Advances in Flow Injection Analysis and Related Techniques

1. Auflage 2008
ISBN: 978-0-08-093212-5
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, Band Volume 54, 808 Seiten

Reihe: Comprehensive Analytical Chemistry

The concept of flow injection analysis (FIA) was first proposed in 1975 by Ruzicka and Hansen, and this initiated a field of research that would, over more than three decades, involve thousands of researchers, and which has to date resulted in close to 20,000 publications in the international scientific literature. Since its introduction, a number of books, including some specialized monographs, have been published on this subject with the latest in 2000. However, in this decade there has been a number of significant advances in the flow analysis area, and in particular in sequential injection analysis (SIA) techniques, and more recently with the introduction of Lab on a Valve (LOV) and bead injection flow systems. This book aims to cover the most important advances in these new areas, as well as in classical FIA, which still remains the most popular flow analysis technique used in analytical practice. Topics covered in the 23 chapters include the fundamental and underlying principles of flow analysis and associated equipment, the fluid-dynamic theory of FIA, an extensive coverage of detection methods (e.g. atomic and molecular spectrometry, electroanalytical methods). In addition, there are several chapters on on-line separation (e.g. filtration, gas diffusion, dialysis, pervaporation, solvent and membrane extraction, and chromatography), as well as on other sample pretreatment techniques, such as digestion. The book also incorporates several chapters on major areas of application of flow analysis in industrial process monitoring (e.g food and beverages, drugs and pharmaceuticals), environmental and agricultural analysis and life sciences. The contributing authors, who include the founders of flow injection analysis, are all leading experts in flow analytical techniques, and their chapters not only provide a critical review of the current state of this area, but also suggest future trends. - Provides a critical review of the current state of and future trends in flow analytical techniques - Offers a comprehensive elucidation of the principles and theoretical basis of flow analysis - Presents important applications in all major areas of chemical analysis, from food products to environmental concerns

Autoren/Hrsg.

Inhaltsverzeichnis

1;Front cover;1
2;Copyright page;3
3;Comprehensive Analytical Chemistry: Advances in Flow Injection Analysis and Related Techniques;6
4;Contents;8
5;Contributors to Volume 54;16
6;Volumes in the series;20
7;Preface;24
8;Series Editor's Preface;26
9;Foreword;28
10;Part I: Introduction to Flow Analysis;30
10.1;Chapter 1. Flow Injection Analysis: Its Origins and Progress;32
10.1.1;1. The conception of FIA;32
10.1.2;2. The infancy of FIA;36
10.1.3;3. Placing FIA into context;38
10.1.4;4. The early years of FIA;40
10.1.5;5. The dissemination of FIA: the human factor;44
10.1.6;6. Miniaturisation of FIA;44
10.1.7;7. Concluding remarks;47
10.1.8;References;50
10.2;Chapter 2. From Beaker to Programmable Microfluidics;52
10.2.1;1. Introduction;52
10.2.2;2. Sequential Injection and Programmable Flow;55
10.2.3;3. Miniaturization;57
10.2.4;4. Mixing and Dispersion;57
10.2.5;5. Mixing by Diffusion and Reynolds Number;64
10.2.6;6. muSI and Lab-on-Valve Design;65
10.2.7;7. Methods;66
10.2.8;8. Conclusions;72
10.2.9;Acknowledgment;73
10.2.10;References;73
10.3;Chapter 3. Theoretical Basis of Flow Injection Analysis;76
10.3.1;1. Introduction;76
10.3.2;2. Mass Transfer in FIA Systems;77
10.3.3;3. Chemical Kinetic Phenomena;95
10.3.4;4. Sensing Mechanism;100
10.3.5;Abbreviations and Nomenclature;103
10.3.6;References;104
10.4;Chapter 4. Principles of Flow Injection Analysis;110
10.4.1;1. Introduction;110
10.4.2;2. Sample Dispersion in Flow Injection and Sequential Injection Analysis Systems;113
10.4.3;3. Components of Flow Injection and Sequential Injection Analysis Systems;116
10.4.4;4. Operational Modes of FIA and Related Techniques;127
10.4.5;5. Conclusion;134
