.
Present invention also offers the preparation method of fluorine ion colorimetric probe, it is by by corresponding 4- tert-butyl diphenyls
Siloxy compound of benzaldehyde category is obtained with the reaction of 2- cyanobenzothiazole classes compound.
In the preparation method of fluorine ion colorimetric probe of the invention, reaction temperature is 20~100 DEG C；Reaction time is 2h
~10h；4- tert-butyl diphenyl siloxy compound of benzaldehyde category is for about with the mol ratio of 2- cyanobenzothiazole class compounds
1：1 to 5：1.
Fluorine ion colorimetric probe of the invention can be acted on fluorine ion, produce the change of absorption spectrum (while adjoint
Different color changes), so as to realize the quantitative determination to fluorine ion.
Specifically, fluorine ion colorimetric probe of the invention is acted on other anion can not cause absorption respectively
The obvious change of spectrum, so as to realize the Selective recognition to fluorine ion, and then can be optionally used for excluding other anion
In the presence of the interference of the quantitative determination to fluorine ion.
Selectively, the good stability of fluorine ion colorimetric probe of the invention, and then can for a long time preserve and use.
Further, fluorine ion colorimetric probe of the invention is quick high-selectivity fluorine ion colorimetric probe, and synthesis letter
It is single, be conducive to commercialized popularization and application.
Brief description of the drawings
Fig. 1 (Fig. 1 a and Fig. 1 b) is influences of the various concentrations NaF (0~200 μM) to probe (10 μM) absorption spectrum.
Fig. 2 is influence of the different analytes (100 μM) to probe (10 μM) absorption spectrum.
Fig. 3 is influence of the different analytes (100 μM) to probe (10 μM) absorption spectrum quantitative analysis NaF (100 μM).
Fig. 4 is probe (10 μM) to 100 μM of test results of concentration NaF response times.
Specific embodiment：
The present invention proposes synthetic route, method and its light spectrality of above-mentioned quick high-selectivity fluorine ion colorimetric probe
Energy.
Fluorine ion colorimetric probe of the invention is a class 4- tert-butyl diphenyl siloxy styrene compounds, and it has
Following general structure
The synthetic route and method of above-mentioned fluorine ion colorimetric probe are as follows：
Quick high-selectivity identification fluorine ion colorimetric probe of the invention is noteworthy characterized by being capable of quick high-selectivity ground
Identification fluorine ion, and/or quantitative analysis accurately can be carried out to fluorine ion in the presence of other high concentration anionics.Important
It is that the mode that fluorine ion colorimetric probe of the invention can also be observed with " bore hole " carries out qualitative and quantitative analysis.
The present invention will be illustrated in greater detail by by following examples below.Following examples are merely illustrative,
It should be understood that the present invention is not limited by following embodiments.
Embodiment 1
(scheme 1) is by 174mg (1.0mmol) 2- cyanobenzothiazoles, 361mg (1.0mmol) 4- tert-butyl diphenyl silicon
Epoxide benzaldehyde and 50 μ L triethylamines are dissolved in 20mL ethanol, and at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains crude product, so
Dichloromethane and mixed system (v/v, 1 of petroleum ether are used afterwards:1) pillar layer separation is carried out, faint yellow pure product is obtained
310mg, yield is 60 ﹪.
(scheme 2) is by 174mg (1.0mmol) 2- cyanobenzothiazoles, 542mg (1.5mmol) 4- tert-butyl diphenyl silicon
Epoxide benzaldehyde and 50 μ L triethylamines are dissolved in 20mL ethanol, and at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains crude product, so
Dichloromethane and mixed system (v/v, 1 of petroleum ether are used afterwards:1) pillar layer separation is carried out, faint yellow pure product is obtained
372mg, yield is 72 ﹪.
1H-NMR(400MHz,CDCl3)δ(*10-6):1.04 (s, 9H), 6.77 (d, J=8.0Hz, 2H), 7.29-7.41
(m, 8H), 7.63 (d, J=8.0Hz, 4H), 7.72-7.77 (m, 3H), 7.94 (d, J=8.0Hz, 1H), 7.98 (s, 1H)；13C-
NMR(100MHz,CDCl3)δ(*10-6):18.51,25.44,101.43,116.01,119.70,120.61,122.36,
124.58,124.73,125.83,126.76,127.05,129.33,130.97,131.54,133.78,134.43,145.57,
152.62,158.56,162.43.ESI-MS calculated value C32H29N2OSSi[M+H]+517；Measured value 517.
Embodiment 2
The present inventor has carried out following test：A () various concentrations NaF (0~200 μM) is to (10 μM) absorptions of probe
The influence of spectrum；Absorption intensity and NaF concentration (0,1,2,4,6,8,10,15,20,30,40,60 μ for adding at (b) 485nm
M the linear relationship between).Said determination is carried out in acetonitrile, and all spectrum tests are all that NaF adds work at 25 DEG C
With what is measured after 20min.Result is referring to Fig. 1.
It will be seen from figure 1 that along with the increase of NaF concentration in probe solution, absorption spectrum gradually rises, and 0~
The linear relationship into good with absorption value in 60 μM of NaF concentration ranges.Therefore, probe of the invention can relatively accurately determine to treat
Survey the content of fluorine ion in blood sample or environment.
