CN106749093A - One kind is for detecting palladium ion fluorescence probe, preparation method and application - Google Patents
One kind is for detecting palladium ion fluorescence probe, preparation method and application Download PDFInfo
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- CN106749093A CN106749093A CN201611114183.5A CN201611114183A CN106749093A CN 106749093 A CN106749093 A CN 106749093A CN 201611114183 A CN201611114183 A CN 201611114183A CN 106749093 A CN106749093 A CN 106749093A
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- 239000000523 sample Substances 0.000 title claims abstract description 94
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical class NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 150000003053 piperidines Chemical class 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- 229960004011 methenamine Drugs 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002027 dichloromethane extract Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 19
- 229910052763 palladium Inorganic materials 0.000 description 17
- 229910021645 metal ion Inorganic materials 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000007995 HEPES buffer Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 150000002941 palladium compounds Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- ILEIUTCVWLYZOM-UHFFFAOYSA-N 2-hydroxy-5-methylbenzaldehyde Chemical class CC1=CC=C(O)C(C=O)=C1 ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 210000004072 lung Anatomy 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000165940 Houjia Species 0.000 description 1
- 210000004100 adrenal gland Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
-
- 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"
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (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)
Abstract
The invention discloses one kind for detecting palladium ion fluorescence probe, while providing its preparation method and application.The fluorescence probe can quick response and high selectivity detection palladium ion.It is of the invention for detecting palladium ion fluorescence probe, it has the structure as shown in formula 1 or 2：Wherein R is H, CH3Or t Bu.
Description
Technical field
The present invention relates to a kind of fluorescence probe, preparation method and application, more specifically to one kind for detect palladium from
Sub- fluorescence probe, preparation method and application.
Background technology
Palladium reserves on earth are rare, and due to the limitation of digging condition, the yield of palladium seldom, belongs to noble metal, but gather around
Have been widely used, in chemistry, palladium is applied to big quantitative response mainly as catalyst, while palladium is also used for manufacturing dentistry material
Material, wrist-watch and surgery device etc..What the palladium that the mankind contact in life was caused mainly due to automobile tail gas cleaning treatment device,
In device for purifying and treating tail gas, palladium purifies the harmful substance in vehicle exhaust with platinum, rhodium as the active component of catalyst,
But in purification process, make platinum, palladium, rhodium in the form of particulate matter with net due to reasons such as high temperature, chemical reaction, mechanical frictions
Exhaust emissions after change is converted into halide in environment under certain condition, enters biological by empty gas and water and soil
Chain, the health to human body produces potential infringement.Palladium and its compound orally take the photograph people and absorb little, and the palladium compound of suction is main
Lung is stranded in, the palladium after absorption is transported to the organs such as liver,kidney,spleen, adrenal gland, lung, bone quickly, can be with macromolecular in human body
There is Complex effect in material, such as DNA, RNA, vitamin, protein, so as to suppress the normal function of cell.Therefore, quantitative inspection
The content of palladium ion is surveyed to maintaining human normal vital movement to have great significance.
Mainly have currently used for detection palladium ion method：Atomic absorption spectrography (AAS), plasma emlssion spectrometry, inductance coupling
Close ICP-MS, SPME-high performance liquid chromatography and fluorescent spectrometry.But time-consuming for these methods, response
Slowly, complex process, and fluorescent spectrometry can well overcome these shortcomings, so needing to develop high selectivity detection palladium ion
Fluorescence probe.
The content of the invention
The technical problems to be solved by the invention are：Overcome the shortcomings of that prior art is present, there is provided for detecting palladium ion
Fluorescence probe, while providing its preparation method and application.The fluorescence probe can quick response and high selectivity detection palladium ion.
Technology design of the invention is as follows：The alternative of probe 1 and 2 is reacted with palladium ion and produces green and red glimmering
Light.The reaction is not disturbed by other metal ions, can produce fluorescence intensity in the short time, and the fluorescence intensity for producing and palladium from
Sub- concentration linear correlation, the present invention prepares probe 1 and 2 and uses it for the selective enumeration method of palladium ion first first.
