CN102621353A - Method for studying light induced electron transfer - Google Patents
Method for studying light induced electron transfer Download PDFInfo
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- CN102621353A CN102621353A CN2012101082781A CN201210108278A CN102621353A CN 102621353 A CN102621353 A CN 102621353A CN 2012101082781 A CN2012101082781 A CN 2012101082781A CN 201210108278 A CN201210108278 A CN 201210108278A CN 102621353 A CN102621353 A CN 102621353A
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Abstract
The invention provides a method for studying light induced electron transfer with a scanning electrochemical microscopy (SECM). According to the method, a zinc protoporphyrin complex and benzoquinone are used to construct a light induced electron transfer process in a light system II; in the SECM, an SECM probe is used as a working electrode, conducting glass modified with the zinc protoporphyrin complex is used as a substrate electrode, and light induced electron transfer is realized through regulating the distance and electrode potential difference between the two electrodes. The method provided by the invention can be used to construct a platform for simulating a photoelectron transfer reaction in a biological system.
Description
Technical field
The present invention relates to a kind of photosynthesis of simulating nature circle, study the method for photoinduction electron transfer again with scan-type electrochemical microscope.
Background technology
The most basic process of biological phenomena is a charge movement, no matter is energy conversion, or nerve conduction; No matter be photosynthesis or respiratory; Or even origin of life, the thinking of brain, the transmission of gene; All relevant closely with electron transport; The oxidation-reduction process of biomacromolecule has decisive role for the energy conversion and the metabolism of life entity, and galvanochemistry is one of most basic subject in the life science.Biological respinse is studied in characteristic electron transport by carrying out with biomolecule inside between the biomolecule, and purpose is for metabolism of illustrating living things system and conversion process of energy, understands the mechanism of life system and physiological function.Therefore, the electron transport Study on Mechanism of relevant living things system, life process essence is significant for disclosing.The transfer process of electronics on solid-liquid, liquid/liquid interface is basic physical chemical behavior; Be prevalent among the natural every field; It is multidisciplinary to relate to chemistry, physics, life science, material science and microelectronics etc., and its research has important significance for theories and application prospects.Because porphyrins has unique electronic structure and photoelectric properties, and have good light and thermally stable property and be easy to characteristics such as cutting modification, so have very big application potential in the high-tech field of materials.For example, aspect nonlinear optical material, porphyrin can be used for light amplitude limit, Laser Modulation, optical bistability, phase conjugation and the light material etc. that opens the light.Also evoked researcher's deep interest in field application prospects such as others such as liquid crystal material, magnetic material, luminescent material and storage mediums.In recent years, porphyrin is used to some photodetachments widely, research such as electron transfer among photoelectric sensing and the II of mimic photosynthesis system.
Scan-type electrochemical microscope (SECM) is based on not development and the on-the-spot new technology that detects of the galvanochemistry of a kind of resolution between ordinary optical microscope and STM that generates of ultramicroelectrode (UME) and PSTM at the beginning of the eighties (STM) of the seventies.Because it has chemical sensitivity; Thereby not only can study the homogeneous reaction dynamics in probe and suprabasil out-phase reaction kinetics and the solution; Differentiate the electrochemical nonuniformity of electrode surface microcell; Provide the pattern of conductor and insulator surface, but also can carry out little processing, study many important bioprocess etc. material.
Summary of the invention
The present invention seeks to solve the effective ways that prior art lacks photoelectron transfer reaction in the research biosystem, provide a kind of, study the method for photoinduction electron transfer with SECM through the mimic photosynthesis process of electron transfer on.
The present invention realizes that above-mentioned purpose adopts following technical scheme
A kind of method of studying the photoinduction electron transfer, this method step is following:
(1) successively zinc protoporphyrin complex and Nafion solution are spin-coated on the conductive glass surface;
(2) in the benzoquinones WS, will make up three-electrode system as the probe of the scan-type electrochemical microscope of working electrode and contrast electrode with to electrode, with step (1) electro-conductive glass as basal electrode;
(3) in scan-type electrochemical microscope; Between working electrode and basal electrode, applying is enough to make benzoquinones to be reduced to the electrode electricity potential difference of quinhydrones; Be in illumination and unglazed respectively at basal electrode according under the condition; Regulate the distance of working electrode, detect change in current, obtain the feedback profile of electric current with variable in distance to basal electrode;
(4) in scan-type electrochemical microscope, be zero-potential point with the basal electrode, apply negative potential to working electrode, detect basal electrode and be in illumination and unglazed, the time dependent response curve of electric current respectively according under the condition.
Further, the current potential that applies to working electrode of step (4) for-0.2V～-0.5V.
Further, the zinc protoporphyrin complex is at N, in the dinethylformamide solvent with nitrogen protection under, in 80～100 ℃ of heating reflux reactions, product is used chloroform extraction with tetraphenylporphyrin and zinc acetate, purified again obtaining.
Beneficial effect: the present invention has studied out-phase (solid-liquid) photoinduction electronic transfer process through design SECM INTERFACE MODEL mimic photosynthesis effect, and this method has comparatively significant meaning for photoelectron transfer reaction among the research photosynthetical system II.Simultaneously; Also studied the possibility that light-induced reaction takes place in theory; Be illustrated under the photoinduction situation in conjunction with experimental result, electron transfer reaction can take place with the probe molecule HQ of aqueous phase in the ITO electro-conductive glass that is modified with zinc protoporphyrin, and under the feedback model of distance and electric current; Obtain typical positive feedback curve, the photoinduction electron transfer reaction that out-phase has taken place under light conditions is described.Under light On/Off pattern; Photocurrent is the state of more stable variation; Explain that the zinc protoporphyrin complex has excellent light acquisition performance; Can be with catching visible light, and convert stable electric energy into, so the zinc protoporphyrin complex can be used for the structure of DSSC and some photoelectric devices.Above-mentioned description of test the inventive method can be used for the research of interface photoinduction electron transfer, this method has significant meaning in the transmission of research photoelectron, for photoelectron transfer reaction in the simulation biosystem has made up platform.
Description of drawings
Fig. 1 is a photoinduction electron transfer synoptic diagram, and left side figure is a photoelectron transmittance process in the nature photosynthesis, and right figure is a photoinduction electronic transfer process under the SECM pattern of the present invention.
Fig. 2 is the electrode assembly synoptic diagram under the SECM pattern of the present invention.
Fig. 3 sees figure for the signal of operation instrument SECM.
Uv absorption spectra of Fig. 4 zinc protoporphyrin (A) and steady-state fluorescence spectrogram (B).
The stable state cyclic voltammogram of Fig. 5 SECM probe of the present invention in the 1mmol/L benzoquinones WS.
Feedback profile figure under Fig. 6 SECM pattern of the present invention.
The time dependent response curve of electric current under Fig. 7 SECM pattern of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
The clear occurring in nature of left chart among Fig. 1 is arranged in the photoinduction electronic transfer process of chlorophyll photosystem II; Right figure is that the simple optical on the modeling interface that we make up under the SECM pattern is induced electronic transfer process; Because porphyrin is the core group of some biomacromolecules (like chlorophyll, protoheme, cobalamin); Ubiquinone (plastoquinone) is an important electron carrier among the photosystem II; So the present invention adopts and to do basal electrode by the ITO electro-conductive glass of zinc protoporphyrin complex decorating, the probe molecule in the solution then adopt benzoquinones (benzoquinone, BQ).
The energy level of used Gauss computed in software ZnTPP and HQ (quinhydrones).HOMO of molecule (HOMO highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) value have reflected their chemical property, and on behalf of molecule, the HOMO value lose the ability of electronics, and the representative of LUMO value obtains the ability of electronics; If the HOMO value is big more, just explain that this molecule betatopic ability is strong more; If the LUMO value is low more, it is strong more to explain that molecule is accepted the ability of electronics.Can find out from result of calculation, ZnTPP be excited the back from the HOMO energy level transition to lumo energy, this LUMO value is low than the LUMO value of HQ, so it is very strong electron acceptor, can and HQ between the generation electronics transmission.Result of calculation is following:
Therefore, the detailed process of electron transfer is following under the photoinduction of the present invention:
In above-mentioned electron level and electronic transfer process, the ZnTPP* representative is in the zinc protoporphyrin of excited state, E
TipBe in the experiment probe tip of SECM to the voltage that basal electrode applied, when its reach-0.2～-during 0.5V, BQ is reduced into HQ.Under light conditions; ZnTPP absorption luminous energy transits to more, and high level becomes ZnTPP*; The ZnTPP* instability loses electronics becomes oxidation state (
); The electron transport that loses is to the conduction band (CB) of basal electrode,
and the HQ generation bimolecular redox reaction that is diffused into the basal electrode surface.On the other hand; Increase along with BQ concentration in the solution; ZnTPP* can be through forming
for the BQ molecule electron transport that loses, and therefore the electronics that is present in the basal electrode conduction band can pass to
.
Test used instrument and reagent
Scan-type electrochemical microscope SECM (CHI 900, U.S. CH instrument company), the probe of SECM adopt diameter to be the Pt ultramicroelectrode of 25 μ m, and be as shown in Figure 3, and 1-is the container of probe, 2-dress medium solution;
The UV-1100 ultraviolet spectrophotometer, the RF-540 XRF;
Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.);
Alundum (Al polishing powder (0.30 mm, 0.05 mm, Shanghai occasion China instrument reagent company);
When making up three-electrode system, adopt Ag/AgCl contrast electrode (CHI111, U.S. CH instrument company) and platinum to electrode, the probe of SECM is a working electrode;
Light source (400～700nm): LA-410UV-3 (Japanese HAYASHI instrument company);
Nafion solution (Shanghai Bohr's chemical reagent company limited).
Concrete experimentation
1) pre-service of ITO electro-conductive glass
Use acetone, ethanol, each 15min of redistilled water sonicated ITO electro-conductive glass successively, with the redistilled water flushing, nitrogen dries up subsequent use again.
2) processing of working electrode
The used working electrode of this experiment is the probe of SECM; It is the Pt ultramicroelectrode; Respectively with the alundum (Al polishing powder of 0.30 mm and the 0.05 mm electrode of on cotton gauze, polishing, the sensitivity of raising probe is rinsed probe tip well with redistilled water then before each experiment.
3) preparation of zinc protoporphyrin complex
Synthetic route as above adds the tetraphenylporphyrin (TPP) of 100mg and the N of 20ml respectively, dinethylformamide (DMF) in three mouthfuls of round-bottomed flasks; Heating for dissolving behind the feeding nitrogen 10min, adds the 2.0g zinc acetate and refluxed 3 hours in 80 ℃ of following heated and stirred; Course of reaction, stops to stir after reacting completely with thin layer chromatography (TLC) monitoring (developping agent is a chloroform); Be cooled to room temperature, add secondary water, divide three extractions with the 50mL chloroform; Use 5 * 100mL saturated common salt water washing organic phase again, dry with anhydrous Na 2SO4, get brick-red crude product.Crude product is dissolved in chloroform, crosses post with silicagel column, and chloroform is an eluent, collects first colour band, solvent evaporated, and vacuum drying, recrystallization gets red crystals 0.088g, and productive rate is about 61.9%.
4) modification of basal electrode
The used basal electrode of this experiment is the ITO electro-conductive glass.1mL ZnTPP chloroformic solution is spin-coated on the ITO conductive glass surface, carries out surface washing with acetone, ethanol, redistilled water successively then, to remove surface impurity; Dry; Again Nafion solution is spin-coated on this surface, thereby obtains uniform film at the ITO conductive glass surface, subsequent use.
5) with working electrode, contrast electrode, electrode and basal electrode are assembled and are connected with computing machine by shown in Figure 2; Working electrode is connected with the negative pole of power supply; Basal electrode is connected with the positive pole of power supply, and it is the benzoquinones WS of 1mmol/L that the medium solution when three-electrode system and basal electrode work adopts concentration.
6) between the probe (being working electrode) of SECM and ITO electro-conductive glass (being basal electrode), apply-the electrode electricity potential difference of 0.4V; Regulate the distance of working electrode to basal electrode; The flow through electric current of working electrode of detection changes with the distance of two electrodes; Promptly get feedback profile, respectively the feedback profile of test substrate electrode under illumination and unglazed photograph apart from-electric current.
7) with the basal electrode be zero-potential point; Apply-the 0.4V current potential to working electrode; The distance of adjustment SECM probe and ITO electro-conductive glass is between 10～100mm, and with source alignment ITO electro-conductive glass, visible luminous energy was radiated at the ITO conductive glass surface when light source was opened.Then, detect the variation of electric current under light source On/Off pattern, obtain the time dependent response curve of electric current.
Fig. 4 is the uv absorption spectra (A) and the steady-state fluorescence spectrogram (B) of made zinc protoporphyrin complex, and the insertion figure of Fig. 4 (A) is the amplifier section at place, 550nm peak.From spectrogram, red shift takes place in the Soret band, and absorption peak strength slightly reduces.Porphyrin (belongs to π-π at Q
*Transition) have four absorption peaks, generate after the complex, become an absorption peak, the minimizing of Q band absorption peak is because free porphyrin belongs to D
2hPoint group, porphyrin metal complex then belong to C
4VPoint group generates after the complex, and symmetry strengthens and makes the cause of the decreased number of absorption peak.Porphyrin forms after the complex, can cause the minimizing of Q band and the red shift of Soret band.The minimizing of Q band and to weaken reason be to form after the complex; The porphyrin ring center is occupied by metallic ion, last 4 the N atoms of the big ring of porphyrin all with the central metallic ions coordination, thereby the metalloporphyrin molecular symmetry is improved; Energy level near, show as the minimizing of Q band and weaken.Dotted line is an excitation spectrum among Fig. 4 (B), and solid line is an emission spectrum, and visible by figure, zinc protoporphyrin also demonstrates stronger exciting and emissive porwer on the steady-state fluorescence spectrogram.
Fig. 5 is the stable state cyclic voltammogram of working electrode in the 1mmol/L benzoquinones WS, explains that SECM probe (Pt ultramicroelectrode) has good electrochemical behavior.
Fig. 6 is the feedback profile of the distance-electric current of experiment gained, and coordinate L is the normalization distance, L=d/a; Wherein, d is that two distance between electrodes, a are the radius (12.5 μ m) of Pt ultramicroelectrode, and dotted line is a theoretical value; Solid line is the experiment measuring value, and experiment relatively meets with notional result.Curve a is the feedback profile of basal electrode gained under illumination for the ITO electro-conductive glass of modifying with zinc protoporphyrin; Curve b is the feedback profile of basal electrode gained under unglazed photograph for the ITO electro-conductive glass of modifying with zinc protoporphyrin; The feedback profile that curve c is is basal electrode gained under unglazed photograph with naked ITO electro-conductive glass; Can find out that from three curves curve a is typical positive feedback curve, explain the photoinduction electron transfer has taken place between ZnTPP and HQ under illumination condition.
Fig. 7 is the time dependent response curve of photocurrent of experiment gained, can find out that when optical radiation, electric current is the trend of increase in time; When no optical radiation, electric current reduces in time; When light source during in On/Off state alternate, electric current demonstrates corresponding Changing Pattern.
Claims (3)
1. a method of studying the photoinduction electron transfer is characterized in that, this method step is following:
(1) successively zinc protoporphyrin complex and Nafion solution are spin-coated on the conductive glass surface;
(2) in the benzoquinones WS, will make up three-electrode system as the probe of the scan-type electrochemical microscope of working electrode and contrast electrode with to electrode, with step (1) electro-conductive glass as basal electrode;
(3) in scan-type electrochemical microscope; Between working electrode and basal electrode, applying is enough to make benzoquinones to be reduced to the electrode electricity potential difference of quinhydrones; Be in illumination and unglazed respectively at basal electrode according under the condition; Regulate the distance of working electrode, detect change in current, obtain the feedback profile of electric current with variable in distance to basal electrode;
(4) in scan-type electrochemical microscope, be zero-potential point with the basal electrode, apply negative potential to working electrode, detect basal electrode and be in illumination and unglazed, the time dependent response curve of electric current respectively according under the condition.
2. according to the method for the said research photoinduction of claim 1 electron transfer, it is characterized in that: the current potential that step (4) applies to working electrode for-0.2V～-0.5V.
3. according to the method for the said research photoinduction of claim 1 electron transfer; It is characterized in that: said zinc protoporphyrin complex is at N; In the dinethylformamide solvent and under the nitrogen protection; In 80～100 ℃ of heating reflux reactions, product is used chloroform extraction with tetraphenylporphyrin and zinc acetate, purified again obtaining.
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| CN103342471A (en) * | 2013-07-05 | 2013-10-09 | 西北师范大学 | Photoelectric nanometer composite membrane material and preparation method and application thereof |
| CN107192858A (en) * | 2016-03-14 | 2017-09-22 | 江苏卓芯电子科技有限公司 | The super-resolution electrochemistry image measuring device measured simultaneously with electrochemical luminescence |
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| CN103342471A (en) * | 2013-07-05 | 2013-10-09 | 西北师范大学 | Photoelectric nanometer composite membrane material and preparation method and application thereof |
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Application publication date: 20120801 |