CN105255481A - Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof - Google Patents
Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof Download PDFInfo
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Abstract
The invention provides a phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof, relates to fluorescent molecular probes and synthesis and application thereof and aims to solve the problem that an existing Fe<3+> fluorescent probe is prone to being interfered by pH, concentration and other metal ions. The fluorescent molecular probe is 4-methyl-7-hydroxide radical-8-[2-(1- phenyl group-1H-phenanthrene and [9, 10-d] imidazole-2-)benzene ammonia methylene]-2H-pyran-2-ketone. The phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe is formed by conducting condensation on 1-N-phenyl group-2-(2-aminophenyl)-1H-phenanthrene and [9, 10-d] imidazole and 4-methyl-7-hydroxide radical-8- formyl group coumarin, and the yield is 75-85%. The fluorescent molecular probe is dissolved in mixed liquid of N, N- dimethylformamide and an HEPES buffering solution, existence of iron ions is judged through the absorbance value or fluorescence intensity change before and after adding of test samples, and the fluorescent molecular probe can be used for detection of Fe<3+> pollution in water.
Description
Technical field
The present invention relates to synthesis and the application of the fluorescent molecular probe detected for iron ion.
Background technology
Ferro element occupies the metallic element of second as content in the earth's crust, is also the trace element that in human body, content is the highest, and iron all has a very important role in the metabolism at different levels of organism.In the vital movement of human body, as the formation of the enzymes such as hormone secretion, cytopigment, myeloperoxidase, Terminal oxidase and catalase, to the transhipment of oxygen in blood, the transfer of genic synthesis, proton, intracellular osmotic pressure regulate and the aspect such as acid base equilibrium maintenance, not only there is the participation of bulky metals ferro element, also have some trace even effect of trace iron ions.Therefore, the detection of iron ion all has great significance to bio-science and medical science.It is fluorescent probe and the imdazole derivatives fluorescent probe of fluorophor that the fluorescent probe of existing detection iron ion has with tonka bean camphor, is wherein article " being preced with the Fe3+ highly selective fluorescence chemical sensor of 6 compounds based on the azepine 18 with temparin the group " (HighlyselectivefluorescentchemosensorforFe that the fluorescent probe compounds of fluorophor is published in the 1-4 page of " inorganic chemistry communication " (Inorg.Chem.Comm.) the 42nd phase in 2014 with tonka bean camphor
3+detectionbasedondiaza-18-crown-6etherappendedwithdualcou marins) on, its structural formula is as shown in a formula:
Imdazole derivatives fluorescent probe is published in article on the 1257-1263 page of " Chinese science: chemistry " (ScienceChinaChemisty) the 57th volume the 9th phase in 2014 " reversible identification Fe in an aqueous phase
3+and H
2pO
4the fluorescence chemical sensor of " open-closed-open " " (AreversiblefluorescentchemosensorforFe
3+andH
2pO
4with " on-off-on " switchinginaqueousmedia) on, its structural formula is as shown in b formula.
Two kinds of above-mentioned fluorescent probe identification Fe
3+main employing two kinds of signal characteristics, that probe molecule is in conjunction with producing new emission peak after iron ion and showing as Fluorescence Increasing or cancellation at original transmitting site respectively, but this signal all exists the impact being easily subject to pH, concentration, other metal ion disturbances, the prohibited data detection that causes easily being interfered in recognition process is true.
Summary of the invention
The present invention will solve existing identification Fe
3+fluorescent probe be vulnerable to the impact technical problem that causes prohibited data detection true of pH, concentration, other metal ion disturbances, and provide a kind of two fluorophor ratio fluorescent molecular probe of phenanthro-imidazoles-tonka bean camphor of detecting for iron ion and synthetic method thereof.
The two fluorophor ratio fluorescent molecular probe of phenanthro-imidazoles-tonka bean camphor for iron ion detection of the present invention is 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, its structural formula is:
The preparation method of the two fluorophor ratio fluorescent molecular probe of the above-mentioned phenanthro-imidazoles-tonka bean camphor for iron ion detection adopts 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] imidazoles and the condensation of 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor form, and its reaction formula is as follows:
Its concrete synthesis step is:
One, by 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] mol ratio of imidazoles and 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor is 1:(1 ~ 5), by 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] imidazoles and 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor join in acid solvent, stirring at room temperature reaction 10 ~ 60min, obtains reaction mixture;
Two, reaction mixture is poured in distilled water, after pH value being adjusted to 8 ~ 10, separate out a large amount of solid; Filter, collect filter cake;
Three, by filter cake ethyl acetate and sherwood oil recrystallization, obtain 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, be the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor detected for iron ion.
