SAMPLE PREPARATION TECHNIQUES IN ANALYTICAL CHEMISTRY
CONTENTS CHAPTER SAMPLE PREPARATION: AN ANALYTICAL PERSPECTIVE 1 1 THE MEASUREMENT PROCESS 1 1 1 QUALITATIVE AND QUANTITATIVE ANALYSIS 1 1 2 METHODS OF QUANTITATION 1 2 ERRORS IN QUANTITATIVE ANALYSIS: ACCURACY AND PRECISION 1 2 1 ACCURACY 1 2 2 PRECISION 1 2 3 STATISTICAL ASPECTS OF SAMPLE PREPARATION 1 3 METHOD PERFORMANCE AND METHOD VALIDATION 1 3 1 SENSITIVITY 1 3 2 DETECTION LIMIT 1 3 3 RANGE OF QUANTITATION 1 3 4 OTHER IMPORTANT PARAMETERS 1 3 5 METHOD VALIDATION 1 4 PRESERVATION OF SAMPLES 1 4 1 VOLATILIZATION 1 4 2 CHOICE OF PROPER CONTAINERS 1 4 3 ABSORPTION OF GASES FROM THE ATMOSPHERE 1 4 4 CHEMICAL CHANGES 1 4 5 PRESERVATION OF UNSTABLE SOLIDS 1 5 POSTEXTRACTION PROCEDURES 1 5 1 CONCENTRATION OF SAMPLE EXTRACTS 1 5 2 SAMPLE CLEANUP 1 6 QUALITY ASSURANCE AND QUALITY CONTROL DURING SAMPLE PREPARATION 1 6 1 DETERMINATION OF ACCURACY AND PRECISION 1 6 2 STATISTICAL CONTROL 1 6 3 MATRIX CONTROL 1 6 4 CONTAMINATION CONTROL REFERENCES SECTION A EXTRACTION AND ENRICHMENT IN SAMPLE PREPARATION CHAPTER PRINCIPLES OF EXTRACTION AND THE EXTRACTION OF SEMIVOLATILE ORGANICS FROM LIQUIDS 2 1 PRINCIPLES OF EXTRACTION 2 1 1 VOLATILIZATION 2 1 2 HYDROPHOBICITY 2 1 3 ACID–BASE EQUILIBRIA 2 1 4 DISTRIBUTION OF HYDROPHOBIC IONOGENIC ORGANIC COMPOUNDS 2 2 LIQUID–LIQUID EXTRACTION 2 2 1 RECOVERY 2 2 2 METHODOLOGY 2 2 3 PROCEDURES 2 2 4 RECENT ADVANCES IN TECHNIQUES 2 3 LIQUID–SOLID EXTRACTION 2 3 1 SORPTION 2 4 SOLID-PHASE EXTRACTION 2 4 1 SORBENTS IN SPE 2 4 2 SORBENT SELECTION 2 4 3 RECOVERY 2 4 4 METHODOLOGY CONTENTS 2 4 5 PROCEDURES 2 4 6 RECENT ADVANCES IN SPE 2 5 SOLID-PHASE MICROEXTRACTION 2 5 1 SORBENTS 2 5 2 SORBENT SELECTION 2 5 3 METHODOLOGY 2 5 4 RECENT ADVANCES IN TECHNIQUES 2 6 STIR BAR SORPTIVE EXTRACTION 2 6 1 SORBENT AND ANALYTE RECOVERY 2 6 2 METHODOLOGY 2 6 3 RECENT ADVANCES IN TECHNIQUES 2 7 METHOD COMPARISON CHAPTER EXTRACTION OF SEMIVOLATILE ORGANIC COMPOUNDS FROM SOLID MATRICES 3 1 INTRODUCTION 3 1 1 EXTRACTION MECHANISM 3 1 2 PREEXTRACTION PROCEDURES 3 1 3 POSTEXTRACTION PROCEDURES 3 2 SOXHLET AND AUTOMATED SOXHLET 3 2 1 SOXHLET EXTRACTION 3 2 2 AUTOMATED SOXHLET EXTRACTION 3 2 3 COMPARISON BETWEEN SOXTEC AND SOXHLET 3 3 ULTRASONIC EXTRACTION 3 