CN109490283A - Application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion - Google Patents
Application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion Download PDFInfo
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- CN109490283A CN109490283A CN201811404476.6A CN201811404476A CN109490283A CN 109490283 A CN109490283 A CN 109490283A CN 201811404476 A CN201811404476 A CN 201811404476A CN 109490283 A CN109490283 A CN 109490283A
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Abstract
The invention discloses application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion, it is to detect fluorine ion using Electrochemiluminescince, and described four (p-hydroxybenzene) porphyrin-β-CD supermolecule is as electrochemical luminescence reagent.The process that Electrochemiluminescince detects fluorine ion includes using four (p-hydroxybenzene) porphyrin-β-CD supermolecules as electrochemical luminescence reagent, K2S2O8For coreagent, fluorine ion and electrochemical luminescence reagent and the mixed electrochemical luminescence intensity of coreagent, ECL intensity and F are detected‑Concentration in 2~100 μm of olL‑1Between there are good linear relationships.Compared with existing Fluoride Analysis, detection method operating process of the invention is simple and convenient, and sensitivity and selectivity are high.
Description
Technical field
The present invention relates to a kind of application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion.
Background technique
Fluorine is one of microelement important in human body, and fluoride is in the form of fluorine ion, and investigation display, fluorine divides extensively
It is distributed in natural water, the major part containing fluorine in human body in bone and tooth, fluoride and human life activity and tooth, bone
Tissue metabolism is closely related.Fluorine is tooth and the indispensable ingredient of bone, and a small amount of fluorine can promote tooth enamel confrontation bacterium
The resistance of sour corrosion, prevents saprodontia.But the excessive intake of fluorine, fluorine ion can be generated with the calcium binding in blood
Insoluble calcirm-fluoride, to further result in hypocalcemia, that is, the fluorine poisoning often said.Therefore, day is fast and accurately detected
The content of fluorine ion is extremely important in regular supplies.In recent years the study found that related electrochemical luminescence (ECL) sensor detect fluorine from
There is the problems such as detection is insensitive, and stability is low in the rare report of document of son.
The supermolecule that cyclodextrin is constructed in conjunction with porphyrin is because having both the superior physics of porphyrin, chemistry and optical signature and ring
The good water-soluble, molecule distinguishability of dextrin and in mimetic enzyme catalysis, life science, medicine controlled releasing, electronic transfer process etc.
Aspect is widely used, as (" spectroscopic methodology studies assembling of the porphyrin large biological molecule in ordered media ", Shanxi is big by Guo Xiliang
Learn, in June, 2004) by by the DMSO solution of (p- hydroxy phenyl) porphyrin of meso- tetra- (THPP) and beta-cyclodextrin, solution
Mixing stands 30min with phosphate buffer Controlled acidity, and successfully assembling obtains THPP- β-CD supermolecule.But it is not related
Cyclodextrin-Porphyrin supermolecule is used for the report of fluorine ion detection.
Summary of the invention
It is an object of the invention to the statuses according to above-mentioned background technique, provide a kind of four (p-hydroxybenzene) porphyrins-
Application of the β-CD supermolecule in detection fluorine ion.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
Application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion, it is characterized in that: using electrification
It learns luminescence method and detects fluorine ion, wherein described four (p-hydroxybenzene) porphyrin-β-CD supermolecule is as electrochemical luminescence reagent.
A kind of method of Electrochemiluminescince detection fluorine ion, comprising: with four (p-hydroxybenzene) porphyrin-β-CD supermolecules
For electrochemical luminescence reagent, K2S2O8For coreagent, detects fluorine ion and electrochemical luminescence reagent and coreagent are mixed
Electrochemical luminescence intensity.The specific steps of the method include:
(1) the fluorine ion standard solution of series of concentrations is prepared；
(2) by four (p-hydroxybenzene) porphyrin-β-CD supermolecules and K2S2O8It is added in phosphate buffer, obtains electrification
Learn luminescence reagent solution；
(3) the fluorine ion standard solution of step (1) is mixed with the electrochemical luminescence reagent solution of step (2), detection electricity
Chemiluminescence intensity obtains the standard curve or linear equation of electrochemical luminescence intensity and fluorinion concentration；
(4) fluoride solution to be measured is mixed with the electrochemical luminescence reagent solution of step (2), detection electrochemical luminescence is strong
Degree, the concentration of fluorine ion in fluoride solution to be measured is obtained by the standard curve or linear equation of step (3).
Preferably, the pH=7.0 of the phosphate buffer.
Preferably, the electrochemical window for detecting electrochemical luminescence intensity is -0.2V~-1.6V.
Four (p-hydroxybenzene) porphyrin-β-CD/K of the present invention2S2O8The ECL intensity and F of system-Concentration in 2~100 μ
mol·L-1Between there are good linear relationships: lnI0/ I=0.1083+0.0122C (F-), coefficient R2=0.9957.With
Existing Fluoride Analysis is compared, and detection method operating process of the invention is simple and convenient, and sensitivity and selectivity are high.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is THPP- β-CD/K2S2O8System and THPP/K2S2O8The ECL intensity contrast figure of system.
Fig. 2 is THPP- β-CD/K2S2O8The ECL stability of 23 circle of system scanning.
Fig. 3 is THPP- β-CD/K2S2O8F is added in system-(illustration is that F is added to the ECL intensity contrast figure of front and back-Front and back
The ratio between natural logrithm of ECL intensity and F-Relational graph between concentration).
Fig. 4 is THPP- β-CD/K2S2O8System is to F-The selectivity of detection.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
(1) preparation of THPP- β-CD supramolecular materials
Four (p-hydroxybenzene) porphyrins (THPP) are dissolved in n,N-Dimethylformamide (DMF), 0.1mmolL is obtained-1
THPP solution.β-CD powder is dissolved in water and is configured to solution, obtains 0.9mmolL-1β-CD solution.500 μ L are above-mentioned
Prepared THPP solution is in 500 μ L, pH=7.0,0.1molL-1After being protonated in phosphate buffer solution, 150 μ L of addition,
0.9mmol·L-1β-CD, shake up, stand 15min, obtain THPP- β-CD supermolecule, it is spare.
(2)F-Concentration Testing
1. glass-carbon electrode is successively used 0.3 μm and 0.05 μm of aluminium oxide powder sanding and polishing by, second distillation is then used
Water rinses, for use.
2. the laboratory uses traditional three-electrode system: naked glass-carbon electrode (GCE, diameter 3.0mm) is as work electricity
Pole, Ag/AgCl electrode (the KCl solution containing saturation) are used as reference electrode, and platinum column electrode is used as to electrode.MPI-A type capillary electricity
Swimming-electrochemiluminescence analysis instrument (purchase is in Xi'an Analytical Instruments Co., Ltd.) is sent out for electrochemistry and electrochemistry
Light experiment.
③.F-The preparation of standard solution: the KF for weighing correct amount is dissolved in water, and is configured to 1mmol·L-1KF it is molten
Liquid, then it is diluted to the standard solution of serial various concentration, it is spare.
4., using the PBS buffer solution of pH=7.0 as supporting electrolyte, liquid-transfering gun accurately pipettes that 100 μ L are above-mentioned successfully to be made
Standby THPP- β-CD supramolecular materials are added 5mL phosphate buffer and (contain 0.1molL-1K2S2O8) in, obtain electrochemistry
Luminescence reagent solution, K2S2O8As coreagent, THPP- β-CD supermolecule detects electrochemistry hair as electrochemical luminescence reagent
The photomultiplier tube bias of light time, electrochemiluminescence analysis instrument are set as 800V, sweep fast 0.1V·S-1, electrochemical window -0.2~-
1.6V。
As shown in Figure 1, under the same conditions, THPP- β-CD/K2S2O8The ECL intensity of system is THPP/K2S2O8System
6 times.
As shown in Fig. 2, THPP- β-CD/K2S2O8The ECL intensity of the circle of system continuous scanning 23 is simultaneously unchanged, shows THPP-
β-CD/K2S2O8With good electrochemical luminescence stability.
5. is by the F of certain volume-Standard solution is mixed with the electrochemical luminescence reagent solution of certain volume, uses electrochemistry
Electrochemical luminescence (ECL) intensity of front and back, the photomultiplier tube bias of electrochemiluminescence analysis instrument is added in luminescence analyzer detection
It is set as 800V, sweeps fast 0.1V·S-1, electrochemical window is in -0.2~-1.6V.
As shown in figure 3, fluorine ion is to THPP- β-CD/K2S2O8The ECL signal of system has quenching effect, and ECL intensity
Concentration with F- is in 2~100 μm of olL-1Between there are good linear relationships: 1nI0/ I=0.1083+0.0122C (F-),
Coefficient R2=0.9957.I0For F is added-Preceding THPP- β-CD/K2S2O8The ECL intensity of system, I are that F is added-THPP- β-afterwards
CD/K2S2O8The ECL intensity of system, C (F-) it is F-Concentration.
6. presses step 5. identical condition, fluoride solution to be measured is mixed with electrochemical luminescence reagent solution, detection electricity
Chemiluminescence intensity utilizes ECL intensity and F-Standard curve (or linear equation) obtain fluorine ion in fluoride solution to be measured
Concentration.
7. is 10mmol.L with concentration-1Interfering ion (Na+、Fe3+、K+、Ca2+、Cl-、Br-、I-Deng) solution substitution F-
Electrochemical luminescence (ECL) intensity of front and back is added in solution, detection interfering ion.
As seen from Figure 4, although the concentration of interfering ion is 10mmolL-1·, the concentration of target detection thing F- is 20 μ
mol·L-1, but F-To THPP- β-CD/K2S2O8Efficiency far is quenched greater than Na in system ECL signal+、Fe3+、K+、Ca2+、
Cl-、Br-、I-Plasma, that is, THPP- β-CD/K2S2O8System is to F-Detecting has very high selectivity, in system simultaneously
Existing above-mentioned ion pair F-Detection does not interfere.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (5)
1. application of four (p-hydroxybenzene) porphyrin-β-CD supermolecules in detection fluorine ion, it is characterised in that: use electrochemistry
Luminescence method detects fluorine ion, wherein described four (p-hydroxybenzene) porphyrin-β-CD supermolecule is as electrochemical luminescence reagent.
2. a kind of method of Electrochemiluminescince detection fluorine ion, comprising: be with four (p-hydroxybenzene) porphyrin-β-CD supermolecules
Electrochemical luminescence reagent, K2S2O8For coreagent, fluorine ion and electrochemical luminescence reagent and the mixed electricity of coreagent are detected
Chemiluminescence intensity.
3. according to the method described in claim 2, it is characterized by: the specific steps of the method include:
(1) the fluorine ion standard solution of series of concentrations is prepared；
(2) by four (p-hydroxybenzene) porphyrin-β-CD supermolecules and K2S2O8It is added in phosphate buffer, obtains electrochemistry hair
Light reagent solution；
(3) the fluorine ion standard solution of step (1) is mixed with the electrochemical luminescence reagent solution of step (2), detects electrochemistry
Luminous intensity obtains the standard curve or linear equation of electrochemical luminescence intensity and fluorinion concentration；
(4) fluoride solution to be measured is mixed with the electrochemical luminescence reagent solution of step (2), detects electrochemical luminescence intensity,
The concentration of fluorine ion in fluoride solution to be measured is obtained by the standard curve or linear equation of step (3).
4. according to the method described in claim 3, it is characterized by: the pH=7.0 of the phosphate buffer.
5. according to the method described in claim 3, it is characterized by: detection electrochemical luminescence intensity electrochemical window be -0.2V~-
1.6V。
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| CN201811404476.6A CN109490283B (en) | 2018-11-23 | 2018-11-23 | Application of tetra (p-hydroxyphenyl) porphyrin-beta-CD supramolecules in detecting fluoride ions |
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| CN201811404476.6A CN109490283B (en) | 2018-11-23 | 2018-11-23 | Application of tetra (p-hydroxyphenyl) porphyrin-beta-CD supramolecules in detecting fluoride ions |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018144A (en) * | 2019-04-17 | 2019-07-16 | 南京理工大学 | Inorganic ions electrochemiluminescdetection detection method based on ZnTCPP@MOF |
| CN111239110A (en) * | 2020-02-10 | 2020-06-05 | 西北师范大学 | Construction method of porphyrin derivative with aggregation-induced emission performance applied to electrochemiluminescence system |
Citations (2)
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| CN102899028A (en) * | 2012-08-03 | 2013-01-30 | 杭州师范大学 | Metering type fluorinion fluorescence probe and preparation method |
| CN103193786A (en) * | 2013-05-07 | 2013-07-10 | 中国工程物理研究院核物理与化学研究所 | Water-soluble fullerene-tetra(p-hydroxy phenyl) porphyrin as well as preparation method and application thereof |
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Patent Citations (2)
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| CN102899028A (en) * | 2012-08-03 | 2013-01-30 | 杭州师范大学 | Metering type fluorinion fluorescence probe and preparation method |
| CN103193786A (en) * | 2013-05-07 | 2013-07-10 | 中国工程物理研究院核物理与化学研究所 | Water-soluble fullerene-tetra(p-hydroxy phenyl) porphyrin as well as preparation method and application thereof |
Non-Patent Citations (2)
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| JING CHEN 等: "Design of a novel naked-eye and turn-on fluorescence sensor based onthe 5,10,15,20-(4-sulphonatophenyl) porphyrin (TPPS4)-Hg2+system:Monitoring of glutathione (GSH) in real samples and DFT calculation", 《SENSORS AND ACTUATORS B》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018144A (en) * | 2019-04-17 | 2019-07-16 | 南京理工大学 | Inorganic ions electrochemiluminescdetection detection method based on ZnTCPP@MOF |
| CN111239110A (en) * | 2020-02-10 | 2020-06-05 | 西北师范大学 | Construction method of porphyrin derivative with aggregation-induced emission performance applied to electrochemiluminescence system |
| CN111239110B (en) * | 2020-02-10 | 2022-07-22 | 西北师范大学 | Construction method of porphyrin derivative with aggregation-induced emission performance applied to electrochemiluminescence system |
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