CN1477385A - Synthesis of 2,6-diaminemethylpyridine derivative fluoescence chemical sensor molecule and its application - Google Patents
Synthesis of 2,6-diaminemethylpyridine derivative fluoescence chemical sensor molecule and its application Download PDFInfo
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- CN1477385A CN1477385A CNA031783511A CN03178351A CN1477385A CN 1477385 A CN1477385 A CN 1477385A CN A031783511 A CNA031783511 A CN A031783511A CN 03178351 A CN03178351 A CN 03178351A CN 1477385 A CN1477385 A CN 1477385A
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Abstract
The present invention relates to a method for synthesizing 2,6-diaminomethylpyridine derivative fluorescence chemical sensor molecule and its application. It can be used for making selective fluorescence enhancement identification of transition metal and heavy metal ions in the aqueoue solution, also can be used for making transion metal and heavy metal ion detection in the microenvironments of biological tissue cell, and subcellular organelle, and can be used for making transition metal and heavy metal ion detection in the water, sewage, emulsion and suspension system. The described compound can be fixedly loaded on the polymer or solid surface by means of reactive group in the fluorescence chemical sensor molecule.
Description
Technical field the present invention relates to 2, the synthetic and application in transition metal and heavy metal ion fluorescence enhancing identification of 6-diamines pyridine derivatives and analog fluorescence chemical sensor molecule.
Background technology transition metal and heavy metal are present in occurring in nature widely, and many elements wherein obtain widely applying in mankind's activity.Therefore, marked change has taken place in natural distribution in them, and this change produces very important influence to the sustainable development meeting of human society.Some elements wherein have irreplaceable effect in life process, and the other element just has very strong toxicity to life entity when low concentration very.The detection of these materials all has great importance to life, environment and medical science and worker, agricultural production etc.
The fluorescence chemical sensor detection technique is applied to the detection of transition metal and heavy metal ion, can realize the original position of microenvironment, detection in real time.But make the fluorophore cancellation because transition metal and heavy metal ion can shift by spin an orbit coupling and electronics or energy usually, cause detection sensitivity to descend.In addition, the solvation tendency of the identification base of metallic ion and fluorescence chemical sensor molecule in aqueous solution is better than organic solvent, and the bonding properties of fluorescence chemical sensor molecule and object ion is descended.But the fluorescence chemical sensor molecule that in fact, can use in aqueous solution just has wide practical value.In sum, design, synthesize and in aqueous solution, to have optionally, and can realize that the fluorescence chemical sensor molecule that fluorescence strengthens still is a challenging research work.Present existing a few successful example is based on all that macrocyclic compound such as crown ether realizes.The example that the fluorescence probe that the fluorescence of the non-crown compound that some chemical reactions of inducing based on metallic ion realize strengthens is also arranged, but that these reactions can not realize is reversible fast, that is to say that this fluorescence probe system can not realize real-time detection.
At present, owing to contain the synthetic more complicated of heteroatomic crown ether-like macrocyclic compound in the prior art, therefore, design the molecular compound of fluorescence chemical sensor that a class formation is simple relatively, be easy to synthesize, in various solution, suiting especially, the selectivity fluorescence to transition metal and heavy metal ion strengthens identification in aqueous solution, becomes the main target that the present invention will solve.
Summary of the invention the present invention is used for 2 of transition metal and heavy metal ion selectivity fluorescence enhancing identification detection, 6-diamines pyridine derivatives fluorescence chemical sensor molecule, and this compound has following general structure:
In the formula: R
1, R
2, R
3=hydrogen, halogen, C
1-C
12Alkyl, C
1-C
12Alkoxy, carboxyl, ester group, hydroxyl, phenyl; X
1, X
2=nitrogen-atoms; F
1, F
2=1-2 fluorescent chromophore; Q
1, Q
2=C
1-C
12Alkylidene.
