CN100498323C - Electrochemical biological sensor sensing film and its preparing method and use - Google Patents
Electrochemical biological sensor sensing film and its preparing method and use Download PDFInfo
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- CN100498323C CN100498323C CNB2007100993781A CN200710099378A CN100498323C CN 100498323 C CN100498323 C CN 100498323C CN B2007100993781 A CNB2007100993781 A CN B2007100993781A CN 200710099378 A CN200710099378 A CN 200710099378A CN 100498323 C CN100498323 C CN 100498323C
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Abstract
A method for preparing sensitive film of electrochemical-biological transducer includes mixing manganese bioxide nanoslice sol with aqueous solution of myoglobin, coating mixed solution on surface of solid carrier, dipping and stewing prepared solid carrier into solution of polyethylene butyral after said carrier is dried in order to obtain a layer of biological-function sensitive film on surface of solid carrier.
Description
Technical field
The invention belongs to electrochemica biological sensor and preparing technical field thereof, particularly relate to a kind of electrochemical biological sensor sensing film and preparation method thereof and purposes, the electrochemica biological sensor function sensitive membrane that contains myoglobins/manganese dioxide nano-plates is applicable to the application in environmental contaminants such as nitrite, the sulfide mensuration.
Background technology
Electrochemica biological sensor is a kind of new sensing assays technology that grows up in recent decades.Advantages such as electrochemica biological sensor has the selectivity height, sensing range is wide, highly sensitive, instrument and equipment is simple, easy to operate are used widely at numerous areas such as clinical diagnosis, Industry Control, food and Pharmaceutical Analysis, bio-pharmaceutical exploitation, environmental analysis and military affairs.
Along with the reinforcement of people's environmental protection consciousness, the measurement that electrochemica biological sensor is applied to environmental pollutants has become one of important development direction of electrochemica biological sensor research.As at document (1) Sensors andActuators B, 2004, among the 102:162-168, people such as Yunhui Yang elder generation is at the mercaptoethylmaine of the smooth gold electrode surfaces self-assembled monolayer of cleaning, and then with glutaraldehyde as cross linker horseradish peroxidase is modified on this electrode and to be prepared enzyme function sensitive membrane, under the situation that the p-dihydroxy-benzene electron mediator exists, can be used for the detection of sulfide based on the electrochemica biological sensor of this sensitive membrane, its range of linearity is 0.5～12.7 μ M, signal to noise ratio (S/N ratio) is 3 o'clock, and the detection of sulfide is limited to 0.3 μ M.But the preparation technology of above-mentioned sensitive membrane is complicated and the more expensive horseradish peroxidase of use price; The use of electron mediator has then increased the complicacy of test operation, and is difficult to realize on-line testing.
Nano material has that specific surface area is big, the surfactivity center is many, the physicochemical property of high adsorption capacity and multiple uniqueness, nano material is introduced in the electrochemical biological sensor sensing film, electron mediator can be avoided using, and the performance index such as response sensitivity, enhancing stability and antijamming capability of sensor can be improved.As at document (2) Analytical Chemistry, 2005, among the 77:8068-8074, people such as Aihua Liu are fixed on myoglobins and constitute myoglobins/titanate nanotube sensitive membrane on the graphite electrode by titanate nanotube, based on the electrochemical sensor of this sensitive membrane to H
2O
2The range of linearity of response is 2～160 μ M, and signal to noise ratio (S/N ratio) is 3 o'clock, detects to be limited to 0.6 μ M.But the electrochemica biological sensor based on myoglobins/nano material sensitive membrane also only is used to detect H mostly
2O
2, O
2Deng material, the mensuration of using it for environmental contaminants such as nitrite, sulfide yet there are no report.
Summary of the invention:
The object of the present invention is to provide a kind of electrochemical biological sensor sensing film and preparation method thereof and purposes, a kind of new manganese dioxide nanometer sheet material is incorporated in the biological sensor sensing film, and, be applied in the mensuration of environmental contaminants such as nitrite, sulfide with the cheaper expensive peroxidase of myoglobins replacement price of price.
Myoglobin content is 2.3～33.2 μ g/cm in myoglobins provided by the invention/manganese dioxide nano-plates sensitive membrane
2, manganese dioxide nano-plates content is 0.2～10.2 μ g/cm
2Above-mentioned manganese dioxide nano-plates has negative charge and has the thickness of 1～5nm and the lateral dimension of 200～2000nm.
