Principles and Practice of Modern Chromatographics Methods

Front Matter
Preface
	Preface to first edition
Introduction and overview
	Introduction
	Coverage
	Chromatographic separation simply explained
	Classification of chromatography
		Mobile phase
			Reversed-phase and normal-phase chromatography
		Development mode
		Technique
			Planar and column chromatography
				Column types
		Separation mechanism
			Adsorption chromatography
			Partition chromatography
			Bonded phase chromatography
			Hydrophilic interaction liquid chromatography (HILIC)
			Ion-exchange chromatography
			Ion-interaction chromatography
			Size-exclusion chromatography
			Affinity chromatography
			Micellar or Pseudophase liquid chromatography
			Complexation chromatography
			Ion-exclusion chromatography
			Chiral chromatography
		Other systems of classification
	Chromatography: Publications and equipment sales
	Applications of chromatography
		Qualitative applications
		Quantitative applications
		Chromatographic metabolomics
		Preparative applications
	Comparison of chromatographic techniques
		Analyte characteristics
		Characteristics of the sample matrix
		Purpose of the analysis
	Historical aspects
		Historical developments in the theory of chromatography
		Concluding remarks
	Obtaining assistance
	References
Theoretical considerations
	Introduction
	Theory of chromatography
		Why bother with theory?
		Model or theory, which is it?
		Taxonomy of models
			Equilibrium models
			Kinetic models
			Macroscopic kinetic models
			Microscopic kinetic models
	Retention, dispersion, and distortion
		Measures of peak asymmetry
		Distribution isotherms
	Retention: Thermodynamics and molecular interactions
	Retention
		Prediction of retention
		Stationary phase selection
		Method development
	Measures of chromatographic retention
		Planar techniques
		Column techniques
			Retention factor, k
			Retention time
				Compressible mobile phases
			Retention volume
			Net and specific retention volume
	Dispersion
		Plate theory
			Plate height
		Rate theory
			Factors contributing to dispersion or zone broadening: Van Deemter equation
				The A term: Eddy diffusion
				The B term: Molecular or longitudinal diffusion
				The C term: Resistance to mass transfer
			Van Deemter plot
	Is it resolution or separation?
		Measures of separation and resolution
			Separation factor
			Resolution
			Peak capacity and Trennzahl
			Summary
		Optimizing resolution
			Column length
			Retention factor
				General elution problem
			Column efficiency
			Column selectivity
			Summary
	Extra-column dispersion
		Worked example
	Summary: Retention and dispersion
	Column testing
	References
Planar chromatography
	Introduction
		Paper chromatography
			Mobile phases for paper chromatography
		Thin layer chromatography
	Why thin layer chromatography?
		Comparison of conventional TLC and HPTLC
		Comparison of TLC with other techniques
	Theoretical considerations
	Sample application in TLC
	Plate development in TLC
		Development chambers
		Development techniques
			Linear development
				Vertical and horizontal development (one-dimensional single development)
				One-dimensional multiple and continuous development
				Two-dimensional development
			Rotational development
				Circular and anti-circular development
				Forced flow development
	Innovation in TLC
		Forced flow conditions
		Ultrathin layer chromatography
		Hyphenated techniques
	Thin layer plates
	Stationary phases
		Polar inorganic adsorbents
			Silica gel
			Alumina
			Others
			Activity
				Pre-loading
				Standardization of activity
			Activity order of different adsorbents
			Layer pre-treatment
		Non-polar inorganic adsorbents
		Modified adsorbents
		Non-polar bonded phases
		Polar bonded phases
		Other phases
	Mobile phases
		Mobile phase optimization
			Normal-phase systems
			Reversed-phase systems
	Detection: Qualitative analysis
		Direct examination
		Spray reagents
		Spectrometry
			Mass spectrometry
				Analyte sampling and ionization
		Miscellaneous
	Quantitative analysis
		In situ visual evaluation
		Elution techniques
		Densitometry
			Slit scanning densitometers
				Transmittance mode
				Reflectance mode
				Combined transmittance-reflectance mode
				Decrease of phosphorescence
				Fluorescence mode
				Instrumentation
			Diode-array densitometers
			Image analysers
	Separations
	References
Gas chromatography
	Introduction
		Samples analysed by GC
		Organization of this chapter
	Mobile phases and delivery systems
		Safety considerations
		Carrier gas delivery systems
			Carrier gas purification
		Choosing a mobile phase
		Carrier gas flow
			Regulation of carrier gas flow and pressure control
			Measurement of carrier gas flow
			Practical considerations
	Sample introduction in GC
		Septa
		Microsyringes
			Manual syringe handling techniques
				Packed columns
				Open tubular columns
			Auto injection
		Sample inlet systems
			Packed column
			Open tubular column
				Split injection
				Splitless injection
				Cool on-column injection
				Programmed temperature vaporizer
					Summary
				Large volume injection
			Pyrolysis gas chromatography
			Headspace gas chromatography
	Column packings and hardware
		Columns
			Packed columns
			Open tubular columns
				Column diameter
				Column length
				Stationary phase film thickness
					Column diameter and film thickness
		Column packings
			Gas solid chromatography
				Stationary phases
					Inorganic oxides
					Carbon adsorbents
					Molecular sieves
					Porous polymers
			Gas liquid chromatography
				Solid supports
				Stationary phases
					Representative stationary phases
				Selection of a stationary phase
				Classification of stationary phases
				Summary
		Column installation