The technical scheme that the present invention solves its technical problem is as follows：
It is of the invention for detecting palladium ion fluorescence probe, it has the structure as shown in formula 1 or 2：
Wherein R is H, CH3Or t-Bu.
The preparation method of the above-mentioned fluorescence probe of the present invention, it is comprised the following steps：
2- hydroxyl -5- alkylbenzaldehydes, 2- amino-benzenethiols, sodium pyrosulfite are dissolved in dry DMF, reaction life
Into material 3, material 3 and methenamine are dissolved in trifluoroacetic acid, reaction product matter 4, then by material 4 and propargyl bromide,
Potassium carbonate is dissolved in DMF, and reaction obtains probe 1；Probe 1 and 1,3- indenes diketone, piperidines are added in tetrahydrofuran again, instead
Probe 2 should be obtained.
The above-mentioned preparation method of the present invention, its is anti-when further technical scheme is described reaction product matter 3 for it
It is back flow reaction 3 hours or more at 100 DEG C -120 DEG C to answer condition；Its reaction condition is 90 during described reaction product matter 4
Back flow reaction 6 hours or more at DEG C -100 DEG C；Described reaction obtains its reaction condition of probe 1 to react 15 hours at room temperature
Or more；Described reaction obtains its reaction condition of probe 2 to react 6 hours or more at room temperature.
The above-mentioned preparation method of the present invention, its further technical scheme is to comprise the following steps:
Described reaction product matter 3 its reaction terminate after first distilled water is added in product, refilter, washing simultaneously
Dry cake, products therefrom is material 3；
Described reaction product matter 4 its reaction terminate after hydrochloric acid is added in product, then extracted with dichloromethane
Take, and wash with water, be spin-dried for organic phase, then make eluant, eluent with dichloromethane, on a silica gel column after purifying crude product, the product for obtaining
Thing is material 4；
Described reaction obtains adding water in reactant after probe 1 its reaction terminates, then is extracted with ethyl acetate, then
Dried with anhydrous magnesium sulfate, finally make eluant, eluent with dichloromethane and n-hexane, on a silica gel column after purifying crude product, obtained
Product is probe 1；
Described reaction obtains extracting reactant dichloromethane and water after probe 2 its reaction terminates, organic phase nothing
Water magnesium sulfate is dried, and is spin-dried for, then makees eluant, eluent with dichloromethane and n-hexane, on a silica gel column after purifying crude product, is obtained
Product be probe 2.
The above-mentioned preparation method of the present invention, its further technical scheme can also be described 2- hydroxyl -5- alkyl
The consumption mass ratio of benzaldehyde, 2- amino-benzenethiols and sodium pyrosulfite is 1:1:1-1：1：3；Described material 3 and Wu Luotuo
The consumption mass ratio of product is 1:1-1：3；Described material 4 is 1 with the consumption mass ratio of propargyl bromide, potassium carbonate:1-1：3；It is described
Probe 1 and 1,3- indenes diketone, the consumption mass ratio of piperidines be 3:1-1：3.
The present invention also provides application of the above-mentioned fluorescence probe in palladium ion is detected.
The invention has the advantages that：
1) two kinds of fluorescence probes of the invention are colourless in the solution and unstressed configuration, with palladium ion reaction after show yellow, probe 1
Strong green fluorescence is sent, probe 2 sends strong red fluorescence.
2) using after fluorescence probe of the invention, detection sensitivity is high, and two kinds of probes respectively can to the test limit of palladium ion
Up to 10-7M and 10-8M。
3) only with palladium ion there is fluorescence reaction in fluorescence probe of the present invention, reactionless to other metal ions, with very
Good selectivity and specificity.And, there are Detection results to the palladium ion of other forms.