The preparation method of myoglobins of the present invention/manganese dioxide nano-plates biological sensor sensing film is:
The preparation of A manganese dioxide nano-plates
A-1 presses OH
-With Mn
2+Amount of substance is than being 3:1～4:1, H
2O
2With Mn
2+Amount of substance will contain the NaOH of 0.6～0.8mol/L and the H of 1.2～1.5mol/L than for 6:1～8:1
2O
2Mixed aqueous solution join the Mn (NO of 0.3～0.4mol/L fast
3)
2In the aqueous solution, vigorous stirring reaction 20～30 minutes is filtered, and filter cake is transferred in the polytetrafluoroethylcontainer container; Press OH
-With MnO
2Amount of substance is than being 2:1～4:1 and filling degree 40%～80%, adding concentration is the NaOH solution of 2～3mol/L, stir into pasty state, polytetrafluoroethylcontainer container is sealed in the water heating kettle,, water heating kettle is naturally cooled to room temperature 150～160 ℃ of hydrothermal treatment consists 15～20 hours, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 8～9, with filter cake in 70～80 ℃ of air atmospheres dry 6～9 hours, obtains layered manganese oxide.
A-2 is according to H
+Be 10:1～15:1 with layered manganese oxide amount of substance ratio, above-mentioned layered manganese oxide pressed powder is joined the HNO that concentration is 1.0～1.5mol/L
3In the aqueous solution, 10～35 ℃ of stirring reactions 3～5 days were changed the HNO of 1.0 once new～1.5mol/L therebetween every 24 hours
3Aqueous solution with the mixed liquor suction filtration, is 6～7 with deionized water wash to filtrate pH value after reaction finishes, and with filter cake in 70～80 ℃ of air atmospheres dry 6～9 hours, obtains hydrogen and exchanges manganese dioxide.
It is that 25% Tetramethylammonium hydroxide and deionized water are according to quality (gram) that A-3 exchanges manganese dioxide, massfraction with hydrogen; Volume (milliliter): volume (milliliter) is that the ratio of 1:6:100～2:10:100 is mixed, and 10～35 ℃ were descended ultrasonic 20～30 minutes, and gained colloidal sol is manganese dioxide nano-plates colloidal sol, and it is standby in 0.15～1.5mg/mL scope to adjust concentration.
The preparation of B myoglobins/manganese dioxide nano-plates sensitive membrane
Manganese dioxide nano-plates colloidal sol and the concentration that with concentration is 0.15～1.5mg/mL be 2～5mg/mL the myoglobins phosphate buffer solution by volume the ratio of 1:5～6:1 mix, be coated in clean glass-carbon electrode surface with mixing drop, after 3～5 ℃ of following dryings, it was immersed in the polyvinyl butyral ethanolic solution 1～10 minute, vapor away solvent under 10～35 ℃, form one deck myoglobins/manganese dioxide nano-plates biological function sensitive membrane on the glass-carbon electrode surface.
Adopt FDAC S-4700 type field emission scanning electron microscope (FESEM) that the layered manganese oxide presoma of hydro-thermal reaction method preparation is characterized, the result as shown in Figure 1, the layered manganese oxide presoma is a sheet, thickness is 10-30nm.Manganese dioxide nano-plates after adopting FDAC H-800 type transmission electron microscope (TEM) to the stripping layer characterizes, and the results are shown in shown in Figure 2ly, and the manganese dioxide nano-plates thickness behind the stripping layer is about 1～5nm.Adopt FESEM that myoglobins/layered manganese oxide film and myoglobins/manganese dioxide nano-plates film morphology are characterized, the result respectively as shown in Figure 3 and Figure 4, myoglobins/layered manganese oxide film is agglomerated into the sheet of 5-15 μ m at the glass carbon surface, and myoglobins/manganese dioxide nano-plates film surface continuous formation.
