J. L. Capelo-Martínez obtained his PhD in chemistry in 2002 from the University of Vigo, Spain, where he was associate professor from 1999 to 2002. In December 2004 he became Research Fellow at the Associated Laboratory REQUIMTE, as well as at the Chemistry Department of the New University of Lisbon, and in 2006 was invited as an auxiliary professor to the same institution. His research work is related to new uses of ultrasonic energy as a tool at the Analytical Chemistry Laboratory. Dr. Capelo has more than fifty manuscripts and several patents to his name, he is a regular referee for various analytical journals and a member of the advisory board of the Analytical Journal TALANTA.

"The book can be recommended to practicing analytical chemists who need to develop more efficient strategies for analysis, and in general to those practitioners who need to improve analytical methodological performance. It could also serve as a valuable starting point for researching new avenues in the analytical use of ultrasound." (Anal Bioanal Chem, 2009) "Analytical Applications is a practical book that emphasizes some of the latest developments in the implementation of ultrasound in the analytical lab." (Analytical and Bioanalytical Chemistry, August 2009)

• Preface XIList of Contributors XIII1 The Power of Ultrasound 1Hugo Miguel Santos, Carlos Lodeiro, and José-Luis Capelo-Martínez1.1 Introduction 11.2 Cavitation 11.2.1 Parameters Affecting Ultrasonic Cavitation 31.2.1.1 Frequency 31.2.1.2 Intensity 41.2.1.3 Solvent 51.2.1.4 Temperature 51.2.1.5 External Pressure and Bubbled Gas 51.2.1.6 Direct and Indirect Ultrasonic Application 61.3 Common Ultrasonic Devices Used in Analytical Chemistry 61.3.1 Ultrasonic Bath 61.3.1.1 Types of Ultrasonic Baths 71.3.1.2 How to Locate the Most Efficient Place Inside an Ultrasonic Bath 81.3.1.3 Temperature Control 81.3.1.4 Shape and Material of Reaction Container 91.3.2 The Ultrasonic Probe 91.3.2.1 Parts of an Ultrasonic Probe 101.3.2.2 Types of Ultrasonic Probes 101.3.2.3 Dead Zones 111.3.2.4 How to Choose the Correct Ultrasonic Probe 121.3.2.5 Temperature Control 131.3.2.6 Shape and Material of Reaction Container 141.4 Current Ultrasonic Devices for New Analytical Applications 14References 152 Ultrasonic Energy as a Tool for Sample Treatment for the Analysis of Elements and Elemental Speciation 17Hugo Miguel Santos, Carlos Lodeiro, and José-Luis Capelo-Martínez2.1 Introduction 172.2 Parameters Influencing Element Ultrasonic Solid–Liquid Extraction 172.2.1 Extracting Reagent 172.2.1.1 Extracting Reagents for Total Element Extraction 182.2.1.2 Extracting Reagents for Elemental Speciation 192.2.1.3 Extracting Reagents for Sequential Extraction Schemes 192.2.2 Matrix Properties 202.2.2.1 Type of Matrix 202.2.2.2 Mass of Matrix 202.2.2.3 Sample Size 222.2.3 Ultrasonic Device 222.2.3.1 Type of Ultrasonic Device 222.2.3.2 Time of Ultrasonication 232.2.3.3 Ultrasonic Amplitude 232.2.3.4 Ultrasonic Frequency 232.2.3.5 Temperature of Sonication 232.3 US-SLE from Soils and Sediments 242.4 US-SLE from Sewage Sludge 242.5 US-SLE Extraction from Plants 242.6 Extraction from Soft Tissues 272.7 Total Element Determination 272.7.1 US-SLE and US-SS for F-AAS 272.7.2 US-SLE and US-SS for ET-AAS 282.7.3 US-SLE and US-SS for CV and HG Employed with AAS or AFS 282.8 Elemental Fractionation and Elemental Speciation 302.8.1 What is Speciation? 302.8.2 Shortening Sequential Fractionation Schemes 312.8.3 Speciation for Soils and Sediments 342.8.4 Speciation from Plants 342.8.5 Speciation from Soft Tissues 362.8.6 Speciation from Other Types of Samples 432.9 On-Line Applications 452.9.1 Open and Closed Systems 462.9.2 UB 472.9.3 UP 472.10 Current Trends 482.10.1 Accelerating Liquid–Liquid Extractions 482.10.2 Chemical Vapor Formation 492.11 Conclusion 49References 503 Ultrasonic Assisted Extraction for the Analysis of Organic Compounds by Chromatographic Techniques 55Raquel Rial-Otero3.1 Introduction 553.2 Overview of Classic and Modern Extraction Procedures for Organics 563.3 Ultrasonic Assisted Extraction (UAE) 603.3.1 Basic Principles 603.3.2 Parameters Influencing Ultrasonic Assisted Extraction 613.3.2.1 Amount of Sample 613.3.2.2 Sample Particle Size 613.3.2.3 