Essentials in Modern HPLC Separations

Front-Matter_2022_Essentials-in-Modern-HPLC-Separations
Essentials in Modern HPLC Separations
Preface_2022_Essentials-in-Modern-HPLC-Separations
Preface
Chapter-1---Introductory-information-rega_2022_Essentials-in-Modern-HPLC-Sep
1. Introductory information regarding HPLC
1.1 Preliminary discussion about HPLC
General comments
What is chromatography and what is HPLC?
Types of equilibria in HPLC
Role of polarity in HPLC
Applications of HPLC in chemical analysis
Nonanalytical applications of analytical HPLC
1.2 Main types of HPLC
Criteria for the classification of HPLC procedures
A classification of HPLC types based on the nature of stationary and mobile phase
Relation between the type of HPLC, equilibrium type, and molecular interactions
1.3 Flow of a typical HPLC analysis
General aspects
Selection of the type of HPLC for a particular application
Sample collection and sample preparation for HPLC
References
Chapter-2---Overview-of-HPLC-instrumentatio_2022_Essentials-in-Modern-HPLC-S
2. Overview of HPLC instrumentation and its use
2.1 Description of main components of HPLC instrumentation
General comments
Description of a typical HPLC instrument
Solvent supply system
Pumping systems
Tubing and connectors
Injectors and autosamplers
Column holders
Chromatographic columns
General comments regarding detectors
UV-Vis spectrometric detectors
Fluorescence and chemiluminescence detectors
Refractive index detectors
Electrochemical detectors
Mass spectrometric detectors
Evaporative light-scattering detectors
Other types of detectors
Selection of a detector in HPLC
Other devices that can be part of the HPLC system
More complex or special HPLC setups
Instrument control and data processing unit
Selection of the HPLC system and transition from HPLC to UPLC
References
Chapter-3---Parameters-for-the-characterizati_2022_Essentials-in-Modern-HPLC
3. Parameters for the characterization of HPLC separation
3.1 Parameters describing the chromatographic peak
General aspects
Flow rate of the mobile phase
Retention time
Run time
Retention volume
Migration rate
Equilibrium constant and phase ratio in HPLC separations
Retention factor
General equation of solute retention
Characteristics of an ideal peak shape in chromatography
Efficiency of a chromatographic column
Factors contributing to peak broadening and van Deemter equation
Application of van Deemter equation
Peak asymmetry
Statistical moments for the description of peak characteristics
Peak characterization using exponentially modified Gaussian shape
3.2 Parameters describing the separation
General aspects
Selectivity (separation factor)
Resolution
Peak capacity
3.3 Summary of chromatographic peak and separation characteristics
General comments
3.4 Parameters related to quantitation in HPLC
General comments
Quantitation parameters from the chromatographic peak
Sample volume and amount injected in the chromatographic column
Limit of detection in HPLC
Limit of quantitation
3.5 Parameters characterizing the gradient separation
General comments
Retention factor in gradient separations
Other parameters for the characterization of chromatograms in gradient separations
References
Chapter-4---Equilibrium-types-in-HP_2022_Essentials-in-Modern-HPLC-Separatio
4. Equilibrium types in HPLC
4.1 Partition equilibrium
General comments
Liquid–liquid partition
Dependence of retention factor on mobile phase composition in partition chromatography
Distribution coefficient
Peak shape in partition chromatography
Evaluation of retention factor from liquid–liquid distribution constants
4.2 Adsorption equilibrium
Liquid–solid equilibrium
Dependence of retention factor on mobile phase composition in adsorption equilibrium
Peak shape in adsorption chromatography
4.3 Equilibrium involving ions
General aspects
Retention equilibrium involving ions
Equilibrium of ions in the presence of a complexing reagent
4.4 Equilibrium in size exclusion processes
General aspects
Equilibrium between interstitial mobile phase and pore mobile phase
4.5 The influence of pH and of additives on retention equilibria
Preliminary information about pH
Dependence of compound structure on pH
The influence of pH on partition equilibrium
Dependence on pH of octanol/water distribution coefficient Dow
Influence on separation of additives not involved in the equilibrium