The using method of the two fluorophor ratio fluorescent molecular probe of the above-mentioned phenanthro-imidazoles-tonka bean camphor for iron ion detection is carried out according to the following steps:
One, two for the phenanthro-imidazoles-tonka bean camphor being used for iron ion detection fluorophor ratio fluorescent molecular probe is dissolved in the mixed solution of DMF and HEPES buffered soln, obtains fluorescent molecular probe solution; The wherein pH=7.4 of HEPES buffered soln mixed solution, in mixed solution, the volume ratio of DMF and HEPES buffered soln is 7:3, and in mixed solution, the concentration of fluorescent molecular probe is 10 μm of ol/L;
Two, get fluorescent molecular probe solution, add testing sample wherein, mix, obtain sample solution;
Three, with ultraviolet spectrophotometer test fluorescent molecular probe solution at wavelength be the absorbance A at 260nm place
1, then test the absorbance A that sample solution is 260nm place at wavelength
2if, A2≤20%A
1, then can judge in sample containing Fe
3+; Or with the fluorescence intensity B of fluorescence spectrophotometer test fluorescent molecular probe solution when emission wavelength is 426nm
1, then test the fluorescence intensity B of sample solution when emission wavelength is 426nm
2if, B
2≤ 20%B
1, then judge in sample containing Fe
3+.
This Fe containing phenanthro-imidazoles and tonka bean camphor two kinds of fluorophors of the present invention
3+fluorescent probe can realize in water environment system Fe
3+selective recognition function, not by the interference of other metal ions in the aqueous solution, there is stronger immunity from interference.This fluorescent molecular probe itself and identification Fe
3+be have stable fluorescence intensity in 2 ~ 13 scopes in pH value afterwards, fluorescence property is stablized.This fluorescent molecular probe identification response is very fast, can complete the Fe in aqueous systems environment in 0.5 minute
3+.
The synthesis desired raw material of this fluorescent molecular probe is simple and easy to get, and cost is lower; Reaction only needs a step, and step is simple; Reaction times is short, at room temperature completes, and reaction conditions is gentle, and product only need be obtained by means re-crystallization, and separating-purifying process is simple, and synthetic yield is high, and productive rate is up to 75 ~ 85%.
Fluorescent probe of the present invention can be applicable to Fe in aqueous systems
3+in detecting the early stage of polluting, there is high using value.
Accompanying drawing explanation
Fig. 1 is the ultraviolet spectrogram of fluorescent molecular probe in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system in embodiment 1, and X-coordinate is wavelength, and ordinate zou is absorbancy.
Fig. 2 is the fluorescence emission spectrogram of fluorescent molecular probe in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system in embodiment 1, and X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 3 is the metallic cation (Al that in embodiment 1, fluorescent molecular probe adds 400 μm of ol/L concentration in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system
3+, Zn
2+, Ag
+, Ca
2+, Mg
2+, Fe
3+, Hg
2+, Pb
2+, Na
+, Ba
2+, Ni
2+, K
+, Cu
2+, Cr
3+, Cd
2+, Co
2+) fluorescence emission spectrum changing conditions afterwards, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 4 is the Fe that in embodiment 1, fluorescent molecular probe adds 400 μm of ol/L concentration in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system
3+from the fluorescence emission spectrum changing conditions after the different coexistent metallic ions of 400 μm of ol/L concentration, X-coordinate is metal ion, and ordinate zou is fluorescence intensity.
Fig. 5 is that in embodiment 1, fluorescent molecular probe is in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system, and fluorescence emission spectrum is with Fe
3+the changing conditions that concentration (0 – 120 equivalent) increases, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 6 is that the fluorescence intensity of fluorescent molecular probe in embodiment 1 is with Fe
3+concentration curve figure;
Fig. 7 is that in embodiment 1, fluorescent molecular probe detects Fe
3+the mensuration graphic representation of lowest detectable limit;
Fig. 8 is that in embodiment 1, fluorescent molecular probe, in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system, adds the Fe of 400 μm of ol/L concentration
3+the fluorescence emission spectrum changing conditions of front and back under different pH value (pH value is from 2 – 13) condition, X-coordinate is pH, and ordinate zou is fluorescence intensity.
