CN113514511B - Preparation of porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence - Google Patents
Preparation of porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence Download PDFInfo
- Publication number
- CN113514511B CN113514511B CN202110416311.6A CN202110416311A CN113514511B CN 113514511 B CN113514511 B CN 113514511B CN 202110416311 A CN202110416311 A CN 202110416311A CN 113514511 B CN113514511 B CN 113514511B
- Authority
- CN
- China
- Prior art keywords
- metal organic
- functional metal
- organic framework
- porphyrin
- tcpp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- 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
- G01N21/76—Chemiluminescence; Bioluminescence
Abstract
The invention discloses preparation of a porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence. FeCl is added 3 ·6H 2 O and 2-amino terephthalic acid are dissolved in DMF, and are subjected to hydrothermal reaction at 110-120 ℃ for 40-48 h, and then cooled to room temperature, centrifuged, washed and dried to obtain amino functional metal organic framework NH 2 -MILs (Fe); dissolving an amino functional metal organic framework and tetra-carboxyl phenyl porphyrin (TCPP) in DMF, performing hydrothermal reaction at 110-120 ℃ for 12-14 h, centrifuging, washing and drying to obtain a porphyrin modified amino functional metal organic framework TCPP@NH 2 ‑MIL（Fe）。NH 2 MIL (Fe) can be used as a coreactant to promote coreactant S 2 O 8 2‑ Thereby generating a large amount of ECL reaction intermediate SO near TCPP 4 •‑ Shortening SO 4 •‑ The distance between the light source and the excited state of the TCPP is less, so that the ECL signal of the TCPP is greatly enhanced, and the water solubility and the electrochemiluminescence intensity of the TCPP are well improved.
Description
Technical Field
The invention belongs to the field of electrochemiluminescence, and relates to preparation of an amino functional metal organic framework modified by porphyrin and application of the amino functional metal organic framework in electrochemiluminescence.
Background
Effective coreactant S 2 O 8 2- ECL signal of TCPP can be greatly enhanced because S can be reduced electrochemically 2 O 8 2- Production of important ECL reaction intermediate SO 4 •- . However, S 2 O 8 2- Is limited in solubility of the formed SO 4 •- Unstable in aqueous solutions. SO leading to reaction with TCPP 4 •- The concentration was low and ECL signal was unsatisfactory. Therefore, in order to obtain a satisfactory ECL signal, it is necessary to find a method of inducing not only S 2 O 8 2- Decomposition into SO 4 •- And shorten SO 4 •- Distance from the excited state of TCPP. In the ECL field, metal-organic frameworks are promising sensing materials due to their high loading capacity, large surface area and adjustable pore structure.
Disclosure of Invention
The invention aims to provide a preparation method of a porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence.
1. Preparation of porphyrin modified amino functional metal organic framework
The preparation method of the porphyrin modified amino functional metal organic framework comprises the following steps:
(1) FeCl is added 3 ·6H 2 O and 2-amino terephthalic acid are dissolved in DMF, and are subjected to hydrothermal reaction at 110-120 ℃ for 40-48 h, and then cooled to room temperature, centrifuged, washed and dried to obtain amino functional metal organic framework NH 2 MILs (Fe). Wherein FeCl 3 ·6H 2 The mass ratio of O to 2-amino terephthalic acid is 1:1-1:1.5; and the drying is carried out in a vacuum oven at 60-70 ℃ for 10-12 hours.
(2) Dissolving an amino functional metal organic framework and tetra-carboxyl phenyl porphyrin in DMF, reacting for 12-14 h at 110-120 ℃, centrifuging, washing and drying to obtain a porphyrin modified amino functional metal organic framework TCPP@NH 2 MILs (Fe). Wherein the amino functional metal organicThe mass ratio of the framework to the tetracarboxyl phenyl porphyrin is 1:1.