Chaotropic salts influence on equilibria
4.6 The influence of temperature on retention equilibrium
General aspects
Evaluation of thermodynamic parameters of a separation from van't Hoff plots
Nonlinear dependence of the retention factor on 1/T
Evaluation of enthalpy–entropy compensation from van't Hoff plots
High-temperature HPLC
4.7 Reactions occurring in HPLC column
General comments
Enantiomerization and diastereomerization
Tautomerism
References
Chapter-5---Intermolecular-interacti_2022_Essentials-in-Modern-HPLC-Separati
5. Intermolecular interactions
5.1 Forces between molecules
General comments
Charge to charge interactions
Energy of an ion in a continuous medium
Polar molecules
Ion to dipole interactions
Dipole to dipole interactions
Polarizability of molecules
Ion to molecule interactions
Dipole to molecule interactions
Nonpolar molecule to molecule interactions
Unified view of interactions in the absence of ions
Lennard–Jones potential
Hydrogen bond interactions
Charge transfer or donor–acceptor interactions
Stacking and inclusion in supermolecular systems
Other types of bonds
The effect of a solvent on molecular interactions
Solvophobic effects
Chaotropic and kosmotropic interactions
5.2 Forces between molecules and a charged surface
General comments
Charge to charged-surface interactions
Neutral molecule to charged-surface interactions
References
Chapter-6---Characterization-of-analytes-a_2022_Essentials-in-Modern-HPLC-Se
6. Characterization of analytes and matrices
6.1 Properties of solutes important for HPLC separation
Solutes classification based on their chemical structure
Classification based on the role of the analyte in everyday life
Comments on physico-chemical properties of analytes and matrices
Molecular weight
Acidic or basic character of analytes
van der Waals molecular volume and area
Molecular shape
Molar volume
Molecular polarity
Partial charge distribution
Isoelectric point
Octanol/water partition constant and its use for polarity estimation
Thermodynamic parameters related to solubility of nonelectrolyte compounds
Activity coefficient from enthalpy of mixing
Solubility in water from octanol/water partition constant
Correlation between van der Waals molecular surface and octanol/water partition constant
Solvatochromic parameters for solute characterization
Other parameters for solute characterization
6.2 Physico-chemical properties related to detection
General comments
Gas-phase acidity and basicity in MS process of ion formation
The role of analyte polarity in MS detection
6.3 Properties of matrix related to HPLC separation and detection
General comments
Matrix effects on the separation in HPLC
Matrix effects on HPLC detection
References
Chapter-7---Mobile-phases-and-their-pro_2022_Essentials-in-Modern-HPLC-Separ
7. Mobile phases and their properties
7.1 Characterization of liquids as eluents in HPLC
General comments
Characterization of solvents with Hildebrand solubility parameter
Miscibility of solvents and solubility one in another
Solvent characterization using octanol/water partition constant Kow
Solvent characterization based on liquid–gas partition
Solvatochromic model and Kamlet–Taft parameters
Eluotropic strength
Solvent characterization based on other parameters
Solvent properties of liquid mixtures
7.2 Additional physical properties of liquids affecting separation
General comments
Solvent density, viscosity, and diffusion coefficient
Surface tension
Dielectric constant, dipole moment, and polarizability
Hydrogen bonding of solvent molecules
Solvent boiling point
7.3 Properties of liquids affecting HPLC detection
General comments
Refractive index
UV cut-off
Fluorescence
Solvent influence in MS detection
Solvent properties related to other detection techniques
7.4 Buffers and additives
General comments
Buffer pH
Buffer capacity
Common buffers used in HPLC
Buffers in partially aqueous solvent mixtures
The influence of temperature on the pH of buffers
Solubility of buffers in partially organic mobile phases
Additives
Influence of buffers and additives on column stability and properties
Suitability of buffers and additives for the detection in HPLC
7.5 General use of solvents as mobile phase
General comments
Solvent purity in HPLC
Flow rate, temperature, and degassing of mobile phase
The use of “green” solvents as mobile phase in HPLC