Extraction Solvent 613.3.2.4 pH of Extracting Solution 623.3.2.5 Solvent Volume 623.3.2.6 Sonic Power 623.3.2.7 Frequency 633.3.2.8 Extraction Time 633.3.2.9 Extraction Temperature 633.3.3 Applications 633.3.3.1 Liquid Samples 643.3.3.2 Solid Samples 643.3.3.3 Clean-Up 703.4 Coupling Ultrasound with Other Extraction Techniques 713.4.1 Coupling Solid Phase Microextraction (SPME) and Ultrasound 713.4.1.1 Improving the Extraction Procedure in Direct-SPME 713.4.1.2 Improving the Extraction Procedure in HS-SPME 733.4.1.3 Facilitating the Desorption Process 733.4.2 Coupling Stir Bar Sorptive Extraction (SBSE) and Ultrasound 743.5 Comparison between UAE and Other Extraction Techniques 753.6 Conclusion 76References 774 Electrochemical Applications of Power Ultrasound 81Neil Vaughan Rees and Richard Guy Compton4.1 Introduction 814.2 Electrochemical Cell and Experimental Setup 874.3 Voltammetry Under Insonation 874.4 Trace Detection by Stripping Voltammetry 884.4.1 Classical Electroanalysis 894.4.2 Electroanalysis Facilitated by Ultrasound 904.4.3 Applications of Sono-Anodic Stripping Voltammetry (Sono-ASV) 904.5 Biphasic Sonoelectroanalysis 904.5.1 Determination of Lead in Petrol 904.5.2 Extraction and Determination of Vanillin 924.5.3 Detection of Copper in Blood 924.6 Microelectrodes and Ultrasound 934.6.1 Insights into Bubble Dynamics 934.6.2 Measurement of Potentials of Zero Charge (PZC) 954.6.3 Particle Impact Experiments 964.7 Conclusion 102References 1035 Power Ultrasound Meets Protemics 107Hugo Miguel Santos, Carlos Lodeiro, and José-Luis Capelo-Martínez5.1 Introduction 1075.2 Protein Identification through Mass-Based Spectrometry Techniques and Peptide Mass Fingerprint 1085.3 Classic In-Gel Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1085.4 Ultrasonic Energy for the Acceleration of In-Gel Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1115.4.1 Washing, Reduction and Alkylation Steps 1115.4.2 In-Gel Protein Digestion Process 1135.4.2.1 Sample Handling 1135.4.2.2 Sonication Volume 1155.4.2.3 Sonication Time 1155.4.2.4 Sonication Amplitude 1155.4.2.5 Protein to Trypsin Ratio 1155.4.2.6 Temperature 1165.4.2.7 Solvent 1165.4.2.8 Minimum Amount of Protein Identified 1165.4.2.9 Reduction and Alkylation Steps 1175.4.2.10 Comparison with Other Types of Rapid Sample Treatments 1175.4.2.11 Influence of Protein Staining 1175.5 Classic In-Solution Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1185.6 Ultrasonic Energy for the Acceleration of the In-Solution Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1215.6.1 In-Solution Protein Denaturation 1215.6.2 In-Solution Protein Reduction and Alkylation 1225.6.3 In-Solution Protein Digestion 1245.6.4 Clean In-Solution Protein Digestion 1245.7 Conclusion 125References 1266 Beyond Analytical Chemistry 129Carlos Lodeiro and José-Luis Capelo-Martínez6.1 Introduction 1296.2 Sonochemistry for Organic Synthesis 1296.3 Ultrasonic Enhanced Synthesis of Inorganic Nanomaterials 1376.4 Sonochemistry Applied to Polymer Science 1396.4.1 Introduction to Polymers 1396.4.2 Ultrasonication in Sample Treatment for Polymer Characterization 1406.4.2.1 Introduction to Polymer Characterization 1406.4.2.2 Overview of Sample Preparation for MALDI Analysis of Polymers 1416.4.2.3 Ultrasonic Energy as a Tool for Fast Sample Treatment for the Characterization of Polymers by MALDI 1426.4.3 Ultrasonic-Induced Polymer Degradation for Polymer Characterization 1456.4.4 Ultrasonication for the Preparation of Imprinted Polymers 1456.5 Conclusion 148References 148Index 151

J. L. Capelo-Martínez obtained his PhD in chemistry in 2002 from the University of Vigo, Spain, where he was associate professor from 1999 to 2002. In December 2004 he became Research Fellow at the Associated Laboratory REQUIMTE, as well as at the Chemistry Department of the New University of Lisbon, and in 2006 was invited as an auxiliary professor to the same institution. His research work is related to new uses of ultrasonic energy as a tool at the Analytical Chemistry Laboratory. Dr. Capelo has more than fifty manuscripts and several patents to his name, he is a regular referee for various analytical journals and a member of the advisory board of the Analytical Journal TALANTA.

