polysaccharide

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

Polysaccharides are long carbohydrate molecules of repeated monomer units joined together by glycosidic bonds. They range in structure from linear to highly branched. 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 or homoglycan, but when more than one type of monosaccharide is present they are called heteropolysaccharides or heteroglycans.^[3][4]

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.

Structure

Natural saccharides are generally built of simple carbohydrates called monosaccharides with general formula (CH₂O)_n where n is three or more. A typical monosaccharide has the structure H-(CHOH)_x(C=O)-(CHOH)_y-H, that is, an aldehyde or ketone with many hydroxyl groups added, usually one on each carbon atom that is not part of the aldehyde or ketone functional group. Examples of monosaccharides are glucose, fructose, and glyceraldehyde^[5]

Amylose is a linear polymer of glucose mainly linked with α(1→4) bonds. It can be made of several thousands of glucose units. It is one of the two components of starch, the other being amylopectin.

Polysaccharides are composed of long chains of monosaccharide units bound together by glycosidic bonds. Polysaccharides contain more than ten monosaccharide units. Definitions of how large a carbohydrate must be to fall into the categories polysaccharides or oligosaccharides vary according to personal opinion.

Polysaccharides is an important class of biological polymers. Their function in living organisms is usually either structure- or storage-related. Starch (a polymer of glucose) is used as a storage polysaccharide in plants, being found in the form of both amylose and the branched amylopectin. In animals, the structurally similar glucose polymer is the more densely branched glycogen, sometimes called 'animal starch'. Glycogen's properties allow it to be metabolized more quickly, which suits the active lives of moving animals.

Cellulose and chitin are examples of structural polysaccharides. Cellulose is used in the cell walls of plants and other organisms, and is claimed to be the most abundant organic molecule on earth.^[6] It has many uses such as a significant role in the paper and textile industries, and is used as a feedstock for the production of rayon (via the viscose process), cellulose acetate, celluloid, and nitrocellulose. Chitin has a similar structure, but has nitrogen-containing side branches, increasing its strength. It is found in arthropod exoskeletons and in the cell walls of some fungi. It also has multiple uses, including surgical threads.

Polysaccharides also include callose or laminarin, chrysolaminarin, xylan, arabinoxylan, mannan, fucoidan and galactomannan.

Function

Nutrition

Polysaccharides are common sources of energy. Many organisms can easily break down starches into glucose, however, most organisms cannot metabolize cellulose or other polysaccharides like chitin and arabinoxylans. These carbohydrates types can be metabolized by some bacteria and protists. Ruminants and termites, for example, use microorganisms to process cellulose.

Even though these complex carbohydrates are not very digestible, they may comprise important dietary elements for humans. Called dietary fiber, these carbohydrates enhance digestion among other benefits. The main action of dietary fiber is to change the nature of the contents of the gastrointestinal tract, and to change how other nutrients and chemicals are absorbed.^[7][8] Soluble fiber binds to bile acids in the small intestine, making them less likely to enter the body; this in turn lowers cholesterol levels in the blood.^[9] Soluble fiber also attenuates the absorption of sugar, reduces sugar response after eating, normalizes blood lipid levels and, once fermented in the colon, produces short-chain fatty acids as byproducts with wide-ranging physiological activities (discussion below). Although insoluble fiber is associated with reduced diabetes risk, the mechanism by which this occurs is unknown.^[10]

Not yet formally proposed as an essential macronutrient, dietary fiber is nevertheless regarded as important for the diet, with regulatory authorities in many developed countries recommending increases in fiber intake.^{[7][8][11][12]}

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 of 24–30 glucose units is one unit of Amylopectin). 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 formations of starches are the ways that plants store glucose.

Glycogen

Schematic 2-D cross-sectional view of glycogen. A core protein of glycogenin is surrounded by branches of glucose units. The entire globular granule may contain approximately 30,000 glucose units.^[13]

A view of the atomic structure of a single branched strand of glucose units in a glycogen molecule.

Glycogen serves as the secondary long-term energy storage in animal and fungal cells, with the primary energy stores being held in adipose tissue. Glycogen is made primarily by the liver and the muscles, but can also be made by glycogenesis within the brain and stomach.^[14]

Glycogen is the analogue of starch, a glucose polymer in plants, and is sometimes referred to as animal starch, having a similar structure to amylopectin but more extensively branched and compact than starch. Glycogen is a polymer of α(1→4) glycosidic bonds linked, with α(1→6)-linked branches. Glycogen is found in the form of granules in the cytosol/cytoplasm in many cell types, and plays an important role in the glucose cycle. Glycogen forms an energy reserve that can be quickly mobilized to meet a sudden need for glucose, but one that is less compact than the energy reserves of triglycerides (lipids).

In the liver hepatocytes, glycogen can compose up to eight percent of the fresh weight (100–120 g in an adult) soon after a meal.^[15] Only the glycogen stored in the liver can be made accessible to other organs. In the muscles, glycogen is found in a low concentration (one to two percent of the muscle mass). However, the amount of glycogen stored in the body—especially within the muscles, liver, and red blood cells^[16][17][18]—mostly depends on physical training, basal metabolic rate, and eating habits such as intermittent fasting. Small amounts of glycogen are found in the kidneys, and even smaller amounts in certain glial cells in the brain and white blood cells. The uterus also stores glycogen during pregnancy to nourish the embryo.^[15]

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

• It is an energy reserve for animals.
• It is the chief form of carbohydrate stored in animal body.
• It is insoluble in water. It turns red when mixed with iodine.
• It also yields glucose on hydrolysis.

Structural polysaccharides

Arabinoxylans

Arabinoxylans are found in both the primary and secondary cell walls of plants and are the copolymers of two pentose sugars: arabinose and xylose.

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 such as termites can digest cellulose, because bacteria possessing the enzyme are present in their gut. Cellulose is insoluble in water. It does not change color when mixed with iodine. On hydrolysis, it yields glucose. It is the most abundant carbohydrate in nature.

Chitin

Chitin is one of many naturally occurring polymers. It forms a structural component of many animals, such as exoskeletons. 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.

Pectins

Pectins are a family of complex polysaccharides that contain 1,4-linked α-D-galactosyluronic acid residues. They are present in most primary cell walls and in the non-woody parts of terrestrial plants.

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 (e.g., peptidoglycan), and important virulence factors (e.g., Poly-N-acetylglucosamine in S. aureus), to permitting the bacterium to survive in harsh environments (e.g., Pseudomonas aeruginosa in the human lung).^[19] 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 (e.g., new antibiotics and vaccines) and the commercial exploitation to develop novel applications.^[20][21]

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.^[22] 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.^[23] 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.^[24]

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