CN108559300A - A kind of preparation of side's acid cyanines copper ion probe and detection method - Google Patents
A kind of preparation of side's acid cyanines copper ion probe and detection method Download PDFInfo
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- CN108559300A CN108559300A CN201810318958.3A CN201810318958A CN108559300A CN 108559300 A CN108559300 A CN 108559300A CN 201810318958 A CN201810318958 A CN 201810318958A CN 108559300 A CN108559300 A CN 108559300A
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 83
- 239000000523 sample Substances 0.000 title claims abstract description 61
- 239000002253 acid Substances 0.000 title claims abstract description 37
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 239000011591 potassium Substances 0.000 claims abstract description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002932 luster Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- XTIGGAHUZJWQMD-UHFFFAOYSA-N 1-chloro-2-methoxyethane Chemical group COCCCl XTIGGAHUZJWQMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- GOKUDEWVRNZXDZ-UHFFFAOYSA-N 1-bromo-3-(3-bromopropoxy)propane Chemical class BrCCCOCCCBr GOKUDEWVRNZXDZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- -1 haloethyl methyl ethers Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 150000002476 indolines Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/007—Squaraine dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
-
- 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)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Engineering & Computer Science (AREA)
- Photoreceptors In Electrophotography (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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
A kind of side's acid cyanines copper ion probe, molecular structural formula are：
Description
Technical field
The invention belongs to chemical analysis and detection field, more particularly to the preparation of a kind of copper ion probe and detection method.
Background technology
Copper ion is widely present in nature, is the important object of life science and environment scientific domain research, to copper
The identification and detection of ion are one of main tasks of analytical chemistry, detect Cu2+Technology mainly have atomic absorption spectrography (AAS), purple
Outside-visible absorption spectroscopy, electrochemical methods and Inductively coupled plasma-mass spectrometry etc..UV-Vis Spectrophotometry is examined
Survey Cu2+, generally require and realized by the color developing agent with specific absorption, such as Biomolecule detection kit or nanometer
Grain[1-3], gel color developing agent[4]And organic dyestuff[5-7]Deng.But its manufacturing cost is relatively high, and detection method and operation compare
It is cumbersome, and detect and wait for the time of result longer.
Present invention design has synthesized a kind of squarylium cyanine dyes, can be used as detection of the probe for copper ion, cost of manufacture
Cheap, detection method is simple, has the color response signal that can visually debate and higher detection sensitivity to copper ion, realizes
Quick detection to copper ion.
Invention content
The object of the present invention is to provide a kind of of low cost, detection methods simply, detection sensitivity is higher and detection is quick
The sour cyanines copper ion probe in side preparation and detection method.
The molecular structural formula of the sour cyanines copper ion probe in side of the present invention is：
The preparation method of above-mentioned side's acid cyanines copper ion probe is as follows：
(1) synthesis of intermediate：
0.5-0.75mL 2- haloethyl methyl ethers are added by every gram of 2,3,3- trimethyl -3H- indoline -5- potassium sulfonate
Ratio mixes 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates and 2- haloethyl methyl ethers, then presses every gram of 2,3,3- front threes
The ratio of 10-20mL o-dichlorohenzenes is added in base -3H- indoline -5- potassium sulfonates, by 2,3,3- trimethyl -3H- indoline -5- sulphurs
Sour potassium and 2- haloethyl methyl ether mixed solutions are added in o-dichlorohenzene, anti-at 110-140 DEG C under inert gas protection
It answers 8-16 hours, solvent is removed after cooling, the ratio that 1.2-2.0mL isopropanols are added in every 1g obtained solids is ground to solid
Body is in fine powdered, and filtering, it is intermediate to obtain red solid；
The 2- haloethyls methyl ether is 2- chloroethyl methyl ethers or 2- bromo-ethyl-methyl ethers；
(2) synthesis of the sour cyanines copper ion probe in side：
The ratio of the side's 0.18-0.19g acid and 10-30mL mixed solvents is added in every gram of intermediate, it will be made in step (1)
Standby intermediate and square acid are added in the mixed solvent, and the mixed solvent volume ratio is n-butanol：Toluene：Pyridine=4:4:5,
It is reacted 5-10 hours at 110-130 DEG C under inert gas protection, solvent is removed after cooling, obtained solid is dissolved in methanol,
Isopropanol is added to there is blue metallic luster solid to be precipitated, it is that respective party acid cyanines copper ion is visited that blue solid is obtained after separating-purifying
Needle.
