CN107629008A - A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method - Google Patents
A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method Download PDFInfo
- Publication number
- CN107629008A CN107629008A CN201710968079.0A CN201710968079A CN107629008A CN 107629008 A CN107629008 A CN 107629008A CN 201710968079 A CN201710968079 A CN 201710968079A CN 107629008 A CN107629008 A CN 107629008A
- Authority
- CN
- China
- Prior art keywords
- phenanthro
- imidazoles
- fluorescence probe
- small molecule
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IEYCWGXLZRPWIT-MUFRIFMGSA-N [O-][N+](c(cc1)cc(/C=N/c2cc(-c3nc4c(cccc5)c5c(cccc5)c5c4[nH]3)ccc2)c1O)=O Chemical compound [O-][N+](c(cc1)cc(/C=N/c2cc(-c3nc4c(cccc5)c5c(cccc5)c5c4[nH]3)ccc2)c1O)=O IEYCWGXLZRPWIT-MUFRIFMGSA-N 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method, the present invention is to solve existing Fe3+Fluorescence probe is only suitable to the noisy technical problem of identification of acid and neutral environment-identification, other metals to iron ion.The phenanthro- imidazoles small molecule Fe of the present invention3+The structural formula of fluorescence probe is:Synthetic method:First, with phenanthrenequione, m-nitrobenzaldehyde and ammonium acetate synthetic intermediate compound I;2nd, midbody compound I, Raney's nickel and hydrazine hydrate solution synthetic intermediate compound II are recycled;3rd, phenanthro- imidazoles small molecule Fe is synthesized with 5 nitrosalicylaldehydes with midbody compound II3+Fluorescence probe.This probe can recognize that Fe in the aqueous phase system that pH value is 3~123+, not by other ion interferences, available for Fe in water3+Pollution detection.
Description
Technical field
The present invention relates to a kind of Fe3+Fluorescence probe and its synthetic method.
Background technology
Iron is one of most important trace element in human body, in importance or quantitatively all occupy the first.
Asiderosis can cause a variety of diseases in human body, but excessive iron can also exist it is potentially hazardous, therefore to the detection of iron ion
Have very important significance.In recent years, more and more researchers have started the research work to iron ion fluorescence probe.
Li Bo et al. report rhodamine B derivative under sour environment to the recognition performance of ferric ion [organic chemistry,
2015,35,2629-2635] research discovery Fe3+Can be with the fluorescence of Selective long-range DEPT rhodamine B derivative.2016,《Change
Learn reagent》Disclosed article《The synthesis of iron ion fluorescence probe and spectrum property》In report the rhodamine under neutral environment and spread out
Recognition performance of the biology to ferric ion.2011《Sensor and actuator B:Chemistry》(Sensors
andActuators B:Chemical article disclosed in 1106-1111 pages of 160 phases)《Formed by the bonding pattern of bimodulus
Multi-functional identification Cu2+And Fe3+Fluorescence probe》(Multifunctional fluorescent probe selective
For Cu (II) and Fe (III) with dual-mode of binding approach) and 2015《Inorganic chemistry Europe
Journal》(EurJIC) article disclosed in 311-317 pages《A kind of simple naphthylamines fluorescence probe is selectively known in mixed aqueous solution
Other HgII、FeIIAnd FeIII:Application in terms of biological cell and gate》(A Simple Fluorescent Probe
Derived fromNaphthylamine for Selective Detection of HgII,FeII and FeIII Ions
in Mixed Aqueous Media:Applications in Living Cells and Logic Gates) be all on
The technology of iron ion identification, in this two articles, host compound in addition to it can identify iron ion, also to bivalent cupric ion and
Ferrous ion has recognition performance.
According to the research for iron ion fluorescence probe of current document report, following two defects are primarily present:
1. host compound can only have recognition performance under acid or neutral environment to iron ion, that is to say, that
Identification has limitation under alkaline environment;
2. host compound not only has recognition performance to iron ion, other metal ions can also be identified, so
Say, identification does not have selectivity.
The content of the invention
The present invention is to solve existing Fe3+Fluorescence probe is only suitable to acid and neutral environment-identification, other metals pair
The noisy technical problem of identification of iron ion, and a kind of phenanthro- imidazoles small molecule Fe is provided3+Fluorescence probe and its synthesis are with making
Use method.Phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method.
