Electroanalysis in Biomedical and Pharmaceutical Sciences Voltammetry, Amperometry, Biosensors, Applications Sibel A
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Monographs in Electrochemistry Series Editor: F. Scholz Sibel A. Ozkan Jean-Michel Kauffmann Petr Zuman Electroanalysis in Biomedical and Pharmaceutical Sciences Voltammetry, Amperometry, Biosensors, Applications Sibel A. Ozkan • Jean-Michel Kauffmann • Petr Zuman in collaboration with Ana Maria Oliveira Brett, Christopher Brett, Bengi Uslu, Philippe Hubert, Eric Rozet, Cobra Parsajoo, Ste´phanie Patris, Ahmad Sarakbi Electroanalysis in Biomedical and Pharmaceutical Sciences Voltammetry, Amperometry, Biosensors, Applications Sibel A. Ozkan Jean-Michel Kauffmann Faculty of Pharmacy Faculty of Pharmacy Department of Analytical Chemistry Universite´ Libre de Bruxelles Ankara University Brussels, Belgium Tandogan, Ankara Ankara Turkey Petr Zuman Department of Chemistry and Biomolecular Science Clarkson University Potsdam, New York USA ISSN 1865-1836 ISSN 1865-1844 (electronic) Monographs in Electrochemistry ISBN 978-3-662-47137-1 ISBN 978-3-662-47138-8 (eBook) DOI 10.1007/978-3-662-47138-8 Library of Congress Control Number: 2015944207 Springer Heidelberg New York Dordrecht London © Springer-Verlag Berlin Heidelberg 2015 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Printed on acid-free paper Springer-Verlag GmbH Berlin Heidelberg is part of Springer Science+Business Media (www.springer.com) Authors of Chapters The chapters have been written by the following authors: Chapter 1 Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Petr Zuman Department of Chemistry, Clarkson University, Potsdam, NY, USA Chapter 2 Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Petr Zuman Department of Chemistry, Clarkson University, Potsdam, NY, USA Chapter 3 Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Ana Maria Oliveira-Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Christopher M.A. Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Chapter 4 Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey vii viii Authors of Chapters Christopher M.A. Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Ana Maria Oliveira-Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Chapter 5 Ste´phanie Patris Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite´ Libre de Bruxelles, Bruxelles, Belgium Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite´ Libre de Bruxelles, Bruxelles, Belgium Chapter 6 Cobra Parsajoo Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectro- chemistry, Universite´ Libre de Bruxelles, Bruxelles, Belgium Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite´ Libre de Bruxelles, Bruxelles, Belgium Chapter 7 Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Bengi Uslu Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Ahmad Sarakbi Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectro- chemistry, Universite Libre de Bruxelles, Bruxelles, Belgium Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite Libre de Bruxelles, Bruxelles, Belgium Chapter 8 Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, TURKEY Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite Libre de Bruxelles, Bruxelles, Belgium Philippe Hubert Department of Pharmacy, CIRM, Laboratory of Analytical Chemistry, Universite´ de Lie`ge (ULg), Lie`ge, Belgium Eric Rozet Department of Pharmacy, CIRM, Laboratory of Analytical Chemistry, Universite´ de Lie`ge (ULg), Lie`ge, Belgium Authors of Chapters ix Chapter 9 Bengi Uslu Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Sibel A. Ozkan Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite´ Libre de Bruxelles, Bruxelles, Belgium Chapter 3 Electroanalytical Techniques Most Frequently Used in Drug Analysis Contents 3.1 Introduction ................................................................................ 45 3.2 Linear Sweep and Cyclic Voltammetry ................................................... 49 3.3 Step and Pulse Voltammetry .............................................................. 55 3.3.1 Staircase Voltammetry ............................................................ 57 3.3.2 Normal Pulse Voltammetry ....................................................... 58 3.3.3 Differential Pulse Voltammetry ................................................... 59 3.3.4 Square Wave Voltammetry ........................................................ 62 3.4 Alternating Current Voltammetry ......................................................... 65 3.5 Stripping Techniques ...................................................................... 67 3.5.1 Anodic Stripping Voltammetry ................................................... 69 3.5.2 Cathodic Stripping Voltammetry .................................................. 72 3.5.3 Adsorptive Stripping Voltammetry ............................................... 73 3.5.4 Abrasive Stripping Voltammetry .................................................. 75 3.5.5 Potentiometric Stripping Analysis ................................................ 76 3.6 Conclusions ................................................................................ 77 References ........................................................................................ 78 3.1 Introduction Amongst the variety of electrochemical methods and techniques available for drug analysis, voltammetry, i.e. the recording of the current, as a function of applied potential, has become the most important and widespread. Sweep voltammetry in unstirred solution, based on continuously varying the potential that is applied across the electrode–solution interface and measuring the resulting current, where the predominant mode of mass transport is diffusion, is one of the most important and useful techniques for the study of electrochemical reactions and their mechanisms [1–10]. The form of the current–potential curves at stationary electrodes, in unstirred solution, depends on the rate of change of applied potential. Analysing these curves can give information about the kinetics and mechanism of reactions associated with electron transfer at the electrode © Springer-Verlag Berlin Heidelberg 2015 45 S.A. Ozkan et al., Electroanalysis in Biomedical and Pharmaceutical Sciences, Monographs in Electrochemistry, DOI 10.1007/978-3-662-47138-8_3 46 3 Electroanalytical Techniques Most Frequently Used in Drug Analysis surface, since the faradaic current that flows at any time is proportional to the rate of the electrochemical reaction taking place at the electrode. The current observed in a voltammetric experiment is dependent upon: 1. The rate at which material arrives from the bulk of solution to the electrode, mass transport 2. The rate of electron transfer across the electrode–solution interface, the charge transfer kinetics. When the electron transfer rate is sufficiently fast, the electrochemical reaction is limited by the rate of mass transport of ions or molecules from bulk solution to or from the electrode surface. There are three types of mass transport: Convection Migration Diffusion When any one of these types of movement is insufficient to transport the reactant to, or the product from, the electrode surface concentration polarisation is observed [1–10]. The simplest way of transferring reactants to the vicinity of the electrode surface is by mechanical means such as agitation or stirring, i.e. forced convection. Forced convection decreases concentration polarisation and is often not important on a short time scale. In an unstirred solution, there may be effects of natural convection, due to vibrations and temperature and density gradients. There is a group of techniques, hydrodynamic