Fig. 9 is that in embodiment 1, fluorescent molecular probe, in DMF/HEPES buffered soln (v/v=7/3, pH=7.4) system, adds Fe
3+the changing conditions that front and back fluorescence emission spectrum responds in time, X-coordinate is the test duration, and ordinate zou is fluorescence intensity.
Embodiment
Embodiment one: the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection of present embodiment is 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, its structural formula is:
Embodiment two: the preparation method of the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection described in embodiment one is as follows:
One, by 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] mol ratio of imidazoles and 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor is 1:(1 ~ 5), by 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] imidazoles and 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor join in acid solvent, stirring at room temperature reaction 10 ~ 60min, obtains reaction mixture;
Two, reaction mixture is poured in distilled water, after pH value being adjusted to 8 ~ 10, separate out a large amount of solid; Filter, collect filter cake;
Three, by filter cake ethyl acetate and sherwood oil recrystallization, obtain 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, be the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor detected for iron ion.
Embodiment three: present embodiment and embodiment two are glacial acetic acid, the vitriol oil or formic acid unlike the acid solvent in step one; Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two or three adopt aqueous sodium hydroxide solution unlike adjust ph in step 2; Other is identical with embodiment two or three.
Embodiment five: one of present embodiment and embodiment two to three are 1:(10 ~ 15 unlike the volume ratio of ethyl acetate in step 3 and sherwood oil); Other is identical with one of embodiment two to three.
Embodiment six: the using method of the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection described in embodiment one is carried out according to the following steps:
One, two for the phenanthro-imidazoles-tonka bean camphor being used for iron ion detection fluorophor ratio fluorescent molecular probe is dissolved in the mixed solution of DMF and HEPES buffered soln, obtains fluorescent molecular probe solution; The wherein pH=7.4 of HEPES buffered soln mixed solution, in mixed solution, the volume ratio of DMF and HEPES buffered soln is 7:3, and in mixed solution, the concentration of fluorescent molecular probe is 10 μm of ol/L;
Two, get fluorescent molecular probe solution, add testing sample wherein, mix, obtain sample solution;
Three, with ultraviolet spectrophotometer test fluorescent molecular probe solution at wavelength be the absorbance A at 260nm place
1, then test the absorbance A that sample solution is 260nm place at wavelength
2if, A
2≤ 20%A
1, then can judge in sample containing Fe
3+; Or with the fluorescence intensity B of fluorescence spectrophotometer test fluorescent molecular probe solution when emission wavelength is 426nm
1, then test the fluorescence intensity B of sample solution when emission wavelength is 426nm
2if, B
2≤ 20%B
1, then can judge in sample containing Fe
3+.
HEPES buffered soln is 4-hydroxyethyl piperazine ethanesulfonic acid buffered soln.
Beneficial effect of the present invention is verified by following examples:
Embodiment 1: the preparation method of the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection of the present embodiment is as follows:
One, by 385mg (1mmol) 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] imidazoles and 204mg (1mmol) 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor join in 15mL glacial acetic acid, stirring at room temperature reaction 20min, obtains reaction mixture;
Two, reaction mixture is poured in distilled water, after pH value being adjusted to 9 by NaOH solution, separate out a large amount of solid; Filter, collect filter cake;
Three, by filter cake ethyl acetate and sherwood oil recrystallization, obtain 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, be the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor detected for iron ion.As calculated, productive rate is 85%.