The inert gas includes nitrogen or argon gas.
Detection method of the above-mentioned side's acid cyanines copper ion probe to copper ion：
The sour cyanines copper ion probe in side is dissolved in CH3In CN solution, it is configured to 10-4-10-6The solution of M takes the matched solution of 4mL
In cuvette, its absorption spectrum is tested, the solution to be measured of 10-40 μ L is then added thereto again, is uniformly mixed, then it is inhaled
Spectrum is received to be tested；Before and after record and comparison copper ion solution to be measured are added, purple of side's acid cyanines copper ion probe at 642nm
The absorption intensity of outside-visible absorption spectra, and the solution colour variation of watcher's acid cyanines copper ion probe, if absorption spectrum
Absorption intensity at 642nm reduces, while the sour cyanines copper ion probe solution colour in side becomes faint yellow from blue, then illustrates to be measured
Contain copper ion in solution.
The present invention has the following advantages that compared with prior art：
1, the synthetic route of the sour cyanines copper ion probe in side is simple, raw material be easy to get and post-process it is simple and convenient.
2, the sour cyanines copper ion probe in side has copper ion in acetonitrile solution a special recognition capability, and response speed compared with
Soon, detection sensitivity is higher, and testing result has the color change that apparent naked eyes can be known.
Description of the drawings
Fig. 1 is the synthetic route schematic diagram of the sour cyanines copper ion probe in present invention side.
Fig. 2 is mass spectrum (ESI-MS) figure of the sour cyanines copper ion probe in present invention side, and main peak is [M-2K]2-(m/z)=
334.9。
Fig. 3 is that Cu is being added in the sour cyanines copper ion probe in side prepared by the embodiment of the present invention 12+Front and back CH3CN solution it is ultraviolet-
Visible absorption spectra figure.
Fig. 4 is side sour cyanines copper ion probe CH in the presence of different metal ions prepared by the embodiment of the present invention 13CN solution
UV-visible absorption spectrum.
Fig. 5 is side sour cyanines copper ion probe CH in the presence of different metal ions prepared by the embodiment of the present invention 13CN solution
Middle addition Cu2+Competition block diagram afterwards.
Fig. 6 is the sour cyanines copper ion probe in side of the preparation of the embodiment of the present invention 1 in CH3In CN solution to copper ion it is ultraviolet-
Visible absorbance titrates collection of illustrative plates.
Specific implementation mode
Embodiment 1：
As shown in Figure 1, the preparation of side's acid cyanines copper ion probe：
1) intermediate synthesizes：By 2g 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates and 1.2mL 2- bromoethyl methyl
Ether is added in 20mL o-dichlorohenzenes, is reacted 8 hours at 110 DEG C under inert gas protection.Solvent, gained are removed after cooling
It is in fine powdered that solid is ground to solid with 2.4mL isopropanols, and filtering, it is intermediate to obtain red solid.
2) synthesis of the sour cyanines copper ion probe in side：Intermediate 1g and the side's 0.18g acid prepared in step 1) are added to
10mL mixed solvents (volume ratio 4:4:5 n-butanol, the mixed solvent of toluene and pyridine) in, under nitrogen protection in 110
It is reacted 5 hours at DEG C, solvent is removed after cooling, obtained solid is dissolved in methanol, and isopropanol is added to there is blue metallic luster solid
Body is precipitated, and it is respective party acid cyanines copper ion probe that blue solid is obtained after separating-purifying.
As shown in Fig. 2, its main peak of the sour cyanines copper ion probe in the side prepared is [M-2K]2-(m/z)=334.9.
