CN102676158B - Pyrene-contained bis-imidazole type fluorescence probe as well as synthetic method and application thereof - Google Patents

Abstract

The invention discloses a pyrene-contained bis-imidazole type fluorescence probe, which has the following structural formula, wherein n in the formula I is 2 or 3 or 4 or 6. A synthetic method for the pyrene-contained bis-imidazole type fluorescence probe comprises the following steps of synthesizing 1-pyrene methyl chloride, synthesizing bis-imidazole alkane, synthesizing the pyrene-contained bis-imidazole type fluorescence probe and the like. The invention also discloses an application of the pyrene-contained bis-imidazole type fluorescence probe to detecting heavy metal ions in lauryl sodium sulfate aqueous solution.

Description

Containing the two imidazole type fluorescent probes of pyrene and synthetic method and application

Technical field

The present invention relates to a kind of fluorescent probe of measuring heavy metal ion in lauryl sodium sulfate aqueous solution.

Background technology

The toxic action of day by day serious problem of environmental pollution, especially heavy metal ion exists serious threat to human health and environmental quality.Rare earth also belongs to heavy metal ion, valuable Nonrenewable resources, there are important scientific research and economic use value, because its application at aspects such as agricultural fertilizer, catalyzer, medical diagnosiss increases day by day, make originally in the earth's crust, to become in the rare earth of stable state the soluble ree of easy entered environment.14 kinds of elements in lanthanon all belong to rare earth element, and China is the country that rare earth reserves are maximum, smuggled abroad, and caused national great attention when long-term a large amount of outlet by lawless person.Therefore, developing a kind of sensitive detection method carrys out detection and Identification heavy metal ion and has great importance.

At present, in method for detection of metal ion, common method comprises: inductively coupled plasma/atomic emission spectrum (ICP/AES), inductively coupled plasma mass spectrum spectrography (ICPMS), atomic absorption spectrometry (AAS) and multiple wet chemical method (as volumetry, gravimetry and colorimetric method etc.).The sensitivity of these methods and recognition accuracy are relatively high, but need to consume a large amount of time and financial resources, while especially needing to measure a large amount of sample, can not carry out in-site detecting.And fluorescence chemical sensor due to its have highly sensitive, without reference hierarchy, can imaging and the advantage such as output signal abundant (such as fluorescence intensity, maximum emission wavelength, spectrum pattern, fluorescence lifetime and fluorescence anisotropy etc.), adopt fluorescence chemical sensor to detect metal ion, can address the above problem well.The fluorescence chemical sensor that Patrizia Grandini group is simply mixed to form fluorescence species (8-anilino-1-naphthalene sulfonic acid, ANS) and tensio-active agent (CTABr) in the aqueous solution is realized the highly sensitive sensing to Cu (II).The people such as Yan Zhao adopt the fluorescence chemical sensor of Rhodamine Derivatives to realize the detection to Cu (II) in the cell of water and work.And these sensors can only detect single metal ion, can not realize many kinds of metal ions is detected simultaneously.Be to provide a kind of method that many kinds of metal ions is detected and distinguished in to lauryl sodium sulfate aqueous solution in the urgent technical problem solving of the current need in detection technique field.

Summary of the invention

A technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned technology, provide a kind of highly sensitive, selectivity good, test specification is wide containing the two imidazole type fluorescent probes of pyrene.

Another technical problem to be solved by this invention is to provide a kind of synthetic method simply to contain the synthetic method of the two imidazole type fluorescent probes of pyrene.

To be solved by this invention also have a technical problem to be as providing a kind of new purposes containing the two imidazole type fluorescent probes of pyrene.

Solving the problems of the technologies described above adopted technical scheme is the following compound of structural formula:

Formula I

N in formula I is 2 or 3 or 4 or 6.

