CN107098852A - The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application - Google Patents
The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application Download PDFInfo
- Publication number
- CN107098852A CN107098852A CN201710471033.8A CN201710471033A CN107098852A CN 107098852 A CN107098852 A CN 107098852A CN 201710471033 A CN201710471033 A CN 201710471033A CN 107098852 A CN107098852 A CN 107098852A
- Authority
- CN
- China
- Prior art keywords
- picolines
- amine
- fluorescence probe
- modified
- derivatives
- 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*(C)CNS(C(CC1)C(C**)C2*1C(C1)*1*(C)C2C(C)C*(C)=*C)(=O)=O Chemical compound CC*(C)CNS(C(CC1)C(C**)C2*1C(C1)*1*(C)C2C(C)C*(C)=*C)(=O)=O 0.000 description 3
- UPYSGFWVMLQLGJ-UHFFFAOYSA-N CCCOCCOCCN Chemical compound CCCOCCOCCN UPYSGFWVMLQLGJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- 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
- C09K2211/1003—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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application, the structural formula of fluorescence probe isN=2,3 or 4 in formula.The fluorescence probe is connected fluorescent reporter group pyrene and metal ion acceptor by being flexibly connected arm, and regulating and controlling effect and the combination of acceptor using lauryl sodium sulfate assembly, is realized to 13 metal ion species Cu2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+Differentiation detection.Fluorescence probe of the present invention has the advantages that good chemical stability, fast response time, sensitivity is high, distinction is good, sample consumption is small, data acquisition is simple, can immediately, on-line determination metal ion.
Description
Technical field
The invention belongs to metal ion detection technical field, and in particular to a kind of that the two of metal ion is determined in aqueous phase
(2- picolines) amine-modified pyrene derivatives fluorescence probe and its synthetic method.
Background technology
The various aspects that heavy metal ion infiltration is produced and lived in people, its toxicity is higher and is difficult to remove, therefore
The detection of heavy metal ion enjoys people to pay close attention to.Accurately and quickly detect and differentiate the heavy metal ion in environment, for
Food security, Improvement of Ecological Environment and human health suffer from extremely important meaning.But traditional " lock-spoon " type high selection
Property sensor use can not meet the detection demand to complex sample, therefore be badly in need of development complex sample can be carried out it is effective
The high flux detection means of analysis.
Sensor array is grown up based on recognizing animal olfactory system operation principle, has interaction by multiple
Each sensing unit in the sensing unit composition of response, array has different degrees of response to different analytes, and
Each sensing unit also has different degrees of response to same analyte, therefore the feature that can be formed for specific analyte refers to
Line collection of illustrative plates, realizes the Division identification to multiple analyte.Using the larger sensing unit of number come real more than traditional sensor array
Existing interaction response, although with preferable finger-print recognition capability, but frequently result in that sample consumption is big, data acquisition process
The problems such as process is cumbersome.Therefore, people have developed the single fluorescence sense system based on multi-wavelength interaction response, same to have finger
Line spectrum recognition ability, greatly reduces the consumption of sample, and can just be realized to same analyte by single pass
Data acquisition, simplify data acquisition, be increasingly becoming new study hotspot.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of auxiliary in lauryl sodium sulfate (SDS) aggregation
Have the advantages that two (2- picolines) amine that distinction is good, test scope is wide, sample consumption is small, data acquisition is simple are repaiied down
The pyrene derivatives fluorescence probe of decorations, and provide a kind of synthetic method and application for the fluorescence probe.
Solve the structure of the amine-modified pyrene derivatives fluorescence probe of two (the 2- picolines) that are used of above-mentioned technical problem
Formula is as follows：
N=2,3 or 4 in formula.