4) preparation is simple for fluorescence probe of the present invention, it is easy to large-scale production.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention I -1 is obtained the (R=-CH of fluorescence probe 13) sterling1HNMR schemes.
Fig. 2 is that the embodiment of the present invention I -1 is obtained the (R=-CH of fluorescence probe 13) sterling high resolution mass spectrum figure.
Fig. 3 is the (R=-CH of I -2 fluorescence probe of the embodiment of the present invention 13) with each metal ion species react fluorescence emission
Spectrum.
Fig. 4 is the (R=-CH of I -2 fluorescence probe of the embodiment of the present invention 13) ultraviolet-visible absorption spectroscopy.
Fig. 5 is the (R=-CH of I -3 fluorescence probe of the embodiment of the present invention 13) with palladium ion reaction fluorescence increment graph.
Fig. 6 is the (R=-CH of I -3 fluorescence probe of the embodiment of the present invention 13) to the fluorescence intensity working curve of palladium ion concentration.
Fig. 7 is the (R=-CH of I -4 fluorescence probe of the embodiment of the present invention 13) to three kinds of fluorescence intensities of multi-form palladium concentration
Working curve.
Fig. 8 is that the embodiment of the present invention II -1 is obtained the (R=-CH of fluorescence probe 23) sterling1HNMR schemes.
Fig. 9 is that the embodiment of the present invention II -1 is obtained the (R=-CH of fluorescence probe 23) sterling high resolution mass spectrum figure.
Figure 10 is the (R=-CH of II -2 fluorescence probe of the embodiment of the present invention 23) with each metal ion species react fluorescent emission
Spectrum.
Figure 11 is the (R=-CH of II -2 fluorescence probe of the embodiment of the present invention 23) ultraviolet-visible absorption spectroscopy.
Figure 12 is the (R=-CH of II -3 fluorescence probe of the embodiment of the present invention 23) with palladium ion reaction fluorescence increment graph.
Figure 13 is the (R=-CH of II -3 fluorescence probe of the embodiment of the present invention 23) bent to the fluorescence intensity work of palladium ion concentration
Line.
Figure 14 is the (R=-CH of II -4 fluorescence probe of the embodiment of the present invention 23) strong to the fluorescence of three kinds of multi-form palladium concentration
Degree working curve.
Specific embodiment
With reference to the accompanying drawings and in conjunction with the embodiments I, II couple of present invention is described in further detail.But the invention is not restricted to
Given example.
Embodiment I -1 prepares the (R=-CH of probe 1 of release green fluorescence3)
5g 2- hydroxy-5-methyl benzaldehydes, 4.6g 2- aminothiophenols and 6g sodium pyrosulfites are dissolved in 50mL's
In DMF；Flowed back 3 hours at 110 DEG C；After reaction terminates, room temperature is cooled to, adds 50mL distillation water washings, produce precipitation,
Inwardly drying obtains 8.5g white solid matters 3 in vacuum drying for filtering, washing filter cake 5 times, and the solid that will be obtained；Weigh
2.5g gained materials 3, are dissolved in the trifluoroacetic acid of 15mL with 4.5g hexas, are flowed back 6 hours at 100 DEG C；Instead
After should terminating, the HCl 200mL washings of 4mol/L are added, acid solution extracts organic phase with dichloromethane, adds salt washing
Wash, point liquid, organic phase is dried with anhydrous magnesium sulfate, filtering, concentration；With dichloromethane as eluant, eluent, purify on a silica gel column thick
Product, obtains 2g light yellow solids material 4；Then 0.5g materials 4 are dissolved into DMF, and add 0.616g potassium carbonate, room temperature
Lower stirring 20 minutes, adds 0.531g propargyl bromides afterwards, reacts 15 hours at room temperature；After reaction terminates, water is added, use acetic acid second
Ester extracts organic phase, adds salt water washing, and point liquid, organic phase is dried with anhydrous magnesium sulfate, filtering, concentration；With dichloromethane
With n-hexane (2:3, V/V) it is eluant, eluent, purifying crude product, obtains (the R=- of 0.4g white solids probe 1 on a silica gel column
CH3), the as (R=-CH of probe 13) sterling (1HNMR schemes and high resolution mass spectrum figure is shown in Fig. 1, Fig. 2).Gained fluorescence probe sterling reality
It is 307 to survey molecular weight.
The present embodiment process route：
Embodiment I -2 is obtained the spectral quality of palladium ion fluorescence probe and each metal ion species
Weigh 3mg embodiments I -1 and palladium ion fluorescence probe is obtained, be made into the 10mL DMSO solutions that concentration is 1mM, as
Mother liquor.
Fluorescence spectrum is tested：The 30 above-mentioned mother liquors of μ L are added in a certain amount of HEPES buffer solution (pH7.4), Ran Houfen
Each metal ion species are not added：Pd2+, Pb2+, Cr3+, Ag+, Cu2+, Li+, Fe2+, Zn2+, Eu3+, Co3+, Hg2+, Zr4+, Cs2+, K+,
Na+, Cd2+, Fe3+, Mg2+, Ni2+, Mn2+, Al3+, Ca2+One of, make Pd2+Final concentration of 100 μM, other metal ions are final concentration of
200 μM, final concentration of 10 μM of fluorescence probe.5min is reacted under normal temperature, its fluorescence emission is tested under 356nm excitation wavelengths
Spectrum.It is 10nm to excite with the slit width of transmitting：5nm.Acquired results are as shown in Figure 3.
Absorption spectrum is tested：The 30 above-mentioned mother liquors of μ L are added in a certain amount of HEPES buffer solution (pH7.4), Ran Houjia
Enter metal ion Pd2+, make Pd2+Final concentration of 100 μM, final concentration of 10 μM of fluorescence probe.After 5min being reacted under normal temperature, test
Its absorption spectrum.Acquired results are as shown in Figure 4.
Result above shows：
(1) it is in the solution in itself colourless and unstressed configuration that embodiment I -1 is obtained fluorescence probe, but with the addition of palladium ion,
The probe produces absorption at 393nm, and green fluorescence is produced at 543nm.
(2) embodiment I -1 is obtained fluorescence probe has the selectivity and specificity of height to palladium ion.
Embodiment I -3 is obtained the spectral quality of palladium ion fluorescence probe and palladium ion product
Mother liquor in 30 μ L embodiments I -2 is added in a certain amount of HEPES buffer solution (pH7.4), is subsequently adding not
With the palladium chloride solution of equivalent, make final concentration of 10 μM of fluorescence probe, palladium ion final concentration is respectively 0 μM, 2 μM, 4 μM, 6 μ
M, 8 μM, 10 μM, 12 μM, 14 μM, 16 μM, 18 μM, 20 μM, 22 μM.After reacting 5min under normal temperature, its fluorescence emission spectrum is measured.
Its fluorescence emission spectrum is tested under 356nm excitation wavelengths.It is 10nm to excite with the slit width of transmitting：5nm.Gained fluorescence
Increment graph is shown in Fig. 5；Working curve is made with the fluorescence intensity data at 543nm, Fig. 6 is as a result seen.
Should test result indicate that, reacted fluorescence intensity increases with the increase of palladium ion concentration；When using final concentration
During 10 μM of fluorescence probe, fluorescence intensity is linear with palladium ion concentration in the range of 0-22 μM after reaction, can be used for
The quantitative determination of palladium ion.
Embodiment I -4 is obtained palladium ion fluorescence probe to three kinds of selectivity of containing palladium compound
Mother liquor in 30 μ L embodiments I -2 is added in a certain amount of HEPES buffer solution (pH7.4), is then added respectively
Enter the palladium bichloride of 0 μ L and 30 μ L, chlorine palladium acid ammonia, ammonium acetate solution makes final concentration of 10 μM of fluorescence probe, palladium ion final concentration
It is 100 μM.After reacting 5min under normal temperature, its fluorescence emission spectrum is measured.Its fluorescent emission is tested under 357nm excitation wavelengths
Spectrum.It is 10nm to excite with the slit width of transmitting：5nm.With fluorescence intensity data of three kinds of containing palladium compounds at 543nm with
Do not add fluorescence intensity data ratio of the palladium ion at 543nm to make working curve, as a result see Fig. 7.
Should test result indicate that：Embodiment I -1 is obtained fluorescence probe and can detect the palladium ion of multi-form, with universal
Applicability.
Embodiment II -1 prepares the (R=-CH of probe 2 of release red fluorescence3)
5g 2- hydroxy-5-methyl benzaldehydes, 4.6g 2- aminothiophenols and 6g sodium pyrosulfites are dissolved in 50mL's
In DMF；Flowed back 3 hours at 110 DEG C；After reaction terminates, room temperature is cooled to, adds 50mL distillation water washings, produce precipitation,
Filtering, washing filter cake 5 times, and the solid that will be obtained are dried in vacuum drying chamber and obtain 8.5g white solid matters 3；Weigh
2.5g gained materials 3, are dissolved in the trifluoroacetic acid of 15mL with 4.5g hexas；Flowed back 6 hours at 100 DEG C；Instead
After should terminating, the HCl 200mL washings of 4mol/L are added, acid solution extracts organic phase with dichloromethane, adds salt washing
Wash, point liquid, organic phase is dried with anhydrous magnesium sulfate, filtering, concentration；With dichloromethane as eluant, eluent, purify on a silica gel column thick
Product, obtains 2g light yellow solids material 4；Then 0.5g materials 4 are dissolved into DMF, and add 0.616g potassium carbonate, room temperature
Lower stirring 20 minutes, adds 0.531g propargyl bromides afterwards, reacts 15 hours at room temperature；After reaction terminates, water is added, use acetic acid second
Ester extracts organic phase, adds salt water washing, and point liquid, organic phase is dried with anhydrous magnesium sulfate, filtering, concentration；With dichloromethane
With n-hexane (2:3, V/V) it is eluant, eluent, purifying crude product, obtains 0.4g white solids 1 on a silica gel column；By 0.307g whites
Solid and 0.161g 1,3- indenes diketone are dissolved in 20mL tetrahydrofurans, then three drop piperidines are added dropwise, and are reacted 6 hours at room temperature；
After the completion of reaction, water is added, organic phase is extracted with dichloromethane, add salt water washing, point liquid, organic phase anhydrous magnesium sulfate
Dry, filtering, concentration；With dichloromethane and n-hexane (2:1, V/V) it is eluant, eluent, purifying crude product, obtains on a silica gel column
(the R=-CH of 0.12g yellow solids probe 23), the as (R=-CH of probe 23) sterling (1HNMR schemes and high resolution mass spectrum figure is shown in Fig. 8,
Fig. 9).Gained fluorescence probe sterling actual measurement molecular weight is 435.
This case process route：
Embodiment II -2 is obtained the spectral quality of palladium ion fluorescence probe and each metal ion species
Weigh 3mg embodiments II -1 and palladium ion fluorescence probe is obtained, be made into the 10mL DMF solutions that concentration is 1mM, as
Mother liquor.
Fluorescence spectrum is tested：The 30 above-mentioned mother liquors of μ L are added to a certain amount of THF-HEPES buffer solutions (5:2v/v,
PH7.4 in), each metal ion species are then respectively adding：Pd2+, Pb2+, Cr3+, Ag+, Cu2+, Li+, Fe2+, Zn2+, Eu3+, Co3+,
Hg2+, Zr4+, Cs2+, K+, Na+, Cd2+, Fe3+, Mg2+, Ni2+, Mn2+, Al3+, Ca2+One of, make Pd2+Final concentration of 100 μM, other
Final concentration of 200 μM of metal ion, final concentration of 10 μM of fluorescence probe.20min is reacted at 37 DEG C, in 437nm excitation light waves
Its fluorescence emission spectrum is tested under length.It is 5nm to excite with the slit width of transmitting.Acquired results are as shown in Figure 10.
