CN102313726A - Fluorescent reagent for detecting specificity of aluminium ions based on aggregation-induced emission principle - Google Patents
Fluorescent reagent for detecting specificity of aluminium ions based on aggregation-induced emission principle Download PDFInfo
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- CN102313726A CN102313726A CN201110220408A CN201110220408A CN102313726A CN 102313726 A CN102313726 A CN 102313726A CN 201110220408 A CN201110220408 A CN 201110220408A CN 201110220408 A CN201110220408 A CN 201110220408A CN 102313726 A CN102313726 A CN 102313726A
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- aluminium ion
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Abstract
The invention discloses a fluorescent reagent for detecting specificity of aluminium ions based on an aggregation-induced emission principle. The fluorescent reagent is represented as sodium4-(2, 5-diphenyl-1H-pyrrole-1-yl)benzoate (TriPP-COONa). The fluorescent reagent has fluorescence enhancement specific response to the aluminium ions, has the detection limit of 1 mu M (27 mu g/ L) which is lower than the aluminium ion concentration (no higher than 200 mu g/ L) in drinking water stipulated by the World Health Organization, is free of the interference of other ions, such as K+, Mg2+, Ca2+, Ba2+, Ni2+, and has short response time. The fluorescence intensity of the fluorescent reagent has good linear relationship within the aluminium ion concentration range of 1 mu M to 11 mu M. According to the linear equation in the invention, the quantitive detection of the concentration of aluminium ions in the water sample can be realized conveniently and rapidly.
Description
Technical field
The present invention is based on " aggregation inducing is luminous " principle, relate to and a kind ofly have high selectivity, high sensitivity, fast quantification and detect aluminum ions fluorescent reagent and detection method thereof.
Background technology
The content of aluminium element in the earth's crust is only second to oxygen and silicon, occupies the 3rd, is the abundantest metallic element of content in the earth's crust, and it is closely bound up that it uses lives very extensive again and people.If often drink the water that aluminium salt purified, eat the food that contains aluminium salt, like deep-fried twisted dough sticks (100 grams contain 0.33 gram alum in the deep-fried twisted dough sticks approximately), bean jelly, canned beverage etc., or often use aluminum saucepan, all be easy to make aluminium element in human body, to accumulate gradually.And the toxicity that aluminium ion causes slowly, be difficult for discovering.When running up to a certain degree, will produce neurotoxicity, consequence will be very serious.Researcher finds that very early excessive aluminium ion has very big harm to human body.Many achievements in research confirmed aluminium ion run up in vivo a certain amount of after, will damage nervous system, thereby influence function of brain cell, cause decrease of memory, thinking ability is blunt.For a long time, have neurovirulent aluminium ion and be considered to one of inducement of senile dementia (R.A.Yokel, Fundam.Appl.Toxicol.1987,9,795-806; V.Bernuzzi, D.Desor, P.R.Lehr, Teratology.1989,40,21-27; G.Muller, V.Bernuzzi, D.Desor, et al., Teratology.1990,42,253-261; J.M.Donald, M.S.Golub, et al., Neurotoxicol.Teratol.1989,11,341-351; M.Golub, M.E.Gershwin, et al., Fundam.Appl.Toxicol.1987,8,346-357; E.House, J.Collingwood, A.Khan, O.Korchazkina, G.Berthon, C.J.Exley, Alzheimer ' s Dis.2004,6,291-301; G.McAdam, P.J.Newman, I.McKenzie, C.Davis, et al., Struct.Health Monit.2005,4,47-56).Aluminum ions concentration must not surpass 200 μ g/L in World Health Organization's regulation potable water for this reason.Therefore, in order effectively to prevent the harm of aluminium element, just become very important for aluminum ions detection to human health.
In the past for the fluoroscopic examination of metallic ion based on following several kinds of theories and method: (1) photoinduction electric charge shifts (PET); (2) FRET effect; (3) heavy metal atom quenching effect.Because shortcomings such as these detection method sensitivity are low, poor selectivity, the synthetic complicacy of used detectable still are in test, development stage so far, do not spread in the middle of the practical application always.Ion detection means commonly used now often need be leaned on expensive instruments such as atomic absorption spectrum, X-ray fluorescence spectra, and cost is too high, and time and effort consuming.In order to solve above-mentioned variety of problems, the present invention provides one to synthesize simply, and response has the quantitative aluminium ion detection means of high sensitivity and high selectivity rapidly simultaneously.