3 1 SELECTED APPLICATIONS AND COMPARISON WITH SOXHLET 3 4 SUPERCRITICAL FLUID EXTRACTION 3 4 1 THEORETICAL CONSIDERATIONS 3 4 2 INSTRUMENTATION 3 4 3 OPERATIONAL PROCEDURES 3 4 4 ADVANTAGES/DISADVANTAGES AND APPLICATIONS OF SFE 3 5 ACCELERATED SOLVENT EXTRACTION CONTENTS 3 5 1 THEORETICAL CONSIDERATIONS 3 5 2 INSTRUMENTATION 3 5 3 OPERATIONAL PROCEDURES 3 5 4 PROCESS PARAMETERS 3 5 5 ADVANTAGES AND APPLICATIONS OF ASE 3 6 MICROWAVE-ASSISTED EXTRACTION 3 6 1 THEORETICAL CONSIDERATIONS 3 6 2 INSTRUMENTATION 3 6 3 PROCEDURES AND ADVANTAGES/ DISADVANTAGES 3 6 4 PROCESS PARAMETERS 3 6 5 APPLICATIONS OF MAE 3 7 COMPARISON OF THE VARIOUS EXTRACTION TECHNIQUES EXTRACTION OF VOLATILE ORGANIC COMPOUNDS FROM SOLIDS AND LIQUIDS 4 1 VOLATILE ORGANICS AND THEIR ANALYSIS 4 2 STATIC HEADSPACE EXTRACTION 4 2 1 SAMPLE PREPARATION FOR STATIC HEADSPACE EXTRACTION 4 2 2 OPTIMIZING STATIC HEADSPACE EXTRACTION E‰CIENCY AND QUANTITATION 4 2 3 QUANTITATIVE TECHNIQUES IN STATIC HEADSPACE EXTRACTION 4 3 DYNAMIC HEADSPACE EXTRACTION OR PURGE AND TRAP 4 3 1 INSTRUMENTATION 4 3 2 OPERATIONAL PROCEDURES IN PURGE AND TRAP 4 3 3 INTERFACING PURGE AND TRAP WITH GC 4 4 SOLID-PHASE MICROEXTRACTION CONTENTS 4 4 1 SPME METHOD DEVELOPMENT FOR VOLATILE ORGANICS 4 4 2 CHOOSING AN SPME FIBER COATING 4 4 3 OPTIMIZING EXTRACTION CONDITIONS 4 4 4 OPTIMIZING SPME–GC INJECTION 4 5 LIQUID–LIQUID EXTRACTION WITH LARGE- VOLUME INJECTION 4 5 1 LARGE-VOLUME GC INJECTION TECHNIQUES 4 5 2 LIQUID–LIQUID EXTRACTION FOR LARGE-VOLUME INJECTION 4 6 MEMBRANE EXTRACTION 4 6 1 MEMBRANES AND MEMBRANE MODULES 4 6 2 MEMBRANE INTRODUCTION MASS SPECTROMETRY 4 6 3 MEMBRANE EXTRACTION WITH GAS CHROMATOGRAPHY 4 6 4 OPTIMIZATION OF MEMBRANE EXTRACTION 4 7 CONCLUSIONS PREPARATION OF SAMPLES FOR METALS ANALYSIS 5 1 INTRODUCTION 5 2 WET DIGESTION METHODS 5 2 1 ACID DIGESTION—WET ASHING 5 2 2 MICROWAVE DIGESTION 5 2 3 COMPARISON OF DIGESTION METHODS 5 2 4 PRESSURE ASHING 5 2 5 WET ASHING FOR SOIL SAMPLES 5 3 DRY ASHING 5 3 1 ORGANIC EXTRACTION OF METALS 5 3 2 EXTRACTION WITH SUPERCRITICAL FLUIDS 5 3 3 ULTRASONIC SAMPLE PREPARATION CONTENTS 5 4 SOLID-PHASE EXTRACTION FOR PRECONCENTRATION 5 5 SAMPLE PREPARATION FOR WATER SAMPLES 5 6 PRECIPITATION METHODS 5 7 PREPARATION OF SAMPLE SLURRIES