Absorption spectrum is tested：The 30 above-mentioned mother liquors of μ L are added to a certain amount of THF-HEPES buffer solutions (5：2v/v,
PH7.4 in), it is subsequently adding metal ion Pd2+, make Pd2+Final concentration of 100 μM, final concentration of 10 μM of fluorescence probe.At 37 DEG C
Lower reaction 20min, tests its absorption spectrum.Acquired results are as shown in figure 11.
Result above shows：
(1) it is in the solution in itself colourless and unstressed configuration that embodiment II -1 is obtained fluorescence probe, but with the addition of palladium ion,
The probe produces absorption at 425nm, and red fluorescence is produced at 642nm.
(2) embodiment II -1 is obtained fluorescence probe has the selectivity and specificity of height to palladium ion.
Embodiment II -3 is obtained the spectral quality of palladium ion fluorescence probe and palladium ion product
Mother liquor in 30 μ L embodiments II -2 is added to a certain amount of THF-HEPES buffer solutions (5：2v/v, pH7.4)
In, the palladium chloride solution of different equivalents is subsequently adding, make final concentration of 10 μM of fluorescence probe, palladium ion final concentration is respectively 0 μ
M, 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 7 μM, 8 μM, 9 μM, 10 μM, 11 μM, 12 μM, 13 μM.20min is reacted at 37 DEG C
Afterwards, its fluorescence emission spectrum is measured.Its fluorescence emission spectrum is tested under 437nm excitation wavelengths.Excite the slit with transmitting
Width is 5nm.Gained fluorescence increment graph is shown in Figure 12；Working curve is made with the fluorescence intensity data at 642nm, figure is as a result seen
13。
Should test result indicate that, reacted fluorescence intensity increases with the increase of palladium ion concentration；When using final concentration
During 10 μM of fluorescence probe, fluorescence intensity is linear with palladium ion concentration in the range of 0-13 μM after reaction, can be used for
The quantitative determination of palladium ion.
Embodiment II -4 is obtained palladium ion fluorescence probe to three kinds of selectivity of containing palladium compound
Mother liquor in 30 μ L embodiments II -2 is added to a certain amount of THF-HEPES buffer solutions (5：2v/v, pH7.4)
In, 0 μ L and 30 μ L palladium bichlorides are then respectively adding, chlorine palladium acid ammonia, ammonium acetate solution makes final concentration of 10 μM of fluorescence probe,
Final concentration of 100 μM of palladium ion.After reacting 20min at 37 DEG C, its fluorescence emission spectrum is measured.In 437nm excitation wavelengths
Lower its fluorescence emission spectrum of test.It is 5nm to excite with the slit width of transmitting.It is glimmering at 642nm with three kinds of containing palladium compounds
Light intensity data makes working curve with fluorescence intensity data ratio of the palladium ion at 642nm is not added, and as a result sees Figure 14.
Should test result indicate that：Embodiment II -1 is obtained fluorescence probe and can detect the palladium ion of multi-form, with general
Time applicability.
In addition to the implementation, the present invention can also have other embodiment.All use equivalents or equivalent transformation shape
Into technical scheme, all fall within the protection domain of application claims.
Claims (6)
1. it is a kind of for detecting palladium ion fluorescence probe, it is characterised in that described probe has the structure as shown in formula 1 or 2：
Wherein R is H, CH3Or t-Bu.
2. a kind of preparation method of fluorescence probe as claimed in claim 1, it is characterised in that comprise the following steps：
2- hydroxyl -5- alkylbenzaldehydes, 2- amino-benzenethiols, sodium pyrosulfite are dissolved in dry DMF, reaction product
Matter 3, material 3 and methenamine is dissolved in trifluoroacetic acid, reaction product matter 4, then by material 4 and propargyl bromide, carbonic acid
Potassium is dissolved in DMF, and reaction obtains probe 1；Probe 1 and 1,3- indenes diketone, piperidines are added in tetrahydrofuran again, are reacted
To probe 2.
3. preparation method according to claim 2, it is characterised in that its reaction condition is during described reaction product matter 3
Back flow reaction 3 hours or more at 100 DEG C -120 DEG C；Its reaction condition is 90 DEG C -100 DEG C during described reaction product matter 4
Lower back flow reaction 6 hours or more；Described reaction obtains its reaction condition of probe 1 to react 15 hours or more at room temperature；
Described reaction obtains its reaction condition of probe 2 to react 6 hours or more at room temperature.
4. preparation method according to claim 3, it is characterised in that comprise the following steps:
Described reaction product matter 3 its reaction terminate after first distilled water is added in product, refilter, wash and dry
Filter cake, products therefrom is material 3；
Described reaction product matter 4 its reaction terminate after hydrochloric acid is added in product, then with dichloromethane extract, and
Wash with water, be spin-dried for organic phase, then make eluant, eluent with dichloromethane, on a silica gel column after purifying crude product, the product for obtaining is i.e.
It is material 4；
Described reaction obtains adding water in reactant after probe 1 its reaction terminates, then is extracted with ethyl acetate, then with nothing
Water magnesium sulfate is dried, and finally makees eluant, eluent with dichloromethane and n-hexane, on a silica gel column after purifying crude product, the product for obtaining
As probe 1；
Described reaction obtains extracting reactant dichloromethane and water after probe 2 its reaction terminates, the anhydrous sulphur of organic phase
Sour magnesium is dried, and is spin-dried for, then makees eluant, eluent with dichloromethane and n-hexane, on a silica gel column after purifying crude product, the product for obtaining
Thing is probe 2.
5. preparation method according to claim 2, it is characterised in that described 2- hydroxyl -5- alkylbenzaldehydes, 2- amino -
Benzenethiol is 1 with the consumption mass ratio of sodium pyrosulfite:1:1-1：1：3；Described material 3 and the consumption mass ratio of methenamine
It is 1:1-1：3；Described material 4 is 1 with the consumption mass ratio of propargyl bromide, potassium carbonate:1-1：3；Described probe 1 and 1,3- indenes
Diketone, the consumption mass ratio of piperidines are 3:1-1：3.
6. application of a kind of fluorescence probe as claimed in claim 1 in palladium ion is detected.
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| CN111138329A (en) * | 2020-01-13 | 2020-05-12 | 福建师范大学 | Preparation method and application of AIE fluorescent probe for detecting palladium ions |
| CN111205242A (en) * | 2020-02-24 | 2020-05-29 | 山西大学 | Benzothiazole derivative and synthesis method and application thereof |
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| CN109206351A (en) * | 2018-09-18 | 2019-01-15 | 许昌学院 | A kind of near infrared fluorescent probe, preparation method and application for surveying palladium ion based on flower cyanines structure |
| CN109206351B (en) * | 2018-09-18 | 2021-06-29 | 许昌学院 | Cyanine structure based near-infrared fluorescent probe for detecting palladium ions, and preparation method and application thereof |
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| CN111205242A (en) * | 2020-02-24 | 2020-05-29 | 山西大学 | Benzothiazole derivative and synthesis method and application thereof |
| CN113004220A (en) * | 2021-03-12 | 2021-06-22 | 南京工业大学 | Esterase detection fluorescent probe, preparation method and application |
| CN113004220B (en) * | 2021-03-12 | 2022-03-11 | 南京工业大学 | Esterase detection fluorescent probe, preparation method and application |
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