In the molecular compound of fluorescence chemical sensor structure of above-mentioned general formula, the open-chain structure with certain semi-rigid conformation; The identification base that has a plurality of nitrogen-atoms helps discerning the selective binding of base to the metallic ion of certain radius and electronics composition; The two ends of molecule are connected with fluorescent chromophore, and these two fluorescent chromophores are controlled by the nitrogen-atoms of discerning base section by photoinduction electron transfer (PET).When the nitrogen-atoms in the identification base combined with metallic ion, the PET process was blocked, and two fluorescent chromophores brighten simultaneously, helped improving identification sensitivity.Can form base and swash the fluorophore of forming compound maybe the fluorophore of resonance energy transfer can take place the time when select connecting two, this fluorescence chemical sensor molecule can not only show the switch effect, abundanter change in fluorescence can occur simultaneously.Fluorescence chemical sensor molecule with 4-amido naphthalimide fluorophore is an example, connect base and then adopt semirigid piperazine ring, this is to be beneficial to the electron transfer of system owing to consider the rigidity that fluorescent chemicals should have an appropriateness, and have help weaken since transition metal ion near the fluorophore in the compound and contingent cancellation effect; Have certain flexibility simultaneously so that when complexation of metal ions, can make suitable configuration adjustment, increase the ability of complexing, detect lower limit thereby reduce.The amino that links to each other with aromatic ring on the piperazine ring becomes the electron-donating group of fluorescent chromophore, then as the part of the electron donor and the metallic ion combined function group of photoinduction electron transfer, the hexatomic ring skeleton is as the path of photoinduction electron transfer for fats portion.
4-amido naphthalimide fluorophore is one to be pushed away by force-La electron system fluorophore, has very high fluorescence quantum yield and big Stokes (Stokes) displacement.Electronics position one side that pushes away at fluorescent chromophore links to each other with identification division (being identified the acceptor portion of thing) by connecting base, and such structure helps electron donor to chromophoric transfer.
4-amido naphthalimide fluorophore is a fluorophore that is easy to synthetic multiple derivant, connects chain alkyl on the naphthalimide nitrogen-atoms and helps by hydrophobic interaction, makes the identification base section near cyclic conformation, helps identification.Certainly, the introducing of chain alkyl can cause the hydrophobicity of whole fluorescence chemical sensor molecule, but can be by the application in the micella solubilising realization aqueous solution.On the naphthalimide nitrogen-atoms, connect 2-(2-hydroxy ethoxy) ethyl reactive group, the water wettability that helps whole fluorescence chemical sensor molecule, not only be convenient to the application of fluorescence chemical sensor molecule in aqueous solution, and further the deriving and the immobilized reaction active groups that provides of this molecule is provided, immobilizedly on polyester, polyethers, olefin copolymer, make sensor component.
Fluorescence chemical sensor molecule involved in the present invention, can be easily by being with the fluorescent chemicals and 2 of reaction active groups such as primary amine groups, secondary amine, 6-dichloromethyl pyridine (2,6-two bromo methyl cycloheptapyridines, 2,6-two (pyrovinic acid METH) pyridine etc.) and derivant condensation thereof obtain.
Fluorescence chemical sensor molecule of the present invention can be measured metallic ion in the mixed solution of water, organic solvent (as methyl alcohol, ethanol, b propanol, acetonitrile etc.) and water and alcohol.The compound in the mixed solvent of second alcohol and water (1: 9) (in the trishydroxymethylaminomethane of 0.01M-HCl buffer solution) synthetic as embodiment 3 is at multiple metallic ion such as Hg
2+, Cd
2+, pb
2+, Ag
+, Zn
2+, K
+, Na
+, Mg
2+, Ca
2+, Cr
3+, Fe
3+, Cu
2+, Co
2+, Ni
2+Deng in, to Hg
2+Show fabulous selectivity fluorescence and strengthen identification (fluorescence strengthens about 10 times).From present open report, Hg of the present invention
2+The fluorescence chemical sensor molecule be one of a few the most successful example, and, be wherein unique fluorescence chemical sensor molecule with the simple identification of big ring based structures such as non-crown ether.