Effect of the present invention can be found out from the electrode performance of modifying with sensitive membrane provided by the invention.The sensitive membrane modified electrode for preparing on glass-carbon electrode with the inventive method is a working electrode, platinum electrode is to electrode, the Ag/AgCl electrode is the contrast electrode group, it is 6.5～7.0 phosphate buffered solution that three-electrode system is placed the pH value, adopts U.S. CHI660B electrochemical workstation to carry out electro-chemical test.Adopt the i-t method at-0.78V (vs.Ag/AgCl) test electrode to NaNO
2Response current, the result as shown in Figure 5, the current-responsive time is less than 4s, measuring N aNO
2The range of linearity be 0.05～5mM, be 3 o'clock in signal to noise ratio (S/N ratio), detect and be limited to 6.6 μ M.Adopt the i-t method at-0.30V (vs.Ag/AgCl) test electrode to Na
2The response current of S, the result adds Na as shown in Figure 6
2Behind the S, because Na
2S makes electric current sharply be decreased to a stable value to the inhibiting effect of protein active, and the response time is less than 3s, inhibitor Na in electric current drop-out value and the solution
2The concentration of S is directly proportional, with formula I%=100 (I
0-I)/I
0Calculate inhibiting rate, wherein I% is an inhibiting rate, I
0With I be respectively current value before and after inhibitor adds, calculate Na according to inhibiting rate
2The concentration of S, measuring N a
2The range of linearity of S is 30～120 μ M.
The invention has the advantages that: adopt the myoglobins/manganese dioxide nano-plates sensitive membrane of the present invention's preparation can be applied to the mensuration of environmental contaminants such as nitrite, sulfide, and have the advantage that sensitive membrane preparation technology is simple, cost is low.
Description of drawings
Fig. 1 is the FESEM figure of the synthetic layered manganese oxide presoma of hydro-thermal of the present invention.
Fig. 2 is the TEM figure of manganese dioxide nano-plates of the present invention.
Fig. 3 is the FESEM figure of myoglobins of the present invention/layered manganese oxide precursor thin-film.
Fig. 4 is the FESEM figure of myoglobins of the present invention/manganese dioxide nano-plates film.
Fig. 5 is that myoglobins of the present invention/manganese dioxide nano-plates sensitive membrane modified electrode is to NaNO
2The i-t curve of catalysis.Horizontal ordinate-time t (unit: second, s); Ordinate-current i (unit: microampere, μ A).
Illustration is modified electrode response current and substrate NaNO
2The concentration relationship curve, horizontal ordinate-NaNO
2Concentration (unit: micromole, μ M); Ordinate-current i (unit: microampere, μ A).
Fig. 6 is Na of the present invention
2The i-t curve that S suppresses myoglobins/manganese dioxide nano-plates sensitive membrane modified electrode.Horizontal ordinate-time t (unit: second, s); Ordinate-current i (unit: microampere, μ A).
Illustration is inhibiting rate and mortifier Na
2S concentration relationship curve.Horizontal ordinate-Na
2The concentration of S (unit: micromole, μ M); Ordinate-inhibiting rate I% (unit: percentage %)
Embodiment
The preparation of A manganese dioxide nano-plates colloidal sol:
A-1 contains 0.6mol/L NaOH and 1.5mol/L H with 200mL
2O
2Mixed solution join 100mL fast and contain 0.4mol/L Mn (NO
3)
2Solution in, vigorous stirring reaction 20 minutes is filtered, and filter cake is transferred in the 100mL teflon cup, adding 40mL concentration is the NaOH solution of 2mol/L, stirs in the pasty state, the teflon cup is sealed in the water heating kettle, 150 ℃ of hydrothermal treatment consists 15 hours.Water heating kettle being naturally cooled to room temperature, open the still suction filtration, is 8 with deionized water filter wash cake to filtrate pH value.With filter cake in 70 ℃ of air atmospheres dry 6 hours, obtain layered manganese oxide.
A-2 joins the HNO that 300mL concentration is 1mol/L with the above-mentioned layered manganese oxide pressed powder of 2.6g
3In the solution, 15 ℃ of stirring reactions 3 days were changed the HNO of once new 1mol/L therebetween every 24 hours
3Solution.With the mixed liquor suction filtration, be 6 with deionized water wash to filtrate pH value, with filter cake in 70 ℃ of air atmospheres dry 6 hours, obtain hydrogen exchange manganese dioxide.
A-3 gets 1g hydrogen exchange manganese dioxide and is dispersed in the 100mL deionized water, adds the 6mL massfraction again and be 25% Tetramethylammonium hydroxide, 15 ℃ ultrasonic 20 minutes down, gained colloidal sol is manganese dioxide nano-plates colloidal sol, adjusting concentration is that 1.5mg/mL is standby.
