Capillary electrophoresis of carbohydrates: from monosaccharides to complex polysaccharides (Volpi N. Editor)

Capillary electrophoresis (CE) encompasses a range of related separation techniques that use narrow-bore fused-silica capillaries to separate a complex array of large and small molecules. Due to its high resolving power and sensitivity, CE has been applied in the analysis of simple and complex carbohydrates, such as intact oligosaccharides and glycosaminoglycans-derived oligosaccharides and disaccharides providing concentration and structural characterization data essential for understanding their biological functions. Simple carbohydrates and complex oligosaccharides and polysaccharides are a class of ubiquitous (macro)molecules exhibiting a wide range of biological functions. The recent advent of enhanced enzymatic, chemical and analytical tools for the study of these sugars has triggered a genuine explosion in the field of glycomics. In particular, the study of complex oligosaccharides and heteropolysac¬charides has led to deeper insight into how specific sugar structures modulate cellular phenotypes. An increased understanding of the structure-function relationship has led to the discovery of new pharmaceuticals for the treat¬ment of serious diseases, such as cancer. This area of research is rapidly expanding and is expected to have a major impact on future therapeutic regimens.This Volume on the capillary electrophoresis of carbohydrates provides the reader with the latest break-throughs and improvements in CE and CE techniques applied to monosaccharides up to complex oligo- and polysaccharides. Chapter 1 presents an overview on the application of CE and CE- mass spectrometric (MS) in the analysis of simple carbohydrates without any previous derivatization step. Various detection techniques such as spectrophotometric detection, electrochemical detection, MS but also less common techniques are discussed. Finally, a wide-ranging list of CE and CE-MS applications in the field of carbohydrate analysis published during the last decade is reported. Chapter 2 covers all the currently used derivatization procedures, by means of chromophore or fluorophore incorporation, their mechanistic details and the merits attributed to each approach with the aim of enhancing sensitivity and also of improving analyte separation. Chapter 3 focuses on CE, CE-MS and tandem MS, on the separation and characterization of lipopolysaccharides along with some acidic polysaccharides and derived oligosaccharides and disaccharides, which are important (macro)molecules belonging to bacteria. Chapter 4 gives an outline of microchip-based CE analysis of complex natural heteropolysaccharides, known as glycosaminoglycans, which affords rapid analysis on a time scale of seconds. This technology has great potential as a tool for routine assessment of pharmaceutical preparations and for clinical diagnosis. Chapter 5 discusses the use of CE as an analytical approach for the detection of biofilm positivity in particular microorganisms, as well as for the separation of biofilm-positive and -negative strains, considering that the biofilm-positive surfaces are usually covered with specific extracellular polysaccharide substances that play a key role in biofilm formation and function. Chapter 6 illustrates the capacity of CE in the structural characterization of polysaccharide mono- and oligomer constituents, surveying several applications on chemically and enzymatically degraded polysaccharides. Furthermore, CE was also demonstrated to be highly reliable for the determination of polysaccharides in biological samples, due to the possibility of analyzing rather complex matrices even without any pre-treatment, a distinctive feature with respect to other separation strategies. In relation to this versatility, Chapter 7 features a survey on the more recent applications and d