Summary of the invention:
The fluorescent chemicals 4-that the present invention designed (2,5-diphenyl-1H-pyrroles-1-yl)-Sodium Benzoate (Sodium 4-(2,5-diphenyl-1H-pyrrol-1-yl) benzoate is hereinafter to be referred as TriPP-COONa) structural formula is following:
1H NMR (400MHz, D
2O/d8-tetrahydrofuran): δ 8.02-8.00 (d, 2H), 7.29-7.28 (d, 6H), 7.18-7.16 (d, 4H), 7.09-7.07 (d, 2H), 6.52 (s, 2H) explain as follows to TriPP-COONa with by the characteristic of the prepared fluorescent reagent of this compound:
(1) 1,2,5 the pyrroles have connected a phenyl ring that can rotate freely respectively, and this makes this compound in solution, absorb the energy of excited state molecule owing to rotating in the singly-bound, makes fluorescent quenching thereby cause non-radiative energy to shift.
(2) after TriPP-COONa assembled, intermolecular interaction was restricted rotating freely of phenyl ring, thereby the non-radiative energy that has hindered excited state molecule shifts, and causes fluorescence to strengthen (being that aggregation inducing is luminous) greatly.
(3) TriPP-COONa contains the carboxylic acid sodium structure, gives this compound certain water-soluble, and this fluorescent reagent can directly be used for water sample detection, and is simple and practical, and is low to environment, man body pollution.Fluorescent reagent provided by the present invention can be selected water and tetrahydrofuran, water and ethanol, water and the preparation of acetone equal solvent of different proportion as required; In instance of the present invention; Fluorescent reagent is prepared according to water and tetrahydrofuran volume ratio at 3: 1; Still have fluorescence for the aluminium ion of 1 μ M (27 μ g/L) concentration and strengthen response, be far smaller than aluminum ions concentration standard (200 μ g/L) in the potable water of health organization regulation.And this reagent fluorescence intensity presents the good linear relation in 1 μ M to 11 μ M aluminium ion concentration scope.
(4) the TriPP-COONa synthetic method is simple, and productive rate is high, and raw materials cost is cheap, possesses the industrialization advantage.
(5) water-tetrahydrofuran solution of TriPP-COONa has specific fluorescence response for aluminium ion; The carboxylate radical electrostatic coupling effect of aluminium ion and TriPP-COONa that has three positive charges is very strong; Water-soluble variation after the coupling; Be easy to form the suspended particle of aggregative state, and the interior rotation of aggregative state molecule is restricted, will causes the fluorescence signal of this fluorescent reagent to strengthen greatly.For other metallic ions such as K
+, Mg
2+, Ca
2+, Ce
2+, Hg
2+, Fe
3+, Ag
+, Cu
2+, Cr
2+, Ba
2+, Ni
2+, Pb
2+, Zn
2+, owing to reasons such as its good water solubility or heavy atom quenching effect all do not have tangible fluorescence response.
(6) TriPP-COONa fluorescent reagent provided by the invention is based on the luminous principle of aggregation inducing that causes with aluminum ions electrostatic coupling effect; This gathering (deposition) process is compared many rapidly with processes such as ligand complex, hydrogen bond action or chemical reactions; Therefore very fast for aluminum ions detection response; Its fluorescence intensity almost just has significant enhancing in the aluminum ions while of introducing, reaches an effect of response fast.
(7) the fluorescent reagent antijamming capability by the TriPP-COONa preparation is stronger, under the situation of different kinds of ions coexistence, still can realize well aluminum ions specificity fluorescent identification.
In sum, TriPP-COONa fluorescent reagent provided by the present invention has specificity fluorescent identification preferably for aluminium ion, and the preparation method is simple; With low cost, detection time is rapid, and effect is obvious; Pollution to environment and human body is less, is a kind of convenient and practical fluorescent reagent.