The preparation of B myoglobins/manganese dioxide nano-plates biological sensor sensing film:
The phosphate buffer solution of getting 60 μ L concentration and be 1.5mg/mL stripped MnO 2 colloidal sol and 10 μ L concentration and be the 3.2mg/mL myoglobins mixes, and is coated in clean glass-carbon electrode surface (myoglobins is in electrode surface concentration: 3.6 μ g/cm mixing drop
2, manganese dioxide nano-plates is in electrode surface concentration: 10.2 μ g/cm
2), after 4 ℃ of following dryings, it was immersed in the polyvinyl butyral ethanolic solution 1 minute, vapor away solvent under 15 ℃, form one deck myoglobins/manganese dioxide nano-plates sensitive membrane on the glass-carbon electrode surface.
With modified glassy carbon electrode is working electrode, and the Ag/AgCl electrode is as contrast electrode, and as to electrode, experimental temperature is 20 ± 1 ℃ with platinum filament, and test system is the phosphate buffer solution of pH=6.5.Adopt the i-t method at-0.78V (vs.Ag/AgCl) test electrode to NaNO
2Response current (as shown in Figure 5), the response time, signal to noise ratio (S/N ratio) was 3 o'clock less than 4s, detected to be limited to 6.6 μ M, the range of linearity is 0.05～5mM.Adopt the i-t method at-0.30V (vs.Ag/AgCl) test electrode to Na
2The response current of S (as shown in Figure 6), the response time is measured Na less than 3s
2The range of linearity of S is 30～120 μ M.The stability of this electrode is more than 1 month.
The preparation of A manganese dioxide nano-plates colloidal sol:
A-1 contains 0.8mol/L NaOH and 1.2mol/L H with 200mL
2O
2Mixed solution join 135mL fast and contain 0.3mol/L Mn (NO
3)
2Solution in, vigorous stirring reaction 25 minutes is filtered, and filter cake is transferred in the 100mL teflon cup, adding 40mL concentration is the NaOH solution of 3mol/L, stirs in the pasty state, the teflon cup is sealed in the water heating kettle, 155 ℃ of hydrothermal treatment consists 17 hours.Water heating kettle being naturally cooled to room temperature, open the still suction filtration, is 8.5 with deionized water filter wash cake to filtrate pH value.With filter cake in 75 ℃ of air atmospheres dry 8 hours, obtain layered manganese oxide.
A-2 joins the HNO that 300mL concentration is 1.2mol/L with the above-mentioned layered manganese oxide pressed powder of 2.6g
3In the solution, 20 ℃ of stirring reactions 4 days were changed the HNO of once new 1.2mol/L therebetween every 24 hours
3Solution.With the mixed liquor suction filtration, be 6.5 with deionized water wash to filtrate pH value, with filter cake in 70 ℃ of air atmospheres dry 8 hours, obtain hydrogen exchange manganese dioxide.
A-3 gets 1g hydrogen exchange manganese dioxide and is dispersed in the 100mL deionized water, adds the 6mL massfraction again and be 25% Tetramethylammonium hydroxide, 20 ℃ ultrasonic 30 minutes down, gained colloidal sol is manganese dioxide nano-plates colloidal sol, adjusting concentration is that 0.15mg/mL is standby.
The preparation of B myoglobins/manganese dioxide nano-plates biological sensor sensing film:
The phosphate buffer solution of getting 10 μ L concentration and be 0.15mg/mL stripped MnO 2 colloidal sol and 10 μ L concentration and be the 2mg/mL myoglobins mixes, and is coated in clean glass-carbon electrode surface (myoglobins is in electrode surface concentration: 8 μ g/cm mixing drop
2, manganese dioxide nano-plates is in electrode surface concentration: 0.6 μ g/cm
2), after 3 ℃ of following dryings, it was immersed in the polyvinyl butyral ethanolic solution 10 minutes, vapor away solvent under 20 ℃, form one deck myoglobins/manganese dioxide nano-plates sensitive membrane on the glass-carbon electrode surface.
With modified glassy carbon electrode is working electrode, and the Ag/AgCl electrode is as contrast electrode, and as to electrode, experimental temperature is 20 ± 1 ℃ with platinum filament, and test system is the phosphate buffer solution of pH=7.0.Adopt the i-t method at-0.78V (vs.Ag/AgCl) test electrode to NaNO
2Response current, the response time, signal to noise ratio (S/N ratio) was 3 o'clock less than 6s, detected to be limited to 63 μ M, the range of linearity is 0.5～4.5mM.Adopt the i-t method at-0.30V (vs.Ag/AgCl) test electrode to K
2The response current of S, the response time is measured K less than 5s
2The range of linearity of S is 0.27～1.17mM.The stability of this electrode is more than 25 days.
