MULTISENSOR SYSTEMS FOR CHEMICAL ANALYSIS MATERIALS AND SENSORS. edited by Larisa Lvova Dmitry Kirsanov Corrado Di Natale Andrey Legin

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1 MULTISENSOR SYSTEMS FOR CHEMICAL ANALYSIS MATERIALS AND SENSORS edited by Larisa Lvova Dmitry Kirsanov Corrado Di Natale Andrey Legin

3 MULTISENSOR SYSTEMS FOR CHEMICAL ANALYSIS

5 MULTISENSOR SYSTEMS FOR CHEMICAL ANALYSIS MATERIALS AND SENSORS edited by Larisa Lvova Dmitry Kirsanov Corrado Di Natale Andrey Legin

6 Published by Pan Stanford Publishing Pte. Ltd. Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore editorial@panstanford.com Web: British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Multisensor Systems for Chemical Analysis: Materials and Sensors Copyright 2014 by Pan Stanford Publishing Pte. Ltd. All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher. For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher. ISBN (Hardcover) ISBN (ebook) Printed in the USA

7 Contents Preface xiii 1. Developing Sensing Materials for Multisensor Systems on the Basis of Extraction Data 1 Dmitry Kirsanov, Vasiliy Babain, and Andrey Legin 1.1 Introduction Liquid Extraction Ion-Selective Sensors Potentiometric Multisensor Systems Case Study 1: A Multisensor System for Determination of Heavy Metals in Model Surface Waters Case Statement Experimental Results Outline Case Study 2: Quantification of Lanthanides in Complex Acidic Mixtures Case Statement Experimental Results and Discussion Outline Case Study 3: Water Toxicity Estimation in Terms of Bioassay Case Statement Experimental Results Outline Conclusion Photocurable Polymer Membrane Ion Sensors and Their Application for Multicomponent Analysis 41 Natalia Abramova and Andrey Bratov 2.1 Introduction 42

8 vi Contents 2.2 Ion-Sensitive Field-Effect Transistors Membrane Formation Photocurable Membranes Photolithographic Process of Membrane Formation Possible Problems of Photocurable Polymers Copolymerizable Plasticizers Application for Multicomponent Analysis Conclusions and Perspectives Metallic Sensors in Multisensor Analysis 69 Larisa Lvova, Arnaldo D Amico, Andrea Pede, Corrado Di Natale, and Roberto Paolesse 3.1 Introduction Electrochemical Methods and Sensors Classification Modern Electrochemical Methods Sensors Applied in Electrochemical Methods Metallic Electrodes Classification Introduction to Electrochemical Measurements Voltammetry Electrical Double Layer Charging and Diffusion Currents Diffusion and Diffuse Layers Other Currents Influencing Voltammetric Signal Electrochemical Measurement Set-up Electrochemical Instrumentation Potentiometry Factors Influencing the Potential of the Metallic Electrode Models Describing the Potential Formation in Metallic Faradic Electrodes Mixed-potential model and Butler Volmer kinetic theory 89

9 Contents vii The model for the assessment of interfering processes in faradic electrodes The Kelvin Probe Functioning Principle Kelvin Probe Sensor Voltammetric and Potentiometric Metallic Sensors Arrays Voltammetric Arrays Potentiometric Metallic Multisensor Arrays Case study: discrimination of soils and fertilizers with metallic multisensor system Application of Single Metallic Electrodes for Multisensor Analysis Task Solving Toward Miniaturization of Metallic Multisensor Arrays Combinations and Comparisons of Metallic Multisensor with Other Analytical Systems Problems Related to the Electrochemical Metallic Multisensor Systems Application How to Choose the Suitable Electrode Materials? Surface Recovery Problem: Polishing and Cleaning versus Disposable Multisensor New Measurement and Data Treatment Techniques Electronic Noise Shot noise Thermal noise Flicker noise Burst noise g r noise Sensor Drift Metallic Multisensor Arrays Employing Other Transduction Principles 124

10 viii Contents 3.9 Some Curious Examples of Metallic Sensors Conclusions Sensor Arrays Based on Phthalocyanines: New Developments on Nanostructured and Biomimetic Electrochemical Sensors 139 María Luz Rodríguez-Méndez, Constantin Apetrei, Cristina Medina-Plaza, Raquel Muñoz, and José Antonio de Saja 4.1 Introduction Phthalocyanines Properties of Phthalocyanine Molecules Preparation of Electrochemical Sensors Based on Phthalocyanines Classical Methods to Prepare Sensors Based on Phthalocyanines Preparation of Nanostructured Sensors Based on Phthalocyanines Main Types of Electrochemical Sensors Based on Phthalocyanines Ion-Selective Electrodes: Potentiometric Sensors Based on Phthalocyanines Electrocatalytic Electrodes Based on Phthalocyanines Electrodes containing nanoparticles and nanotubes Electrocatalytic electrodes based on nanostructured thin films Voltammetric Sensors Based on Phthalocyanines Electroactive phthalocyanines Response to ionic solutions Response to electroactive solutions Impedimetric Sensors Biosensors Electronic Tongues Based on Phthalocyanines Potentiometric Electronic Tongues 158