10.4.6;Abbreviations;134
10.4.7;References;135
10.5;Chapter 5. Bibliometrics;140
10.5.1;1. Introduction;140
10.5.2;2. Analytes;141
10.5.3;3. Application Areas;143
10.5.4;4. Detection Techniques;147
10.5.5;5. Other Interesting Statistics;150
10.5.6;6. Future Trends;150
10.5.7;Abbreviations;153
10.5.8;References;154
11;Part II: On-Line Sample Manipulation;156
11.1;Chapter 6. On-Line Sample Pretreatment: Dissolution and Digestion;158
11.1.1;1. Introduction;158
11.1.2;2. Dissolution;159
11.1.3;3. Digestion;164
11.1.4;Abbreviations and Definitions;183
11.1.5;References;184
11.2;Chapter 7. On-Line Sample Pretreatment: Extraction and Preconcentration;188
11.2.1;1. Introduction;188
11.2.2;2. Liquid-Liquid Extraction (Solvent Extraction, SE) without Membrane;189
11.2.3;3. Liquid-Solid Extraction (Solid Phase Extraction, SPE) of Organic and Inorganic Substances;200
11.2.4;4. Gas-Liquid Extraction Based on Mass Transfer;217
11.2.5;5. On-Line Pretreatment System, Including Computer-Controlled Automated Systems;225
11.2.6;Abbreviations;227
11.2.7;References;228
11.3;Chapter 8. Membrane-Based Separation Techniques: Dialysis, Gas Diffusion and Pervaporation;232
11.3.1;1. Introduction;233
11.3.2;2. The General Membrane-Based Separation Module;233
11.3.3;3. The Continuous Manifold;236
11.3.4;4. Detectors;240
11.3.5;5. Chemical Reactions Involved;240
11.3.6;6. Dialysis;241
11.3.7;7. Microdialysis;247
11.3.8;8. Gas Diffusion;252
11.3.9;9. Analytical Pervaporation;255
11.3.10;Abbreviations;260
11.3.11;References;261
11.4;Chapter 9. Membrane-Based Separation Techniques: Liquid-Liquid Extraction and Filtration;264
11.4.1;1. Introduction;264
11.4.2;2. Membrane-Based Continuous Liquid-Liquid Extraction;265
11.4.3;3. Continuous Filtration;283
11.4.4;Abbreviations;290
11.4.5;References;291
11.5;Chapter 10. Chromatographic Separations;294
11.5.1;1. Introduction;294
11.5.2;2. Separation Columns Used in Flow Analysis;296
11.5.3;3. Pharmaceutical Applications of Sequential Injection Chromatography;306
11.5.4;4. Comparison of Sequential Injection Chromatography and High Performance Liquid Chromatography;307
11.5.5;5. Other Chromatographic Approaches;309
11.5.6;6. Future Trends;310
11.5.7;Abbreviations;313
11.5.8;References;313
11.6;Chapter 11. Flow Injection Analysis-Capillary Electrophoresis;316
11.6.1;1. Introduction;316
11.6.2;2. Fundamentals of Capillary Electrophoresis;317
11.6.3;3. On-Line Coupling of FIA and CE;320
11.6.4;4. Electrokinetically Pumped Flow Analysis;331
11.6.5;5. Conclusions;334
11.6.6;Abbreviations;334
11.6.7;Acknowledgments;335
11.6.8;References;335
12;Part III. Detection;338
12.1;Chapter 12. Photometry;340
12.1.1;1. Introduction;340
12.1.2;2. Fundamentals of Spectrophotometric Measurements;343
12.1.3;3. Instrumental Aspects of Flow-Through Spectrophotometry;346
12.1.4;4. Background Absorbance Correction;361
12.1.5;5. Refractive Index (Schlieren) Effects;363
12.1.6;6. Conclusions and Outlook;367
12.1.7;Abbreviations;369
12.1.8;References;369
12.2;Chapter 13. Luminescence;372
12.2.1;1. Introduction;372
12.2.2;2. Photoluminescence;373
12.2.3;3. Chemiluminescence;378
12.2.4;4. Electrochemiluminescence;387
12.2.5;5. Future directions;396
12.2.6;Abbreviations;398
12.2.7;References;399
12.3;Chapter 14. Atomic Spectroscopic Detection;404
12.3.1;1. Introduction;404
12.3.2;2. Interfacing the Flow Network with Detection Devices;407
12.3.3;3. Flow Systems as Front-End Vehicles for On-Line Processing of Aqueous Samples;408
12.3.4;4. Flow Systems as Front-End Vehicles for On-Line Processing of Solid Samples;426
12.3.5;5. Hyphenation with Atomic Spectroscopic Detectors;430
12.3.6;Abbreviations;431
12.3.7;References;432
12.4;Chapter 15. Vibrational Spectrometry;436
12.4.1;1. A Short Note on the Evolution of Flow Injection Analysis in Recent Years;436
12.4.2;2. Vibrational Techniques as Detectors in Flow Injection Analysis;437
12.4.3;3. Scientometric Evolution of Vibrational Spectrometry in Flow Injection Analysis;437
12.4.4;4. Objectives;438
12.4.5;5. Infrared Spectrometry;439
12.4.6;6. Raman Spectrometry;459
12.4.7;7. Concluding Remarks and Outlook;464
12.4.8;Abbreviations;260
12.4.9;Acknowledgments;465
12.4.10;References;261
