Advances in Flow Injection Analysis and Related Techniques (eBook)

Spas D. Kolev, Ian D. McKelvie (Herausgeber)

eBook Download: PDF | EPUB

2008 | 1. Auflage
808 Seiten
Elsevier Science (Verlag)
978-0-08-093212-5 (ISBN)

Infos

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

Inhalt

Front cover 1
Copyright page 3
Comprehensive Analytical Chemistry: Advances in Flow Injection Analysis and Related Techniques 6
Contents 8
Contributors to Volume 54 16
Volumes in the series 20
Preface 24
Series Editor's Preface 26
Foreword 28
Part I: Introduction to Flow Analysis 30
Chapter 1. Flow Injection Analysis: Its Origins and Progress 32
1. The conception of FIA 32
2. The infancy of FIA 36
3. Placing FIA into context 38
4. The early years of FIA 40
5. The dissemination of FIA: the human factor 44
6. Miniaturisation of FIA 44
7. Concluding remarks 47
References 50
Chapter 2. From Beaker to Programmable Microfluidics 52
1. Introduction 52
2. Sequential Injection and Programmable Flow 55
3. Miniaturization 57
4. Mixing and Dispersion 57
5. Mixing by Diffusion and Reynolds Number 64
6. muSI and Lab-on-Valve Design 65
7. Methods 66
8. Conclusions 72
Acknowledgment 73
References 73
Chapter 3. Theoretical Basis of Flow Injection Analysis 76
1. Introduction 76
2. Mass Transfer in FIA Systems 77
3. Chemical Kinetic Phenomena 95
4. Sensing Mechanism 100
Abbreviations and Nomenclature 103
References 104
Chapter 4. Principles of Flow Injection Analysis 110
1. Introduction 110
2. Sample Dispersion in Flow Injection and Sequential Injection Analysis Systems 113
3. Components of Flow Injection and Sequential Injection Analysis Systems 116
4. Operational Modes of FIA and Related Techniques 127
5. Conclusion 134
Abbreviations 134
References 135
Chapter 5. Bibliometrics 140
1. Introduction 140
2. Analytes 141
3. Application Areas 143
4. Detection Techniques 147
5. Other Interesting Statistics 150
6. Future Trends 150
Abbreviations 153
References 154
Part II: On-Line Sample Manipulation 156
Chapter 6. On-Line Sample Pretreatment: Dissolution and Digestion 158
1. Introduction 158
2. Dissolution 159
3. Digestion 164
Abbreviations and Definitions 183
References 184
Chapter 7. On-Line Sample Pretreatment: Extraction and Preconcentration 188
1. Introduction 188
2. Liquid-Liquid Extraction (Solvent Extraction, SE) without Membrane 189
3. Liquid-Solid Extraction (Solid Phase Extraction, SPE) of Organic and Inorganic Substances 200
4. Gas-Liquid Extraction Based on Mass Transfer 217
5. On-Line Pretreatment System, Including Computer-Controlled Automated Systems 225
Abbreviations 227
References 228
Chapter 8. Membrane-Based Separation Techniques: Dialysis, Gas Diffusion and Pervaporation 232
1. Introduction 233
2. The General Membrane-Based Separation Module 233
3. The Continuous Manifold 236
4. Detectors 240
5. Chemical Reactions Involved 240
6. Dialysis 241
7. Microdialysis 247
8. Gas Diffusion 252
9. Analytical Pervaporation 255
Abbreviations 260
References 261
Chapter 9. Membrane-Based Separation Techniques: Liquid-Liquid Extraction and Filtration 264
1. Introduction 264
2. Membrane-Based Continuous Liquid-Liquid Extraction 265
3. Continuous Filtration 283
Abbreviations 290
References 291
Chapter 10. Chromatographic Separations 294
1. Introduction 294
2. Separation Columns Used in Flow Analysis 296
3. Pharmaceutical Applications of Sequential Injection Chromatography 306
4. Comparison of Sequential Injection Chromatography and High Performance Liquid Chromatography 307
5. Other Chromatographic Approaches 309
6. Future Trends 310
Abbreviations 313
References 313
Chapter 11. Flow Injection Analysis-Capillary Electrophoresis 316
1. Introduction 316
2. Fundamentals of Capillary Electrophoresis 317
3. On-Line Coupling of FIA and CE 320
4. Electrokinetically Pumped Flow Analysis 331
5. Conclusions 334
Abbreviations 334
Acknowledgments 335
References 335
Part III. Detection 338
Chapter 12. Photometry 340
1. Introduction 340
2. Fundamentals of Spectrophotometric Measurements 343
3. Instrumental Aspects of Flow-Through Spectrophotometry 346
4. Background Absorbance Correction 361
5. Refractive Index (Schlieren) Effects 363
6. Conclusions and Outlook 367
Abbreviations 369
References 369
Chapter 13. Luminescence 372
1. Introduction 372
