CN106229586A - A bovine serum albumin strengthens ascorbic acid/glucose fuel cell and application thereof - Google Patents

A bovine serum albumin strengthens ascorbic acid/glucose fuel cell and application thereof Download PDF

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CN106229586A
CN106229586A CN201610616696.XA CN201610616696A CN106229586A CN 106229586 A CN106229586 A CN 106229586A CN 201610616696 A CN201610616696 A CN 201610616696A CN 106229586 A CN106229586 A CN 106229586A
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serum albumin
ascorbic acid
fuel cell
bovine serum
glucose
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CN106229586B (en
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王奕
梁兴煇
李红
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South China Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

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Abstract

The invention belongs to photocatalytic fuel cell field, disclose a bovine serum albumin and strengthen ascorbic acid/glucose Optical Electro-Chemistry fuel cell and application thereof.The present invention is with bovine serum albumin sensitization CdS/TiO2Electrode makees light anode, utilizes bovine serum albumin to enhance ascorbic acid/glucose at ultraviolet excitation CdS/TiO2Photochemical catalytic oxidation on electrode, and based on it, have developed a photocatalytic fuel cell, its open-circuit voltage is 0.64V, peak power 6.33 μ W cm‑2, short circuit current is 0.126mA cm‑2, photoelectric transformation efficiency is 10.7%.The method uses serum albumin to reduce mediator as photosensitized oxidation, and in blood, ascorbic acid and glucose make fuel, have the advantages such as low cost, environmental protection, photoelectric transformation efficiency height, good biocompatibility.

