CN107892675A - A kind of palladium ion probe and its preparation and application - Google Patents
A kind of palladium ion probe and its preparation and application Download PDFInfo
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- CN107892675A CN107892675A CN201711025112.2A CN201711025112A CN107892675A CN 107892675 A CN107892675 A CN 107892675A CN 201711025112 A CN201711025112 A CN 201711025112A CN 107892675 A CN107892675 A CN 107892675A
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- 239000000523 sample Substances 0.000 title claims abstract description 91
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 16
- 230000004044 response Effects 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- -1 benzo thiophenes Azoles Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IJIZGXLRGRKYDV-HIXSDJFHSA-N CCSCCN(CCSCC)c1ccc(/C=C(/C2=CCCc(cccc3)c3S2)\C#N)cc1 Chemical compound CCSCCN(CCSCC)c1ccc(/C=C(/C2=CCCc(cccc3)c3S2)\C#N)cc1 IJIZGXLRGRKYDV-HIXSDJFHSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- INDVHSOTVXHNMA-UHFFFAOYSA-N acetonitrile;1,3-benzothiazole Chemical compound CC#N.C1=CC=C2SC=NC2=C1 INDVHSOTVXHNMA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 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
- 230000001766 physiological effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 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
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to a kind of palladium ion probe.The probe is low to palladium ion test limit, and the response time is short, and influences detection in the absence of coexisting ion, is a kind of good colorimetric probe, and colorimetric probe can be used as to be used to detect metal palladium ion.The invention further relates to a kind of preparation method of palladium ion probe, preparing raw material cost is cheap, and step is simple.It can be used for the content of quick detection palladium ion using the palladium ion probe of the present invention as colorimetric probe.
Description
Technical field
The invention belongs to molecular probe technology field, is related to a kind of palladium ion probe and its preparation and application.
Background technology
Palladium has unique physicochemical properties, and the various uses (including chemistry and biologic applications) of nearest palladium starts to attract
People pay close attention to.However, widely using for palladium may adversely affect to environment and biosystem, therefore, it is necessary to it is adapted to
Detection method adversely affects and investigated its beneficial biological effect to assess.Research shows that the intake of the daily palladium of human body is more than
15 μ g can be caused to damage to human body.Palladium ion can be combined with large biological molecule in vivo, upset the normal physiological activity of cell with
Signal transduction process etc., serious body illness can be triggered.
The conventional method of analysis of metallics detection needs the complicated sample preparation before analyzing and separable programming, it is also necessary to
Costly instrument and trained operator, certain methods quantitative reappearance in the palladium ion for determining trace
Difference.Other conventional method of analysis is mainly used in analyzing in vitro, and a definite limitation is formed to analysis in vivo.The fluorescence light of suitable probe
Spectrum or uv-vis spectra will can provide ideal detection method for metal ion detection.Importantly, probe can be with
Internal and external cell imaging is carried out, the bioprocess that target analytes are related to for research provides reliable instrument, available for disease
The clinical diagnosis and monitoring of disease.
It is more synthesis step to be present in existing palladium ion probe, low yield, exist in the application the response time it is longer the problems such as,
Therefore, design a kind of raw material to be easy to get, the palladium ion probe that synthesis step is few and the response time is short has great importance.
The content of the invention
An object of the present invention is in view of the shortcomings of the prior art, there is provided a kind of palladium ion probe, the probe is to metal
The ionic palladium Ion response time is short, and influences detection in the absence of coexisting ion, is good colorimetric probe.
The second object of the present invention is to provide the preparation method of above-mentioned palladium ion probe, and this method is simple, and cost of material
It is cheap.
The third object of the present invention is to provide the purposes of above-mentioned palladium ion probe.
Therefore, the present inventor has carried out substantial amounts of research, inventor, which studies, finds compound (I) in methanol-water
(V/V=20:1-5:1) it is short to the palladium ion response time in solution, and detection is influenceed in the absence of coexisting ion, therefore can be with
The palladium ion in water or organic solvent is detected as colorimetric probe.