2. Characterization of porphyrin-modified amino-functional metal-organic frameworks
1、SEM
NH 2 MIL (Fe) (a) and TCPP@NH 2 The scanning electron microscope of MIL (Fe) (b) is shown in FIG. 1. As can be seen from the SEM image, NH was prepared 2 Scanning electron microscopy of MILs (Fe) has a typical octahedral morphology with smooth surfaces; TCPP@NH 2 The MIL (Fe) surface became rough, loaded with small particles, indicating that TCPP was successfully loaded on NH 2 On MIL (Fe), it was demonstrated that TCPP@NH 2 Successful preparation of MILs (Fe).
2. Infrared spectrum
NH 2 MIL (Fe) and TCPP@NH 2 The IR spectrum of MIL (Fe) is shown in FIG. 2. From the infrared spectrum, it can be seen that TCPP@NH 2 MIL (Fe) and NH 2 Compared with the infrared spectrum of MIL (Fe), the peak intensity near 3500nm is obviously enhanced, which proves that TCPP is successfully loaded and the structure of the amino-functionalized metal-organic framework is not destroyed, which proves that TCPP@NH 2 MILs (Fe) synthesis was successful.
3. Fluorescence spectrum
NH 2 MIL (Fe) and TCPP@NH 2 The fluorescence spectrum of MIL (Fe) is shown in FIG. 3. As can be seen from the fluorescence spectrum, NH 2 MIL (Fe) has blue fluorescence at 430nm, TCPP has emission peaks at 650nm and 720nm under excitation of 400nm, TCPP@NH 2 In the emission spectrum of MIL (Fe), it can be seen that it has TCPP and NH at 440, 640 and 720nm 2 Characteristic emission of MIL (Fe), and TCPP@NH 2 The characteristic emission peak of TCPP in MIL (Fe) is slightly Lan Yi compared to the original TCPP, indicating TCPP@NH 2 Successful preparation of MILs (Fe).
3. TCPP@NH 2 Application of MIL (Fe) in electrochemiluminescence system
Porphyrin modified amino functional metal organic skeleton is used as a coreaction promoter and a luminescent reagent, and K is used as 2 S 2 O 8 As a co-reactant, the buffer solution is phosphate, ag/AgCl is used as a reference electrode, a platinum electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode to construct an electrochemiluminescence system. The concentration of the porphyrin modified amino functional metal organic framework is 1mg/mL. K (K) 2 S 2 O 8 The concentration of (2) is 0.1-0.2M. The pH value of the phosphate buffer solution is 7-7.5. Between the potential window range of-0.2 and-1.6V, the TCPP@NH is studied 2 Electrochemiluminescence intensity and ECL performance of MILs (Fe).
TCPP@ NH 2 The electrochemiluminescence intensity profile of MILs (Fe) is shown in fig. 4. It can be seen that TCPP has an ECL strength of 4000 and TCPP@NH 2 The ECL strength of MIL (Fe) was 12000, 3 times that of TCPP, demonstrating the use of NH 2 MILs (Fe) as a co-reaction promoter increases ECL strength of TCPP in aqueous phase.
TCPP@ NH 2 The stability of MIL (Fe) is shown in FIG. 5. At K 2 S 2 O 8 At a concentration of 0.1m, ph=7 in pbs, tcpp with NH 2 -MILs (Fe) concentration ratio of 1: under 1, TCPP@NH is obtained 2 -MIL（Fe）/ K 2 S 2 O 8 Electrochemiluminescence intensity-time diagram of system continuously scanned for 20 circles, TCPP@NH 2 -MIL（Fe）/ K 2 S 2 O 8 The cathodic ECL strength of the system was relatively stable with a relative standard deviation of 0.69%.
In summary, the preparation method is simple and has good water solubility and stability. The TCPP modified amino-functional metal organic framework not only can increase the load of TCPP, but also can be used as a coreactant to promote coreactant S 2 O 8 2- Thereby generating a large amount of ECL reaction intermediate SO near TCPP 4 •- Thereby shortening SO 4 •- The distance from the excited state of TCPP,and the energy loss is small, so that the ECL signal of the TCPP is greatly amplified, and the water solubility and the electrochemiluminescence intensity of the TCPP are well improved.
Drawings
FIG. 1 is NH 2 -MIL（Fe）（a）、TCPP@ NH 2 SEM image of MILs (Fe) (b).
FIG. 2 is TCPP, NH 2 -MIL（Fe），TCPP@ NH 2 -infrared spectrogram of MILs (Fe).
FIG. 3 is TCPP, NH 2 -MIL（Fe），TCPP@ NH 2 Fluorescence spectrum of MILs (Fe).
FIG. 4 is TCPP, NH 2 -MIL（Fe），TCPP@ NH 2 Electrochemiluminescence intensity plot of MILs (Fe).
FIG. 5 is TCPP@NH 2 -stability profile of MILs (Fe).
Detailed Description
The preparation of the porphyrin modified amino functional metal organic framework and the application thereof in electrochemiluminescence are further described below by specific embodiments.
EXAMPLE 1 preparation of porphyrin-modified amino-functional Metal organic frameworks
(1) 0.2703g FeCl 3 ·6H 2 O and 0.1811g of 2-amino terephthalic acid are dissolved in 10ml of DMF, the mixture is subjected to hydrothermal reaction at 110-120 ℃ for 40-48 h, then the mixture is cooled to room temperature, precipitate is separated from the mixture by centrifugation, and the mixture is washed with DMF and ethanol for 3 times respectively; finally, drying the obtained solid in a vacuum oven at 60-70 ℃ for 10-12 hours to obtain NH 2 -MIL（Fe）。
(2) Dissolving 0.3g of amino functional metal organic framework and 0.3g of tetra-carboxyl phenyl porphyrin in 6ml of DMF, reacting for 12-14 h at 110-120 ℃, centrifuging, washing and drying to obtain porphyrin modified amino functional metal organic framework TCPP@NH 2 -MIL（Fe）。
EXAMPLE 2 TCPP@NH 2 Application of MIL (Fe) in electrochemiluminescence system
(1) Characterization of Glassy Carbon Electrode (GCE)
Sample solution: configuration of0.1M potassium ferricyanide K 3 [Fe(CN) 6 ]Potassium ferrocyanide (K) 4 [Fe(CN) 6 ]) The solution was ready for use.
The glassy carbon electrode is characterized firstly, so that the electrode is ensured to be clean, and the experimental accuracy is improved. The glassy carbon surface of the glassy carbon electrode was polished on a cloth sequentially with 0.3 μm and 0.05 μm alumina abrasive grains, and then the remaining abrasive grains were rinsed with ultrapure water. Electrochemical characterization of working electrode by cyclic voltammetry scanning, 0.1-0.2M potassium ferricyanide K 3 [Fe(CN) 6 ]Potassium ferrocyanide (K) 4 [Fe(CN) 6 ]) In the solution, ag/AgCl is used as a reference electrode, a platinum electrode is used as a counter electrode, a glassy carbon electrode is used as a working electrode to form a three-electrode system, the three-electrode system is scanned between a potential window of-0.2V and 0.6V, and experimental results show that the potential difference between the oxidation peak potential and the reduction peak potential is 75mV, so that the electrode is completely treated, and the ECL performance test can be used for subsequent experiments.
(2) Electrochemical and ECL test procedure
The well characterized electrodes were used for ECL and electrochemical tests, and K containing 0.1M was added to the cell 2 S 2 O 8 5mL of phosphate buffer solution (PBS, pH=7) as a coreactant was added with 0.1mL of 1mg/mL of TCPP@NH 2 The TCPP@NH was studied in the range of-0.2 to-1.6V in the presence of an aqueous solution of MIL (Fe) 2 Electrochemiluminescence intensity and ECL performance of MILs (Fe). TCPP@NH 2 The electrochemiluminescence intensity of MIL (Fe) is 3 times that of TCPP, and the MIL (Fe) has good stability and reproducibility.
Claims (8)
1. A preparation method of porphyrin modified amino functional metal organic framework comprises the following steps:
(1) FeCl is added 3 ·6H 2 O and 2-amino terephthalic acid are dissolved in DMF, and are subjected to hydrothermal reaction at 110-120 ℃ for 40-48 h, and then cooled to room temperature, centrifuged, washed and dried to obtain amino functional metal organic framework NH 2 -MIL（Fe）；
(2) Dissolving amino functional metal organic skeleton and tetracarboxyl phenyl porphyrin in DMF, dissolving inReacting for 12-14 h at 110-120 ℃, centrifuging, washing and drying to obtain porphyrin modified amino functional metal organic framework TCPP@NH 2 -MIL（Fe）。
2. The method for preparing the porphyrin modified amino-functional metal organic framework according to claim 1, wherein the method comprises the following steps: in step (1), feCl 3 ·6H 2 The mass ratio of O to 2-amino terephthalic acid is 1:1-1:1.5.
3. The method for preparing the porphyrin modified amino-functional metal organic framework according to claim 1, wherein the method comprises the following steps: in the step (1), the drying is carried out in a vacuum oven at 60-70 ℃ for 10-12 hours.
4. The method for preparing the porphyrin modified amino-functional metal organic framework according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the amino functional metal organic framework to the tetracarboxyl phenyl porphyrin is 1:1.
5. Use of the porphyrin modified amino-functional metal organic framework prepared by the preparation method according to any one of claims 1-4 in an electrochemiluminescence system, characterized in that: porphyrin modified amino functional metal organic skeleton is used as a coreaction promoter and a luminescent reagent, and K is used as 2 S 2 O 8 As a co-reactant, the buffer solution is phosphate, ag/AgCl is used as a reference electrode, a platinum electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode to construct an electrochemiluminescence system.
6. The use of the porphyrin-modified amino-functional metal organic framework according to claim 5 in an electrochemiluminescence system, wherein: the concentration of the porphyrin modified amino functional metal organic framework is 1mg/mL.
7. The use of the porphyrin-modified amino-functional metal organic framework according to claim 5 in an electrochemiluminescence system, characterized in thatThe method comprises the following steps: k (K) 2 S 2 O 8 The concentration of (2) is 0.1-0.2M.
8. The use of the porphyrin-modified amino-functional metal organic framework according to claim 5 in an electrochemiluminescence system, wherein: the pH value of the phosphate buffer solution is 7-7.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110416311.6A CN113514511B (en) | 2021-04-19 | 2021-04-19 | Preparation of porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110416311.6A CN113514511B (en) | 2021-04-19 | 2021-04-19 | Preparation of porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113514511A CN113514511A (en) | 2021-10-19 |
| CN113514511B true CN113514511B (en) | 2023-08-29 |
Family
ID=78062869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110416311.6A Active CN113514511B (en) | 2021-04-19 | 2021-04-19 | Preparation of porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113514511B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368579B (en) * | 2022-07-05 | 2023-06-27 | 南京大学 | Preparation method and application of nano-enzyme with manganese porphyrin as metal organic framework |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106950219A (en) * | 2017-04-21 | 2017-07-14 | 西北师范大学 | A kind of ECL new systems are to Fe3+Detection method |
| CN106955739A (en) * | 2017-03-22 | 2017-07-18 | 西北师范大学 | A kind of redox graphene/porphyrin/platinum nano composite material and its preparation and application |
| CN109575912A (en) * | 2018-11-26 | 2019-04-05 | 西北师范大学 | A method of enhancing tetracarboxylic phenyl porphyrin electrochemical luminescence intensity |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017052474A1 (en) * | 2015-09-23 | 2017-03-30 | Nanyang Technological University | A metal-organic framework nanosheet |
-
2021