12.5;Chapter 16. Electrochemical Detection;470
12.5.1;1. Introduction;470
12.5.2;2. Detector Design;473
12.5.3;3. Conductometric Measurements;473
12.5.4;4. Potentiometric Measurements;476
12.5.5;5. Voltammetric and Amperometric Measurements;479
12.5.6;6. Coulometric Measurements;484
12.5.7;7. Conclusions;486
12.5.8;Acknowledgments;486
12.5.9;References;487
12.6;Chapter 17. Miscellaneous Detection Systems;490
12.6.1;1. Introduction;490
12.6.2;2. Conductometric Detectors;492
12.6.3;3. Miscellaneous Non-Spectrophotometric, Optical Detection Systems;493
12.6.4;4. Radiometric Detection;503
12.6.5;5. Thermometric and Enthalpimetric Detection;505
12.6.6;6. Dynamic Surface Tension Detector;506
12.6.7;7. Mass Spectrometry;508
12.6.8;8. Nuclear Magnetic Resonance (NMR);509
12.6.9;9. Piezoelectric Detection;510
12.6.10;10. X-Ray Fluorescence;514
12.6.11;11. Conclusion;534
12.6.12;Abbreviations;534
12.6.13;References;535
13;Part IV: Applications of Flow Injection Analysis;540
13.1;Chapter 18. Food, Beverages and Agricultural Applications;542
13.1.1;1. Introduction;542
13.1.2;2. Applications: Beverages;543
13.1.3;3. Applications: Plants and Vegetables;574
13.1.4;4. Applications: Milk and Dairy Products;575
13.1.5;5. Applications: Meat and Fish Products;576
13.1.6;6. Miscellaneous Food Products;577
13.1.7;Abbreviations;577
13.1.8;References;578
13.2;Chapter 19. Life Sciences Applications;588
13.2.1;1. Introduction;588
13.2.2;2. Deoxyribonucleic Acid (DNA) Assays;589
13.2.3;3. Assays of Proteins, Peptides and Amino Acids;595
13.2.4;4. Immunoassays;604
13.2.5;5. Enzymatic Assays;610
13.2.6;6. Cellular Analysis;614
13.2.7;7. Perspectives;615
13.2.8;Abbreviations;616
13.2.9;References;617
13.3;Chapter 20. Pharmaceutical Applications;620
13.3.1;1. Introduction;620
13.3.2;2. Automated Analytical Flow Methods in Pharmaceutical Research;623
13.3.3;3. Automated Analytical Flow Methods in Pharmaceutical Production and Drug Quality Control;628
13.3.4;Abbreviations;642
13.3.5;References;642
13.4;Chapter 21. Industrial and Process Analysis Applications;646
13.4.1;1. Introduction;646
13.4.2;2. The Advantages and Weakness of Flow Analysis Applied to Industry;648
13.4.3;3. Process Analysers Based on Flow Systems;656
13.4.4;4. Selected Applications of Flow Analysis to Industrial and Process Analysis;658
13.4.5;5. Conclusion;664
13.4.6;Abbreviations;665
13.4.7;References;666
13.5;Chapter 22. Environmental Applications: Atmospheric Trace Gas Analyses;668
13.5.1;1. Introduction;669
13.5.2;2. Collection of Trace Gases;669
13.5.3;3. Integration of a Gas Collector into a Flow Analysis System;679
13.5.4;4. Flow System Miniaturization for Atmospheric Analysis;685
13.5.5;5. Illustrative Examples;690
13.5.6;6. Applications to Breath Analysis;702
13.5.7;7. Ancillary Systems for Field Monitoring;704
13.5.8;8. Conclusions;709
13.5.9;Acknowledgments;709
13.5.10;References;710
13.6;Chapter 23. Environmental Applications: Waters, Sediments and Soils;714
13.6.1;1. Challenges of Environmental Analysis;715
13.6.2;2. Instrumentation and Modes of Application;721
13.6.3;3. Range of Sample Types;727
13.6.4;4. Applications;734
13.6.5;5. Future Trends;780
13.6.6;Abbreviations and Definitions;781
13.6.7;References;783
14;Subject Index;790
15;Colour Plate Section;808

Leseproben

Chapter 2 From Beaker to Programmable Microfluidics
Jaromir Ružicka Publisher Summary
This chapter discusses the development of solution-handling techniques from manual to mechanized and into a microfluidic format. It focuses on microsequential injection (µSI) techniques for their versatility that opens unexplored avenues for further research in the dynamic field of analytical chemistry. Compared to traditional flow injection analysis (FIA) that operates on continuous forward flow, sequential injection (SI), bead injection (BI), and sequential injection chromatography (SIC) utilize flow programming for enhancing their usefulness and reducing the consumption of reagents. Miniaturization, mixing, dispersion, and reagent-based assays are described. The chapter also explores the way in which flow programing in µSI format can, due to its unprecedented flexibility, accommodate all the analytical techniques in the same instrument. The goal, therefore, is to design microfluidic analytical systems that are visually transparent so that their function can be observed and understood, allowing any malfunction to be identified by sight. The challenge is to design the simplest possible system configuration, comprising ideally only one pump and one valve. 1 INTRODUCTION
