CN105153217A - Efficient preparation method of colorimetric probe - Google Patents

Efficient preparation method of colorimetric probe Download PDF

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Publication number
CN105153217A
CN105153217A CN201510534774.7A CN201510534774A CN105153217A CN 105153217 A CN105153217 A CN 105153217A CN 201510534774 A CN201510534774 A CN 201510534774A CN 105153217 A CN105153217 A CN 105153217A
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fluorion
probe
tert
cyanobenzothiazole
reaction
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CN201510534774.7A
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CN105153217B (en
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叶龙武
郭艳
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Hangzhou Baiyu Biotechnology Co., Ltd
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Jinjiang Shangjing Fuben Environmental Protection Science & Technology Co Ltd
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Abstract

The invention relates to an efficient preparation method of a colorimetric probe. In the method, reaction temperature is 20 DEG C-100 DEG C; reaction time is 2h-10h; a molar ratio of a 4-tert-butyldiphenylsilyloxy benzaldehyde compound to a 2-cyanobenzothiazole compound is 1:1 to 5:1. The method enables efficient and quick synthesis of the colorimetric probe for measuring fluorine ions; this probe is capable of highly selectively recognizing the fluorine ions and also capable of quantitatively and qualitatively analyzing the fluorine ions with bare eyes. The method can be finished just at room temperature, requires only a single step of reaction and allows simplicity of synthesis.