The synthetic method step of above formula compound is as follows:

1, synthetic 1-pyrene methyl chloride

Under the condition of nitrogen gas that is 0.6～0.8mL/s at flow velocity, add 1-pyrene methylol to filling in the double-neck flask of methylene dichloride, add again pyridine, under condition of ice bath, getting thionyl chloride is splashed in double-neck flask, room temperature reaction 12 hours, 1-pyrene methylol and pyridine, the mol ratio of thionyl chloride is 1: 1.5: 6.5, after stopped reaction, reaction solution is poured in ice, be stirred to ice-out, separate organic phase with separating funnel, with redistilled water by organic phase continuous washing 3～5 times for several times, collect organic phase, and spend the night with anhydrous sodium sulfate drying, remove solvent, obtain 1-pyrene methyl chloride, the compound representing by formula II.Its reaction equation is as follows:

Formula II

2, synthetic two imidazoles alkane

To filling in the double-neck flask of methyl-sulphoxide, add imidazoles and sodium hydroxide, 65 ℃ are reacted 1 hour, get two bromoalkanes and splash in double-neck flask, continue reaction 3 hours, the mol ratio of imidazoles and two bromoalkanes, sodium hydroxide is 2: 2: 1, after reaction solution is cooled to room temperature, be poured in frozen water, suction filtration, uses twice, redistilled water recrystallization, obtain the compound that two imidazoles alkane represents by formula III, its reaction equation is as follows:

Formula III

Two above-mentioned bromoalkanes are glycol dibromide, 1,3-dibromopropane, Isosorbide-5-Nitrae-dibromobutane, 1, any one in 6-dibromo-hexane.

3, synthetic containing the two imidazole type fluorescent probes of pyrene

Under the argon gas condition that is 0.6～0.8mL/s at flow velocity, in the three-necked flask of toluene, add two imidazoles alkane to filling, the 1-pyrene methyl chloride toluene solution of getting 0.064mol/L splashes in three-necked flask, refluxes 24 hours, and 1, the mol ratio of the two imidazoles butane of 4-and 1-pyrene methyl chloride is 1: 1～5, product first washs 3～5 times with ether, then uses washing with acetone 3～5 times, by recrystallizing methanol, obtain containing the two imidazole type fluorescent probes of pyrene, its reaction equation is as follows:

Formula I

In synthetic containing in the two imidazole type fluorescent probe steps 3 of pyrene of the present invention, under the argon gas condition that is 0.6～0.8mL/s at flow velocity, add 1 to filling in the three-necked flask of toluene, the two imidazoles butane of 4-, the 1-pyrene methyl chloride toluene solution of getting 0.064mol/L splashes in three-necked flask, reflux 24 hours, 1, the optimum mole ratio of the two imidazoles butane of 4-and 1-pyrene methyl chloride is 1: 3, product is first with ether washing 3～5 times, use again washing with acetone 3～5 times, by recrystallizing methanol, obtain containing the two imidazole type fluorescent probes of pyrene.

Containing the purposes of the two imidazole type fluorescent probes of pyrene heavy metal ion in the aqueous solution that detects sodium lauryl sulphate, described heavy metal ion is cupric ion (Cu (II)), cobalt ion (Co (II)), neodymium ion (Nd (III)), praseodymium ion (Pr (III)), erbium ion (Er (III)), holmium ion (Ho (III)) and gadolinium ion (Gd (III)).Its using method is as follows:

To be dissolved in the aqueous solution of 4mmol/L sodium lauryl sulphate containing the two imidazole type fluorescent probes of pyrene, be made into the aqueous solution of the 4mmol/L sodium lauryl sulphate containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 0 μ mol/L～15.0 μ mol/L heavy metal ion, after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength be 490nm place measure fluorescence intensity, excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with concentration of heavy metal ion in lauryl sodium sulfate aqueous solution.In the time that being 0 μ mol/L～15.0 μ mol/L, concentration of heavy metal ion presents linear relationship.In lauryl sodium sulfate aqueous solution, the linear equation of heavy metal ion is:

I＝b+k[M ⁿ⁺]

In formula I be in lauryl sodium sulfate aqueous solution under different concns heavy metal ion there is the ratio of lower 490nm place fluorescence intensity, k is slope, b is intercept.

Chemical stability containing the two imidazole type fluorescent probes of pyrene is good, fast response time, highly sensitive, selectivity good, can directly detect with fluorescent instrument, as the single photon counting time resolution fluorescence spectral instrument of FLS920 model or other similar optical detecting instruments.Adopt synthetic method of the present invention synthetic be applicable to the mensuration of heavy metal ion in lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene.

Accompanying drawing explanation

Fig. 1 is the linear diagram containing the two imidazole type fluorescent probes detection cupric ions of pyrene (Cu (II)) prepared by embodiment 1.

Fig. 2 is the linear diagram containing the two imidazole type fluorescent probes detection cobalt ions of pyrene (Co (II)) prepared by embodiment 1.