Embodiment 3
Influence of the different analytes (100 μM) to probe (10 μM) absorption spectrum.Analyte includes：Chlorion Cl-, bromine from
Sub- Br-, iodide ion I-, sulfate ion SO4 2-, nitrate ion NO3 -, nitrite ion NO2 -, thiocyanate ion SCN-
With fluorine ion F-, their concentration is 100 μM.All test conditions are completed in acetonitrile, and all spectrum are all 25
Measured after analyte addition effect 20min at DEG C.The probe storing solution (1mM) for pipetting 50 μ L puts 5mL colorimetric cylinders into, then
3mL acetonitriles are added, then pipettes the above-mentioned analyte storing solutions (10mM) of 50 μ L and added in colorimetric cylinder, be then settled to 5mL with acetonitrile.
Shake up, stand 20min, you can determine.Result is as shown in Figure 2.
Figure it is seen that probe has selectivity very high to fluorine ion, can be carried out instead with fluorine ion in specific manner
Should.In acetonitrile solution, compared with other analytes, so after probe reacts with fluorine ion, absorption spectrum is increased significantly；And
After other Common Anions existed in organism are acted on probe there is no significant change in absorption intensity.
Embodiment 4
Influence of the different analytes (100 μM) to probe (10 μM) absorption spectrum quantitative analysis fluorine ion (100 μM).Point
Analysis thing includes：Chlorion Cl-, bromide ion Br-, iodide ion I-, sulfate ion SO4 2-, nitrate ion NO3 -, nitrite anions from
Sub- NO2 -, thiocyanate ion SCN-With fluorine ion F-, their concentration is 100 μM.All test conditions are complete in acetonitrile
Into, and all spectrum measure all at 25 DEG C after analyte addition effect 20min.Result is as shown in Figure 3.
From figure 3, it can be seen that other Common Anions existed in organism will not significantly interfere with probe to fluorine ion
Qualitative and quantitative is detected.
Embodiment 5
Probe (10 μM) is to 100 μM of test results of concentration NaF response times.First, the probe storing solution of 50 μ L is pipetted
(1mM) is put into 5mL colorimetric cylinders, and the acetonitrile of 4.5mL is added to it, then pipettes the NaF storing solutions (10mM) of 50 μ L, finally uses second
Nitrile is settled to 5mL, quickly shakes up, and timing is determined.Result is as shown in Figure 4.
Figure 4, it is seen that after NaF adds probe solution to react, its absorption intensity is that significant change, 20 points occur
Absorption intensity tends towards stability after clock.This elevated rapidity of absorption intensity illustrates that this probe can be completely used for fluorine with explicitly
The instant detection of ion.
Claims (8)
1. it is used to detect the colorimetric probe of fluorine ion, it has following structure
2. the method for preparing the colorimetric probe of claim 1, including by 2- cyanogen methylbenzothiazole, 4- tert-butyl diphenyls
Silica benzaldehyde and triethylamine are dissolved in ethanol, and stirring reaction is separated afterwards for a period of time at 15-25 DEG C.
3. method according to claim 2, wherein methods described is stirred at 15 DEG C and carried out.
4. method according to claim 2, wherein methods described is stirred at 25 DEG C and carried out.
5. method according to claim 2, wherein 2- cyanogen methylbenzothiazole and 4- tert-butyl diphenyl silica benzaldehydes
Mol ratio is 1：1-1：1.5.
6. method according to claim 2, the reaction time therein is 8-10 hours.
7. method according to claim 6, the reaction time therein is 8 hours.
8. method according to claim 2, separation therein includes filtering and chromatography.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187941B (en) * | 2016-07-27 | 2018-10-12 | 济南大学 | A kind of sensitive highly selective colorimetric probe that can identify inorganic mercury and organic mercury simultaneously |
| CN107365326B (en) * | 2017-07-24 | 2019-08-20 | 湖北大学 | It is a kind of for detecting the fluorescence probe and preparation method thereof of fluorine ion in living cells |
| CN107892675A (en) * | 2017-10-27 | 2018-04-10 | 陕西学前师范学院 | A kind of palladium ion probe and its preparation and application |
| CN107652968B (en) * | 2017-11-06 | 2019-11-12 | 北京理工大学 | A kind of peroxidating nitrosyl fluorescence probe and its preparation method and application |
| CN108623624A (en) * | 2018-06-12 | 2018-10-09 | 兰州大学 | A method of differentiating toothpaste with fluoride with probe S-F bore holes |
| CN110373181B (en) * | 2019-07-09 | 2021-05-04 | 济南大学 | Fluorescent probe for detecting fluorine ions |
| CN113390489B (en) * | 2021-04-28 | 2022-08-30 | 江苏新晖测控科技有限公司 | Dual-state adjustable probe for radar liquid level meter |
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| CN104449677A (en) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | Specific fluorescent probe for recognizing fluorine ions and application of specific fluorescent probe |
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| CN104449677A (en) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | Specific fluorescent probe for recognizing fluorine ions and application of specific fluorescent probe |
Non-Patent Citations (2)
| Title |
|---|
| A DFT/TDDFT study of the excited state intramolecular proton transfer based sensing mechanism for the aqueous fluoride chemosensor BTTPB;Jun-Sheng Chen et al.;《RSC Adv.》;20131107;第4卷;254-259 * |
| A Rapid Aqueous Fluoride Ion Sensor with Dual Output Modes;Rui Hu et al.;《Angew. Chem. Int. Ed.》;20101231;第49卷;4915-4918 * |
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Effective date of registration: 20201028 Address after: Room 207, 2 / F, building 5, No. 688, Bin'an Road, Changhe street, Binjiang District, Hangzhou City, Zhejiang Province Patentee after: Hangzhou Baiyu Biotechnology Co.,Ltd. Address before: 362200 Fujian city of Quanzhou province Jinjiang City Meiling Street Quanan Road No. 1003. Patentee before: Jinjiang shangjingfuben Environmental Protection Technology Co.,Ltd. |
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