CN108863945A - A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application - Google Patents
A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application Download PDFInfo
- Publication number
- CN108863945A CN108863945A CN201810619502.0A CN201810619502A CN108863945A CN 108863945 A CN108863945 A CN 108863945A CN 201810619502 A CN201810619502 A CN 201810619502A CN 108863945 A CN108863945 A CN 108863945A
- Authority
- CN
- China
- Prior art keywords
- probe
- solution
- phenanthro
- imidazoles
- ion
- 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.)
- Pending
Links
- 0 CC(c1ccccc1O)=CC*c1c([*-]c2ccccc2)c2ccccc2c2ccccc12 Chemical compound CC(c1ccccc1O)=CC*c1c([*-]c2ccccc2)c2ccccc2c2ccccc12 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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"
-
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed 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
- 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
-
- 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"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application, it is related to detecting Fe3+The probe and its preparation and application of ion.The present invention is to solve existing Fe3+Ion fluorescence probe synthesis step is complicated, to Fe3+Detection specificity it is poor, the response time is too long, cannot achieve the technical issues of intuitive quickly detection.Phenanthro- imidazoles Fe of the invention3+The structural formula of probe is：Preparation method：Reaction is heated in acidic organic solvent with phenanthrenequione, salicylide, ammonium acetate, aniline, lye is then added, crude product is precipitated, then recrystallize, obtain phenanthro- imidazoles Fe3+Probe.Fe is detected by the variation of " access " of Tyndall phenomenon or by the fluorescence intensity change of fluorescence spectrum using the probe3+, it can be used for environment and biochemical field.
Description
Technical field
The present invention relates to a kind of detection Fe3+The probe and its preparation and application of ion.
Background technique
Metal-ion fluorescent probe attracts attention because of it in the extensive use of environment and biochemical field.Wherein, Fe3+
It participates in the synthesis of DNA and RNA and maintains the processes such as intracellular osmotic pressure and acid-base balance, Fe3+Missing can cause a variety of physiology
Motility disorder leads to heart disease, diabetes, even certain tumours.Therefore it develops and design quickly and accurately detects Fe3+Ion
Probe has important theory and actual application meaning.Zhang Lingfei etc. exists《Chinese Journal of Inorganic Chemistry》The 7th phases of volume 26 in 2010
A kind of monosubstituted rhodamine-Thiacalixarene derivative Fe is reported on 1183-1188 pages3+Ion fluorescence probe, the probe
Main body calixarenes synthesis step is more, and experiment post-processing is complicated, need to carry out column chromatography for separation with chloroform and acetone toxic organic solvent,
Yield is only 26%.《Inorganic chemistry communication》(Inorganic chemistry communications) was 14 phases in 2011
1656-1658 pages of disclosure has reported a kind of anthracene-pyridine Fe3+Ion fluorescence probe, the probe is in identification Fe3+It is also while ion
Other Zn2+And Cu2+Ion, recognition performance be not single-minded；《Chemical communication》(Chemical Communications) was at 2012
Pages 4600~4602 of 38 phases report entitled《The BODIPY dyestuff for improving Stokes ' displacement is shifted by bond energy in living body
Fe in cell3+Ion detection》, the BODIPY dyestuff reported in article is to Fe3+The response time of ion identification is 30min, response
Time is longer, and sensitivity is not high；《Spectrum journal A：Molecule and biomolecular spectroscopy》(Spectrochimica Acta Part
A:Molecular and Biomolecular Spectroscopy) it is reported in the 569-574 pages of article of the 5th phase in 2014
Road methyldisulfanylphenyl-urea fluorescence probe, the probe dimethyl sulfoxide and aqueous solution (v/v, 8:2) realization pair in mixed system
Fe3+Identification, but excessive dimethyl sulfoxide organic solvent is used in identification system, it is impossible to be used in biological detection, and not to environment
Benefit.Currently, Fe reported in the literature3+Ion fluorescence probe can only all use expensive fluorescence other than with drawbacks described above
Spectrometer is detected, and detection mode is single, is difficult to realize and in real time, quickly, is intuitively detected.
Summary of the invention
The present invention is to solve existing Fe3+Ion fluorescence probe synthesis step is complicated, to Fe3+Detection specificity compared with
Difference, the response time is too long, cannot achieve the technical issues of intuitive quickly detection, and provides a kind of phenanthro- imidazoles Fe3+Probe and its
Preparation and application.
Phenanthro- imidazoles Fe of the invention3+The structural formula of probe is：
It can use Tyndall phenomenon or fluorescence spectrum to detect Fe3+。
Above-mentioned phenanthro- imidazoles Fe3+The preparation method of probe carries out according to the following steps：
It one, is in molar ratio 1 by phenanthrenequione, salicylide, ammonium acetate, aniline:1:1:(1~3) is put into condensing unit
Reactor in, acidic organic solvent is added, stirs and be warming up to boiling reflux, reacts 9~12h, is cooled to room temperature；
Two, pH value is adjusted to 6~7 using alkaline aqueous solution, there is solid precipitation；It filters, filter cake is washed with water, and collects filter
Cake, it is dry, obtain crude product；
Three, crude product is recrystallized with organic solvent, obtains phenanthro- imidazoles Fe3+Probe.