CH3Detection of side's acid cyanines copper ion probe to copper ion in CN solution：
The sour cyanines copper ion probe in side is dissolved in CH3In CN solution, it is configured to 10-5The solution of M.Take the matched solution of 4mL in than
In color ware, its absorption spectrum is tested, 20 μ L are then added thereto again and contain the 10 of copper ion-2M Cu2+(5 equivalent) ethyl alcohol waits for
Solution is surveyed, is uniformly mixed, then its absorption spectrum is tested.Before and after record and comparison copper ion solution to be measured are added, side's acid
The absorption intensity of uv-visible absorption spectra of the cyanines copper ion probe at 642nm, and watcher's acid cyanines copper ion probe is molten
Liquid color change, if the absorption intensity at absorption spectrum 642nm reduces, while the sour cyanines copper ion probe solution colour in side is by blue
Become faint yellow, then illustrate to contain copper ion in solution to be measured, testing result is as shown in figure 3, absorption peak of the probe in acetonitrile
In 642nm, after copper ion is added, absorption intensity is greatly reduced at 642nm.
There is the sour cyanines copper ion probe CH in lower section in different metal ions3The absorption of CN solution responds：
The sour cyanines copper ion probe in side is dissolved in CH3In CN solution, it is configured to 10-5The solution of M, take the matched solution of 4mL in than
In color ware, then 20 μ L 10 are added thereto-2M different metal ions (Ag+,Al3+,Ca2+,Cd2+,Ce3+,Co3+,Cr3+,Cu+,Fe3 +,Hg2+,K+,Mg2+,Mn2+,Na+,Ni2+,Pb2+,Sn2+,Sn4+,Zn2+, Cu2+) ethanol solution (5 equivalent), test its absorb light
Spectrum, test results are shown in figure 4.
There is the CH of the sour cyanines copper ion probe in lower section in different metal ions3Cu is added in CN solution2+Competition afterwards：
The sour cyanines copper ion probe in side is dissolved in CH3In CN solution, it is configured to 10-4The solution of M takes the matched solution of 4mL respectively
In cuvette, 20 μ L 10 are added-2M different metal ions ethanol solution (5 equivalent) tests its absorption spectrum, records at 642nm
Absorption peak strength adds 20 μ L 10-2M Cu2+Ethanol solution (5 equivalent) tests its absorption spectrum, records and is absorbed at 642nm
Peak intensity.Absorption peak strength being recorded twice and block diagram being made to different metal ions, the results are shown in Figure 5, different metal ions
Including：Ag+,Al3+,Ca2+,Cd2+,Ce3+,Co3+,Cr3+,Cu+,Fe3+,Hg2+,K+,Mg2+,Mn2+,Na+,Ni2+,Pb2+,Sn2+,
Sn4+,Zn2+, addition copper ion is 5 equivalents, and side's acid cyanines copper ion probe is in CH3Ag in CN solution+,Cu+,Hg2+,K+,Mg2+,Ni2 +,Sn2+, and Sn4+In the presence of at 642nm absorption intensity it is unchanged, in Al3+,Ca2+,Cd2+,Ce3+,Co3+,Cr3+,Fe3+,Mn2+,
Na+,Pb2+And Zn2+In the presence of at 642nm absorption intensity have small reduction, be added after copper ion that absorption peak disappears completely at 642nm
It loses.
CH3Side's acid cyanines copper ion probe titrates the absorption of copper ion in CN solution：
The sour cyanines copper ion probe in side is dissolved in CH3In CN solution, it is configured to 10-6The solution of M, take the matched solution of 4mL in than
In color ware, its absorption spectrum is tested, 10 are added in batches-2M Cu(NO3)2Solution is added 4 μ L (0.1 equivalent) and tests every time
Its absorption spectrum is ultimately joined to 3 equivalents.It takes the absorption intensity value at test result 642nm to do figure to copper ion equivalent, that is, visits
Absorption for copper ion titrates collection of illustrative plates, as shown in Figure 6.
Embodiment 2：
The preparation of side's acid cyanines copper ion probe：
1) by 2g 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates, 1.5mL 2- chloroethyl methyl ethers and 40mL neighbour two
Chlorobenzene is added into flask, is reacted at 140 DEG C under nitrogen protection under argon gas protection in 8 hours.Solvent, gained are removed after cooling
It is in fine powdered that solid is ground to solid with 4mL isopropanols, is ground, and filtering obtains red solid i.e. intermediate.