- 2021-04-19 CN CN202110416311.6A patent/CN113514511B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106955739A (en) * | 2017-03-22 | 2017-07-18 | 西北师范大学 | A kind of redox graphene/porphyrin/platinum nano composite material and its preparation and application |
| CN106950219A (en) * | 2017-04-21 | 2017-07-14 | 西北师范大学 | A kind of ECL new systems are to Fe3+Detection method |
| CN109575912A (en) * | 2018-11-26 | 2019-04-05 | 西北师范大学 | A method of enhancing tetracarboxylic phenyl porphyrin electrochemical luminescence intensity |
Non-Patent Citations (1)
| Title |
|---|
| Ji Zhou 等.A novel approach to prepare polyaniline/Polypyrrole@Cu-BTC/NH2-MIL-101(Fe) MOFs for electromagnetic wave absorption.《Ceramics International》.2020,第46卷19758–19766. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113514511A (en) | 2021-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Recent advances in co-reaction accelerators for sensitive electrochemiluminescence analysis | |
| CN107478621B (en) | Metabolizable generation H in quantitative detection serum2O2Biomolecule method | |
| Zhang et al. | Zirconium–metalloporphyrin frameworks as a three-in-one platform possessing oxygen nanocage, electron media, and bonding site for electrochemiluminescence protein kinase activity assay | |
| Tse et al. | Electrocatalysis of dihydronicotinamide adenosine diphosphate with quinones and modified quinone electrodes | |
| CN109651621B (en) | Zirconium-based metal organic framework composite material and preparation method and application thereof | |
| CN113514511B (en) | Preparation of porphyrin modified amino functional metal organic framework and application thereof in electrochemiluminescence | |
| CN107325095B (en) | A kind of lysosome hypochlorous acid fluorescence probe and its preparation method and application | |
| Li et al. | Self-enhanced electrogenerated chemiluminescence of ruthenium (II) complexes conjugated with Schiff bases | |
| Geng et al. | Instant hydrogel formation of terpyridine-based complexes triggered by DNA via non-covalent interaction | |
| Sandroni et al. | Iridium and ruthenium complexes covalently bonded to carbon surfaces by means of electrochemical oxidation of aromatic amines | |
| Kosov et al. | Novel phenyl-substituted pyrazinoporphyrazine complexes of rare-earth elements: Optimized synthetic protocols and physicochemical properties | |
| Zhao et al. | Host–guest recognition coupled with triple signal amplification endows an electrochemiluminescent biosensor with enhanced sensitivity | |
| Xu et al. | BODIPY-based metal–organic frameworks as efficient electrochemiluminescence emitters for telomerase detection | |
| Ji et al. | A sensitive dual-signal electrochemiluminescence immunosensor based on Ru (bpy) 3 2+@ HKUST-1 and Ce 2 Sn 2 O 7 for detecting the heart failure biomarker NT-proBNP | |
| Wang et al. | Doubly N-confused phlorin and phlorinone analogue | |
| Wu et al. | Catalytic hairpin assembly coupled with Ir (III) complex sensitization strategy for split-type photoelectrochemical biosensing | |
| Orman et al. | Novel 2, 6-dimethoxyphenoxy alpha substituted phthalocyaninato metal complexes: Electrochemistry, In situ spectroelectrochemistry and oxygen electrocatalysis | |
| Wu et al. | Ruthenium–bipyridine complexes bearing fullerene or carbon nanotubes: synthesis and impact of different carbon-based ligands on the resulting products | |
| CN106349248B (en) | A kind of Metalloporphyrins and its preparation method and application | |
| CN110441379A (en) | A kind of glucose sensor and preparation method thereof of the derivative NiC of Ni-MOF | |
| Huang et al. | Fabrication of new magnetic nanoparticles (Fe3O4) grafted multiwall carbon nanotubes and heterocyclic compound modified electrode for electrochemical sensor | |
| CN113848201B (en) | Electrochemiluminescence biosensor for detecting ulinastatin | |
| CN114957684A (en) | TCPP (Ni) -Co electrode material and preparation method thereof | |
| CN112903771A (en) | Method for improving luminous intensity of porphyrin ECL system | |
| CN111912888B (en) | Electrochemiluminescence sensor based on eutectic micro-nano material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |