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Quantitative Microchip Capillary Electrophoresis for Inorganic Ion Analysis at the Point of Care

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Quantitative Microchip Capillary Electrophoresis for Inorganic Ion Analysis at the Point of Care QUANTITATIVE MICROCHIP CAPILLARY ELECTROPHORESIS FOR INORGANIC ION ANALYSIS AT THE POINT OF CARE Elwin Vrouwe Promotiecommissie Voorzitter: Prof.dr.ir. A.J. Mouthaan Universiteit Twente Promotor: Prof.dr.ir. A. van den Berg Universiteit Twente Assistent promotor: Dr. R. Luttge Universiteit Twente Leden: Prof.dr. T. Hankemeier Universiteit Leiden Prof. U. Karst Universiteit Twente Prof. Th. Laurell Lund University Dr. H.A.G. Niederländer Rijksuniversiteit Groningen Dr. W. Olthuis Universiteit Twente Prof.dr. I. Vermes Universiteit Twente The research in this work was supported by the Technology Foundation STW, applied science division of NWO and the technology program of the Ministry of Economic Affairs Print: Febodruk BV, Enschede © E.X. Vrouwe, Enschede, 2005 No part of this work may be reproduced by print, photocopy or any other means without the permission in writing from the author. ISBN 90-9019293-X QUANTITATIVE MICROCHIP CAPILLARY ELECTROPHORESIS FOR INORGANIC ION ANALYSIS AT THE POINT OF CARE PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Universiteit Twente, op gezag van rector magnificus, prof.dr. W.H.M. Zijm, volgens beluit van het College voor Promoties in het openbaar te verdedigen op vrijdag 15 april 2005 om 13.15 uur door Elwin Xander Vrouwe geboren op 2 december 1974 te Alphen aan den Rijn Dit proefschrift is goedgekeurd door: Promotor: Prof.dr.ir. A. van den Berg Assistent promotor: Dr. R. Luttge Contents 1 Scope and outline ..........................................................................................5 1.1 Introduction .............................................................................................................6 1.2 Microchip capillary electrophoresis of inorganic ions for point-of-care analysis..6 1.2.1 Inorganic ion analysis......................................................................................6 1.2.2 Microchip CE analysis of inorganic ions ........................................................7 1.2.3 Point-of care analysis.......................................................................................8 1.3 Lithium therapy for manic depression ....................................................................8 1.3.1 Manic depression.............................................................................................8 1.3.2 Lithium treatment ..........................................................................................10 1.4 Drinking water monitoring....................................................................................10 1.5 Outline of this thesis..............................................................................................10 1.6 References .............................................................................................................11 2 Microchip capillary electrophoresis ...........................................................13 2.1 Introduction ...........................................................................................................14 2.2 Fundamentals of capillary electrophoresis............................................................14 2.2.1 Migration of ions in electric fields ................................................................14 2.2.2 Electroosmotic flow.......................................................................................16 2.2.3 Capillary electrophoresis separation modes ..................................................18 2.3 Microchip design and separation performance ................................................19 2.3.1 Sample loading and plug shaping..................................................................19 2.3.2 Dimension of the microfluidic channels........................................................21 2.3.3 Electromigration dispersion...........................................................................26 2.4 Detection methods for inorganic ions ...................................................................26 2.4.1 Detection methods compatible with capillary electrophoresis......................27 2.4.2 Conductivity detection...................................................................................29 2.4.3 On-chip electrolyte conductivity measurement.............................................31 2.4.4 Implementation of on-chip conductivity detection .......................................36 2.5 Background electrolyte .........................................................................................37 2.6 Chip interfacing to the outside world....................................................................38 2.7 Conclusions ...........................................................................................................39 2.8 References .............................................................................................................40 3 Capillary electrophoresis of metal ions in glass microchips...................45 3.1 Introduction ...........................................................................................................46 3.2 Simulation of microchip CE separations ..............................................................46 3.3 Capillary electrophoresis on glass microchips......................................................50 3.3.1 Manufacture of glass chips............................................................................50 3.3.2 Entry tests of glass microchips......................................................................51 3.3.3 Separation of calibration mixtures.................................................................53 3.3.4 Optimization of the microchip performance..................................................58 3.3.5 Surface characterization.................................................................................64 3.3.6 Peak shape distortions caused by surface interaction....................................69 3.4 Conclusions ...........................................................................................................70 3.5 References .............................................................................................................71 4 Determination of lithium in whole blood with microchip capillary electrophoresis ............................................................................................75 4.1 Introduction ...........................................................................................................76 4.2 Measuring whole blood with microchip CE .........................................................76 4.2.1 Standards of clinical analysis.........................................................................76 4.2.2 On-chip removal of blood cells .....................................................................77 4.2.3 Microchip analysis of lithium in blood..........................................................78 4.3 Materials and methods...........................................................................................78 4.3.1 Reagents.........................................................................................................78 4.3.2 Blood samples................................................................................................79 4.3.3 Microfabricated CE chips ..............................................................................79 4.3.4 Surface coating ..............................................................................................80 4.3.5 Capillary electrophoresis on microfabricated chips ......................................80 4.4 Results and discussion...........................................................................................81 4.4.1 Sample loading and electrokinetic transport of red blood cells in uncoated channels...................................................................................................................81 4.4.2 Sample loading and electrokinetic transport of red blood cells in coated channels...................................................................................................................84 4.4.3 Quantitation of lithium in serum and whole blood........................................85 4.5 Conclusions ...........................................................................................................88 4.6 References .............................................................................................................89 5 Microchip analysis of lithium in blood using moving boundary electrophoresis and zone electrophoresis ................................................93 5.1 Introduction ...........................................................................................................94 5.2 Analytical principle ...............................................................................................97 5.2.1 Moving boundary electrophoresis .................................................................97 5.2.2 Concentration adjustment across the stationary boundary ............................98 5.2.3 Concentration profile in moving boundary zones .........................................99 5.3 Materials and methods.........................................................................................103 5.3.1 Reagents and sample....................................................................................103 5.3.2 Microfabricated CE chips ............................................................................103 5.3.3 Capillary electrophoresis
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