| 英文摘要 | 第1-12页 |
| 摘要 | 第12-16页 |
| ACKNOWLEDGMENTS | 第16-18页 |
| 致谢 | 第18-20页 |
| 详细摘要 | 第20-51页 |
| 论文概述 | 第51-86页 |
| General introduction | 第86-90页 |
| Part I Bibliography | 第90-116页 |
| 1. Introduction | 第92-93页 |
| 2. Mass transport | 第93-95页 |
| ·General introduction about mass transport | 第93-94页 |
| ·Recent advancements in the study of mass transport | 第94-95页 |
| Mass transport in microfluidic systems and 1ab-on-chips | 第94页 |
| Mass transport in polymers | 第94-95页 |
| Mass transport in biological and pharmaceutical areas | 第95页 |
| 3. Establishment of concentration profiles | 第95-102页 |
| ·Evolution of concentration profiles | 第95-97页 |
| ·Techniques of establishing concentration profiles | 第97-102页 |
| ·Optical and spectroscopic methods | 第97-99页 |
| Infrared spectroscopy | 第97页 |
| Ultraviolet- visible (UV-visible) spectroscopy | 第97-98页 |
| Raman spectroscopy | 第98页 |
| The other techniques | 第98-99页 |
| ·Electrochemical methods | 第99-102页 |
| Electrochemical detection with potentiometric mode | 第99-101页 |
| Electrochemical detection in amperometric mode | 第101-102页 |
| 4. Mapping concentration profiles with ultramicroelectrodes as local probes | 第102-114页 |
| ·About ultramicroelectrodes | 第102-109页 |
| ·Introduction of UMEs | 第102-104页 |
| ·Advantages of UMEs and their applications | 第104-109页 |
| Advantages of UMEs | 第104-105页 |
| Applications of UMEs | 第105-109页 |
| ·UMEs in amperometric mode as local probes | 第109-114页 |
| ·Controlled amperometric detection | 第110-113页 |
| ·Steady state amperometric detection | 第113-114页 |
| 5. Conclusion | 第114-116页 |
| Part II Applications of mapping concentration profiles on the study of the role of spontaneous convection in mass transport | 第116-160页 |
| 1. Introduction | 第118-120页 |
| 2. Model describing the contribution of spontaneous convectionto mass transport | 第120-134页 |
| ·Establishment of the model | 第120-126页 |
| ·Nernst diffusion layer model | 第120-121页 |
| ·Introduction of fluid particles and spatial-dependent Dconv | 第121-122页 |
| ·General equation of mass transport with diffusion / convection in one direction | 第122-123页 |
| ·Evolution of the diffusion coefficient Dconv as a function of space | 第123-125页 |
| ·Introduction of the apparent diffusion coefficient Dapp | 第125-126页 |
| ·Steady state diffusion imposed by spontaneous convection | 第126-128页 |
| ·Value of the convection layer thickness | 第126-127页 |
| ·Expression of the steady state concentration profile | 第127-128页 |
| ·Transition from transient diffusion to steady state diffusion | 第128-131页 |
| ·Competition between spontaneous convection and non-planar diffusion for the accomplishment of the steady state | 第131-134页 |
| 3 Study of the role of spontaneous convection during cyclic voltammetry | 第134-143页 |
| ·Theory | 第135-137页 |
| ·Experimental | 第137-143页 |
| ·Concentration profiles mapped at different potentials during cyclic voltammetry | 第138-141页 |
| ·Cyclic voltammograms at different scan rates | 第141-143页 |
| 4 Competition between spontaneous convection and non-planar diffusion | 第143-156页 |
| ·Theory | 第143-152页 |
| ·Steady-state. regimes | 第144-147页 |
| Steady state with pure diffusion | 第144页 |
| Steady state controlled by spontaneous convection | 第144-146页 |
| Isoconcentration lines on the surface of the electrode | 第146-147页 |
| ·Elaboration of a zone diagram | 第147-149页 |
| ·Diagram describing the transitions between the different zones | 第149-152页 |
| Transition between convection and diffusion | 第150页 |
| Other transitions | 第150-151页 |
| Diagram describing the transitions between the different zones | 第151-152页 |
| ·Experimental concentration profiles | 第152-156页 |
| 5 Discussion and conclusion | 第156-160页 |
| Part III Study of density gradients inducing convection through mapping concentrations profiles in the diffusion layer of an electrode | 第160-188页 |
| 1. Introduction | 第162-163页 |
| 2. Theory | 第163-165页 |
| Contribution of density gradients inducing convection to mass transport | 第164-165页 |
| 3. Experimental | 第165-186页 |
| ·About the experimental setup | 第165-167页 |
| ·Study of chronoamperometric behaviours with only spontaneous convection and diffusion as the forms of mass transport | 第167-170页 |
| Transient chronoamperometric behaviours as the function of the electrode size | 第168-170页 |
| ·Study of density gradients inducing convection | 第170-186页 |
