polysaccharide

3D structure of cellulose, a beta-glucan polysaccharide.

Polysaccharides are polymeric carbohydrate structures, formed of repeating units (either mono- or di-saccharides) joined together by glycosidic bonds. These structures are often linear, but may contain various degrees of branching. Polysaccharides are often quite heterogeneous, containing slight modifications of the repeating unit. Depending on the structure, these macromolecules can have distinct properties from their monosaccharide building blocks. They may be amorphous or even insoluble in water. ^[1][2]

When all the monosaccharides in a polysaccharide are the same type the polysaccharide is called a homopolysaccharide, but when more than one type of monosaccharide is present they are called heteropolysaccharides.

Examples include storage polysaccharides such as starch and glycogen, and structural polysaccharides such as cellulose and chitin.

Polysaccharides have a general formula of C_x(H₂O)_y where x is usually a large number between 200 and 2500. Considering that the repeating units in the polymer backbone are often six-carbon monosaccharides, the general formula can also be represented as (C₆H₁₀O₅)_n where 40≤n≤3000

Storage polysaccharides

Starches

Starches are glucose polymers in which glucopyranose units are bonded by alpha-linkages. It is made up of a mixture of Amylose (15–20%) and Amylopectin (80–85%). Amylose consists of a linear chain of several hundred glucose molecules and Amylopectin is a branched molecule made of several thousand glucose units (every chain 24–30 glucose unit). Starches are insoluble in water. They can be digested by hydrolysis, catalyzed by enzymes called amylases, which can break the alpha-linkages (glycosidic bonds). Humans and other animals have amylases, so they can digest starches. Potato, rice, wheat, and maize are major sources of starch in the human diet. The formation of starches are the way that plants store glucose.

Glycogen

Glycogen.

Glycogen is a polysaccharide that is found in animals and is composed of a branched chain of glucose residues. It is stored in liver and muscles.

Structural polysaccharides

Cellulose

The structural component of plants are formed primarily from cellulose. Wood is largely cellulose and lignin, while paper and cotton are nearly pure cellulose. Cellulose is a polymer made with repeated glucose units bonded together by beta-linkages. Humans and many other animals lack an enzyme to break the beta-linkages, so they do not digest cellulose. Certain animals can digest cellulose, because bacteria possessing the enzyme are present in their gut. The classic example is the termite.

Chitin

Chitin is one of many naturally occurring polymers. It is one of the most abundant natural materials in the world. Over time it is bio-degradable in the natural environment. Its breakdown may be catalyzed by enzymes called chitinases, secreted by microorganisms such as bacteria and fungi, and produced by some plants. Some of these microorganisms have receptors to simple sugars from the decomposition of chitin. If chitin is detected, they then produce enzymes to digest it by cleaving the glycosidic bonds in order to convert it to simple sugars and ammonia.

Chemically, chitin is closely related to chitosan (a more water-soluble derivative of chitin). It is also closely related to cellulose in that it is a long unbranched chain of glucose derivatives. Both materials contribute structure and strength, protecting the organism.

Acidic polysaccharides

Acidic polysaccharides are polysaccharides that contain carboxyl groups, phosphate groups and/or sulfuric ester groups.

Bacterial polysaccharides

Bacterial polysaccharides represent a diverse range of macromolecules that include peptidoglycan, lipopolysaccharides, capsules and exopolysaccharides; compounds whose functions range from structural cell-wall components (eg. peptidoglycan), and important virulence factors (eg Poly-N-acetylglucosamine in S. aureus), to permitting the bacterium to survive in harsh environments (eg Pseudomonas aeruginosa in the human lung).^[3] Polysaccharide biosynthesis is a tightly regulated, energy intensive process and understanding the subtle interplay between the regulation and energy conservation, polymer modification and synthesis, and the external ecological functions is a huge area of research. The potential benefits are enormous and should enable for example the development of novel antibacterial strategies (eg new antibiotics and vaccines) and the commercial exploitation to develop novel applications.^[4][5]

Bacterial capsular polysaccharides

Pathogenic bacteria commonly produce a thick, mucous-like, layer of polysaccharide. This "capsule" cloaks antigenic proteins on the bacterial surface that would otherwise provoke an immune response and thereby lead to the destruction of the bacteria. Capsular polysaccharides are water soluble, commonly acidic, and have molecular weights on the order of 100-1000 kDa. They are linear and consist of regularly repeating subunits of one to six monosaccharides. There is enormous structural diversity; nearly two hundred different polysaccharides are produced by E. coli alone. Mixtures of capsular polysaccharides, either conjugated or native are used as vaccines.

Bacteria and many other microbes, including fungi and algae, often secrete polysaccharides as an evolutionary adaptation to help them adhere to surfaces and to prevent them from drying out. Humans have developed some of these polysaccharides into useful products, including xanthan gum, dextran, welan gum, gellan gum, diutan gum and pullulan.

Most of these polysaccharides exhibit interesting and very useful visco-elastic properties when dissolved in water at very low levels.^[6] This gives many foods and various liquid consumer products, like lotions, cleaners and paints, for example, a viscous appearance when stationary, but fluidity when the slightest shear is applied, such as when wiped, poured or brushed. This property is referred to as pseudoplasticity, or shear thinning.

Aqueous solutions of the polysaccharide alone have a curious behavior when stirred. After stopping, the swirl continues due to momentum, then stops, and then reverses direction briefly. This recoil demonstrates the elastic effect of the polysaccharide chains previously streched in solution, returning to their relaxed state.

Cell-surface polysaccharides play diverse roles in bacterial ecology and physiology. They serve as a barrier between the cell wall and the environment, mediate host-pathogen interactions, and form structural components of biofilms. These polysaccharides are synthesized from nucleotide-activated precursors (called nucleotide sugars) and, in most cases, all the enzymes necessary for biosynthesis, assembly and transport of the completed polymer are encoded by genes organized in dedicated clusters within the genome of the organism. Lipopolysaccharide is one of the most important cell-surface polysaccharides, as it plays a key structural role in outer membrane integrity, as well as being an important mediator of host-pathogen interactions.

The enzymes that make the A-band (homopolymeric) and B-band (heteropolymeric) O-antigens have been identified and the metabolic pathways defined.^[7] The exopolysaccharide alginate is a linear copolymer of β-1,4-linked D-mannuronic acid and L-guluronic acid residues, and is responsible for the mucoid phenotype of late-stage cystic fibrosis disease. The pel and psl loci are two recently discovered gene clusters that also encode exopolysaccharides found to be important for biofilm formation. Rhamnolipid is a biosurfactant whose production is tightly regulated at the transcriptional level, but the precise role that it plays in disease is not well understood at present. Protein glycosylation, particularly of pilin and flagellin, is a recent focus of research by several groups and it has been shown to be important for adhesion and invasion during bacterial infection.^[8]

See also

• Polysaccharide encapsulated bacteria
• Glycans
• Exopolysaccharide
• Beta-glucans
• Oligosaccharide Nomenclature

References

External links

Wikimedia Commons has media related to: Polysaccharides

• Polysaccharide Structure
• Applications and commercial sources of polysaccharides
• European Polysaccharide Network of Excellence