BIOCHEMISTRY ASSIGMNENT HANAN AL SALLOUM SEMESTER 4 10090307

Redox potentials
Oxidation-Reduction is the transfer of electrons from electron donor to electron acceptor. The electron-donating molecule in a oxidation-reduction reaction is called the reducing agent or reductant and the electron-accepting molecule is the oxidizing agent or oxidant.. oxidation-reduction potential ( or redox potential), sE : is defined as a measure of the affinity of a substance for electrons. It decide the loss (or the gain) of electrons. A positive E: the substance has a higher affinity for electrons , accept electrons easily. A negative E: the substance has a lower affinity for electrons , donate electrons easily. Electrons always move from compounds with lower reduction potential to compounds with higher reduction potential ( more positive). Standard reduction potential, E , is a measure of the tendency of oxidant to gain electrons, to become reduced, a potential energy.So, the more negative the reduction potential is, the easier a reductant can reduce an oxidant and The more positive the reductive potential is, the easier an oxidant can oxidize a reductant .. When a substance has lower affinity for electrons than hydrogen , it has a negative redox potential . if the substance has a positive redox potential, it has a higher affinity for electrons than hydrogen .Thus NADH , a strong reducing agent , has a negative redox potential (-0.32V) , whereas a strong oxidant like oxygen has a positive redox potential (+0.82).

Biological oxidation
oxidation of metabolic fuels (carbohydrate, proteins and lipids), catalyzed by intracellular enzymes. The purpose of oxidation is to obtain energy in the form of ATP, which is known as the energy currency of the living cells. Electron Transport is electrons carried by reduced coenzymes (NADH or FADH2) are passed sequentially through a chain of proteins and coenzymes (so called electron transport chain) to O2 .

Oxidative Phosphorylation Coupling electron Transport (Oxidation) and ATP synthesis (Phosphorylation).The free energy available as a consequence of transferring 2 electrons from NADH or succinate to molecular oxygen is 57 and 36 kcal/mol, respectively. Oxidative phosphorylation traps this energy as the high-energy phosphate of ATP. In order for oxidative phosphorylation to proceed, two principal conditions must be met. First, the inner mitochondrial membrane must be physically intact so that protons can only reenter the mitochondrion by a process coupled to ATP synthesis. Second, a high concentration of protons must be developed on the outside of the inner membrane. The energy of the proton gradient is known as the chemiosmotic potential, or proton motive force (PMF). This potential is the sum of the concentration difference of protons across the membrane and the difference in electrical charge across the membrane. The 2 electrons from NADH generate a 6-proton gradient. Thus, oxidation of 1 mole of NADH leads to the availability of a PMF with a free energy of about 31.2 kcal (6 x 5.2 kcal). The energy of the gradient is used to drive ATP synthesis as the protons are transported back down their thermodynamic gradient into the mitochondrion. Electrons return to the mitochondrion through the integral membrane protein known as ATP synthase (or Complex V). ATP synthase is a multiple subunit complex that binds ADP and inorganic phosphate at its catalytic site inside the mitochondrion, and requires a proton gradient for activity in the forward direction. ATP synthase is composed of 3 fragments: F0, which is localized in the membrane; F1, which protrudes from the inside of the inner membrane into the matrix; and oligomycin sensitivity-conferring protein (OSCP), which connects F0 to F1.

Enzymes involved in redox reactions

There are many k/as Oxidoreductases which includes : oxidases, dehydrogenases, hydroperoxidaes and oxygenases. Oxidases use oxygen as an electron acceptor Dehydrogenases cant use as an electron acceptor Hydroperoxidases use H2O2 as a substrate Oxygenases catalyse the direct transfer of O2 into the substrate Oxidases & dehydrogenases involved in respiration; hydroperoxidases neutralize free radicals & oxygenases are involved in biotransformation

Oxidases Catalyze the removal of hydrogen from a substrate with the involvement of oxygen as a H acceptor Exist in two different forms : some of them are copper containing as, Cytochrome oxidase - the terminal component of ETC which transfer the e - finally to O2. Other are flavoproteins as , L aminoacid oxidase, xanthine oxidase

Dehydrogenases Perform 2 main functions: 1. Transfer hydrogen from one substrate to another in a coupled O/R reaction 2. As components of Electron transport chain o Dehydrogenases use coenzymes nicotinamides & riboflavin - as hydrogen carriers

Hydroperoxidases Includes 2 sets of enzymes : catalase and peroxidases Peroxidases reduce H2O2 at the expense of several other substances H2O2 + AH2 2H2O + A o Catalase uses H2O2 as electron acceptor & electron donor 2H2O2 2H2O

Oxygenases Catalyse the incorporation of O2 into subtrates in 2 steps - Oxygen is dound to the active site of the enzyme - bound O2 is reduced or transferred to the substrate Consists of two sets of enzymes 1. Dioxygenases : incorporate both atoms of oxygen into the substrate ; A + O2 AO2 2. Monooxygenases : incorporates one atom of oxygen into the substrate & the other is reduced to water A H + O2 + ZH2 A OH + H2O + Z

HIGH ENERGY COMPOUNDS High energy compounds or energy rich compounds is usually applied to substances in the biological system which on hydrolysis yield free energy equal to or greater than that of ATP i.e. G= -7.3 kcal/mol. The high energy compounds have anhydride bonds. Adenosine Triphosphate (ATP) ATP (adenosine triphosphate) the molecule of energy for cells, drives many biochemical reactions like muscle contraction, DNA and protein synthesis, etc ATP Synthase- enzyme that catalyses ATP synthesis and hydrolysis.It is A membrane enzyme Found in bacterial plasma membranes ,the thylacoid membrane in chloroplasts and The inner mitochondrial membrane of eukaryotic cells. It Consists of two domains F0 and F1. Hydrophobic F0 domain sits in the membrane - performs proton translocation . And Hydrophillic F1 portion protrudes from membrane - performs ATP synthesis/hydrolysis . also 3 alternating alpha and beta subunits .

Reference: 1) D M Vasudevan, S. Sreekumari, V. Kannan . textbook of biochemistry for medical students .jaypee 2011.sixth edition 2) www. themedicalbiochemistrypage.org