		Measuring system performance
			Column bleed
			Solvent and unretained solute test
			Column efficiency
			System activity
				Ratio testing
		Column care and use
	Detectors
		Make-up gas
		Thermal conductivity detector
		Flame ionization detector
		Electron capture detector
		Thermionic ionization detector
		Flame photometric detector
		Other detectors
		Dual detection
	Column temperature and temperature programming
		Temperature programming
	Derivatization
		Silylation
		Acylation
		Alkylation
		Oxime formation
	Innovation
		Multi-column gas chromatography
		High-speed gas chromatography
		High temperature gas chromatography
		Micro gas chromatography
	Separations
		Gas solid chromatography
			Mechanism of gas solid chromatography
			Applications
		Gas liquid chromatography
			Mechanism of gas liquid chromatography
			Applications
	References
High performance liquid chromatography: Instrumentation and techniques
	Introduction
	From HPLC to UHPLC and beyond
	Solvent delivery systems
		General requirements
		Materials of construction
		Mobile phase reservoirs
		Reciprocating HPLC pumps
		Multisolvent pumps
		Other types of HPLC pump
	Sample introduction in HPLC
		Manual injection
		Autosamplers
			Autosampler vials and microplates
	Column packings and hardware
		Columns
		Column packings
			Packed columns
			Monolithic and other columns
		Column packing and preparation methods
		Column configuration and hardware
		Column dimensions
		Measuring column performance
		Column care and use
	Detectors
		Introduction
		UV-visible absorbance detectors
		Fluorescence detectors
		Electrochemical detectors
		Refractive index detectors
		Conductivity detectors
		Aerosol-based detectors
		Other detectors
		Detector requirements for UHPLC
	Post-column derivatization
	Gradient elution
		Introduction
		Gradient elution theory and optimization
		Dwell volume and gradient elution
		Gradient applications and considerations
	Multidimensional liquid chromatography
	References
High performance liquid chromatography: Separations
	Introduction
		Chromatographic separations
		Organization of this chapter
	Separation of neutral compounds
		Normal-phase chromatography
			Introduction
			Mechanism of normal-phase chromatography
			Stationary phases for normal-phase chromatography
			Mobile phases for normal-phase chromatography
				Solvent strength
				Solvent selectivity
				Effect of water
			Applications of normal-phase chromatography
		Reversed-phase liquid chromatography
			Introduction
			Mechanism of reversed-phase chromatography
			Stationary phases for reversed-phase liquid chromatography
				Bonded phase silica columns
				Silica and silica functionalization
				Ligands used for bonded phase silica columns
				Characteristics of bonded phase silica columns
				Hybrid reversed-phase columns
				Choosing a reversed-phase column
			Mobile phases for reversed-phase liquid chromatography
				Solvent classification
				Solvent strength
				Solvent selectivity
				Other factors
			Applications of reversed-phase liquid chromatography
		Hydrophilic interaction liquid chromatography
			Introduction
			Mechanism of hydrophilic interaction liquid chromatography
			Stationary phases for hydrophilic interaction liquid chromatography
			Mobile phases for hydrophilic interaction liquid chromatography
			Applications of hydrophilic interaction liquid chromatography
		Size exclusion chromatography
			Introduction
			Mechanism of size exclusion chromatography
			Stationary phases for size exclusion chromatography
			Mobile phases for size exclusion chromatography
			Applications of size exclusion chromatography
	Techniques for ionic and ionizable species
		Ion-suppression chromatography
		Ion-interaction chromatography
			Introduction
			Stationary and mobile phases for ion-interaction chromatography
			Mechanism of ion-interaction chromatography
			Factors affecting retention in ion-interaction chromatography
			Applications of ion-interaction chromatography
		Ion-exchange chromatography
			Introduction
			Mechanism of ion-exchange chromatography
			Stationary and mobile phases for ion-exchange chromatography
			Factors affecting retention in ion-exchange chromatography
			Applications of ion-exchange chromatography
		Ion chromatography
			Introduction
			Stationary and mobile phases for ion chromatography
			Mechanism of ion chromatography
			Applications of ion chromatography
		Ion-exclusion chromatography
			Introduction
			Mechanism of ion-exclusion chromatography
			Stationary and mobile phases for ion-exclusion chromatography
			Factors affecting retention in ion-exclusion chromatography
			Applications of ion-exclusion chromatography
	Specialty separation modes
		Hydrophobic interaction chromatography
		Affinity chromatography
		Complexation chromatography
		Chiral chromatography
	Choosing a chromatographic method
	References
Supercritical fluid chromatography
	Introduction
		History
		Instrumentation
		Factors affecting retention
	Mobile phases and delivery systems
		Safety considerations
		Hardware
			Back pressure regulators
		Mobile phases
			Alternatives to carbon dioxide
			Modifiers
			Mobile phase flow
			Temperature/Pressure effects
	Sample introduction in SFC
	Column packings and hardware
		Open tubular columns
		Packed column SFC
	Detectors
	Programming techniques
	Separations
	References
Coupled systems
	Introduction
	Multidimensional chromatography
		LC-GC and LCxGC
	Hyphenated techniques
		Mass spectrometry
		Infrared spectrometry
		Nuclear magnetic resonance spectrometry
		GC-based
			Gas chromatography-mass spectrometry
				Ionization methods
				Mass analyser
					Scanning mode
					Data
			Gas chromatography-Fourier transform infrared spectrometry
			GC-MS or GC-FTIR?
