CN106883183B - One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof - Google Patents
One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof Download PDFInfo
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Abstract
One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof, the present invention relates to one kind to be used for Cu2+Fluorescence probe of detection and the preparation method and application thereof.The present invention is to solve existing fluorescent molecular probes to Cu2+Detection it is poorly reversible, vulnerable to other metal ion disturbances the technical issues of.The structural formula of reversible fluorescence probe of the invention are as follows:Preparation method: one, with phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate synthetic intermediate compound I；Two, midbody compound I, Raney's nickel, ethyl alcohol, hydrazine hydrate synthetic intermediate compound II；Three, it with midbody compound II and bigcatkin willow aldehyde reaction, obtains for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection.Reversible fluorescence probe and Cu when detection2+Fluorescence intensity extraction is gone out after effect；Add Cr3+Afterwards, fluorescence intensity is restored, and can be used for Cu in water2+With Cr3+Pollution detection.
Description
Technical field
The present invention relates to one kind to be used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method thereof.
Background technique
Copper is a kind of very important transition metal element.To adjusting physiological mechanism, maintenance physiological equilibrium in life entity
It played an important role；In nature, copper is one of the metal that the mankind use earliest, usually be can detecte out in environment
Cu2+The presence of ion.However, the Cu being present in excess2+Organism and environment are adversely affected, for example, nervus retrogression disease
Disease just with Cu excessive in human body2+It is related；And if Cu in drinking water2+It is excessive, then it can cause the gastrointestinal dysfunction of people, because
This is to Cu2+Detection is carried out to have very important significance.In recent years, more and more researchers have started Cu2+Fluorescence probe
Research work.Page 1784~1791 reports of the meter little Long et al. in " Chemical Journal of Chinese Universities " 2016 the 10th phase of volume 37
Two kinds of rhodamine derivative Cu2+Fluorescence probe, under daylight, Cu2+Both rhodamine derivatives can be made by colourless
Become orange or pink；2015, " Chemical Journal of Chinese Universities " the 2nd phase page 287~292 report of volume 36 in 2015
Two kinds of new type water-solubility benzazole derivative Cu2+Fluorescence probe, research finds Cu2+The property of can choose extracts both benzazoles that go out
The fluorescence of derivative." RSC progress " (RSC Advances) article disclosed in page 22613-22616 of 4 phases in 2014
A kind of " novel fluorescence probe to copper ion and lead ion with differential responses based on pyridines Styryl cyanine dyestuff " (A
new fluorescent probe based on styrylcyanine dye containing pyridine:
dissimilar fluorescent response to Cu2+and Pb2+With the article " inspection disclosed in page 46800-46805
Survey the fluorescence probe of magnesium ion and copper ion in living cells " (A fluorescent probe for the detection of
Mg (II) and Cu (II) and its application for imaging in living cells) it is all about Cu2+
The technology of identification.In this two articles, host compound is in addition to that can identify Cu2+Outside, also respectively to Pb2+And Mg2+With identification
Performance.
According to reported in the literature for Cu at present2+The research of fluorescence probe is primarily present following two defect:
1.Cu2+The extraction disposable recognition performance that goes out or enhance can only be carried out to the fluorescence of host compound, without can
Inverse recognition performance；
2. host compound is in addition to that can identify Cu2+Outside, also there is recognition performance to other metal ions, so, vulnerable to it
His metal ion disturbance, identification do not have specificity.
Summary of the invention
The present invention is to solve existing fluorescent molecular probes to Cu2+Detection it is poorly reversible, vulnerable to other metal ions
The technical issues of interference, and the host compound provided is to Cu2+With singleness identity and realize reversible (off-on-off)
One kind of fluorescence signal response detection is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof.
