Phytochemistry

WEEK 2
 II
Factors Related to Secondary
Metabolic of Plant
 Understanding the phytochemical
diversity of plants
Chemical diversity impact to the biology variations in plants:
• Phytochemical richness - is the most straightforward component of chemodiversity. The number
of compounds a plant species produces should be largely dependent on the number of enzymes
that make up the corresponding biosynthetic pathways.
• Variation in it has been documented on all levels of biological organization, including between
tissues, individuals, populations, species, orders, and communities.
• Phytochemical disparity - dissimilarities between chemical compounds may be calculated in a
number of different ways, based on e.g. their molecular substructures, physicochemical
properties, molecular fingerprints or what biosynthetic pathways or enzymes produce them.
 The role of chemotaxonomy in
phytochemistry
• Merriam-Webster defines chemotaxonomy as the method of biological classification based on similarities
and dissimilarities in the structure of certain compounds among the organisms being classified.
• The phenolics, alkaloids, terpenoids, and non-protein amino acids, are the four important and widely
exploited groups of compounds utilized for chemotaxonomic classification. These groups of compounds
exhibit a wide variation in chemical diversity, distribution, and function
• Three broad categories of compounds are used in chemotaxonomy:
1. Primary metabolites - utilized by the plant itself for growth and development
2. Secondary metabolites - used for protection and defense against predators and pathogens
3. Glycosides - the compounds in which one or more sugars are combined with non-sugar molecules
through glycosidic linkage. Based on the linkage. The glycosides are grouped as O-glycoside, C-
glycoside, N-glycoside and S-glycoside
 Synergy and other interactions in
phytomedicines
• Synergistic interactions are of vital importance in phytomedicines, to explain
difficulties in always isolating a single active ingredient, and explain the efficacy of
apparently low doses of active constituents in a herbal product.
• Synergistic interactions could be enhanced bioavailability, cumulative effects or
simply the additive properties of the constituents require further research.
• In general, synergistic effects are considered to be positive, with the low doses used
perceived as a benefit, although it is obvious that there may also be negative aspects .
• Usually, a report of herbal medicines ADR is still limited since its clinical
manifestations do not seem to be common like synthetic medicines
 Synergy and other interactions in
phytomedicines
• Positive synergistic interactions, for example, an ancient recipe named Ayurveda which uses many fixed
combination formulae with “Trikatu”. This mixture contains black pepper, Piper longum, and ginger,
Zingiber officinalis.
Black pepper: contains the alkaloid
piperine, which is known to increase
the bioavailability of a number of
drugs such as vasicine (also known
as peganine), an antiasthmatic
alkaloid from Adhatoda vesica

Black pepper

Piper longum Zingiber officinalis

 Synergy and other interactions in
phytomedicines
• Negative interactions, for example, the presence of tannins in a herbal drug, which may hinder the
absorption of proteins and alkaloids, or the induction of enzymes such as cytochrome P450 which may
accelerate drug metabolism resulting in blood levels of actives too low for a therapeutic effect.
• Hypericum perforatum extract, where interactions with oral contraceptives have been reported.
• Synthetic drugs which well known for their potential to interact and patients taking them are warned not to
combine their medication with any other unless under medical supervision.
• Herbal products with reputed synergistic activity should not be used if they are potent herbs used in
conditions where the dose is crucial. Foxglove, digitalis, is not a suitable herbal remedy for congestive heart
failure and heart insufficiency grade I and II as the therapeutic index is so low.
Prospect market for herbal medicines
Prospect market for herbal medicines
Commercial herbal medicines in Indonesia
Back to the nature trend!
 Extraction: maceration
Maceration is an ancient technique in which the whole or selected parts of a vegetable sample (or other natural
extracts) are kept in contact with a specific solvent, for a certain period of time, which can range from some hours to
days, at room or higher temperatures. Usually to extract secondary metabolites such as flavonoids.
 Extraction: percolation
Percolation (from Latin percolare 'to filter, trickle through') refers to the movement and filtering of fluids
through porous materials. For example coffee percolation to obtain caffeine (alkaloid), where the solvent is water,
the permeable substance is the coffee grounds, and the soluble constituents are the chemical compounds that give
coffee its color, taste, and aroma.
 Extraction: shoxlet
The soxhlet extraction method uses a small amount of solvent and is very cost-effective. The Soxhlet extraction
uses the solvent reflux and siphon principle to continuously extract the solid matter by pure solvent, which saves
the solvent extraction efficiency and high efficiency. This technique is useful to determine the lipid and fat
contents of animal and plant tissue.
 Extraction: supercritical fluid extraction
Supercritical fluid extraction (SFE) is the process of separating one component (the extractant) from another (the
matrix) using supercritical fluids as the extracting solvent such as CO 2.
 Polarity, solubility, and concentration
factor
Polarity - the bond or the molecular polarities depend upon the electronegativities of the atoms or the molecules.
A molecule is basically said to be either a polar molecule, non-polar molecule, or ionic molecule.
• Polar molecules - a polar molecule is usually formed when the one end of the molecule is said to possess
more positive charges whereas the opposite end of the molecule has negative charges. Example: H 2O and
CH3OH, etc.
• Non-polar molecules - a molecule that does not have the charges present at the end due to the reason that
electrons are finely distributed and those which symmetrically cancel out each other are the non-polar
molecules. Example: C2H5OH, C6H14, etc.

POLAR MOLECULES NON-POLAR MOLECULES

 Polarity, solubility, and concentration
factor
Solubility - the maximum ability for one substance to dissolve (solute) into another substance (solvent). In
familiar cases, a solute is a solid (e.g., sugar, salt) and a solvent is a liquid (e.g., water, chloroform), but the
solute or solvent might be a gas, liquid, or solid. The solvent can either be a pure substance or a mixture.

Solubility – also defined as the grams of solute in 1L solutions (g/L)

So, what most influences the solubility of a substance in a solvent?

Solubility depends on the nature of the solute and solvent, temperature, and pressure (for gasses), solute particle
size, and polarity.
 Polarity, solubility, and concentration
factor
What is the difference between miscibility and solubility?

If a substance is soluble at all proportions in a specific solvent, it is called miscible it or possesses the property
called miscibility. For example, ethanol and water are completely miscible with each other. On the other hand,
oil and water do not mix or dissolve in each other. Oil and water are considered to be immiscible.

Concentration factor - the amount by which an element must be increased above its normal abundance in order
to make it extractable.