The phenanthro- imidazoles small molecule Fe of the present invention3+The structural formula of fluorescence probe is:
Above-mentioned phenanthro- imidazoles small molecule Fe3+The synthetic method of fluorescence probe, carry out according to the following steps:
First, midbody compound I synthesis:
By phenanthrenequione, m-nitrobenzaldehyde and ammonium acetate according to 1:(1.4~1.6):The mol ratio of (1.8~2.1) is added to
In reactor, glacial acetic acid is added as solvent, after being warming up to 80~110 DEG C and stirring 6~10h, reaction stops, and is cooled to room
Temperature, adds water into reactor, then adjusts pH value to filter, obtain yellow solid to 8~10 with sodium hydroxide solution, after drying, then
With re-crystallizing in ethyl acetate, then filter, dry, obtain midbody compound I;
2nd, midbody compound II synthesis:
The hydrazine hydrate solution that midbody compound I, Raney's nickel and mass percentage concentration are 78~83% is weighed, wherein among
The ratio of the amount of body compound I material and the quality of Raney's nickel is 1mmol:(0.15~0.2) g, midbody compound I material
Amount and mass percentage concentration be 78~83% the ratio of volume of hydrazine hydrate solution be 1mmol:(3~5) mL;First by intermediate
Compound I and Raney's nickel are added in reactor, are added ethanol as solvent, are passed through nitrogen protection, under agitation, drop
Add the hydrazine hydrate solution that mass percentage concentration is 80%, after being added dropwise, be warming up to 60~80 DEG C, react 6~9h, be cooled to room
Temperature, filter, washed with ethyl acetate, rotary evaporation removes filtrate, obtains midbody compound II;
3rd, Fe3+The synthesis of fluorescence probe:
It is 1 according to the mol ratio of midbody compound II and 5- nitrosalicylaldehydes:The ratio of (1~3) weighs intermediate
Compound II and 5- nitrosalicylaldehyde, is added in reactor, and it is solvent to add acid medium, and stirring at normal temperature reacts 2~4h, instead
After should terminating, into reaction system adding water quenching goes out reaction, then adjusts pH value to 8~10 with sodium hydroxide solution, precipitation solid, so
After filtered, filter cake is simultaneously washed to neutrality, dry after, obtain phenanthro- imidazoles small molecule Fe3+Fluorescence probe.
The building-up process of the present invention can use following formula to represent:
The invention provides one kind in aqueous phase system, in the range of pH value is 3~12, there is high selectivity, response spirit
It is quick and not by the phenanthro- imidazoles small molecule Fe of other metal ion disturbances3+Fluorescence probe.The fluorescence probe can select to identify Fe3+,
Not by K+、Ba2+、Ca2+、Na2+、Mg2+、Zn2+、Cr3+、Cd2+、Ni2+、Co2+、Pb2+、Cu2+、Ag+、Al3+And Hg2+Deng other ions
Interference, and the response time is only 10min, for Fe3+Inspection, fast and easy.The letter of this Small-molecule probe synthesis step
List, easy post-processing, yield are higher.
Brief description of the drawings
Fig. 1 is to test the 1 phenanthro- imidazoles small molecule Fe prepared3+Ultra-violet absorption spectrum of the fluorescence probe to different metal ions
Figure;
Fig. 2 is to test the 1 phenanthro- imidazoles small molecule Fe prepared3+Fluorescence emission spectrum of the fluorescence probe to different metal ions
Figure;
Fig. 3 is to test the 1 phenanthro- imidazoles small molecule Fe prepared3+Fluorescence probe in the presence of other metal ions,
Fe3+The fluorescence emission spectrogram of compound of fluorescence probe
Fig. 4 is to test the 1 phenanthro- imidazoles small molecule Fe prepared3+Fluorescence of the fluorescence probe in the concentration of different iron ions
Launching light spectrogram;
Fig. 5 is to test the 1 phenanthro- imidazoles small molecule Fe prepared3+Fluorescent emission of the fluorescence probe under the conditions of different pH is strong
Degree figure;
Fig. 6 is to test the 1 phenanthro- imidazoles small molecule Fe prepared3+Fluorescent emission of the fluorescence probe in different complexation times is strong
Degree figure.
Embodiment
Embodiment one:The phenanthro- imidazoles small molecule Fe of present embodiment3+The structural formula of fluorescence probe is:
Embodiment two:Phenanthro- imidazoles small molecule Fe described in embodiment one3+The synthesis side of fluorescence probe
Method, carry out according to the following steps:
First, midbody compound I synthesis:
By phenanthrenequione, m-nitrobenzaldehyde and ammonium acetate according to 1:(1.4~1.6):The mol ratio of (1.8~2.1) is added to
In reactor, glacial acetic acid is added as solvent, after being warming up to 80~110 DEG C and stirring 6~10h, reaction stops, and is cooled to room
Temperature, adds water into reactor, then adjusts pH value to filter, obtain yellow solid to 8~10 with sodium hydroxide solution, after drying, then
With re-crystallizing in ethyl acetate, then filter, dry, obtain midbody compound I;
2nd, midbody compound II synthesis:
The hydrazine hydrate solution that midbody compound I, Raney's nickel and mass percentage concentration are 78~83% is weighed, wherein among
The ratio of the amount of body compound I material and the quality of Raney's nickel is 1mmol:(0.15~0.2) g, midbody compound I material
Amount and mass percentage concentration be 78~83% the ratio of volume of hydrazine hydrate solution be 1mmol:(3~5) mL;First by intermediate
Compound I and Raney's nickel are added in reactor, are added ethanol as solvent, are passed through nitrogen protection, under agitation, drop
Add the hydrazine hydrate solution that mass percentage concentration is 80%, after being added dropwise, be warming up to 60~80 DEG C, react 6~9h, be cooled to room
Temperature, filter, washed with ethyl acetate, rotary evaporation removes filtrate, obtains midbody compound II;
3rd, Fe3+The synthesis of fluorescence probe:
It is 1 according to the mol ratio of midbody compound II and 5- nitrosalicylaldehydes:The ratio of (1~3) weighs intermediate
Compound II and 5- nitrosalicylaldehyde, is added in reactor, and it is solvent to add acid medium, and stirring at normal temperature reacts 2~4h, instead
After should terminating, into reaction system adding water quenching goes out reaction, then adjusts pH value to 8~10 with sodium hydroxide solution, precipitation solid, so
After filtered, filter cake is simultaneously washed to neutrality, dry after, obtain phenanthro- imidazoles small molecule Fe3+Fluorescence probe.
