CN106883183A - One kind is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method and application - Google Patents
One kind is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method and application Download PDFInfo
- Publication number
- CN106883183A CN106883183A CN201710106165.0A CN201710106165A CN106883183A CN 106883183 A CN106883183 A CN 106883183A CN 201710106165 A CN201710106165 A CN 201710106165A CN 106883183 A CN106883183 A CN 106883183A
- Authority
- CN
- China
- Prior art keywords
- phenanthro
- imidazoles
- detection
- solution
- fluorescence probe
- 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
- 0 Cc(cccc1)c1C(*1)=Nc2c1c(cccc1)c1c1c2cccc1 Chemical compound Cc(cccc1)c1C(*1)=Nc2c1c(cccc1)c1c1c2cccc1 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
One kind is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method and application, Cu is used for the present invention relates to one kind2+Fluorescence probe of detection and preparation method and application.The present invention is to solve existing fluorescent molecular probe to Cu2+Detection it is poorly reversible, easily by other metal ion disturbances technical problem.The structural formula of reversible fluorescence probe of the invention is:Preparation method:First, with phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate synthetic intermediate compound I;2nd, midbody compound I, Raney's nickel, ethanol, hydrazine hydrate synthetic intermediate compound II;3rd, with midbody compound II and bigcatkin willow aldehyde reaction, obtain for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection.Reversible fluorescence probe and Cu during detection2+Fluorescence intensity extraction is gone out after effect;Add Cr3+Afterwards, fluorescence intensity is recovered, and can be used for Cu in water2+With Cr3+Pollution detection.
Description
Technical field
It is used for Cu the present invention relates to one kind2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method thereof.
Background technology
Copper is a kind of very important transition metal.To regulation physiological mechanism, maintenance physiological equilibrium in life entity
Played an important role;In nature, copper is one of metal that the mankind use earliest, can usually be detected in environment
Cu2+The presence of ion.However, the Cu being present in excess2+Organism and environment are adversely affected, such as, and nervus retrogression disease
Disease just with human body in excess Cu2+It is relevant;And if Cu in drinking water2+It is excessive, then 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.Meter little Long et al. exists《SCI》Page 1784~1791 of the 10th phase of volume 2016 the 37th report
Two kinds of rhodamine derivative Cu2+Fluorescence probe, under daylight, Cu2+Both rhodamine derivatives can be made by without discoloration
It is orange or pink;2015,《SCI》The 2nd phase page 287~292 of volume 36 in 2015 reports two
Plant new type water-solubility benzazole derivative Cu2+Fluorescence probe, research find Cu2+Both benzazoles derivative of going out can selectively be extracted
The fluorescence of thing.《RSC is in progress》(RSC Advances) article disclosed in page 22613-22616 of 4 phases of 2014《A kind of base
In the novel fluorescence probe to copper ion and lead ion with differential responses of pyridines Styryl cyanine dyestuff》(A new
fluorescent probe based on styrylcyanine dye containing pyridine:dissimilar
fluorescent response to Cu2+and Pb2+With the article disclosed in page 46800-46805《Magnesium in detection living cells
The fluorescence probe of ion and copper ion》(A fluorescent probe for the detection of Mg(II)and Cu
(II) and its application for imaging in living cells) all it is on Cu2+The technology of identification.This
In two articles, host compound is except that can recognize Cu2+Outward, also respectively to Pb2+And Mg2+With recognition performance.
According to current document report for Cu2+The research of fluorescence probe, is primarily present following two defects:
1.Cu2+Extraction can only be carried out to the fluorescence of host compound to go out or enhanced disposable recognition performance, without can
Inverse recognition performance;
2. host compound is except being capable of identify that Cu2+Outward, also there is recognition performance to other metal ions, so, Yi Shouqi
His metal ion disturbance, identification does not have selectivity.
The content of the invention
The present invention is to solve existing fluorescent molecular probe to Cu2+Detection it is poorly reversible, easily receive other metal ions
The technical problem of interference, and the host compound for providing 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 preparation method and application.
