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Carbohydrates

Carbohydrates are one of the four main classes of macromolecules that make up all cells and are an essential part of our diet; grains, fruits, and vegetables are all natural sources. While we may be most familiar with the role carbohydrates play in nutrition, they also have a variety of other essential functions in humans, animals, plants, and bacteria. In this section, we will discuss and review basic concepts of carbohydrate structure and nomenclature, and a variety of functions they play in cells.

Molecular structures

In their simplest form, carbohydrates can be represented by the stoichiometric formula (CH₂O)_n, where _n is the number of carbons in the molecule. For simple carbohydrates, the ratio of carbon-to-hydrogen-to-oxygen in the molecule is 1:2:1. This formula also explains the origin of the term “carbohydrate”: the components are carbon (“carbo”) and the components of water (“hydrate”). Simple carbohydrates are classified into three subtypes: monosaccharides, disaccharides, and polysaccharides, which will be discussed below. While simple carbohydrates fall nicely into this 1:2:1 ratio, carbohydrates can also be structurally more complex. For example, many carbohydrates contain functional groups (remember them from our basic discussion about chemistry) besides the obvious hydroxyl. For example, carbohydrates can have phosphates or amino groups substituted at a variety of sites within the molecule. These functional groups can provide additional properties to the molecule and will alter its overall function. However, even with these types of substitutions, the basic overall structure of the carbohydrate is retained and easily identified.

Nomenclature

One issue with carbohydrate chemistry is the nomenclature. Here are a few quick and simple rules:

1. Simple carbohydrates, such as glucose, lactose, or dextrose, end with an "-ose."
2. Simple carbohydrates can be classified based on the number of carbon atoms in the molecule, as with triose (three carbons), pentose (five carbons), or hexose (six carbons).
3. Simple carbohydrates can be classified based on the functional group found in the molecule, i.e ketose (contains a ketone) or aldose (contains an aldehyde).
4. Polysaccharides are often organized by the number of sugar molecules in the chain, such as in a monosaccharide, disaccharide, or trisaccharide.

For a short video on carbohydrate classification, see the 10-minute Khan Academy video by clicking here.

Monosaccharides

Monosaccharides ("mono-" = one; "sacchar-" = sweet) are simple sugars; the most common is glucose. In monosaccharides, the number of carbons usually ranges from three to seven. If the sugar has an aldehyde group (the functional group with the structure R-CHO), it is known as an aldose; if it has a ketone group (the functional group with the structure RC(=O)R'), it is known as a ketose.

Figure 1. Monosaccharides are classified based on the position of their carbonyl group and the number of carbons in the backbone. Aldoses have a carbonyl group (indicated in green) at the end of the carbon chain and ketoses have a carbonyl group in the middle of the carbon chain. Trioses, pentoses, and hexoses have three, five, and six carbons in their backbones, respectively. Attribution: Marc T. Facciotti (own work).

Glucose versus galactose

Galactose (part of lactose, or milk sugar) and glucose (found in sucrose, glucose disaccharride) are other common monosaccharides. The chemical formula for glucose and galactose is C₆H₁₂O₆; both are hexoses, but the arrangements of the hydrogens and hydroxyl groups are different at position C₄. Because of this small difference, they differ structurally and chemically and are known as chemical isomers because of the different arrangement of functional groups around the asymmetric carbon; both of these monosaccharides have more than one asymmetric carbon (compare the structures in the figure below).

Fructose versus both glucose and galactose

A second comparison can be made when looking at glucose, galactose, and fructose (the second carbohydrate that with glucose makes up the disaccharide sucrose and is a common sugar found in fruit). All three are hexoses; however, there is a major structural difference between glucose and galactose versus fructose: the carbon that contains the carbonyl (C=O).