Embodiment three:Present embodiment is from the reaction temperature in step 1 unlike embodiment two
100 DEG C, reaction time 10h.It is other identical with embodiment two.
Embodiment four:PH value in present embodiment step 1 unlike embodiment two or three is
9.It is other identical with embodiment two or three.
Embodiment five:Hydrogen-oxygen in step 1 unlike one of present embodiment and embodiment two to four
The mass percentage concentration for changing sodium solution is 8%~12%.It is other identical with one of embodiment two to four.
Embodiment six:Reacted in step 2 unlike one of present embodiment and embodiment two to five
Temperature is 95 DEG C, reaction time 8h.It is other identical with one of embodiment two to five.
Embodiment seven:Among in step 3 unlike one of present embodiment and embodiment two to six
The mol ratio of body compound II and 5- nitrosalicylaldehydes is 1:2.It is other identical with one of embodiment two to six.
Embodiment eight:Unlike one of present embodiment and embodiment two to seven described in step 3
Acid medium be glacial acetic acid, the concentrated nitric acid that mass percentage concentration is 65%~68%, mass percentage concentration be 36~37%
Concentrated hydrochloric acid or benzoic acid.It is other identical with one of embodiment two to seven.
Embodiment nine:Normal temperature in step 3 unlike one of present embodiment and embodiment two to eight
Stirring reaction 3h.It is other identical with one of embodiment two to eight.
Embodiment ten:Hydrogen-oxygen in step 3 unlike one of present embodiment and embodiment two to nine
The mass percentage concentration for changing sodium solution is 8%~12%.It is other identical with one of embodiment two to nine.
Embodiment 11:PH in step 3 unlike one of present embodiment and embodiment two to ten
It is worth for 9;It is other identical with one of embodiment two to ten.
With following case verification beneficial effects of the present invention:
Experiment 1:The phenanthro- imidazoles small molecule Fe of this experiment3+The synthetic method of fluorescence probe, carry out according to the following steps:
First, midbody compound I synthesis:
Weigh the there-necked flask that phenanthrenequione 5.0mmol, m-nitrobenzaldehyde 7.5mmol, ammonium acetate 10.0mmol are added to 100mL
In, and the glacial acetic acid for adding 40mL thereto is warming up to 110 DEG C as solvent, and be stirred continuously, during the course of the reaction, use TLC
(solvent is ethyl acetate and petroleum ether to tracing detection, V (ethyl acetate):V (petroleum ether)=3:7) after, reaction carries out 8h, instead
Substantially completely reaction should be stopped, being cooled to room temperature, 50mL water is added in there-necked flask, is placed in 200mL beaker, uses matter
Measuring the sodium hydroxide solution that percentage concentration is 10% adjusts pH value to filter to 9, obtain yellow solid, dried in 100 DEG C of baking oven
5h;After drying, it is re-dissolved in 30mL ethyl acetate, after being heated to boiling reflux stirring 2h, is cooled to room temperature, there are a large amount of solids
Separate out, filter, drying, obtain midbody compound I;
The yield for the midbody compound I that this step obtains is 94%, fusing point:271~273 DEG C.With infrared spectrum, nuclear-magnetism
Hydrogen is composed and nuclear-magnetism carbon stave levies midbody compound I, and obtained result is as follows:
IR(KBr,cm–1):3607,1676,1593,1531,1455,1347,754,740.1H NMR(600MHz,
DMSO):δ (ppm) 13.826 (s, 1H), 9.158 (t, J=7.20Hz, 1H), 8.879 (d, J=7.80Hz, 2H), 8.763-
8.745 (m, 1H), 8.583 (d, J=7.20Hz, 2H), 8.338-8.319 (m, 1H), 7.897 (t, J=7.80Hz, 1H),
7.767 (t, J=7.20Hz, 2H), 7.687-7.660 (m, 2H), 7.135 (d, J=7.80Hz, 1H)13C NMR(150MHz,
DMSO):δ(ppm)148.36,146.71,135.34,132.06,131.79,131.16,130.58,129.24,129.03,
127.23,127.09,126.69,125.71,125.39,124.35,124.10,123.71,123.45,121.98,121.83,
120.16.