7.6 Solvents for sample injection and for needle wash
General comments
The role of sample solvent in the chromatographic process
Effect of sample solvent on detection
Solvents for the needle wash
7.7 Gradient elution
General comments
Gradient of solvent composition
Gradient of pH or of additive concentration
Gradient in flow rate
Gradient in separation temperature
Usefulness of gradient vs. isocratic elution
References
Chapter-8---Analytical-HPLC-columns-and-thei_2022_Essentials-in-Modern-HPLC-
8. Analytical HPLC columns and their characteristics
8.1 Construction of an HPLC column
General comments
External body of the column
Packing of particles in the chromatographic column
Physical characteristics of the solid supports for the packed columns
Chemical characteristics of the solid supports for the packed columns
Silica and ethylene-bridged silica as solid support for the stationary phase
Silica-based monolithic chromatographic columns
Core-shell particles in packed columns
Hydride-based silica
Other inorganic support materials
Porous graphitic carbon and other carbon-based materials
Organic polymers used as support for stationary phases
Derivatization of silica solid support
Direct synthesis of silica materials with an active bonded phase surface
Derivatization of silica hydride supports
Derivatization of presynthesized organic polymers
Synthesis of organic polymers with active groups
Synthesis of organic polymeric monoliths with active functionalities
Coated or immobilized (grafted) polymeric stationary phases on silica
Metal-organic frameworks used as stationary phase for HPLC
8.2 Column properties affecting separation
General comments
Dimensions of the column body affecting separation
Physical properties of stationary phase affecting separation
Chemical characteristics of stationary phase affecting separation
Octanol/water distribution constant used to describe polarity of the active groups in the stationary phase
8.3 Selection of a column for an HPLC separation
General comments
The use of guard columns and cartridges
Column protection, cleaning, regeneration, and storing
Selection of columns for orthogonal separations
References
Chapter-9---Reversed-phase-HPLC_2022_Essentials-in-Modern-HPLC-Separations
9. Reversed-phase HPLC
9.1 Retention and elution process in RP-HPLC
General comments
Retention/elution in RP-HPLC
Equilibrium type in RP-HPLC separation
Molecular interactions in RP-HPLC
Retention results based on molecular interactions evaluation
Other interactions affecting RP-HPLC separations
9.2 Stationary phases and columns for RP-HPLC
General comments
Specific procedures for the synthesis of stationary phases in RP-HPLC
Basic physical properties of hydrophobic stationary phases and columns
Basic chemical characteristics of RP-type stationary phases
Advances in the construction of common RP-columns
Availability of special types of hydrophobic columns
9.3 Parameters used for the characterization of RP-HPLC phases and columns
General comments
Efficiency of columns (theoretical plate number)
Retention capability of columns used in RP-HPLC
Methylene selectivity and general selectivity for hydrophobic columns
Peak asymmetry for RP-HPLC columns
Hydrophobic subtraction model for selectivity characterization
Various other parameters and tests for RP-HPLC column characterization
Tests for the evaluation of aging of the chromatographic column
9.4 Selection of the column in RP-HPLC
General comments
Sample nature in RP-HPLC and its influence on column selection
Column choice from several possibilities
9.5 Mobile phases in reversed-phase liquid chromatography
General comments
Water and mobile phases with high water content
Alcohols used in mobile phase
Acetonitrile
Other solvents used in RP-HPLC
9.6 Selection of mobile phase in RP-HPLC
General comments
9.7 Prediction of parameters describing the separation in RP-HPLC
General comments
Estimation of retention factor k′ for similar systems at different mobile phase compositions
Evaluation of retention factor k′ from octanol/water partition constants Kow or Dow
Calculation of retention factor from van der Waals molecular surface of the analyte
Prediction of log k′ based on solute, mobile phase, and stationary phase characteristics
Evaluation of the energies of interaction in the separation system
Other approaches
References