Description of drawings Fig. 1 is the fluorogram when adding the variable concentrations mercury ion; Wherein: ordinate FI is a fluorescence intensity, and abscissa Em/nm is an emission wavelength.Fig. 2 is the relation of ion concentration of mercury and fluorescence intensity; Wherein ordinate is a fluorescence intensity, abscissa [Hg
2+]/10
-5Mol/L is an ion concentration of mercury.Fig. 3 is the influence of coexistent metallic ion to mercury identification; Wherein: ordinate FI is a fluorescence intensity, and abscissa is a coexistent metallic ion.
The present invention's design, a class 2 of synthesizing, 6-diamines pyridine derivatives fluoescence chemical sensor molecule has the structure phase To simply, synthetic method is easy, and the selective fluorescence to transition metal and heavy metal ion in the aqueous solution strengthens the identification spirit Quick, and can realize the characteristics such as device, both it can be applied in biological tissue, cell, and the microenvironment such as subcellular organelle in Transition metal and detection of heavy metal ion; Also can be by the reactive group in the fluoescence chemical sensor molecule that it is immobilized On polyester, polyethers, olefin copolymer, realize device.
Embodiment
Embodiment 1
The compound (1) of 149mg (0.44mmol) is dissolved in the 30mL acetonitrile, adds 35.2mg (0.20mmol) 2 then, 6-dichloromethyl pyridine.Stir reflux 10 hours, cooling, standing over night then.Leach yellow solid from reaction mixture, separate with column chromatography, obtaining product (2) is yellow solid, yield 77%, fusing point: 233.8-235.5 ℃.
1H?NMR(CDCl
3，400M)δ0.97(t，6H，J＝7.4Hz)，1.44(m，4H，)，1.71(m，4H，)，2.88(s，8H)，3.34(s，8H)，3.86(s，4H)，4.17(t，4H，j＝7.6)，7.21(d，J＝8Hz，2H)，7.43(d，J＝8Hz，2H)，7.67(t，J＝8Hz，2H)，7.72(t，J＝8Hz，1H)，8.41(d，J＝8Hz，2H)，8.50(d，J＝8Hz，2H)，8.56(d，j＝8Hz，2H)。
The compound (3) of 198mg (0.44mmol) is dissolved in the 20mL acetonitrile, adds 35.2mg (0.20mmol) 2 then, 6-dichloromethyl pyridine.Stir reflux 10 hours, cooling, standing over night then.Leach yellow solid from reaction mixture, separate with column chromatography, obtaining product (4) is yellow solid, yield 80%, fusing point: 122.9-123.9 ℃.
1H?NMR(CDCl
3，400M)，δ0.87(t，6H，J＝6.8Hz)，1.24-1.41(m，36H，)，1.71(m，4H)，2.89(s，8H)，3.34(s，8H)，3.87(t，4H)，4.15(t，4H，j＝7.6)，7.21(d，J＝8Hz，2H)，7.43(d，J＝8Hz，2H)，7.67(t，J＝8Hz，2H)，7.72(t，J＝8Hz，1H)，8.41(d，J＝gHz，2H)，8.50(d，J＝8Hz，2H)，8.56(d，J＝8Hz，2H)。
Embodiment 3
The compound (5) of 163mg (0.44mmol) is dissolved in the 50mL acetonitrile, adds 35.2mg (0.20mmol) 2 then, 6-dichloromethyl pyridine.Stir reflux 10 hours, cooling, standing over night then.Leach yellow solid from reaction mixture, separate with column chromatography, obtaining product (6) is yellow solid, yield 82%, fusing point: 115.6-117.4 ℃.