The preparation method of the amine-modified pyrene derivatives fluorescence probe of above-mentioned two (2- picolines) is made up of following step：
1st, pyrene sulfonyl-derivatives are synthesized
Under inert atmosphere and condition of ice bath, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise to the oxygen-containing alkane of diaminourea
In chloroform soln, after completion of dropping, reaction is stirred at room temperature 2~8 hours, isolates and purifies, obtain the following pyrene sulphur of structural formula
Acyl derivative：
The oxygen-containing alkane of above-mentioned diaminourea be 1,8- diaminourea -3,6- dioxies octane, 3,6,9- trioxaundecane -1,
11- diamines or the oxa- hexadecane -1,16- diamines of 3,6,9,12- tetra-.
2nd, two (2- picolines) amine derivatives are synthesized
Under nitrogen protection, 2- chloromethyl pyridine hydrochlorides are dissolved in ultra-pure water, sequentially add aniline, hydroxide
Sodium, hexadecyltrimethylammonium chloride, are stirred at room temperature 24 hours, isolate and purify, and obtain two (2- picolines) aniline；Then exist
Under condition of ice bath, the dimethyl formamide solution of two (2- picolines) aniline is added dropwise into the dimethylformamide of POCl3
In, in 90 DEG C of heating responses 3 hours after dripping, reaction solution is poured into water after having reacted, K is then used2CO3It is neutralized to pH value
For 6~8, isolate and purify, obtain two following (2- picolines) amine derivatives of structural formula：
3rd, the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) of synthesis
It is 2 that pyrene sulfonyl-derivatives, two (2- picolines) amine derivatives are added into dichloromethane and methanol volume ratio:
In 1 mixed liquor, anhydrous sodium sulfate is added, is stirred at room temperature 12 hours, is filtered out sodium sulphate, solvent is spin-dried for, obtain grease；
At 0 DEG C, the grease is dissolved in methanol, and adds sodium borohydride, is stirred at room temperature 45 minutes, uses saturation NaHCO3The aqueous solution
Quenching reaction, isolates and purifies, obtains the amine-modified pyrene derivatives fluorescence probe of two (2- picolines).
In above-mentioned steps 1, the mol ratio of preferably pyrene sulfonic acid chloride and the oxygen-containing alkane of diaminourea is 1:(8~12).
In above-mentioned steps 2, preferably aniline and 2- chloromethyl pyridine hydrochlorides, sodium hydroxide, cetyl trimethyl chlorination
The mol ratio of ammonium is 1:(1.5~3):(2~3):Mole of (0.02~0.1), two (2- picolines) aniline and POCl3
Than for 1:(7~8).
In above-mentioned steps 3, preferably two (2- picolines) amine derivatives and pyrene sulfonyl-derivatives, anhydrous sodium sulfate, boron
The mol ratio of sodium hydride is 1:(1.1~1.5):(1~1.3):(0.3~0.8).
Application of the fluorescence probe of the present invention in detection metal ion is distinguished, described metal ion is Cu2+、Co2+、Ni2 +、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+, specific detection method is as follows：
1st, solution is prepared
By the methanol solution and 5mmol/L of pyrene derivatives fluorescence probe amine-modified 2.5mmol/L bis- (2- picolines)
The second distillation aqueous solution of lauryl sodium sulfate is well mixed, and (2- picolines) amine-modified pyrene two in mixed solution is spread out
The concentration of biological fluorescent labeling is 10 μm of ol/L, and fluorescence probe sensor is used as using the mixed solution.
2nd, criteria classification collection of illustrative plates is drawn
The known metal ion of various concentrations is added into fluorescence probe sensor, fluorescence intensity is measured with luminoscope, and
According to the log (I/I under different emission0) value with principle component analysis data processing method draw metal ion criteria classification
Collection of illustrative plates.
3rd, testing sample is detected
Method according to above-mentioned steps 2 measures the fluorescence intensity added after metal ion sample to be measured with luminoscope, calculates
log(I/I0) value, according to principle component analysis data processing method processing data, combined standard classification collection of illustrative plates can determine Cu2+、
Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+Species.
