CN105131935A - Rapid high-selectivity fluorine ion colorimetric probe and preparation method therefor - Google Patents
Rapid high-selectivity fluorine ion colorimetric probe and preparation method therefor Download PDFInfo
- Publication number
- CN105131935A CN105131935A CN201510534709.4A CN201510534709A CN105131935A CN 105131935 A CN105131935 A CN 105131935A CN 201510534709 A CN201510534709 A CN 201510534709A CN 105131935 A CN105131935 A CN 105131935A
- Authority
- CN
- China
- Prior art keywords
- probe
- fluorion
- fluorine ions
- colorimetric probe
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention relates to a rapid high-selectivity fluorine ion colorimetric probe and a preparation method therefor. The probe not only can highly selectively recognize fluorine ions, but also can quantitatively and qualitatively analyze the fluorine ions by way of observation in naked eyes. The probe can be used for quickly responding to the fluorine ions, so that the fluorine ions can be immediately detected. The probe is stable in property, and can be stored and used for a long time. In addition, the probe further can be used for quantitatively analyzing the fluorine ions by virtue of absorption spectroscopy and has relatively strong anti-interference capacity. The probe is synthesized by a room temperature method, requires only one step reaction, and is simple to synthesize.
Description
Technical field
The present invention relates to as fluorion colorimetric probe, its preparation method and it is to the application of the quick high-selectivity identification of fluorion.
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 invention provides 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).
Fig. 4 is probe (10 μMs) test result to 100 μMs of concentration NaF time of response.
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 general structure
Synthetic route and the method for above-mentioned fluorion colorimetric probe 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 ﹪.
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.
Embodiment 4
Different analyte (100 μMs) is on the impact of probe (10 μMs) absorption spectrum quantitative analysis fluorion (100 μMs).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.Result as shown in Figure 3.
As can be seen from Figure 3, other Common Anions existed in organism can not obviously disturb probe to detect the qualitative and quantitative of fluorion.
Embodiment 5
Probe (10 μMs) test result to 100 μMs of concentration NaF time of response.First, the probe storing solution (1mM) pipetting 50 μ L is put in 5mL colorimetric cylinder, adds the acetonitrile of 4.5mL to it, then pipettes the NaF storing solution (10mM) of 50 μ L, is finally settled to 5mL with acetonitrile, shakes up fast, and timing measures.Result as shown in Figure 4.
As can be seen from Figure 4, after NaF adds probe solution reaction, namely there is considerable change in its absorption intensity, after 20 minutes, absorption intensity tends towards stability.The rapidity that this absorption intensity raises and palpability illustrate that this probe may be used for the instant detection of fluorion completely.
Claims (8)
1., for detecting the colorimetric probe of fluorion, it has following structure
2. prepare the method for the colorimetric probe of claim 1, comprising 2-cyanobenzothiazole, 4-tert-butyl diphenyl siloxy phenyl aldehyde and triethylamine are dissolved in ethanol, be separated after stirring reaction for some time at 15-25 DEG C.
3. method according to claim 2, wherein said method stirs at 15 DEG C carries out.
4. method according to claim 2, wherein said method stirs at 25 DEG C carries out.
5. method according to claim 2, wherein the mol ratio of 2-cyanobenzothiazole and 4-tert-butyl diphenyl siloxy phenyl aldehyde is 1:1-1:1.5.
6. method according to claim 2, the reaction times is wherein 8-10 hour.
7. method according to claim 6, the reaction times is wherein 8 hours.