Description of drawings
Fig. 1: the fluorogram in TriPP-COONa fluorescent reagent (100 μ M) after the adding 50 μ M different ions.From left to right be Zn successively
2+, Pb
2+, Cr
2+, Ba
2+, Cu
2+, Mg
2+, Al
3+, Ca
2+, Ni
2+, Ce
2+, Ag
+, K
+, Fe
3+, Hg
2+
Fig. 2: the fluorescence intensity of TriPP-COONa fluorescent reagent (100 μ M) is change curve in time.
Fig. 3: fluorogram (a) and the linear relationship typical curve (b) 1 μ M-11 μ M concentration range in of TriPP-COONa fluorescent reagent (100 μ M) under the different aluminum ion concentration.
Fig. 4: in TriPP-COONa fluorescent reagent (100 μ M), add 50 μ M Al
3+With the fluorescence intensity figure that records behind the interfering ion.From left to right be successively: Al
3+, Al
3++ K
+, Al
3++ Mg
2+, Al+Ba
2+, Al
3++ Ni
2+, Al
3++ K
+, Mg
2+, Ca
2+, Ba
2+, Ni
2+
Embodiment:
Instance 1: selectivity identification test
Get the volumetric flask of a 100ml, press the TriPP-COONa solution of volume ratio preparation in 1: the 3 100 μ M of tetrahydrofuran and water, get 4ml solution, inject 50 μ M different ions respectively.14 kinds of ions of this experimental selection (disturb test sample all to adopt the nitrate solution of metal for getting rid of negative ion) as follows: Al
3+, K
+, Mg
2+, Ca
2+, Ce
2+, Hg
2+, Fe
3+, Ag
+, Cu
2+, Cr
2+, Ba
2+, Ni
2+, Pb
2+, Zn
2+Compare the power of the fluoroscopic examination signal of different ions for ease, the maximum emission intensity that we will contain the fluorescent reagent of different ions is depicted as histogram (excitation wavelength 326nm), sees Fig. 1.
Instance 2: detection time test
Get the TriPP-COONa fluorescent reagent that 4ml instance 1 is provided; At first measure the fluorescence intensity that adds aluminium ion blank fluorescent reagent before; Inject the aluminium ion of 50 μ M then to it; Survey its fluorescence intensity at once, whenever surveyed first order fluorescence intensity till the fluorescence intensity of this fluorescent reagent no longer significant change takes place subsequently at a distance from 30 seconds.The fluorescence that this instance records changing trend diagram is in time seen Fig. 2.
Instance 3: detection by quantitative test
Get the TriPP-COONa fluorescent reagent that instance 1 is provided; Increase aluminum ions concentration (from 1 μ M to 28 μ M) gradually; Excite the fluorogram of a series of fluorescent reagents that obtain to see Fig. 3 (a) at the 326nm place; The embedded little figure in the upper left corner is the fluorescence intensity changing trend diagram at maximum emission wavelength 460nm place, and 1 μ M sees Fig. 3 (b) to the linear relationship chart in the 11 μ M concentration ranges.
Instance 4: polyion interference test
In order to test the antijamming capability of the fluorescent reagent that this invention provides, we have introduced 5 kinds of interfering ions, are respectively K
+, Mg
2+, Ca
2+, Ba
2+, Ni
2+, be made into the TriPP-COONa fluorescent reagent of 100 μ M according to the compound method in the instance 2, in 6 test tubes of label 1-6, accurately add the above-mentioned fluorescent reagent of 4ml respectively, accurately in test tube 1-6, inject the Al of 50 μ M subsequently respectively
3+And K
+, the Al of 50 μ M
3+And Mg
2+, the Al of 50 μ M
3+And Ca
2+, the Al of 50 μ M
3+And Ba
2+, the Al of 50 μ M
3+And Ni
2+And 50 μ M Al
3+With whole interfering ions, excite in the 326nm wavelength, the fluorescence intensity that records is seen Fig. 4.
Replace distilled water preparation fluorescent reagent under the 326nm excitation wavelength, to measure its fluorescence intensity water sample (this laboratory tap water); The linear function that obtains according to instance 3 calculates aluminum ions content below 1 μ M (27 μ g/L), meets the standard (200 μ g/L) of the World Health Organization (WHO).