Description

Efficiently prepare the method for colorimetric probe
Technical field
The present invention relates to the high efficiency preparation method of the 4-tert-butyl diphenyl siloxy styrene compound as fluorion colorimetric probe.
Background technology
In environmental and biological materials, negatively charged ion is ubiquitous, and it is present in air, water and soil in environment, is present in the organ of human body, cell, or even in enchylema, it plays extremely important role in environment and the ecosystem.And as fluorion minimum in negatively charged ion, be the essential element of biological life activity, important role in dental care and treatment osteoporosis etc.In order to contain enough fluorions in human body, it as a kind of important additive, is usually used in toothpaste, medicine and tap water by people.But excessive fluorine not only to hydrobiont and the toxic effect of plant, also can cause serious human health problems.The Sodium Fluoride (NaF) of such as higher concentration can disturb normal cellular metabolism.Acute absorption fluorine that is heavy dose of or absorption low dosage for a long time, can cause acute stomach trouble and kidney disorder, tooth and bone chronic poisoning, lithiasis, serious even can cause death.At present, the whole world still has many people drinking the water source containing high fluorine, and this creates threat to the health of the mankind.
Given this, study a kind of fluorion that can detect and exist and the method for content, have extremely important effect regardless of in the treatment of clinical disease, protection of the environment or academic research.Although the method detecting fluorion has a lot, unfortunately capillary electrophoresis sensitivity is low, the poor reproducibility of fluoride ion selective electrode, and the cost of fluorion nucleus magnetic resonance is high, seriously limits its application and development.Because colorimetric probe is simple to operate, with low cost, even molecular recognition signal can be converted to the change of color, not need expensive instrument directly can naked eye, therefore, colorimetric probe has significant advantage compared with other recognition methodss.
Summary of the invention
This area urgent need one prepares simple quick high-selectivity fluorion colorimetric probe, thus effectively can detect fluorion.For this reason, the present invention has synthesized the fluorion colorimetric probe of a class novelty, and its synthesis is simple, stability is high and/or selectivity is high, and/or can identify fluorion fast.
Specifically, the present invention relates to a kind of fluorion colorimetric probe, it is 4-tert-butyl diphenyl siloxy styrene compound.
Present invention also offers the preparation method of fluorion colorimetric probe, it is by corresponding 4-tert-butyl diphenyl siloxy compound of benzaldehyde category and 2-cyanobenzothiazole compounds being reacted obtained.
In the preparation method of fluorion colorimetric probe of the present invention, temperature of reaction is 20 ~ 100 DEG C; Reaction times is 2h ~ 10h; The mol ratio of 4-tert-butyl diphenyl siloxy compound of benzaldehyde category and 2-cyanobenzothiazole compounds is about 1:1 to 5:1.
Fluorion colorimetric probe of the present invention can act on fluorion, produces the change (change of simultaneous distinct colors) of absorption spectrum, thus realizes the detection by quantitative to fluorion.
Specifically, fluorion colorimetric probe of the present invention carries out acting on the obvious change that all can not cause absorption spectrum respectively with other negatively charged ion, thus the Selective recognition realized fluorion, and then optionally for getting rid of the existence of other negatively charged ion to the interference of the quantitative assay of fluorion.
Selectively, the good stability of fluorion colorimetric probe of the present invention, and then use can be preserved for a long time.
Further, fluorion colorimetric probe of the present invention is quick high-selectivity fluorion colorimetric probe, and synthesis is simple, is conducive to business-like applying.
Accompanying drawing explanation
Fig. 1 (Fig. 1 a and Fig. 1 b) is the impact of different concns NaF (0 ~ 200 μM) on probe (10 μMs) absorption spectrum.
Fig. 2 is the impact of different analyte (100 μMs) on probe (10 μMs) absorption spectrum.
Fig. 3 is the impact of different analyte (100 μMs) on probe (10 μMs) absorption spectrum quantitative analysis NaF (100 μMs).
Embodiment:
The present invention proposes the synthetic route of above-mentioned quick high-selectivity fluorion colorimetric probe, method and spectrum property thereof.
Fluorion colorimetric probe of the present invention is a class 4-tert-butyl diphenyl siloxy styrene compound, and it has following structure
Synthetic route and the method for fluorion colorimetric probe of the present invention are as follows:
The notable feature of quick high-selectivity identification fluorion colorimetric probe of the present invention can identify fluorion to quick high-selectivity, and/or accurately can carry out quantitative analysis to fluorion under the existence of other high concentration anionics.Importantly, fluorion colorimetric probe of the present invention can also carry out qualitative and quantitative analysis by the mode that " bore hole " observes.
Below will by illustrating in greater detail the present invention by following examples.Following examples are only illustrative, should be understood that the present invention not by the restriction of following embodiment.
Embodiment 1
174mg (1.0mmol) 2-cyanobenzothiazole, 361mg (1.0mmol) 4-tert-butyl diphenyl siloxy phenyl aldehyde and 50 μ L triethylamines are dissolved in 20mL ethanol by (scheme 1), at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains thick product, then mixed system (the v/v of methylene dichloride and sherwood oil is used, 1:1) carry out pillar layer separation, obtain faint yellow pure product 310mg, productive rate is 60 ﹪.
174mg (1.0mmol) 2-cyanobenzothiazole, 542mg (1.5mmol) 4-tert-butyl diphenyl siloxy phenyl aldehyde and 50 μ L triethylamines are dissolved in 20mL ethanol by (scheme 2), at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains thick product, then mixed system (the v/v of methylene dichloride and sherwood oil is used, 1:1) carry out pillar layer separation, obtain faint yellow pure product 372mg, productive rate is 72 ﹪.
174mg (1.0mmol) 2-cyanobenzothiazole, 542mg (1.5mmol) 4-tert-butyl diphenyl siloxy phenyl aldehyde and 50 μ L piperidines are dissolved in 20mL ethanol by (scheme 3), at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains thick product, then mixed system (the v/v of methylene dichloride and sherwood oil is used, 1:1) carry out pillar layer separation, obtain faint yellow pure product 419mg, productive rate is 81 ﹪.
174mg (1.0mmol) 2-cyanobenzothiazole, 722mg (2.0mmol) 4-tert-butyl diphenyl siloxy phenyl aldehyde and 50 μ L piperidines are dissolved in 20mL ethanol by (scheme 4), at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains thick product, then mixed system (the v/v of methylene dichloride and sherwood oil is used, 1:1) carry out pillar layer separation, obtain faint yellow pure product 455mg, productive rate is 88 ﹪.
174mg (1.0mmol) 2-cyanobenzothiazole, 1083mg (3.0mmol) 4-tert-butyl diphenyl siloxy phenyl aldehyde and 50 μ L piperidines are dissolved in 20mL ethanol by (scheme 5), at 25 DEG C after stirring reaction 8h, filtration under diminished pressure obtains thick product, then mixed system (the v/v of methylene dichloride and sherwood oil is used, 1:1) carry out pillar layer separation, obtain faint yellow pure product 481mg, productive rate is 93 ﹪.
1h-NMR (400MHz, CDCl 3) 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, CDCl 3) 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 C 32h 29n 2oSSi [M+H] +517; Measured value 517.
Embodiment 2
The present inventor has carried out following test: (a) different concns NaF (0 ~ 200 μM) is on the impact of probe (10 μMs) absorption spectrum; Linear relationship between the absorption intensity at (b) 485nm place and the NaF concentration (0,1,2,4,6,8,10,15,20,30,40,60 μMs) added.Said determination carries out in acetonitrile, and all spectrum tests all at 25 DEG C NaF add effect 20min after record.Result is see Fig. 1.
As can be seen from Figure 1, along with the increase of NaF concentration in probe solution, absorption spectrum raises gradually, and becomes good linear relationship with absorption value in 0 ~ 60 μM of NaF concentration range.Therefore, probe of the present invention more accurately can determine the content of fluorion in blood sample to be measured or environment.
Embodiment 3
Different analyte (100 μMs) is on the impact of probe (10 μMs) absorption spectrum.Analyte comprises: chlorion Cl -, bromide anion Br -, iodide ion I -, sulfate ion SO 4 2-, nitrate ion NO 3 -, nitrite ion NO 2 -, thiocyanate ion SCN -with fluorion F -, their concentration is 100 μMs.All test conditions complete in acetonitrile, and all spectrum all at 25 DEG C analyte add effect 20min after record.The probe storing solution (1mM) pipetting 50 μ L is put in 5mL colorimetric cylinder, then adds 3mL acetonitrile, then pipettes the above-mentioned analyte storing solution (10mM) of 50 μ L and add in colorimetric cylinder, is then settled to 5mL with acetonitrile.Shake up, leave standstill 20min, can measure.Result as shown in Figure 2.
As can be seen from Figure 2, probe has very high selectivity to fluorion, can react with fluorion in specific manner.In acetonitrile solution, compared with other analytes, so after probe and fluorion react, absorption spectrum is increased significantly; And organism in exist other Common Anions and probe effect after absorption intensity there is not considerable change.
Although with above embodiments describing the present invention, should be understood that, under the prerequisite not deviating from spirit of the present invention, the present invention can further modify and change, and these are modified and variation all belongs within protection scope of the present invention.