Compared with prior art, the present invention has following beneficial technique effect：
1st, the present invention introduces energy and metal using the chain molecule containing oligomerization ethyoxyl and secondary amine as hydrophily linking arm
Acceptor groups two (2- picolines) amine of ion specific binding, is prepared for the amine-modified pyrene derivatives of two (2- picolines)
Fluorescence probe, the fluorescence probe is using high, abundant to microenvironment sensitivity, the fluorescence output signal pyrene of fluorescence quantum yield as report base
Group, the characteristics of launching with monomer and excimer multi-fluorescence is expected to assign the identification of aggregation system multi-wavelength interaction response
Performance, possibility is provided for the new supermolecule fluorescence sense system of establishment.
2nd, it is of the invention by two (2- picolines) amine-modified pyrene derivatives fluorescence probe and anionic surfactant
Lauryl sodium sulfate is assembled, and is prepared for supermolecule fluorescent optical sensor, and the chemical stability of the fluorescent optical sensor is good, bio-compatible
Property it is good and good with multi-wavelength interaction response, fast response time, distinction, single sensing system can be achieved to 13 kinds of metals
Ion Cu2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+Division identification.
3rd, fluorescence probe synthetic method of the present invention is simple to operate, low for equipment requirements, is adapted to instrumentation.
Brief description of the drawings
Fig. 1 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Cu2+Solution
Fluorescence intensity change curve map.
Fig. 2 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Co2+Solution
Fluorescence intensity change curve map.
Fig. 3 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Ni2+Solution
Fluorescence intensity change curve map.
Fig. 4 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Cr3+Solution
Fluorescence intensity change curve map.
Fig. 5 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Hg2+Solution
Fluorescence intensity change curve map.
Fig. 6 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Fe3+Solution
Fluorescence intensity change curve map.
Fig. 7 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Zn2+Solution
Fluorescence intensity change curve map.
Fig. 8 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Cd2+Solution
Fluorescence intensity change curve map.
Fig. 9 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Al3+Solution
Fluorescence intensity change curve map.
Figure 10 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Pb2+Solution
Fluorescence intensity change curve map.
Figure 11 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Ca2+Solution
Fluorescence intensity change curve map.
Figure 12 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Mg2+Solution
Fluorescence intensity change curve map.
Figure 13 be embodiment 1 prepare two (2- picolines) it is amine-modified pyrene derivatives fluorescence probe detection Ba2+Solution
Fluorescence intensity change curve map.
Figure 14 is the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) for preparing of embodiment 1 at different wave length
(379,399,460,501nm) to the change in fluorescence log (I/I of 13 metal ion species (concentration be 10 μm ol/L)0) value column
Figure.
Figure 15 is the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) for preparing of embodiment 1 at different wave length
(379,399,460,501nm) to the change in fluorescence log (I/I of 13 metal ion species (concentration be 50 μm ol/L)0) value column
Figure.
Figure 16 is the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) for preparing of embodiment 1 at different wave length
(379,399,460,501nm) to the change in fluorescence log (I/I of 13 metal ion species (concentration be 100 μm ol/L)0) value column
Figure.
Figure 17 is the log (I/I in Figure 140) the criteria classification figure drawn according to principle component analysis data processing method of data
Spectrum.
Figure 18 is the log (I/I in Figure 150) the criteria classification figure drawn according to principle component analysis data processing method of data
Spectrum.
