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Overview of Metabolism Part -1

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19 views22 pages

Overview of Metabolism Part -1

Gh

Uploaded by

sahil1121verma
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Online_BSc(H)zoology_4thSem_Biochemistry

Overview of Metabolism Part -1

Dr. Shruti Sharma (Department of Zoology, ANDC)


Metabolism
 Metabolism is the sum of all the chemical transformations
taking place in a cell or organism, occurs through a series of
enzyme-catalyzed reactions that constitute metabolic
pathways.
 Each of the consecutive steps in a metabolic pathway brings
about a specific, small chemical change, usually the removal,
transfer, or addition of a particular atom or functional group.
 The precursor is converted into a product through a series of
metabolic intermediates called metabolites.
 The term intermediary metabolism is often applied to the
combined activities of all the metabolic pathways that
interconvert precursors, metabolites, and products of low
molecular weight.
Catabolism
 Catabolism is the degradative phase of metabolism in
which organic nutrient molecules (carbohydrates, fats, and
proteins) are converted into smaller, simpler end
products (such as lactic acid, CO2, NH3).

 Catabolic pathways release energy, some of which is


conserved in the formation of ATP and reduced electron
carriers (NADH, NADPH, and FADH2); the rest is lost as
heat.
Anabolism
 In anabolism, also called biosynthesis, small, simple
precursors are built up into larger and more complex
molecules, including lipids, polysaccharides, proteins, and
nucleic acids.

 Anabolic reactions require an input of energy, generally in


the form of the phosphoryl group transfer potential of
ATP and the reducing power of NADH, NADPH, and
FADH2.
Energy relationships between catabolic and anabolic
pathways
 Some metabolic pathways are linear, and some are
branched, yielding multiple useful end products from a
single precursor or converting several starting materials
into a single product.

 In general, catabolic pathways are convergent and anabolic


pathways are divergent.

 Some pathways are cyclic: one starting component of the


pathway is regenerated in a series of reactions that
converts another starting component into a product.
Types of nonlinear metabolic pathways
 Most cells have the enzymes to carry out both the
degradation and the synthesis of the important categories
of biomolecules.

 The simultaneous synthesis and degradation of any


biomolecule would be wasteful. Therefore, it is prevented
by reciprocally regulating the anabolic and catabolic
reaction sequences: when one sequence is active, the
other is suppressed.

 Metabolic pathways are regulated at several levels, from


within the cell and from outside. The most immediate
regulation is by the availability of substrate.
 Most cells have the capacity to carry out thousands of
specific, enzyme-catalyzed reactions and most of the
reactions in living cells fall into one of five general
categories:
 (1) oxidation-reductions
 (2) reactions that make or break carbon–carbon bonds
 (3) internal rearrangements, isomerizations, and eliminations
 (4) group transfers and
 (5) free radical reactions.
 Reactions within each general category usually proceed
by a limited set of mechanisms and often employ
characteristic cofactors.
Oxidation-reduction reactions
 Carbon atoms encountered in biochemistry can exist in
five oxidation states, depending on the elements with
which carbon shares electrons.

 In many biological oxidations, a compound loses two


electrons and two hydrogen ions these reactions are
commonly called dehydrogenations and the enzymes that
catalyze them are called dehydrogenases.

 E.g.
 In some, a carbon atom becomes covalently bonded to an
oxygen atom.
 The enzymes that catalyze these oxidations are generally
called oxidases or, if the oxygen atom is derived directly
from molecular oxygen (O2), oxygenases.
 Every oxidation must be accompanied by a reduction, in
which an electron acceptor acquires the electrons
removed by oxidation. Oxidation reactions generally
release energy.
 Most living cells obtain the energy needed for cellular
work by oxidizing metabolic fuels such as carbohydrates
or fat; photosynthetic organisms can also trap and use the
energy of sunlight.
Reactions that make or break carbon–carbon bonds
 Heterolytic cleavage of a C=C bond yields a carbanion
and a carbocation.
 The formation of a C-C bond involves the combination of a
nucleophilic carbanion and an electrophilic carbocation.

 Groups with electronegative atoms play key roles in these


reactions.

 Carbonyl groups are particularly important in the chemical


transformations of metabolic pathways.

 The carbon of a carbonyl group has a partial positive charge


due to the electron-withdrawing nature of the adjacent
bonded oxygen, and thus is an electrophilic carbon.
 The presence of a carbonyl group can also facilitate the
formation of a carbanion on an adjoining carbon, because
the carbonyl group can delocalize electrons through
resonance.

 The importance of a carbonyl group is evident in three


major classes of reactions in which C-C bonds are
formed or broken. These are:-
 Aldol condensations
 Claisen condensations and
 Decarboxylations
Carbon–carbon bond formation reactions

 (a)The carbon atom of a carbonyl group is an electrophile by virtue of the electronwithdrawing capacity of
the electronegative oxygen atom.
 (b) ) Within a molecule, delocalization of electrons into a carbonyl group facilitates the transient formation
of a carbanion on an adjacent carbon.
 (c) Some of the major reactions involved in the formation and breakage of C-C bonds in biological systems.
Internal rearrangements, isomerizations, and eliminations

 Another common type of cellular reaction is an intramolecular


rearrangement, in which redistribution of electrons results in
isomerization, transposition of double bonds, or cis-trans
rearrangements of double bonds.

 An example of isomerization is the formation of fructose 6-


phosphate from glucose 6-phosphate during sugar metabolism.

 A simple transposition of a C=C bond occurs during


metabolism of the common fatty acid oleic acid.

 Elimination of water introduces a C=C bond between two


carbons that previously were saturated (as in the enolase
reaction).
 Isomerization and elimination reactions.
Group transfer reactions
 The transfer of acyl, glycosyl, and phosphoryl groups from one
nucleophile to another is common in living cells.
 Acyl group transfer generally involves the addition of a nucleophile to
the carbonyl carbon of an acyl group to form a tetrahedral
intermediate.

 The chymotrypsin reaction is one example of acyl group transfer.


 Glycosyl group transfers involve nucleophilic substitution at C-1 of a
sugar ring, which is the central atom of an acetal.
 Phosphoryl group transfers play a special role in
metabolic pathways.
 Phosphorus can form five covalent bonds. In Pi , four
equivalent phosphorus–oxygen bonds share some
double-bond character, and the anion has a tetrahedral
structure.
 As oxygen is more electronegative than phosphorus, the
sharing of electrons is unequal: the central phosphorus
bears a partial positive charge and can therefore act as an
electrophile.
 In a very large number of metabolic reactions, a
phosphoryl group (-PO32-) is transferred from ATP to an
alcohol or to a carboxylic acid.
 When a nucleophile attacks the electrophilic phosphorus
atom in ATP, a relatively stable pentacovalent structure is
formed as a reaction intermediate.

 The large family of enzymes that catalyze phosphoryl


group transfers with ATP as donor are called kinases.
 Hexokinase, for example, “moves” a phosphoryl group
from ATP to glucose.
Free radical reactions
 The homolytic cleavage of covalent bonds to generate
free radicals has now been found in a range of
biochemical processes.

 Some examples are the reactions of methylmalonyl-CoA


mutase, ribonucleotide reductase and DNA photolyase.

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