Fig. 3 is the linear diagram containing the two imidazole type fluorescent probes detection neodymium ions of pyrene (Nd (III)) prepared by embodiment 1.

Fig. 4 is the linear diagram containing the two imidazole type fluorescent probes detection praseodymium ions of pyrene (Pr (III)) prepared by embodiment 1.

Fig. 5 is the linear diagram containing the two imidazole type fluorescent probes detection erbium ions of pyrene (Er (III)) prepared by embodiment 1.

Fig. 6 is the linear diagram containing the two imidazole type fluorescent probes detection holmium ions of pyrene (Ho (III)) prepared by embodiment 1.

Fig. 7 is the linear diagram containing the two imidazole type fluorescent probes detection gadolinium ions of pyrene (Gd (III)) prepared by embodiment 1.

Fig. 8 be embodiment 1 prepare containing the two imidazole type fluorescent probes of pyrene to cupric ion (Cu (II)) and cobalt ion (Co (II)) component-bar chart.

Fig. 9 be embodiment 1 prepare containing the two imidazole type fluorescent probes of pyrene to neodymium ion (Nd (III)), praseodymium ion (Pr (III)), erbium ion (Er (III)), holmium ion (Ho (III)) and gadolinium ion (Gd (III)) component-bar chart.

Embodiment

Below in conjunction with accompanying drawing and example, the present invention is described in more detail, but the invention is not restricted to these embodiment.

Embodiment 1

The present embodiment is as follows containing the structural formula of the two imidazole type fluorescent probes of pyrene:

Formula I

N in formula I is 4.

Its synthetic method is as follows:

1, synthetic 1-pyrene methyl chloride

Under the condition of nitrogen gas that is 0.6～0.8mL/s at flow velocity, add 0.2g 1-pyrene methylol to filling in the double-neck flask of 25mL methylene dichloride, add again 100 μ L pyridines, under condition of ice bath, getting 400 μ L thionyl chlorides is splashed in double-neck flask, room temperature reaction 12 hours, 1-pyrene methylol and pyridine, the mol ratio of thionyl chloride is 1: 1.5: 6.5, after stopped reaction, reaction solution is poured in ice, be stirred to ice-out, separate organic phase with separating funnel, with redistilled water by organic phase continuous washing 3～5 times for several times, collect organic phase, and spend the night with anhydrous sodium sulfate drying, remove solvent, obtain synthetic 1-pyrene methyl chloride, the compound representing by formula II, its reaction equation is as follows:

Formula II

2, synthetic Isosorbide-5-Nitrae-bis-imidazoles butane

To filling in the double-neck flask of 10mL methyl-sulphoxide, add 3.4g imidazoles and 2g sodium hydroxide, 65 ℃ are reacted 1 hour, get 5.4g Isosorbide-5-Nitrae-dibromobutane and splash in double-neck flask, continue reaction 3 hours, imidazoles and 1, the mol ratio of 4-dibromobutane, sodium hydroxide is 2: 2: 1, is poured in frozen water suction filtration after reaction solution is cooled to room temperature, with twice, redistilled water recrystallization, the two imidazoles alkane of the formula of obtaining, the compound representing by III, its reaction equation is as follows:

Formula III

3, synthetic containing the two imidazole type fluorescent probes of pyrene

Under the argon gas condition that is 0.6～0.8mL/s at flow velocity, add 0.2g Isosorbide-5-Nitrae-bis-imidazoles butane to filling in the three-necked flask of 50mL toluene, the 1-pyrene methyl chloride toluene solution 0.8g that gets 0.064mol/L splashes in three-necked flask, reflux 24 hours, the mol ratio of Isosorbide-5-Nitrae-bis-imidazoles butane and 1-pyrene methyl chloride is 1: 3, and product is first with ether washing 3～5 times, use again washing with acetone 3～5 times, by recrystallizing methanol, obtain containing the two imidazole type fluorescent probes of pyrene, its reaction equation is as follows:

Formula I

The nuclear magnetic data containing the two imidazole type fluorescent probes of pyrene of said structure formula I is: ¹h NMR (δ ppm, 300MHz, DMSO-d ₆): 9.47 (1H), 8.14-8.50 (9H), 7.82-7.88 (2H), 6.24 (2H), 4.19 (2H), 1.72 (2H).