Of the invention is used for Cu2+The structural formula of the phenanthro- imidazoles reversible fluorescence probe of detection are as follows:
Above-mentioned is used for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection, sequentially includes the following steps:
One, the synthesis of midbody compound I:
Phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate are put into reactor according to 1: 1.5: 2 molar ratio, add ice
Acetic acid is as solvent, and after being warming up to 90~110 DEG C and stirring 6~10h, reaction stops, and is cooled to room temperature, is added into reactor
Water, then with 10% sodium hydroxide solution tune pH value to 8~10, filter, obtain yellow solid；After drying, then use ethyl acetate
Recrystallization, then filter, dry, obtain midbody compound I；
Two, the synthesis of midbody compound II:
Weigh midbody compound I, Raney's nickel, ethyl alcohol, the hydrazine hydrate solution that mass percentage concentration is 80%；It is wherein intermediate
The ratio of the quality of the amount and Raney's nickel of the substance of body compound I is 1mmol:(0.15~2) g；The substance of midbody compound I
The ratio of amount and the volume of ethyl alcohol is 1mmol:(25~40) mL；The amount of the substance of midbody compound I is with mass percentage concentration
The ratio of the volume of 80% hydrazine hydrate solution is 1mmol:3~4mL；Midbody compound I and Raney's nickel are added to reactor
In, ethyl alcohol is added as solvent, is passed through nitrogen protection, under agitation, the hydration that mass percentage concentration is 80% is added dropwise
Hydrazine solution after being added dropwise, is warming up to 65~85 DEG C, reacts 5~9h, be cooled to room temperature, filter, washed with ethyl acetate, revolves
After turning evaporative removal filtrate, gray solid is obtained, after dry, then with re-crystallizing in ethyl acetate, then filter, dry, obtain centre
Body compound II；
Three, Cu2+The synthesis of fluorescence probe:
According to 1:(1~3) molar ratio weigh midbody compound II and salicylide, be added in reactor, then to its
Middle addition acid medium is stirred to react 1~4h as solvent, after reaction, water quenching reaction is added into reaction system, then
With 10% sodium hydroxide solution tune pH value to 8~10, solid is precipitated；Then it being filtered, filter cake is washed with water to neutrality, and it is dry,
Re-crystallizing in ethyl acetate is used again, is obtained for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection.
Acid medium described in step 3 is more preferably the concentrated sulfuric acid that mass percentage concentration is 98%, quality percentage
Concentrated nitric acid, glacial acetic acid or the formic acid that concentration is 65~68%.
Of the invention is used for Cu2+The application of the phenanthro- imidazoles reversible fluorescence probe of detection is by the phenanthro- imidazoles reversible fluorescence
Probe is used for Cu2+And/or Cr3+It is successive detection or individually detection.
Utilize phenanthro- imidazoles reversible fluorescence probe in detecting Cu2+Method, sequentially include the following steps:
One, by pH=6.8~7.4, concentration be 0.01mol/L HEPES buffer solution and DMF be by volume that 1:1 is mixed
It closes uniformly, obtains solvent；
Two, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe of detection is obtained with step 1 is
1.0×10-5The solution of mol/L, obtains bulk solution；
Three, solution to be measured is added in bulk solution, obtains mixed liquor；
Four, under conditions of excitation wavelength is 360nm, exciting slit width is 10, bulk solution and mixed liquor are detected
Fluorescence emission spectrum can determine that in solution to be measured if the fluorescence intensity extraction of mixed liquor is gone out and contain Cu2+。
Utilize phenanthro- imidazoles reversible fluorescence probe in detecting Cr3+Method, sequentially include the following steps:
One, by pH=6.8~7.4, concentration be 0.01mol/L HEPES buffer solution and DMF be by volume that 1:1 is mixed
It closes uniformly, obtains solvent；
Two, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe of detection is obtained with step 1 is
1.0×10-5The solution of mol/L, obtains bulk solution；
Three, the Cu that concentration is 0.10mol/L is separately added into bulk solution2+, 5min is stood after being sufficiently mixed, obtains phenanthrene
And imidazoles fluorescent molecule-Cu2+Complex solution；
Four, solution to be measured is added to phenanthro- imidazoles fluorescent molecule-Cu2+In complex solution, mixed liquor is obtained；
Five, under conditions of excitation wavelength is 360nm, exciting slit width is 10, detection bulk solution, phenanthro- imidazoles are glimmering
Optical molecule-Cu2+The fluorescence emission spectrum of complex solution and mixed liquor, if blended liquid phase is for phenanthro- imidazoles fluorescent molecule-
Cu2+The fluorescence intensity of complex solution enhances, then can determine that in solution to be measured and contain Cr3+。
Synthesis process of the invention can be used following formula to indicate:
Of the invention is used for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection be one kind in aqueous phase system, pH be 6.8~
In 7.4 environment, there is highly selective, high sensitivity reversible phenanthro- imidazoles Cu2+Fluorescence probe.The fluorescence probe can selectivity
Identify Cu2+, recognition performance is single-minded.Utilize phenanthro- imidazoles reversible fluorescence probe in detecting Cu2+During, phenanthro- imidazoles and Cu2+Shape
At complex compound, it is denoted as phenanthro- imidazoles fluorescent molecule-Cu2+Complex compound, the complex compound keep the fluorescence of phenanthro- imidazoles fluorescent molecule strong
Degree extraction is gone out, for detecting Cu2+；Phenanthro- imidazoles fluorescent molecule-Cu2+Complex compound continues and Cr3+After complexing, fluorescence intensity can be one
Determine to restore in degree, be used to Cr3+Test for identification is carried out, reversible (off-on-off) fluorescence of the fluorescent molecular probe is completed
Signal response.