Figure 19 is the log (I/I in Figure 160) the criteria classification figure drawn according to principle component analysis data processing method of data
Spectrum.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1st, pyrene sulfonyl-derivatives are synthesized
Under nitrogen protection and ice bath stirring condition of the flow velocity for 0.6mL/s, to three mouthfuls of burnings for filling 60mL chloroforms
1.48g (9.97mmol) 1,8- diaminourea -3,6- dioxy octanes are added in bottle, then by 0.3g (0.997mmol) pyrene sulfonic acid chloride
It is dissolved in after 50mL chloroforms and is added drop-wise to the speed of 6s/ drops in three-necked flask, drips rear room temperature stirring reaction 2 hours, will
Reaction solution is washed 5~8 times with saturated common salt, is then stayed overnight with anhydrous sodium sulfate drying, then is washed with 1mol/L hydrochloric acid, so
Neutralized afterwards with 3mol/L sodium hydrate aqueous solutions, make solution ph be 7 after use chloroform extraction, collected organic layer, rotation
It is dry, pyrene sulfonyl-derivatives (Py-EOA) are obtained, its reaction equation is as follows：
2nd, two (2- picolines) amine derivatives are synthesized
Under nitrogen protection, 1.524g (12mmol) 2- chloromethyl pyridine hydrochlorides are dissolved in 2.5mL ultra-pure waters, then added
Enter 0.558g (6mmol) aniline, 3mL5mol/L sodium hydrate aqueous solutions, 20mg (0.15mmol) cetyl trimethyl chlorination
Ammonium, is stirred at room temperature 24 hours, is extracted with dichloromethane, uses anhydrous sodium sulfate drying after extract washing, removes dichloromethane, obtain
To crude product, crude product dichloromethane is 4 by volume with ethyl acetate:1 mixed solvent is pure as eluant, eluent column chromatography
Change, gained beige solid is sterling two (2- picolines) aniline (BPA).
1mL (17mmol) POCl3 is added dropwise in 2mL dimethylformamides and cooled down in ice bath, then will
The solution is stirred 0.5 hour.0.600g (2.18mmol) two (2- picolines) aniline is dissolved in 1mL dimethylformamides
It is placed in separatory funnel, is added dropwise in the dimethylformamide of POCl3, it is small in 90 DEG C of heating responses 3 after dripping
When, reaction solution is poured into 5mL water after having reacted, K is used2CO3It is neutralized to pH value to be 6~8 and stir, is then extracted with dichloromethane
Take, with anhydrous sodium sulfate drying, remove organic solvent, obtain crude product；Crude product acetone, n-hexane are 1 by volume:1
Mixed solvent as eluant, eluent column chromatography purify, obtain the amine-modified pyrene derivatives (BPAB) of two (2- picolines), its is anti-
Answer equation as follows：
3rd, the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) of synthesis
Pyrene derivatives amine-modified 0.31g (1mmol) two (2- picolines), 0.45g (1.1mmol) pyrene sulfonyl are spread out
It is 2 that biology, which is added to 2mL dichloromethane with methanol volume ratio,:In 1 mixed liquor, 0.14g (1mmol) anhydrous slufuric acid is added
Sodium, is stirred at room temperature 12 hours, filters out sodium sulphate, solvent is spin-dried for, obtain grease.At 0 DEG C, the grease is added to
In 50mL methanol, and 0.02g (0.5mmol) sodium borohydride is added, be stirred at room temperature 45 minutes, by reaction saturation NaHCO3
The aqueous solution is quenched, and methanol is removed under reduced pressure, residue is dissolved in water.By aqueous phase with dichloromethane extract 3 times, merging it is organic
Salt water washing mutually is used, then with anhydrous sodium sulfate drying, after filtering, solvent is removed in vacuum, crude product is obtained, then use dichloromethane
It is 8 by volume with methanol:1 mixed solvent is purified as eluant, eluent column chromatography, obtains two (2- picolines) amine-modified
Pyrene derivatives fluorescence probe (PB), its yield is 86%, and reaction equation is as follows：
The nuclear magnetic data of the amine-modified pyrene derivatives fluorescence probe of above-mentioned two (2- picolines) is：1H NMR(400MHz,
CDCl3,ppm):δ9.04(s,1H),8.66(s,1H),8.56(s,2H),8.18(m,7H),7.58(s,2H),7.20(m,
6H),6.67(s,2H),4.77(s,4H),3.95(s,2H),3.67(s,2H),3.45(s,6H),3.08(s,2H),2.89(s,
2H)。
Embodiment 2
The amine-modified pyrene derivatives fluorescence probe of two following (2- picolines) of composite structure formula：
In the synthesis pyrene sulfonyl-derivatives step 1 of embodiment 1, by 1,8- diaminourea -3,6- dioxy octanes used
Replaced with the 3 of equimolar amounts, 6,9- trioxaundecane -1,11- diamines, other steps are same as Example 1, obtain two (2-
Picoline) amine-modified pyrene derivatives fluorescence probe.
