CN107314991A - Schiff base compound as cyanide ion and copper ion fluorescence probe application - Google Patents
Schiff base compound as cyanide ion and copper ion fluorescence probe application Download PDFInfo
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Abstract
The present invention relates to application of the schiff base compound as cyanide ion and copper ion fluorescence probe, this method can be quick, easy, efficient and specific cyanide ion and copper ion detected.The technical solution adopted by the present invention is：Schiff base compound as cyanide ion and copper ion fluorescence probe application.Its structural formula of such schiff bases is：The pH=7.4 of described phosphate buffer, concentration is 10mM, and the volume ratio of phosphate buffer and acetonitrile is 1:2.
Description
First, technical field：
The present invention relates to field of bioanalysis, and in particular to schiff base compound is glimmering as cyanide ion and copper ion
The application of light probe.
2nd, background technology：
Hypertoxic cyanide ion is a kind of highly important raw material in the synthesis of medicine, insecticide and fertilizer, and its is extensive
Applied to the fields such as medical science, metallurgy, plating (Journal of Materials Processing Technology, 2001,
119(3):336-343.).Scientific investigations showed that after cyanide ion enters blood circulation, cyanide ion and the cell in blood
Chromo-oxidase produces reaction, and the cascade reaction of inhibitory enzyme makes it lose electron transmission ability so that breathing chain interruption, so that
Cause intracellular anoxic to cause nervous centralis wadding disorderly, cell death by suffocation (Chemical is caused when serious
Communications,2014(50):11583-11586).Therefore, the detection for cyanide ion has highly important meaning
Justice.The method of detection cyanogen root has voltammetry, titration, electrochemical process and chromatography (Hydrometallurgy, 2011,106
(4):135-140；Chemistry-A European Journal,2014,20(41):13226-13233；Biosensors
and Bioelectronics,2005,20(12):2581-2593；Society Reviews,2010,39(1):127-
137.), but these methods be required for costliness equipment, and detection time-consuming, be difficult to realize in time analysis etc. extensive use.Therefore
Need to find method that is simple, quick, economically detecting cyanogen root.
Copper ion plays highly important adjustment effect as a kind of trace element in human body in various physiology courses.So
And, the excess and shortage of copper ion can all cause the lesion of body, and copper, which lacks, can cause coronary sclerosis to form coronary disease
Disease；Excessive copper ion can cause central lesion, have impact on the kidney of human body, liver, lung and other positions, very
To causing serious disease, such as Parkinson's and Alzheimer's.The copper ion of excessive concentrations can cause water in the environment
Body bacterium, the death of algae, for water environment cause serious pollution (Journal of Luminescence, 2016,180,
292–300；RSC Advances,2016,6,102096-102101.).Therefore, the selective enumeration method of copper ion is protected in environment
Tool is of great significance in terms of shield and health.At present, conventional copper ion detection method has atomic absorption method, ion
The methods such as chromatography, Electrochemical Detection.Compared to these detection methods, fluorescence detection method has real-time, quick, easy, choosing
The advantages of selecting property and high sensitivity, it is considered to be the effective ways of detection cation and anion.
Fluorescence detection method is widely used in many fields at present, such as biomolecule detection, medical pathologies research, ring
Border pollutant monitoring etc..
The present invention is used for fluoroscopic examination cyanogen root and copper ion using schiff base compound as fluorescence probe.Such seat
The cyclization in the presence of cyanide ion and copper ion of husband's alkali cpd is aoxidized.Such schiff base compounds be used for as cyanogen root and copper from
There is presently no report for the application of sub- fluorescence probe.
3rd, the content of the invention
The schiff base compound that provides of the present invention is used for the application as cyanogen root and copper ion fluorescence probe, this method
Can be quick, easy, efficient and specific cyanide ion and copper ion be detected.
To achieve the above object, the technical solution adopted by the present invention is：
Schiff base compound as cyanide ion and copper ion fluorescence probe application.
Such described schiff base compounds are used as cyanide ion and copper in the mixed system of phosphate buffer and acetonitrile
The application of ion fluorescence probe.
Its structural formula of such schiff bases is：
The pH=7.4 of described phosphate buffer, concentration is 10mM, and the volume ratio of phosphate buffer and acetonitrile is 1:2.
