Biochemistry 2

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standard reduction potential (Eo)

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tendency of an electron donor to reduce conjugate acceptor under standard conditions

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negative Eo

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redox couple that tends to donate electrons to standard hydrogen electrode (SHE)

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positive Eo

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redox couple that tends to accept electrons from SHE

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complex I

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NADH delivers electrons to FMN which are passed to Fe-S and ultimately CoQ

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complex II

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succinate delivers electrons to FAD which are passed to Fe-S and ultimately CoQ

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complex III

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electrons from CoQ are passed to cytochrome, Fe-S and cytochrome and then to an isolated cytochrome

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complex IV

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electrons are passed to two cytochromes and ultimately O2

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FE-S centers

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usually attached to protein via cysteine residues, contain 1-4 Fe atoms, non-heme Fe

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Coenzyme Q

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redox occurs 1 electron at a time, gateway between 2 electron carriers and 1 electron carrier

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cytochromes

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include b, c, and a, contain protoporphyrin IX, cytochrome oxidase catalyzes the last step in electron tx. (reduce O2 to water)

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antimycin A

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antibiotic which inhibits enz cytochrome c reductase at complex III

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rotenone

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insecticide that inhibits tx of electrons from FeS in complex I to CoQ and prevents NADH from being used to produce ATP

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cyanide

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ions bind to Fe in cytochrome oxidase in complex IV and irreversibly changes shape of active site

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F1 sphere

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knoblike structure of APT synthase that synthesies ATP, located outside membrane, 5 subunits

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F0 stalk

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portion of ATP synthase embedded in membrane (inhibited by oligomycin)

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3 conformations of ATP synthase

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Loose (L), Tight (T), and Open (O)

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cytochrome P450

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active in liver, ER, involved in hydroxylation (increasing solubility), primary method of drug metab

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superoxide dismutase

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inactivates reactive oxygen radical to hydrogen peroxide

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catalase

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inactivates hydrogen peroxide to water

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gluthanione peroxidase

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inactivates hydrogen peroxide to water, req gluthathione and NADPH

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Cori cycle

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lactate produced from anaerobic glycolysis is reox to pyruvate in liver

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glycogenin

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sm protein which assembles short chain of glucose residues

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lipases

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enzymes that hydrolyze triacylglycerols into glycerol and fas, secreted by pancreas into duodenum, only active at water/oil interface

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emulsifying agents

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amphiphatic molecules that stabilize emulsions

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bile acids

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made by the liver, stored in gall bladder, synthesized from cholesterol, good emulsifying agents

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chylomicrons

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solubilized form of digested lipids, transport absorbed lipids from intestine to circulation

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lipoproteins

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have a lipid and a protein part, emulsifying agents that keep lipids soluble in circulation

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VLDL

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transport lipids from liver to body tissues

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LDL

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transport lipids from liver to body tissue

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IDL

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transport lipids from liver to body tissues

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HDL

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transport lipids from body tissues back to liver

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normal LDL level

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150-200 mg/100 mL in circulation

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steps of fatty acid oxidation

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1. activation (cytoplasm)
2. tx into mitochondria
3. ox rxns (mitochondria)

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fatty acid activation

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activated by attaching CoA molecule, 2 high E phosphate bonds hydrolyzed

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carnitine palmitoyl transferase-1

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adds carnitine for transfer through carnitine carrier protein into mitochondria

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carnitine palmitoyl transferase-2

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removes carnitine once fatty acid is inside mitochondria

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oxidation of fatty acids

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occurs at beta-carbon (carbon #3) through a series of 4 steps

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acyl CoA dehydrogenase

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dehydrogenation - double bond formed between carbons 2 and 3, requires FAD

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enoyl CoA hydratase

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hydration at double bond, requires water

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hydroxyacyl CoA dehydrogenase

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makes double bond to oxygen at carbon 3, weakens bond between carbons 2 and 3, requires FAD

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thiolase

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breaks bond between carbons 2 and 3, requires CoASH

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ATP/carbon for fat

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8.2

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ATP/carbon for glucose

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6.3

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propionyl CoA

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produced in addition to acetyl CoA from oxidation of fatty acids with more than one carbon, ends up as succinyl CoA

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ketogenesis

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acetyl CoA converted to ketone bodies in mitochondria of liver cells

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ketoacyl CoA transferase

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enzyme in all tissues except liver that enables them to use ketone bodies for energy by converting to acetyl CoA

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fatty acid biosynthesis

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essential for bio membranes, nutrient storage; occurs in cytoplasm

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3 reactions of fa biosynthesis

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syn of malonyl CoA; activation by attachment to ACP; hydrophobic chain elongation

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acetyl CoA carboxylase

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carboxylation syn malonyl CoA, requires B7

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malonyl CoA-ACP transferase

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activation by ACP

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elongation of hydrophobic chain

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occurs in cycles, each cycle=4 reactions (condensation, reduction, dehydration, reduction)

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inhibitors of bacterial fa syn

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INH, triclosan

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pentose-phosphate pathway

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alt to glycolysis, usually anabolic, provides NADPH for biosynthesis, ribose-5-phosphate for nucleotides/nucleic acids, digest pentose sugars from digestion of nucleic acids

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oxidative phase

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G6P dehydrogenase oxidizes G6P to form lactone

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deficiency of G6P dehydrogenase

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unable to produce adequate NADPH which is required for inactivation of damaging oxygen sp, sensitive to drugs which create oxidative stress

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Wernicke-Korsakoff syndrome

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mental disorder leading to paralysis and loss of memory, mutation in transketolase leads to increase in Km to TPP

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oxidative phosphorylation

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process using conc gradient generated via electron transport chain to drive syn of ATP via ATP synthase

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chemiosmotic coupling

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using desire to equilibrate conc across membrane to power comformation change/turning of F1F0 complex