The structural formula for knowing midbody compound I from characterization result is
2nd, midbody compound II synthesis:
2.0mmol midbody compound I, 0.35g Raney's nickels are added in 50mL three-necked flask and 30mL ethanol is molten
Agent, after 2 minutes nitrogen is passed through, stirring, and the water that 7.5mL mass percentage concentrations are 80% is slowly added dropwise with constant pressure funnel
Hydrazine solution is closed, after being added dropwise, after being warming up to 80 DEG C of back flow reaction 6h, (solvent is V ethyl acetate with TLC tracing detections:V
Petroleum ether=3:7), reaction substantially completely, after being cooled to room temperature, is filtered, washed five times with ethyl acetate, rotary evaporation filtrate,
Obtain gray solid;Re-crystallizing in ethyl acetate is used after drying again, after being heated to boiling reflux stirring 2h, room temperature is cooled to, has big
Measure solid to separate out, filter, dry, midbody compound II.The yield for the midbody compound II that this step obtains is 73%, is melted
Point:197~198 DEG C;
Characterized with infrared spectrum, nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum, obtained result is as follows:
IR(KBr,cm–1):3435,3362,1608,1595,1461,761,723.1H NMR(600MHz,DMSO):δ
(ppm) 13.336 (s, 1H), 8.854 (d, J=7.20Hz, 2H), 8.580 (d, J=7.80Hz, 2H), 7.732 (t, J=
7.20Hz, 2H), 7.629 (t, J=7.80Hz, 2H), 7.570 (s, 1H), 7.449 (d, J=7.20Hz, 1H), 7.240 (t, J
=7.80Hz, 1H), 6.705 (d, J=7.20Hz, 1H), 5.351 (s, 2H)13C NMR(150MHz,DMSO):δ(ppm)
149.92,149.03,136.74,130.86,129.19,127.43,127.35,127.30,126.99,126.96,126.89,
125.04,124.88,123.93,123.61,122.39,121.88,121.68,114.94,113.74,111.52.
The structural formula for knowing midbody compound II from characterization result is
3rd, Fe3+The synthesis of fluorescence probe:
0.46g (1.5mmol) midbody compounds II, 0.25g (1.5mmol) 5- nitro water is added into there-necked flask successively
Poplar aldehyde, then 25mL glacial acetic acid is added in there-necked flask as solvent, stirring at normal temperature reaction 2h, after reaction terminates, to reactant
Water quenching is added in system to go out reaction, then is placed in 200mL beaker, with the sodium hydroxide solution tune pH that mass percentage concentration is 10%
Then value is filtered, filter cake is washed to neutrality, drying to 9.After drying, phenanthro- imidazoles small molecule Fe is obtained3+Fluorescence probe.
In this step, phenanthro- imidazoles small molecule Fe3+The yield of fluorescence probe is 91%.
Phenanthro- imidazoles small molecule Fe3+The fusing point of fluorescence probe is>300℃.
Characterized with infrared spectrum and nuclear magnetic resoance spectrum, obtained result is as follows:
IR(KBr,cm–1):3435,3060,1617,1595,1566,1493,1450,1277,759.1H NMR
(600MHz,DMSO):δ (ppm) 14.229 (s, 1H), 13.555 (s, 1H), 9.328 (s, 1H), 8.875 (d, J=9.6Hz,
2H), 8.792 (d, J=7.20Hz, 1H), 8.617 (d, J=7.20Hz, 1H), 8.562 (d, J=7.80Hz, 1H), 8.371
(s,1H),8.324-8.301(m,2H),7.787-7.662(m,5H),7.617(dd,J1=6.40Hz, J2=6.20Hz, 1H),
7.197 (d, J=9Hz, 1H)13C NMR(150MHz,DMSO):δ(ppm)170.81,166.96,162.31,148.82,
148.13,139.85,135.93,132.17,131.18,130.79,129.83,129.05,128.63,128.19,127.64,
125.90,125.65,124.93,124.33,122.45,121.99,119.94,119.43,118.76.
It was found from characterization result more than, phenanthro- imidazoles small molecule Fe3+The structural formula of fluorescence probe is:
Phenanthro- imidazoles small molecule Fe prepared by this experiment3+Fluorescence probe carries out spectrum property test, and step is as follows:
First, the configuration of storing solution
By phenanthro- imidazoles small molecule Fe3+Fluorescence probe using N,N-dimethylformamide (DMF) be solvent be configured to concentration as
1.0×10–4Mol/L main body storing solution, it is standby;
Metal nitrate, chlorate are configured to the metal ion storing solution that concentration is 0.1mol/L, it is standby;
HEPES cushioning liquid:It is put into 250mL volumetric flask, is used with HEPES 0.60g
Distilled water constant volume, 0.01mol/L solution is made into, is shaken up, after static 3 hours, adjusted pH value with sodium hydroxide solution, be made into pH
It is worth the cushioning liquid for 7.4~12, pH value is adjusted with salpeter solution, is made into the cushioning liquid that pH value is 3~6.Shake up, it is standby.
2nd, spectrum property is tested
It is 1.0 × 10 that concentration is added into 10.0mL volumetric flask–4Mol/L main body storing solution 1mL, adding concentration is
0.1mol/L metal ion to be measured, with the HEPES cushioning liquid constant volumes that concentration is 0.01mol/L, pH=7.4.Now, main body
With Fe3+Molar concentration rate is 1:50.After constant temperature 1h, the test of ultra-violet absorption spectrum and fluorescence emission spectrum is carried out respectively.