Claims (5)
1. quantitative aluminium ion fluorescence detection method; It is characterized in that with following compound 4-(2; 5-diphenyl-1H-pyrroles-1-yl)-Sodium Benzoate (the prepared fluorescent reagent of sodium4-(2,5-diphenyl-1H-pyrrol-1-yl) benzoate is called for short TriPP-COONa).
This compound has the aggregation inducing emitting characteristics, and is promptly not luminous in solution, assembling
The characteristic that fluorescence strengthens under the attitude.
2. according to the aluminium ion investigating method of claim 1, the concentration that it is characterized in that the TriPP-COONa fluorescent reagent is 10
-4M.
3. according to the aluminium ion investigating method of claim 1, it is characterized in that preparing the TriPP-COONa fluorescent reagent, the ratio of water and tetrahydrofuran is 3: 1.
4. according to the described aluminium ion fluorescence detection method of claim 1,2 and 3, it is characterized in that aluminum ions detectability is reached WHO standard (200 μ g/L).
5. according to the described aluminium ion fluorescence detection method of claim 1,2 and 3, it is characterized in that:
Fluorescence increases than in aluminium ion concentration 1 μ M-11 μ M scope, presenting linear relationship.
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| CN104194771A (en) * | 2014-08-08 | 2014-12-10 | 北京理工大学 | Fluorescent reagent for trace serum albumin, and preparation and application of fluorescent reagent |
| CN107011244A (en) * | 2017-04-20 | 2017-08-04 | 北京理工大学 | Benzocyclobutane diene with AEE effects and azole derivatives and its preparation |
| CN108675952A (en) * | 2018-06-21 | 2018-10-19 | 北京理工大学 | Polyaryl replaces the fluorescent chemicals and preparation method thereof of fulvene and pyrrole structure |
| CN108864056A (en) * | 2018-08-03 | 2018-11-23 | 北京理工大学 | Near infrared fluorescent compound and its preparation method and application with AIE performance |
| CN111307773A (en) * | 2020-03-13 | 2020-06-19 | 北京理工大学 | Application of fluorescent compound in detecting and/or distinguishing natural plant compounds |
-
2011
- 2011-08-03 CN CN201110220408A patent/CN102313726A/en active Pending
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| CN104194771A (en) * | 2014-08-08 | 2014-12-10 | 北京理工大学 | Fluorescent reagent for trace serum albumin, and preparation and application of fluorescent reagent |
| CN104194771B (en) * | 2014-08-08 | 2016-05-25 | 北京理工大学 | The albuminous fluorometric reagent of a kind of detection Small Volume Serum, preparation method and application |
| CN104178133A (en) * | 2014-08-19 | 2014-12-03 | 北京理工大学 | Fluorescent material capable of visual detection of ammonia gas as well as preparation method and application of fluorescent material |
| CN104178133B (en) * | 2014-08-19 | 2017-01-25 | 北京理工大学 | Fluorescent material capable of visual detection of ammonia gas as well as preparation method and application of fluorescent material |
| CN107011244A (en) * | 2017-04-20 | 2017-08-04 | 北京理工大学 | Benzocyclobutane diene with AEE effects and azole derivatives and its preparation |
| CN107011244B (en) * | 2017-04-20 | 2019-06-28 | 北京理工大学 | Benzocyclobutane diene with AEE effect and azole derivatives and its preparation |
| CN108675952A (en) * | 2018-06-21 | 2018-10-19 | 北京理工大学 | Polyaryl replaces the fluorescent chemicals and preparation method thereof of fulvene and pyrrole structure |
| CN108675952B (en) * | 2018-06-21 | 2021-07-13 | 北京理工大学 | Fluorescent compound with polyaryl substituted fulvene pyrrole structure and preparation method thereof |
| CN108864056A (en) * | 2018-08-03 | 2018-11-23 | 北京理工大学 | Near infrared fluorescent compound and its preparation method and application with AIE performance |
| CN111307773A (en) * | 2020-03-13 | 2020-06-19 | 北京理工大学 | Application of fluorescent compound in detecting and/or distinguishing natural plant compounds |
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Application publication date: 20120111 |