			Other hyphenated techniques involving GC
		LC based
			Liquid chromatography-mass spectrometry
				Ionization methods
				Mass analyser
				Enhancing specificity
				UHPLC
			Liquid chromatography-nuclear magnetic resonance spectrometry
			Liquid chromatography-fourier transform infrared spectrometry
		SFC-based
	References
Analyses
	Introduction
	Detectors for chromatography
		Specifications
			Sensitivity
			Linear response
			Dynamic range
			Minimum detectable quantity
			Time constant and response time
			Selectivity of response
			Other factors
			Noise
		Classification
	Data handling
		Peak area versus peak height measurement
		Manual approaches
		Computerized approaches
			Data acquisition
			Data processing
				Peak shape
				Peak finding
				Integration
					Mathematical peak deconvolution
		Chromatography data management system report
			Chromatographic efficiency
	Qualitative analysis
		Retention parameters
			Relative retention
			Retention indices
				Gas chromatography
				High-performance liquid and supercritical fluid chromatography
			Retention and molecular structure
		Chemical methods
		Peak trapping and off-line spectrometric methods
		Selective detectors
		Coupled techniques
	Quantitative analysis
		Calibration procedures
			Normalization
			External calibration
			Internal standard
			Standard addition
			Worked examples
				Case 1. The gas chromatographic determination of xylenes in a commercial mixture
				Case 2. The characterization of a vegetable oil by gas chromatographic determination of fatty acid content.
				Case 3. Determination of nicotinic acid in instant coffee
				Case 4. Determination of bromate in bread dough
				Case 5. The determination of polychlorinated biphenyls in environmental samples
				Case 6. The determination of ethanol in a blood sample
				Case 7. The determination of cocaine
				Case 8. The determination of caffeine and theobromine in chocolate products
		What can be done if no analyte is detected?
	Metabolomics and chromatography
		Measurement of analytical signal
			Separation
				Gas chromatography
				Liquid chromatography
				Supercritical fluid chromatography
				Two-dimensional chromatography
			Detection
		Data handling
			Peak detection
			Peak alignment
			Normalization
			Compound annotation
			Chemometrics
		Applications
	References
Sample handling in chromatography
	Introduction
	Why bother with sample handling?
	Sample collection procedures
	Sustainable green chemistry
	Sample preparation
		Solvent extraction
			Efficiency in liquid-liquid extraction
			Selection of extracting solvent
			Extraction modes
				Batch extraction
				Continuous extraction
				Countercurrent extraction
			Extraction of solid samples
		Supercritical fluid extraction
			Instrumentation
			Selecting a supercritical fluid and extraction conditions
		Microwave- and sonication-assisted solvent extraction
		Accelerated solvent extraction
		Membrane-assisted techniques
			Filtration
			Microfiltration
			Ultrafiltration (and nanofiltration)
			Reverse osmosis
			Dialysis
		Volatilization processes
			Sublimation
			Freeze drying
			Distillation
				Fractional distillation
				Steam distillation
				Assisted co-distillation
		Chromatography
			Columns
			Separation mechanisms
				Adsorption
					Column packings
					Mobile phase
				Ion Exchange
				Size Exclusion
		Solid-phase extraction
			Modes of operation
			Applications
		Microextraction techniques
	Pre-concentration techniques
	References
Preparative chromatography
	Introduction
		History
		Theoretical considerations
	Thin layer chromatography
		Plates for PTLC
		Sample application
		Mobile phases
		Layer development
		Visualization
		Applications
	Gas chromatography
		Instrumentation
		Applications
	Supercritical fluid chromatography
		Instrumentation
		Applications
	High-performance liquid chromatography
		Instrumentation
		Separations
		Applications
	References
Index
	A
	B
	C
	D
	E
	F
	G
	H
	I
	K
	L
	M
	N
	O
	P
	Q
	R
	S
	T
	U
	V
	W
	Z