"The book can be recommended to practicing analytical chemists who need to develop more efficient strategies for analysis, and in general to those practitioners who need to improve analytical methodological performance. It could also serve as a valuable starting point for researching new avenues in the analytical use of ultrasound." (Anal Bioanal Chem, 2009) "Analytical Applications is a practical book that emphasizes some of the latest developments in the implementation of ultrasound in the analytical lab." (Analytical and Bioanalytical Chemistry, August 2009)

• Preface XIList of Contributors XIII1 The Power of Ultrasound 1Hugo Miguel Santos, Carlos Lodeiro, and José-Luis Capelo-Martínez1.1 Introduction 11.2 Cavitation 11.2.1 Parameters Affecting Ultrasonic Cavitation 31.2.1.1 Frequency 31.2.1.2 Intensity 41.2.1.3 Solvent 51.2.1.4 Temperature 51.2.1.5 External Pressure and Bubbled Gas 51.2.1.6 Direct and Indirect Ultrasonic Application 61.3 Common Ultrasonic Devices Used in Analytical Chemistry 61.3.1 Ultrasonic Bath 61.3.1.1 Types of Ultrasonic Baths 71.3.1.2 How to Locate the Most Efficient Place Inside an Ultrasonic Bath 81.3.1.3 Temperature Control 81.3.1.4 Shape and Material of Reaction Container 91.3.2 The Ultrasonic Probe 91.3.2.1 Parts of an Ultrasonic Probe 101.3.2.2 Types of Ultrasonic Probes 101.3.2.3 Dead Zones 111.3.2.4 How to Choose the Correct Ultrasonic Probe 121.3.2.5 Temperature Control 131.3.2.6 Shape and Material of Reaction Container 141.4 Current Ultrasonic Devices for New Analytical Applications 14References 152 Ultrasonic Energy as a Tool for Sample Treatment for the Analysis of Elements and Elemental Speciation 17Hugo Miguel Santos, Carlos Lodeiro, and José-Luis Capelo-Martínez2.1 Introduction 172.2 Parameters Influencing Element Ultrasonic Solid–Liquid Extraction 172.2.1 Extracting Reagent 172.2.1.1 Extracting Reagents for Total Element Extraction 182.2.1.2 Extracting Reagents for Elemental Speciation 192.2.1.3 Extracting Reagents for Sequential Extraction Schemes 192.2.2 Matrix Properties 202.2.2.1 Type of Matrix 202.2.2.2 Mass of Matrix 202.2.2.3 Sample Size 222.2.3 Ultrasonic Device 222.2.3.1 Type of Ultrasonic Device 222.2.3.2 Time of Ultrasonication 232.2.3.3 Ultrasonic Amplitude 232.2.3.4 Ultrasonic Frequency 232.2.3.5 Temperature of Sonication 232.3 US-SLE from Soils and Sediments 242.4 US-SLE from Sewage Sludge 242.5 US-SLE Extraction from Plants 242.6 Extraction from Soft Tissues 272.7 Total Element Determination 272.7.1 US-SLE and US-SS for F-AAS 272.7.2 US-SLE and US-SS for ET-AAS 282.7.3 US-SLE and US-SS for CV and HG Employed with AAS or AFS 282.8 Elemental Fractionation and Elemental Speciation 302.8.1 What is Speciation? 302.8.2 Shortening Sequential Fractionation Schemes 312.8.3 Speciation for Soils and Sediments 342.8.4 Speciation from Plants 342.8.5 Speciation from Soft Tissues 362.8.6 Speciation from Other Types of Samples 432.9 On-Line Applications 452.9.1 Open and Closed Systems 462.9.2 UB 472.9.3 UP 472.10 Current Trends 482.10.1 Accelerating Liquid–Liquid Extractions 482.10.2 Chemical Vapor Formation 492.11 Conclusion 49References 503 Ultrasonic Assisted Extraction for the Analysis of Organic Compounds by Chromatographic Techniques 55Raquel Rial-Otero3.1 Introduction 553.2 Overview of Classic and Modern Extraction Procedures for Organics 563.3 Ultrasonic Assisted Extraction (UAE) 603.3.1 Basic Principles 603.3.2 Parameters Influencing Ultrasonic Assisted Extraction 613.3.2.1 Amount of Sample 613.3.2.2 Sample Particle Size 613.3.2.3 Extraction Solvent 