Chapter-10---Other-HPLC-separations-performed-on_2022_Essentials-in-Modern-H
10. Other HPLC separations performed on hydrophobic stationary phases
10.1 Nonaqueous RP-HPLC
General comments
Mobile phase composition in NARP
Utility of NARP compared to RP-HPLC
10.2 Ion pair liquid chromatography
General comments
Ion-pairing mechanisms
Partition model in IP
Electrostatic model in IP
Stationary phases in ion pair chromatography
Mobile phase in ion pair chromatography
Chaotropes in ion pairing
10.3 Hydrophobic interaction chromatography (HIC)
General comments
Retention mechanism in HIC
10.4 Micellar, microemulsion, and other types of HPLC performed on hydrophobic phases
Micellar liquid chromatography
Microemulsion liquid chromatography
Other liquid chromatography types on hydrophobic phases
References
Chapter-11---Hydrophilic-interaction-liquid_2022_Essentials-in-Modern-HPLC-S
11. Hydrophilic interaction liquid chromatography
11.1 Retention and elution process in HILIC
General comments
Equilibrium type for retention/elution in HILIC
Description of molecular interactions in HILIC
Retention results based on molecular interactions in HILIC
11.2 Polar stationary phases and columns
General comments
Specific procedures for the synthesis of polar phases
Physical properties of polar stationary phases and columns
Chemical characteristics of polar stationary phases
Bare silica stationary phases
HILIC stationary phases with a bonded surface
Silica hydride–based phases
Advances in the construction of HILIC columns
11.3 Retention and separation properties of polar stationary phases
General comments
Parameters and tests for HILIC column characterization
11.4 Selection of the column in HILIC separations
General comments
Selection of the nature of stationary phase for the column
Selection of physical column characteristics in HILIC
Other parameters important in HILIC column selection
11.5 Mobile phase in HILIC
General comments
Double role of the mobile phase in HILIC
The gradient elution in HILIC separations
Ion-pairing additives for HILIC separations
Influence of mobile phase on detection in HILIC
11.6 Prediction of parameters describing the separation in HILIC
General comments
Estimation of retention factor k′ for similar systems at different mobile phase compositions
Other estimation procedures for HILIC parameters
References
Chapter-12---Other-HPLC-separations-performed-o_2022_Essentials-in-Modern-HP
12. Other HPLC separations performed on polar stationary phases
12.1 Normal phase liquid chromatography
General comments
NPC compared to HILIC
Mobile phase in NPC
12.2 Other chromatographic techniques based on polar interactions
Aqueous normal phase liquid chromatography
Electrostatic repulsion hydrophilic interaction chromatography
References
Chapter-13---Ion-exchange--ion-moderated--and-lig_2022_Essentials-in-Modern-
13. Ion exchange, ion-moderated, and ligand exchange liquid chromatography
13.1 Retention and elution in ion exchange liquid chromatography
General comments
Retention/elution in ion exchange chromatography
Separation in ion chromatography
Retention of neutral molecules on ion exchange phases
Retention in ion-moderated chromatography
Retention in ligand exchange and immobilized metal affinity chromatography
Ion exclusion
13.2 Stationary phases and columns for ion exchange and related HPLC techniques
Types of ion exchange phases
Ion-moderated and ligand exchange phases
Summary of procedures for the synthesis of ion exchange phases
Latex-agglomerated ion exchangers
Cation exchange phases based on silica
Organic polymeric cation exchange phases
Anion exchange phases based on silica
Organic polymeric anion exchange phases
Zwitterionic stationary phases
Capillary IC columns
Other IC stationary phases
13.3 Characterization of ion exchange stationary phases
General comments
Ionic loading capacity measurement
Solvent compatibility of ionic phases
Phase affinity for specific ions
Hydrophobicity of IC columns
13.4 Selection of an ion exchange stationary phase
General comments
Separation of small ions by IC
Separation of ionic organic molecules
Separation of neutral organic molecules
Separation of proteins and nucleic acids
13.5 Mobile phase in ion exchange and ion-moderated liquid chromatography
General comments
Mobile phase in cation exchange chromatography
Mobile phase in anion exchange chromatography