In glucose and galactose, the carbonyl group is on the C₁ carbon, forming an aldehyde group. In fructose, the carbonyl group is on the C₂ carbon, forming a ketone group. The former sugars are called aldoses based on the aldehyde group that is formed; the latter is designated as a ketose based on the ketone group. Again, this difference gives fructose different chemical and structural properties from those of the aldoses, glucose, and galactose, even though fructose, glucose, and galactose all have the same chemical composition: C₆H₁₂O₆.

Figure 2. Glucose, galactose, and fructose are all hexoses. They are structural isomers, meaning they have the same chemical formula (C₆H₁₂O₆) but a different arrangement of atoms.

Linear versus ring form of the monosaccharides

Monosaccharides can exist as a linear chain or as ring-shaped molecules. In aqueous solutions, monosaccharides are usually found in ring form (Figure 3). Glucose in a ring form can have two different arrangements of the hydroxyl group (OH) around the anomeric carbon (C₁ that becomes asymmetric in the process of ring formation). If the hydroxyl group is below C₁ in the sugar, it is said to be in the alpha (α) position, and if it is above C₁ in the sugar, it is said to be in the beta (β) position.

Figure 3. Five- and six-carbon monosaccharides exist in equilibrium between linear and ring form. When the ring forms, the side chain it closes on is locked into an α or β position. Fructose and ribose also form rings, although they form five-membered rings as opposed to the six-membered ring of glucose.

Disaccharides

Disaccharides ("di-" = two) form when two monosaccharides undergo a dehydration reaction (also known as a condensation reaction or dehydration synthesis). During this process, the hydroxyl group of one monosaccharide combines with the hydrogen of another monosaccharide, releasing a molecule of water and forming a covalent bond. A covalent bond formed between a carbohydrate molecule and another molecule (in this case, between two monosaccharides) is known as a glycosidic bond. Glycosidic bonds (also called glycosidic linkages) can be of the alpha or the beta type.

Figure 4. Sucrose is formed when a monomer of glucose and a monomer of fructose are joined in a dehydration reaction to form a glycosidic bond. In the process, a water molecule is lost. By convention, the carbon atoms in a monosaccharide are numbered from the terminal carbon closest to the carbonyl group. In sucrose, a glycosidic linkage is formed between the C₁ carbon in glucose and the C₂ carbon in fructose.

Common disaccharides include lactose, maltose, and sucrose (Figure 5). Lactose is a disaccharide consisting of the monomers glucose and galactose. It is found naturally in milk. Maltose, or malt/grain sugar, is a disaccharide formed by a dehydration reaction between two glucose molecules. The most common disaccharide is sucrose, or table sugar, which is composed of the monomers glucose and fructose.

Figure 5. Common disaccharides include maltose (grain sugar), lactose (milk sugar), and sucrose (table sugar).

 

Sucrose	Lactose	Maltose

Polysaccharides

A long chain of monosaccharides linked by glycosidic bonds is known as a polysaccharide ("poly-" = many). The chain may be branched or unbranched, and it may contain different types of monosaccharides. The molecular weight may be 100,000 Daltons or more, depending on the number of monomers joined. Starch, glycogen, cellulose, and chitin are primary examples of polysaccharides.

Starch is the stored form of sugars in plants and is made up of a mixture of amylose and amylopectin; both are polymers of glucose. Plants are able to synthesize glucose. Excess glucose, the amount synthesized that is beyond the plant’s immediate energy needs, is stored as starch in different plant parts, including roots and seeds. The starch in the seeds provides food for the embryo as it germinates and can also act as a source of food for humans and animals who may eat the seed. Starch that is consumed by humans is broken down by enzymes, such as salivary amylases, into smaller molecules, such as maltose and glucose.

Starch is made up of glucose monomers that are joined by 1-4 or 1-6 glycosidic bonds; the numbers 1-4 and 1-6 refer to the carbon number of the two residues that have joined to form the bond. As illustrated in Figure 6, amylose is starch formed by unbranched chains of glucose monomers (only 1-4 linkages), whereas amylopectin is a branched polysaccharide (1-6 linkages at the branch points).

Figure 6. Amylose and amylopectin are two different forms of starch. Amylose is composed of unbranched chains of glucose monomers connected by 1-4 glycosidic linkages. Amylopectin is composed of branched chains of glucose monomers connected by 1-4 and 1-6 glycosidic linkages. Because of the way the subunits are joined, the glucose chains have a helical structure. Glycogen (not shown) is similar in structure to amylopectin but more highly branched.

Glycogen

Glycogen is a common stored form of glucose in humans and other vertebrates. Glycogen is the animal equivalent of starch and is a highly branched molecule usually stored in liver and muscle cells. Whenever blood glucose levels decrease, glycogen is broken down to release glucose in a process known as glycogenolysis.

Glycogen

Cellulose

Cellulose is the most abundant natural biopolymer. The cell wall of plants is mostly made of cellulose, which provides structural support to the cell. Wood and paper are mostly cellulosic in nature. Cellulose is made up of glucose monomers that are linked by β 1-4 glycosidic bonds.

Figure 7. In cellulose, glucose monomers are linked in unbranched chains by β 1-4 glycosidic linkages. Because of the way the glucose subunits are joined, every glucose monomer is flipped relative to the next one, resulting in a linear, fibrous structure.

Note: possible discussion

Cellulose is not very soluble in water in its crystalline state; this can be approximated by the stacked cellulose fiber depiction above. Can you suggest a reason for why (based on the types of interactions) it might be so insoluble?

As shown in the figure above, every other glucose monomer in cellulose is flipped over, and the monomers are packed tightly as extended, long chains. This gives cellulose its rigidity and high tensile strength—which is so important to plant cells. While the β 1-4 linkage cannot be broken down by human digestive enzymes, herbivores such as cows, koalas, buffalos, and horses are able, with the help of the specialized flora in their stomach, to digest plant material that is rich in cellulose and use it as a food source. In these animals, certain species of bacteria and protists reside in the rumen (part of the digestive system of herbivores) and secrete the enzyme cellulase. The appendix of grazing animals also contains bacteria that digest cellulose, giving it an important role in the digestive systems of ruminants. Cellulases can break down cellulose into glucose monomers that can be used as an energy source by the animal. Termites are also able to break down cellulose because of the presence of other organisms in their bodies that secrete cellulases.

Interactions with carbohydrates

We have just discussed the various types and structures of carbohydrates found in biology. The next thing to address is how these compounds interact with other compounds. The answer to that is that it depends on the final structure of the carbohydrate. Because carbohydrates have many hydroxyl groups associated with the molecule, they are therefore excellent H-bond donors and acceptors. Monosaccharides can quickly and easily form H-bonds with water and are readily soluble. All of those H-bonds also make them quite "sticky". This is also true for many disaccharides and many short-chain polymers. Longer polymers may not be readily soluble.

Finally, the ability to form a variety of H-bonds allows polymers of carbohydrates or polysaccharides to form strong intramolecular and intermolocular bonds. In a polymer, because there are so many H-bonds, this can provide a lot of strength to the molecule or molecular complex, especially if the polymers interact. Just think of cellulose, a polymer of glucose, if you have any doubts.

 

The Role of Acid/Base Chemistry in General Biology

We have learned that the behavior of chemical functional groups depends on the composition, order, and properties of their constituent atoms. We will see that pH, a measure of the hydrogen ion concentration of the solution, can alter chemical properties of some key biological functional groups in ways that change how they interact with other molecules and thus their biological role.

For example, some functional groups on the amino acid molecules that make up proteins can exist in different chemical states depending on the pH. We will learn that the chemical state of these functional groups in the context of a protein can have a profound effect on the shape of the protein or on its ability to carry out chemical reactions. As we move through the course we will see many examples of this type of chemistry in different contexts. 

While some paradoxes to this rule can be found in the chemistry of concentrated solutions, in General Biology it is convenient to formally define pH as:

\[ pH = -\log_{10} [H^+]\]

In the equation above, the square brackets surrounding [H⁺] indicate concentration. If necessary, try a math review at wiki-logarithm or kahn-logarithm. Also see: definition-concentration or wiki-concentration.

Hydrogen ions are spontaneously generated in pure water by the dissociation (ionization) of a small percentage of water molecules into equal numbers of hydrogen (H⁺) ions and hydroxide (OH^-) ions. The OH^- that result from the ionization of water departs into the sea of water molecules interacting with other molecules through polar interactions, while the now "free" (unbonded) H⁺ ions produced by the ionization associates with water molecules (line two of the figure below) to create a new molecule called a hydronium ion, H₃O⁺.  At some point the hydroxide ion from line 1 in the figure below will rejoin with a proton and reform another water molecule.  

While most H⁺ ions in solution really exist as H₃O⁺ ions, we usually represent the H₃O⁺ in figures or equations more simply as H⁺. Why?  Because it is easier. Just keep in mind, when you see H⁺ referred to in the text, figures, or in equations, it usually represents H₃O⁺.

Figure 1: Water spontaneously dissociates into a proton and hydroxyl group. The proton will combine with a water molecule forming a hydronium ion.
Attribution: Marc T. Facciotti

The pH of a solution is a measure of the concentration of hydrogen ions in a solution (or the number of hydronium ions). The concentration of hydrogen ions determines how acidic or how basic a solution is.  

The pH scale is logarithmic and ranges from 0 to 14 (Figure 2). We define pH=7.0 as neutral. We call anything with a pH below 7.0 acidic and any reported pH above 7.0 alkaline or basic. Extremes in pH in either direction from 7.0 are often considered inhospitable to life, although examples exist to the contrary. pH levels in the human body usually range between 6.8 and 7.4, except in the stomach where the pH is more acidic, typically between 1 and 2. Some microbial species like Sulfolobus acidocaldarius thrive in hyper acidic environments with pH < 3 while others like Natronomonas pharaonis have been found living in lakes with pH > 11. These organisms are classified as "extremophiles" for their abilities to thrive in extreme environments. Proteins from these organisms are sometimes used in industrial processes where their ability to withstand environmental stress is a valued property.  

Figure 2: The pH scale ranging from acidic to basic with various biological compounds or substances that exist at that particular pH. Attribution: Marc T. Facciotti

 

For Additional Information

Watch this video for an expanded explanation of pH and its relationship to [H+] and the logarithmic scale.

 

Let's work out an example to see how the pH scale works.

For reference: 1 mole (mol) of a substance (which can be atoms, molecules, ions, etc.), is defined as being equal to 6.02 x 10²³ particles of the substance. Therefore, 1 mole of water is equal to 6.02 x 10²³ water molecules.

Mathematically this can be written as:
1 mol= 6.02x10²³ particles in a substance
1 mol H₂O= 6.02x10²³ water molecules

Example: The concentration of hydrogen ions dissociating from pure water is approximately 1 × 10^-7 moles H⁺ ions per liter of water. The pH is calculated as the negative of the base 10 logarithm of this unit of concentration. The log₁₀ of 1×10^-7 is -7.0, and the negative of this number yields a pH of 7.0, which is also known as neutral pH.

Mathematically this can be represented as:
 pH= -log₁₀[H⁺]
pH= -log₁₀[1×10^-7] 
pH= 7.0 (neutral pH)

The figure below provides another way to visualize the difference between acidic and basic solutions. While this figure is not a completely accurate representation of relative amounts of H⁺ and OH^- at all values of pH - H⁺ and OH^- concentrations don't really go to zero solution - it nevertheless captures the inverse relationship between proton and hydroxide ion concentrations by graphically illustrating how proton concentration decreases as pH increases while the hydroxide ion concentration simultaneously increases. 

 

 

   Figure 3:  A graphical representation of acidity and basicity.  This figure illustrates the relationship between H⁺ and OH^- concentrations on the pH scale.  At low pH values H⁺ ions are plentiful.  As the pH increases the relative abundance of OH^- ions increase while H⁺ abundance decreases.

                                                                                                            Attribution: Mary O. Aina

This inverse relationship between pH and the concentration of protons confuses many students - take the time to convince yourself that you "get it." One way could be to predict whether different pH values are acidic or basic and then do the calculations to make sure. Start by trying these practice questions.

Knowledge Check Quiz

 

 

 

Acids and Bases

Acids and bases are molecules that can influence the pH of a solution. In General Biology it is often convenient to use the Brønsted-Lowry definition of acids and bases.  Using this formalism we define:

Acids = molecules that can donate a proton to another molecule (including water to form a hydronium ion)
Bases = molecules that can accept a proton from another molecule 

When protons from acidic molecules dissociate from their "parent" they increase the H⁺ concentration and thereby lower the pH of the solution. By contrast, when a base absorbs a "free" proton from a solution onto the "parent" molecule, the decrease in proton concentration in solution results in a shift to higher pH values.

Generically we can represent acids and bases as follows:

 

Figure 4:  Generic Acids and Bases.  This figure shows the behavior of Brønsted-Lowry acids and bases. The acid (A in a light purple circle) starts in a protonated form bound to an H⁺ ion, drawn as a red H. The acid deprotonates, shedding its H⁺ into solution or to another molecule. Meanwhile the base (B in a light green circle) begins deprotonated and absorbs a proton (red H⁺⁾ from solution or other molecule.  
Attribution: Marc T. Facciotti

 

In the figure above, the molecule A^- - the deprotonated form of the acid AH - can also be referred to as the conjugate base of the acid AH. Likewise the molecule BH⁺ - the protonated form of the base B - can be referred to as the conjugate acid of the base B.  

We call acids that completely dissociate into A^- and H⁺ ions at equilibrium strong acids. These reactions are characterized by an equilibrium position that lies far to the right (favoring product formation) and their chemical equations are therefore often draw with a single arrow separating reactants and products. By contrast, acids that do NOT completely dissociate into A^- and H⁺ ions at equilibrium are weak acids. Depending on the pH it is common to find both protonated and deprotonated forms of the acid (or both the acid and it's conjugate base) in solution at the same time. The chemical equations representing these reactions are therefore usually depicted with double arrows, indicating that the protonation/deprotonation of A^-/AH, respectively, is reversible.  

Two important examples of weak acids/bases in biology are the carboxyl and amino functional groups. At physiological pH values (around pH = 7) the carboxyl group tends to behave as an acid by donating it's proton to solution or other molecules. Under the same conditions, the amino group tends to act as a base, absorbing protons from solution or other molecules. As we will soon see, these and other protonation/deprotonation reactions are critically play key roles in many biological processes.  

 

Figure 5: The carboxylic acid group acts as an acid by releasing a proton. This can increase the number of protons in solution and thus decrease the pH. The amino group acts as a base by accepting hydrogen ions, which can decrease the number of hydrogen ions in solutions, thus increasing the pH.
Attribution: Marc T. Facciotti (original work)

                                                                                                                                                                                                                                                                                                                                                                                            

   

Additional pH resources

Here are some additional links on pH and pKa to help learn the material. Note that there is an additional module devoted to pKa.

ChemLibreText Links

• Determining and calculating pH
• pH and pKa 
  • This has an expanded discussion about pH that is a bit more detailed than how we present the concept.

Khan Academy Links

• What is pH
• strong acids and bases
• weak acids
• weak acid-base equilibria
• pH and pKa

Simulations

• Acid-base simulation. -------
  • ----------embed this in document---------

Extra pH Links

• https://chemclass-ol.org/logarithms-and-ph
• https://web.mst.edu/~gbert/logs/pH.html
• http://www.biology.arizona.edu/biomath/tutorials/applications/pH.html
• Intro to acids, bases, pH