In the ir data of the two fluorophor ratio fluorescent molecular probe of phenanthro-imidazoles-tonka bean camphor detected for iron ion prepared by the present embodiment, the DMSO solvent that replaces at deuterium
1hNMR modal data and
13cNMR spectral data is as follows:
IR(KBr,cm
-1):3061,1737,1615,1597,1497,1452,753,698。
1HNMR(600MHz,DMSO)δ(ppm):14.14(s,1H),9.12(s,1H),8.93(dd,J
1＝8.4Hz,J
2＝14.4Hz,2H),8.85(d,J＝8.4Hz,1H),7.76(t,J＝7.2Hz,1H),7.72-7.69(m,2H),7.65-7.63(m,2H),7.57(t,J＝7.8Hz,2H),7.51(t,J＝7.3Hz,1H),7.47(t,J＝7.9Hz,2H),7.43(d,J＝7.6Hz,2H),7.36(m,2H),7.13(d,J＝8.3Hz,1H),6.70(d,J＝9.0Hz,1H),6.26(s,1H),2.37(s,3H)。
13CNMR(150MHz，DMSO)δ(ppm):164.94，159.54,157.77,154.46,149.77,146.78,137.65,137.04,132.60,131.71,131.11,130.24,130.16,128.91,128.77,128.14,127.95,127.45,127.28,127.13,127.09,126.72,126.20,125.77,125.02,124.10,122.76,122.68,120.69,118.87,114.40,111.58,111.02,106.87,40.51。
The structural formula that can obtain the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection prepared by the present embodiment from above data is as follows:
its chemical name is: 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one.
The fluorescent molecular probe prepared by the present embodiment carries out UV spectrum detection, method is as follows: by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9, 10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is 10 μm of ol/L, by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9, 10-d] imidazoles-2-) phenylamino methylene radical] and-2H-pyran-2-one join DMF/HEPES cushion (v/v=7/3, pH=7.4) in solution, its ultra-violet absorption spectrum is detected after 30min, the uv absorption spectra obtained as shown in Figure 1, as shown in Figure 1, the ultraviolet maximum absorption wavelength of fluorescent molecular probe prepared by the present embodiment is at 260nm.(note: DMF/HEPES cushions (v/v=7/3, pH=7.4) solution refers to the mixed solution of DMF and HEPES buffered soln, wherein HEPES buffered soln pH=7.4, in mixed solution, the volume ratio of DMF and HEPES buffered soln is 7:3)
Fluorescent molecular probe prepared by the present embodiment carry out fluorescence emission spectrum test, method is as follows: by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is 10 μm of ol/L, fluorescent molecular probe is joined DMF/HEPES and cushion (v/v=7/3, pH=7.4) in solution, detect its fluorescence emission spectrum after 30min, fluorescence emission spectrogram as shown in Figure 2.As shown in Figure 2, fluorescent molecular probe prepared by the present embodiment has emission peak at 426nm place, and fluorescence intensity is stronger.
Fluorescence emission spectrum after the test fluorescent molecular probe prepared of the present embodiment and different metal ionization, concrete grammar is as follows:
By 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is 10 μm of ol/L, by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] and-2H-pyran-2-one join DMF/HEPES cushion (v/v=7/3, pH=7.4) in solution, be that 400 μm of ol/L add a metal ion species by the concentration of metal ion again, the fluorescence emission spectrum of solution after 30min, wherein metal ion is respectively Al
3+, Zn
2+, Ag
+, Ca
2+, Mg
2+, Fe
3+, Hg
2+, Pb
2+, Na
+, Ba
2+, Ni
2+, K
+, Cu
2+, Cr
3+, Cd
2+and Co
2+, as shown in Figure 3, as shown in Figure 3, after adding different metal ions, characteristic emission peak does not have obvious blue shift or red shift to the fluorescence emission spectrogram obtained, but fluorescence intensity has change in various degree.When adding Fe
3+time, fluorescence intensity cancellation is to original 1/6; When the ion added is Ag
+and Cu
2+time, fluorescence intensity has cancellation by a small margin; When the ion added is Al
3+, Zn
2+, Ca
2+, Mg
2+, Hg
2+, Pb
2+, Na
+, Ba
2+, Ni
2+, K
+, Cr
3+, Cd
2+, Co
2+time, fluorescence intensity and fluorescent molecular probe are more or less the same, and fluorescence intensity is almost constant.Therefore, fluorescent molecular probe 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one is to Fe
3+there are good selectivity and separating capacity; Simultaneously to Ag
+and Cu
2+also selective to a certain extent.
The fluorescent molecular probe prepared by the present embodiment carries out the test of anti-metal ion interference, method is as follows: by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is 10 μm of ol/L, by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] and-2H-pyran-2-one join DMF/HEPES cushion (v/v=7:3, pH=7.4) in solution, then the common metal ion (Al of 400 μm of ol/L is added respectively
3+, Zn
2+, Ag
+, Ca
2+, Mg
2+, Hg
2+, Pb
2+, Na
+, Ba
2+, Ni
2+, K
+, Cu
2+, Cr
3+, Cd
2+, Co
2+) and Fe
3+, detect the fluorescence emission spectrum change of solution after 30min, get peak fluorescence intensity and compare (as shown in Figure 4).As seen from Figure 4, other common metal ion (Al
3+, Zn
2+, Ag
+, Ca
2+, Mg
2+, Hg
2+, Pb
2+, Na
+, Ba
2+, Ni
2+, K
+, Cu
2+, Cr
3+, Cd
2+, Co
2+) and Fe
3+while exist, Fe
3+still can make the fluorescence intensity generation cancellation of fluorescent molecular probe, cancellation intensity with not exist when disturb metal ion suitable, i.e. fluorescent molecular probe Fe
3+selective recognition by the interference of other metal ions.
Fluorescent molecular probe prepared by detection the present embodiment is to Fe
3+optionally sensitivity, concrete grammar is as follows: by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is 10 μm of ol/L, by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] and-2H-pyran-2-one join DMF/HEPES cushion (v/v=7:3, pH=7.4), in solution, the Fe of 0.01 ~ 120 equivalent is added
3+, the fluorescence pattern changing conditions (as shown in Figure 5) tested out; As seen from Figure 5, along with Fe
3+the continuous increase of amount, the intensity of the emission peak at 426nm place constantly reduces, and works as Fe
3+concentration when being about 100 times of the concentration of fluorescent molecular probe, fluorescence is cancellation completely almost.Fig. 6 is that fluorescence intensity is with Fe
3+concentration curve figure, also can image find out from Fig. 6, fluorescence intensity is with Fe
3+the increase of amount, fluorescence intensity constantly reduces, and amplitude slows down gradually, and when reaching 100 equivalent, fluorescence intensity almost no longer changes, and fluorescent quenching is complete, and fluorescence intensity is with Fe
3+change in concentration is good linear relationship.
Fig. 7 is that the fluorescent molecular probe of the present embodiment detects Fe
3+the mensuration graphic representation of lowest detectable limit.X-coordinate is Fe
3+the logarithmic value of concentration, ordinate zou Y=(I – I
min)/(I
max– I
min), wherein I
minfor Fe
3+fluorescence intensity when concentration is 0, I
maxfor Fe
3+fluorescence intensity when concentration is 30 μm of ol/L, I is the fluorescence intensity under other concentration, and linear fit equation is Y=1.3499X+1.0066, R=0.9974, calculates lowest detection and is limited to 0.107 μm of ol/L concentration.
Test pH value, on the impact of fluorescent molecular probe prepared by the present embodiment, namely detects fluorescent molecular probe and add Fe under different pH condition
3+front and back change in fluorescence situation, specific as follows: by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is that 10 μm of ol/L are by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical] and-2H-pyran-2-one add DMF/HEPES cushion (v/v=7:3, pH=7.4), in solution, the fluorescence emission spectrum under different pH condition between 2 – 13 is measured respectively.Same mensuration adds the Fe of 400 μm of ol/L
3+afterwards different pH condition fluorescence emission spectrum spectrum, result is as shown in Figure 8.As seen from Figure 8, fluorescent molecular probe is when pH value 2 – 4, and fluorescence intensity slightly strengthens with the increase of pH value; When at pH>4, fluorescence intensity is little with the increase change of pH.Add Fe
3+after, the fluorescence intensity of fluorescent molecular probe obviously weakens, and fluorescent quenching is obvious, and fluorescence intensity is less with pH value change.Fluorescent molecular probe in this explanation the present embodiment is to Fe
3+be identified in and there is stable fluorescence intensity in pH value range widely, less by pH value change.
Fluorescent molecular probe prepared by test the present embodiment is to Fe
3+time of response, concrete grammar is as follows: by 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9, 10-d] imidazoles-2-) phenylamino methylene radical] concentration of-2H-pyran-2-one is 10 μm of ol/L4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-s [9, 10-d] imidazoles-2-) phenylamino methylene radical] and-2H-pyran-2-one join DMF/HEPES cushion (v/v=7:3, pH=7.4) in solution, under different time conditions (0.5, 2.0, 3.5, 5.0, 6.5, 8.0, 9.5, 11.0min) test its fluorescence emission spectrum.Equally, in identical system, add the Fe of 400 μm of ol/L
3+, under measuring different time conditions (0.5,2.0,3.5,5.0,6.5,8.0,9.5,11.0min) survey its fluorescence emission spectrum, the maximum value of getting in fluorescence emission spectrum obtains probe to Fe
3+corresponding time changing curve, as shown in Figure 9.As can see from Figure 9, Fe is being added
3+after, fluorescent molecular probe and Fe within 0.5 minute
3+namely complexing can be completed, the complete quencher of fluorescent emission intensity.Illustrate that this probe is to Fe
3+response very fast, just can complete complexing within half a minute, reality detect application in have extraordinary instantaneity advantage.
Embodiment 2: the preparation method of the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection of the present embodiment is as follows:
One, by 385mg (1mmol) 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] to join 20mL mass percentage concentration be in the vitriol oil of 98% for imidazoles and 408mg (2mmol) 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor, stirring at room temperature reaction 30min, obtains reaction mixture;
Two, reaction mixture is poured in distilled water, after pH value being adjusted to 10 by NaOH solution, separate out a large amount of solid; Filter, collect filter cake;
Three, by filter cake ethyl acetate and sherwood oil recrystallization, obtain 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, be the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor detected for iron ion.As calculated, productive rate is 81%.
The two fluorophor ratio fluorescent molecular probe of phenanthro-imidazoles-tonka bean camphor detected for iron ion prepared by the present embodiment ir data, in the DMSO solvent that replaces at deuterium
1hNMR modal data and
13cNMR spectral data is as follows:
IR(KBr,cm
-1):3061,1737,1615,1597,1497,1452,753,698.
1HNMR(600MHz,DMSO)δ(ppm):14.14(s,1H),9.12(s,1H),8.93(dd,J
1＝8.4Hz,J
2＝14.4Hz,2H),8.85(d,J＝8.4Hz,1H),7.76(t,J＝7.2Hz,1H),7.72-7.69(m,2H),7.65-7.63(m,2H),7.57(t,J＝7.8Hz,2H),7.51(t,J＝7.3Hz,1H),7.47(t,J＝7.9Hz,2H),7.43(d,J＝7.6Hz,2H),7.36(m,2H),7.13(d,J＝8.3Hz,1H),6.70(d,J＝9.0Hz,1H),6.26(s,1H),2.37(s,3H).
13CNMR(150MHz，DMSO)δ(ppm):164.94，159.54,157.77,154.46,149.77,146.78,137.65,137.04,132.60,131.71,131.11,130.24,130.16,128.91,128.77,128.14,127.95,127.45,127.28,127.13,127.09,126.72,126.20,125.77,125.02,124.10,122.76,122.68,120.69,118.87,114.40,111.58,111.02,106.87,40.51.
The structural formula that can obtain the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection prepared by the present embodiment from above data is as follows:
its chemical name is: 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one.
Embodiment 3: the preparation method of the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection of the present embodiment is as follows:
One, by 385mg (1mmol) 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] imidazoles and 1020mg (5mmol) 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor join in 20mL formic acid, stirring at room temperature reaction 60min, obtains reaction mixture;
Two, reaction mixture is poured in distilled water, after pH value being adjusted to 8 by NaOH solution, separate out a large amount of solid; Filter, collect filter cake;
Three, by filter cake ethyl acetate and sherwood oil recrystallization, obtain 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, be the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor detected for iron ion.As calculated, productive rate is 79%.
The two fluorophor ratio fluorescent molecular probe of phenanthro-imidazoles-tonka bean camphor detected for iron ion prepared by the present embodiment ir data, in the DMSO solvent that replaces at deuterium
1hNMR modal data and
13cNMR spectral data is as follows:
IR(KBr,cm
-1):3061,1737,1615,1597,1497,1452,753,698.
1HNMR(600MHz,DMSO)δ(ppm):14.14(s,1H),9.12(s,1H),8.93(dd,J
1＝8.4Hz,J
2＝14.4Hz,2H),8.85(d,J＝8.4Hz,1H),7.76(t,J＝7.2Hz,1H),7.72-7.69(m,2H),7.65-7.63(m,2H),7.57(t,J＝7.8Hz,2H),7.51(t,J＝7.3Hz,1H),7.47(t,J＝7.9Hz,2H),7.43(d,J＝7.6Hz,2H),7.36(m,2H),7.13(d,J＝8.3Hz,1H),6.70(d,J＝9.0Hz,1H),6.26(s,1H),2.37(s,3H).