Embodiment 2

Structural formula (n is 4) containing the two imidazole type fluorescent probes of pyrene is identical with embodiment 1.Its synthetic method step is as follows:

Contain in the two imidazole type fluorescent probe steps 3 of pyrene synthetic, under the argon gas condition that is 0.6～0.8mL/s at flow velocity, add 0.2g Isosorbide-5-Nitrae-bis-imidazoles butane to filling in the three-necked flask of toluene, the 1-pyrene methyl chloride toluene solution of getting 0.27g 0.064mol/L splashes in three-necked flask, reflux 24 hours, the mol ratio of Isosorbide-5-Nitrae-bis-imidazoles butane and 1-pyrene methyl chloride is 1: 1, and product is first with ether washing 3～5 times, use again washing with acetone 3～5 times, use recrystallizing methanol.

Other step is identical with embodiment 1.Synthetic containing the two imidazole type fluorescent probes of pyrene.

Embodiment 3

Structural formula (n is 4) containing the two imidazole type fluorescent probes of pyrene is identical with embodiment 1.Its synthetic method step is as follows:

Contain in the two imidazole type fluorescent probe steps 3 of pyrene synthetic, under the argon gas condition that is 0.6～0.8mL/s at flow velocity, add 0.2g Isosorbide-5-Nitrae-bis-imidazoles butane to filling in the three-necked flask of toluene, the 1-pyrene methyl chloride toluene solution of getting 1.35g 0.064mol/L splashes in three-necked flask, reflux 24 hours, the mol ratio of Isosorbide-5-Nitrae-bis-imidazoles butane and 1-pyrene methyl chloride is 1: 5, and product is first with ether washing 3～5 times, use again washing with acetone 3～5 times, use recrystallizing methanol.

Other step is identical with embodiment 1.Synthetic containing the two imidazole type fluorescent probes of pyrene.

Embodiment 4

Structural formula containing the two imidazole type fluorescent probes (n is 2) of pyrene is as follows:

Formula I

Its synthetic method step is as follows:

In above embodiment 1～3, synthetic 1-pyrene methyl chloride step 1 is identical with embodiment 1.In the two imidazoles ethane steps 2 of synthetic 1,2-, Isosorbide-5-Nitrae-dibromobutane used is replaced with equimolar glycol dibromide, and other step in this step is identical with embodiment 1.Other step is identical with corresponding embodiment.Synthetic containing the two imidazole type fluorescent probes of pyrene.

Embodiment 5

Structural formula containing the two imidazole type fluorescent probes (n is 3) of pyrene is as follows:

Formula I

In above embodiment 1～3, synthetic 1-pyrene methyl chloride step 1 is identical with embodiment 1.In the two imidazoles propane steps 2 of synthetic 1,3-, Isosorbide-5-Nitrae-dibromobutane used is with equimolar 1, the replacement of 3-dibromopropane, and other step in this step is identical with embodiment 1.Other step is identical with corresponding embodiment.Synthetic containing the two imidazole type fluorescent probes of pyrene.

Embodiment 6

Structural formula containing the two imidazole type fluorescent probes (n is 6) of pyrene is as follows:

Formula I

In above embodiment 1～3, synthetic 1-pyrene methyl chloride step 1 is identical with embodiment 1.In synthetic 1,6 pair of imidazoles hexane step 2, Isosorbide-5-Nitrae-dibromobutane used is with equimolar 1, the replacement of 6-dibromo-hexane, and other step in this step is identical with embodiment 1.Other step is identical with corresponding embodiment.Synthetic containing the two imidazole type fluorescent probes of pyrene.

Embodiment 7

Containing the purposes of the two imidazole type fluorescent probes of pyrene cupric ion (Cu (II)) in the aqueous solution that detects sodium lauryl sulphate, its using method is as follows:

To be dissolved in the aqueous solution of 4mmol/L sodium lauryl sulphate containing the two imidazole type fluorescent probes of pyrene, be made into the aqueous solution of the 4mmol/L sodium lauryl sulphate containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 2.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L cupric ions (Cu (II)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, excitation-emission slit is 3nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with cupric ion in the aqueous solution of sodium lauryl sulphate (Cu (II)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in cupric ion (Cu (II)) concentration, as shown in Figure 1, in Fig. 1, cupric ion in the aqueous solution of fluorescence intensity and sodium lauryl sulphate (Cu (II)) concentration is linear, and linear equation is:

I=1.11+0.27[Cu(II)]