1H?NMR(CDCl
3，400M)，δ2.89(s，8H)，3.35(s，8H)，3.66(s，4H)，3.68(s，4H)，3.85(t，J＝5.3，4H)，3.86(s，4H，)，4.43(t，4H，j＝5.4)，7.21(d，J＝8Hz，2H)，7.42(d，J＝8Hz，2H)，7.67(t，J＝8Hz，2H)，7.72(t，J＝8Hz，1H)，8.41(d，J＝8Hz，2H)，8.50(d，J＝8Hz，2H)，8.56(d，J＝8Hz，2H)。
Compound among the embodiment 3 (6) is dissolved in the mixed solvent (1: 9) of second alcohol and water, and compound concentration is 1.0 * 10
-5The buffer solution of the trihydroxy methyl nitrogen methylmethane hydrochloride (0.01M) of mol/L, measure its fluorescence: excitation wavelength is 410nm, maximum emission wavelength is 540nm (Fig. 1).Fluorescence intensity increases thereupon when adding the mercuric salt of different amounts.As can be seen from Figure 2 have between reasonable linear zone between mercury salt concentration and the fluorescence intensity, and excessive mercury salt does not cause cancellation yet.
Under the test condition among the embodiment 4, study the disturbed condition of other metallic ion to compound (6) identification mercury.Mercury ion and compound (6) concentration is 1.0 * 10
-5Mol/L adds 1.0 * 10 respectively
-5Mol/L and 5.0 * 10
-5The Zn of mol/L
2+, Cr
3+, Ag
+, Ca
2+, Fe
3+, pb
2+, Mg
2+, Co
2+, Ni
2+, Cu
2+, Cd
2+, K
+, by the discovery of comparing with the contrast experiment who does not add interfering ion, interfering ion to the influence of fluorescence intensity 15% with interior (Fig. 3).As seen fluorescence chemical sensor molecule of the present invention is to Hg
2+, the good selectivity that has.Compare Hg at other metallic ion
2+Do not produce remarkable interference during 5 times of concentration excess yet.
Claims (5)
1, a class is characterized in that by the molecular compound of fluorescence chemical sensor that semi-rigid open-chain structure, recognition group and fluorescent chromophore constitute this compounds has following general structure
In the formula: R
1, R
2, R
3=hydrogen, halogen, C
1-C
12Alkyl, C
1-C
12Alkoxy, carboxyl, ester group, hydroxyl, phenyl; X
1, X
2=nitrogen-atoms; F
1, F
2=1-2 fluorescent chromophore; Q
1, Q
2=C
1-C
12Alkylidene.
2,, it is characterized in that and on polyester, polyethers, olefin copolymer, to make sensor component with 2-(2-hydroxy ethoxy) the ethyl reactive group that connects on the fluorescent chromophore naphthalimide nitrogen-atoms in this compound is immobilized according to the described molecular compound of fluorescence chemical sensor of claim 1.
3, a class has the purposes of the described molecular compound of fluorescence chemical sensor of claim 1, it is characterized in that this compounds can be used for biological tissue, cell, subcellular organelle, water, industry and sanitary sewage, organic solvent, emulsion, transition metal in the suspending liquid and heavy metal ion selectivity fluorescence strengthen identification and detect.
4,, it is characterized in that organic solvent is methyl alcohol, ethanol, b propanol, the mixed solvent of acetonitrile and water and alcohol according to the purposes of the described molecular compound of fluorescence chemical sensor of claim 3.
