Carbohydrates

Carbohydrates include both sugars and the polymers of sugars. The simplest carbohydrates are the monosaccharides, or single sugars, also known as simple sugars. Disaccharides are double sugars, consisting of two monosaccharides joined by a condensation reaction. The carbohydrates that are macromolecules arepolysaccharides, polymers composed of many sugar building blocks.

Sugars

Monosaccharides (from the Greek monos, single, and sacchar, sugar) generally have molecular formulas that are some multiple of the unit CH2O

The structure and classification of some monosaccharides. Sugars may be aldoses (aldehyde sugars, top row) or ketoses (ketonesugars, bottom row), depending on the location of the carbonyl group (dark orange). Sugars are also classified according to the length of their carbon skeletons. A third point of variation is the spatial arrangement around asymmetric carbons (compare, for example, the purple portions of glucose and galactose).

Glucose, the most common monosaccharide, is of central importance in the chemistry of life. In the structure of glucose, we can see the trademarks of a sugar: The molecule has a carbonyl group and multiple hydroxyl groups (–OH). Depending on the location of the carbonyl group, a sugar is either an aldose (aldehyde sugar) or a ketose (ketone sugar). Glucose, for example, is an aldose; fructose, a structural isomer of glucose, is a ketose. (Most names for sugars end in –ose.) Another criterion for classifying sugars is the size of the carbon skeleton, which ranges from three to seven carbons long. Glucose, fructose, and other sugars that have six carbons are called hexoses. Trioses (three–carbon sugars) and pentoses (five–carbon sugars) are also common.

Still another source of diversity for simple sugars is in the spatial arrangement of their parts around asymmetric carbons. Glucose and galactose, for example, differ only in the placement of parts around one asymmetric carbon. What seems like a small difference is significant enough to give the two sugars distinctive shapes and behaviours.

Although it is convenient to draw glucose with a linear carbon skeleton, this representation is not completely accurate. In aqueous solutions, glucose molecules, as well as most other sugars, form rings.

Monosaccharides, particularly glucose, are major nutrients for cells. In the process known as cellular respiration, cells extract the energy stored in glucose molecules. Not only are simple sugar molecules a major fuel for cellular work, but their carbon skeletons serve as raw material for the synthesis of other types of small organic molecules, such as amino acids and fatty acids. Sugar molecules that are not immediately used in these ways are generally incorporated as monomers into disaccharides or polysaccharides.

A disaccharide consists of two monosaccharides joined by a glycosidic linkage , a covalent bond formed between two monosaccharides by a dehydration reaction. For example, maltose is a disaccharide formed by the linking of two molecules of glucose.

 

Also known as malt sugar, maltose is an ingredient used in brewing beer. The most prevalent disaccharide is sucrose, which is table sugar. Its two monomers are glucose and fructose (Figure 5.5b). Plants generally transport carbohydrates from leaves to roots and other nonphotosynthetic organs in the form of sucrose. Lactose, the sugar present in milk, is another disaccharide, in this case a glucose molecule joined to a galactose molecule.

Polysaccharides

Polysaccharides are macromolecules, polymers with a few hundred to a few thousand monosaccharides joined by glycosidic linkages. Some polysaccharides serve as storage material, hydrolyzed as needed to provide sugar for cells. Other polysaccharides serve as building material for structures that protect the cell or the whole organism. The architecture and function of a polysaccharide are determined by its sugar monomers and by the positions of its glycosidic linkages.

Storage Polysaccharides

Starch , a storage polysaccharide of plants, is a polymer consisting entirely of glucose monomers. Most of these monomers are joined by 1–4 linkages (number 1 carbon to number 4 carbon), like the glucose units in maltose (see Figure 5.5a). The angle of these bonds makes the polymer helical. The simplest form of starch, amylose, is unbranched. Amylopectin, a more complex form of starch, is a branched polymer with 1–6 linkages at the branch points.

Plants store starch as granules within cellular structures called plastids, which include chloroplasts.

Synthesizing starch enables the plant to stockpile surplus glucose. Because glucose is a major cellular fuel, starch represents stored energy. The sugar can later be withdrawn from this carbohydrate “bank” by hydrolysis, which breaks the bonds between the glucose monomers. Most animals, including humans, also have enzymes that can hydrolyze plant starch, making glucose available as a nutrient for cells. Potato tubers and grains—the fruits of wheat, corn, rice, and other grasses—are the major sources of starch in the human diet.

Animals store a polysaccharide called glycogen , a polymer of glucose that is like amylopectin but more extensively branched (Figure 5.6b). Humans and other vertebrates store glycogen mainly in liver and muscle cells. Hydrolysis of glycogen in these cells releases glucose when the demand for sugar increases. This stored fuel cannot sustain an animal for long, however. In humans, for example, glycogen stores are depleted in about a day unless they are replenished by consumption of food.

Structural Polysaccharides

Organisms build strong materials from structural polysaccharides. For example, the polysaccharide called cellulose is a major component of the tough walls that enclose plant cells. On a global scale, plants produce almost 1011 (100 billion) tons of cellulose per year; it is the most abundant organic compound on Earth. Like starch, cellulose is a polymer of glucose, but the glycosidic linkages in these two polymers differ. The difference is based on the fact that there are actually two slightly different ring structures for glucose .

When glucose forms a ring, the hydroxyl group attached to the number 1 carbon is positioned either below or above the plane of the ring. These two ring forms for glucose are called alpha (α) and beta (β), respectively. In starch, all the glucose monomers are in the α configuration (Figure 5.7b), the arrangement we saw in Figures 5.4 and 5.5. In contrast, the glucose monomers of cellulose are all in the β configuration, making every other glucose monomer upside down with respect to its neighbours (Figure 5.7c).

The differing glycosidic links in starch and cellulose give the two molecules distinct three–dimensional shapes. Whereas a starch molecule is mostly helical, a cellulose molecule is straight (and never branched), and its hydroxyl groups are free to hydrogen–bond with the hydroxyls of other cellulose molecules lying parallel to it. In plant cell walls, parallel cellulose molecules held together in this way are grouped into units called microfibrils

These cable–like microfibrils are a strong building material for plants as well as for humans, who use wood, which is rich in cellulose, for lumber.

Enzymes that digest starch by hydrolyzing its α linkages are unable to hydrolyze the β linkages of cellulose because of the distinctly different shapes of these two molecules. In fact, few organisms possess enzymes that can digest cellulose. Humans do not; the cellulose in our food passes through the digestive tract and is eliminated with the feces. Along the way, the cellulose abrades the wall of the digestive tract and stimulates the lining to secrete mucus, which aids in the smooth passage of food through the tract. Thus, although cellulose is not a nutrient for humans, it is an important part of a healthful diet. Most fresh fruits, vegetables, and whole grains are rich in cellulose. On food packages, “insoluble fiber” refers mainly to cellulose.

Some microbes can digest cellulose, breaking it down to glucose monomers. A cow harbors cellulose–digesting bacteria in the rumen, the first compartment in its stomach.

The bacteria hydrolyze the cellulose of hay and grass and convert the glucose to other nutrients that nourish the cow. Similarly, a termite, which is unable to digest cellulose by itself, has microbes living in its gut that can make a meal of wood. Some fungi can also digest cellulose, thereby helping recycle chemical elements within Earth’s ecosystems.

Another important structural polysaccharide is chitin , the carbohydrate used by arthropods (insects, spiders, crustaceans, and related animals) to build their exoskeletons.

An exoskeleton is a hard case that surrounds the soft parts of an animal. Pure chitin is leathery, but it becomes hardened when encrusted with calcium carbonate, a salt. Chitin is also found in many fungi, which use this polysaccharide rather than cellulose as the building material for their cell walls. Chitin is similar to cellulose, except that the glucose monomer of chitin has a nitrogen–containing appendage.