Claims (7)

1. for the preparation of the method for the detection probes of detection fluorion, it comprises and is dissolved in ethanol by 2-cyanobenzothiazole, 4-tert-butyl diphenyl siloxy phenyl aldehyde and triethylamine, be separated after stirring reaction for some time at 15-25 DEG C, wherein the equation of chemical reaction is as follows:
And wherein the mol ratio of 2-cyanobenzothiazole and 4-tert-butyl diphenyl siloxy phenyl aldehyde is 1:2 to 1:3.
2. method according to claim 1, wherein said method stirs at 25 DEG C carries out.
3. method according to claim 1, wherein the mol ratio of 2-cyanobenzothiazole and 4-tert-butyl diphenyl siloxy phenyl aldehyde is 1:2.
4. method according to claim 1, wherein the mol ratio of 2-cyanobenzothiazole and 4-tert-butyl diphenyl siloxy phenyl aldehyde is 1:3.
5. method according to claim 1, the reaction times is wherein 8-10 hour.
6. method according to claim 5, the reaction times is wherein 8 hours.
7. method according to claim 1, separation is wherein undertaken by filtration and chromatography.
CN201510534774.7A 2015-08-27 2015-08-27 The method for efficiently preparing colorimetric probe Active CN105153217B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187941A (en) * 2016-07-27 2016-12-07 济南大学 One can identify inorganic mercury and organomercurial sensitive high selectivity colorimetric probe simultaneously

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610955A (en) * 2014-05-16 2015-05-13 中南大学 Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610955A (en) * 2014-05-16 2015-05-13 中南大学 Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YU PENG ET AL.: "A Selective, Sensitive, Colorimetric, and Fluorescence Probe for Relay Recognition of Fluoride and Cu(II) Ions with "Off−On−Off" Switching in Ethanol−Water Solution", 《J. ORG. CHEM.》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187941A (en) * 2016-07-27 2016-12-07 济南大学 One can identify inorganic mercury and organomercurial sensitive high selectivity colorimetric probe simultaneously

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