2) synthesis of the sour cyanines copper ion probe in side：Intermediate 1g and the side's 0.19g acid prepared in step 1) are added to
30mL mixed solvents (volume ratio 4:4:5 n-butanol, the mixed solvent of toluene and pyridine) in, under protection of argon gas in 130
It is reacted 10 hours at DEG C, solvent is removed after cooling, obtained solid is dissolved in methanol, and isopropanol is added to there is blue metallic luster solid
Body is precipitated, and it is respective party acid cyanines copper ion probe that blue solid is obtained after separating-purifying.
Embodiment 3：
The preparation of side's acid cyanines copper ion probe
1) 2g 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates and 1mL 2- chloroethyl methyl ethers are added to 30mL
In o-dichlorohenzene, reacted 16 hours at 120 DEG C under inert gas protection.Solvent, obtained solid 3.2mL are removed after cooling
It is in fine powdered that isopropanol, which is ground to solid, and filtering, it is intermediate to obtain red solid.
2) intermediate 1g and the side's 0.18g acid prepared in step 1) are added to 13mL mixed solvents (volume ratio 4:
4:5 n-butanol, toluene and pyridine mixed solvent) in, it reacts 8 hours, is removed after cooling molten at 120 DEG C under nitrogen protection
Agent, obtained solid are dissolved in methanol, and isopropanol is added to there is blue metallic luster solid to be precipitated, blue solid is obtained after separating-purifying
As respective party acid cyanines copper ion probe.
Embodiment 4：
The synthesis of side's acid cyanines copper ion probe
1) 2g 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates and 1.1mL 2- bromo-ethyl-methyl ethers are added to
In 30mL o-dichlorohenzenes, reacted 10 hours at 130 DEG C under inert gas protection.Solvent is removed after cooling, obtained solid is used
It is in fine powdered that 3.2mL isopropanols, which are ground to solid, and filtering, it is intermediate to obtain red solid.
2) synthesis of the sour cyanines copper ion probe in side：Intermediate 1g and the side's 0.19g acid prepared in step 1) are added to
15mL mixed solvents (volume ratio 4:4:5 n-butanol, the mixed solvent of toluene and pyridine) in, under nitrogen protection in 130
It is reacted 6 hours at DEG C, solvent is removed after cooling, obtained solid is dissolved in methanol, and isopropanol is added to there is blue metallic luster solid
Body is precipitated, and it is respective party acid cyanines copper ion probe that blue solid is obtained after separating-purifying.
Claims (5)
1. a kind of side's acid cyanines copper ion probe, it is characterised in that：Its structural formula is：
2. the preparation method of the sour cyanines copper ion probe in the side of claim 1, it is characterised in that：
(1) synthesis of intermediate：
The ratio of 0.5-0.75mL 2- haloethyl methyl ethers is added by every gram of 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates,
2,3,3- trimethyl -3H- indoline -5- potassium sulfonates and 2- haloethyl methyl ethers are mixed, then press every gram of 2,3,3- trimethyls -
The ratio of 10-20mL o-dichlorohenzenes is added in 3H- indoline -5- potassium sulfonates, by 2,3,3- trimethyl -3H- indoline -5- potassium sulfonates
It is added in o-dichlorohenzene with 2- haloethyl methyl ether mixed solutions, reacts 8- at 110-140 DEG C under inert gas protection
16 hours, solvent is removed after cooling, the ratio that 1.2-2.0mL isopropanols are added in every 1g obtained solids is ground to solid and is in
Fine powdered, filtering, it is intermediate to obtain red solid；
(2) synthesis of the sour cyanines copper ion probe in side：
The ratio of the side's 0.18-0.19g acid and 10-30mL mixed solvents is added in every gram of intermediate, it will be prepared in step (1)
Intermediate and square acid are added in the mixed solvent, and the mixed solvent volume ratio is n-butanol：Toluene：Pyridine=4:4:5, lazy
Property gas shield under reacted 5-10 hours at 110-130 DEG C, remove solvent after cooling, obtained solid is dissolved in methanol, is added
For isopropanol to there is blue metallic luster solid to be precipitated, it is respective party acid cyanines copper ion probe that blue solid is obtained after separating-purifying.