Phenanthro- imidazoles Fe of the invention3+The synthesis process of probe can be used following reaction equation to indicate：
Utilize above-mentioned phenanthro- imidazoles Fe3+Probe detects Fe by Tyndall phenomenon3+Method, carry out according to the following steps：
One, by phenanthro- imidazoles Fe3+Probe is that solvent is configured to main body stock solution with methanol (MeOH), wherein main body stock solution
Middle phenanthro- imidazoles Fe3+The concentration of probe is 100~300 μm of ol/L；
Two, main body stock solution is diluted to phenanthro- miaow with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 again
Azoles Fe3+The concentration of probe is 10~30 μm of ol/L, obtains probe solution A1；
Three, part probe solution A is taken1Sample to be tested is added thereto, is uniformly mixed, obtains test sample solution A2；
Four, use red laser pen for light source, the light for issuing red laser pen penetrates probe solution A respectively1And survey
Test agent solution A2, from the direction perpendicular to light, if in probe solution A1It is middle the " logical of a red light occur
Road ", and in test sample solution A2Middle nothing " access " or " access " are compared with probe solution A1" access " it is of light color, then can sentence
Determine in test sample solution containing Fe3+Ion.
Utilize above-mentioned phenanthro- imidazoles Fe3+Probe detects Fe by fluorescence spectrum3+Method, carry out according to the following steps：
One, by phenanthro- imidazoles Fe3+Probe is that solvent is configured to main body stock solution with methanol (MeOH), wherein main body stock solution
Middle phenanthro- imidazoles Fe3+The concentration of probe is 100~300 μm of ol/L；
Two, main body stock solution is diluted to phenanthro- miaow with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 again
Azoles Fe3+The concentration of probe is 10~30 μm of ol/L, obtains probe solution A1；
Three, part probe solution A is taken1Sample to be tested is added thereto, is uniformly mixed, obtains test sample solution A2；
Four, using 329nm as excitation wavelength, probe solution A is tested using Fluorescence Spectrometer1Fluorescent emission in 480nm
Spectrum, fluorescent emission intensity are denoted as I1；
Five, using 329nm as excitation wavelength, using Fluorescence Spectrometer test sample solution A2Fluorescent emission in 480nm
Spectrum, fluorescent emission intensity I2；
If six, I2≤0.81I1, then determine to contain Fe in sample to be tested3+Ion.
Phenanthro- imidazoles Fe provided by the invention3+Ion probe is using the raw material one-step synthesis being easy to get, and post-processing is simple, is produced
Rate is 60%~85%, at low cost；This probe both can intuitively be observed using simple laser pen by Tyndall phenomenon
The variation of bright " access " carrys out the Fe in qualitative detection aqueous environment3+The presence of ion, response are rapidly, easy to use.It can also be with
Fe is detected by the fluorescence intensity change of fluorescence spectrum3+The presence of ion, and detect and do not changed by other metal ions and pH
It influences, detecting and selecting property is high, sensitivity is high.Detection process is completed in 30s, and rapidly, easy to use, response quickly is imitated for response
Fruit is obvious.It can be used for environment and biochemical field.
Detailed description of the invention
Fig. 1 be embodiment 1 prepare fluorescence probe (20 μm of ol/L) and its with different metal ions (200 μm of ol/L, K+、
Ca2+、Na+、Mg2+、Al3+、Zn2+、Fe3+、Pb2+、Ba2+、Cu2+、Hg2+、Ag+、Cr3+、Cd2+、Co2+And Ni2+) fluorescence when coexisting
Volume efficiency figure, abscissa are ionic species, and ordinate is fluorescence intensity ratio value (F480)；
Fig. 2 is the fluorescence probe of the preparation of embodiment 1 in other metal ions (200 μm of ol/L, Fe3+、K+、Ca2+、Na+、Mg2 +、Al3+、Zn2+、Ba2+、Cu2+、Hg2+、Ag+、Cd2+、Co2+、Cr3+、Ni2+And Pb2+In the presence of, Fe is added3+Ion (200
μm ol/L) fluorescence spectra, abscissa is wavelength, and ordinate is fluorescence intensity；
Fig. 3 is the fluorescence probe (20 μm of ol/L) of the preparation of embodiment 1 with Fe3+Ion concentration changes the glimmering of (0~1mmol/L)
Optical emission spectroscopy figure, abscissa are wavelength, and ordinate is fluorescence intensity；
Fig. 4 is fluorescence probe (20 μm of ol/L) prepared by embodiment 1 and its addition Fe3+With pH value after ion (1mmol/L)
Variation
Fig. 5 is that Fe is added in fluorescence probe (20 μm of ol/L) prepared by embodiment 13+Ion (1mmol/L) afterwards fluorescence intensity with
The curve graph of time change, abscissa are the time, and ordinate is fluorescence intensity；
Specific embodiment
Specific embodiment one：The phenanthro- imidazoles Fe of present embodiment3+The structural formula of probe is：
It can use Tyndall phenomenon or fluorescence spectrum to detect Fe3+。
Specific embodiment two：Phenanthro- imidazoles Fe described in specific embodiment one3+The preparation method of probe, by following step
It is rapid to carry out：
It one, is in molar ratio 1 by phenanthrenequione, salicylide, ammonium acetate, aniline:1:1:(1~3) is put into condensing unit
Reactor in, acidic organic solvent is added, stirs and be warming up to boiling reflux, reacts 9~12h, is cooled to room temperature；
Two, pH value is adjusted to 6~7 using alkaline aqueous solution, there is solid precipitation；It filters, filter cake is washed with water, and collects filter
Cake, it is dry, obtain crude product；
Three, crude product is recrystallized with organic solvent, obtains phenanthro- imidazoles Fe3+Probe.