Therefore, first aspect present invention provides a kind of palladium ion probe, for the compound of structural formula such as formula (I), this hair
It is also known as compound (1) in bright：
Second aspect of the present invention provides a kind of preparation method of palladium ion probe as described in the first aspect of the invention, bag
Include：
Step 1, [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde will be mixed in a solvent with benzothiazole acetonitrile
Afterwards, back flow reaction, solvent is evaporated off, the crude product of the compound of structural formula such as formula (I) is made.
In above-mentioned reaction, shown in the structural formula such as formula (II) to [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde,
It is also known as compound (2) in the present invention；It is also known as shown in the structural formula such as formula (III) of benzothiazole -2- acetonitriles, in the present invention and changes
Compound (3).Chemical equation in step 1 is as shown in Figure 1.
According to the present invention, in step 1, to [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde and benzothiazole -2-
The mol ratio of acetonitrile is 1:0.9 to 1:1.2, preferably 1:1.2.
In one embodiment of the invention, in step 1, the solvent is organic solvent, and it includes but is not limited to first
Alcohol, ethanol etc..
According to the present invention, step 2 is also included after step 1：Step 1 is made to the compound of structural formula such as formula (I)
Crude product isolated and purified, be made structural formula such as formula (I) compound sterling.
In one embodiment of the invention, also include preparing to [N, N- bis--(2- ethylmercapto groups)-second before step 1
Base]-benzaldehyde the step of：[compound will be also known as in the present invention to [1.4- bis--(the chloro- ethyls of 2-)-amino]-benzaldehyde
(4)] it is well mixed in a solvent with ethyl mercaptan, back flow reaction simultaneously isolates and purifies reaction product, obtains to [N, N- bis--(2- second
Sulfenyl)-ethyl]-benzaldehyde.
The present invention a further embodiment in, above-mentioned preparation to [N, N- bis--(2- ethylmercapto groups)-ethyl]-
In the step of benzaldehyde, the solvent is organic solvent, including but not limited to ethanol etc..
In the specific embodiment of the present invention, the step of preparing palladium ion probe using the inventive method, is as follows：
(1) will be to [1.4- bis--(the chloro- ethyls of 2-)-amino]-benzaldehyde (735mg, 3mmol), sodium (230mg, 10mmol)
It is dissolved in ethyl mercaptan (443mg, 7mmol) in organic solvent, such as ethanol, is heated to reflux 10-12 hours, steam solvent, is utilized
Silica gel column chromatography separation obtains intermediate product to [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde.
(2) benzothiazole -2- acetonitriles (348mg, 2mmol) are dissolved in organic solvent, such as ethanol, add above-mentioned steps
(1) intermediate product prepared in is well mixed, back flow reaction 2-4 is small to [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde
When, thin-layer chromatography board monitoring extent of reaction is used in course of reaction.
(3) after reaction terminates, it is evaporated under reduced pressure and removes solvent in above-mentioned steps (2), obtain the compound of structural formula such as formula (I)
Solid crude product.
(4) crude product prepared in (3) is purified by column chromatography, obtains the compound of structural formula such as formula (I)
Sterling.
After above-mentioned synthetic reaction terminates, using NMR (Bruker AVANCE 300MHz type NMRs,
Bruker companies, Switzerland) carry out nuclear magnetic resonance spectroscopy to palladium ion probe sterling is made.
Visited using ultraviolet-uisible spectrophotometer (UV-8000S types, Shanghai Yuan Xi Instrument Ltd.) to palladium ion is made
Pin sterling carries out ultraviolet absorption spectroscopy.
Third aspect present invention provides a kind of palladium ion probe as described in the first aspect of the invention and visited as colorimetric
Application in pin.
According to the present invention, it is used to detect metal palladium ion using palladium ion probe as colorimetric probe.
According to certain embodiments of the present invention, it is used to detect metal palladium ion using palladium ion probe as colorimetric probe
Method includes that Pd will be contained2+Testing sample be added in colorimetric probe solution, then estimate the change and/or survey of the system color
Try the UV absorption change of the system.
In the present invention, the testing sample is water and/or organic solvent, that is, the testing sample is water, organic solvent
Or the mixed liquor of water and organic solvent.
According to the present invention, the colorimetric probe solution is matched somebody with somebody by the compound of structural formula such as formula (I) with methanol-water mixed solution
System forms.