FOR DIRECT AAS ANALYSIS 5 8 HYDRIDE GENERATION METHODS 5 9 COLORIMETRIC METHODS 5 10 METAL SPECIATION 5 10 1 TYPES OF SPECIATION 5 10 2 SPECIATION FOR SOILS AND SEDIMENTS 5 10 3 SEQUENTIAL SCHEMES FOR METALS IN SOIL OR SEDIMENT 5 10 4 SPECIATION FOR METALS IN PLANT MATERIALS 5 10 5 SPECIATION OF SPECI?C ELEMENTS 5 11 CONTAMINATION DURING METAL ANALYSIS 5 12 SAFE HANDLING OF ACIDS SECTION B SAMPLE PREPARATION FOR NUCLEIC ACID ANALYSIS CHAPTER SAMPLE PREPARATION IN DNA ANALYSIS 6 1 DNA AND ITS STRUCTURE 6 1 1 PHYSICAL AND CHEMICAL PROPERTIES OF DNA 6 1 2 ISOLATION OF DNA 6 2 ISOLATION OF DNA FROM BACTERIA 6 2 1 PHENOL EXTRACTION AND PRECIPITATION OF DNA 6 2 2 REMOVAL OF CONTAMINANTS FROM DNA 6 3 ISOLATION OF PLASMID DNA 6 3 1 PLASMID DNA PREPARATION 6 3 2 PURI?CATION OF PLASMID DNA 6 4 GENOMIC DNA ISOLATION FROM YEAST CONTENTS 6 5 DNA FROM MAMMALIAN TISSUES 6 5 1 BLOOD 6 5 2 TISSUES AND TISSUE CULTURE CELLS 6 6 DNA FROM PLANT TISSUE 6 7 ISOLATION OF VERY HIGH MOLECULAR WEIGHT DNA 6 8 DNA AMPLI?CATION BY POLYMERASE CHAIN REACTION 6 8 1 STARTING A PCR REACTION 6 8 2 ISOLATION OF DNA FROM SMALL REAL- WORLD SAMPLES FOR PCR 6 9 ASSESSMENT OF QUALITY AND QUANTITATION OF DNA 6 9 1 PRECAUTIONS FOR PREPARING DNA 6 9 2 ASSESSMENT OF CONCENTRATION AND QUALITY 6 9 3 STORAGE OF DNA SAMPLE PREPARATION IN RNA ANALYSIS 7 1 RNA: STRUCTURE AND PROPERTIES 7 1 1 TYPES AND LOCATION OF VARIOUS RNAS 7 2 RNA ISOLATION: BASIC CONSIDERATIONS 7 2 1 METHODS OF EXTRACTION AND ISOLATION OF RNA 7 3 PHENOL EXTRACTION AND RNA RECOVERY: BASIC PRINCIPLES 7 3 1 EXAMPLES OF RNA ISOLATION USING PHENOL EXTRACTION 7 4 GUANIDINIUM SALT METHOD 7 4 1 EXAMPLES OF RNA ISOLATION USING GUANIDINIUM SALTS 7 5 ISOLATION OF RNA FROM NUCLEAR AND CYTOPLASMIC CELLULAR FRACTIONS CONTENTS 7 6 REMOVAL OF DNA CONTAMINATION FROM RNA 7 7 FRACTIONATION OF RNA USING CHROMATOGRAPHY METHODS 7 7 1 FRACTIONATION OF SMALL RNA BY HPLC 7 7 2 MRNA ISOLATION BY A‰NITY CHROMATOGRAPHY 7 8 ISOLATION OF RNA FROM SMALL NUMBERS OF CELLS 7 9 IN VITRO SYNTHESIS OF RNA 7 10 ASSESSMENT OF QUALITY AND QUANTITATION OF RNA 7 11 STORAGE OF RNA TECHNIQUES FOR THE EXTRACTION, ISOLATION, AND PURIFICATION OF NUCLEIC ACIDS 8 1 INTRODUCTION 8 2 METHODS OF CELL LYSIS 8 2 1 MECHANICAL METHODS OF CELL