Description

A bovine serum albumin strengthens ascorbic acid/glucose fuel cell and application thereof
Technical field
The invention belongs to photocatalytic fuel cell field, be specifically related to a bovine serum albumin and strengthen ascorbic acid/Portugal Grape sugar fuel cell and application thereof.
Background technology
Glucose, ascorbic acid and serum albumin in blood plays very important physiology merit in vital movement Energy.Glucose is as the energy supply material of human body, and ascorbic acid is as the metabolism of necessary vitamin participation substance in vivo, and serum Albumin is as transport and operate endogenous and the carrier protein of exogenous material, these materials phase interaction in physiological conditions With, and maintain normal vital movement.It addition, bovine serum albumin (BSA) is tied with human serum albumin (HSA) owing to having Structure height is similar, abundance, be easy to the feature such as purification, low cost, therefore often as sero-abluminous representative.To this end, It is desirable that use serum albumin to reduce mediator as photosensitized oxidation, in blood, ascorbic acid and glucose make fuel, Construct a Optical Electro-Chemistry fuel cell.
At present the catalyst such as enzyme, coenzyme, microorganism, metal complex, metal and metal-oxide has been used for promoting anti-bad Hematic acid and the oxidation of glucose, and it is applied to their structure analyzing detection and each money fuel cell.But, serum albumin It is a kind of non-oxide reproducibility albumen, is typically easy to absorption and causes electrode activity to decline at electrode surface, so being difficult to Electronics and the transmission of material, therefore the most not yet have the report using serum albumin as photosensitized oxidation reduction mediator. Can not only be combined with ascorbic acid in view of bovine serum albumin, and it contains two tryptophans on 134 and 212 (Trp) chromophoric group can be caused the change of bovine serum albumin configuration on Nano semiconductor electrode, simultaneously by ultraviolet excitation Produced oxidoreduction mediator by photoinduction and promote the photochemical catalytic oxidation of ascorbic acid.It addition, ascorbic acid is with glucose all Having polyhydric circulus, its oxidation product aoxidizes possibly as the catalysis of oxidant mediating glucose.
Summary of the invention
In place of overcoming shortcoming and defect of the prior art, research blood in serum albumin, ascorbic acid and Interaction between glucose, it is achieved the serum albumin in blood reduces mediator as photosensitized oxidation, strengthens antagonism The photochemical catalytic oxidation of bad hematic acid/glucose, the primary and foremost purpose of the present invention is to provide a bovine serum albumin to strengthen Vitamin C Acid/glucose fuel cell.This battery is with bovine serum albumin sensitization CdS/TiO2Electrode is as light anode, and carbon felt is as the moon Pole, in blood, ascorbic acid and glucose make fuel, and oxygen, as oxidant, builds Optical Electro-Chemistry fuel under ultraviolet radiation Battery.
It is still another object of the present invention to provide above-mentioned bovine serum albumin and strengthen ascorbic acid/glucose fuel cell Application.
The object of the invention is achieved through the following technical solutions:
A bovine serum albumin strengthens ascorbic acid/glucose fuel cell, and this fuel cell is with bovine serum albumin Bai Minhua CdS/TiO2Electrode makees light anode, is the electrolyte solution containing ascorbic acid and glucose in anode pool；Make with carbon felt Negative electrode, is buffer solution in cathode pool, and is maintained under saturated oxygen atmosphere encloses；Build under ultraviolet radiation and form Optical Electro-Chemistry Fuel cell.
Described bovine serum albumin sensitization CdS/TiO2Electrode is prepared in accordance with the following methods: take containing 0.1mmol/ The buffer 10 μ L of the bovine serum albumin of L, is added drop-wise to CdS/TiO2The coating film area of electrode, puts in baking oven 40 DEG C and is dried 12h, obtains bovine serum albumin sensitization CdS/TiO2Electrode, puts into camera bellows and saves backup.
Described fuel cell peak power under ultraviolet radiation reaches 6.33 μ W cm-2, short circuit current is 0.126mA cm-2, electricity conversion is 10.7%.
Described bovine serum albumin concentration in electrolyte solution is 0.0001～0.01mol/L；Described ascorbic acid with And glucose concentration in electrolyte solution is 0.001～0.4mol/L.
Described electrolyte solution be concentration be containing 0.1mol/L sodium chloride, 0.02mol/L trishydroxymethylaminomethane Buffer solution, its pH value is 7.2.
It is connected with saturated potassium chloride salt bridge between described anode pool and cathode pool.
The intensity of described ultraviolet radiation is 35 μ W cm-2。
It is white that above-mentioned bovine serum albumin strengthens ascorbic acid/glucose fuel cell serum in photoanalysis, blood In the detection of the evaluation of the interaction relationship between albumen and ascorbic acid and glucose and ascorbic acid and glucose Application.
The principle of the present invention:
The present inventor for glucose in blood, ascorbic acid and the feature of sero-abluminous 26S Proteasome Structure and Function, in order to Rationally play their functionality advantage, construct a novel Optical Electro-Chemistry fuel cell.The present invention have selected to be had well The Nano cadmium sulphide (CdS) of photoelectric properties and nano titanium oxide (TiO2), and it is affixed to conduct in electro-conductive glass substrate Light anode.Further, since carbon felt (CF) has the features such as high, big, the 3 D stereo network structure of porosity of specific surface area, so energy Enough accelerate the process of catalytic reaction, be the good cathode material as reduction oxygen.Finally, under ultraviolet radiation, by above-mentioned Light anode and negative electrode build a bovine serum albumin and strengthen ascorbic acid/glucose Optical Electro-Chemistry fuel cell, it is achieved that cattle Serum albumin is as ascorbic acid and glucose in photosensitized oxidation reduction mediator catalysis oxygenate blood.
Compared with the existing methods, the present invention has the following advantages and beneficial effect:
(1) present invention carrys out sensitization light anode with the serum albumin in blood, makes simple, has high photocatalysis and lives Property, good biocompatibility；
(2) present invention with in blood rich in material make fuel, oxygen makees oxidant, environment friendly and pollution-free；
(3) present invention achieves bovine serum albumin and strengthen the photochemical catalytic oxidation of ascorbic acid/glucose；
(4) photocatalytic fuel cell constructed by the present invention the most normally works；
(5) photocatalytic fuel cell that the present invention builds peak power under ultraviolet excitation reaches 6.33 μ W cm-2, short Road electric current is 0.126mA cm-2, electricity conversion is 10.7%.
Accompanying drawing explanation
Fig. 1 is bovine serum albumin sensitization CdS/TiO made in the embodiment of the present invention 12Light anode is containing not jljl Linear voltammetric scan curve in the electrolyte of matter, wherein curve 1,2,3,4 corresponds respectively at buffer, glucose, anti-bad Measurement result in hematic acid and ascorbic acid/glucose；
Fig. 2 is that Optical Electro-Chemistry fuel cell constructed in the embodiment of the present invention 1 is in the electrolyte containing different material Photoelectric current changes over curve, and wherein curve 1,2,3,4 corresponds respectively at buffer, glucose, ascorbic acid and anti-bad Measurement result in hematic acid/glucose；
Fig. 3, Fig. 4 are respectively in the embodiment of the present invention 1 power density and the electricity of constructed Optical Electro-Chemistry fuel cell Current density is with the change curve of cell voltage.Wherein curve 1,2 corresponds respectively to CdS/TiO under dark condition2Electrode is anti-bad Measurement result in hematic acid and ascorbic acid/glucose, curve 3 is then corresponding to CdS/TiO under illumination condition2Electrode is at Vitamin C Measurement result in acid/glucose.It addition, curve 4,5,6,7 corresponds respectively to bovine serum albumin sensitization under illumination condition CdS/TiO2Electrode measurement result in ascorbic acid, ascorbic acid/glucose, buffer and glucose.
Specific implementation method
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this. According to purpose of design of the present invention, use allied substances replacement and the size and dimension of the material used is changed, such as Change the electrode size size of the photocatalytic fuel cell of the present invention, or change electrode outward appearance, simply change bovine serum albumin In vain, ascorbic acid or glucose consumption etc. all should belong to the scope of the present invention；Experimental technique employed in following embodiment is such as Without supplementary notes, it is the existing conventional method of the art；The material that used, reagent etc., as without supplementary notes, being The reagent commercially obtained and material.
Embodiment 1 builds ultraviolet excitation bovine serum albumin and strengthens ascorbic acid/glucose fuel cell
The bovine serum albumin sensitization CdS/TiO of the present embodiment2Electrode, is prepared by the following method and obtains:
(1) indium tin oxide-coated glass (ITO) is immersed the prepared scattered TiO of ethanol2(after 450 DEG C of calcination processing) After solution, carry out three liftings, make solution be attached in substrate, after taking-up, this electrode is put in baking oven after 40 DEG C of dry 12h Obtain TiO2Electrode, puts into camera bellows and preserves.
(2) method using cyclic voltammetry electro-deposition, working electrode is TiO2Electrode, is titanium plate electrode to electrode, ginseng Being saturated calomel electrode than electrode, form three-electrode system, electrolyte is for sulfur containing 0.01mol/L Caddy (Cleary), 0.01mol/L sulfur PH 2.0 solution of acid sodium, the potential range of deposition is-0.3V～-0.9V, sweeps speed for 0.05V s-1, the scanning number of turns is 100 circles, Take out the electrode that deposit and put in baking oven after 40 DEG C of dry 12h process, obtaining CdS/TiO2Electrode, puts into camera bellows and preserves standby With.
(3) take the bovine serum albumin buffer 10 μ L containing 0.1mmol/L, be added drop-wise to CdS/TiO2The plated film district of electrode Territory, puts into 40 DEG C of dry 12h in baking oven, obtains bovine serum albumin sensitization CdS/TiO2Electrode, puts into camera bellows and saves backup.
The structure of the Optical Electro-Chemistry fuel cell of the present embodiment, concrete operation step is as follows:
With prepared bovine serum albumin sensitization CdS/TiO2Electrode, as light anode, adds 0.1mol/L chlorine in anode pool Change sodium, 0.02mol/L trishydroxymethylaminomethane (pH 7.2), 0.1mol/L glucose and 0.1mol/L ascorbic acid, and lead to Enter nitrogen and remove the oxygen in anode pool；Using carbon felt as negative electrode, cathode pool adds 0.1mol/L sodium chloride and 0.02mol/L Trishydroxymethylaminomethane (pH 7.2), and persistently lead to oxygen to be maintained at saturated oxygen atmosphere and enclose under, with saturated between two electrode cell Potassium chloride salt bridge is connected；Build under ultraviolet radiation and form Optical Electro-Chemistry fuel cell, be proposed by the invention a Bovine serum albumin strengthens ascorbic acid/glucose fuel cell.
Embodiment 2 ascorbic acid and ascorbic acid promote the electrocatalytic oxidation of glucose
To the bovine serum albumin sensitization CdS/TiO prepared in embodiment 12Electrode is at ascorbic acid and Vitamin C Carrying out linear voltammetric scan in acid/glucose, concrete operation step is as follows:
The bovine serum albumin sensitization CdS/TiO made with embodiment 12Electrode is as working electrode, and Ti electrode is as right Electrode, saturated calomel electrode, as reference electrode, builds three-electrode system and connects upper electrochemical workstation, using linear volt-ampere Scan method measures the electric current in buffer (1), glucose (2), ascorbic acid (3) and glucose/ascorbic acid (4) respectively With the change curve (Fig. 1) of current potential, in order to illustrate bovine serum albumin sensitization CdS/TiO2Electrode Ascorbic Acid and Vitamin C Acid promotes the electrocatalysis of glucose, and result is as shown in Figure 1.