In some embodiments of the invention, the concentration of the colorimetric probe solution is 10-5-10-6mol/L.This can be managed
Xie Wei, with the total volume meter of the colorimetric probe solution, the content in the colorimetric probe solution such as the compound of formula (I) is
10-5-10-6mol/L。
In other embodiments of the present invention, the volume ratio of methanol and water is (5- in the methanol-water mixed solution
20):1。
Palladium ion probe is short to the metal ion response time in the present invention, and influences detection in the absence of coexisting ion, therefore,
Colorimetric probe can be used as to be used to detect palladium ion.
In certain specific embodiments of the invention, the compound (1) of the present invention is used for palladium ion in the aqueous solution
Detection.Compound of the structural formula as shown in formula (I) is used as colorimetric probe, Pd will be contained2+Testing sample be added to concentration and be
10-5-10-6React 30 seconds in mol/L colorimetric probe solution, then bore hole estimates the system (testing sample is molten with colorimetric probe
The mixed liquor of liquid) color change situation and/or test the UV absorption situation of change of the system.
In other embodiments of the present invention, the compound (I) of the present invention is used for palladium ion in the aqueous solution
Detection.Compound of the structural formula as shown in formula (I) is used as colorimetric probe, different amounts of Pd will be contained2+Testing sample add
It is 10 to enter to concentration-5-10-6Reacted 30 seconds in mol/L colorimetric probe solution, then record the body with ultraviolet-visual spectrometer
The spectrum change situation of system's (mixed liquor of testing sample and colorimetric probe solution).
In the other embodiment of the present invention, the palladium ion probe of the present invention is used to detect in organic solvent
Palladium ion.Compound of the structural formula as shown in formula (I) is used as colorimetric probe, Pd will be contained2+Organic solvent in be added to it is dense
Spend for 10-5-10-6In mol/L colorimetric probe solution, then bore hole estimates system (testing sample and the colorimetric probe solution
Mixed liquor) color change situation and/or test the UV absorption situation of change of the system.
Heretofore described term " colorimetric " refers to that acting on its front and rear color with probe molecule using metal ion becomes
The method changed and carry out colorimetric estimation.
Heretofore described term " bore hole colorimetric " refers to that acting on its front and rear color using metal ion and probe molecule sends out
Changing and the method for carrying out bore hole colorimetric.
Compound of the structural formula prepared according to the methods of the invention as shown in formula (I), low raw-material cost, preparation method letter
It is single.Compound of the structural formula of the present invention as shown in formula (I), it is short to the metal ion response time, and coexisting ion shadow is not present
Detection is rung, is a kind of good colorimetric probe, can be used for detecting the metal palladium ion in the aqueous solution or organic solvent.By basis
Compound of the structural formula made from the inventive method as shown in formula (I) is as bore hole colorimetric probe, to the palladium ion response time
Have 30 seconds.Compound of the structural formula of the present invention as shown in formula (I) realizes the detection to palladium ion as colorimetric probe, is fast
Fast Sensitive Detection palladium ion provides a kind of potential detection material.
Brief description of the drawings
The present invention is described in further detail below in conjunction with the accompanying drawings：
Fig. 1 is the chemical equation of step (2) in the embodiment of the present invention 1；The implication of reference is as follows in figure：1 structure
Compound of the formula as shown in formula (I), i.e. compound (1)；2 pairs of [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehydes；3 benzo thiophenes
Azoles -2- acetonitriles；4 [1.4- bis--(the chloro- ethyls of 2-)-amino]-benzaldehydes.
Fig. 2 is UV absorption light of the obtained compound (1) in the presence of different metal ions in the embodiment of the present invention 1
Spectrum.
Fig. 3 be in the embodiment of the present invention 1 obtained compound (1) in Pd2+In the presence of color change.
Embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with drawings and examples, these realities
Apply example only serve it is illustrative, it is not limited to application of the invention, NM specific experiment side in the following example
Method, generally carried out according to normal experiment method.
Embodiment
Embodiment 1：Compound of the preparation structure formula as shown in formula (I), i.e. compound (1).
(1) ethyl mercaptan is dissolved in organic solvent, such as ethanol, then according to ethyl mercaptan:Sodium=1:10 mol ratio adds
Enter metallic sodium, react 1h, then to [1.4- bis--(the chloro- ethyls of 2-)-amino]-benzaldehyde and ethyl mercaptan according to 1:4 mol ratio
It is added in above-mentioned mixed solution, is heated to reflux 10-12 hours, steams solvent, is separated using silica gel column chromatography and produced among obtaining
Thing is to [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde, yield 51%.