The preparation of A manganese dioxide nano-plates colloidal sol:
A-1 contains 0.7mol/L NaOH and 1.2mol/L H with 175mL
2O
2Mixed solution join 100mL fast and contain 0.35mol/L Mn (NO
3)
2Solution in, vigorous stirring reaction 30 minutes is filtered, filter cake is transferred in the 100mL teflon cup, and adding 56mL concentration is the NaOH solution of 2.5mol/L, stirs in the pasty state, the teflon cup is sealed in the water heating kettle, 160 ℃ of hydrothermal treatment consists 20 hours.Water heating kettle being naturally cooled to room temperature, open the still suction filtration, is 9 with deionized water filter wash cake to filtrate pH value.With filter cake in 80 ℃ of air atmospheres dry 9 hours, obtain layered manganese oxide.
A-2 joins the HNO that 300mL concentration is 1.5mol/L with the above-mentioned layered manganese oxide pressed powder of 2.6g
3In the solution, 35 ℃ of stirring reactions 5 days were changed once new 1.5mol/LHNO therebetween every 24 hours
3Solution.With the mixed liquor suction filtration, be 7 with deionized water wash to filtrate pH value, with filter cake in 80 ℃ of air atmospheres dry 9 hours, obtain hydrogen exchange manganese dioxide.
A-3 gets 1g hydrogen exchange manganese dioxide and is dispersed in the 100mL deionized water, adds the 6mL massfraction again and be 25% Tetramethylammonium hydroxide, 35 ℃ ultrasonic 25 minutes down, gained colloidal sol is manganese dioxide nano-plates colloidal sol, adjusting concentration is that 1.0mg/mL is standby.
The preparation of B myoglobins/manganese dioxide nano-plates biological sensor sensing film:
The phosphate buffer solution of getting 10 μ L concentration and be 1.0mg/mL stripped MnO 2 colloidal sol and 50 μ L concentration and be the 5mg/mL myoglobins mixes, and is coated in clean glass-carbon electrode surface (myoglobins is in electrode surface concentration: 33.2 μ g/cm mixing drop
2, manganese dioxide nano-plates is in electrode surface concentration: 1.3 μ g/cm
2), after 5 ℃ of following dryings, it was immersed in the polyvinyl butyral ethanolic solution 5 minutes, vapor away solvent under 35 ℃, form one deck myoglobins/manganese dioxide nano-plates sensitive membrane on the glass-carbon electrode surface.
With modified glassy carbon electrode is working electrode, and the Ag/AgCl electrode is as contrast electrode, and as to electrode, experimental temperature is 20 ± 1 ℃ with platinum filament, and test system is the phosphate buffer solution of pH=7.0.Adopt the i-t method at-0.78V (vs.Ag/AgCl) test electrode to KNO
2Response current, the response time, signal to noise ratio (S/N ratio) was 3 o'clock less than 5s, detected to be limited to 20 μ M, the range of linearity is 32～107mM.Adopt the i-t method at-0.30V (vs.Ag/AgCl) test electrode to Na
2The response current of S, the response time, the range of linearity of measuring Na2S was 10～50 μ M less than 4s.The stability of this electrode is more than 25 days.
Claims (5)
1, a kind of electrochemical biological sensor sensing film is characterized in that: sensitive membrane is made up of myoglobins and the manganese dioxide nano-plates that has negative charge, and wherein myoglobin content is 2.3～33.2 μ g/cm
2, the manganese dioxide nano-plates content that has negative charge is 0.2～10.2 μ g/cm
2
2, sensitive membrane as claimed in claim 1 is characterized in that: the described manganese dioxide nano-plates that has negative charge has the thickness of 1～5nm and the lateral dimension of 200～2000nm.
3, a kind of method for preparing the described electrochemical biological sensor sensing film of claim 1, it is characterized in that: the manganese dioxide nano-plates colloidal sol that has negative charge and the concentration that with concentration is 0.15～1.5mg/mL be 2～5mg/mL the myoglobins phosphate buffer solution by volume the ratio of 1:5～6:1 mix, be coated in clean glass-carbon electrode surface with mixing drop, after 3～5 ℃ of following dryings, it was immersed in the polyvinyl butyral ethanolic solution 1～10 minute, vapor away solvent under 10～35 ℃, form one deck myoglobins/have manganese dioxide nano-plates biological function sensitive membrane of negative charge on glass-carbon electrode surface.