Specific embodiment three：Present embodiment acidity described in step 1 unlike specific embodiment two has
Solvent is formic acid, glacial acetic acid, trifluoroacetic acid, benzene sulfonic acid or p-methyl benzenesulfonic acid；It is other to be identical with embodiment two.
Specific embodiment four：Present embodiment adjusts pH value unlike specific embodiment two or three in step 2
Use alkaline aqueous solution for 3% NaOH aqueous solution, 5% Na2CO3Aqueous solution, 5% NaHCO3Aqueous solution, 3% KOH water
Solution or 3% K2CO3Aqueous solution；It is other identical as specific embodiment two or three.
Specific embodiment five：It is tied again in step 3 unlike one of present embodiment and specific embodiment two to four
The ethyl acetate and petroleum ether that brilliant organic solvent is are 1 by volume：Mixed liquor, ethyl acetate and the n-hexane of (1~5) are pressed
Volume ratio is 1：The mixed liquor of (1~5) either ethyl acetate and methylene chloride are 1 by volume：The mixed liquor of (1~5).Its
It is identical as one of specific embodiment two to four.
Specific embodiment six：Utilize phenanthro- imidazoles Fe described in specific embodiment one3+Probe passes through Tyndall phenomenon
Detect Fe3+The method of ion carries out according to the following steps：
One, by phenanthro- imidazoles Fe3+Probe is that solvent is configured to main body stock solution with methanol (MeOH), wherein phenanthro- imidazoles
Fe3+The concentration of probe is 100~300 μm of ol/L；
Two, main body stock solution is diluted to phenanthro- miaow with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 again
Azoles Fe3+The concentration of probe is 10~30 μm of ol/L, obtains probe solution A1；
Three, part probe solution A is taken1Sample to be tested is added thereto, is uniformly mixed, obtains test sample solution A2；
Four, use red laser pen for light source, the light for issuing red laser pen penetrates probe solution A respectively1And survey
Test agent solution A2, from the direction perpendicular to light, if in probe solution A1It is middle the " logical of a red light occur
Road ", and in test sample solution A2Middle nothing " access " or " access " are compared with probe solution A1" access " it is of light color, then can sentence
Determine in test sample solution containing Fe3+Ion.
Specific embodiment seven：The preparation of present embodiment and HEPES buffer solution unlike specific embodiment six
Method is：It is put into the volumetric flask of 250mL with n-2-Hydroxyethylpiperazine-N'-2-ethanesulfonic acid 0.60g, with distilled water constant volume, is made into
The solution of 0.01mol/L, shakes up, after static 3 hours, with sodium hydroxide solution tune pH value, be made into pH value be 7.4~12 it is slow
Solution is rushed, with nitric acid solution tune pH value, is made into the buffer solution that pH value is 3~6.It is other identical as specific embodiment six.
Specific embodiment eight：Present embodiment red laser in step 4 unlike specific embodiment six or seven
650~660nm of wavelength, the power of pen are 5~50mW.It is other identical as specific embodiment six or seven.
Specific embodiment nine：Utilize phenanthro- imidazoles Fe described in specific embodiment one3+Probe is examined by fluorescence spectrum
Survey Fe3+Method, carry out according to the following steps：
One, by phenanthro- imidazoles Fe3+Probe is that solvent is configured to main body stock solution with methanol (MeOH), wherein phenanthro- imidazoles
Fe3+The concentration of probe is 100~300 μm of ol/L；
Two, main body stock solution is diluted to phenanthro- miaow with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 again
Azoles Fe3+The concentration of probe is 10~30 μm of ol/L, obtains probe solution A1；
Three, part probe solution A is taken1Sample to be tested is added thereto, is uniformly mixed, obtains test sample solution A2；
Four, using 329nm as excitation wavelength, probe solution A is tested using Fluorescence Spectrometer1Fluorescent emission in 480nm
Spectrum, fluorescent emission intensity are denoted as I1；
Five, using 329nm as excitation wavelength, using Fluorescence Spectrometer test sample solution A2Fluorescent emission in 480nm
Spectrum, fluorescent emission intensity I2；
If six, I2≤0.81I1, then determine to contain Fe in sample to be tested3+Ion.