Phenanthro- imidazoles small-molecule fluorescent probe is first investigated to the Selective recognition of metal ion, the solvent of selection is volume ratio
It is 1:1 DMF/HEPES mixed solution (wherein, the concentration of HEPES cushioning liquid is 0.01mol/L, pH=7.4), prepare
It is 1.0 × 10 into concentration-5Mol/L bulk solution, then the K that concentration is 0.10mol/L is separately added into host compound+、
Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Fe3+、Cd2+、Ni2+、Co2+、Pb2+、Cu2+、Ag+、Al3+And Hg2+Metal ion, and point
Ultra-violet absorption spectrum is not determined, as a result as shown in figure 1, representing host compound phenanthro- imidazoles small molecule Fe in figure with L3+Fluorescence is visited
Pin.As can be known from Fig. 1, after adding different metal ions, it can be seen that K+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Cd2+、
Cu2+、Ni2+、Co2+、Pb2+、Hg2+、Ag+And Al3+It is similar with the ultra-violet absorption spectrum curve shape and absorbance of main body.Add Fe3 +Afterwards, in UV absorption wave spectrum, wavelength is that the absorbance at 425nm is remarkably reinforced, and intensity is about the 2 of host compound L
Times.Therefore, can be with initial guess from uv absorption spectra, host compound is to Fe3+With selection evident characteristics.
Continuation further verifies the phenanthro- imidazoles small-molecule fluorescent probe of this experiment preparation to Fe3+With Selective recognition
Characteristic, it is 325nm in excitation wavelength, in the case that exciting slit width is 10, the test of fluorescence emission spectrum is carried out to it, obtained
The fluorescence emission spectral intensity arrived, as a result as shown in Figure 2.As can be known from Fig. 2, the fluorescence emission wavelengths of main body are 400nm, fluorescence
Intensity is 600a.u. or so.After adding different metal ions, it can be seen that K+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cd2+、Ni2+、
Co2+、Cr3+、Pb2+、Hg2+、Ag+、Al3+And Cu2+With being influenceed less on the fluorescence intensity of main body, intensity is in 600a.u. or so.
And add Fe3+Afterwards, fluorescence intensity is substantially gone out to 150a.u. or so, is quenched the 1/4 of original intensity.Therefore, from fluorescent emission
Spectrum it was determined that host compound to Fe3+With selection evident characteristics.
In order to further verify the phenanthro- imidazoles small-molecule fluorescent probe of this experiment preparation to Fe3+With Selective recognition
Characteristic.It is 1 with volume ratio:1 DMF/HEPES mixed solution (wherein, the concentration of HEPES cushioning liquid is 0.01mol/L,
PH=7.4) it is solvent, compound concentration is 1.0 × 10-5Mol/L bulk solution, in bulk solution being separately added into concentration is
5.0×10–4Mol/L K+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Cd2+、Ni2+、Co2+、Pb2+、Cu2+、Ag+、Al3+And Hg2+
Metal ion solution.5min is stood after being sufficiently mixed, then is separately added into 1.0 × 10-5Mol/L Fe3+After be well mixed.Now,
Host compound/metal ion/Fe3+The molar concentration rate of three is 1:50:50.It is 325nm in excitation wavelength after constant temperature 1h,
In the case that exciting slit width is 10.0nm, the test of fluorescence emission spectrum is carried out to it.Obtained fluorescence emission spectrum is strong
It is as shown in Figure 3 to spend result.In other metal ions (K+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Cd2+、Ni2+、Co2+、Pb2+、
Cu2+、Ag+、Al3+And Hg2+) in the presence of, Fe3+When being coexisted with other metal ions, host compound identifies with iron ion
Fluorescence intensity do not influenceed by other metal ions.That is, subject highlighting is not disturbed in the presence of other metal ions
Compound is to Fe3+Identification.Therefore, Fig. 3 can prove host compound to Fe3+With selection evident characteristics.It can be illustrated again
He identifies Fe by metal ion to host compound3+Without influence.
In order to examine or check Fe3+Concentration is to Fe3+The influence of fluorescence probe fluorescence intensity, it is 1 with volume ratio:1 DMF/HEPES
Mixed solution (wherein, the concentration of HEPES cushioning liquid is 0.01mol/L, pH=7.4) be solvent, prepare host compound
Solution, gradually the concentration of increase iron ion (for the 0 to 100 of body concentration work as by concentration of metal ions in host compound solution
Amount), and the test of fluorescence emission spectrum is carried out to it.Test result is as shown in figure 4, from fig. 4, it can be seen that with Fe3+Concentration
Increase, fluorescence intensity is gradually reduced.During to 80 equivalent, go out to minimum value 50a.u. or so.It is further continued for increasing Fe3+Concentration
When, fluorescence intensity no longer changes substantially.
Under different pH value of solution (3~12) values, pH value is investigated and Fe is identified to host compound3+Fluorescence emission spectrum
Situation of change.Fluorescence intensity is as shown in Figure 5 with pH situation of change.As can be seen from Figure 5:The fluorescence intensity of host compound
Little with pH change change, either in acid, neutrality or under conditions of alkalescence, the fluorescence intensity of main body all exists
600a.u. left and right.When to bulk solution (1.0 × 10-5Mol/L Fe is added in)3+(5.0×10-4Mol/L after), it is 3 to investigate pH
Host compound is to Fe between~123+The change in fluorescence situation of identification.As a result find, in this pH value range, Fe3+Can
The fluorescence of host compound is set to go out, and fluorescence intensity is held essentially constant.That is, the change of pH value is to the glimmering of main body
Luminous intensity and main body identification Fe3+Fluorescence intensity almost without influence.This result of study illustrates the host compound and Fe3+'s
Fluorescence identifying can be realized under different pH value.
