CN101004404B - Electrode modified by chloride, oxide enzyme capable of catalyzing organic reaction in high effect - Google Patents
Electrode modified by chloride, oxide enzyme capable of catalyzing organic reaction in high effect Download PDFInfo
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- CN101004404B CN101004404B CN2007100368206A CN200710036820A CN101004404B CN 101004404 B CN101004404 B CN 101004404B CN 2007100368206 A CN2007100368206 A CN 2007100368206A CN 200710036820 A CN200710036820 A CN 200710036820A CN 101004404 B CN101004404 B CN 101004404B
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Abstract
A myeloperoxidase modified electrode for effectively catalyzing organic reaction is prepared for utilizing molecular assembling film technique to fix trace amount of myeloperoxidase on electrode under electrostatic action, using obtained myeloperoxidase modified electrode as operation electrode and using chemical means to generate hydrogen peroxide at home position for greatly raising conversion efficiency of organic chemical reaction.
Description
Technical field
The present invention relates to the electrochemical catalysis field, specifically, relate to utilize the chloroperoxidase modified electrode of molecule assembling membrane technology preparation energy efficient catalytic organic reaction.
Background technology
In general, if can realize using the biological enzyme organic chemical reactions, then required little energy, material toxicity is little, meets requirement on environmental protection.At present, that application is more in catalytic oxidation is peroxidase (peroxidase), and it has existence extensively, the advantage that the source is easy to get, the more important thing is, utilize hydrogen peroxide and other superoxide, do not need the participation of accessory factor can finish oxidation reaction as oxygen donor.Yet, utilize the system of superoxide enzymatic, generally be in the potpourri of peroxidase and raw material, to carry out.Such catalyst system and catalyzing is difficult to enzyme be recycled after finishing catalytic reaction again.And, in the peroxidase catalyst system and catalyzing, must add hydrogen peroxide with expensive equipment such as constant flow pump, in case the hydrogen peroxide addition just can not cause the inactivation of enzyme at that time.So this class catalyst system and catalyzing cost is quite high, utility appliance is also very expensive.
Chloroperoxidase (Chloroperoxidase, be called for short CPO) be a kind of special enzyme that from marine fungi Caldariomycesfumago, extracts, it utilizes hydrogen peroxide and other superoxide as oxygen donor, does not need the participation of accessory factor can finish oxidation reaction.Reaction, especially its special structures such as catalytic oxidation dehydrogenation, oxidative halogenation, epoxidation, hydrogen peroxide disproportionation and oxygen transmission have very high chiral selectivity and stability when catalyse organic reaction effectively.
There is report to estimate to utilize the CPO can the catalysis various organic reactions, seen all CPO to be placed in the research report and implemented catalyse organic reaction in the solution.The scholars such as DouglasS.Clark in California, USA university Berkeley branch school carry out the even dispersion that emulsification improves CPO by adding surfactant, thereby the turn over number TTN (Total turnover number) that makes the catalysis hydrocarbon oxidation than the raising of other report ten times, this is the best result of report at present.Yet, have also wherein very that important problem is, in reaction system, add hydrogen peroxide with constant flow pump, this just needs to buy expensive constant flow pump, simultaneously, in case the amount that adds hydrogen peroxide can reduce the activity of enzyme greater than the required amount of reaction the time.
Therefore, need a kind ofly can recycle enzyme, and cost is low, method simple to operate is come catalytic reaction.
Summary of the invention
The object of the present invention is to provide a kind of chloroperoxidase modified electrode of using, can efficient catalytic be the organic reaction of oxygen donor with the hydrogen peroxide.
Second purpose of the present invention is to provide the preparation method with the chloroperoxidase modified electrode.
The present invention adopts molecular self-assembled monolayer, and (Self-assembled monolayer, SAM) technology is fixedly modified on electrode catalyse organic reaction effectively with CPO.Utilize electrostatic force that molecule is assembled into electrode surface layer by layer, thereby, the enzyme of trace is fixed on the electrode, and produce hydrogen peroxide with the electrochemical method original position, realize the reversible electron transfer reaction of enzyme, and then when reaching catalyse organic reaction, can use enzyme repeatedly.
The electrode that chloroperoxidase of the present invention is modified, the organic reaction of energy efficient catalytic; Electrode surface comprises the unimolecular layer modified membrane of chloroperoxidase, and this chloroperoxidase unimolecular layer internal layer and skin are respectively positively charged polycation layer.Be that electrode surface is followed successively by positively charged polycation layer, chlorine peroxidase unimolecular layer and positively charged polycation layer.
Described electrode is gold electrode or glass-carbon electrode.
Used polycation is diallyl dimethyl ammoniumchloride (PDDA) or polyethyleneimine (PEI).
Preparation method's principle is to utilize electrostatic force to be assembled into positively charged polycation and electronegative chloroperoxidase molecule on the electrode layer by layer, the chloroperoxidase molecule is assembled the positively charged polycation of one deck outward again, to guarantee the stability of enzyme.By such method, the oxide enzyme can be fixed on the electrode.
Employed electrode can be gold electrode or glass-carbon electrode.
If electrode is a gold electrode, then can utilize the interaction property between gold electrode and the sulfydryl to assemble one deck sulfydryl propane sulfonic acid salt earlier, as unithiol, make it electronegative, utilize electrostatic interaction to carry out the assembling of polycation and chloroperoxidase unimolecular layer in succession then.Concrete steps comprise:
A handles polishing electrode earlier and cleans;
B is placed on sulfydryl propane sulfonic acid salt ethanolic solution with electrode, assembles in unithiol (MPS) solution as 0.1-1mg/ml, makes it to be with negative charge; General built-up time is 16-24h;
C is placed on electrode in the said polycation solution and assembles then, makes it the lotus that becomes positively charged;
D is placed into electrode in the chloroperoxidase solution subsequently and assembles, and makes it the chloroperoxidase of adsorption band negative charge;
E is put into electrode in the said polycation solution and assembles.
As use glass-carbon electrode, then can omit the b step, that is:
A handles polishing electrode earlier and cleans;
B is placed on electrode in the said polycation solution and assembles then, makes it the lotus that becomes positively charged;
C is placed into electrode in the chloroperoxidase solution subsequently and assembles, and makes it the chloroperoxidase of adsorption band negative charge;
D is put into electrode in the said polycation solution and assembles.
The said polycation solution concentration range of using is 1-5mg/ml.Being placed on the time of assembling in the said polycation solution is 10-60min.
The polycation that can select for use has diallyl dimethyl ammoniumchloride (PDDA) or polyethyleneimine (PEI).
The chloroperoxidase solution concentration scope of using is 1x10
-6-1x10
-5Mol/L.
Being placed on the time of assembling in the chloroperoxidase solution is 1-20h.
CPO modified electrode provided by the invention, catalyse organic reaction especially can be applicable to halogenation effectively.Because its special structure has good chiral selectivity and stability when catalyse organic reaction.Thereby, in production and many fields such as environmental treatment and biology sensor of organic synthesis, pharmaceutical intermediate wide application prospect is arranged all.
As under the oxygen existence condition, utilize galvanochemistry to promote original position and produce hydrogen peroxide, can under the condition that does not add hydrogen peroxide, (or claim a chlorine Ketene dimethyl, chlorination generation dichloro dimetone (dichlorodimedon) monochlorodimedon) by efficient catalytic one chlorine dimetone.Utilize the method for laminated assembling technology fixation of C PO, can realize the reversible electron transport of CPO enzyme on electrode, thereby reduced the consumption of enzyme, good stability, and can realize recycling of enzyme, and cost is reduced greatly, be a kind of efficient, long-acting and eco-friendly catalyst system and catalyzing that is worthy to be popularized.
Owing to be that galvanochemistry promotes original position generation hydrogen peroxide, also just avoided the improper problem that causes enzyme deactivation of hydrogen peroxide addition, do not need for guaranteeing that an amount of hydrogen peroxide attaches expensive equipment such as constant flow pump, can make cost reduce greatly yet.
It is simple to have equipment based on the organic reaction of electrochemical method catalysis, advantages such as processing ease, and with low cost, be easy to industrialization, thereby have broad application prospects.This research work on the one hand yet there are no domestic and international report.
Description of drawings
Fig. 1 does not have the electrode of chloroperoxidase modification and the cyclic voltammogram of the electrode that chloroperoxidase is modified.
The longitudinal axis is an electric current, and the μ A of unit, transverse axis are current potential, the mV of unit; Condition is: the 50mmol/L phosphate buffer of pH=5, sweep velocity 100mV/s.Curve a is the cyclic voltammetry curve of no chloroperoxidase modified electrode; Curve b is the cyclic voltammetry curve of chloroperoxidase modified electrode.
Fig. 2 is a working electrode with the electrode that the electrode and the chloroperoxidase of no chloroperoxidase modification are modified respectively, the uv absorption spectra in 0.1mol/L one chlorine dimetone (with the 20mmol/L phosphate buffer solution preparation of pH=2.75) before and after the electrolysis.
Curve a is the uv absorption spectra before the electrolysis, dotted line b is the PDDA-MPS/Au electrode ultra-violet absorption spectrum behind electrolysis 1h under the-0.6V current potential in a chlorine dimetone solution that does not have a fixation of C PO, it is working electrode that curve c, d, e are respectively the electrode (PDDA-CPO-PDDA-MPS/Au) of having fixed CPO, the ultra-violet absorption spectrum that records under-0.6V current potential behind electrolysis 1h, 2h and the 4h.
Embodiment
The main agents unithiol of using among the embodiment (MPS), diallyl dimethyl ammoniumchloride (PDDA), polyethyleneimine (PEI), chloroperoxidase (CPO), a chlorine dimetone are available from Sigma company.It is pure that all the other reagent are all analysis; Except that specifying, research solution is all prepared with ultrapure water.
Electrochemical measurement adopts three-electrode system.With the modified electrode of molecule self-assembling method fixation of C PO layer by layer is working electrode; Saturated calomel electrode (SCE) is a contrast electrode, and the platinized platinum electrode is an auxiliary electrode.
Embodiment 1
The gold disk electrode is polished on abrasive paper for metallograph earlier, uses the Al of 0.3,0.05 μ m more successively
2O
3The powder polishing.Then, use the ultrapure water ultrasonic cleaning, clean the back with 50% chloroazotic acid again and take out, assemble 16h, assemble 30min, 3.95x10 in 3mg/mL diallyl dimethyl ammoniumchloride (PDDA) solution with the ethanolic solution that places 0.2mg/mL unithiol (MPS) behind the water wash successively
-6Assembling 10h moves among the 3mg/mL PDDA again and assembles 30min among the CPO of mol/L (pH=5.0).With promptly making the modified electrode of having fixed CPO after the ultrapure water flushing, note is made the PDDA-CPO-PDDA-MPS/Au electrode, can be used for the catalysis organic chemical reactions.
As working electrode, saturated calomel electrode (SCE) is a contrast electrode with this electrode, and the platinized platinum electrode is an auxiliary electrode, under the oxygen free condition, carries out cyclic voltammetry scan in the 50mmol/L of pH=5 phosphate buffer, and sweep velocity is 100mV/s, and the result as shown in Figure 1.Can see, (Fig. 1 curve a) not see the redox current peak on the electrode that no CPO modifies, on the PDDA-CPO-PDDA-MPS/Au electrode, then show the cyclic voltammetry curve (Fig. 1 curve b) of a pair of typical redox current peak, show direct electron transport has taken place between CPO and the electrode.
A chlorine dimetone of getting the 0.1mmol/L of 8mL phosphate buffer solution (pH=2.75) preparation is an end liquid, with the PDDA-CPO-PDDA-MPS/Au electrode that makes among the embodiment 1 is working electrode, saturated calomel electrode (SCE) is a contrast electrode, and the platinized platinum electrode is an auxiliary electrode.Logical oxygen saturation keeps oxygen atmosphere before the reaction in the reaction.Under the current potential of-0.6V, carry out electrolysis.The absorbance of measuring the electrolysis front and back with ultraviolet spectrum analyzer changes.The result as shown in Figure 2.
This modified electrode is seen Fig. 2 to the test findings of chlorine dimetone catalytic chlorination reaction.Can be clear that curve a is the last chlorine dimetone of an electrolysis solution absorbency; The modified electrode that does not have fixation of C PO be working electrode in a chlorine dimetone solution behind the electrolysis 1h, the absorbance at the feature uv absorption wavelength place of a chlorine dimetone does not change (seeing Fig. 2 dotted line b).And the modified electrode of having fixed CPO is in a chlorine dimetone behind electrolysis 1h and the 2h, absorbance significantly reduces (Fig. 2 curve c and d), behind continuous electrolysis 4h, absorbance is reduced to 0 (Fig. 2 curve e), shows that this moment, one chlorine dimetone was the dichloro dimetone by catalytic chlorination all.
Above-mentioned test findings proves, produces the chlorination reaction of the CPO molecule assembling film catalysis efficiently one chlorine dimetone of hydrogen peroxide by the electrochemical method original position.
Embodiment 3
With the PDDA in another kind of polycation polyethyleneimine (PEI) alternate embodiment 1, other steps are identical with embodiment 1, and the PEI-CPO-PEI-MPS/Au electrode that resulting CPO modifies also can obtain identical catalytic effect.
With the gold electrode in the glass-carbon electrode alternate embodiment 1, equally to pre-service such as electrode polish, can save the number of assembling steps of MPS, identical among other steps afterwards and the embodiment 1.Also can obtain on the glass-carbon electrode of resulting fixation of C PO with gold electrode on identical catalytic effect.