Specific embodiment ten：The preparation of present embodiment and HEPES buffer solution unlike specific embodiment nine
Method is：It is put into the volumetric flask of 250mL with n-2-Hydroxyethylpiperazine-N'-2-ethanesulfonic acid 0.60g, with distilled water constant volume, is made into
The solution of 0.01mol/L, shakes up, after static 3 hours, with sodium hydroxide solution tune pH value, be made into pH value be 7.4~12 it is slow
Solution is rushed, with nitric acid solution tune pH value, is made into the buffer solution that pH value is 3~6.It is other identical as specific embodiment nine.
Beneficial effects of the present invention are verified with following embodiment：
Embodiment 1：The phenanthro- imidazoles Fe of the present embodiment3+The preparation method of probe carries out according to the following steps：
One, respectively by phenanthrenequione 1.04g (5.0mmol), salicylide 0.52mL (5.0mmol), ammonium acetate 0.39g
(5.0mmol), aniline 0.55mL (6.0mmol) is added to 50mL and has in the there-necked flask of condensing unit, and is added thereto
The glacial acetic acid of 25mL is warming up to boiling reflux as solvent, is stirred continuously, during the reaction, with (the expansion of TLC tracing detection
Agent is ethyl acetate and petroleum ether, V (ethyl acetate)：V (petroleum ether)=3:7) after, reaction carries out 10h, fully reacting stops
Reaction, is cooled to room temperature；
Two, 50mL water is added in there-necked flask, is placed in the beaker of 200mL, with 5% NaHCO3Aqueous solution is by pH value
6 are adjusted to, there is solid precipitation；It filtering, filter cake is washed with water, and collects filter cake, and it is dry, obtain crude product；
It three, is 1 with the volume ratio of ethyl acetate and petroleum ether：3 mixed solvent recrystallizes crude product, obtains phenanthro- miaow
Azoles Fe3+Probe.The yield of the probe is 85%.Fusing point：168~171 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):3435,3051,1610,1585,1493,1481,757.1H NMR(600MHz,DMSO)δ：
11.82 (s, 1H, OH), 8.96 (d, J=8.4Hz, 1H, ArH), 8.91 (d, J=8.4Hz, 1H, ArH), 8.61 (d, J=
7.2Hz, 1H, ArH), 7.81 (t, J=7.2Hz, 1H, ArH), 7.73 (m, 6H, ArH), 7.58 (t, J=7.2Hz, 1H, ArH),
7.35 (t, J=7.2Hz, 1H, ArH), 7.22 (m, 1H, ArH), 7.05 (m, 2H, ArH), 6.94 (d, J=7.8Hz, 1H,
ArH),6.66(m,1H,ArH).13C NMR(150MHz,DMSO)δ(ppm):138.5,135.3,131.4,130.8,129.3,
128.2,127.3,126.4,125.9,125.9,124.2,122.3,120.7,118.7,117.1,115.6.
From the available phenanthro- imidazoles Fe manufactured in the present embodiment of above data3+The structural formula of probe is as follows：
By phenanthro- imidazoles Fe manufactured in the present embodiment3+The test analysis of probe progress fluorescence spectrum performance and Tyndall phenomenon
It is as follows：
One, the configuration of stock solution
By phenanthro- imidazoles Fe3+Probe with the main body stock solution that methanol (MeOH) is that solvent is configured to that concentration is 200 μm of ol/L,
It is spare；
Metal nitrate is configured to the metal ion stock solution that concentration is 0.1mol/L, it is spare；
HEPES buffer solution：It is put into the volumetric flask of 250mL, is used with n-2-Hydroxyethylpiperazine-N'-2-ethanesulfonic acid 0.60g
Distilled water constant volume is made into the solution of 0.01mol/L, shakes up, and after static 3 hours, with sodium hydroxide solution tune pH value, is made into pH
The buffer solution that value is 7.4~12 is made into the buffer solution that pH value is 3~6 with nitric acid solution tune pH value, spare.
Two, fluorescence spectrum performance test
By phenanthro- imidazoles Fe manufactured in the present embodiment3+Probe is used for fluorescence spectrometry, and method is as follows：By main body stock solution
Being diluted to concentration with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 is 20 μm of ol/L, obtains probe solution；Point
The K that concentration is 200 μm of ol/L is added not into probe solution+、Ca2+、Na+、Mg2+、Al3+、Zn2+、Fe3+、Pb2+、Ba2+、Cu2+、
Hg2+、Ag+、Cr3+、Cd2+、Co2+And Ni2+The mass ratio of the material of metal ion to be measured, probe and metal ion to be measured is 1:10.Often
After temperature places 2h, using 329nm as excitation wavelength, fluorescence probe is measured respectively and its in launch wavelength is after metal ion is added
Fluorescence emission spectrum at 480nm, as a result as shown in Figure 1.From fig. 1, it can be seen that Fe is added3+Afterwards the fluorescence intensity of test fluid be quenched for
0.28 times of former fluorescence probe emissive porwer.Concentration is added as (K after the different metal ions of 200 μm of ol/L+、Ca2+、Na+、Mg2 +、Al3+、Zn2+、Pb2+、Ba2+、Cu2+、Hg2+、Ag+、Cr3+、Cd2+、Co2+And Ni2+), the fluorescence intensity of fluorescence probe changes not
Greatly.Therefore, can be with initial guess from fluorescence spectrum, probe compound is to Fe3+Characteristic with selective enumeration method.