Embodiment 3
The amine-modified pyrene derivatives fluorescence probe of two following (2- picolines) of composite structure formula：
In the synthesis pyrene sulfonyl-derivatives step 1 of embodiment 1, by 1,8- diaminourea -3,6- dioxy octanes used
Replaced with the 3 of equimolar amounts, 6,9,12- tetra- oxa- hexadecane -1,16- diamines, other steps are same as Example 1, obtain two
(2- picolines) amine-modified pyrene derivatives fluorescence probe.
Embodiment 4
The pyrene derivatives fluorescence probe that two (2- picolines) of embodiment 1 are amine-modified is distinguishing detection Cu2+、Co2+、Ni2 +、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+In purposes, detection method is as follows：
1st, solution is prepared
By the methanol solution and 5mmol/L of pyrene derivatives fluorescence probe amine-modified 2.5mmol/L bis- (2- picolines)
The second distillation aqueous solution of lauryl sodium sulfate is well mixed, and (2- picolines) amine-modified pyrene two in mixed solution is spread out
The concentration of biological fluorescent labeling is 10 μm of ol/L, regard the mixed solution as fluorescence probe sensor.
2nd, criteria classification collection of illustrative plates is drawn
2.5mL fluorescence probe sensors are taken respectively in cuvette, using single photon fluorescence spectrometer (FS5,
Edinburgh its fluorescence intensity I) is measured0, light source is 150W xenon lamp, and the excitation wavelength of sample is 351nm, excites and sends out
It is respectively 5.5 and 1.3nm to penetrate slit.It is added dropwise 2.5 × 10 respectively thereto-3Mol/L Cu (NO3)2、Co(NO3)2、Ni(NO3)2、
Cr(NO3)2、HgCl2、Fe(NO3)3、Zn(NO3)2、Cd(NO3)2、Al(NO3)3、Pb(NO3)2、Ca(NO3)2、Mg(NO3)2、Ba
(NO3)2The aqueous solution, with capillary stirring make its be well mixed, make metal ion in resulting solution concentration be 0~200 μ
Mol/L, using the fluorescence intensity I of single photon fluorescence spectrometer measurement solution.After solution reaches balance, fluorescence is drawn respectively strong
Degree is with Cu2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The fluorescence spectrum of change in concentration
Figure, is as a result shown in Fig. 1~13, and by gathering two monomer peaks of the amine-modified pyrene derivatives fluorescence probe of two (2- picolines)
379nm and 399nm, distorts the fluorescence at the emission peak 460nm of the excimer and emission peak 501nm of perfect excimer
Intensity, calculates log (I/I during different metal ions concentration0) value, draw concentration of metal ions be 10 μm of ol/L, 50 μm of ol/L,
During 100 μm of ol/L, wavelength is respectively 379,399,460, the log (I/I at 501nm0) value typical cylindrical figure, as a result see Figure 14
~16.4 D data is reduced to by two dimension according to principle component analysis data processing method, this 2-D data is plotted as criteria classification
Collection of illustrative plates, is as a result shown in Figure 17~19.
From Figure 14~19, fluorescence probe sensor of the present invention can realize the interaction response to 13 metal ion species, lead to
The fluorescence intensity crossed at collection different wave length, makes log (I/I0) to the block diagram of concentration of metal ions, it is possible to realize to 13
The finger-print identification of metal ion species, is further reduced to two dimension by principle component analysis data processing method by 4 D data,
Contrast standard classification collection of illustrative plates, realizes the Division identification to 13 metal ion species.
3rd, testing sample is detected
Measured according to the method described above with luminoscope in probe and add the fluorescence intensity I after metal ion sample to be measured, calculated
log(I/I0) value, according to principle component analysis data processing method processing data, combined standard classification collection of illustrative plates can determine Cu2+、
Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+Species.