Correlation coefficient r is 0.9915, the ratio of the lower 490nm of (Cu (II)) existence place fluorescence intensity under different concns in the aqueous solution that in formula, I is sodium lauryl sulphate, and k is 0.27, b is 1.11.The calculation formula of analytical chemistry volume two (the third edition July calendar year 2001) relation conefficient that correlation coefficient r is published by Higher Education Publishing House is calculated:

$r=\±\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}(x_i-\stackrel{\‾}{x})(y_i-\stackrel{\‾}{y})}{{\left[\underset{i-1}{\overset{n}{\mathrm{\Σ}}}{(x_i-\stackrel{\‾}{x})}^2\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{(y_i-\stackrel{\‾}{y})}^2\right]}^{\frac{1}{2}}}$

Formula IV

From relation conefficient, the linear relationship of cupric ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Cu (II)) concentration is fine.

Embodiment 8

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects cobalt ion (Co (II)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 2.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L cobalt ions (Co (II)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with cobalt ion in lauryl sodium sulfate aqueous solution (Co (II)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in cobalt ion (Co (II)) concentration, as shown in Figure 2, in Fig. 2, cobalt ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Co (II)) concentration is linear, and linear equation is:

I=0.95+0.19[Co(II)]

Correlation coefficient r is 0.9987, in formula I be in lauryl sodium sulfate aqueous solution under different concns cobalt ion (Co (II)) there is the ratio of lower 490nm place fluorescence intensity, k is 0.19, b is 0.95.Correlation coefficient r calculates by formula IV, and from relation conefficient, the linear relationship of cobalt ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Co (II)) concentration is fine.

Embodiment 9

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects neodymium ion (Nd (III)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L neodymium ions (Nd (III)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, and excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with neodymium ion in lauryl sodium sulfate aqueous solution (Nd (III)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in neodymium ion (Nd (III)) concentration, as shown in Figure 3, in Fig. 3, neodymium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Nd (III)) concentration is linear, and linear equation is:

I=0.99+0.15[Nd(III)]

Correlation coefficient r is 0.9811, in formula I be in lauryl sodium sulfate aqueous solution under different concns neodymium ion (Nd (III)) there is the ratio of lower 490nm place fluorescence intensity, k is 0.15, b is 0.99.Correlation coefficient r calculates by formula IV, and from relation conefficient, the linear relationship of neodymium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Nd (III)) concentration is fine.

Embodiment 10

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects praseodymium ion (Pr (III)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L praseodymium ions (Pr (III)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, and excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with praseodymium ion in lauryl sodium sulfate aqueous solution (Pr (III)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in praseodymium ion (Pr (III)) concentration, as shown in Figure 4, in Fig. 4, praseodymium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Pr (III)) concentration is linear, and linear equation is:

I=0.95+0.07[Pr(III)]

Correlation coefficient r is 0.9911, in formula I be in lauryl sodium sulfate aqueous solution under different concns praseodymium ion (Pr (III)) there is the ratio of lower 490nm place fluorescence intensity, k is 0.07, b is 0.95.Correlation coefficient r calculates by formula IV, and from relation conefficient, the linear relationship of praseodymium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Pr (III)) concentration is fine.

Embodiment 11

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects erbium ion (Er (III)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L erbium ions (Er (III)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, and excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with erbium ion in lauryl sodium sulfate aqueous solution (Er (III)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in erbium ion (Er (III)) concentration, as shown in Figure 5, in Fig. 5, erbium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Er (III)) concentration is linear, and linear equation is:

I=0.95+0.14[Er(III)]

Correlation coefficient r is 0.9895, in formula I be in lauryl sodium sulfate aqueous solution under different concns erbium ion (Er (III)) there is the ratio of lower 490nm place fluorescence intensity, k is 0.14, b is 0.95.Correlation coefficient r be 0.9895 by IV calculate, from relation conefficient, the linear relationship of erbium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Er (III)) concentration is fine.

Embodiment 12

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects holmium ion (Ho (III)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L holmium ions (Ho (III)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, and excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with holmium ion in lauryl sodium sulfate aqueous solution (Ho (III)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in holmium ion (Ho (III)) concentration, as shown in Figure 6, in Fig. 6, holmium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Ho (III)) concentration is linear, and linear equation is:

I=0.99+0.16[Ho(III)]

Correlation coefficient r is 0.9816, in formula I be in lauryl sodium sulfate aqueous solution under different concns holmium ion (Ho (III)) there is the ratio of lower 490nm place fluorescence intensity, k is 0.16, b is 0.99.Correlation coefficient r calculates by formula IV, and from relation conefficient, the linear relationship of holmium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Ho (III)) concentration is fine.

Embodiment 13

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects gadolinium ion (Gd (III)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, add successively 1.0 μ mol/L, 3.0 μ mol/L, 5.0 μ mol/L, 7.0 μ mol/L, 10.0 μ mol/L, 15.0 μ mol/L gadolinium ions (Gd (III)), after mixing, with luminoscope be 350nm at maximum excitation wavelength, emission wavelength is that fluorescence intensity is measured at 490nm place, and excitation-emission slit is 2nm.Fluorescence intensity when recording solution reaches balance, draws the fluorescence spectrum figure that fluorescence intensity changes with gadolinium ion in lauryl sodium sulfate aqueous solution (Gd (III)) concentration.While being 0 μ mol/L～15.0 μ mol/L, present linear relationship in gadolinium ion (Gd (III)) concentration, as shown in Figure 7, in Fig. 7, gadolinium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Gd (III)) concentration is linear, and linear equation is:

I=1.0+0.01[Gd(III)]

Correlation coefficient r is 0.9847, in formula I be in lauryl sodium sulfate aqueous solution under different concns gadolinium ion (Gd (III)) there is the ratio of lower 490nm place fluorescence intensity, k is 0.01, b is 1.0.Correlation coefficient r calculates by formula IV, and from relation conefficient, the linear relationship of gadolinium ion in fluorescence intensity and lauryl sodium sulfate aqueous solution (Gd (III)) concentration is fine.

Embodiment 14

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects cupric ion (Cu (II)) and cobalt ion (Co (II)) in lauryl sodium sulfate aqueous solution, its using method is as follows:

Adopt FLS920 type single photon counting time resolution fluorescence spectral instrument to the synthetic fluorescent probe of embodiment 1, the differentiation of cupric ion in lauryl sodium sulfate aqueous solution (Cu (II)) and cobalt ion (Co (II)) to be tested as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the aqueous solution of the 4mmol/L sodium lauryl sulphate containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, with luminoscope be 350nm at maximum excitation wavelength, recording maximum emission wavelength 490nm place fluorescence intensity is I, add respectively 15.0 μ mol/L cupric ions (Cu (II)) and cobalt ion (Co (II)), mix, when recording solution reaches balance, maximum emission wavelength is that the fluorescence intensity at 490nm place is I ₀, add respectively 15.0 μ mol/L glycine (Gly), recording emission wavelength is that 490nm place fluorescence intensity is also I ₀, with I/I ₀as shown in Figure 8, excitation-emission slit is 2nm in mapping.In Fig. 8, curve a is the fluorescence intensity curves of 0 μ mol/LCu (II), and curve b is the fluorescence intensity curves of 15 μ mol/L Cu (II), and curve c is the fluorescence intensity curves of 15 μ mol/L glycine (Gly); Curve d is the fluorescence intensity curves of 0 μ mol/L Co (II), and e is the fluorescence intensity curves of 15 μ mol/L Co (II), and f is the fluorescence intensity curves of 15 μ mol/L glycine (Gly); As seen from Figure 8, in solution after 15 μ mol/L Cu (II) quenchers, added 15 its fluorescence intensities of μ mol/L glycine (Gly) can return to original half, and in the solution after 15 μ mol/L Co (II) quenchers, added 15 its fluorescence intensities of μ mol/L glycine (Gly) that considerable change does not occur.Therefore, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L, can well distinguish cupric ion (Cu (II)) and cobalt ion (Co (II)).

Embodiment 15

Containing the two imidazole type fluorescent probes of pyrene, in the purposes that detects the differentiation of erbium (Er (III)), gadolinium (Gd (III)), neodymium (Nd (III)), praseodymium (Pr (III)) and holmium (Ho (III)) ion in lauryl sodium sulfate aqueous solution, its using method is as follows:

Adopt FLS920 type single photon counting time resolution fluorescence spectral instrument to the synthetic fluorescent probe of embodiment 1, the differentiation of erbium in the aqueous solution of 4mmol/L sodium lauryl sulphate (Er (III)), gadolinium (Gd (III)), neodymium (Nd (III)), praseodymium (Pr (III)) and holmium (Ho (III)) ion to be tested as follows:

To be dissolved in 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene, be made into the 4mmol/L lauryl sodium sulfate aqueous solution containing the two imidazole type fluorescent probes of pyrene of 1.0 μ mol/L, get this solution of 2.5mL in cuvette, with luminoscope be 350nm at maximum excitation wavelength, record maximum emission wavelength 490nm place fluorescence intensity, add respectively 5.0 μ mol/L erbiums (Er (III)), gadolinium (Gd (III)), neodymium (Nd (III)), praseodymium (Pr (III)) and holmium (Ho (III)) ion, after mixing, 375nm when recording solution reaches balance, 390nm, 460nm, the fluorescence intensity at 490nm place, adopt main component analytical method (PCA) to distinguish five kinds of ions.As shown in Figure 9, in curve a, be neodymium ion (Nd (III)), in curve b, be praseodymium ion (Pr (III)), in curve c, be erbium ion (Er (III)), in curve d, be holmium ion (Ho (III)), in curve e, be gadolinium ion (Gd (III)), Fig. 9 is visible, and prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6in the 4mmol/L lauryl sodium sulfate aqueous solution of μ mol/L, can well distinguish erbium ion (Er (III)), gadolinium ion (Gd (III)), neodymium ion (Nd (III)), praseodymium ion (Pr (III)) and holmium ion (Ho (III)).

In order to verify beneficial effect of the present invention, contriver adopt embodiment 1 synthetic carried out the research trial of great many of experiments chamber containing the two imidazole type fluorescent probes of pyrene (when test referred to as fluorescent probe), various test situation are as follows:

That 1, prepared by embodiment 1 is configured to containing the two imidazole type fluorescent probes of pyrene the 4mmol/L lauryl sodium sulfate aqueous solution that concentration is 1.0 μ mol/L, adopt the single photon counting time resolution fluorescence spectral instrument of FLS920 type to prepared fluorescent probe, heavy metal ion in 4mmol/L lauryl sodium sulfate aqueous solution to be measured, the concentration and probe concentration of measuring is 1 × 10 ^-6mol/L, in system, the concentration of sodium lauryl sulphate is 4mmol/L, tests by the working method of instrument, test result is as shown in Fig. 1-7:

In Fig. 1, curve a is the fluorescence intensity curves of 0 μ mol/L Cu (II), b is the fluorescence intensity curves of 1.0 μ mol/L Cu (II), c is the fluorescence intensity curves of 2.0 μ mol/L Cu (II), d is the fluorescence intensity curves of 3.0 μ mol/L Cu (II), e is the fluorescence intensity curves of 5.0 μ mol/L Cu (II), f is the fluorescence intensity curves of 7.0 μ mol/L Cu (II), g is the fluorescence intensity curves of 10.0 μ mol/L Cu (II), h is the fluorescence intensity curves of 15.0 μ mol/L Cu (II), as seen from Figure 1, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Cu (II) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Cu (II).

In Fig. 2, curve a is the fluorescence intensity curves of 0 μ mol/L Co (II), b is the fluorescence intensity curves of 1.0 μ mol/L Co (II), c is the fluorescence intensity curves of 2.0 μ mol/L Co (II), d is the fluorescence intensity curves of 3.0 μ mol/L Co (II), e is the fluorescence intensity curves of 5.0 μ mol/L Co (II), f is the fluorescence intensity curves of 7.0 μ mol/L Co (II), g is the fluorescence intensity curves of 10.0 μ mol/L Co (II), h is the fluorescence intensity curves of 15.0 μ mol/L Co (II), as seen from Figure 2, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Co (II) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Co (II).

In Fig. 3, curve a is the fluorescence intensity curves of 0 μ mol/L Nd (III), b is the fluorescence intensity curves of 1.0 μ mol/L Nd Nd (III), c is the fluorescence intensity curves of 3.0 μ mol/L Nd (III), d is the fluorescence intensity curves of 5.0 μ mol/L Nd Nd (III), e is the fluorescence intensity curves of 7.0 μ mol/L Nd (III), f is the fluorescence intensity curves of 10.0 μ mol/L Nd Nd (III), g is the fluorescence intensity curves of 15.0 μ mol/L Nd (III), as seen from Figure 3, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Nd (III) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Nd (III).