5,, it is characterized in that transition metal and heavy metal ion are Hg according to the purposes of the described molecular compound of fluorescence chemical sensor of claim 3
2+, Cd
2+, Pb
2+, Ag
+, Zn
2+, Cr
3+, Fe
3+, Cu
2+, Co
2+, Ni
2+
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|---|---|---|---|
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|---|---|---|---|
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| CN100483112C (en) * | 2006-05-19 | 2009-04-29 | 湖南大学 | Fluorescent chemical sensor for detecting water content in organic solvent and application thereof |
| CN101343538B (en) * | 2008-08-25 | 2011-03-23 | 华东理工大学 | Fluorescence silica gel particle and uses thereof |
| CN102190670A (en) * | 2011-03-22 | 2011-09-21 | 中国科学院理化技术研究所 | Fluorescence chemical sensor and preparation method and application thereof |
| CN102746452A (en) * | 2012-07-18 | 2012-10-24 | 浙江大学 | Fluorescent sensor for detecting hydrosulfate ions as well as preparation method and application thereof |
| CN104558972A (en) * | 2015-02-12 | 2015-04-29 | 齐齐哈尔大学 | Fluorescence sensing membrane for detecting Fe<3+> as well as preparation method and application of fluorescence sensing membrane |
| CN104977237A (en) * | 2015-07-01 | 2015-10-14 | 北京理工大学 | Method used for in-situ detection of CO2 generation rate in organelles of single living cell |
| CN107501178A (en) * | 2017-08-24 | 2017-12-22 | 西南大学 | Naphthalimide analog derivative and its preparation method and application |
| KR101815791B1 (en) * | 2016-11-15 | 2018-01-05 | 숙명여자대학교산학협력단 | Bis(naphthalimide-piperazine) derivative, method for preparing the same and method for detecting strong acid using the same |
| CN107602449A (en) * | 2017-09-12 | 2018-01-19 | 常州工程职业技术学院 | A kind of preparation and application of the Zn complex fluorescence probe with graphite-like structure |
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2003
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Cited By (14)
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| CN100483112C (en) * | 2006-05-19 | 2009-04-29 | 湖南大学 | Fluorescent chemical sensor for detecting water content in organic solvent and application thereof |
| CN101343538B (en) * | 2008-08-25 | 2011-03-23 | 华东理工大学 | Fluorescence silica gel particle and uses thereof |
| CN102190670A (en) * | 2011-03-22 | 2011-09-21 | 中国科学院理化技术研究所 | Fluorescence chemical sensor and preparation method and application thereof |
| CN102190670B (en) * | 2011-03-22 | 2013-11-20 | 中国科学院理化技术研究所 | Fluorescence chemical sensor and preparation method and application thereof |
| CN102746452A (en) * | 2012-07-18 | 2012-10-24 | 浙江大学 | Fluorescent sensor for detecting hydrosulfate ions as well as preparation method and application thereof |
| CN102746452B (en) * | 2012-07-18 | 2014-01-15 | 浙江大学 | Fluorescent sensor for detecting hydrosulfate ions as well as preparation method and application thereof |
| CN104558972A (en) * | 2015-02-12 | 2015-04-29 | 齐齐哈尔大学 | Fluorescence sensing membrane for detecting Fe<3+> as well as preparation method and application of fluorescence sensing membrane |
| CN104558972B (en) * | 2015-02-12 | 2016-08-10 | 齐齐哈尔大学 | One is used for detecting Fe3+fluorescence sense film and preparation method thereof |
| CN104977237A (en) * | 2015-07-01 | 2015-10-14 | 北京理工大学 | Method used for in-situ detection of CO2 generation rate in organelles of single living cell |
| CN104977237B (en) * | 2015-07-01 | 2018-02-23 | 北京理工大学 | CO in a kind of in situ detection single living cell inner cell organ2The method of generating rate |
| KR101815791B1 (en) * | 2016-11-15 | 2018-01-05 | 숙명여자대학교산학협력단 | Bis(naphthalimide-piperazine) derivative, method for preparing the same and method for detecting strong acid using the same |
| CN107501178A (en) * | 2017-08-24 | 2017-12-22 | 西南大学 | Naphthalimide analog derivative and its preparation method and application |
| CN107501178B (en) * | 2017-08-24 | 2020-07-28 | 西南大学 | Naphthalimide derivative and preparation method and application thereof |
| CN107602449A (en) * | 2017-09-12 | 2018-01-19 | 常州工程职业技术学院 | A kind of preparation and application of the Zn complex fluorescence probe with graphite-like structure |
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| Publication number | Publication date |
|---|---|
| CN1237050C (en) | 2006-01-18 |
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