(2) benzothiazole -2- acetonitriles are dissolved in organic solvent, such as ethanol, according to 1:1 mol ratio adds above-mentioned steps
(1) intermediate product prepared in is well mixed, back flow reaction 2-4 is small to [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde
When.After steaming solvent, gained crude product carries out separating-purifying, prepare compound (1) sterling, yield 68% through column chromatography.
Using NMR (Bruker AVANCE 300MHz type NMRs, Bruker companies, Switzerland) to system
Obtain compound (1) sterling and carry out nuclear magnetic resonance spectroscopy, it is as a result as follows：
1HNMR(300MHz,CDCl3):8.01 (1H), 8.1 (1H), 6.71 (2H), 7.72 (2H), 7.53 (2H), 2.67
(2H), 2.48 (2H), 3.72 (2H), 1.25 (2H), 8.27 (1H)
13CNMR(75MHz,CDCl3):160.5,136.2,153.5,148.8,124.5,121.6,124.7,111.7,
129.7,111.7,124.5,125.3,129.7,29.6,29.6,25.5,25.5,118.8,60.1,60.1,107.7,
153.5,14.7,14.7.
Embodiment 2：Prepare compound (1).
By [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde obtained in the step of embodiment 1 (1) and benzothiazole second
Nitrile is according to 1:1.2 mol ratio is dissolved in organic solvent methanol, stirs lower back flow reaction 10 hours, after steaming solvent, with methanol
As solvent, red compound (1), yield 87% is made using the method for recrystallization.
Embodiment 3：
Compound (1) prepared by embodiment 1 as colorimetric probe be added to methanol-water mixed solution (methanol and water
Volume ratio is 20:1) in, concentration is configured to as 10-6Mol/L colorimetric probe solution, and the identical (metal of concentration is added thereto
The concentration of ion is 10-5Mol/L the aqueous solution of different metal ions), naked eye is then carried out, as a result sees Fig. 2；And adopt
Ultra-violet absorption spectrum point is carried out with ultraviolet-uisible spectrophotometer (UV-8000S types, Shanghai Yuan Xi Instrument Ltd., China)
Analysis, is as a result shown in Fig. 3.
Fig. 2 result shows, synthesized compound (1) be yellow in methanol-water solution in the present invention, addition palladium from
After son, only need 30 seconds, solution is become colorless (No. 1 sample in Fig. 2) by yellow, adds other metal ions, and solution colour is (yellow
Color) constant (2-16 samples in Fig. 2) is kept, therefore compound (1) may be used as colorimetric probe detection metal palladium ion.
Fig. 3 result shows that synthesized compound (1) is strong to have at 450nm in methanol-water solution in the present invention
Absworption peak, add after palladium ion, the absworption peak of solution is moved at 350nm, and absorption peak strength is decreased obviously, and adds other gold
Belong to ion, the absorption peak position of solution is held essentially constant, and absorption peak strength is increased slightly.Therefore compound (1) may be used as
Colorimetric probe detects metal palladium ion.
It is above-mentioned test result indicates that, compound (1) is good to the selectivity of palladium ion as colorimetric probe, and the response time is short,
Only 30 seconds；Analyzed by Fig. 2 and ultraviolet spectra Fig. 3, it can be seen that compound (1) is as choosing of the colorimetric probe to palladium ion
Selecting property is good.
Embodiment 4：Palladium ion is detected using compound (1) as probe molecule.
Compound (1) prepared by embodiment 1 as colorimetric probe be added to methanol-water mixed solution (methanol and water
Volume ratio is 10:1) in, concentration is configured to as 10-5Mol/L colorimetric probe solution, take respectively pure water, running water, river and
Lake water 2mL, in the colorimetric probe solution for sequentially adding equivalent, react 30 seconds, then detect its uv-vis spectra, experiment shows
Palladium ion content is larger in river and lake water, and palladium ion content is relatively low in running water and pure water.
Embodiment 5：The titrimetry detected using compound (1) as probe molecule to palladium ion.