Detailed description of the invention
Fig. 1 is 1 preparation of test for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection is to the ultraviolet of different metal ions
Abosrption spectrogram；
Fig. 2 is 1 preparation of test for Cu2+Fluorescence of the phenanthro- imidazoles reversible fluorescence probe of detection to different metal ions
Launching light spectrogram；
Fig. 3 is 1 preparation of test for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection is existing for other metal ions
In the case of, Cu2+The fluorescence emission spectrogram of compound of fluorescence probe；
Specific embodiment
Specific embodiment 1: the reversible phenanthro- imidazoles Cu of present embodiment2+The structural formula of fluorescence probe are as follows:
Specific embodiment 2: the described of preparation specific embodiment one is used for Cu2+The phenanthro- imidazoles of detection is reversible glimmering
The method of light probe, sequentially includes the following steps:
One, the synthesis of midbody compound I:
Phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate are put into reactor according to 1: 1.5: 2 molar ratio, add ice
Acetic acid is as solvent, and after being warming up to 90~110 DEG C and stirring 6~10h, reaction stops, and is cooled to room temperature, is added into reactor
Water, then with 10% sodium hydroxide solution tune pH value to 8~10, filter, obtain yellow solid；After drying, then use ethyl acetate
Recrystallization, then filter, dry, obtain midbody compound I；
Two, the synthesis of midbody compound II:
Weigh midbody compound I, Raney's nickel, ethyl alcohol, the hydrazine hydrate solution that mass percentage concentration is 80%；It is wherein intermediate
The ratio of the quality of the amount and Raney's nickel of the substance of body compound I is 1mmol:(0.15~2) g；The substance of midbody compound I
The ratio of amount and the volume of ethyl alcohol is 1mmol:(25~40) mL；The amount of the substance of midbody compound I is with mass percentage concentration
The ratio of the volume of 80% hydrazine hydrate solution is 1mmol:3~4mL；Midbody compound I and Raney's nickel are added to reactor
In, ethyl alcohol is added as solvent, is passed through nitrogen protection, under agitation, the hydration that mass percentage concentration is 80% is added dropwise
Hydrazine solution after being added dropwise, is warming up to 65~85 DEG C, reacts 5~9h, be cooled to room temperature, filter, washed with ethyl acetate, revolves
After turning evaporative removal filtrate, gray solid is obtained, after dry, then with re-crystallizing in ethyl acetate, then filter, dry, obtain centre
Body compound II；
Three, Cu2+The synthesis of fluorescence probe:
According to 1:(1~3) molar ratio weigh midbody compound II and salicylide, be added in reactor, then to its
Middle addition acid medium is stirred to react 1~4h as solvent, after reaction, water quenching reaction is added into reaction system, then
With 10% sodium hydroxide solution tune pH value to 8~10, solid is precipitated；Then it being filtered, filter cake is washed with water to neutrality, and it is dry,
Re-crystallizing in ethyl acetate is used again, is obtained for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection.
Specific embodiment 3: present embodiment is situated between from acidity described in step 3 unlike specific embodiment two
Matter be mass percentage concentration be 98% the concentrated sulfuric acid, mass percentage concentration be 65~68% concentrated nitric acid, glacial acetic acid or formic acid.Its
It is identical with embodiment two.
Specific embodiment 4: reaction temperature of the present embodiment unlike specific embodiment two or three in step 1
Degree is 95 DEG C, reaction time 8h.It is other identical as specific embodiment two or three.
Specific embodiment 5: the pH unlike one of present embodiment and specific embodiment two to four in step 1
It is worth to 9.It is other identical as one of specific embodiment two to four.
Specific embodiment 6: being reacted in step 2 unlike one of present embodiment and specific embodiment two to five
Temperature is 78 DEG C, reaction time 8h.It is other identical as one of specific embodiment two to five.