3. the preparation method of side's acid cyanines copper ion probe according to claim 2, it is characterised in that：The 2- haloethyls first
Base ether is 2- chloroethyl methyl ethers or 2- bromo-ethyl-methyl ethers.
4. the preparation method of side's acid cyanines copper ion probe according to claim 2, it is characterised in that：The inert gas is
Nitrogen or argon gas.
5. using the detection method of the sour cyanines copper ion probe in the side of claim 1, it is characterised in that：
(1) the sour cyanines copper ion probe in side is dissolved in CH3In CN solution, it is configured to 10-4-10-6The solution of M, take the matched solution of 4mL in
In cuvette, its absorption spectrum is tested, the solution to be measured of 10-40 μ L is then added thereto again, is uniformly mixed, then it is absorbed
Spectrum is tested；Before and after record and comparison copper ion solution to be measured are added, purple of side's acid cyanines copper ion probe at 642nm
The absorption intensity of outside-visible absorption spectra, and the solution colour variation of watcher's acid cyanines copper ion probe, if absorption spectrum
Absorption intensity at 642nm reduces, while the sour cyanines copper ion probe solution colour in side becomes faint yellow from blue, then illustrates to be measured
Contain copper ion in solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810318958.3A CN108559300B (en) | 2018-04-11 | 2018-04-11 | Preparation and detection method of squarylium cyanine copper ion probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810318958.3A CN108559300B (en) | 2018-04-11 | 2018-04-11 | Preparation and detection method of squarylium cyanine copper ion probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108559300A true CN108559300A (en) | 2018-09-21 |
| CN108559300B CN108559300B (en) | 2020-01-07 |
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| CN201810318958.3A Active CN108559300B (en) | 2018-04-11 | 2018-04-11 | Preparation and detection method of squarylium cyanine copper ion probe |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112812767A (en) * | 2021-01-22 | 2021-05-18 | 常州大学 | Squarylium cyanine probe based on N, N-di (2-picolyl) amine (DPA) and preparation method and application thereof |
| CN115356302A (en) * | 2021-08-16 | 2022-11-18 | 国家卫生健康委职业安全卫生研究中心(国家卫生健康委煤炭工业职业医学研究中心) | Preparation method and application of copper ion detection test paper |
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| CN101328319A (en) * | 2008-07-02 | 2008-12-24 | 燕山大学 | Water-soluble bridged ring polymethine 3H-indole cyanine dyes ultrasonic synthetic method |
| CN101723874A (en) * | 2008-10-31 | 2010-06-09 | 深圳迈瑞生物医疗电子股份有限公司 | Cyanine compound and application thereof in dyeing biological samples |
| CN102786459A (en) * | 2012-08-16 | 2012-11-21 | 常州大学 | Squarylium type chemical sensor for colorimetric identification of copper ion and preparation method thereof |
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| CN101328319A (en) * | 2008-07-02 | 2008-12-24 | 燕山大学 | Water-soluble bridged ring polymethine 3H-indole cyanine dyes ultrasonic synthetic method |
| CN101723874A (en) * | 2008-10-31 | 2010-06-09 | 深圳迈瑞生物医疗电子股份有限公司 | Cyanine compound and application thereof in dyeing biological samples |
| CN102786459A (en) * | 2012-08-16 | 2012-11-21 | 常州大学 | Squarylium type chemical sensor for colorimetric identification of copper ion and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112812767A (en) * | 2021-01-22 | 2021-05-18 | 常州大学 | Squarylium cyanine probe based on N, N-di (2-picolyl) amine (DPA) and preparation method and application thereof |
| CN115356302A (en) * | 2021-08-16 | 2022-11-18 | 国家卫生健康委职业安全卫生研究中心(国家卫生健康委煤炭工业职业医学研究中心) | Preparation method and application of copper ion detection test paper |
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