Curve 1 is shown that in buffer, and electric current is very mild with potential change, oxidation current signal does not occurs；So After rear addition glucose, curve 2 display electric current with potential change trend compared with curve 1 almost unchanged, individualism is described Glucose be difficult at bovine serum albumin sensitization CdS/TiO2Electrocatalytic oxidation is there is on electrode；If being individually added into ascorbic acid Time, curve 3 occurs in that a fairly obvious oxidation peak, its spike potential is 0.31V, and current intensity is 40.7 μ A, illustrates Ascorbic acid can be at bovine serum albumin sensitization CdS/TiO2There is electrocatalytic oxidation on electrode, and can fire as one Material；When being simultaneously introduced ascorbic acid and glucose, curve 4 also occurs in that an oxidation peak, and its spike potential is 0.33V, electric current Intensity is 50.8 μ A, and compared to curve 3, current potential is more or less the same, and electric current adds 10.2 μ A cm-2, improve 24.9%, explanation Ascorbic acid not only serves as fuel, and can remarkably promote glucose electrocatalytic oxidation.
Embodiment 3 ultraviolet light strengthens the photochemical catalytic oxidation of ascorbic acid/glucose
The Optical Electro-Chemistry fuel cell building embodiment 1 is tested, and concrete operation step is as follows:
Connecting Optical Electro-Chemistry anode of fuel cell and negative electrode with resistance box, the resistance of fixed resistance case is 10,000 ohm, when waiting Between spacing control switch lamp, electric current density (Fig. 2) versus time curve of survey calculation Optical Electro-Chemistry fuel cell.
Being shown that in buffer in curve 1, time dark, no signal current occurs, and under ultraviolet radiation, goes out Having showed an obvious photoelectric current, value is 6.72 μ A cm-2；After being subsequently adding glucose, curve 2 shows when dark also without electricity Stream signal occurs, and the photoelectric current under ultraviolet radiation is 6.73 μ A cm-2, almost unchanged compared to curve 1, illustrate individually The glucose existed is difficult at bovine serum albumin sensitization CdS/TiO2Photochemical catalytic oxidation is there is on electrode；If only adding Vitamin C During acid, in curve 3, occur in that value is 5.2 μ A cm-2Dark current, the total current under illumination is 9.56 μ A cm-2, with song Line 1 is compared, and improves 42.3%, illustrates that ascorbic acid can be at bovine serum albumin sensitization CdS/TiO2Light is occurred to urge on electrode Change oxidation；When being simultaneously introduced ascorbic acid and glucose, the dark current of curve 4 display is 6.44 μ A cm-2, total under illumination Electric current is 10.3 μ A cm-2, compared to curve 3, dark current, total current all significantly increase, and compared with curve 1, improve 53.1%, illustrate that ascorbic acid can promote that glucose is at bovine serum albumin sensitization CdS/TiO2Photocatalytic-oxidation is there is on electrode Change.
Under embodiment 4 ultraviolet light spoke, bovine serum albumin strengthens ascorbic acid/glucose fuel cell performance
Test to the Optical Electro-Chemistry fuel battery performance that embodiment 1 builds, concrete operation step is as follows:
Use resistance box to connect light anode and the negative electrode of Optical Electro-Chemistry fuel cell, change the resistance value of resistance box, and survey Amount calculates the power density (Fig. 3) of photocatalytic fuel cell and electric current density (Fig. 4) change curve with cell voltage.
Test uses CdS/TiO the most in the dark2The fuel cell that electrode builds, curve 1 is shown that the most anti- During bad hematic acid, the open-circuit voltage of fuel cell is 0.247V, and short circuit current is 73.9 μ A cm-2, and reach at 0.077V High-power 2.71 μ W cm-2；When being then simultaneously introduced ascorbic acid and glucose, curve 2 shows the open-circuit voltage of fuel cell For 0.283V, short circuit current is 83.11 μ A cm-2, and at 0.09V, reach peak power 3.1 μ W cm-2, compared to curve 1, the open-circuit voltage of fuel cell, short circuit current, peak power etc. both increase, and illustrate that glucose can in the presence of ascorbic acid With at CdS/TiO2Electrocatalytic oxidation is there is on electrode；Then under ultraviolet light spoke, test uses CdS/TiO2The light that electrode builds Electrochemical fuel cell, curve 3 shows that the open-circuit voltage of ascorbic acid/glucose fuel cell is 0.6V, and short circuit current is 0.1mA·cm-2, at 0.1V, reach peak power 4.57 μ W cm-2, compared to curve 2, the OCP of fuel cell, short Road electric current, peak power etc. both increase, and the addition of ultraviolet light makes the peak power of fuel cell improve 47.4%.Then, Under ultraviolet light spoke, test uses bovine serum albumin sensitization CdS/TiO2The Optical Electro-Chemistry fuel cell that light anode builds, bent Line 6 shows in buffer, and the open-circuit voltage of Optical Electro-Chemistry fuel cell is 0.61V, and short circuit current is 5.4 μ A cm-2, Peak power 1.7 μ W cm is reached at 0.4V-2, and after adding glucose, curve 7 shows that the open-circuit voltage of fuel cell is 0.61V, short circuit current is 5.6 μ A cm-2, at 0.4V, reach peak power 1.72 μ W cm-2, compared to curve 6, fuel The open-circuit voltage of battery, short circuit current, peak power etc. are the most almost unchanged, illustrate in the presence of only glucose, and glucose is difficult With at bovine serum albumin sensitization CdS/TiO2Photochemical catalytic oxidation is there is on electrode；If be individually added into ascorbic acid, curve 4 shows The open-circuit voltage showing Optical Electro-Chemistry fuel cell is 0.62V, and short circuit current is 0.105mA cm-2, at 0.1V, reach maximum work Rate 5.36 μ W cm-2；In the presence of when glucose and ascorbic acid while, curve 5 shows the open-circuit voltage of photocatalytic fuel cell For 0.64V, short circuit current is 0.126mA cm-2, at 0.1V, reach peak power 6.33 μ W cm-2, electricity conversion Being 10.7%, compared to curve 3, the OCP of fuel cell, short circuit current, peak power etc. both increase, wherein maximum Power enhances 38.5%, illustrates present invention achieves under ultraviolet radiation, and bovine serum albumin strengthens ascorbic acid/Fructus Vitis viniferae The photochemical catalytic oxidation of sugar, improves the performance of Optical Electro-Chemistry fuel cell.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify, All should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (8)

  1. The most a bovine serum albumin strengthens ascorbic acid/glucose fuel cell, it is characterised in that: this fuel cell is with cattle Serum albumin sensitization CdS/TiO2Electrode makees light anode, is the electrolyte solution containing ascorbic acid and glucose in anode pool； Make negative electrode with carbon felt, cathode pool is buffer solution, and be maintained under saturated oxygen atmosphere encloses；Build under ultraviolet radiation and formed Optical Electro-Chemistry fuel cell.
  2. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell, and its feature exists In: described bovine serum albumin sensitization CdS/TiO2Electrode is prepared in accordance with the following methods: take the cattle containing 0.1mmol/L Sero-abluminous buffer 10 μ L, is added drop-wise to CdS/TiO2The coating film area of electrode, puts into 40 DEG C of dry 12h in baking oven, To bovine serum albumin sensitization CdS/TiO2Electrode, puts into camera bellows and saves backup.
  3. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell, and its feature exists Under: described fuel cell is at ultraviolet radiation, peak power reaches 6.33 μ W cm-2, short circuit current is 0.126mA cm-2, light Electricity transformation efficiency is 10.7%.
  4. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell, and its feature exists In: described bovine serum albumin concentration in electrolyte solution is 0.0001～0.01mol/L；Described ascorbic acid and Fructus Vitis viniferae Sugar concentration in electrolyte solution is 0.001～0.4mol/L.
  5. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell, and its feature exists In: described electrolyte solution be concentration be that the buffering containing 0.1mol/L sodium chloride, 0.02mol/L trishydroxymethylaminomethane is molten Liquid, its pH value is 7.2.
  6. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell, and its feature exists In: it is connected with saturated potassium chloride salt bridge between described anode pool and cathode pool.
  7. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell, and its feature exists In: the intensity of described ultraviolet radiation is 35 μ W cm-2。
  8. A bovine serum albumin the most according to claim 1 strengthens ascorbic acid/glucose fuel cell and divides at photoelectricity Analysis, the evaluation of the interaction relationship between serum albumin and ascorbic acid and glucose in blood and ascorbic acid and Application in the detection of glucose.
CN201610616696.XA 2016-07-29 2016-07-29 A bovine serum albumin(BSA) enhancing ascorbic acid/glucose fuel cell and its application Expired - Fee Related CN106229586B (en)

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CN107768692A (en) * 2017-08-31 2018-03-06 华南师范大学 A poly-dopamine enveloped carbon nanometer tube strengthens ascorbic acid/glucose fuel cell
CN107782777A (en) * 2017-08-31 2018-03-09 华南师范大学 A kind of either high redox activity bovine serum albumin(BSA) carbon nano-tube combination electrode and its preparation method and application
CN108017794A (en) * 2017-10-24 2018-05-11 华南师范大学 A kind of methylene blue-bovine serum albumin(BSA) composite membrane and its preparation method and application
CN111118532A (en) * 2019-11-21 2020-05-08 华南师范大学 Method for preparing zinc gluconate based on photo-enhanced fruit fuel cell

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CN111118532B (en) * 2019-11-21 2021-12-10 华南师范大学 Method for preparing zinc gluconate based on photo-enhanced fruit fuel cell

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