Compared with prior art, the invention has the advantages that and effect：
1. instant invention overcomes the defect of conventional analysis method, using schiff base as fluorescence probe be used for cyanogen root from
The detection of son and copper ion, this method can be quick, easy, efficient and specific cyanide ion and copper ion detected；
2. the invention provides a class using dialdehyde compound as parent, acted on by the amino of aldehyde radical and aromatic amine derivant
The schiff base compounds with symmetrical structure of generation.Such schiff base compounds is in strong nucleopilic reagent cyanide ion and oxidisability
Collective effect ShiShimonoseki epoxidation of copper ion, generation can send the cyclization product of strong blue-fluorescence；
3. schiff base compounds used in the present invention prepare it is simple, be readily synthesized.Such schiff bases chemicals to cyanogen root from
The detection of son and copper ion has high selectivity and high sensitivity, can accurately and rapidly detect cyanide ion and copper ion, right
There is no any response in other metal cations and anion；
4., schiff base compounds of the present invention can be used for the fluoroscopic examination of cyanide ion and copper ion, be environment measuring
There is provided effective analysis method.
4th, illustrate
Fig. 1 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in is
1 μM of schiff bases 1, first adds 20 μM of cyanide ions, adds 20 μM of copper ions, after 1 minute, after 2 minutes, after 3 minutes, 4 minutes
The variation diagram of fluorescence intensity afterwards；
Fig. 2 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in is
1 μM of schiff bases 6, first adds 20 μM of cyanide ions, adds 20 μM of copper ions, after 1 minute, after 2 minutes, after 3 minutes, 4 minutes
Afterwards, after 5 minutes, after 6 minutes, after 7 minutes, after 8 minutes, after 9 minutes, the variation diagram of the fluorescence intensity after 10 minutes；
Fig. 3 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 20 μM of CN-Afterwards, then it is separately added into 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 7 μM, 8 μM, 9 μM, 10 μM
Copper ion, its fluorescence intensity at maximum emission wavelength 439nm changes with time figure；
Fig. 4 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 20 μM of CN-Afterwards, then it is separately added into the copper ions (1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM) of various concentrations
Its at maximum emission wavelength 439nm fluorescence intensity with different copper ion concentration linear relationship charts；
Fig. 5 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 20 μM of CN-Afterwards, 8 μM of copper ions are added or 10 μM of other metal cations are separately added into and (are followed successively by Al3 +, Ba2+, Ca2+, Cd2+, Co2+, Fe2+, Fe3+, K+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+, Cr3+, Li+, Na+, Hg2+) fluorescence intensity
Variation diagram；
Fig. 6 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 20 μM of CN-Afterwards, then it is separately added into the fluorescence block diagram of various metal cations effect；Black post：Schiff
Alkali 1 adds the change of the fluorescence under its maximum emission wavelength 439nm after 10 μM of other metal ions；Grey post：Schiff bases 1 adds
Enter the change of the fluorescence after 10 μM of other metal ions and 5 μM of copper ions under its maximum emission wavelength 439nm, from left to right according to
Secondary is Al3+, Ba2+, Ca2+, Cd2+, Co2+, Fe2+, Fe3+, K+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+, Cr3+, Li+, Na+, Hg2+；
Fig. 7 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 8 μM of Cu2+Afterwards, then it is separately added into 1 μM, 5 μM, 10 μM, 20 μM, 25 μM, 30 μM, 40 μM of cyanide ions, its
Fluorescence intensity changes with time figure at maximum emission wavelength 439nm；
Fig. 8 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 8 μM of Cu2+Afterwards, then be separately added into various concentrations cyanide ion (1 μM, 5 μM, 10 μM, 20 μM, 25 μM,
30 μM) its most at big launch wavelength 439nm fluorescence intensity with different cyanide ion concentration linear relationships；
Fig. 9 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μM
Schiff bases 1, first adds 8 μM of Cu2+Afterwards, then 50 μM of cyanide ions are separately added into or 50 μM of other anion are separately added into (be followed successively by
S2-, SCN-, SO3 2-, SO4 2-, S2O3 2-, ClO4 -, P2O4 2-, CO3 2-, HCO3 2-, Cl-, Br-, I-, NO2 -, NO3 -, CH3COO-) fluorescence
Strength Changes figure；
Figure 10 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μ
M schiff bases 1, first adds 8 μM of Cu2+Afterwards, then with various anion the fluorescence block diagram acted on；Black post：Schiff bases 1 adds 50 μ
The change of fluorescence after the other anion of M under its maximum emission wavelength 439nm；Grey post：Schiff bases 1 adds 50 μM of other the moon
The change of fluorescence after ion and 50 μM of cyanide ions under its maximum emission wavelength 439nm, from left to right S successively2-, SCN-,
SO3 2-, SO4 2-, S2O3 2-, ClO4 -, P2O4 2-, CO3 2-, HCO3 2-, Cl-, Br-, I-, NO2 -, NO3 -, CH3COO-；
Figure 11 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μ
M schiff bases 6, first adds 20 μM of Cu2+Afterwards, then it is separately added into 1 μM, 10 μM, 20 μM, 30 μM, 40 μM of cyanide ions, it is in maximum
Launch wavelength fluorescence intensity at 399nm changes with time figure；
Figure 12 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in, concentration is 1 μ
M schiff bases 6, first adds 20 μM of Cu2+Afterwards, cyanide ion (1 μM, 10 μM, 20 μM, 30 μM, 40 μ of various concentrations are being separately added into
M) its maximum emission wavelength at 399nm fluorescence intensity with different cyanide ion concentration linear relationships；
Figure 13 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 2, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, after 7 minutes, after 8 minutes, after 9 minutes, the variation diagram of the fluorescence intensity after 10 minutes；
Figure 14 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 7, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, after 7 minutes, after 8 minutes, after 9 minutes, after 10 minutes, after 11 minutes, fluorescence intensity after 12 minutes
Variation diagram；
Figure 15 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 3, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, after 7 minutes, after 8 minutes, after 9 minutes, after 10 minutes, after 11 minutes, fluorescence intensity after 12 minutes
Variation diagram；
Figure 16 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 8, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, the variation diagram of the fluorescence intensity after 7 minutes；
Figure 17 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 4, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, after 7 minutes, the variation diagram of the fluorescence intensity after 8 minutes；
Figure 18 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 9, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, after 7 minutes, after 8 minutes, after 9 minutes, the variation diagram of the fluorescence intensity after 10 minutes；
Figure 19 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 5, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 2 minutes, after 3 minutes, after 4 minutes, 5
After minute, after 6 minutes, after 7 minutes, after 8 minutes, after 9 minutes, after 10 minutes, after 11 minutes, after 12 minutes, after 13 minutes, 14
After minute, after 15 minutes, the variation diagram of the fluorescence intensity after 16 minutes；
Figure 20 is the mixed system (v in acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) concentration is added in
For 1 μM of schiff bases 10, first add after 20 μM of cyanide ions, add 20 μM of copper ions, after 10 minutes, after 15 minutes, 20 minutes
Afterwards, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, the variation diagram of the fluorescence intensity after 50 minutes.
5th, embodiment：
Schiff base compound, it is characterised in that its structural formula of such schiff bases is：
Such described schiff base compounds are in phosphate buffer (10mM, pH=7.4) and acetonitrile (v:V=1:2) mixed
The application of cyanide ion and copper ion fluorescence probe is used as in zoarium system.
Background fluorescence itself is weaker at low concentrations for such schiff base compounds, and cyanide ion is used as the extremely strong parent of nucleophilicity
Core reagent can be with the carbon-to-nitrogen double bon of attack schiff bases, while generation can send the cyclization of hyperfluorescence under the effect of oxidisability copper ion
Product.
Such schiff base compounds only have fluorescence response to cyanide ion and copper ion, for other anion and metal
Cation does not have fluorescence response.This kind of schiff base compounds can specifically in fluoroscopic examination solution cyanide ion and copper from
Son, such as following synthesis type：
The schiff bases 1-10 of synthesis is dissolved into anhydrous acetonitrile and is made into 1mM mother liquors；Potassium cyanide solid dissolving is to going
10mM cyanide ion solution is made into ionized water；It is molten that Salzburg vitriol solid dissolving is made into 10mM copper ions into deionized water
Liquid.
9 kinds of embodiments given below, specifically with schiff bases 1 and schiff bases 6 this two groups of testers for cyanide ion and copper
Ion detection is described in detail, and other several groups of compounds are according to the results show, and its effect is completely similar.
Embodiment one：(the X=OH of schiff base compounds 1；R1=OCH3；R2=t-Bu) cyanide ion and copper ion are responded
Time series analysis
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, fluorescence intensity, adding solution after schiff bases 1 does not almost have fluorescence；Add the 10mM cyanogen roots of 6 μ L preparations
Ion, fluorescence intensity change, fluorescence intensity is almost unchanged；Add the 10mM copper ions of 6 μ L preparations, fluorescence intensity
Change, fluorescence intensity is remarkably reinforced.And change fluorescence intensity over time gradually strengthens, the fluorescence when the time reaching 4 minutes
Intensity tends towards stability (see Fig. 1).
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, after the 10mM cyanide ions for adding 6 μ L preparations, then it is 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 to be separately added into concentration
μM, 7 μM, 8 μM, 9 μM, 10 μM of copper ions, detection fluorescence intensity at its maximum emission wavelength 439nm changes with time, when
Fluorescence intensity is substantially achieved when the copper ion concentration of addition reaches 8 μM keeps constant (see Fig. 3) after maximum, and 4 minutes.
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, after the 10mM copper ions for adding 2.4 μ L preparations, then it is 1 μM, 5 μM, 10 μM, 20 μM, 25 μ to be separately added into concentration
M, 30 μM, 40 μM of cyanide ions, detection fluorescence intensity at its maximum emission wavelength 439nm changes with time, when addition
Fluorescence intensity is substantially achieved when cyanide ion concentration reaches 30 μM keeps constant (see Fig. 7) after maximum, and 6 minutes.
Embodiment two：(the X=OH of schiff base compounds 1；R1=OCH3；R2=t-Bu) quantitative detection application to copper ion
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, after the 10mM cyanide ions for adding 6 μ L preparations, then copper ion (1 μM, 2 μM, 3 μ of various concentrations are separately added into
M, 4 μM, 5 μM, 6 μM), detection fluorescence intensity at maximum emission wavelength 439nm under different copper ion concentrations obtains linear relationship
Figure is (see Fig. 4).The concentration of copper ion is that fluorescence intensity is the longitudinal axis at transverse axis (unit is μ Μ), 439nm.Wherein fluorescence intensity (y)
A linear equation is met with copper ion concentration (X)：Y=-113.79+113.5 × x, correlation coefficient r=0.966.Schiff alkalizes
(the X=OH of compound 1；R1=OCH3；R2=t-Bu) available for the quantitative detection application to copper ion.
Embodiment three：(the X=OH of schiff base compounds 1；R1=OCH3；R2=t-Bu) should to the quantitative detection of cyanide ion
With
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, add 2.4 μ L preparation 10mM copper ions after, then be separately added into various concentrations cyanide ion (1 μM, 5 μM,
10 μM, 20 μM, 25 μM, 30 μM), detection fluorescence intensity at maximum emission wavelength 439nm under different cyanide ion concentration is obtained
Linear relationship chart (see Fig. 8).The concentration of cyanide ion is that fluorescence intensity is the longitudinal axis at transverse axis (unit is μ Μ), 439nm.Wherein
Fluorescence intensity (y) meets a linear equation with cyanide ion concentration (X)：Y=-0.022+12.855 × x, correlation coefficient r=
0.985.(the X=OH of schiff base compounds 1；R1=OCH3；R2=t-Bu) available for the quantitative detection application to cyanide ion.
Example IV：(the X=OH of schiff base compounds 1；R1=OCH3；R2=t-Bu) to copper ion selective enumeration method application
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, the 10mM cyanide ions of 6 μ L preparations are added, the 10mM copper ions of 2.4 μ L preparations is added or is separately added into 3 μ
L concentration is the other metal cation (Al of 10mM3+, Ba2+, Ca2+, Cd2+, Co2+, Fe2+, Fe3+, K+, Mg2+, Mn2+, Ni2+, Pb2+,
Zn2+, Cr3+, Li+, Na+, Hg2+), fluorescence intensity changes (see Fig. 5), only adds the enhancing of copper ion fluorescence intensity.Take 3 μ L
The mother liquor of schiff bases 1 is added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in 3mL, then add
Enter the 10mM cyanide ions of 6 μ L preparations, then be separately added into 3 μ L concentration for other metal cations of the 10mM in addition to copper ion
(Al3+, Ba2+, Ca2+, Cd2+, Co2+, Fe2+, Fe3+, K+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+, Cr3+, Li+, Na+, Hg2+), detection
Fluorescence intensity change, black post is to add other metal cation fluorescence intensity levels at maximum emission wavelength 439nm；Take 3 μ L
The mother liquor of schiff bases 1 is added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1) in 3mL, then add
Enter 6 μ L preparation 10mM cyanide ions, then be separately added into 3 μ L preparation the other metal cations of 10mM and 1.5 μ L prepare
10mM copper ions, fluorescence intensity change, grey post is to add other metal cations and copper ion in maximum emission wavelength
Fluorescence intensity level at 439nm (see Fig. 6).In the mixing of the acetonitrile containing cyanide ion and phosphate buffer (10mM, pH=7.4)
In system, (the X=OH of schiff bases 1；R1=OCH3；R2=t-Bu) it can be used for copper ion selective enumeration method application.
Embodiment five：(the X=OH of schiff base compounds 1；R1=OCH3；R2=t-Bu) should to cyanide ion selective enumeration method
With
The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, the 10mM copper ions of 2.4 μ L preparations are added, then are separately added into the 10mM cyanide ions or difference of 15 μ L preparations
15 μ L concentration are added for the other anion (S of 10mM2-, SCN-, SO3 2-, SO4 2-, S2O3 2-, ClO4 -, P2O4 2-, CO3 2-, HCO3 2-,
Cl-, Br-, I-, NO2 -, NO3 -, CH3COO-), fluorescence intensity changes (see Fig. 9), only adds cyanide ion fluorescence intensity and increases
By force.The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1)
In 3mL, the 10mM copper ions of 2.4 μ L preparations are added, then it is its in addition to cyanide ion of 10mM to be separately added into 15 μ L concentration
Its anion (S2-, SCN-, SO3 2-, SO4 2-, S2O3 2-, ClO4 -, P2O4 2-, CO3 2-, HCO3 2-, Cl-, Br-, I-, NO2 -, NO3 -,
CH3COO-), fluorescence intensity change, black post is to add other anion fluorescence intensities at maximum emission wavelength 439nm
Value；The mother liquor of 3 μ L schiff bases 1 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1)
In 3mL, add 2.4 μ L preparation 10mM copper ions, then be separately added into 15 μ L preparation the other anion of 10mM and 15 μ L match somebody with somebody
The 10mM cyanide ions of system, fluorescence intensity change, grey post is to add other anion and cyanide ion in emission maximum
Fluorescence intensity level at wavelength 439nm (see Figure 10).In the acetonitrile containing copper ion and phosphate buffer (10mM, pH=7.4)
In mixed system, (the X=OH of schiff bases 1；R1=OCH3；R2=t-Bu) it can be used for cyanide ion selective enumeration method application.
Embodiment six：(the X=OH of schiff base compounds 6；R1=H；R2=t-Bu) to cyanide ion and copper ion response time
Analysis
The mother liquor of 3 μ L schiff bases 6 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, fluorescence intensity, adding solution after schiff bases 6 does not almost have fluorescence；Add the 10mM cyanogen roots of 6 μ L preparations
Ion, fluorescence intensity change, fluorescence intensity is almost unchanged；Add the 10mM copper ions of 6 μ L preparations, fluorescence intensity
Change, fluorescence intensity is remarkably reinforced.And change fluorescence intensity over time gradually strengthens, the fluorescence when the time reaching 10 minutes
Intensity tends towards stability (see Fig. 2).The mother liquor of 3 μ L schiff bases 6 is taken to be added to the mixed of acetonitrile and phosphate buffer (10mM, pH=7.4)
Zoarium system (v:V=2:1) in 3mL, after the 10mM copper ions for adding 6 μ L preparations, then it is 1 μM, 10 μM, 20 to be separately added into concentration
μM, 30 μM, 40 μM of cyanide ions, detection fluorescence intensity at its maximum emission wavelength 399nm changes with time (see Figure 11),
As cyanide ion concentration increase fluorescence intensity gradually strengthens, when cyanide ion concentration reaches that 40 μM of fluorescence intensities are substantially achieved
Keep constant after maximum, and 4 minutes.
Embodiment seven：(the X=OH of schiff base compounds 6；R1=H；R2=t-Bu) quantitative detection application to cyanide ion
The mother liquor of 3 μ L schiff bases 6 is taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=
2:1) in 3mL, the 10mM copper ions of 6 μ L preparations are added, then are separately added into cyanide ion (1 μM, 10 μM, 20 μ of various concentrations
M, 30 μM, 40 μM), detection fluorescence intensity at maximum emission wavelength 399nm under different cyanide ion concentration obtains linear relationship
Figure is (see Figure 12).The concentration of cyanide ion is that fluorescence intensity is the longitudinal axis at transverse axis (unit is μ Μ), 399nm.Wherein fluorescence intensity
(y) a linear equation is met with cyanide ion concentration (X)：Y=-0.54+3.679 × x, correlation coefficient r=0.963.Schiff
(the X=OH of alkali cpd 6；R1=H；R2=t-Bu) available for the quantitative detection application to cyanide ion.