Compound (1) prepared by embodiment 2 as colorimetric probe be added to methanol-water mixed solution (methanol and water
Volume ratio is 5:1) in, concentration is configured to as 10-6Mol/L colorimetric probe solution, is sequentially added not into colorimetric probe solution
Same amount, such as 0.1-2 times of equivalent, i.e. (0.1-2) × 10--6Mol/L palladium ion solution, the change of its uv-vis spectra is determined,
And drawn by linear analysis, the probe can reach 10 to the test limit of palladium ion-8mol/L。
The present inventor passes through many experiments, find compound (1) as colorimetric probe in water to palladium ion
Only need 30 seconds cans that obvious response occurs, can be reacted completely after 1 minute.
From above-described embodiment as can be seen that compound (1) as probe in water it is short to the response time of palladium ion and right
The response intensity of palladium ion is high, good, the quick detection available for different water head site palladium ions of selectivity.
It should be noted that the foregoing is only presently preferred embodiments of the present invention, it is only used for explaining the present invention, does not form
Any limitation of the invention.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word be descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by the scope provided in the claims in the present invention
It is interior that the present invention is modified, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although wherein
The present invention of description is related to specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed spy
Usual practice, on the contrary, the present invention can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of palladium ion probe, it is the compound of structural formula such as formula (I)：
2. a kind of preparation method of the palladium ion probe described in claim 1, including：
Step 1, [N, N- bis--(2- ethylmercapto groups)-ethyl]-benzaldehyde will be mixed in a solvent with benzothiazole -2- acetonitriles
Afterwards, back flow reaction, solvent is evaporated off, the crude product of the compound of structural formula such as formula (I) is made.
3. preparation method according to claim 2, it is characterised in that：It is described to [N, N- bis--(2- second sulphur in step 1
Base)-ethyl] mol ratio of-benzaldehyde and benzothiazole -2- acetonitriles is 1:0.9 to 1:1.2.
4. the preparation method according to Claims 2 or 3, it is characterised in that：
Also include step 2 after step 1：The crude product that step 1 is made to the compound of structural formula such as formula (I) is divided
From purifying, the sterling of the compound of obtained structural formula such as formula (I).
5. application of the palladium ion probe in as colorimetric probe described in claim 1.
6. the application described in claim 5, it is characterised in that：Using palladium ion probe as colorimetric probe be used for detect Metal Palladium from
Son.
7. application according to claim 6, it is characterised in that be used to detect metal using palladium ion probe as colorimetric probe
The method of palladium ion includes that Pd will be contained2+Testing sample be added in colorimetric probe solution, then estimate the change of the system color
Change and/or test the UV absorption change of the system.
8. application according to claim 7, it is characterised in that the testing sample is water and/or organic solvent.
9. the application according to claim 7 or 8, it is characterised in that the colorimetric probe solution is by structural formula such as formula (I)
Compound is formulated with methanol-water mixed solution.
10. application according to claim 9, it is characterised in that the concentration of the colorimetric probe solution is 10-5-10-6mol/
L；And/or the volume ratio of methanol and water is (5-20) in the methanol-water mixed solution:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627837A (en) * | 2019-09-10 | 2019-12-31 | 齐鲁工业大学 | Metal organic framework material for detecting carbon monoxide, preparation method and application |
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| CN104761549A (en) * | 2015-02-12 | 2015-07-08 | 陕西学前师范学院 | Palladium ion probe and preparation and application thereof |
| CN105131935A (en) * | 2015-08-27 | 2015-12-09 | 晋江尚京富本环保科技有限公司 | Rapid high-selectivity fluorine ion colorimetric probe and preparation method therefor |
| CN106187941A (en) * | 2016-07-27 | 2016-12-07 | 济南大学 | One can identify inorganic mercury and organomercurial sensitive high selectivity colorimetric probe simultaneously |
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| CN105131935A (en) * | 2015-08-27 | 2015-12-09 | 晋江尚京富本环保科技有限公司 | Rapid high-selectivity fluorine ion colorimetric probe and preparation method therefor |
| CN106187941A (en) * | 2016-07-27 | 2016-12-07 | 济南大学 | One can identify inorganic mercury and organomercurial sensitive high selectivity colorimetric probe simultaneously |
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Application publication date: 20180410 |