11 Contents ix Voltammetric Electronic Tongues Impedance Electronic Tongues Bioelectronic Tongues Other Electronic Tongues Conclusion and Future Trends Lignin Applications in Chemical Sensing 181 Alisa Rudnitskaya and Dmitry V. Evtuguin 5.1 Lignin: Structure and Properties Wood Chemistry Wood types and wood cell structure and composition Cellulose Hemicellulose Lignin Pulping Kraft process Sulfite process Organosolv process Lignin Applications Lignin-Based Sensors Sensors Based on Thin-Films and Self-Organized Layers Manufacturing of thin-film lignin sensors Applications of lignin thin-film sensors Sensors Based on Lignin Copolymers Synthesis of lignin-based polymers Application of polymeric lignin-based sensors BioElectronic Tongues: When the Sensor Array Incorporates Biosensors 211 Manel del Valle, Xavier Cetó, and Manuel Gutiérrez-Capitán 6.1 Introduction Building of a BioElectronic Tongue 213

12 x Contents BioElectronic Tongues in the Literature BioElectronic Tongue Employing Potentiometric Sensors Fabrication of the Potentiometric Biosensors Potentiometric Characterization of the Biosensors Response Modeling of the BioElectronic Tongue Application BioElectronic Tongue Employing Voltammetric Sensors Fabrication of the Amperometric Biosensors Voltammetric Characterization of the Biosensors Response Modeling of the BioElectronic Tongue Conclusion Microsensor Systems for Environmental and Biomedical Analysis 247 Wei Cai, Huixin Zhao, Chengxiong Wu, Ning Hu, Da Ha, and Ping Wang 7.1 Microelectrode Array Sensor Principle Fabrication Characterization Microscopic characterization Electrochemical characterization in sulfuric acid Electrochemical characterization in K 3 Fe(CN) Light-Addressable Potentiometric Sensor Principle Fabrication Characterization Environmental Application: Detecting Heavy Metal in Water 265

13 Contents xi Automatic Analysis Instrument MEA cell MLAPS cell Heavy Metal Detection in Water Detection of Zn 2+, Cd 2+, Pb 2+, and Cu 2+ with MEA Detection of Fe 3+ and (Cr 2 O 7 ) 2 with MLAPS In-situ and Wireless Monitoring In-situ monitoring Wireless monitoring Biomedical Application: Monitoring Cellular Microenvironment Cell-Based Biosensors Using MEA and LAPS MEA as cell-based biosensors LAPS as cell-based biosensors Cell-Based Biosensor System for MEA and LAPS MEA measurement system Microphysiometer for monitoring the extracellular microenvironment Cell semiconductor hybrid LAPS detecting system Cell physiological multiparameter automatic analysis instrument Application in Cell Physiological Analysis and Drug Evaluation Pharmacological applications of MEA Drug analysis and evaluation of LAPS The Use of Nanostructured Films in Sensing Applications 303 Antonio Riul, Jr., Celina Massumi Miyazaki, Cléber A. R. Dantas, and Osvaldo N. Oliveira, Jr. 8.1 Introduction Fabrication of Ultrathin Films 304

14 xii Contents Langmuir Blodgett Technique Layer-by-Layer Technique Impedance Spectroscopy Measurements Theoretical Fundamentals Impedance Applied in e-tongue System Equivalent Electric Circuit Analysis Nanostructured Thin Films in Sensors Extending the e-tongue Concept to Biosensors Final Remarks Nanoplate Field-Effect Capacitors: A New Transducer Structure for Multiparameter (Bio-)Chemical Sensing 333 Arshak Poghossian, Maryam Weil, and Michael J. Schöning 9.1 Introduction Metal Insulator Semiconductor Capacitor Capacitive EIS Sensor An Array of Field-Effect Nanoplate EISOI Capacitors Fabrication of Nanoplate SOI Capacitors C V Characteristics of Nanoplate EISOI Sensors Multiparameter (Bio-)Chemical Sensing with an Array of Field-Effect Nanoplate SOI Capacitors ph Sensitivity of Nanoplate EISOI Capacitors Penicillin Detection with an EISOI Sensor Chip Electrical Detection of Layer-by-Layer Adsorption of Polyelectrolytes Label-Free Electrical Detection of DNA Hybridization and Denaturation by Means of Nanoplate EISOI Sensors Modified with Gold Nanoparticles Conclusions 364 Index 375