4, in accordance with the method for claim 3, it is characterized in that: the described manganese dioxide nano-plates that has negative charge prepares by following technology:
(1) presses OH
-With Mn
2+Amount of substance is than being 3:1～4:1, H
2O
2With Mn
2+Amount of substance will contain the NaOH of 0.6～0.8mol/L and the H of 1.2～1.5mol/L than for 6:1～8:1
2O
2Mixed aqueous solution join the Mn (NO of 0.3～0.4mol/L fast
3)
2In the aqueous solution, vigorous stirring reaction 20～30 minutes is filtered, and filter cake is transferred in the polytetrafluoroethylcontainer container; Press OH
-With MnO
2Amount of substance is than being 2:1～4:1 and filling degree 40%～80%, adding concentration is the NaOH solution of 2～3mol/L, stir into pasty state, polytetrafluoroethylcontainer container is sealed in the water heating kettle,, water heating kettle is naturally cooled to room temperature 150～160 ℃ of hydrothermal treatment consists 15～20 hours, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 8～9, with filter cake in 70～80 ℃ of air atmospheres dry 6～9 hours, obtains layered manganese oxide;
(2) according to H
+Be 10:1～15:1 with layered manganese oxide amount of substance ratio, above-mentioned layered manganese oxide pressed powder is joined the HNO that concentration is 1.0～1.5mol/L
3In the aqueous solution, 10～35 ℃ of stirring reactions 3～5 days were changed the HNO of a 1.0～1.5mol/L therebetween every 24 hours
3Aqueous solution with the mixed liquor suction filtration, is 6～7 with deionized water wash to filtrate pH value after reaction finishes, and with filter cake in 70～80 ℃ of air atmospheres dry 6～9 hours, obtains hydrogen and exchanges manganese dioxide;
(3) hydrogen to be exchanged manganese dioxide, massfraction be 25% Tetramethylammonium hydroxide and deionized water according to quality g: volume ml: volume ml is that the ratio of 1:6:100～2:10:100 is mixed, 10～35 ℃ were descended ultrasonic 20～30 minutes, gained colloidal sol is the manganese dioxide nano-plates colloidal sol that has negative charge, and it is standby in 0.15～1.5mg/mL scope to adjust concentration.
5, the purposes of the described electrochemical biological sensor sensing film of a kind of claim 1 is characterized in that: be used for the mensuration of nitrite to environmental pollutants or sulfide, wherein nitrite comprises NaNO
2, KNO
2, sulfide comprises Na
2S, K
2S, H
2S.
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| CN101281158B (en) * | 2008-05-20 | 2010-11-17 | 北京化工大学 | DNA sensitivity electrode modified by hydrotalcite nanometer slice and preparation thereof |
| CN101718739A (en) * | 2009-12-14 | 2010-06-02 | 北京化工大学 | Manganese dioxide nano-sheet modified electrode and preparing method thereof and using method thereof |
| CN102590317B (en) * | 2012-01-17 | 2013-10-30 | 齐齐哈尔大学 | PH composite electrode method for measuring content of nitrite ions in solution |
| CN104316580B (en) * | 2014-10-20 | 2018-03-27 | 中南林业科技大学 | A kind of method of nanogold enzyme sensor detection water nitrite |
| CN114047237A (en) * | 2021-11-17 | 2022-02-15 | 云南大学 | Application of manganese dioxide nanocomposite in nitrite detection, electrochemical sensor, preparation method and detection method |
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Non-Patent Citations (4)
| Title |
|---|
| Electrochemical Catalysis of Styrene Epoxidation with Films ofMnO2 Nanoparticles and H2O2. Laura Espinal等.Journal of American Chemical Society,Vol.126 No.24. 2004 |
| Electrochemical Catalysis of Styrene Epoxidation with Films ofMnO2 Nanoparticles and H2O2. Laura Espinal等.Journal of American Chemical Society,Vol.126 No.24. 2004 * |
| Immobilization of Myoglobin on Phosphate and PhosphonateGrafted-Zirconia Nanoparticles. Francesca Bellezza等.Langmuir,Vol.21 No.24. 2005 |
| Immobilization of Myoglobin on Phosphate and PhosphonateGrafted-Zirconia Nanoparticles. Francesca Bellezza等.Langmuir,Vol.21 No.24. 2005 * |
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