2. Photoluminescence 373
3. Chemiluminescence 378
4. Electrochemiluminescence 387
5. Future directions 396
Abbreviations 398
References 399
Chapter 14. Atomic Spectroscopic Detection 404
1. Introduction 404
2. Interfacing the Flow Network with Detection Devices 407
3. Flow Systems as Front-End Vehicles for On-Line Processing of Aqueous Samples 408
4. Flow Systems as Front-End Vehicles for On-Line Processing of Solid Samples 426
5. Hyphenation with Atomic Spectroscopic Detectors 430
Abbreviations 431
References 432
Chapter 15. Vibrational Spectrometry 436
1. A Short Note on the Evolution of Flow Injection Analysis in Recent Years 436
2. Vibrational Techniques as Detectors in Flow Injection Analysis 437
3. Scientometric Evolution of Vibrational Spectrometry in Flow Injection Analysis 437
4. Objectives 438
5. Infrared Spectrometry 439
6. Raman Spectrometry 459
7. Concluding Remarks and Outlook 464
Abbreviations 260
Acknowledgments 465
References 261
Chapter 16. Electrochemical Detection 470
1. Introduction 470
2. Detector Design 473
3. Conductometric Measurements 473
4. Potentiometric Measurements 476
5. Voltammetric and Amperometric Measurements 479
6. Coulometric Measurements 484
7. Conclusions 486
Acknowledgments 486
References 487
Chapter 17. Miscellaneous Detection Systems 490
1. Introduction 490
2. Conductometric Detectors 492
3. Miscellaneous Non-Spectrophotometric, Optical Detection Systems 493
4. Radiometric Detection 503
5. Thermometric and Enthalpimetric Detection 505
6. Dynamic Surface Tension Detector 506
7. Mass Spectrometry 508
8. Nuclear Magnetic Resonance (NMR) 509
9. Piezoelectric Detection 510
10. X-Ray Fluorescence 514
11. Conclusion 534
Abbreviations 534
References 535
Part IV: Applications of Flow Injection Analysis 540
Chapter 18. Food, Beverages and Agricultural Applications 542
1. Introduction 542
2. Applications: Beverages 543
3. Applications: Plants and Vegetables 574
4. Applications: Milk and Dairy Products 575
5. Applications: Meat and Fish Products 576
6. Miscellaneous Food Products 577
Abbreviations 577
References 578
Chapter 19. Life Sciences Applications 588
1. Introduction 588
2. Deoxyribonucleic Acid (DNA) Assays 589
3. Assays of Proteins, Peptides and Amino Acids 595
4. Immunoassays 604
5. Enzymatic Assays 610
6. Cellular Analysis 614
7. Perspectives 615
Abbreviations 616
References 617
Chapter 20. Pharmaceutical Applications 620
1. Introduction 620
2. Automated Analytical Flow Methods in Pharmaceutical Research 623
3. Automated Analytical Flow Methods in Pharmaceutical Production and Drug Quality Control 628
Abbreviations 642
References 642
Chapter 21. Industrial and Process Analysis Applications 646
1. Introduction 646
2. The Advantages and Weakness of Flow Analysis Applied to Industry 648
3. Process Analysers Based on Flow Systems 656
4. Selected Applications of Flow Analysis to Industrial and Process Analysis 658
5. Conclusion 664
Abbreviations 665
References 666
Chapter 22. Environmental Applications: Atmospheric Trace Gas Analyses 668
1. Introduction 669
2. Collection of Trace Gases 669
3. Integration of a Gas Collector into a Flow Analysis System 679
4. Flow System Miniaturization for Atmospheric Analysis 685
5. Illustrative Examples 690
6. Applications to Breath Analysis 702
7. Ancillary Systems for Field Monitoring 704
8. Conclusions 709
Acknowledgments 709
References 710
Chapter 23. Environmental Applications: Waters, Sediments and Soils 714
1. Challenges of Environmental Analysis 715
2. Instrumentation and Modes of Application 721
3. Range of Sample Types 727
4. Applications 734
5. Future Trends 780
Abbreviations and Definitions 781
References 783
Subject Index 790
Colour Plate Section 808

Textauszug

Chapter 2

From Beaker to Programmable Microfluidics

Jaromir Růžička

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...

Produkt-Details

• Erscheint lt. Verlag: 21.11.2008
• Sprache: englisch
• Themenwelt: Medizin / Pharmazie ► Gesundheitsfachberufe
• Themenwelt: Studium ► 2. Studienabschnitt (Klinik) ► Pharmakologie / Toxikologie
• Themenwelt: Naturwissenschaften ► Chemie ► Analytische Chemie
• Themenwelt: Technik ► Umwelttechnik / Biotechnologie
• ISBN-10: 0-08-093212-6 / 0080932126
• ISBN-13: 978-0-08-093212-5 / 9780080932125