Embodiment eight：Other schiff base compounds are to cyanide ion and copper ion response time analysis
Other schiff bases are identical with the process of embodiment one for cyanide ion and copper ion response time detection method, point
The other Schiff alkali liquors of 3 μ L are not taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:1)
In 3mL, fluorescence intensity；Add the 10mM cyanide ions fluorescence intensity change of 6 μ L preparations；Add 6 μ L preparations
10mM copper ions fluorescence intensity change, increase over time respectively detection different time under fluorescence intensity change,
Until fluorescence intensity reaches stabilization (see Figure 13-Figure 20).Except 20 minutes 5 response times of schiff bases, the response time of schiff bases 10
50 minutes outer, and the response of schiff bases 2,3,4,7,8 and 9 is all relatively rapider, and fluorescence intensity all tends towards stability at 10 minutes.
Embodiment nine：Schiff base compounds are to cyanogen root and copper ion response property research
3 μ L Schiff alkali liquors are taken to be added to the mixed system (v of acetonitrile and phosphate buffer (10mM, pH=7.4):V=2:
1) in 3mL, the 10mM cyanide ions of 6 μ L preparations are added, the 10mM copper ions of 6 μ L preparations are added, by detecting that fluorescence is strong
Degree change, obtains glimmering under the excitation wavelength and maximum emission wavelength of such schiff base compounds, corresponding maximum emission wavelength
Luminous intensity no longer change needs shortest time and under corresponding maximum emission wavelength fluorescence intensity intensification factor (see
Table 1).High performance liquid chromatography (mobile phase：Acetonitrile/water (v:V=8:2)；Detector：Schiff base compounds 365nm) are detected respectively
Effect of the 1-10 retention time and schiff base compounds with the cyanide ion and copper ion of 50 times of concentration in test system is closed
The retention time of ring product, calculates peak area ratio under different retention times and calculates generation oxidative cyclization product yield, except
The conversion ratio 30% or so of schiff bases 2 and 7, the conversion ratio of other schiff bases all reaches more than 70% (being shown in Table 1).
The first two columns of table 1 is correspondence schiff base compounds 1-10 maximum excitation and launch wavelength；The row of centre one are to pass through
High performance liquid chromatography (mobile phase：Acetonitrile/water (v:V=8:2)；Detector：365nm) to schiff base compounds 1-10 (1 μM) and
Schiff base compounds are in acetonitrile and the mixed system (v of phosphate buffer (10mM, pH=7.4):V=2:1) cyanogen in 50 μM
The analysis of cyclization product after radical ion and the effect of 50 μM of copper ion, i.e., it is worth according to peak area ratio under different retention times is calculated
Corresponding cyclization oxidation product conversion ratio is generated to schiff bases；Most next two columns are in acetonitrile and phosphate buffer (10mM, pH=
7.4) mixed system (v:V=2:1) in, the concentration of schiff bases is 1 μM, after 20 μM of cyanide ions and 20 μM of copper ions are added
Fluorescence intensity under corresponding maximum emission wavelength no longer change needs shortest time and in corresponding emission maximum
Fluorescence intensity intensification factor under wavelength.
Table 1
In summary, such schiff base compounds of the invention have in test system for cyanide ion and copper ion
Response sensitivity and selectivity, can be applied to external to cyanide ion and copper ion detection well.It should be appreciated that appended right
It is required that the scope of the present invention is summarised, under the guiding of present inventive concept, it should be appreciated by one skilled in the art that, to the present invention
The certain change that is carried out of each embodiment scheme, will all be covered by present disclosure.
Claims (4)
1. schiff base compound is used as the application of cyanide ion and copper ion fluorescence probe.
2. schiff base compound according to claim 1 is as the application of cyanide ion and copper ion fluorescence probe,
It is characterized in that：Such described schiff base compounds in the mixed system of phosphate buffer and acetonitrile as cyanide ion and
The application of copper ion fluorescence probe.
3. schiff base compound according to claim 1 or 2 should as cyanide ion and copper ion fluorescence probe
With, it is characterised in that：Its structural formula of such schiff bases is：
4. schiff base compound according to claim 3 is as the application of cyanide ion and copper ion fluorescence probe,
It is characterized in that：The pH=7.4 of described phosphate buffer, concentration is 10mM, and the volume ratio of phosphate buffer and acetonitrile is 1:
2。
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| CN114085206A (en) * | 2021-11-21 | 2022-02-25 | 福州市第二医院（福建省福州中西医结合医院、福州市职业病医院） | 2, 5-thiophene-dimethyl acetal 2-amino-4-methylphenol Schiff base and preparation method and application thereof |
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