15 Contents xiii Preface This book is devoted to the recent advances in the development of artificial sensory systems widely known as electronic tongues (ETs). Although the first publications in this area appeared about two decades ago, we cannot say that the field is fully mature. Much more efforts are required in the development of ETs and in understanding how they work to reach the level of a reliable, albeit unusual, analytical instrument that was the ultimate aim of such research from the very beginning. In the recent years the new sides of the story rapidly emerged, while some selected ET designs and applications deserved intent attention as a real promise for practical analytics. This book will be helpful for a wide range of readers from university students to researchers. The editors clearly understand that just as almost any book of this kind, the present one does not cover the whole range of advancements in the field; however it comprises a lot of real steps forward of the ET technologies and applications described by prominent authors from all over the world. The book comprises nine chapters, organized in the following manner. Chapter 1 deals with the description of how data and substances once developed for liquid extraction of various metals might be used to prepare chemical sensors that can be further employed in multisensor systems for simultaneous determination of several metals in complex mixtures. Several complex but reliable case studies involving sensor arrays employing various extracting agents of different chemical nature are also described in this chapter. Chapter 2 describes some applications of photocurable polymers for ion-selective membrane formation, which is important for sensor mass production. Excellent adhesion to a solid support permits the use of such material in various solid contact electrodes and for the successful development of potentiometric sensor arrays for multicomponent analysis. Chapter 3 deals with nonselective metallic multisensor arrays that are promising materials for the development of low-cost and

16 xiv Preface easy-to-handle analytical systems designated to the estimation of various parameters of foodstuffs, clinical samples, and for environmental monitoring. The application of metallic sensor arrays for the multicomponent analysis of liquid samples over the last two decades is overviewed in the chapter. Chapter 4 is concerned with sensors based on phthalocyanines and arrays of such sensors. Phthalocyanines are among the most suitable materials for electrochemical sensors due to their versatility and their unique electrochemical and electrocatalytic properties. Nanostructured films obtained by layer-by-layer or the Langmuir Blodgett techniques allow for the preparation of biomimetic systems. Electrochemical multisensor systems based on phthalocyanines employ a variety of techniques, including potentiometry, amperometry, cyclic voltammetry, or impedance measurements. Some novel application of lignin for chemical sensors is described in Chapter 5. Lignin is one of the main constituents of wood and is available as a waste product of pulp-and-paper industry. Lignins are versatile materials as the amount and type of functional groups, molecular weight, chemical reactivity, and electrical conductivity depend on lignin origin and can be altered through appropriate modifications. The chapter discusses lignin properties and its recent applications in chemical sensing. Chapter 6 deals with the so-called bioelectronic tongues (BioETs), although the term itself is still to be clarified and widely accepted. Some recent advances in the design of ETs has been the incorporation of biosensors. Such BioETs are only distinguished from the conventional ones in the incorporation of one or several biosensors into the sensor array. The chapter deepens with two case studies, ETs with potentiometric sensors and ETs with devices of voltammetric type. Chapter 7 represents the application of microsensors and microelectrode array (MEA) and light-addressable potentiometric sensors (LAPS) in the environmental and biomedical field. The principles, fabrication, and characterization of MEA and LAPS are reported. An automatic analysis instrument for heavy metal detection for environmental applications is also presented in the chapter. Chapter 8 is concerned with the application of nanostructured films in chemical sensing. The developments on the use of impedance spectroscopy and ultrathin films of different materials

17 Preface xv are reported. The simplicity of such sensor is rather attractive and may be enhanced by the nanostructured thin nature of the materials forming the sensing units. Advantages can also be taken from the supramolecular interactions between the ultrathin films and the liquid samples under analysis. Chapter 9 deals with one of the novel fields nanoplate fieldeffect SOI (silicon-on-insulator) capacitors. An array of such capacitors is presented as a new transducer structure for multiparameter bio- and chemical sensing. The realized sensor chip has been applied for ph and penicillin concentration measurements, electrical monitoring of polyelectrolyte multilayer formation, as well as for the label-free electrical detection of consecutive DNA. This book thus shows a screenshot of diverse research efforts in the ET field and will, hopefully, inspire new fruitful ideas and significant practical advances. The editors would like to thank the editorial and production staff of Pan Stanford Publishing for their help and support. Larisa Lvova Dmitry Kirsanov Corrado Di Natale Andrey Legin Winter 2013

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