A vast majority of (bio)chemical assays rely on precise and reproducible solution handling, since samples and reagents have to be metered, mixed, incubated, heated, separated, and monitored by spectroscopy, electrochemistry, or other means for quantification of target analytes. This chapter follows the development of solution-handling techniques from manual to mechanized, and into a microfluidic format. It focuses on microsequential injection (µSI) techniques, not because of their novelty, but for their well-documented versatility, that opens yet unexplored avenues for further research in this dynamic field of analytical chemistry. Indeed, compared to traditional flow injection analysis (FIA) that operates on continuous forward flow, sequential injection (SI), bead injection (BI), and sequential injection chromatography (SIC) utilize flow programming, to enhance their usefulness and to reduce consumption of reagents. It will be shown how flow programming in µSI format, can, due to its unprecedented flexibility, accommodate all the above-mentioned analytical techniques in the same instrument. Analytical chemistry is the oldest branch of chemistry [1], since prior to the development of quantitative analysis, chemical experimentation remained within the realm of alchemy. It is in Lavoisier’s book [2], where we find the first description of solution-handling tools, including volumetric glassware. By 1806 volumetric analysis was perfected, and has remained in its form almost unchanged to this day [3]. Thus originated the solution-handling method, often referred to as “beaker chemistry”. As time went by, this approach became refined, miniaturized, and mechanized, ultimately evolving into current microwell plate formats that have been designed to meet the needs of high throughput pharmaceutical assays. The characteristic feature of this approach, known as “batch analysis” is that each sample solution is processed within a container (test tube, beaker, microwell), where it is homogenously mixed with auxiliary reagents and the readout (end point, absorbance, etc.) is being taken after equilibrium has been reached. When mechanized for serial assays, the individual containers are moved around, through stations, where samples are pipetted, reagents are added, solutions are mixed, etc., as required by assay protocol. While precise, reproducible, and well suited for parallel processing of slow, and end-point-based assays, batch analysis is labor intensive and it becomes less reliable when microminiaturized down to microlitre volumes, where it suffers from the adverse effects of evaporation, differences in solution viscosities, and inability to carry out separations. For certain applications, such as routine clinical assays, or drug screening, discrete analysers dominate the field, since they offer “black box with prepacked chemistry” approach, albeit at high cost capital investment, and expensive reagent cost and maintenance. It was Tsvett, a botanist, who unwittingly became the father of continuous-flow analysis. In 1906, he published his pioneering work on the separation of components of chlorophyll using column of calcium carbonate, eluted continuously by mobile phase (petroleum ether) [4]. For almost 50 years, chromatography, which Tsvett discovered and named, was the only analytical technique where samples were analysed while being carried by a flow-through tubing towards a detector. This all changed, in 1957, when Skeggs, a clinical chemist, designed an air segmented, continuous-flow analyser (Figure 1), where sample solutions were drawn into a system of flow channels by a peristaltic pump, metered and mixed with reagents on the way to detector, while being heated, filtered, extracted, etc [5,6]. The essential feature of Skegg’s design was