Claims (9)
1. the chloroperoxidase modified electrode of an efficient catalytic organic reaction is characterized in that, electrode surface comprises the unimolecular layer of chloroperoxidase, and the internal layer of described chloroperoxidase unimolecular layer and skin are respectively positively charged polycation layer.
2. the electrode with the chloroperoxidase modification of claim 1 is characterized in that described electrode is gold electrode or glass-carbon electrode.
3. claim 1 electrode is characterized in that, described polycation is diallyl dimethyl ammoniumchloride or polyethyleneimine.
4. the preparation method of each described chloroperoxidase modified electrode of claim 1-3 is characterized in that, when described electrode was gold electrode, the preparation method may further comprise the steps:
A, electrode is polished, cleans;
B, described gold electrode is placed in the ethanolic solution of sulfydryl propane sulfonic acid salt and assembles 16-24h, make it electronegative;
B, electrode is placed in the positively charged said polycation solution assembles;
D, electrode is assembled with chloroperoxidase solution;
E and then electrode assembled with positively charged said polycation solution.
5. the preparation method of the chloroperoxidase modified electrode of claim 4 is characterized in that, described sulfydryl propane sulfonic acid salt is unithiol, and the ethanolic solution mass concentration of unithiol is 0.1-1mg/ml.
6. the preparation method of each described chloroperoxidase modified electrode of claim 1-3 is characterized in that, when described electrode was glass-carbon electrode, the preparation method may further comprise the steps:
A, electrode is polished, cleans;
B, electrode is placed in the positively charged said polycation solution assembles;
C, electrode is assembled with chloroperoxidase solution;
D and then electrode assembled with positively charged said polycation solution.
7. the preparation method of claim 4 or 6 chloroperoxidase modified electrode is characterized in that described polycation is diallyl dimethyl ammoniumchloride or polyethyleneimine.
8. the preparation method of claim 4 or 6 chloroperoxidase modified electrode is characterized in that described said polycation solution concentration is 1-5mg/ml, and described chloroperoxidase solution concentration is 1x10
-6-1x10
-5Mol/L.
9. the preparation method of claim 4 or 6 chloroperoxidase modified electrode is characterized in that built-up time is 10-60min in said polycation solution, and built-up time is 1-20h in chloroperoxidase solution.
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| CN104973661B (en) * | 2014-04-10 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of composite cathode electrode and its preparation method and application |
| CN115184425B (en) * | 2022-07-11 | 2024-01-16 | 陕西师范大学 | Molybdenum disulfide coated nitrogen-containing carbon nanotube fixed CPO biosensor and detection H 2 O 2 Applications of (2) |
Citations (3)
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| US5496452A (en) * | 1990-05-01 | 1996-03-05 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Substrate regenerating biosensor |
| CN1563969A (en) * | 2004-03-22 | 2005-01-12 | 南开大学 | Biological enzyme electrode for biosensor, and its prepn. method |
| CN1766599A (en) * | 2005-09-28 | 2006-05-03 | 华东理工大学 | Nano biologic enzyme electrode |
-
2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496452A (en) * | 1990-05-01 | 1996-03-05 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Substrate regenerating biosensor |
| CN1563969A (en) * | 2004-03-22 | 2005-01-12 | 南开大学 | Biological enzyme electrode for biosensor, and its prepn. method |
| CN1766599A (en) * | 2005-09-28 | 2006-05-03 | 华东理工大学 | Nano biologic enzyme electrode |
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| Juozas Kulys, Regina Vidziunaite.Electrocatalysis by vanadium haloperoxidase.Journal of Electroanalytical Chemistry455 1-2.1998,455(1-2),161-167. |
| Juozas Kulys, Regina Vidziunaite.Electrocatalysis by vanadium haloperoxidase.Journal of Electroanalytical Chemistry455 1-2.1998,455(1-2),161-167. * |
| Tautgirdas Ruzgas, Elisabeth Csoregi, Jenny Emneus.Peroxidase-modified electrodes: Fundamentals andapplication.Analytica Chimica Acta330 2-3.1996,330(2-3),123-128. |
| Tautgirdas Ruzgas, Elisabeth Csoregi, Jenny Emneus.Peroxidase-modified electrodes: Fundamentals andapplication.Analytica Chimica Acta330 2-3.1996,330(2-3),123-128. * |
| 曹树煜，刘均洪.过氧化物酶应用的生物技术进展.化学工业与工程技术24 5.2003,24(5),28-33. |
| 曹树煜,刘均洪.过氧化物酶应用的生物技术进展.化学工业与工程技术24 5.2003,24(5),28-33. * |
| 李文江，周兵，沙晓祥.在固体基质表面制备具有催化活性的含酶分子多层膜.吉林大学自然科学学报 4.2000,(4),75-78. |
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