In Fig. 4, curve a is the fluorescence intensity curves of 0 μ mol/L Pr (III), b is the fluorescence intensity curves of 1.0 μ mol/L Pr (III), c is the fluorescence intensity curves of 3.0 μ mol/L Pr (III), d is the fluorescence intensity curves of 5.0 μ mol/L Pr (III), e is the fluorescence intensity curves of 7.0 μ mol/L Pr (III), f is the fluorescence intensity curves of 10.0 μ mol/L Pr (III), g is the fluorescence intensity curves of 15.0 μ mol/L Pr (III), as seen from Figure 4, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Pr (III) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Pr (III).

In Fig. 5, curve a is the fluorescence intensity curves of 0 μ mol/L Er (III), b is the fluorescence intensity curves of 1.0 μ mol/L Er (III), c is the fluorescence intensity curves of 3.0 μ mol/L Er (III), d is the fluorescence intensity curves of 5.0 μ mol/L Er (III), e is the fluorescence intensity curves of 7.0 μ mol/L Er (III), f is the fluorescence intensity curves of 10.0 μ mol/L Er (III), g is the fluorescence intensity curves of 15.0 μ mol/L Er (III), as seen from Figure 5, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Er (III) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Er (III).

In Fig. 6, curve a is the fluorescence intensity curves of 0 μ mol/L Ho (III), b is the fluorescence intensity curves of 1.0 μ mol/L Ho (III), c is the fluorescence intensity curves of 3.0 μ mol/L Ho (III), d is the fluorescence intensity curves of 5.0 μ mol/L Ho (III), e is the fluorescence intensity curves of 7.0 μ mol/Ho (III), f is the fluorescence intensity curves of 10.0 μ mol/L Ho (III), g is the fluorescence intensity curves of 15.0 μ mol/L Ho (III), as seen from Figure 6, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Ho (III) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Ho (III).

In Fig. 7, curve a is the fluorescence intensity curves of 0 μ mol/L Gd (III), b is the fluorescence intensity curves of 1.0 μ mol/L Gd (III), c is the fluorescence intensity curves of 3.0 μ mol/L Gd (III), d is the fluorescence intensity curves of 5.0 μ mol/L Gd (III), e is the fluorescence intensity curves of 7.0 μ mol/L Gd (III), f is the fluorescence intensity curves of 10.0 μ mol/L Gd (III), g is the fluorescence intensity curves of 15.0 μ mol/L Gd (III), as seen from Figure 7, prepared fluorescent probe is 1 × 10 in concentration and probe concentration ^-6fluorescence intensity in the lauryl sodium sulfate aqueous solution of μ mol/L 4mmol/L along with add system Gd (III) concentration increase its change clearly, illustrate take fluorescent probe in concentration and probe concentration as 1 × 10 ^-6when mol/L, very high to the detection sensitivity of Gd (III).

2, the detection test of fluorescent probe to cupric ion in lauryl sodium sulfate aqueous solution (Cu (II)) and cobalt ion (Co (II))

Adopt FLS920 type single photon counting time resolution fluorescence spectral instrument to the synthetic fluorescent probe of embodiment 1, the detection limit of cupric ion in lauryl sodium sulfate aqueous solution (Cu (II)) and cobalt ion (Co (II)) to be tested by the working method of instrument, and calculate by following formula:

$\mathrm{DL}=\frac{3\×\sqrt{{\mathrm{\Σ}}_{i-1}^n{(I_i-\stackrel{\‾}{I})}^2/n-1}}{\frac{\mathrm{\ΔI}}{\mathrm{\ΔC}}}$

In formula, DL is detection limit, and Measurement and Computation the results are shown in Table 1.

Table 1 embodiment 1 fluorescent probe detection limit to cupric ion and cobalt ion in lauryl sodium sulfate aqueous solution

Metal ion	Detection limit DL (nmol/L)
		Cupric ion	50
Cobalt ion	54

From table 1, the fluorescent probe of the synthesized detection limit that cupric ion and cobalt ion detect in lauryl sodium sulfate aqueous solution is all very low.

Claims (2)

1. containing the purposes of the two imidazole type fluorescent probes of pyrene heavy metal ion in detection lauryl sodium sulfate aqueous solution, the structural formula that should contain the two imidazole type fluorescent probes of pyrene be:

N in formula I is 2 or 3 or 4 or 6.

2. the purposes containing the two imidazole type fluorescent probes of pyrene heavy metal ion in detection lauryl sodium sulfate aqueous solution according to claim 3, is characterized in that: the concentration of described lauryl sodium sulfate aqueous solution is 4mmol/L.

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