8. method according to claim 2, separation wherein comprises filtration and chromatography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510534709.4A CN105131935B (en) | 2015-08-27 | 2015-08-27 | Quick high-selectivity fluorine ion colorimetric probe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510534709.4A CN105131935B (en) | 2015-08-27 | 2015-08-27 | Quick high-selectivity fluorine ion colorimetric probe and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105131935A true CN105131935A (en) | 2015-12-09 |
| CN105131935B CN105131935B (en) | 2017-06-09 |
Family
ID=54717520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510534709.4A Expired - Fee Related CN105131935B (en) | 2015-08-27 | 2015-08-27 | Quick high-selectivity fluorine ion colorimetric probe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105131935B (en) |
Cited By (7)
| 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 |
| CN107365326A (en) * | 2017-07-24 | 2017-11-21 | 湖北大学 | It is a kind of to be used to detect fluorescence probe of fluorine ion and preparation method thereof in living cells |
| CN107652968A (en) * | 2017-11-06 | 2018-02-02 | 北京理工大学 | A kind of peroxidating nitrosyl fluorescence probe and its preparation method and application |
| 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 |
| 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 |
| CN110373181A (en) * | 2019-07-09 | 2019-10-25 | 济南大学 | A kind of fluorescence probe detecting fluorine ion |
| CN113390489A (en) * | 2021-04-28 | 2021-09-14 | 龙武 | Dual-state adjustable probe for radar liquid level meter |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-08-27 CN CN201510534709.4A patent/CN105131935B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| JUN-SHENG CHEN ET AL.: "A DFT/TDDFT study of the excited state intramolecular proton transfer based sensing mechanism for the aqueous fluoride chemosensor BTTPB", 《RSC ADV.》 * |
| RUI HU ET AL.: "A Rapid Aqueous Fluoride Ion Sensor with Dual Output Modes", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (10)
| 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 |
| CN107365326A (en) * | 2017-07-24 | 2017-11-21 | 湖北大学 | It is a kind of to be used to detect fluorescence probe of fluorine ion and preparation method thereof in living cells |
| 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 |
| CN107652968A (en) * | 2017-11-06 | 2018-02-02 | 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 |
| CN110373181A (en) * | 2019-07-09 | 2019-10-25 | 济南大学 | A kind of fluorescence probe detecting fluorine ion |
| CN110373181B (en) * | 2019-07-09 | 2021-05-04 | 济南大学 | Fluorescent probe for detecting fluorine ions |
| CN113390489A (en) * | 2021-04-28 | 2021-09-14 | 龙武 | Dual-state adjustable probe for radar liquid level meter |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105131935B (en) | 2017-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105131935A (en) | Rapid high-selectivity fluorine ion colorimetric probe and preparation method therefor | |
| Spichiger-Keller | Chemical sensors and biosensors for medical and biological applications | |
| Zhou et al. | Design principles of spectroscopic probes for biological applications | |
| Zeng et al. | A colorimetric and ratiometric fluorescent probe for quantitative detection of GSH at physiologically relevant levels | |
| Chao et al. | A ratiometric fluorescence probe for monitoring cyanide ion in live cells | |
| CN105181686B (en) | The method for detecting fluorine ion in environment | |
| CN105259229A (en) | Single-molecule analysis method for detecting medicine | |
| CN111039972B (en) | Application of 4-hydroxycarbazole compound as fluorine ion fluorescent probe | |
| CN108689933A (en) | A kind of hypochlorous fluorescence probe of quick high-selectivity analysis | |
| CN104132920A (en) | Method for measuring Ag<+> or F<-> through fluorescence quenching | |
| CN102633694B (en) | Fluorescent probe for detecting mercapto compounds as well as preparation method and using method of fluorescent probe | |
| CN105777607B (en) | A kind of double indoles salt compounded of iodine of triphenylamine and its synthetic method and application | |
| CN107417638B (en) | A kind of glutathione and cysteine fluorescence probe and preparation method thereof based on 7- nitrobenzofurazan | |
| CN109021000A (en) | A kind of fluorescence probe, synthetic method and application detecting hydrogen peroxide | |
| CN103063629B (en) | Detect the method for sodium/potassium ion ratio and kit and system | |
| CN105445241B (en) | The method that high selectivity detects hydrazine concentration | |
| CN108896750A (en) | A kind of preparation method and purposes of BSA-Au/Ag NCs/OPD/HRP proportional-type fluorescent optical sensor | |
| CN108169196B (en) | Method for rapidly detecting fluorine ions in environment | |
| CN105985291B (en) | A kind of colorimetric fluorescence probe of quick high-selectivity analysis fluorine ion | |
| CN104650105A (en) | Rhodamine B derivative containing 8-aminoquinoline group, preparation method, application and method for carrying out fluorescence analysis on Cr<3+> and Cu<2+> | |
| CN105153217A (en) | Efficient preparation method of colorimetric probe | |
| CN108801993A (en) | A kind of hypochlorous kit of quick high-selectivity analysis | |
| CN116217589A (en) | ONOO-and/or Na for early diagnosis of tumors 2 S 2 Application of fluorescent probe reagent | |
| CN106674048B (en) | A kind of CN- detection reagents and its synthetic method and application | |
| CN108623522A (en) | A kind of hypochlorous method of quick high-selectivity detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
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. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170609 Termination date: 20210827 |