By phenanthro- imidazoles Fe manufactured in the present embodiment3+Probe carries out the test of anti-metal ion interference ability, and method is as follows：
It is 20 μm of ol/L that main body stock solution, which is diluted to concentration with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4, is obtained
Probe solution；The Fe that concentration is 200 μm of ol/L is added into probe solution respectively3+、K+、Ca2+、Na+、Mg2+、Al3+、Zn2+、Ba2 +、Cu2+、Hg2+、Ag+、Cd2+、Co2+、Cr3+、Ni2+And Pb2+Solion stands 5min, then is separately added into 200 after being sufficiently mixed
The Fe of μm ol/L3+After be uniformly mixed.At this point, probe, other metal ions and Fe3+The mass ratio of the material of ion three is 1:10:
10.After room temperature 2h, when excitation wavelength is 329nm, the test of fluorescence emission spectrum is carried out to it, as a result such as Fig. 2
It is shown.In other metal ions (K+、Ca2+、Na+、Mg2+、Al3+、Zn2+、Ba2+、Cu2+、Hg2+、Ag+、Cd2+、Co2+、Cr3+、Ni2+
And Pb2+In the presence of, Fe3+When ion and other metal ions coexist, fluorescence probe detects Fe3+Fluorescence intensity when ion
It is not influenced by other metal ions.Fe3+The intensity that is quenched of ion pair fluorescence probe maintains 0.28 times or so, i.e. fluorescence is visited
For Fe3+Detection not by the interference of other metal ions.
By phenanthro- imidazoles Fe manufactured in the present embodiment3+Probe is carried out for Fe3+The sensitivity test of ion detection, specifically
It is 20 μ that main body stock solution is diluted to concentration with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 as follows by method
Mol/L obtains probe solution；The Fe of 0~1mmol/L is added into probe solution respectively3+Ion measures the variation of its fluorescence spectrum
Situation (as shown in Figure 3).As seen from Figure 3, with Fe3+Ion concentration is continuously increased, and the intensity of the emission peak at 480nm is not
It is disconnected to reduce, work as Fe3+When ion concentration increases to 50 times of fluorescence probe concentration or so, fluorescence is almost quenched.
Test phenanthro- imidazoles Fe manufactured in the present embodiment3+Probe detects Fe under different ph values3+The case where ion,
The specific method is as follows：Main body stock solution, which is diluted to concentration with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4, is
20 μm of ol/L, obtain probe solution；The Fe for 200 μm of ol/L of probe solution and addition that measurement concentration is 20 μm of ol/L respectively3+From
Fluorescence spectrum after son under the conditions of different pH value (between 2~12), as a result as shown in Figure 4.As can be seen from Figure 4, when pH value changes,
The fluorescence intensity of fluorescence probe is substantially without significant change；Fe is added3+Afterwards, fluorescent quenching degree substantially remains in fluorescence probe fluorescence
0.28 times of intensity, the i.e. variation of pH value do not influence fluorescence probe detection Fe3+Ion.This illustrates that the utilization fourth in the present embodiment reaches
That phenomenon or fluorescence spectrum detect Fe3+The phenanthro- imidazoles fluorescence probe of ion has stable fluorescence in extensive pH value range
Intensity is not influenced by pH value variation.
Test phenanthro- imidazoles Fe manufactured in the present embodiment3+The response time of probe, the specific test method is as follows：Main body is stored up
It is 20 μm of ol/L that standby liquid, which is diluted to concentration with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4, and it is molten to obtain probe
Liquid；The Fe of 200 μm of ol/L is added into fluorescence probe solution3+After ion, the fluorescence spectrum variation in 0~300s, knot are measured
Fruit is as shown in Figure 5.From fig. 5, it is seen that Fe is added3+After ion 30s, fluorescence intensity, which has been reduced to, is added Fe3+Ion
Preceding 0.28 times；Primary every 30s test later, fluorescence intensity is held in reduced levels.Illustrate the fluorescence probe to reality
Now to Fe3+The quick detection of ion has good instantaneity.
Three, the test of Tyndall phenomenon
Phenanthro- imidazoles Fe manufactured in the present embodiment is utilized by Tyndall phenomenon3+Probe is used for quickly detecting Fe3+, specifically
Method is as follows：It is respectively 20 μm of ol/L's to concentration in MeOH/HEPES buffer solution (v/v=2/8, pH=7.4) system
The Fe of 0.6mmol/L, 1mmol/L are added in probe solution3+Solion after 1min, uses wavelength 650nm, power 50mW
Red laser pen be light source, close to probe solution and contain Fe3+The glass container side wall of the probe solution of ion, from perpendicular to light
Observe phenomenon in the direction in source.Phenomenon is as follows：When laser pen passes through probe solution, occurs one red bright " access "；Laser pen
By Fe containing 0.6mmol/L3+When ion, red " access " shoals；Laser pen passes through Fe containing 1mmol/L3+It is red when ion
" access " disappears.These phenomenons illustrate, form in probe MeOH/HEPES buffer solution (v/v=2/8, pH=7.4) system
Colloidal solution shows Tyndall phenomenon when light source passes through colloidal solution；Fe3+The addition of ion destroys the colloid ring of system
Border, Tyndall phenomenon weakens or disappears, to realize to Fe3+The open hole detection of ion.This method is easy to operate, and phenomenon is bright
It is aobvious, quickly and effectively, there is good instantaneity in actually detected application, and use cost is lower.