Specific embodiment 7: being stirred in step 3 unlike one of present embodiment and specific embodiment two to six
React 2h.It is other identical as one of specific embodiment two to six.
Specific embodiment 8: pH value in step 3 unlike one of present embodiment and specific embodiment two to seven
It is 9.It is other identical as one of specific embodiment two to seven.
Specific embodiment 9: intermediate in step 3 unlike one of present embodiment and specific embodiment two to eight
The molar ratio of body compound II and salicylide reactant is 1: 2.5.It is other identical as one of specific embodiment two to eight.
Specific embodiment 10: being used for Cu described in specific embodiment one2+The phenanthro- imidazoles reversible fluorescence probe of detection
Application be that the phenanthro- imidazoles reversible fluorescence probe is used for Cu2+And/or Cr3+It is successive detection or individually detection.
Specific embodiment 11: phenanthro- imidazoles reversible fluorescence probe in detecting Cu is utilized2+Method, according to the following steps into
Row:
One, by pH=6.8~7.4, concentration be 0.01mol/L HEPES buffer solution and DMF be by volume that 1:1 is mixed
It closes uniformly, obtains solvent；
Two, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe of detection is obtained with step 1 is
1.0×10-5The solution of mol/L, obtains bulk solution；
Three, solution to be measured is added in bulk solution, obtains mixed liquor；
Four, under conditions of excitation wavelength is 360nm, exciting slit width is 10, bulk solution and mixed liquor are detected
Fluorescence emission spectrum can determine that in solution to be measured if the fluorescence intensity extraction of mixed liquor is gone out and contain Cu2+。
Specific embodiment 12: embodiment and fluorescence described in step 4 unlike specific embodiment 11
Intensity extraction, which is gone out, refers to that fluorescence intensity reduces by 50% or more.It is other identical as specific embodiment 11.
Specific embodiment 13: phenanthro- imidazoles reversible fluorescence probe in detecting Cr is utilized3+Method, according to the following steps into
Row:
One, by pH=6.8~7.4, concentration be 0.01mol/L HEPES buffer solution and DMF be by volume that 1:1 is mixed
It closes uniformly, obtains solvent；
Two, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe of detection is obtained with step 1 is
1.0×10-5The solution of mol/L, obtains bulk solution；
Three, the Cu that concentration is 0.10mol/L is separately added into bulk solution2+, 5min is stood after being sufficiently mixed, obtains phenanthrene
And imidazoles fluorescent molecule-Cu2+Complex solution；
Four, solution to be measured is added to phenanthro- imidazoles fluorescent molecule-Cu2+In complex solution, mixed liquor is obtained；
Five, under conditions of excitation wavelength is 360nm, exciting slit width is 10, detection bulk solution, phenanthro- imidazoles are glimmering
Optical molecule-Cu2+The fluorescence emission spectrum of complex solution and mixed liquor, if blended liquid phase is for phenanthro- imidazoles fluorescent molecule-
Cu2+The fluorescence intensity of complex solution enhances, then can determine that in solution to be measured and contain Cr3+。
Specific embodiment 14: present embodiment from unlike specific embodiment 13 described in step 5 it is glimmering
Luminous intensity enhancing refers to that fluorescence intensity improves 50% or more.It is other identical as specific embodiment 13.
With following case verification beneficial effects of the present invention:
Test 1: this test is used for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection, according to the following steps
It carries out:
One, the synthesis of midbody compound I:
Phenanthrenequione 5mmol, o-nitrobenzaldehyde 7.5mmol, ammonium acetate 10mmol is weighed to be added in the there-necked flask of 50mL, and
The glacial acetic acid that 30mL is added thereto is warming up to 110 DEG C as solvent, and is stirred continuously, and during the reaction, is tracked with TLC
(solvent is ethyl acetate and petroleum ether, V for detection(ethyl acetate): V(petroleum ether)=3: 7), after reaction carries out 10h, reacting substantially complete
Entirely, stop reaction, be cooled to room temperature, 50mL water is added in there-necked flask, is placed in the beaker of 200mL, with 10% hydrogen-oxygen
Change sodium solution tune pH value to 9, suction filtration obtains yellow solid, dry；It after drying, is re-dissolved in the ethyl acetate of 25mL, heating is stirred
It after mixing 2h, is cooled to room temperature, there are a large amount of solids to be precipitated, filter, is dry, obtaining midbody compound I；
The yield for the midbody compound I that this step obtains is 92%, fusing point: 258~260 DEG C.With infrared spectroscopy, nuclear-magnetism
Hydrogen spectrum and nuclear-magnetism carbon stave levy midbody compound I, and obtained result is as follows:
IR(KBr,cm–1): 3074,1616,1575,1537,1453,1364,781,754,734.1H NMR(600MHz,
DMSO) δ: 14.33 (s, H, OH), 9.28 (s, H, NH), 8.90 (d, J=8.40Hz, 2H, ArH), 8.53 (d, J=7.80Hz,
2H, ArH), 8.25 (d, J=8.40Hz, H, ArH), 7.80 (t, J=7.20Hz, 3H, ArH), 7.71 (t, J=7.80Hz,
2H, ArH), 7.26 (d, J=9.0Hz, H, ArH)13C NMR(150MHz,DMSO)δ:149.4,132.8, 131.3,130.4,
128.0,127.5,125.7,125.3,124.6,124.4,122.4.