Gradient elution in ion chromatography
Chromatofocusing
Mobile phase in ion-moderated chromatography
References
Chapter-14---Chiral-HPLC-separation_2022_Essentials-in-Modern-HPLC-Separatio
14. Chiral HPLC separations
14.1 Separation process in chiral liquid chromatography
General comments
Chiral recognition
Other mechanisms for chiral separations
14.2 Stationary phases and columns for chiral separations
Types of chiral phases
Brush or “Pirkle” chiral phases
Cellulose chiral phases
Amylose chiral phases
Cyclodextrins and cyclofructans chiral phases
Crown ether chiral phases
Macrocyclic antibiotics and glycopeptides
Protein chiral phases
Ligand exchange chiral phases
Chiral synthetic polymers
14.3 Characterization of chiral stationary phases
General comments
Retention behavior of enantiomers on chiral stationary phases
14.4 Selection of a chiral stationary phase
General comments
The role of column selection in the development of a method for chiral separations
14.5 Mobile phase in chiral HPLC
Mobile phase for chiral phases
Mobile phase for chiral separations on achiral stationary phase
Ion pairing mechanism for enantioseparation
References
Chapter-15---Size-exclusion-HPLC_2022_Essentials-in-Modern-HPLC-Separations
15. Size exclusion HPLC
15.1 Separation process in size exclusion chromatography
General comments
15.2 Stationary phases and columns for size exclusion HPLC
General comments
Silica-based SEC stationary phases and glass phases
Polymer-based phases used in SEC
New developments
15.3 Characterization of size exclusion phases and columns
General comments
Porosity and particle size
Inertness and recovery
15.4 Selection of a stationary phase in size exclusion HPLC
Selection factors for SEC columns
15.5 Mobile phase for size exclusion separations
General comments
Typical solvents for gel filtration
Typical solvents for gel permeation
15.6 Interaction polymer chromatography
General comments
Gradient temperature in IPC
References
Chapter-16---Affinity--immunoaffinity--and-a_2022_Essentials-in-Modern-HPLC-
16. Affinity, immunoaffinity, and aptamer type HPLC
16.1 Separation process in immunoaffinity HPLC
General comments
16.2 Types of phases and their preparation in affinity and immunoaffinity chromatography
General comments
Supports for stationary phases in immunoaffinity chromatography
The active phase in immunoaffinity chromatography
Other types of affinity chromatography
16.3 Biomimetic liquid chromatography
General comments
Stationary phases used for biomimetic LC
Retention in immobilized artificial membrane LC
References
Chapter-17---Mixed-mode-HPLC_2022_Essentials-in-Modern-HPLC-Separations
17. Mixed-mode HPLC
17.1 Stationary phases with more than one type of active groups
General comments
Stationary phases with mixed mode including RP and HILIC capability
Stationary phases with mixed mode including ion exchange capability
17.2 Mobile phase in mixed-mode HPLC
General comments
References
Chapter-18---Utilization-of-HPLC-in-chemic_2022_Essentials-in-Modern-HPLC-Se
18. Utilization of HPLC in chemical analysis
18.1 Steps in development and implementation of an HPLC separation
General comments
Information for starting the development of an HPLC method
Selections to be made for an HPLC analysis
Comments on the implementation of a method from the literature
Improvement of a method from the literature
Development of a new HPLC method
Method optimization
Method validation
18.2 Application of HPLC for quantitative analysis
General comments
Calibration procedures
Selection of the internal standards in HPLC
References
Appendix-to-Chapter-6_2022_Essentials-in-Modern-HPLC-Separations
Appendix to Chapter 6
Appendix-to-chapter-7_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 7
Appendix-to-chapter-8_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 8
Appendix-to-chapter-9_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 9
Appendix-to-chapter-11_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 11
Appendix-to-chapter-13_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 13
Appendix-to-chapter-14_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 14
Appendix-to-chapter-15_2022_Essentials-in-Modern-HPLC-Separations
Appendix to chapter 15
Index_2022_Essentials-in-Modern-HPLC-Separations
Index
A
B
C
D
E
F
G
H
I
K
L
M
N
O
P
Q
R
S
T
U
V
W
X
Y
Z