13CNMR(150MHz，DMSO)δ(ppm):164.94，159.54,157.77,154.46,149.77,146.78,137.65,137.04,132.60,131.71,131.11,130.24,130.16,128.91,128.77,128.14,127.95,127.45,127.28,127.13,127.09,126.72,126.20,125.77,125.02,124.10,122.76,122.68,120.69,118.87,114.40,111.58,111.02,106.87,40.51.
The structural formula that can obtain the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor for iron ion detection prepared by the present embodiment from above data is as follows:
its chemical name is: 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one.
Claims (6)
1. the two fluorophor ratio fluorescent molecular probe of phenanthro-imidazoles-tonka bean camphor detected for iron ion, it is characterized in that this fluorescent molecular probe is 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, its structural formula is:
2. prepare the method for the two fluorophor ratio fluorescent molecular probe of a kind of phenanthro-imidazoles-tonka bean camphor for iron ion detection according to claim 1, it is characterized in that the method is as follows:
One, by 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] mol ratio of imidazoles and 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor is 1:(1 ~ 5), by 1-N-phenyl-2-(2-aminophenyl)-1H-phenanthro-[9,10-d] imidazoles and 4-methyl-7-hydroxyl-8-aldehyde radical tonka bean camphor join in acid solvent, stirring at room temperature reaction 10 ~ 60min, obtains reaction mixture;
Two, reaction mixture is poured in distilled water, after pH value being adjusted to 8 ~ 10, separate out a large amount of solid; Filter, collect filter cake;
Three, by filter cake ethyl acetate and sherwood oil recrystallization, obtain 4-methyl-7-hydroxyl-8-[2-(1-phenyl-1H-phenanthro-[9,10-d] imidazoles-2-) phenylamino methylene radical]-2H-pyran-2-one, be the two fluorophor ratio fluorescent molecular probe of the phenanthro-imidazoles-tonka bean camphor detected for iron ion.
3. the preparation method of the two fluorophor ratio fluorescent molecular probe of a kind of phenanthro-imidazoles-tonka bean camphor for iron ion detection according to claim 2, is characterized in that acid solvent glacial acetic acid, the vitriol oil or the formic acid in step one.
4. the preparation method of the two fluorophor ratio fluorescent molecular probe of a kind of phenanthro-imidazoles-tonka bean camphor for iron ion detection according to Claims 2 or 3, is characterized in that in step 2, adjust ph adopts sodium hydroxide.
5. the preparation method of the two fluorophor ratio fluorescent molecular probe of a kind of phenanthro-imidazoles-tonka bean camphor for iron ion detection according to Claims 2 or 3, is characterized in that the volume ratio of ethyl acetate and sherwood oil in step 3 is 1:(10 ~ 15).
6. the using method of the two fluorophor ratio fluorescent molecular probe of a kind of phenanthro-imidazoles-tonka bean camphor for iron ion detection according to claim 1, is characterized in that the method is carried out according to the following steps:
One, two for the phenanthro-imidazoles-tonka bean camphor being used for iron ion detection fluorophor ratio fluorescent molecular probe is dissolved in the mixed solution of DMF and HEPES buffered soln, obtains fluorescent molecular probe solution; The wherein pH=7.4 of HEPES buffered soln mixed solution, in mixed solution, the volume ratio of DMF and HEPES buffered soln is 7:3, and in mixed solution, the concentration of fluorescent molecular probe is 10 μm of ol/L;
Two, get fluorescent molecular probe solution, add testing sample wherein, mix, obtain sample solution;
Three, with ultraviolet spectrophotometer test fluorescent molecular probe solution at wavelength be the absorbance A at 260nm place
1, then test the absorbance A that sample solution is 260nm place at wavelength
2if, A
2≤ 20%A
1, then can judge in sample containing Fe
3+; Or with the fluorescence intensity B of fluorescence spectrophotometer test fluorescent molecular probe solution when emission wavelength is 426nm
1, then test the fluorescence intensity B of sample solution when emission wavelength is 426nm
2if, B
2≤ 20%B
1, then can judge in sample containing Fe
3+.
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