The structural formula for knowing midbody compound I from characterization result is
Two, the synthesis of midbody compound II:
2.0mmol midbody compound I, 0.32g Raney's nickel are added in the three-necked flask of 50mL and the ethyl alcohol of 30mL is molten
Agent, after being passed through 2min nitrogen, stirring, and the water that 7.5mL mass percentage concentration is 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 5h, with TLC tracing detection (solvent V(ethyl acetate):
V(petroleum ether)=3: 7), reaction substantially completely, after being cooled to room temperature, is filtered, is washed five times with ethyl acetate, rotary evaporation filtrate obtains
To brown solid and drying.It uses re-crystallizing in ethyl acetate, after heating stirring 2.5h, be cooled to room temperature again, there are a large amount of solids to be precipitated,
It filters, is dry, midbody compound II.
The yield for the midbody compound II that this step obtains is 85%, fusing point: 183~185 DEG C；
It is characterized with infrared spectroscopy, nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum, obtained result is as follows:
IR(KBr,cm–1): 3370,1616,1600,1543,1514,1487,1455,760,751,722,546.1H NMR
(600MHz, DMSO) δ: 13.35 (s, H, NH), 8.85 (d, J=8.40Hz 2H, ArH), 8.58 (d, J=8.40Hz, 2H,
), ArH 7.72 (t, J=7.20Hz, 2H, ArH), 7.62 (t, J=7.20Hz, 2H, ArH), 7.57 (s, H, ArH), 7.45 (d,
J=7.80Hz, H, ArH), 7.23 (t, J=7.80Hz, H, ArH), 6.69 (d, J=7.80Hz, H, ArH), 5.33 (s, 2H,
NH2).13C NMR(150MHz,DMSO)δ:150.8,148.1,130.4,127.9,127.6,125.6,124.4, 122.5,
116.6,115.5,111.2.
The structural formula for knowing midbody compound II from characterization result is
Three, Cu2+The synthesis of fluorescence probe:
0.62g (2.0mmol) midbody compound II, 0.24g (2.0mmol) salicylide is successively added into there-necked flask,
The glacial acetic acid of 20mL is added in there-necked flask again and is used as solvent, stirring at normal temperature reacts 2h, after reaction, adds into reaction system
Enter water quenching reaction, then be placed in the beaker of 200mL, with 10% sodium hydroxide solution tune pH value to 10, then filtered, is filtered
Cake is washed to neutrality, dry, then uses re-crystallizing in ethyl acetate, collects solid, after dry, obtains for Cu2+The phenanthro- miaow of detection
Azoles reversible fluorescence probe.In this step, this is used for Cu2+The yield of the phenanthro- imidazoles reversible fluorescence probe of detection is 80%.
This test is used for Cu2+The fusing point of the phenanthro- imidazoles reversible fluorescence probe of detection is 289~291 DEG C.Melting range is 2
DEG C, illustrate that purity is higher, quality percent purity is greater than 95%.