| ·Effects of density gradients inducing convection on the chronoamperometric currents | 第170-173页 |
| ·Study of the effects of the density gradients inducing convection through the model of spontaneous convection and diffusion | 第173-186页 |
| Evolution of the diffusion layer thickness δ_(layer) | 第173-176页 |
| Evolution of the diffusion layer thickness estimated from the current (δ_(app)) | 第176-179页 |
| Comparison between the convection layer thickness 5conv estimated from δ_(layer)~(stat) and δ _(conv)~' estimated from δ_(app)~(stat) | 第179-186页 |
| 4. Conclusion | 第186-188页 |
| Part IV Study of the contributions of migration and spontaneous convection to mass transport through monitoring steady state concentration profiles in the diffusion layer of an electrode | 第188-208页 |
| 1. Introduction | 第190-192页 |
| 2. Establishment of theoretical concentration profiles | 第192-199页 |
| ·Mass transport with diffusion,migration and convection | 第192-197页 |
| ·Equations of mass transport with diffusion, migration and convection | 第192-193页 |
| ·Resolution of the mass transport equations | 第193-197页 |
| Introduction of dimensionless parameters | 第193-194页 |
| Boundary conditions | 第194-195页 |
| Steady state concentration profiles | 第195-197页 |
| ·Tracing steady state concentration profiles | 第197-199页 |
| ·Reduction of a neutral species with (z, n) being equal to(0,+1) | 第197-199页 |
| ·Oxidation of a species A+ with (z, n) as (+1, -1) | 第199页 |
| 3. Experimental concentration profiles | 第199-206页 |
| ·Experimental currents of A~(z+) and B~((z-n)~+) on the UME probes | 第200-202页 |
| ·Experimental concentration profiles | 第202-206页 |
| ·Reduction of Tetracyanoquinodimethane (TCNQ) as (z,n) = (0,+1) | 第202-203页 |
| ·Oxidation of (Ferrocenylmethyl) trimethylammonium hexafluorophosphate (FcNMe3+, PF6-) | 第203-206页 |
| 4. Conclusion | 第206-208页 |
| Part V Mapping concentration profiles in the diffusion layer of an enzyme-modified electrode: 1. fabrication of enzyme-modified electrodes. | 第208-224页 |
| 1. Introduction | 第210-213页 |
| 2. Mechanism of the chemical polymerisation | 第213-214页 |
| 3. Experimental | 第214-215页 |
| ·Chemicals and reagents | 第214页 |
| ·Electrode fabrication | 第214-215页 |
| ·Measurements | 第215页 |
| 4. Results and discussion | 第215-222页 |
| ·Time dependence of the polymerization and Pt nanoparticles deposition | 第215-216页 |
| ·Characterization of GOD/Pt/PPy electrode | 第216-217页 |
| ·Electrochemical methods to characterize GOD/Pt/PPy electrode in comparison with GOD/PPy electrode and GOD electrode | 第217-221页 |
| ·Reproducibility and stability of the GOD/Pt/PPy electrode | 第221-222页 |
| 5. Conclusions | 第222-224页 |
| General conclusion | 第224-228页 |
| Appendix Experimental | 第228-244页 |
| A1. Chemicals | 第230-232页 |
| A1.1 Electroactive reactants | 第230页 |
| A1.2 Supporting electrolytes | 第230-231页 |
| A1.3 Solvents | 第231-232页 |
| A2. Electrodes fabrication | 第232-238页 |
| A2.1 Fabrication of a classical electrode | 第232-234页 |
| A2.2 UME fabrication and characterization | 第234-238页 |
| A2.2.1 UME fabrication | 第234-236页 |
| A2.2.2 UME characterization | 第236-238页 |
| A3. Experimental setup and procedures | 第238-241页 |
| A3.1. Experimental setup and procedure in diluted solutions | 第238-240页 |
| A3.2. Experimental setup and procedure in concentrated solutions | 第240-241页 |
| A4 Experimental conditions | 第241-244页 |
| A4.1 Experimental conditions for "concentration profiles mapped at different potentials during cyclic voltammetry " (Part.II.3.2.1) | 第241页 |
| A4.2 Experimental conditions for" Cyclic voltammtries at different scan rates to study the effects of spontaneous convection "(Part.II.3.2.2) | 第241-242页 |
| A4.3 Experimental conditions for "Competition between spontaneous convection and non-planar diffusion "(Part.II.4.2)) | 第242页 |
| A4.4 Experimental conditions for "Study of density gradients inducing convection through mapping concentrations profiles in the diffusion layer of an electrode "(Part.III. 3) | 第242-243页 |
| A4.5 Experimental conditions for "Reduction of Tetracyanoquinodimethane (TCNQ) as (z, n) = (0, +1) " (Part.IV.3.2.1) | 第243页 |
| A4.6 Experimental conditions for "Oxidation of (Ferrocenylmethyl)-trimethylammonium hexafluorophosphate (FcNMe3+, PF6-)"(Part.IV.3.2.2) | 第243-244页 |
| Appendix Program. Simulations of steady state concentration profiles in the diffusion layer of different-sized electrodes | 第244-246页 |
| References | 第246-253页 |