air segmentation, which divided the moving carrier stream into many separate segments using numerous air bubbles that prevented intermingling of adjacent samples. Also, friction of liquid with walls of the tubing facilitated homogenous mixing of samples with regents, by promoting solute circulation, within each forward moving liquid segment. Skeggs’ invention became an undisputed success, largely in the field of clinical assays, as almost all clinical laboratories in technically advanced countries used the Technicon Autoanalyser® for serial assays of multiple analytes. Interestingly, academic research, textbooks, and university teachings, mostly ignored this revolutionary approach to solution handling, which dominated the field of real-life assays for the almost 20 years. Figure 1 Skegg’s continuous-flow analyser. Top: samples were drawn from the autosampler carousel (S) by a peristaltic pump that also aspirated air and reagent (R). Air segmented stream was pumped through a reaction coil, air bubbles were removed and reacted mixture was pumped and into a flow through cell, where absorbance was measured. The readout was obtained at a “steady state” flat portion of a peak. Below: air bubbles separated individual aqueous segments, where the circular movement of liquid promoted mixing. Adapted from Ref. [30] with authors permission. It was in 1974, that unexpected, yet in hindsight almost trivial, discovery was made. During investigation of response rate of an electrode, it was realized, that air segmentation was not necessary for performing reagent-based assays. The subsequent study of dispersion of solutes in tubular conduits within nonsegmented, continuous flow, led to the development of a new technique [7], termed FIA. The method was based on combination of three principles: sample injection, controlled dispersion, and reproducible timing [8,9,20]. Sample injection defined the volume of analyte and its initial geometry in the tubular channel, while the controlled dispersion was achieved by holding the flow rate of the carrier stream constant and by maintaining a fixed geometry of the flow path. The precise timing of the start of the assay cycle and of the residence time of the analyte zone in the system was controlled by flow rate and by the volume of the flow path. To begin with, FIA was not well received, since the idea of using controlled dispersion rather than homogenous mixing of sample with reagents was entirely at odds with the accepted concept of reagent-based assays [9]. It took several years before experimental evidence finally prevailed, documenting that the dispersion process and timing of all events could be controlled with such repeatability, confirming that FIA assays, based on monitoring of concentration gradients, and incomplete chemical equilibria, can be as precise and reproducible, as those obtained in the traditional batch format, where sample and reagent solutions are homogenously mixed and chemical equilibrium is attained. The scope of this chapter documents that FIA and its related techniques are now widely used both for routine as well as research work, in laboratories worldwide. After 30 years of existence with over 16,000 papers published on FIA alone, novel, ingenious modifications and applications of flow injection techniques are still being discovered [9]. One of them, termed SI [10], benefits from many offerings of computerization and from advances in software and laboratory hardware. Improved pumps, valves, and miniaturized solid state spectrophotometers and light sources (LED) allowed the initial design of SI methodology to be gradually transformed from proof of concept, to a powerful, miniaturized tool for research and routine applications. The result, µSI is far more versatile than the original, continuous flow-based techniques. 2 SEQUENTIAL INJECTION AND PROGRAMMABLE FLOW
It takes a long time for a novel method to mature and to be accepted. This is because initially, it is difficult to visualize the full potential of a new approach, and to anticipate its future applications. The proof of concept is often hampered by lack of suitable hardware components, that not yet...