It is characterized with infrared spectroscopy and nuclear magnetic resoance spectrum, obtained result is as follows:
IR(KBr,cm–1): 3055,2937,3058,1613,1592,1486,1460,748,720.1H NMR(600MHz,
DMSO) δ: 10.50 (s, H, OH), 8.89 (d, J=7.20Hz, H, ArH), 8.83 (d, J=7.80Hz, H, ArH), 8.69 (d,
J=7.80Hz, H, ArH), 8.08 (d, J=7.20Hz, 2H, ArH), 7.92 (s, H, NH), 7.77 (t, J=7.20Hz, H,
), ArH 7.66 (t, J=7.20Hz, H, ArH), 7.56 (s, 2H, ArH), 7.22 (s, H, CH), 7.18 (t, J=7.20 Hz, H,
), ArH 7.04 (t, J=7.20Hz, H, ArH), 6.98 (d, J=8.40Hz, H, ArH), 6.91 (d, J=7.80Hz, H,
), ArH 6.85 (t, J=7.20Hz, H, ArH), 6.43 (d, J=6.20Hz, H, ArH)13C NMR(150MHz, DMSO)δ:
153.9,146.5,141.8,138.5,131.3,130.2,128.5,128.1,127.8,127.5,127.0,126.7,
126.2,125.6,125.4,124.9,124.5,124.4,124.1,122.9,122.6,121.2,119.7,118.9,
116.3,115.8, 113.5,64.8.
From above characterization result it is found that being used for Cu2+The structural formula of the phenanthro- imidazoles reversible fluorescence probe of detection are as follows:
This test preparation is used for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection carries out spectrum property test, step
It is as follows:
One, the configuration of stock solution
It will be used for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection is solvent preparation with N,N-dimethylformamide (DMF)
It is 1.0 × 10 at concentration–4The host compound solution of mol/L, it is spare；
The preparation of cationic stock solution: the cation that concentration is 0.10mol/L is configured to metal chlorination salt and nitrate
Solution, it is spare；
HEPES buffer solution: the volumetric flask of 250mL is added in the n-2-Hydroxyethylpiperazine-N'-2-ethanesulfonic acid for weighing 0.60g
In, it with distilled water constant volume, is made into the solution of 0.01mol/L and shakes up, after static 2h, with sodium hydroxide solution tune pH value, be made into
PH value is 7.4 buffer solutions.It shakes up, it is spare.
Two, spectrum property is tested
It first investigates and is used for Cu2+Selective recognition of the phenanthro- imidazoles reversible fluorescence probe of detection to metal ion.To
It is 1.0 × 10 that concentration is added in the volumetric flask of 10.0mL–4The host compound solution 1.0mL of mol/L, then it is separately added into concentration
For the K of 0.10 mol/L+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Fe3+、Cd2+、Ni2+、Co2+、Pb2+、Cu2+、 Ag+、Al3+
And Hg2+Metal ion solution is that (wherein, HEPES buffer solution is dense for the mixed solution of 1: 1 DMF/HEPES with volume ratio
Degree is 0.01mol/L, pH=7.4) constant volume, at this point, the molar concentration rate of host compound and metal ion is 1: 10, constant temperature 2h
Afterwards, ultra-violet absorption spectrum is measured respectively, as a result as shown in Figure 1.As can be known from Fig. 1, after different metal ions being added, K+、Ba2+、
Ca2+、Na+、Mg2+、Zn2+、Cr3+、Cd2+、Ni2+、Co2+、Pb2+、 Hg2+、Ag+、Al3+And Fe3+With the ultra-violet absorption spectrum of main body
Curve shape is similar.And Cu is added2+Afterwards, in UV absorption wave spectrum, wavelength is at 420nm, hence it is evident that has a new ultraviolet suction
Peak is received to occur.Therefore, can be with initial guess from uv absorption spectra, host compound (PA) is to Cu2+It is identified with selection
Characteristic.
In order to further verify this test preparation for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection is to Cu2+Have
The characteristic of Selective recognition is mixed solution (wherein, the concentration of HEPES buffer solution of 1: 1 DMF/HEPES with volume ratio
It is solvent for 0.01mol/L, pH=7.4), compound concentration is 1.0 × 10-5The bulk solution of mol/L, in bulk solution respectively
The K that concentration is 0.10mol/L is added+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Cd2+、 Hg2+、Ni2+、Co2+、Pb2+、Cu2+、
Ag+、Al3+And Fe3+Metal ion solution.And excitation wavelength be 360nm exciting slit width be 10 in the case where, to its into
The test of row fluorescence emission spectrum, obtained fluorescence emission spectral intensity, as a result as shown in Figure 2.As can be known from Fig. 2, subject highlighting
The fluorescence emission wavelengths for closing object are 420nm, and fluorescence intensity is 780 a.u or so.After different metal ions are added, K+、Ba2+、
Ca2+、Na+、Mg2+、Zn2+、Cd2+、Ni2+、Co2+、 Cr3+、Pb2+、Hg2+、Ag+、Al3+And Fe3+With the fluorescence intensity shadow to main body
It rings less, intensity is in 770a.u. or so.And Cu is added2+When, fluorescence intensity, which obviously extracts, goes out to 100a.u. or so, and extraction is gone out degree
Based on 7 times of fluorescence intensity.Therefore, from fluorescence emission spectrum it was determined that host compound is to Cu2+It is special with selection identification
Property.
