Carbohydrates and lipids
The formation of polysaccharides and of phospholipids from their component building blocks not only requires the investment of the energy of nucleoside triphosphates but uses these molecules in a novel manner. The biosynthetic reactions described thus far have mainly been accompanied by the formation of energy-rich intermediates (e.g., PEP in <56>) with the formation of either AMP or ADP; however, nucleotides serve as intermediate carriers in the formation of glycogen, starch, and a variety of lipids. This unique process necessitates reactions by which ATP, or another nucleoside triphosphate, which can be readily derived from ATP via reactions of type <43a>, combines with a phosphorylated reactant to form a nucleoside-diphosphate product. Although the change in standard free energy is small in this reaction, the subsequent hydrolysis of the inorganic pyrophosphate also released (reaction <21a>) effectively makes the reaction irreversible in the direction of synthesis. The nucleoside triphosphate is represented as NTP in <77>, and the phosphorylated reactant as R―Ⓟ.
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Reactions of type <77> are catalyzed by pyrophosphorylases, reaction <21a> by inorganic pyrophosphatase.
Formation of storage polysaccharides
In the formation of storage polysaccharides—i.e., glycogen in animals, starch in plants—reaction <77> is preceded by the conversion of glucose 6-phosphate to glucose 1-phosphate, in a reaction catalyzed by phosphoglucomutase (reaction <78>). Glucose 1-phosphate functions as R―Ⓟ in reaction <77a>.
UTP is the specific NTP for glycogen synthesis in animals (<77a>); the products are UDP-glucose and pyrophosphate. In bacteria, fungi, and plants, ATP, CTP, or GTP serves instead of UTP. In all cases the nucleoside diphosphate glucose (NDP-glucose) thus synthesized can donate glucose to the terminal glucose of a polysaccharide chain, thereby increasing the number (n) of glucose molecules by one to n + 1 (reaction <79>). UDP is released in this process, which is catalyzed by glycogen synthetase. Starch synthesis in plants occurs by an analogous pathway catalyzed by amylose synthetase; ADP-glucose rather than UDP-glucose is the preferred glucose donor (<79a>). Similarly, cellulose, the major structural polysaccharide in plant cell walls, is synthesized in some plants by reaction <79a>; other plants undergo analogous reactions in which GDP-glucose or CDP-glucose acts as the glucose donor.
Nucleoside diphosphate sugars also participate in the synthesis of disaccharides; for example, common table sugar, sucrose (consisting of glucose and fructose), is formed in sugarcane by the reaction sequence shown in <80> and <81>; UDP-glucose and fructose 6-phosphate first form a phosphorylated derivative of sucrose, sucrose 6′-phosphate, which is hydrolyzed to sucrose and inorganic phosphate.
Lactose, which consists of galactose and glucose, is the principal sugar of milk. It is synthesized in the mammary gland as shown in <82>; UDP-galactose and glucose react to form lactose; UDP is also a product.
Formation of lipids
The neutral fats, or triglycerides, that constitute storage lipids, and the phospholipid components of lipoproteins and membranes, are synthesized from their building blocks by a route that branches after the first biosynthetic reaction. Initially, one molecule of glycerol 1-phosphate, the intermediate derived from carbohydrate catabolism, and two molecules of the appropriate fatty acyl coenzyme A (formed as described above; see Lipid components) combine, yielding phosphatidic acid (reaction <83>).
This reaction occurs preferentially with acyl coenzyme A derivatives of fatty acids containing 16 or 18 carbon atoms. In reaction <83>, R and R′ represent the hydrocarbon moieties (Ch3(CH2)n―) of two fatty acid molecules. A triglyceride molecule (neutral fat) is formed from phosphatidic acid in a reaction catalyzed by a phosphatase that results in loss of the phosphate group (reaction <84>); the diglyceride thus formed can then accept a third molecule of fatty acyl coenzyme A (represented as R″C∥OS―CoA in <84a>).
In the biosynthesis of phospholipids, however, phosphatidic acid is not hydrolyzed; rather, it acts as the R―Ⓟ in reaction <77>, the NTP here being cytidine triphosphate (CTP). A CDP-diglyceride is produced, and inorganic pyrophosphate is released (<77b>). CDP-diglyceride is the common precursor of a variety of phospholipids. In subsequent reactions, each catalyzed by a specific enzyme, CMP is displaced from CDP-diglyceride by one of three compounds—serine, inositol, or glycerol 1-phosphate—to form CMP and, respectively, phosphatidylserine, phosphatidylinositol (in <85b>), or 3-phosphatidyl-glycerol 1′-phosphate (PGP; in <85c>). These reactions differ from those of polysaccharide biosynthesis (<79>, <82>) in that phosphate is retained in the phospholipid, and the nucleotide product (CMP) is therefore a nucleoside monophosphate rather than the diphosphate. These compounds can react further: phosphatidylserine to give, sequentially, phosphatidylethanolamine and phosphatidylcholine; phosphatidylinositol to yield mono- and diphosphate derivatives that are components of brain tissue and of mitochondrial membranes; and PGP to yield the phosphatidylglycerol abundant in many bacterial membranes and the diphosphatidylglycerol that is also a major component of mitochondrial and bacterial membranes.
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Nucleic acids and proteins
As with the synthesis of polysaccharides and lipids, the formation of the nucleic acids and proteins from their building blocks requires the input of energy. Nucleic acids are formed from nucleoside triphosphates, with concomitant elimination of inorganic pyrophosphate, which is subsequently hydrolyzed via reaction <21a>. Amino acids also are activated, forming, at the expense of ATP, aminoacyl-complexes. This activation process is also accompanied by loss of inorganic pyrophosphate. But, although these biochemical processes are basically similar to those involved in the biosynthesis of other macromolecules, their occurrence is specifically subservient to the genetic information in DNA. DNA contains within its structure the blueprint both for its own exact duplication and for the synthesis of a number of types of RNA, among which is a class termed messenger RNA (mRNA). A complementary relationship exists between the sequence of purines (i.e., adenine and guanosine) and pyrimidines (cytosine and thymine) in the DNA comprising a gene and the sequence in mRNA into which this genetic information is transcribed. This information is then translated into the sequence of amino acids in a protein, a process that involves the functioning of a variety of other classes of ribonucleic acids (see heredity: Expression of the genetic code: transcription and translation).