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From Herbal Bioactives and Food Fortification Extraction and Formulation - D.

Suresh

Kumar, page 52

2.2 Biogenesis of secondary metabolites

Plants utilize very specific enzymes to synthesize a multitude of compounds. These enzymes

catalyze reactions in a well-defined sequence of steps. The biochemical sequence of the reactions

involved in the synthesis of one compound is called a metabolic pathway. A few enzymes may

be the components of a metabolic pathway, an example being the synthesis of starch from

adenosine diphosphate. The three enzymes that take part in this bioconversion are adenosine

diphosphate glucose pyrophosphorylase, starch synthase, and starch-branching enzyme (Martin

and Smith, 1995). On the other hand, several enzymes can be present in a metabolic pathway, as

exemplified by the synthesis of gibberellins from mevalonic acid (Yamaguchi, 2008). Enzymes

are also found to catalyze reactions underlying the degradation and storage of the compound in

question. The content of a given compound in a plant is regulated by the enzymes involved in the

various metabolic pathways pertaining to that compound.

Plants, microorganisms, and animals have many unique metabolic pathways. However, the

pathways common to these three forms of living organisms are the pentose phosphate pathway,

glycolysis, and Krebs cycle. Plants synthesize all of the secondary metabolites using sugars,

acetyl coenzyme A (CoA), and amino acids, which are the basic components of the primary

metabolism.
The biosynthetic pathway of monoterpene olefins and abietic acid explains how plants synthesize

complex molecules from simple precursors. The starting material in this case is acetyl CoA,

which is converted to geranyl pyrophosphate via mevalonic acid, isopentyl pyrophosphate, and

dimethylallyl pyrophosphate. The monoterpene olefins -pinene, -pinene, 3-carene,

-phellandrene, and limonene are synthesized from geranyl pyrophosphate, catalyzed by

monoterpene cyclases (Funk et al., 1994).

Alternatively, geranyl phosphate is transformed into farnesyl pyrophosphate and geranyl geranyl

pyrophosphate, which is enzymatically converted to abietadiene, abietadienol, abietadienal, and

abietic acid. These four enzymatic steps involve one cyclase, two hydroxylases, and a

dehydrogenase (Funk et al., 1994).

From Handbook of Herbs and Spices, Volume 3 - edited by K. V. Peter, page 195

Mevalonic acid is a chemical intermediate containing six carbons that is formed in the plant by

the combination of three molecules of acetate, which have, in turn, been derived from acetyl

coenzyme A. This is a universal process in all higher plants and produces compounds vital to the

life processes. The biosynthesis of mono- and sesquiterpenes from mevalonic acid involves three

steps: (i) conversion of mevalonic acid to isopentenyl pyrophosphate (IPP) and 3,3-dimethyl

allyl pyrophosphate (DMAPP), (ii) combination of IPP and DMAPP to give geranyl

pyrophosphate (GPP) and (iii) combination of GPP with IPP to give farnesyl pyrophosphate

(FPP). IPP is the initial product formed from mevalonic acid and it is then converted into

DMAPP by the enzyme isopentenyl pyrophosphate isomerase (Gershenzon and Croteau 1990,

Waterman 1993).
One molecule of IPP and one molecule of DMAPP combine under the influence of geranyl

pyrophosphate synthase to give geranyl phyrophosphate (GPP), the first recognizable

monoterpene. This process is then continued by the addition of another IPP to GPP through the

mediation of a further synthase enzyme, resulting in the production of the first 15-carbon unit,

farnesyl pyrophosphate (FPP).


From Handbook of Nutraceuticals and functional foods 2nd Ed (2007) - Robert E.C.

Wildman - CRC Taylor&Francis, page 28

A. ISOPRENOID DERIVATIVES (TERPENOIDS)

Isoprenoids and terpenoids are terms used to refer to the same class of molecules. These

substances are without question one of the largest groups of plant secondary metabolites. In

accordance with this ranking, they are also the basis of many plant-derived nutraceuticals. Under

this large umbrella are many popular nutraceutical families such as carotenoids, tocopherols,

tocotrienols, and saponins. This group is also referred to as isoprenoid derivatives because the

principal building block molecule is isoprene (Figure 1.2). Isoprene itself is synthesized from

acetyl coenzyme A (CoA), in the well- researched mevalonic acid pathway (Figure 1.3), and the

glycolysis-associated molecules pyruvate and 3-phosphoglycerate in a lesser-understood

metabolic pathway.
FIGURE 1.3. The mevalonic acid pathway.
In both pathways the end product is isopentenyl phosphate (IPP), and IPP is often regarded

as the pivotal molecule in the formation of larger isoprenoid structures. Once IPP is formed, it

can reversibly isomerize to dimethylallyl pyrophosphate (DMAPP) as presented in Figure 1.4.

Both of these five-carbon structures are then used to form geranyl pyrophosphate (GPP), which

can give rise to monoterpenes. Among the monoterpenes are limonene and perillyl alcohol.

FIGURE 1.4. Formation of terpene structures.

From Tropical and Subtropical Fruits Flavors, Color, and Health Benefits -

Guddadarangavvanahally K. Jayaprakasha, page 77

The biosynthesis of IPP occurs through two separate pathways in compartments of endoplasmic

reticulum (mevalonic acid, MVA) and plastids (2-C-methyl-D- erythritol 2,4-cyclodiphosphate,


MEP). In cytoplasmic IPP production, three molecules of acetyl-CoA are condensed to IPP with

a MVA intermediate. During this condensation, three ATPs and two NADPH molecules are

utilized for phosphorylation. However, in plastids, IPP is a produced only after a series of

reactions starting with pyruvate. In C.unshiu, the fruits expressed high levels of terpene synthase

in peels at the early stages of the fruit development. Spatio-temporal data mining studies of

volatile compounds suggest that these compounds are highly regulated at the stage of

transcription.

Furthermore, it was also observed that heat and light stress would increase and strongly induce

the biosynthesis of volatile terpenoids. Several terpene synthase genes are identified and

elucidated using a classical approach called reverse genetics.

The biosynthesis of volatiles is mainly dependent on the activity of the key enzymes as well as

the availability of their substrates. Identification and sequencing the genes responsible for the

production of these enzymes and the information related to their expression levels at various fruit

developmental stages are critical for engineering these genes for efficient production using

alternate hosts such as microbes. Several terpene synthases were found to have homologous

origin in various fruits and vegetables. Previous studies in lemon showed the sequenced genes

for different monoterpene synthases such as -terpinene synthase (ClTS), limonene synthases

(Cl(+)LIMS1 and Cl(+)LIMS2 ), and -pinene synthase (Cl(-)PINS) which catalyzed the

biosynthesis of terpinene, d-limonene and -pinene respectively.


From Industrial Biorenewables A Practical Viewpoint (2016) - Pablo Domnguez de Mara-

John Wiley & Sons, Inc., page 43

Terpenes can be chemically viewed as oligomers of five-carbon isoprene building blocks.

Terpenes biochemically originate from the common C5 building blocks isopentenyl

pyrophosphate (IPP) and its regioisomer dimethylallylpyrophosphate (DMAPP), which are

synthesized from the biogenetic precursor acetyl-CoA.

IPP/DMAPP is converted into geranyl pyrophosphate (GPP), which subsequently is

converted by monoterpene synthase enzymes into a variety of monoterpenes, such as

-pinene, -pinene -3-carene, limonene, and many others (Figure 2.2).