Fluorescent molecule-Cu is investigated again2+Complex compound is to Cr3+With Selective recognition characteristic, the solvent of selection is for volume ratio
The mixed solution (wherein, the concentration of HEPES buffer solution is 0.01mol/L, pH=7.4) of 1: 1 DMF/HEPES is solvent,
Compound concentration is 1.0 × 10-5The bulk solution of mol/L.The Cu that concentration is 0.10mol/L is separately added into bulk solution2+,
5min is stood after being sufficiently mixed.It is separately added into the K of 0.10mol/L again+、Ba2+、Ca2+、Na+、Mg2+、 Zn2+、Cr3+、Cd2+、Ni2 +、Co2+、Pb2+、Hg2+、Ag+、Al3+And Fe3Solution is uniformly mixed.The test of fluorescence emission spectrum is then carried out to it.Test knot
Fruit is as shown in figure 3, other metal ions (K+、Ba2+、Ca2+、Na+、 Mg2+、Zn2+、Cd2+、Ni2+、Co2+、Pb2+、Hg2+、Ag+、
Al3+And Fe3) addition to the fluorescence probe identify Cu2+Almost without influence, but Cr is added3+Fluorescence intensity increases from 100a.u. afterwards
By force to 710a.u. or so, illustrate fluorescent molecule-Cu2+Complex compound is to Cr3+With Selective recognition effect, the fluorescence point is completed
Reversible (off-on-off) fluorescence signal of sub- probe responds.This result has important in the practical application of host compound
Meaning.
This test preparation is used for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection, by testing explanation above with body
Product ratio is 1: 1 DMF/H2The mixed solution (concentration of HEPES buffer solution is 0.01mol/L, pH=7.4) of O is solvent
In system, the host compound is to Cu2+The effect of selective identification, and to other metal ions without evident characteristics, and this is glimmering
Optical molecule-Cu2+Complex compound can also be to Cr3+Carry out Selective recognition.
Test 2: the step of this test tests 1 unlike test 1 three is replaced with operation below: successively to there-necked flask
Middle 98% concentrated sulfuric acid that midbody compound II 0.62g (2.0mmol), salicylide 0.31g (2.5mmol) and 30mL is added
As solvent, stirring at normal temperature reacts 3.5h, after reaction, water quenching reaction is added into reaction system, is placed in 200mL's
In beaker, with 10% sodium hydroxide solution tune pH value to 10, then being filtered, filter cake is washed to neutrality, and it is dry, then use acetic acid
Ethyl ester recrystallization collects solid, obtains reversible phenanthro- imidazoles Cu after dry2+Fluorescence probe.What this test obtained is used for Cu2+Inspection
The structural formula of the phenanthro- imidazoles reversible fluorescence probe of survey are as follows:
Yield is 65%.
Test 3: the step of this test tests 1 unlike test 1 three is replaced with operation below: successively to there-necked flask
The middle formic acid that midbody compound II 0.62g (2.0mmol), salicylide 0.34g (2.8mmol) and 28mL is added is as molten
Agent, stirring at normal temperature react 3h, after reaction, water quenching reaction are added into reaction system, is placed in the beaker of 200mL,
With 10% sodium hydroxide solution tune pH value to 9, then being filtered, filter cake is washed to neutrality, and it is dry, then tied again with ethyl acetate
Crystalline substance collects solid, obtains reversible phenanthro- imidazoles Cu after dry2+Fluorescence probe.The reversible phenanthro- imidazoles Cu that this test obtains2+It is glimmering
The structural formula of light probe are as follows:
Yield is 63%.