613.3.2.4 pH of Extracting Solution 623.3.2.5 Solvent Volume 623.3.2.6 Sonic Power 623.3.2.7 Frequency 633.3.2.8 Extraction Time 633.3.2.9 Extraction Temperature 633.3.3 Applications 633.3.3.1 Liquid Samples 643.3.3.2 Solid Samples 643.3.3.3 Clean-Up 703.4 Coupling Ultrasound with Other Extraction Techniques 713.4.1 Coupling Solid Phase Microextraction (SPME) and Ultrasound 713.4.1.1 Improving the Extraction Procedure in Direct-SPME 713.4.1.2 Improving the Extraction Procedure in HS-SPME 733.4.1.3 Facilitating the Desorption Process 733.4.2 Coupling Stir Bar Sorptive Extraction (SBSE) and Ultrasound 743.5 Comparison between UAE and Other Extraction Techniques 753.6 Conclusion 76References 774 Electrochemical Applications of Power Ultrasound 81Neil Vaughan Rees and Richard Guy Compton4.1 Introduction 814.2 Electrochemical Cell and Experimental Setup 874.3 Voltammetry Under Insonation 874.4 Trace Detection by Stripping Voltammetry 884.4.1 Classical Electroanalysis 894.4.2 Electroanalysis Facilitated by Ultrasound 904.4.3 Applications of Sono-Anodic Stripping Voltammetry (Sono-ASV) 904.5 Biphasic Sonoelectroanalysis 904.5.1 Determination of Lead in Petrol 904.5.2 Extraction and Determination of Vanillin 924.5.3 Detection of Copper in Blood 924.6 Microelectrodes and Ultrasound 934.6.1 Insights into Bubble Dynamics 934.6.2 Measurement of Potentials of Zero Charge (PZC) 954.6.3 Particle Impact Experiments 964.7 Conclusion 102References 1035 Power Ultrasound Meets Protemics 107Hugo Miguel Santos, Carlos Lodeiro, and José-Luis Capelo-Martínez5.1 Introduction 1075.2 Protein Identification through Mass-Based Spectrometry Techniques and Peptide Mass Fingerprint 1085.3 Classic In-Gel Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1085.4 Ultrasonic Energy for the Acceleration of In-Gel Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1115.4.1 Washing, Reduction and Alkylation Steps 1115.4.2 In-Gel Protein Digestion Process 1135.4.2.1 Sample Handling 1135.4.2.2 Sonication Volume 1155.4.2.3 Sonication Time 1155.4.2.4 Sonication Amplitude 1155.4.2.5 Protein to Trypsin Ratio 1155.4.2.6 Temperature 1165.4.2.7 Solvent 1165.4.2.8 Minimum Amount of Protein Identified 1165.4.2.9 Reduction and Alkylation Steps 1175.4.2.10 Comparison with Other Types of Rapid Sample Treatments 1175.4.2.11 Influence of Protein Staining 1175.5 Classic In-Solution Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1185.6 Ultrasonic Energy for the Acceleration of the In-Solution Protein Sample Treatment for Protein Identification through Peptide Mass Fingerprint 1215.6.1 In-Solution Protein Denaturation 1215.6.2 In-Solution Protein Reduction and Alkylation 1225.6.3 In-Solution Protein Digestion 1245.6.4 Clean In-Solution Protein Digestion 1245.7 Conclusion 125References 1266 Beyond Analytical Chemistry 129Carlos Lodeiro and José-Luis Capelo-Martínez6.1 Introduction 1296.2 Sonochemistry for Organic Synthesis 1296.3 Ultrasonic Enhanced Synthesis of Inorganic Nanomaterials 1376.4 Sonochemistry Applied to Polymer Science 1396.4.1 Introduction to Polymers 1396.4.2 Ultrasonication in Sample Treatment for Polymer Characterization 1406.4.2.1 Introduction to Polymer Characterization 1406.4.2.2 Overview of Sample Preparation for MALDI Analysis of Polymers 1416.4.2.3 Ultrasonic Energy as a Tool for Fast Sample Treatment for the Characterization of Polymers by MALDI 1426.4.3 Ultrasonic-Induced Polymer Degradation for Polymer Characterization 1456.4.4 Ultrasonication for the Preparation of Imprinted Polymers 1456.5 Conclusion 148References 148Index 151