It is of the invention for Cu2+The structural formula of the phenanthro- imidazoles reversible fluorescence probe of detection is:
It is above-mentioned for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection, is carried out according to the following steps:
First, the synthesis of midbody compound I:
During phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate put into reactor according to 1: 1.5: 2 mol ratio, ice is added
Used as solvent, after being warming up to 90~110 DEG C and 6~10h of stirring, reaction stops acetic acid, is cooled to room temperature, is added in reactor
Water, then with 10% sodium hydroxide solution adjust pH value to 8~10, suction filtration obtains yellow solid;After drying, then use ethyl acetate
Recrystallization, then suction filtration, drying, obtain midbody compound I;
2nd, the synthesis of midbody compound II:
Weigh the hydrazine hydrate solution that midbody compound I, Raney's nickel, ethanol, mass percentage concentration are 80%;In the middle of wherein
The amount of the material of body compound I is 1mmol with the ratio of the quality of Raney's nickel:(0.15~2) g;The material of midbody compound I
Amount is 1mmol with the ratio of the volume of ethanol:(25~40) mL;The amount of the material 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, ethanol is added as solvent, nitrogen protection is passed through, under agitation, the hydration that mass percentage concentration is 80% is added dropwise
Hydrazine solution, after completion of dropping, is warming up to 65~85 DEG C, reacts 5~9h, is cooled to room temperature, and suction filtration is washed with ethyl acetate, rotation
After turning evaporative removal filtrate, gray solid is obtained, after drying, then with re-crystallizing in ethyl acetate, then suction filtration, drying, obtain centre
Body compound II;
3rd, Cu2+The synthesis of fluorescence probe:
According to 1:The mol ratio of (1~3) weighs midbody compound II and salicylide, is added in reactor, then to it
Middle addition acid medium as solvent, 1~4h of stirring reaction, after reaction terminates, to adding water quenching to go out reaction in reaction system, then
PH value to 8~10 is adjusted with 10% sodium hydroxide solution, solid is separated out;Then suction filtration is carried out, filter cake is washed with water to neutrality, dried,
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
Concentration is 65~68% concentrated nitric acid, glacial acetic acid or formic acid.
It is of the invention 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+Successive detection or individually detection.
Using phenanthro- imidazoles reversible fluorescence probe in detecting Cu2+Method, carry out according to the following steps:
First, by pH=6.8~7.4, concentration for the HEPES cushioning liquid and DMF of 0.01mol/L are by volume 1:1 mixes
Close uniform, obtain solvent;
2nd, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe step one of detection is obtained is 1.0
×10-5The solution of mol/L, obtains bulk solution;
3rd, solution to be measured is added in bulk solution, obtains mixed liquor;
4th, it is under conditions of 360nm, exciting slit width are 10 in excitation wavelength, detection bulk solution and mixed liquor
Fluorescence emission spectrum, if the fluorescence intensity extraction of mixed liquor is gone out, to can determine that and contain Cu in solution to be measured2+。
Using phenanthro- imidazoles reversible fluorescence probe in detecting Cr3+Method, carry out according to the following steps:
First, by pH=6.8~7.4, concentration for the HEPES cushioning liquid and DMF of 0.01mol/L are by volume 1:1 mixes
Close uniform, obtain solvent;
2nd, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe step one of detection is obtained is 1.0
×10-5The solution of mol/L, obtains bulk solution;
3rd, the Cu that concentration is 0.10mol/L is separately added into bulk solution2+, 5min is stood after being sufficiently mixed, obtain phenanthrene
And imidazoles fluorescence molecule-Cu2+Complex solution;
4th, solution to be measured is added to phenanthro- imidazoles fluorescence molecule-Cu2+In complex solution, mixed liquor is obtained;
5th, it is that detection bulk solution, phenanthro- imidazoles is glimmering under conditions of 360nm, exciting slit width are 10 in excitation wavelength
Optical molecule-Cu2+The fluorescence emission spectrum of complex solution and mixed liquor, if blended liquid phase for phenanthro- imidazoles fluorescence molecule-
Cu2+The fluorescence intensity enhancing of complex solution, then to can determine that and contain Cr in solution to be measured3+。
Building-up process of the invention can use following formula to represent:
It is of the invention 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, the reversible phenanthro- imidazoles Cu with high selectivity, high sensitivity2+Fluorescence probe.The fluorescence probe can selectivity
Identification Cu2+, recognition performance is single-minded.Using phenanthro- imidazoles reversible fluorescence probe in detecting Cu2+During, phenanthro- imidazoles and Cu2+Shape
Into complex compound, phenanthro- imidazoles fluorescence molecule-Cu is designated as2+Complex compound, the complex compound makes the fluorescence of phenanthro- imidazoles fluorescence molecule strong
Degree extraction is gone out, for detecting Cu2+;Phenanthro- imidazoles fluorescence molecule-Cu2+Complex compound continues and Cr3+After complexing, fluorescence intensity can be one
Determine to recover in degree, for Cr3+Inspection is identified, reversible (off-on-off) the fluorescence letter of the fluorescent molecular probe is completed
Number response.
Brief description of the drawings
Fig. 1 is the preparation of experiment 1 for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection is to the ultraviolet of different metal ions
Abosrption spectrogram;
Fig. 2 is the preparation of experiment 1 for Cu2+Fluorescence of the phenanthro- imidazoles reversible fluorescence probe of detection to different metal ions
Launching light spectrogram;
Fig. 3 is the preparation of experiment 1 for Cu2+What the phenanthro- imidazoles reversible fluorescence probe of detection existed in other metal ions
In the case of, Cu2+The fluorescence emission spectrogram of compound of fluorescence probe;
Specific embodiment
Specific embodiment one:The reversible phenanthro- imidazoles Cu of present embodiment2+The structural formula of fluorescence probe is:
Specific embodiment two:Prepare the described for Cu of specific embodiment one2+The phenanthro- imidazoles of detection is reversible glimmering
The method of light probe, is carried out according to the following steps:
First, the synthesis of midbody compound I:
During phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate put into reactor according to 1: 1.5: 2 mol ratio, ice is added
Used as solvent, after being warming up to 90~110 DEG C and 6~10h of stirring, reaction stops acetic acid, is cooled to room temperature, is added in reactor
Water, then with 10% sodium hydroxide solution adjust pH value to 8~10, suction filtration obtains yellow solid;After drying, then use ethyl acetate
Recrystallization, then suction filtration, drying, obtain midbody compound I;
2nd, the synthesis of midbody compound II:
Weigh the hydrazine hydrate solution that midbody compound I, Raney's nickel, ethanol, mass percentage concentration are 80%;In the middle of wherein
The amount of the material of body compound I is 1mmol with the ratio of the quality of Raney's nickel:(0.15~2) g;The material of midbody compound I
Amount is 1mmol with the ratio of the volume of ethanol:(25~40) mL;The amount of the material 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, ethanol is added as solvent, nitrogen protection is passed through, under agitation, the hydration that mass percentage concentration is 80% is added dropwise
Hydrazine solution, after completion of dropping, is warming up to 65~85 DEG C, reacts 5~9h, is cooled to room temperature, and suction filtration is washed with ethyl acetate, rotation
After turning evaporative removal filtrate, gray solid is obtained, after drying, then with re-crystallizing in ethyl acetate, then suction filtration, drying, obtain centre
Body compound II;
3rd, Cu2+The synthesis of fluorescence probe:
According to 1:The mol ratio of (1~3) weighs midbody compound II and salicylide, is added in reactor, then to it
Middle addition acid medium as solvent, 1~4h of stirring reaction, after reaction terminates, to adding water quenching to go out reaction in reaction system, then
PH value to 8~10 is adjusted with 10% sodium hydroxide solution, solid is separated out;Then suction filtration is carried out, filter cake is washed with water to neutrality, dried,
Re-crystallizing in ethyl acetate is used again, is obtained for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection.
Specific embodiment three:Present embodiment and acid Jie unlike specific embodiment two described in step 3
Matter is the concentrated sulfuric acid, the concentrated nitric acid that mass percentage concentration is 65~68%, glacial acetic acid or formic acid that mass percentage concentration is 98%.Its
It is identical with specific embodiment two.
Specific embodiment four:Present embodiment and the reaction temperature in step one unlike specific embodiment two or three
It is 95 DEG C to spend, and the reaction time is 8h.Other are identical with specific embodiment two or three.
Specific embodiment five:PH in step one unlike one of present embodiment and specific embodiment two to four
It is worth to 9.Other are identical with one of specific embodiment two to four.
Specific embodiment six:Reacted in step 2 unlike one of present embodiment and specific embodiment two to five
Temperature is 78 DEG C, and the reaction time is 8h.Other are identical with one of specific embodiment two to five.
Specific embodiment seven:Stirred in step 3 unlike one of present embodiment and specific embodiment two to six
Reaction 2h.Other are identical with one of specific embodiment two to six.
Specific embodiment eight:PH value in step 3 unlike one of present embodiment and specific embodiment two to seven
It is 9.Other are identical with one of specific embodiment two to seven.
Specific embodiment nine:In the middle of in step 3 unlike one of present embodiment and specific embodiment two to eight
Body compound II is 1: 2.5 with the mol ratio of salicylide reactant.Other are identical with one of specific embodiment two to eight.
Specific embodiment ten:Described in specific embodiment one for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection
Application be by the phenanthro- imidazoles reversible fluorescence probe be used for Cu2+And/or Cr3+Successive detection or individually detection.
Specific embodiment 11:Using phenanthro- imidazoles reversible fluorescence probe in detecting Cu2+Method, enter according to the following steps
OK:
First, by pH=6.8~7.4, concentration for the HEPES cushioning liquid and DMF of 0.01mol/L are by volume 1:1 mixes
Close uniform, obtain solvent;
2nd, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe step one of detection is obtained is 1.0
×10-5The solution of mol/L, obtains bulk solution;
3rd, solution to be measured is added in bulk solution, obtains mixed liquor;
4th, it is under conditions of 360nm, exciting slit width are 10 in excitation wavelength, detection bulk solution and mixed liquor
Fluorescence emission spectrum, if the fluorescence intensity extraction of mixed liquor is gone out, to can determine that and contain Cu in solution to be measured2+。
Specific embodiment 12:Implementation method and the fluorescence unlike specific embodiment 11 described in step 4
It refers to fluorescence intensity reduction by more than 50% that intensity extraction is gone out.Other are identical with specific embodiment 11.
Specific embodiment 13:Using phenanthro- imidazoles reversible fluorescence probe in detecting Cr3+Method, enter according to the following steps
OK:
First, by pH=6.8~7.4, concentration for the HEPES cushioning liquid and DMF of 0.01mol/L are by volume 1:1 mixes
Close uniform, obtain solvent;
2nd, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe step one of detection is obtained is 1.0
×10-5The solution of mol/L, obtains bulk solution;
3rd, the Cu that concentration is 0.10mol/L is separately added into bulk solution2+, 5min is stood after being sufficiently mixed, obtain phenanthrene
And imidazoles fluorescence molecule-Cu2+Complex solution;
4th, solution to be measured is added to phenanthro- imidazoles fluorescence molecule-Cu2+In complex solution, mixed liquor is obtained;
5th, it is that detection bulk solution, phenanthro- imidazoles is glimmering under conditions of 360nm, exciting slit width are 10 in excitation wavelength
Optical molecule-Cu2+The fluorescence emission spectrum of complex solution and mixed liquor, if blended liquid phase for phenanthro- imidazoles fluorescence molecule-
Cu2+The fluorescence intensity enhancing of complex solution, then to can determine that and contain Cr in solution to be measured3+。
Specific embodiment 14:Present embodiment is glimmering described in step 5 from unlike specific embodiment 13
Luminous intensity enhancing refers to that fluorescence intensity improves more than 50%.Other are identical with specific embodiment 13.
With following case verification beneficial effects of the present invention:
Experiment 1:This experiment for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection, according to the following steps
Carry out:
First, 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 of 30mL is added thereto to as solvent, 110 DEG C are warming up to, and is stirred continuously, during the course of the reaction, 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, react substantially completely,
Stop reaction, be cooled to room temperature, 50mL water is added in there-necked flask, be placed in the beaker of 200mL, with 10% NaOH
Solution adjusts pH value to 9, and suction filtration obtains yellow solid, dries;After drying, it is re-dissolved in the ethyl acetate of 25mL, heating stirring 2h
Afterwards, room temperature is cooled to, there are a large amount of solids to separate out, suction filtration, drying obtain midbody compound I;
The yield of the midbody compound I that this step is obtained is 92%, fusing point:258~260 DEG C.With infrared spectrum, nuclear-magnetism
Hydrogen is composed and nuclear-magnetism carbon stave levies midbody compound I, and the result for obtaining 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
2nd, the synthesis of midbody compound II:
Add the ethanol of 2.0mmol midbody compound I, 0.32g Raney's nickels and 30mL molten in the there-necked flask of 50mL
Agent, after 2min 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 completion of dropping, after being warming up to 80 DEG C of back flow reaction 5h, (solvent is V with TLC tracing detections(ethyl acetate):
V(petroleum ether)=3: 7), substantially completely, after being cooled to room temperature, suction filtration is washed five times with ethyl acetate, and rotary evaporation filtrate obtains for reaction
To brown solid and drying.Re-crystallizing in ethyl acetate is used again, after heating stirring 2.5h, room temperature is cooled to, and there are a large amount of solids to separate out,
Suction filtration, drying, midbody compound II.
The yield of the midbody compound II that this step is obtained is 85%, fusing point:183~185 DEG C;
Composed with infrared spectrum, nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon and characterized, the result for obtaining 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
3rd, Cu2+The synthesis of fluorescence probe:
Successively to addition 0.62g (2.0mmol) midbody compound II, 0.24g (2.0mmol) salicylide in there-necked flask,
The glacial acetic acid of 20mL is added again as solvent in there-necked flask, stirring at normal temperature reaction 2h after reaction terminates, adds in reaction system
Enter water quenching to go out reaction, then be placed in the beaker of 200mL, adjust pH value to 10 with 10% sodium hydroxide solution, then carry out suction filtration, filter
Cake is washed to neutrality, dries, then with re-crystallizing in ethyl acetate, collects solid, after drying, 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 experiment 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, illustrating that purity is higher, quality percent purity is more than 95%.
Characterized with infrared spectrum and nuclear magnetic resoance spectrum, the result for obtaining 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=7.20Hz, 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.
Knowable to characterization result more than, for Cu2+The structural formula of the phenanthro- imidazoles reversible fluorescence probe of detection is:
By this experiment preparation for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection carries out spectrum property test, step
It is as follows:
First, the configuration of storing solution
Cu will be used for2+The phenanthro- imidazoles reversible fluorescence probe of detection is with N,N-dimethylformamide (DMF) for solvent is prepared
It is 1.0 × 10 into concentration–4The host compound solution of mol/L, it is standby;
The preparation of cation storing solution:The cation that concentration is 0.10mol/L is configured to metal chlorination salt and nitrate
Solution, it is standby;
HEPES cushioning liquid:The HEPES for weighing 0.60g adds the volumetric flask of 250mL
In, distilled water constant volume is used, it is made into the solution of 0.01mol/L and shakes up, after static 2h, pH value is adjusted with sodium hydroxide solution, it is made into
PH value is 7.4 cushioning liquid.Shake up, it is standby.
2nd, spectrum property test
First investigate 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 be separately added into concentration and be
The K of 0.10mol/L+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Fe3+、Cd2+、Ni2+、Co2+、Pb2+、Cu2+、Ag+、Al3+And Hg2+
Metal ion solution, is that (wherein, the concentration of HEPES cushioning liquid is for 1: 1 mixed solution of DMF/HEPES with volume ratio
0.01mol/L, pH=7.4) constant volume, now, host compound is 1: 10 with the molar concentration rate of metal ion, after constant temperature 2h,
Ultra-violet absorption spectrum is determined respectively, as a result as shown in Figure 1.As can be known from Fig. 1, after adding different metal ions, K+、Ba2+、Ca2+、
Na+、Mg2+、Zn2+、Cr3+、Cd2+、Ni2+、Co2+、Pb2+、Hg2+、Ag+、Al3+And Fe3+With the ultra-violet absorption spectrum shaped form of main body
Shape is similar to.And add Cu2+Afterwards, in UV absorption wave spectrum, wavelength for 420nm at, hence it is evident that there is a new ultraviolet absorption peak to go out
It is existing.Therefore, can be with initial guess from uv absorption spectra, host compound (PA) is to Cu2+With selection evident characteristics.
In order to further verify this experiment prepare 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 cushioning liquid of 1: 1 DMF/HEPES with volume ratio
It is 0.01mol/L, pH=7.4) it is solvent, compound concentration is 1.0 × 10-5The bulk solution of mol/L, in bulk solution respectively
It is the K of 0.10mol/L to add concentration+、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 of, it is carried out
The test of fluorescence emission spectrum, the fluorescence emission spectral intensity for obtaining, as a result as shown in Figure 2.As can be known from Fig. 2, main body chemical combination
The fluorescence emission wavelengths of thing are 420nm, and fluorescence intensity is 780a.u or so.After adding different metal ions, K+、Ba2+、Ca2+、
Na+、Mg2+、Zn2+、Cd2+、Ni2+、Co2+、Cr3+、Pb2+、Hg2+、Ag+、Al3+And Fe3+With the fluorescence intensity influence on main body not
Greatly, intensity is in 770a.u. or so.And add Cu2+When, fluorescence intensity substantially gone out to 100a.u. or so by extraction, and extraction is gone out based on degree
7 times of body fluorescence intensity.Therefore, from fluorescence emission spectrum it was determined that host compound is to Cu2+With selection evident characteristics.
Fluorescence 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 cushioning liquid 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.The K of 0.10mol/L is separately added into again+、Ba2+、Ca2+、Na+、Mg2+、Zn2+、Cr3+、Cd2+、Ni2+、
Co2+、Pb2+、Hg2+、Ag+、Al3+And Fe3Solution, is well 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 recognize Cu2+Almost without influence, but add Cr3+Fluorescence intensity is enhanced to from 100a.u. afterwards
710a.u. or so, illustrates fluorescence molecule-Cu2+Complex compound is to Cr3+With Selective recognition effect, the fluorescent molecular probe is completed
Reversible (off-on-off) fluorescence signal response.This result has important meaning in the practical application of host compound
Justice.
This experiment prepare for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection, experiment explanation is with body more than
Product ratio is 1: 1 DMF/H2The mixed solution (concentration of HEPES cushioning liquid 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.
Experiment 2:This experiment is replaced from the step of 1 is tested unlike experiment 1 three with following operation:Successively to there-necked flask
Middle addition midbody compound II 0.62g (2.0mmol), salicylide 0.31g (2.5mmol) and 30mL 98% the concentrated sulfuric acid
Used as solvent, stirring at normal temperature reaction 3.5h after reaction terminates, to adding water quenching to go out reaction in reaction system, is placed in 200mL's
In beaker, adjust pH value to 10 with 10% sodium hydroxide solution, then carry out suction filtration, filter cake is washed to neutrality, dries, then use acetic acid
Ethyl ester is recrystallized, and collects solid, and reversible phenanthro- imidazoles Cu is obtained after drying2+Fluorescence probe.This experiment obtain for Cu2+Inspection
The structural formula of the phenanthro- imidazoles reversible fluorescence probe of survey is:
Yield is 65%.