Test 4: the step of this test tests 1 unlike test 1 three is replaced with operation below: successively to there-necked flask
Middle 65% concentrated nitric acid that midbody compound II 0.62g (2.0mmol), salicylide 0.37g (3.0mmol) and 20mL is added
As solvent, stirring at normal temperature reacts 4h, after reaction, water quenching reaction is added into reaction system, is placed in the burning of 200mL
It in cup, with 10% sodium hydroxide solution tune pH value to 10, is then filtered, filter cake is washed to neutrality, dry, then with acetic acid second
Ester recrystallization collects solid, obtains reversible phenanthro- imidazoles Cu after dry2+Fluorescence probe.The reversible phenanthro- imidazoles that this test obtains
Cu2+The structural formula of fluorescence probe are as follows:
Yield is 75%.
Claims (1)
1. utilizing a kind of for Cu2+The phenanthro- imidazoles reversible fluorescence probe in detecting Cr of detection3+Method, it is characterised in that this method
It sequentially includes the following steps:
It one, with DMF is by volume that 1:1 is mixed by the HEPES buffer solution that pH=6.8~7.4, concentration are 0.01mol/L
It is even, obtain solvent；
Two, Cu will be used for2+The solvent compound concentration that the phenanthro- imidazoles reversible fluorescence probe of detection is obtained with step 1 is 1.0 ×
10-5The solution of mol/L, obtains bulk solution；Wherein it is used for Cu2+The structural formula of the phenanthro- imidazoles reversible fluorescence probe of detection are as follows:
Three, the Cu that concentration is 0.10mol/L is separately added into bulk solution2+, 5min is stood after being sufficiently mixed, obtains phenanthro- miaow
Azoles fluorescent molecule-Cu2+Complex solution；
Four, solution to be measured is added to phenanthro- imidazoles fluorescent molecule-Cu2+In complex solution, mixed liquor is obtained；
Five, under conditions of excitation wavelength is 360nm, exciting slit width is 10, detection bulk solution, phenanthro- imidazoles fluorescence point
Son-Cu2+The fluorescence emission spectrum of complex solution and mixed liquor, if blended liquid phase is for phenanthro- imidazoles fluorescent molecule-Cu2+
The fluorescence intensity of complex solution enhances, then can determine that in solution to be measured and contain Cr3+。
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| CN107652288A (en) * | 2017-09-19 | 2018-02-02 | 福建医科大学 | Hg in one kind identification QSG 77012+Imidazo phenanthroline fluorescence probe and preparation method thereof |
| CN107629008B (en) * | 2017-10-18 | 2020-04-14 | 齐齐哈尔大学 | Phenanthroimidazole micromolecule Fe3+Fluorescent probe and synthetic method thereof |
| CN107722008A (en) * | 2017-11-06 | 2018-02-23 | 福建医科大学 | Ag in one kind identification HepG2 cells+2 Aryimidazole phenanthroline probes and preparation method thereof |
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| CN108675990B (en) * | 2018-06-14 | 2020-11-06 | 齐齐哈尔大学 | Detect Cu2+Fluorescent probe, preparation method and preparation and use method of fluorescent test strip |
| CN109147549B (en) * | 2018-08-24 | 2020-08-14 | 北京理工大学 | Multimode anti-counterfeiting method based on luminescent doped quantum dots |
| CN111320585A (en) * | 2020-04-09 | 2020-06-23 | 齐齐哈尔大学 | Double-colorimetric double-fluorescent phenanthroimidazole probe as well as preparation method and application thereof |
| CN111777598B (en) * | 2020-08-10 | 2023-03-17 | 齐齐哈尔大学 | Detect Cu 2+ And can utilize Cu 2+ Detection of HPO4 2– Fluorescent probe and preparation method and application thereof |
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Non-Patent Citations (4)
| Title |
|---|
| Highly selective and sensitive fluorescent probe for the detection of nitrite;Biao Gu,等;《Talanta》;20160129;第152卷;第155-161页尤其是第156页方案1、实验部分2.2.1和2.2.2 |
| Synthesis of phenanthrimidazole from 9,10-phenanthraquinone and aldehydes by molecular iodine as catalyst;Hossein Behmadi,等;《Chinese Chemical Letters》;20091231;第20卷(第1期);第5-8页 |
| 几种基于ESIPT机制铜离子荧光探针的设计、合成及其分析应用;黄礼艳;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170215(第02期);第B014-1714页尤其是第一章和第二章 |
| 几种基于ESIPT机制铜离子荧光探针的设计、合成及其分析应用;黄礼艳;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170215(第02期);第B014-1714页尤其是第二章 |
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