Embodiment 2：The phenanthro- imidazoles Fe of the present embodiment3+The preparation method of probe carries out according to the following steps：
One, respectively by phenanthrenequione 1.04g (5.0mmol), salicylide 0.52mL (5.0mmol), ammonium acetate 0.39g
(5.0mmol), aniline 1.37mL (15.0mmol) is added to 50mL and has in the there-necked flask of condensing unit, and is added thereto
The formic acid of 25mL is warming up to boiling reflux as solvent, is stirred continuously, during the reaction, with TLC tracing detection (solvent
For ethyl acetate and petroleum ether, V (ethyl acetate)：V (petroleum ether)=3:7) after, reaction carries out 10h, fully reacting stops anti-
It answers, is cooled to room temperature；
Two, 50mL water is added in there-necked flask, is placed in the beaker of 200mL, with 5% Na2CO3Aqueous solution is by pH value
6.5 are adjusted to, there is solid precipitation；It filtering, filter cake is washed with water, and collects filter cake, and it is dry, obtain crude product；
It three, is 1 with the volume ratio of ethyl acetate and petroleum ether：3 mixed solvent recrystallizes crude product, obtains phenanthro- miaow
Azoles Fe3+Probe.The yield of the probe is 75%.Fusing point：168~171 DEG C.
Embodiment 3：The phenanthro- imidazoles Fe of the present embodiment3+The preparation method of probe carries out according to the following steps：
One, respectively by phenanthrenequione 1.04g (5.0mmol), salicylide 0.52mL (5.0mmol), ammonium acetate 0.39g
(5.0mmol), aniline 0.92mL (10.0mmol) is added to 50mL and has in the there-necked flask of condensing unit, and is added thereto
The p-methyl benzenesulfonic acid of 25mL is warming up to boiling reflux as solvent, is stirred continuously, during the reaction, with TLC tracing detection,
It is 3 that wherein solvent, which is the volume ratio of ethyl acetate and petroleum ether,:7 mixed liquor, after reaction carries out 9h, fully reacting stops
Reaction, is cooled to room temperature；
Two, 50mL water is added in there-necked flask, is placed in the beaker of 200mL, with 3% K2CO3Aqueous solution is by pH value tune
Section has solid precipitation to 6.5；It filtering, filter cake is washed with water, and collects filter cake, and it is dry, obtain crude product；
It three, is 1 with the volume ratio of ethyl acetate and n-hexane：5 mixed solvent recrystallizes crude product, obtains phenanthro- miaow
Azoles Fe3+Probe.The yield of the probe is 60%.Fusing point：168~171 DEG C.
Embodiment 4：The phenanthro- imidazoles Fe of the present embodiment3+The preparation method of probe carries out according to the following steps：
One, respectively by phenanthrenequione 1.04g (5.0mmol), salicylide 0.52mL (5.0mmol), ammonium acetate 0.39g
(5.0mmol), aniline 0.83mL (9.0mmol) is added to 50mL and has in the there-necked flask of condensing unit, and is added thereto
The trifluoroacetic acid of 25mL is warming up to boiling reflux as solvent, is stirred continuously, during the reaction, with TLC tracing detection,
Middle solvent is that the volume ratio of ethyl acetate and petroleum ether is 3:7 mixed liquor, after reaction carries out 10h, fully reacting stops anti-
It answers, is cooled to room temperature；
Two, 50mL water is added in there-necked flask, is placed in the beaker of 200mL, with 3% NaOH aqueous solution by pH value tune
Section has solid precipitation to 6.5；It filtering, filter cake is washed with water, and collects filter cake, and it is dry, obtain crude product；
It three, is 1 with the volume ratio of ethyl acetate and methylene chloride：4 mixed solvent mixed solvent recrystallizes crude product,
Obtain phenanthro- imidazoles Fe3+Probe.The yield of the probe is 70%.Fusing point：168~171 DEG C.
Embodiment 5：The phenanthro- imidazoles Fe of the present embodiment3+The preparation method of probe carries out according to the following steps：
One, respectively by phenanthrenequione 1.04g (5.0mmol), salicylide 0.52mL (5.0mmol), ammonium acetate 0.39g
(5.0mmol), aniline 1.10mL (12.0mmol) is added to 50mL and has in the there-necked flask of condensing unit, and is added thereto
The benzene sulfonic acid of 25mL is warming up to boiling reflux as solvent, is stirred continuously, during the reaction, with TLC tracing detection, wherein
Solvent is that the volume ratio of ethyl acetate and petroleum ether is 3:7 mixed liquor, after reaction carries out 10h, fully reacting stops anti-
It answers, is cooled to room temperature；
Two, 50mL water is added in there-necked flask, is placed in the beaker of 200mL, with 3% KOH aqueous solution by pH value tune
Section has solid precipitation to 6.5；It filtering, filter cake is washed with water, and collects filter cake, and it is dry, obtain crude product；
It three, is 1 with the volume ratio of ethyl acetate and petroleum ether：5 mixed solvent recrystallizes crude product, obtains phenanthro- miaow
Azoles Fe3+Probe.The yield of the probe is 76%.Fusing point：168~171 DEG C.
Claims (10)
1. a kind of phenanthro- imidazoles Fe3+Probe, it is characterised in that the structural formula of the probe is：
2. a kind of phenanthro- imidazoles Fe3+The preparation method of probe, it is characterised in that this method carries out according to the following steps：
It one, is in molar ratio 1 by phenanthrenequione, salicylide, ammonium acetate, aniline:1:1:(1~3) is put into the anti-of condensing unit
It answers in device, acidic organic solvent is added, stir and be warming up to boiling reflux, react 9~12h, be cooled to room temperature；
Two, pH value is adjusted to 6~7 using alkaline aqueous solution, there is solid precipitation；It filtering, filter cake is washed with water, filter cake is collected,
It is dry, obtain crude product；
Three, crude product is recrystallized with organic solvent, obtains phenanthro- imidazoles Fe3+Probe.
3. a kind of phenanthro- imidazoles Fe according to claim 23+The preparation method of probe, it is characterised in that described in step 1
Acidic organic solvent be formic acid, glacial acetic acid, trifluoroacetic acid, benzene sulfonic acid or p-methyl benzenesulfonic acid.
4. a kind of phenanthro- imidazoles Fe according to claim 2 or 33+The preparation method of probe, it is characterised in that in step 2
Adjusting pH value uses alkaline aqueous solution for 3% NaOH aqueous solution, 5% Na2CO3Aqueous solution, 5% NaHCO3Aqueous solution,
3% KOH aqueous solution or 3% K2CO3Aqueous solution.
5. a kind of phenanthro- imidazoles Fe according to claim 2 or 33+The preparation method of probe, it is characterised in that in step 3
The organic solvent of recrystallization is ethyl acetate and petroleum ether is 1 by volume：Mixed liquor, ethyl acetate and the n-hexane of (1~5)
It is by volume 1：The mixed liquor of (1~5) either ethyl acetate and methylene chloride are 1 by volume：The mixed liquor of (1~5).
6. utilizing a kind of phenanthro- imidazoles Fe described in claim 13+Probe in detecting Fe3+The method of ion, it is characterised in that the party
Method carries out according to the following steps：
One, by phenanthro- imidazoles Fe3+Probe is configured to main body stock solution by solvent of methanol, wherein phenanthro- imidazoles Fe3+Probe it is dense
Degree is 100~300 μm of ol/L；
Two, main body stock solution is diluted to phenanthro- imidazoles Fe with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 again3 +The concentration of probe is 10~30 μm of ol/L, obtains probe solution A1；
Three, part probe solution A is taken1Sample to be tested is added thereto, is uniformly mixed, obtains test sample solution A2；
Four, use red laser pen for light source, the light for issuing red laser pen penetrates probe solution A respectively1And test sample
Solution A2, from the direction perpendicular to light, if in probe solution A1Middle " access " for a red light occur, and
Test sample solution A2Middle nothing " access " or " access " are compared with probe solution A1" access " it is of light color, then can determine that test specimens
Contain Fe in product solution3+Ion.
7. according to claim 6 utilize a kind of phenanthro- imidazoles Fe described in claim 13+Probe in detecting Fe3+Ion
Method, it is characterised in that the preparation method of HEPES buffer solution is：It is put with n-2-Hydroxyethylpiperazine-N'-2-ethanesulfonic acid 0.60g
Enter in the volumetric flask of 250mL, with distilled water constant volume, be made into the solution of 0.01mol/L, shake up, after static 3 hours, uses hydrogen-oxygen
Change sodium solution tune pH value, be made into the buffer solution that pH value is 7.4~12, with nitric acid solution tune pH value, being made into pH value is 3~6
Buffer solution.
8. according to claim 6 utilize a kind of phenanthro- imidazoles Fe described in claim 13+Probe in detecting Fe3+Ion
Method, it is characterised in that 650~660nm of wavelength of red laser pen, power are 5~50mW in step 4.
9. utilizing a kind of phenanthro- imidazoles Fe described in claim 13+Probe in detecting Fe3+The method of ion, it is characterised in that the party
Method carries out according to the following steps：
One, by phenanthro- imidazoles Fe3+Probe is configured to main body stock solution by solvent of methanol, wherein phenanthro- imidazoles Fe3+Probe it is dense
Degree is 100~300 μm of ol/L；
Two, main body stock solution is diluted to phenanthro- imidazoles Fe with the HEPES buffer solution that concentration is 0.01mol/L, pH=7.4 again3 +The concentration of probe is 10~30 μm of ol/L, obtains probe solution A1；
Three, part probe solution A is taken1Sample to be tested is added thereto, is uniformly mixed, obtains test sample solution A2；
Four, using 329nm as excitation wavelength, probe solution A is tested using Fluorescence Spectrometer1Fluorescence emission spectrum in 480nm,
Fluorescent emission intensity is denoted as I1；
Five, using 329nm as excitation wavelength, using Fluorescence Spectrometer test sample solution A2Fluorescence emission spectrum in 480nm,
Fluorescent emission intensity is I2；
If six, I2≤0.81I1, then determine to contain Fe in sample to be tested3+Ion.
10. according to claim 9 utilize a kind of phenanthro- imidazoles Fe described in claim 13+Probe in detecting Fe3+Ion
Method, it is characterised in that the preparation method of HEPES buffer solution is：It is put with n-2-Hydroxyethylpiperazine-N'-2-ethanesulfonic acid 0.60g
Enter in the volumetric flask of 250mL, with distilled water constant volume, be made into the solution of 0.01mol/L, shake up, after static 3 hours, uses hydrogen-oxygen
Change sodium solution tune pH value, be made into the buffer solution that pH value is 7.4~12, with nitric acid solution tune pH value, being made into pH value is 3~6
Buffer solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810619502.0A CN108863945A (en) | 2018-06-12 | 2018-06-12 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810619502.0A CN108863945A (en) | 2018-06-12 | 2018-06-12 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108863945A true CN108863945A (en) | 2018-11-23 |
Family
ID=64339153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810619502.0A Pending CN108863945A (en) | 2018-06-12 | 2018-06-12 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108863945A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111795960A (en) * | 2020-08-10 | 2020-10-20 | 齐齐哈尔大学 | Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof |
Citations (3)
| 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 |
| 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 |
-
2018
- 2018-06-12 CN CN201810619502.0A patent/CN108863945A/en active Pending
Patent Citations (3)
| 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 |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| MANOJ KUMAR NAYAK ET AL.: "Synthesis, characterization and optical properties of aryl and diaryl substituted phenanthroimidazoles", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 * |
| 刘芳妹: "《药物化学实验》", 31 July 2001, 中国医药科技出版社 * |
| 张开诚 等: "《化学实验教程》", 28 February 2014, 华中科技大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111795960A (en) * | 2020-08-10 | 2020-10-20 | 齐齐哈尔大学 | Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Multi-functional lanthanide-CPs based on tricarboxylphenyl terpyridyl ligand as ratiometric luminescent thermometer and highly sensitive ion sensor with turn on/off effect | |
| CN106117230B (en) | Replace rhodamine B amide groups Thiourea fluorescent probe compounds and its preparation method and application | |
| CN106632064B (en) | Reversible dihydroxy phenanthroimidazole Hg2+Fluorescent probe synthesis and methods of use | |
| Zuo et al. | A novel fluorescent sensor based on triphenylamine with AIE properties for the highly sensitive detection of CN− | |
| CN103113380B (en) | Rhodamine derivative and preparation method and application thereof | |
| CN111116459B (en) | Tetraphenyl vinyl cation fluorescent probe and preparation method and application thereof | |
| CN107382905B (en) | Probe for detecting multiple ions and application thereof | |
| CN103940764A (en) | Application of 1,8-naphthalimide derivative as multiple-ion spectrum probe | |
| Rani et al. | Pyrene–antipyrine based highly selective and sensitive turn-on fluorescent sensor for Th (IV) | |
| CN106518749A (en) | Rate type difunctional fluorescence molecular probe for detecting HSO4- ions, SO2 and derivatives thereof | |
| Wang et al. | Highly Sensitive and Selective Fluorescent Probe for Detection of Fe 3+ Based on Rhodamine Fluorophore | |
| CN107629008A (en) | A kind of phenanthro- imidazoles small molecule Fe3+Fluorescence probe and its synthetic method | |
| Yuan et al. | An acidic pH fluorescent probe based on Tröger's base | |
| CN109912555A (en) | A kind of aluminium ion fluorescence probe and preparation method thereof | |
| CN108863945A (en) | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application | |
| Tian et al. | A novel carbonothioate-based benzothiazole fluorescent probe for trace detection of mercury (II) in real water samples | |
| CN110172070B (en) | Fluorescent probe for detecting viscosity and hydrogen peroxide as well as synthesis method and application thereof | |
| CN108640867B (en) | Fluorescent probe compound containing cyano-carbazolyl Schiff base as well as preparation method and application thereof | |
| CN108276371B (en) | Coumarin thiocarbazone derivative and preparation method and application thereof | |
| CN107344947B (en) | A kind of iron ion fluorescent probe molecule and its preparation method and application | |
| CN103012375B (en) | Pyridyl triazole methyl substituted acridine derivative, preparation method and application thereof | |
| Zhu et al. | A facile and highly selective “turn-on” fluorescent chemodosimeter for Hg2+ and its AIE activity | |
| CN108558859A (en) | A kind of preparation and application of the long wave mode Hg2+ fluorescence probes of visualization based on chromene | |
| CN108191760B (en) | Fluorescent probe for detecting Cu (II) and preparation method and application thereof | |
| CN110818702B (en) | Pyridine-coumarin derivative fluorescent probe and preparation method and application thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181123 |
|
| WD01 | Invention patent application deemed withdrawn after publication |