In addition, host compound is to Fe3+The fluorescence corresponding time of identification is very short.Under conditions of pH is 7.4, it is to concentration
1.0×10-5It is 5.0 × 10 that concentration is added in mol/L host compound-4mol/L Fe3+, it is well mixed.Determined after 10min
Its fluorescence emission spectrum, and every 10min tests once, test result is as shown in Figure 6.From fig. 6, it can be seen that in measure
In time, host compound has stable fluorescence intensity, and this host compound illustrated in this patent has in aqueous
There is stable fluorescent emission.Host compound and Fe are determined during 10min3+Fluorescence, fluorescence intensity, which has occurred and that, significantly goes out.
20th, 30,40, during 50min, fluorescence intensity is to be more or less the same with 10min.This explanation, host compound in aqueous can be real
Now to Fe3+Quick identification, and keep the stability of rear fluorescence gone out.This result has in the practical application of host compound
There is important meaning.
This experiment prepares phenanthro- imidazoles small molecule Fe3+Fluorescence probe, experiment explanation is being 1 with volume ratio more than:1
DMF/H2O mixed solution (concentration of HEPES cushioning liquid is 0.01mol/L, pH=7.4) is the master in the system of solvent
Body compound is to Fe3+The effect of selective identification, and response sensitivity protrudes.And to other metal ions without evident characteristics,
And when being coexisted with other metal ions, compound identification Fe is not disturbed3+.Even if changing the environment of pH value of solution, can also realize
To Fe3+Fluorescence identifying.
Experiment 2:The step of this experiment tests 1 unlike experiment 1 three is replaced with following operation:Successively to there-necked flask
The quality hundred of middle addition midbody compound II 0.46g (1.5mmol), 5- nitrosalicylaldehydes 0.42g (2.5mmol) and 20mL
The concentrated nitric acid that concentration is 65~68% is divided stirring at normal temperature reaction 2.5h, after reaction terminates, to be added as solvent into reaction system
Water quenching is gone out reaction, is placed in 200mL beaker, adjusts pH value then to be filtered, filter cake to 9 with 10% sodium hydroxide solution
Neutrality is washed to, is dried.Phenanthro- imidazoles small molecule Fe is obtained after drying3+Fluorescence probe.Small point of the phenanthro- imidazoles that this experiment obtains
Sub- Fe3+The structural formula of fluorescence probe is:
Yield is 47%.
Experiment 3:The step of this experiment tests 1 unlike experiment 1 three is replaced with following operation:Successively to there-necked flask
The benzoic acid of middle addition midbody compound II 0.46g (1.5mmol), 5- nitrosalicylaldehydes 0.50g (3.0mmol) and 20mL
As solvent, stirring at normal temperature reaction 3h, after reaction terminates, water quenching is added into reaction system and is gone out reaction, be placed in 200mL burning
In cup, pH value is adjusted then to be filtered, filter cake is washed to neutrality, drying to 9 with 10% sodium hydroxide solution.Obtained after drying
Phenanthro- imidazoles small molecule Fe3+Fluorescence probe.The phenanthro- imidazoles small molecule Fe that this experiment obtains3+The structural formula of fluorescence probe is:
Yield is 61%.
Experiment 4:The step of this experiment tests 1 unlike experiment 1 three is replaced with following operation:Successively to there-necked flask
Middle addition midbody compound II 0.46g (1.5mmol), the 37% of 5- nitrosalicylaldehydes 0.75g (4.5mmol) and 15mL
Concentrated hydrochloric acid is as solvent, stirring at normal temperature reaction 4h, after reaction terminates, water quenching is added into reaction system and is gone out reaction, is placed in
In 200mL beaker, pH value is adjusted then to be filtered, filter cake is washed to neutrality, dries, and dries to 9 with 10% sodium hydroxide solution
Phenanthro- imidazoles small molecule Fe is obtained after dry3+Fluorescence probe.The phenanthro- imidazoles small molecule Fe that this experiment obtains3+The knot of fluorescence probe
Structure formula is:
Yield is 52%.