Claims (8)
1. the amine-modified pyrene derivatives fluorescence probe of one kind two (2- picolines), it is characterised in that the structural formula of the fluorescence probe
It is as follows：
N=2,3 or 4 in formula.
2. a kind of preparation method of the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) described in claim 1, its
It is characterised by that it is made up of following step：
(1) pyrene sulfonyl-derivatives are synthesized
Under inert atmosphere and condition of ice bath, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise to the trichlorine of the oxygen-containing alkane of diaminourea
In dichloromethane, after completion of dropping, reaction is stirred at room temperature 2~8 hours, isolates and purifies, obtain the following pyrene sulfonyl of structural formula
Derivative；
The oxygen-containing alkane of above-mentioned diaminourea is 1,8- diaminourea -3,6- dioxies octane, 3,6,9- trioxaundecanes -1,11- two
Amine or the oxa- hexadecane -1,16- diamines of 3,6,9,12- tetra-；
(2) two (2- picolines) amine derivatives are synthesized
Under nitrogen protection, 2- chloromethyl pyridine hydrochlorides are dissolved in ultra-pure water, sequentially add aniline, sodium hydroxide, ten
Six alkyl trimethyl ammonium chlorides, are stirred at room temperature 24 hours, isolate and purify, and obtain two (2- picolines) aniline；Then in ice bath
Under the conditions of, the dimethyl formamide solution of two (2- picolines) aniline is added dropwise into the dimethyl formamide solution of POCl3
In, in 90 DEG C of heating responses 3 hours after dripping, reaction solution is poured into water after having reacted, K is then used2CO3It is neutralized to pH value
For 6~8, isolate and purify, obtain two following (2- picolines) amine derivatives of structural formula：
(3) the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) of synthesis
It is 2 that pyrene sulfonyl-derivatives, two (2- picolines) amine derivatives are added into dichloromethane and methanol volume ratio:1
In mixed liquor, anhydrous sodium sulfate is added, is stirred at room temperature 12 hours, is filtered out sodium sulphate, solvent is spin-dried for, obtain grease；0
At DEG C, the grease is dissolved in methanol, and adds sodium borohydride, is stirred at room temperature 45 minutes, uses saturation NaHCO3The aqueous solution is sudden
Go out reaction, isolate and purify, obtain the amine-modified pyrene derivatives fluorescence probe of two (2- picolines).
3. the synthetic method of the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) according to claim 2, its
It is characterised by：In step (1), the mol ratio of the pyrene sulfonic acid chloride and the oxygen-containing alkane of diaminourea is 1:(8~12).
4. the synthetic method of the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) according to claim 2, its
It is characterised by, in step (2), the aniline and 2- chloromethyl pyridine hydrochlorides, sodium hydroxide, cetyl trimethyl chlorination
The mol ratio of ammonium is 1:(1.5~3):(2~3):(0.02~0.1).
5. the synthetic method of the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) according to claim 2, its
It is characterised by, in step (2), the mol ratio of two (2- picolines) aniline and POCl3 is 1:(7~8).
6. the synthetic method of the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) according to claim 2, its
It is characterised by：In step (3), two (2- picolines) amine derivative and pyrene sulfonyl-derivatives, anhydrous sodium sulfate, boron
The mol ratio of sodium hydride is 1:(1.1~1.5):(1~1.3):(0.3~0.8).
7. the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) described in claim 1 detects metal ion distinguishing
In application, described metal ion is Cu2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+
And Ba2+。
8. the amine-modified pyrene derivatives fluorescence probe of two (2- picolines) according to claim 7 is distinguishing detection metal
Application in ion, it is characterised in that：
(1) solution is prepared
By the methanol solution and 5mmol/L 12 of pyrene derivatives fluorescence probe amine-modified 2.5mmol/L bis- (2- picolines)
The second distillation aqueous solution of sodium alkyl sulfate is well mixed, and makes (2- picolines) amine-modified pyrene derivatives two in mixed solution
The concentration of fluorescence probe is 10 μm of ol/L, and fluorescence probe sensor is used as using the mixed solution；
(2) criteria classification collection of illustrative plates is drawn
Into fluorescence probe sensor add various concentrations known metal ion, with luminoscope measure fluorescence intensity, and according to
Log (I/I under different emission0) value with principle component analysis data processing method draw metal ion criteria classification figure
Spectrum；
(3) testing sample is detected
Method according to above-mentioned steps (2) measures the fluorescence intensity added after metal ion sample to be measured with luminoscope, calculates log
(I/I0) value, according to principle component analysis data processing method processing data, combined standard classification collection of illustrative plates can determine Cu2+、Co2+、
Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+Species.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710471033.8A CN107098852B (en) | 2017-06-20 | 2017-06-20 | Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710471033.8A CN107098852B (en) | 2017-06-20 | 2017-06-20 | Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107098852A true CN107098852A (en) | 2017-08-29 |
| CN107098852B CN107098852B (en) | 2020-04-24 |
Family
ID=59663694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710471033.8A Active CN107098852B (en) | 2017-06-20 | 2017-06-20 | Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107098852B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409719A (en) * | 2018-03-29 | 2018-08-17 | 天津农学院 | It is a kind of to be used to detect the organic compound of metal ion content and application in water environment |
| CN112391159A (en) * | 2020-11-27 | 2021-02-23 | 太原理工大学 | Fluorescent probe for simultaneously detecting aluminum ions and zinc ions, preparation and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101004422A (en) * | 2007-01-16 | 2007-07-25 | 大连理工大学 | Fluorescent probe of fluorin - boron dyestuff in use for detecting cadmium ions inside cell |
| KR20110020455A (en) * | 2009-08-24 | 2011-03-03 | 고려대학교 산학협력단 | Pyrene derivatives having cu(ii) ion selectivity, method for preparing therefor, detecting method using the same |
| CN102190670A (en) * | 2011-03-22 | 2011-09-21 | 中国科学院理化技术研究所 | Fluorescence chemical sensor and preparation method and application thereof |
| CN103275697A (en) * | 2013-05-28 | 2013-09-04 | 陕西师范大学 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
| CN104232077A (en) * | 2014-08-28 | 2014-12-24 | 陕西师范大学 | Monopyrene fluorescent probe based on cholesterol modification, and synthesis method and application thereof |
| CN104804724A (en) * | 2014-01-28 | 2015-07-29 | 中国科学院大连化学物理研究所 | Ratio-type variant receptor mercury ion fluorescent probe and its preparation method and use |
| WO2017081684A1 (en) * | 2015-11-11 | 2017-05-18 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd | Biosensors |
-
2017
- 2017-06-20 CN CN201710471033.8A patent/CN107098852B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101004422A (en) * | 2007-01-16 | 2007-07-25 | 大连理工大学 | Fluorescent probe of fluorin - boron dyestuff in use for detecting cadmium ions inside cell |
| KR20110020455A (en) * | 2009-08-24 | 2011-03-03 | 고려대학교 산학협력단 | Pyrene derivatives having cu(ii) ion selectivity, method for preparing therefor, detecting method using the same |
| CN102190670A (en) * | 2011-03-22 | 2011-09-21 | 中国科学院理化技术研究所 | Fluorescence chemical sensor and preparation method and application thereof |
| CN103275697A (en) * | 2013-05-28 | 2013-09-04 | 陕西师范大学 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
| CN104804724A (en) * | 2014-01-28 | 2015-07-29 | 中国科学院大连化学物理研究所 | Ratio-type variant receptor mercury ion fluorescent probe and its preparation method and use |
| CN104232077A (en) * | 2014-08-28 | 2014-12-24 | 陕西师范大学 | Monopyrene fluorescent probe based on cholesterol modification, and synthesis method and application thereof |
| WO2017081684A1 (en) * | 2015-11-11 | 2017-05-18 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd | Biosensors |
Non-Patent Citations (3)
| Title |
|---|
| NAMITA KUMARI等: "A Probe for the Selective and Parts-per-Billion-Level Detection of Copper(II) and Mercury(II) using a Micellar Medium and Its Utility in Cell Imaging", 《CHEMPLUSCHEM》 * |
| NAMITA KUMARI等: "Exclusive Detection of Sub-Nanomolar Levels of Palladium(II) in Water: AnExcellent Probe for Multiple Applications", 《CHEMISTRY-AN ASIAN JOURNAL》 * |
| SHANG WU等: "Ratiometric and selective two-photon fluorescent probe based on PET-ICT for imaging Zn2+ in living cells and tissues", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409719A (en) * | 2018-03-29 | 2018-08-17 | 天津农学院 | It is a kind of to be used to detect the organic compound of metal ion content and application in water environment |
| CN112391159A (en) * | 2020-11-27 | 2021-02-23 | 太原理工大学 | Fluorescent probe for simultaneously detecting aluminum ions and zinc ions, preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107098852B (en) | 2020-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106810511B (en) | PH fluorescence probe and its preparation method and application based on 2- (2 '-hydroxy phenyl) benzothiazole derivant | |
| CN107089945B (en) | A kind of 8-hydroxyquinoline Cu-like ion fluorescence probe with AIE effects and preparation method thereof | |
| CN104017568B (en) | -Application of fluorescent probe containing rhodamine in detecting Hg2+ | |
| CN110964515B (en) | double-Schiff base aluminum ion fluorescent probe, and synthesis method and application thereof | |
| CN112939956B (en) | Fluorescent probe for detecting mercury ions and hypochlorite ions as well as preparation method and application of fluorescent probe | |
| CN104830315A (en) | Bivalent copper ion fluorescent probe and preparation method and application thereof | |
| CN108658838B (en) | Heptamethine indocyanine-based formaldehyde fluorescent probe and preparation method and use method thereof | |
| CN105218570A (en) | A kind of lanthanide series compound and its preparation method and application | |
| CN103387830B (en) | Chromium-ion ratio type fluorescence probe as well as preparation method and application thereof | |
| CN102816086A (en) | Salicylidenehydrazine receptor compound, preparation method and application thereof | |
| CN107434801B (en) | 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application | |
| CN107098852A (en) | The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application | |
| CN105319194B (en) | A kind of method that I and Hg2+ are continuously detected using aggregation-induced emission type fluorescence sense molecule | |
| CN108997401A (en) | A kind of fluorescence probe and preparation method thereof for detecting lead ion | |
| CN108218881B (en) | Mercury ion fluorescent probe based on rhodamine B and preparation method and application thereof | |
| CN105085340B (en) | Diphenylethene group dual cyano benzene two-photon fluorescence probe for detecting and displaying intracellular Hg ion | |
| CN104892504B (en) | One kind can continuously recognize CN‑And Cu2+Sensor molecule and its synthesis and application | |
| CN105968098B (en) | A kind of quinoline substituted containing carbazole, benzimidazole and its preparation method and application | |
| CN107235985A (en) | A kind of fluorescence probe for detecting bivalent cupric ion and preparation method and application | |
| CN103012375B (en) | Pyridyl triazole methyl substituted acridine derivative, preparation method and application thereof | |
| CN103911146B (en) | For detecting Fe 3+and Fe 2+fluorescent small molecule probe and preparation method, using method | |
| CN108219772A (en) | Imidazoles [1,5-a] and pyridine derived species Hg2+Ratio fluorescent probe and its application | |
| CN102621088A (en) | Method for detecting mercury ions (II) based on mercury ion specificity oligonucleotide and nano-gold, and kit | |
| CN109503565A (en) | A kind of cadmium ion detection reagent and its preparation method and application | |
| CN102503875B (en) | Fluorescent probe for detecting copper ions and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |