CN102721732A - Method for determining continuous multi-step electron transfer rate constant of metalloporphyrin complex on liquid-liquid interface - Google Patents
Method for determining continuous multi-step electron transfer rate constant of metalloporphyrin complex on liquid-liquid interface Download PDFInfo
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- CN102721732A CN102721732A CN2012102030159A CN201210203015A CN102721732A CN 102721732 A CN102721732 A CN 102721732A CN 2012102030159 A CN2012102030159 A CN 2012102030159A CN 201210203015 A CN201210203015 A CN 201210203015A CN 102721732 A CN102721732 A CN 102721732A
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Abstract
The invention discloses a method for determining continuous multi-step electron transfer of a metalloporphyrin complex on a liquid-liquid interface. The method comprises the following steps: (1) taking NaClO4 and NaCl as supporting electrolytes, and dissolving K4Fe(CN)6 in water to get a water-phase solution; (2) taking tetrabutyl ammonium perchlorate as the supporting electrolyte, and dissolving the metalloporphyrin complex in nitrobenzene to get an organic-phase solution; (3) dripping the organic-phase solution onto an electrode of pyrolytic graphite to form a thin layer, then placing the electrode of the pyrolytic graphite in the water-phase solution, and using an electrochemical workstation to get a cyclic voltammetry curve with platform current; and (4) regulating the concentration of the K4Fe(CN)6 in the water-phase solution, repeating the step (3), and calculating a electron transfer rate constant value of the metalloporphyrin complex on the liquid-liquid phase according to the concentration of the K4Fe(CN)6 and a corresponding platform current value of the cyclic voltammetry curve. The method has the advantages of simplicity, quickness and easiness in operation.
Description
Technical field
The invention belongs to the liquid/liquid interface electrochemical field, be specifically related to a kind of simple, sensitive, measure the method for metalloporphyrin complex continuous steps electron transfer rate constant on liquid-liquid interface fast.
Background technology
Liquid/liquid interface galvanochemistry be grew up 70 mid-nineties 90s between the galvanochemistry of classics and a kind of new electrochemical method between the chemical sensor; Can be used for simulating biological film model; Investigate biomembranous ion-transfer process mechanism, and to the research of the displacement behavior of the very important medicine of life.The transfer process of electronics on liquid/liquid interface also is one of basic physical chemical process.It not only with many important Sheng Wu ﹑ chemical systems, like chemical sensor, the drug in the pharmacology, the research of phase-transfed catalysis is relevant, also with the simulation biomembranous research closely related.Simultaneously, electron transfer process in the life entity can simulated and study to liquid/liquid interface as the most simply simulating biological film model, thereby reach screening optimal drug molecule, purposes such as control electron transfer process.Therefore, charge transfer process on the research liquid/liquid interface is set up perfect interface process kinetic theory rationally, and for being familiar with, understanding many physiology courses, the secret that discloses life process has great importance.The main method of carrying out the liquid/liquid interface electrochemical research has: the microtubule technology; The droplet electrochemical method, spectroelectrochemistry method, scan-type electrochemical microscope (SECM); Thin layer cyclic voltammetry (TLCV); Second harmonic method of formation (SHG), sum frequency method of formation (SFG), means such as little liquid/liquid interface and computer simulation.Wherein, (Thin-Layer Cyclic Voltammetry TLCV), becomes the new method of charge transfer process on the research liquid/liquid interface to the thin layer cyclic voltammetry that was put forward in 1998 by people such as Anson because of its advantage such as easy, quick, easy to operate.
Summary of the invention
The object of the invention provides the method for a kind of easy, quick, easy-operating mensuration metalloporphyrin complex continuous steps electron transfer on liquid-liquid interface.
The present invention realizes that the technical scheme that above-mentioned purpose adopts is following:
A kind of method of measuring metalloporphyrin complex continuous steps electron transfer rate constant on liquid-liquid interface comprises the steps:
(1) with NaClO
4With NaCl be supporting electrolyte, with K
4Fe (CN)
6Be dissolved in the water, obtain aqueous phase solution;
(2) be supporting electrolyte with tetrabutylammonium perchlorate, the metalloporphyrin complex is dissolved in the nitrobenzene, obtain organic phase solution;
(3) organic phase solution is dripped on the pyrolytic graphite electrode form thin layer, then the pyrolytic graphite electrode is placed aqueous phase solution, obtain having the cyclic voltammetry curve of platform electric current with electrochemical workstation;
(4) regulate K in the aqueous phase solution
4Fe (CN)
6Concentration, repeating step (3) is by K
4Fe (CN)
6Concentration and with it the platform current value of corresponding cyclic voltammetry curve can calculate the value of metalloporphyrin complex electron transfer rate constant on liquid-liquid interface.This electron transfer rate constant can be applicable to the physiological function and the biologically active of postgraduate's object, for it provides the dynamics foundation.
Further, said NaClO
4Concentration be 0.1mol/L, the concentration of said NaCl is 0.1mol/L.
Further, said tetrabutylammonium perchlorate's concentration is 0.01mol/L.
Further, the concentration of said metalloporphyrin complex in nitrobenzene is 0.001mol/L.
Further, said metalloporphyrin complex is the cobalt metalloporphyrin complex.
Beneficial effect:
The present invention adopts thin layer cyclic voltammetry (TLCV), has measured the transfer of cobalt metalloporphyrin complex electronics on water/NITROBENZENE INTERFACE, and has further utilized K
4Fe (CN)
6Concentration is related with the platform current value, calculates the rate constant of electron transfer on the interface, and this method has simple and easy, quick, easy-operating advantage, thereby the dynamics foundation is provided for the physiological function of postgraduate's object and biologically active.。
Description of drawings
Fig. 1 is the cyclic voltammetry curve of pyrolytic graphite electrode in different solutions.
Fig. 2 is i
Obs-c figure.
Fig. 3 is i
ObsThe inverse figure of-c.
Fig. 4 is a different K
4Fe (CN)
6Cyclic voltammetry curve during concentration.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is further specified.
Described in the present invention platform electric current is meant when cyclic voltammetric characterizes, and at the platform that on noble potential scanning gained curve, is occurred by electronegative potential, also is steady-state current.
Electrochemical Characterization among the present invention is that (sectional area is 0.32cm to the employing three-electrode system
2The pyrolytic graphite electrode be working electrode, Ag/AgCl is a contrast electrode, the Pt silk is to electrode) go up at electrochemical workstation CHI-832 (U.S., CHI instrument) and accomplish.
The pre-service of pyrolytic graphite electrode: (1) becomes minute surface with the aluminium oxide powder sanding and polishing of 0.3 μ m and 0.05 μ m successively; (2) use ethanol (volume fraction is 95%), redistilled water ultrasonic cleaning more successively, dry up with nitrogen; (3) the pyrolytic graphite electrode insertion that dries up being contained in the electrolyte solution of the 0.001mol/L potassium ferricyanide and 0.1mol/L potassium chloride, is to electrode with the Pt silk, and Ag/AgCl is a contrast electrode, carries out cyclic voltammetry scan, obtains the pyrolytic graphite electrode of activation.
Pretreated pyrolytic graphite electrode is placed the K of 0.01mol/L
4Fe (CN)
6In the WS, contain 0.1 mol/L NaClO in the WS
4With 0.1 mol/L NaCl,, obtain its cyclic voltammetry curve shown in Fig. 1 A curve as supporting electrolyte.Illustration among Fig. 1 is the cyclic voltammetry curve of pyrolytic graphite electrode in the nitrobenzene solution of 0.001mol/L cobalt metalloporphyrin complex (CoTPP).
Further experiment drips the nitrobenzene of 1.5 μ L and on the pyrolytic graphite electrode, forms thin layer, places above-mentioned K again
4Fe (CN)
6In the WS, since the existence of nitrobenzene thin layer, the K of aqueous phase
4Fe (CN)
6Can't arrive the pyrolytic graphite electrode surface, in the potential range interscan of-0.1～1.2V, peak current disappears, and obtains cyclic voltammetry curve shown in Fig. 1 B curve.
The nitrobenzene that 1.5 μ L are dissolved with 0.001mol/L cobalt metalloporphyrin complex and 0.01mol/L tetrabutylammonium perchlorate drips on the pyrolytic graphite electrode and forms thin layer, places only to contain 0.1 mol/L NaClO again
4In the electrolyte solution of 0.1 mol/L NaCl; Carry out cyclic voltammetry scan; Two pairs of redox peaks have been produced respectively at 0.75V and 1.05V; Its cyclic voltammetry curve is shown in Fig. 1 C curve, and this is illustrated in the two step electron transfer reactions that the cobalt porphyrin has taken place electrode surface, and the tetrabutylammonium perchlorate is as the supporting electrolyte of organic phase.
The nitrobenzene that further 1.5 μ L is dissolved with 0.001mol/L cobalt metalloporphyrin complex and 0.01mol/L tetrabutylammonium perchlorate drips on the pyrolytic graphite electrode and forms thin layer, places the K of 0.01mol/L then
4Fe (CN)
6In the WS, contain 0.1 mol/L NaClO in the WS
4With 0.1 mol/L NaCl, carry out cyclic voltammetry scan, the oxidation peak current of cyclic voltammetry curve sharply raises, and the platform electric current occurred, shown in Fig. 1 D curve.This shows that working as aqueous phase contains K
4Fe (CN)
6The time, along with the increase gradually of voltage, the CoTPP in the organic phase
+And CoTPP
2+On the interface all by the K of aqueous phase
4Fe (CN)
6Be reduced to CoTPP and CoTPP
+, CoTPP that is generated and CoTPP
+Diffuse to electrode surface again oxidation current increased, following oxidation reaction takes place at the pyrolytic graphite electrode surface:
CoTPP?→?CoTPP
+?+?e ；
CoTPP
+?→?CoTPP
2+?+?e ；
Obtained thus by ZnTPP and ZnTPP
+The two steps stable state cyclic process of diffusion control, this phenomenon therefore capable of using is measured cobalt metalloporphyrin complex continuous steps electron transfer rate constant on liquid-liquid interface.
Water is K
4Fe (CN)
6The WS, its supporting electrolyte NaClO
4Be 0.1mol/L with the concentration of NaCl, organic phase is the nitrobenzene that is dissolved with 0.001mol/L cobalt metalloporphyrin complex and 0.01mol/L tetrabutylammonium perchlorate.The above-mentioned nitrobenzene of 1.5 μ L dripped on the pyrolytic graphite electrode form thin layer, then the pyrolytic graphite electrode is placed aqueous phase, be determined at different K
4Fe (CN)
6Cyclic voltammetry curve under the concentration, sweep velocity are 5mV/s.K
4Fe (CN)
6Concentration is respectively 0.01mol/L, 0.015mol/L, 0.02mol/L, 0.025mol/L, 0.03mol/L, 0.035mol/L, 0.04mol/L.
The processing of data: read different K
4Fe (CN)
6Platform current value (the i of concentration cyclic voltammetry curve when (representing) with c
Obs), draw i
Obs-c figure, (Fig. 2 A is a first step electronic transfer process, and Fig. 2 B is the second step electronic transfer process) as shown in Figure 2 can be found out from figure, works as K
4Fe (CN)
6When concentration increases gradually, i
ObsBe tending towards a certain steady state value, and and K
4Fe (CN)
6Concentration is irrelevant.
Get i respectively
ObsWith the inverse of c, draw i
Obs -1-c
-1Figure, (Fig. 3 A is a first step electronic transfer process, and Fig. 3 B is the second step electronic transfer process) as shown in Figure 3, i
Obs -1-c
-1Has extraordinary linear relationship.
According to i
Obs -1-c
-1The slope meter of straight line is calculated the electron transfer rate constant
Wherein, i
DBe limiting diffusion current, F is a Faraday constant, and A is that (this experiment is 0.32cm for the sectional area of pyrolytic graphite electrode
2), c
* NBBe the concentration of cobalt metalloporphyrin complex, D
NBBe coefficient of diffusion, d is the nitrobenzene thickness of thin layer, c
* H2OBe K
4Fe (CN)
6Concentration, k
EtBe the electron transfer rate constant.What formula (5) was represented is when the continuous electron transfer of multistep, between n step and n-1 go on foot, and the concentration of cobalt metalloporphyrin complex and the relation between the limiting diffusion current.The first step that calculates and the second step electron transfer rate constant are respectively 0.2259 cm s
-1M
-1With 0.115335 cm s
-1M
-1
Fig. 4 is a different K
4Fe (CN)
6Cyclic voltammetry curve figure during concentration, wherein, the corresponding K of each curve
4Fe (CN)
6Concentration be: a, 0.01mol/L, b, 0.02mol/L, c, 0.03mol/L, d, 0.04mol/L.
Claims (5)
1. a method of measuring metalloporphyrin complex continuous steps electron transfer rate constant on liquid-liquid interface is characterized in that, comprises the steps:
(1) with NaClO
4With NaCl be supporting electrolyte, with K
4Fe (CN)
6Be dissolved in the water, obtain aqueous phase solution;
(2) be supporting electrolyte with tetrabutylammonium perchlorate, the metalloporphyrin complex is dissolved in the nitrobenzene, obtain organic phase solution;
(3) organic phase solution is dripped on the pyrolytic graphite electrode form thin layer, then the pyrolytic graphite electrode is placed aqueous phase solution, obtain having the cyclic voltammetry curve of platform electric current with electrochemical workstation;
(4) regulate K in the aqueous phase solution
4Fe (CN)
6Concentration, repeating step (3) is by K
4Fe (CN)
6Concentration and with it the platform current value of corresponding cyclic voltammetry curve can calculate the value of metalloporphyrin complex electron transfer rate constant on liquid-liquid interface.
2. according to the method for the said mensuration metalloporphyrin of claim 1 complex continuous steps electron transfer on liquid-liquid interface, it is characterized in that: said NaClO
4Concentration be 0.1mol/L, the concentration of said NaCl is 0.1mol/L.
3. according to the method for the said mensuration metalloporphyrin of claim 1 complex continuous steps electron transfer on liquid-liquid interface, it is characterized in that: said tetrabutylammonium perchlorate's concentration is 0.01mol/L.
4. according to the method for the said mensuration metalloporphyrin of claim 1 complex continuous steps electron transfer on liquid-liquid interface, it is characterized in that: the concentration of said metalloporphyrin complex in nitrobenzene is 0.001mol/L.
5. according to the method for the said mensuration metalloporphyrin of claim 1 complex continuous steps electron transfer on liquid-liquid interface, it is characterized in that: said metalloporphyrin complex is the cobalt metalloporphyrin complex.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931569A (en) * | 2015-05-27 | 2015-09-23 | 西北师范大学 | Thin-layer cyclic voltammetry method for detecting continuous multi-step electron transfer on liquid-liquid interface |
| 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 |
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| CN102192943A (en) * | 2010-03-12 | 2011-09-21 | 西北师范大学 | Method for determining electron transfer rate of liquid/liquid interface |
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| US5874046A (en) * | 1996-10-30 | 1999-02-23 | Raytheon Company | Biological warfare agent sensor system employing ruthenium-terminated oligonucleotides complementary to target live agent DNA sequences |
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| 刘秀辉 等: "薄层液 /液界面电子转移动力学的研究进展", 《分析化学评述与进展》, vol. 34, no. 1, 31 January 2006 (2006-01-31) * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931569A (en) * | 2015-05-27 | 2015-09-23 | 西北师范大学 | Thin-layer cyclic voltammetry method for detecting continuous multi-step electron transfer on liquid-liquid interface |
| 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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Application publication date: 20121010 |