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ANJALI.H.S
BCH.10.05.10
• energy from the sun.
• These molecules are the reduced coenzymes and the high-energy phosphate
compounds.
• Phosphate compounds are considered high energy if they exhibit large negative
free energies of hydrolysis (that is, if ∆ G°´ is more negative than -25 kJ/mol).
• The exact amount of chemical free energy available from the hydrolysis of such
compounds depends on concentration, pH, temperature, and so on
• But the ∆ G°´ values for hydrolysis of these substances are substantially more
negative than for most other metabolic species.
are transient forms of stored energy, meant to carry energy from point to point,
from one enzyme system to another, in the minute-to-minute existence of the cell
• 2. the term HEC should not be construed to imply that these molecules are
unstable and hydrolyze or decompose unpredictably.
Fritz Lipmann and high energy compounds
• Fritz Albert Lipmann (June 12, 1899 – July 24, 1986) was a
German-American biochemist and a co-discoverer in 1945 of
coenzyme A.
cAMP -52.2
1,3-Bisphosphoglycerate -49.6
ADP -35.7
ATP ,excess Mg 2+ -30.5
AMP -35.7
Pyrophosphate -33.6
• ATP is uniquely situated between the very high energy phosphates synthesized in the
breakdown of fuel molecules and the numerous lower-energy acceptor molecules that
are phosphorylated in the course of further metabolic reactions.
• ADP can accept both phosphates and energy from the higher-energy phosphates, and
the ATP thus formed can donate both phosphates and energy to the lower-energy
molecules of metabolism.
• Often called the "molecular unit of currency" of intracellular energy transfer. ATP
transports chemical energy within cells for metabolism.
• One molecule of ATP contains three phosphate groups, and it is produced by ATP
synthase from inorganic phosphate and adenosine diphosphate or adenosine
monophosphate
• The structure consists of a purine base -
Adenine attached to the 1' carbon atom of a
pentose sugar -Ribose.
• When there are many H+ ion one side of a cell membrane, they want to cross to the
less crowded side.
• In the process they travel through ATP synthase, and turn it as they go.
• This turns the enzyme proteins that are outside of the membrane. The energy
gained by rotation turns ADP and phosphate back into ATP.
• So, ATP synthase takes advantage of protons crossing the membrane to return ADP
into ATP fuel.
• ATP is unstable because it has 3 negatively charged phosphate groups linked
together sequentially.
• The negative charges are constantly pushing away from each other.
• Two biologically important acyl phosphates are acetyl phosphate and 1,3-
bisphosphoglycerate.
• Similar role in the Calvin cycle to ADP for form ATP and 3-phosphoglycerate. 1,3BPG in the
Calvin cycle does not produce ATP but instead uses it.
• 20% of 1,3-BPG is not metabolized in glycolytic pathway, instead….
• 2,3BPG is used as a mechanism to oversee the efficient release of oxygen from hemoglobin.
• Low oxygen levels trigger a rise in 1,3BPG levels which in turn raises the level of 2,3BPG
which alters the efficiency of oxygen dissociation from hemoglobin.
• Lactobacilli are another group of bacteria that produce butyrate but because they
also produce lactate they are said to exhibit heterolactate fermentation.
• Lactobacilli ferment glucose to fructose 1,6 bisphosphate
• fructose 1,6 bisphosphate aldolase.
• phosphoketolase.
ENOL PHOSPHATES
• The largest value of G° phosphoenolpyruvate or PEP
• PEP into pyruvate upon transfer of its phosphate to ADP by pyruvate kinase
• It has the high-energy phosphate bond found (-61.9 kJ/ mol )
• In gluconeogenesis
PEP is formed from the decarboxylation of oxaloacetate and hydrolysis of one GTP.
Is a rate-limiting step in gluconeogenesis
GTP + oxaloacetate → GDP + phosphoenolpyruvate + CO2 by PEPCK
• In plants
Used for the synthesis of chorismate through the shikimate pathway → Chorismate
may then be metabolized into the aromatic amino acids (phe, try and tyr)
In C₄ plants, PEP serves as an important substrate in carbon fixation.
PEP + CO2 → oxaloacetate by PEP carboxylase
PYROPHOSPHATE
• In chemistry, the anion, the salts, and the esters of pyrophosphoric acid are called
pyrophosphates
• PPi are essential for normal cellular functioning in virtually all living organisms
• aa is adenylated by ATP
• The exergonic hydrolysis of PPi ( ∆G= -19.2 kj/mol) drives the reaction.
ACETYL CoA
Structure of Acetyl CoA
The structure of Acetyl CoA consists of two parts.
1. Acetyl group
2. Coenzyme A
• Beta- mercaptoethylamine
• Pantothenic acid (not synthesized in man -- an essential nutrient)
• Phosphate
• 3', 5'-adenosine diphosphate
STRUCTURE
• is more exergonic than that of other esters because it is less stabilized by resonance
due to large atomic radius of S that reduces the electronic overlap b/w C and S
compared to C and O.
• In TCA ,cleavage of a thioester (succinyl CoA) releases sufficient free energy to synthesize
GTP from GDP and Pi.
Precursors of Acetyl CoA
Acetyl CoA is at the center of lipid metabolism. It is produced from:
• Fatty acids
• Glucose (through pyruvate)
• Amino acids
• Ketone bodies
Function of CoA
• CoA is a commonly used carrier for activated acyl groups (acetyl, fatty acyl and
others).
• The thioester bond which links the acyl group to CoA has a large negative standard
free energy of hydrolysis = -7.5 kcal/mole. This qualifies it as a high energy bond,
Products of Acetyl CoA Metabolism
• It can be converted to fatty acids, which in turn give rise to:
• triglycerides
• phospholipids
• eicosanoids (e.g., prostaglandins)
• ketone bodies
It is the precursor of cholesterol, which can be converted to:
• steroid hormones
• bile acids
• Overview of Acetyl CoA Metabolism
URIDINE DIPHOSPHOGLUCOSE
• A coenzyme C15H24N2O17P2 that reversibly catalyzes the formation of glucose-1-
phosphate from the corresponding phosphate of galactose and that acts as a donor of
glucose residues in the biosynthesis of glycogen
• UDP-glucose consists of the pyrophosphate group, the pentose sugar ribose, glucose,
and the nucleobase uracil.
• Uridine diphosphate glucose (uracil- diphosphate glucose, UDP-glucose) is a nucleotide sugar.
• Precursor of glycogen and can be converted into UDP-galactose and UDP-glucuronic acid,
which can then be used as substrates by the enzymes that make polysaccharides containing
galactose and glucuronic acid.
• methyl group (CH3) attached to the methionine sulfur atom in SAM is chemically
reactive.
• can be synthesized by formation of guanidinoacetate from Arg and Gly (in kidney)
by methylation (SAM) to creatine (in liver), and phosphorylation by CK(ATP) to
phosphocreatine (in muscle);
• Phosphocreatine is synthesized in the liver and transported to the muscle cells, via
the bloodstream, for storage.
• On the converse, excess ATP can be used during a period of low effort to convert
creatine to phosphocreatine.
• The cell's ability to generate phosphocreatine from excess ATP during rest, as well as
its use of phosphocreatine for quick regeneration of ATP