Claims (10)
- A kind of 1. phenanthro- imidazoles small molecule Fe3+Fluorescence probe, it is characterised in that the structural formula of the fluorescence probe is:
- 2. synthesize a kind of phenanthro- imidazoles small molecule Fe described in claim 13+The method of fluorescence probe, it is characterised in that the synthesis Method is carried out according to the following steps:First, midbody compound I synthesis:By phenanthrenequione, m-nitrobenzaldehyde and ammonium acetate according to 1:(1.4~1.6):The mol ratio of (1.8~2.1) is added to reaction In device, glacial acetic acid is added as solvent, after being warming up to 80~110 DEG C and stirring 6~10h, reaction stops, and is cooled to room temperature, Water is added into reactor, then adjusts pH value to filter to 8~10, obtain yellow solid, after drying, then use with sodium hydroxide solution Re-crystallizing in ethyl acetate, then filter, dry, obtain midbody compound I;2nd, midbody compound II synthesis:Weigh the hydrazine hydrate solution that midbody compound I, Raney's nickel and mass percentage concentration are 78~83%, wherein intermediate The ratio of the amount of compound I material and the quality of Raney's nickel is 1mmol:(0.15~0.2) g, the amount of midbody compound I material The ratio of the volume for the hydrazine hydrate solution for being 78~83% with mass percentage concentration is 1mmol:(3~5) mL;First by intermediate compound Thing I and Raney's nickel are added in reactor, are added ethanol as solvent, are passed through nitrogen protection, under agitation, matter are added dropwise The hydrazine hydrate solution that percentage concentration is 80% is measured, after being added dropwise, 60~80 DEG C is warming up to, reacts 6~9h, be cooled to room temperature, Filter, washed with ethyl acetate, rotary evaporation removes filtrate, obtains midbody compound II;3rd, Fe3+The synthesis of fluorescence probe:It is 1 according to the mol ratio of midbody compound II and 5- nitrosalicylaldehydes:The ratio of (1~3) weighs midbody compound II and 5- nitrosalicylaldehydes, are added in reactor, and it is solvent to add acid medium, and stirring at normal temperature reacts 2~4h, reaction knot Shu Hou, into reaction system adding water quenching goes out reaction, then adjusts pH value to 8~10 with sodium hydroxide solution, precipitation solid, Ran Houjin Row filters, and filter cake is simultaneously washed to neutrality, after drying, obtains phenanthro- imidazoles small molecule Fe3+Fluorescence probe.
- A kind of 3. phenanthro- imidazoles small molecule Fe according to claim 23+The synthetic method of fluorescence probe, it is characterised in that step Reaction temperature in rapid one is 100 DEG C, reaction time 10h.
- A kind of 4. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist PH value in step 1 is 9.
- A kind of 5. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist The mass percentage concentration of sodium hydroxide solution is 8%~12% in step 1.
- A kind of 6. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist Reaction temperature is 95 DEG C in step 2, reaction time 8h.
- A kind of 7. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist The mol ratio of midbody compound II and 5- nitrosalicylaldehydes is 1 in step 3:2.
- A kind of 8. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist Acid medium described in step 3 is glacial acetic acid, mass percentage concentration is 65%~68% concentrated nitric acid, quality percentage are dense Spend the concentrated hydrochloric acid or benzoic acid for 36~37%.
- A kind of 9. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist The mass percentage concentration of sodium hydroxide solution is 8%~12% in step 3.
- A kind of 10. phenanthro- imidazoles small molecule Fe according to Claims 2 or 33+The synthetic method of fluorescence probe, its feature exist PH value is 9 in step 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710968079.0A CN107629008B (en) | 2017-10-18 | 2017-10-18 | Phenanthroimidazole micromolecule Fe3+Fluorescent probe and synthetic method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710968079.0A CN107629008B (en) | 2017-10-18 | 2017-10-18 | Phenanthroimidazole micromolecule Fe3+Fluorescent probe and synthetic method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107629008A true CN107629008A (en) | 2018-01-26 |
CN107629008B CN107629008B (en) | 2020-04-14 |
Family
ID=61105535
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710968079.0A Expired - Fee Related CN107629008B (en) | 2017-10-18 | 2017-10-18 | Phenanthroimidazole micromolecule Fe3+Fluorescent probe and synthetic method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107629008B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108359444A (en) * | 2018-04-27 | 2018-08-03 | 齐齐哈尔大学 | A kind of detection Fe3+And Fe can be utilized3+Detect Ca2+Fluorescence probe and its preparation and application |
CN108863945A (en) * | 2018-06-12 | 2018-11-23 | 齐齐哈尔大学 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
CN110698407A (en) * | 2019-10-21 | 2020-01-17 | 齐齐哈尔大学 | Naked eye or fluorescent Al3+Probe and preparation method and application thereof |
WO2021120653A1 (en) * | 2019-12-16 | 2021-06-24 | 大连理工大学 | Cofactor-substrate probe platform for fast quantitative detection of tumor hypoxia related enzyme |
CN115260163A (en) * | 2022-06-24 | 2022-11-01 | 江西师范大学 | Imidazole type fluorescent molecule containing carbazole structure, preparation method thereof and application of imidazole type fluorescent molecule as fluorescent probe |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105255481A (en) * | 2015-11-16 | 2016-01-20 | 齐齐哈尔大学 | Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof |
CN105694866A (en) * | 2016-04-01 | 2016-06-22 | 齐齐哈尔大学 | Bis-Schiff-base-connected symmetrical phenanthroimidazole Fe<3+> fluorescent probe and preparation method thereof |
CN106632064A (en) * | 2016-11-21 | 2017-05-10 | 齐齐哈尔大学 | Reversible di-hydroxyl phenanthroimidazole Hg<2+> fluorescence probe, and synthesis and use methods |
CN106883183A (en) * | 2017-02-27 | 2017-06-23 | 齐齐哈尔大学 | One kind is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method and application |
-
2017
- 2017-10-18 CN CN201710968079.0A patent/CN107629008B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105255481A (en) * | 2015-11-16 | 2016-01-20 | 齐齐哈尔大学 | Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof |
CN105694866A (en) * | 2016-04-01 | 2016-06-22 | 齐齐哈尔大学 | Bis-Schiff-base-connected symmetrical phenanthroimidazole Fe<3+> fluorescent probe and preparation method thereof |
CN106632064A (en) * | 2016-11-21 | 2017-05-10 | 齐齐哈尔大学 | Reversible di-hydroxyl phenanthroimidazole Hg<2+> fluorescence probe, and synthesis and use methods |
CN106883183A (en) * | 2017-02-27 | 2017-06-23 | 齐齐哈尔大学 | One kind is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method and application |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108359444A (en) * | 2018-04-27 | 2018-08-03 | 齐齐哈尔大学 | A kind of detection Fe3+And Fe can be utilized3+Detect Ca2+Fluorescence probe and its preparation and application |
CN108863945A (en) * | 2018-06-12 | 2018-11-23 | 齐齐哈尔大学 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
CN110698407A (en) * | 2019-10-21 | 2020-01-17 | 齐齐哈尔大学 | Naked eye or fluorescent Al3+Probe and preparation method and application thereof |
CN110698407B (en) * | 2019-10-21 | 2023-09-29 | 齐齐哈尔大学 | Naked eye or fluorescent Al 3+ Probe and preparation method and application thereof |
WO2021120653A1 (en) * | 2019-12-16 | 2021-06-24 | 大连理工大学 | Cofactor-substrate probe platform for fast quantitative detection of tumor hypoxia related enzyme |
CN115260163A (en) * | 2022-06-24 | 2022-11-01 | 江西师范大学 | Imidazole type fluorescent molecule containing carbazole structure, preparation method thereof and application of imidazole type fluorescent molecule as fluorescent probe |
Also Published As
Publication number | Publication date |
---|---|
CN107629008B (en) | 2020-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107629008A (en) | A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method | |
CN105694866B (en) | Symmetric form phenanthro- imidazoles Fe3+ fluorescence probes of double-Schiff base link and preparation method thereof | |
CN106883183B (en) | One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof | |
Shi et al. | Four dual-functional luminescent Zn (II)-MOFs based on 1, 2, 4, 5-benzenetetracarboxylic acid with pyridylbenzimidazole ligands for detection of iron (III) ions and acetylacetone | |
CN101735277B (en) | Fluorescent probe compounds, preparation method and use thereof | |
CN103113380B (en) | Rhodamine derivative and preparation method and application thereof | |
CN106632064B (en) | Reversible dihydroxy phenanthroimidazole Hg2+Fluorescent probe synthesis and methods of use | |
CN108675990A (en) | A kind of detection Cu2+Fluorescence probe, preparation method and fluorescent test paper strip preparation and application | |
CN108359444B (en) | Detecting Fe3+And can utilize Fe3+Detection of Ca2+Fluorescent probes and methods of making and using the same | |
CN110240683A (en) | A kind of covalent organic frame material and preparation method thereof and the application in fluorescent optical sensor | |
CN110078750A (en) | Asymmetric terpyridyl complex compound and its preparation method and application | |
KR101642406B1 (en) | Novel rhodamine-based chemosensors for the detection of Hg2+ in aqueous samples and manufacturing method of the same | |
Jeong et al. | An ‘OFF–ON’fluorescent chemosensor based on rhodamine 6G-2-chloronicotinaldehyde for the detection of Al3+ ions: Part II | |
CN108699345A (en) | The sensor dye sensed in real time for metal ion in aqueous environments | |
Xu et al. | Selective fluorescence detection of anilines and Fe 3+ ions by two lanthanide metal–organic frameworks | |
Shen et al. | A new turn-on fluorescent sensor based on NBD for highly selective detection of Hg 2+ in aqueous media and imaging in live cells | |
CN111004261A (en) | Three-dimensional multifunctional fluorescent zinc complex based on carboxylic acid ligand and application thereof in water pollution detection under acid/alkali conditions | |
CN109265398A (en) | A kind of application of supramolecular organogel and its fluorescence identifying mercury ion | |
Iyer et al. | A review on rhodamine probes for metal ion recognition with a future on artificial intelligence and machine learning | |
CN107698557B (en) | Pyridine bipyrazole acylhydrazone derivative-based fluorescent probe and preparation method and application thereof | |
Xiu et al. | Naphthalene-grafted MOF as a unique fluorescent sensor for “turn-off” detection for Fe3+ and “turn-on” detection for ClO4-in different solvents with high selectivity and sensitivity | |
CN105859722B (en) | It is a kind of being capable of relay identification cryanide ion and the sensor molecule of hydrogen sulfate ion and its synthesis and application | |
CN110628040A (en) | Cd (II) MOF materials based on 5- (4- [1,2,4] triazol-1-phenyl) -1H-tetrazoles | |
CN107540644B (en) | Dicarboxylic acid organic ligand and preparation method and application thereof | |
CN104132920A (en) | Method for measuring Ag<+> or F<-> through fluorescence quenching |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200414 Termination date: 20211018 |