Experiment 3:This experiment is replaced from the step of 1 is tested unlike experiment 1 three with following operation:Successively to there-necked flask
The formic acid of middle addition midbody compound II 0.62g (2.0mmol), salicylide 0.34g (2.8mmol), and 28mL is used as molten
Agent, stirring at normal temperature reaction 3h after reaction terminates, to adding water quenching to go out reaction in reaction system, is placed in the beaker of 200mL,
Adjust pH value to 9 with 10% sodium hydroxide solution, then carry out suction filtration, filter cake is washed to neutrality, dry, then tied again with ethyl acetate
Crystalline substance, collects solid, and reversible phenanthro- imidazoles Cu is obtained after drying2+Fluorescence probe.The reversible phenanthro- imidazoles Cu that this experiment is obtained2+It is glimmering
The structural formula of light probe is:
Yield is 63%.
Experiment 4:This experiment is replaced from the step of 1 is tested unlike experiment 1 three with following operation:Successively to there-necked flask
The concentrated nitric acid of the 65% of middle addition midbody compound II 0.62g (2.0mmol), salicylide 0.37g (3.0mmol), and 20mL
Used as solvent, stirring at normal temperature reaction 4h after reaction terminates, to adding water quenching to go out reaction in reaction system, is placed in the burning of 200mL
In cup, adjust pH value to 10 with 10% sodium hydroxide solution, then carry out suction filtration, filter cake is washed to neutrality, dries, then use acetic acid second
Ester is recrystallized, and collects solid, and reversible phenanthro- imidazoles Cu is obtained after drying2+Fluorescence probe.The reversible phenanthro- imidazoles that this experiment is obtained
Cu2+The structural formula of fluorescence probe is:
Yield is 75%.
Claims (10)
1. it is a kind of to be used for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection, it is characterised in that the structural formula of the reversible fluorescence probe
For:
2. the described one kind for preparing claim 1 is used for Cu2+The method of the phenanthro- imidazoles reversible fluorescence probe of detection, its feature
It is that the method is carried out according to the following steps:
First, the synthesis of midbody compound I:
During phenanthrenequione, o-nitrobenzaldehyde and ammonium acetate put into reactor according to 1: 1.5: 2 mol ratio, glacial acetic acid is added
Used as solvent, after being warming up to 90~110 DEG C and stirring 6~10h, reaction stops, and is cooled to room temperature, to adding water in reactor,
Adjust pH value to 8~10 with 10% sodium hydroxide solution again, suction filtration obtains yellow solid;After drying, then tied again with ethyl acetate
Crystalline substance, then suction filtration, drying, obtain midbody compound I;
2nd, the synthesis of midbody compound II:
Weigh the hydrazine hydrate solution that midbody compound I, Raney's nickel, ethanol, mass percentage concentration are 80%;Wherein intermediate
The amount of the material of compound I is 1mmol with the ratio of the quality of Raney's nickel:(0.15~2) g;The amount of the material of midbody compound I with
The ratio of the volume of ethanol is 1mmol:(25~40) mL;The amount of the material of midbody compound I is 80% with mass percentage concentration
Hydrazine hydrate solution volume ratio be 1mmol:3~4mL;Midbody compound I and Raney's nickel are added in reactor, then
Ethanol is added as solvent, nitrogen protection is passed through, under agitation, the hydrazine hydrate that mass percentage concentration is 80% is added dropwise molten
Liquid, after completion of dropping, is warming up to 65~85 DEG C, reacts 5~9h, is cooled to room temperature, and suction filtration is washed with ethyl acetate, and rotation is steamed
After hair removal filtrate, gray solid is obtained, after drying, then with re-crystallizing in ethyl acetate, then suction filtration, drying, obtain intermediate
Compound II;
3rd, Cu2+The synthesis of fluorescence probe:
According to 1:The mol ratio of (1~3) weighs midbody compound II and salicylide, is added in reactor, then adds thereto
Enter acid medium as solvent, 1~4h of stirring reaction after reaction terminates, to adding water quenching to go out reaction in reaction system, then is used
10% sodium hydroxide solution adjusts pH value to 8~10, separates out solid;Then suction filtration is carried out, filter cake is washed with water to neutrality, dried, then
With re-crystallizing in ethyl acetate, obtain for Cu2+The phenanthro- imidazoles reversible fluorescence probe of detection.
3. according to claim 2 a kind of for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection, it is special
Levy be acid medium described in step 3 for the concentrated sulfuric acid that mass percentage concentration is 98%, mass percentage concentration be 65~
68% concentrated nitric acid, glacial acetic acid or formic acid.
4. the one kind according to Claims 2 or 3 is used for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection,
It is characterized in that the reaction temperature in step one is 95 DEG C, the reaction time is 8h.
5. the one kind according to Claims 2 or 3 is used for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection,
It is characterized in that pH value in step one is to 9.
6. the one kind according to Claims 2 or 3 is used for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection,
It is characterized in that reaction temperature is 78 DEG C in step 2, the reaction time is 8h.
7. the one kind according to Claims 2 or 3 is used for Cu2+The preparation method of the phenanthro- imidazoles reversible fluorescence probe of detection,
It is characterized in that midbody compound II and the mol ratio of salicylide reactant are 1: 2.5 in step 3.
8. utilizing the one kind described in claim 1 is used for Cu2+The phenanthro- imidazoles reversible fluorescence probe in detecting Cu of detection2+Method,
It is characterized in that the method is carried out according to the following steps:
First, by pH=6.8~7.4, concentration for the HEPES cushioning liquid and DMF of 0.01mol/L are by volume 1:1 mixing is equal
It is even, obtain solvent;
2nd, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe step one of detection is obtained be 1.0 ×
10-5The solution of mol/L, obtains bulk solution;
3rd, solution to be measured is added in bulk solution, obtains mixed liquor;
4th, excitation wavelength be 360nm, exciting slit width be 10 under conditions of, detection bulk solution and mixed liquor fluorescence
Emission spectrum, if the fluorescence intensity extraction of mixed liquor is gone out, to can determine that and contain Cu in solution to be measured2+。
9. it is according to claim 8 to utilize a kind of for Cu2+The phenanthro- imidazoles reversible fluorescence probe in detecting Cu of detection2+Side
Method, it is characterised in that it refers to fluorescence intensity reduction by more than 50% that the fluorescence intensity extraction described in step 4 is gone out.
10. utilizing the one kind described in claim 1 is used for Cu2+The phenanthro- imidazoles reversible fluorescence probe in detecting Cr of detection3+Method,
It is characterized in that the method is carried out according to the following steps:
First, by pH=6.8~7.4, concentration for the HEPES cushioning liquid and DMF of 0.01mol/L are by volume 1:1 mixing is equal
It is even, obtain solvent;
2nd, Cu will be used for2+The solution compound concentration that the phenanthro- imidazoles reversible fluorescence probe step one of detection is obtained be 1.0 ×
10-5The solution of mol/L, obtains bulk solution;
3rd, the Cu that concentration is 0.10mol/L is separately added into bulk solution2+, 5min is stood after being sufficiently mixed, obtain phenanthro- miaow
Azoles fluorescence molecule-Cu2+Complex solution;
4th, solution to be measured is added to phenanthro- imidazoles fluorescence molecule-Cu2+In complex solution, mixed liquor is obtained;
5th, it is detection bulk solution, phenanthro- imidazoles fluorescence point under conditions of 360nm, exciting slit width are 10 in excitation wavelength
Son-Cu2+The fluorescence emission spectrum of complex solution and mixed liquor, if blended liquid phase is for phenanthro- imidazoles fluorescence molecule-Cu2+
The fluorescence intensity enhancing of complex solution, then to can determine that and contain Cr in solution to be measured3+。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710106165.0A CN106883183B (en) | 2017-02-27 | 2017-02-27 | One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710106165.0A CN106883183B (en) | 2017-02-27 | 2017-02-27 | One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106883183A true CN106883183A (en) | 2017-06-23 |
CN106883183B CN106883183B (en) | 2019-06-21 |
Family
ID=59179259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710106165.0A Expired - Fee Related CN106883183B (en) | 2017-02-27 | 2017-02-27 | One kind being used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and the preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106883183B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107513063A (en) * | 2017-09-09 | 2017-12-26 | 福建医科大学 | One kind can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof |
CN107629008A (en) * | 2017-10-18 | 2018-01-26 | 齐齐哈尔大学 | A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method |
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 |
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 |
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 |
CN108675990A (en) * | 2018-06-14 | 2018-10-19 | 齐齐哈尔大学 | A kind of detection Cu2+Fluorescence probe, preparation method and fluorescent test paper strip preparation and application |
CN109147549A (en) * | 2018-08-24 | 2019-01-04 | 北京理工大学 | A kind of multimode method for anti-counterfeit based on luminescent dopant quantum dot |
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 |
CN111777598A (en) * | 2020-08-10 | 2020-10-16 | 齐齐哈尔大学 | Detect Cu2+And can utilize Cu2+Detection of HPO42–Fluorescent probe and preparation method and application thereof |
-
2017
- 2017-02-27 CN CN201710106165.0A patent/CN106883183B/en not_active Expired - Fee Related
Non-Patent Citations (3)
Title |
---|
BIAO GU,等: "Highly selective and sensitive fluorescent probe for the detection of nitrite", 《TALANTA》 * |
HOSSEIN BEHMADI,等: "Synthesis of phenanthrimidazole from 9,10-phenanthraquinone and aldehydes by molecular iodine as catalyst", 《CHINESE CHEMICAL LETTERS》 * |
黄礼艳: "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", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107513063A (en) * | 2017-09-09 | 2017-12-26 | 福建医科大学 | One kind can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof |
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 |
CN107629008A (en) * | 2017-10-18 | 2018-01-26 | 齐齐哈尔大学 | A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method |
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 |
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 |
CN108675990A (en) * | 2018-06-14 | 2018-10-19 | 齐齐哈尔大学 | A kind of detection Cu2+Fluorescence probe, preparation method and fluorescent test paper strip preparation and application |
CN109147549A (en) * | 2018-08-24 | 2019-01-04 | 北京理工大学 | A kind of multimode method for anti-counterfeit based on luminescent dopant quantum dot |
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 |
CN111777598A (en) * | 2020-08-10 | 2020-10-16 | 齐齐哈尔大学 | Detect Cu2+And can utilize Cu2+Detection of HPO42–Fluorescent probe and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN106883183B (en) | 2019-06-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106883183A (en) | One kind is used for Cu2+Phenanthro- imidazoles reversible fluorescence probe of detection and preparation method and application | |
CN105694866B (en) | Symmetric form phenanthro- imidazoles Fe3+ fluorescence probes of double-Schiff base link and preparation method thereof | |
Li et al. | Novel thiophene-based colorimetric and fluorescent turn-on sensor for highly sensitive and selective simultaneous detection of Al3+ and Zn2+ in water and food samples and its application in bioimaging | |
Hu et al. | A 2D bilayered metal–organic framework as a fluorescent sensor for highly selective sensing of nitro explosives | |
US8962339B2 (en) | Fluorescent probe compounds, preparation method and application thereof | |
CN106632064B (en) | Reversible dihydroxy phenanthroimidazole Hg2+Fluorescent probe synthesis and methods of use | |
CN107629008A (en) | A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method | |
CN103113380B (en) | Rhodamine derivative and preparation method and application thereof | |
Bhalla et al. | Solvent dependent competition between fluorescence resonance energy transfer and through bond energy transfer in rhodamine appended hexaphenylbenzene derivatives for sensing of Hg 2+ ions | |
CN102863406A (en) | Receptor compound for detecting CN- by colorimetry-fluorescence two channels, synthesis thereof and application thereof | |
Lin et al. | A new photochromic-ligand-based luminescent coordination polymer as a MnO 4− sensor with extremely high sensitivity and excellent selectivity | |
CN111848633B (en) | coumarin-Tr baby's base Fe3+ fluorescent probe and preparation method thereof | |
CN106905343A (en) | Contain two phenanthro- imidazoles fluorescein pH fluorescence probes of hydroxyl and preparation method thereof | |
Huang et al. | Supramolecular assemblies of Zn (ii) complexes with a D–π–A ligand for sensing specific organic molecules | |
Zhu et al. | A benzimidazole-derived fluorescent chemosensor for Cu (ii)-selective turn-off and Zn (ii)-selective ratiometric turn-on detection in aqueous solutions | |
CN111393461A (en) | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof | |
Geng et al. | Improvement of the fluorescent sensing biomarker 3-nitrotyrosine for a new luminescent coordination polymer by size regulation | |
CN104327842B (en) | For fluorescent material and the preparation method of five member ring heterocyclic compound specific detection | |
CN110105379A (en) | A kind of Zn-MOFs complex preparation method with fluorescence identifying | |
CN106749307B (en) | Trihydroxy imidazoles-fluorescein pH fluorescence probe and preparation method thereof | |
CN114409591B (en) | Bishydrazide viologen derivative, preparation method thereof and humidity sensing application | |
Kim et al. | Lithium sensors based on photophysical changes of 1-aza-12-crown-4 naphthalene derivatives synthesized via Buchwald–Hartwig amination | |
Lin et al. | A simple pincer-type chemosensor for reversible fluorescence turn-on detection of zinc ion at physiological pH range | |
CN108863945A (en) | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application | |
CN113845534A (en) | Preparation method and application of luminescent crystal material for detecting high manganese acid radical in extremely sensitive water phase |
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 |
Granted publication date: 20190621 Termination date: 20210227 |
|
CF01 | Termination of patent right due to non-payment of annual fee |