LYSIS 8 2 2 NONMECHANICAL METHODS OF CELL LYSIS 8 3 ISOLATION OF NUCLEIC ACIDS 8 3 1 SOLVENT EXTRACTION AND PRECIPITATION 8 3 2 MEMBRANE FILTRATION 8 4 CHROMATOGRAPHIC METHODS FOR THE PURI?CATION OF NUCLEIC ACIDS 8 4 1 SIZE-EXCLUSION CHROMATOGRAPHY 8 4 2 ANION-EXCHANGE CHROMATOGRAPHY 8 4 3 SOLID-PHASE EXTRACTION 8 4 4 A‰NITY PURI?CATION 8 5 AUTOMATED HIGH-THROUGHPUT DNA PURI?CATION SYSTEMS 8 6 ELECTROPHORETIC SEPARATION OF NUCLEIC ACIDS CONTENTS 8 6 1 GEL ELECTROPHORESIS FOR NUCLEIC ACIDS PURI?CATION 8 6 2 TECHNIQUES FOR THE ISOLATION OF DNA FROM GELS 8 7 CAPILLARY ELECTROPHORESIS FOR SEQUENCING AND SIZING 8 8 MICROFABRICATED DEVICES FOR NUCLEIC ACIDS ANALYSIS 8 8 1 SAMPLE PREPARATION ON MICROCHIPS SECTION C SAMPLE PREPARATION IN MICROSCOPY AND SPECTROSCOPY CHAPTER SAMPLE PREPARATION FOR MICROSCOPIC AND SPECTROSCOPIC CHARACTERIZATION OF SOLID SURFACES AND FILMS 9 1 INTRODUCTION 9 1 1 MICROSCOPY OF SOLIDS 9 1 2 SPECTROSCOPIC TECHNIQUES FOR SOLIDS 9 2 SAMPLE PREPARATION FOR MICROSCOPIC EVALUATION 9 2 1 SECTIONING AND POLISHING 9 2 2 CHEMICAL AND THERMAL ETCHING 9 2 3 SAMPLE COATING TECHNIQUES 9 3 SPECIMEN THINNING FOR TEM ANALYSIS 9 3 1 ION MILLING 9 3 2 REACTIVE ION TECHNIQUES 9 3 3 CHEMICAL POLISHING AND ELECTROPOLISHING 9 3 4 TRIPOD POLISHING 9 3 5 ULTRAMICROTOMY 9 3 6 SPECIAL TECHNIQUES AND VARIATIONS 9 4 SUMMARY: SAMPLE PREPARATION FOR MICROSCOPY CONTENTS 9 5 SAMPLE PREPARATION FOR SURFACE SPECTROSCOPY 9 5 1 ION BOMBARDMENT 9 5 2 SAMPLE HEATING 9 5 3 IN SITU ABRASION AND SCRAPING 9 5 4 IN SITU CLEAVAGE OR FRACTURE STAGE 9 5 5 SAMPLE PREPARATION/TREATMENT OPTIONS FOR IN SITU REACTION STUDIES 9 6 SUMMARY: SAMPLE PREPARATION FOR SURFACE SPECTROSCOPY SURFACE ENHANCEMENT BY SAMPLE AND SUBSTRATE PREPARATION TECHNIQUES IN RAMAN AND INFRARED SPECTROSCOPY 10 1 INTRODUCTION 10 1 1 RAMAN E¤ECT 10 1 2 FUNDAMENTALS OF SURFACE-ENHANCED RAMAN SPECTROSCOPY 10 1 3 ATTENUATED TOTAL RE?ECTION INFRARED SPECTROSCOPY 10 1 4 FUNDAMENTALS OF SURFACE-ENHANCED INFRARED SPECTROSCOPY 10 2 SAMPLE PREPARATION FOR SERS 10 2 1 ELECTROCHEMICAL TECHNIQUES 10 2 2 VAPOR DEPOSITION AND CHEMICAL PREPARATION TECHNIQUES 10 2 3 COLLOIDAL SOL TECHNIQUES 10 2 4 NANOPARTICLE ARRAYS AND GRATINGS 10 3 SAMPLE PREPARATION FOR SEIRA 10 4 POTENTIAL APPLICATIONS