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all the chemical reactions that occur within a cell
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synthesize cellular components, involve increase in molecular order and thus a decrease in entropy, require energy (endergonic)
examples: polymer synthesis, biological reduction of carbon dioxide to sugar (gluconeogenesis) |
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involved in the breakdown of cellular constituents, involve decrease in molecular order and thus and increase in entropy (exergonic), release free energy needed to drive cellular functions
example: glycolysis |
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molecule most commonly used as an energy intermediate
contains 2 energy rich phosphoanhydride bonds |
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a bond of ATP that links together phosphate groups |
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a bond of ATP that links together a phosphate group to a ribose |
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free energy is released when the bond is hydrolyzed (interaction of a compound with water results in the decomposition of that compound) |
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each phosphate group on ATP bears at least one negative charge due to its ionization at the near neutral pH of the cell
these charges repel each other thus straining the covalent bond linking the phosphate groups together
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requires the joining of 2 negatively charged molecules that naturally repel each other
this requires an input of energy to overcome this repulsion |
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carboxylate group of ATP has one e- pair that is delocalized over both the C bonds to O
when e-s are delocalized in this way, the molecule in its most stable configuration |
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overall increase in entropy as a phosphate group is removed from ATP and no longer in a fixed position, thus... |
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the spatial randomization of ADP and phosphate decreases free energy and makes the reaction more exergonic |
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chemotrophic energy metabolism |
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the reactions and pathways by which cells catabolize nutrients and conserve, as ATP, some of the free energy that is released in the breakdown
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sources of energy for a cell |
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carbs, fats, and proteins
these are oxidizable organic compounds whose oxidation level is highly exergonic |
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removal of electrons
often seen as dehydrogenation |
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removal of electrons PLUS the removal of hydrogen ions |
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addition of electrons
endergonic process |
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addition of electrons PLUS the addition of hydrogen ions |
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an important way that cells store chemical energy as reducing power
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oxidation-reduction reactions
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involve a 2 electron and 2 ion(proton) transfer |
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electrons and hydrogens removed from substrate being oxidized are transferred to one of several...
not consumed, but recycled within the cell
most common involved in energy metabolism is NAD+ |
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most common coenzyme that serves as an electron pair acceptor by adding 2 electrons and one proton to its aromatic ring |
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glucose, the 6 carbon sugar |
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C6H12O6
main sugar in blood and thus main energy source for most cells in the body
blood glucose comes from dietary carbs such as sucrose and starch and from breakdown of stored glycogen
important to plants since it is the monosaccharide released upon starch breakdown |
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oxidation of glucose is highly exergonic |
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glucose is a good potential source of energy because its oxidation is highly exergonic with a [image] of -686 kcal/mol for a complete conversion of glucose to carbon dioxide and water using oxygen as the final electron acceptor
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complete oxidation of glucose to carbon dioxide and water in the presence of oxygen |
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oxidation using inorganic electron acceptors other than oxygen |
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in the absence or scarcity of oxygen, most organisms can still extract limited amounts of energy from partial oxidation of glucose but with lower energy yields per molecule of glucose
done via GLYCOLYSIS
electrons that are removed during glucose oxidation are returned to organic molecules later the same way |
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partial oxidation of carbs by anaerobic pathways resulting often in the production of either ethanol and carbon dioxide(alcoholic fermenation) or lactate(lactate fermentation) |
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absolute requirement for oxygen
HUMANS |
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cannot use oxygen as an e- acceptor because O is toxic to such organisms
examples: bacteria found in wounds, sludge, ponds & organisms responsible for gangrene, food poisoning, and methane production |
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glycolysis
(glycolytic pathway) |
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Definition
10-step reaction sequence that converts 1 molecule of glucose into 2 molecules of pyruvate (a 3 carbon compound)
common to both aerobic and anaerobic glucose metabolism and present in almost all organisms
occurs in cytosol
in absence of O, it leads to fermentation
in presence of O, it leads to aerobic respiration
split into 3 phases |
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important features of glycolysis |
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initial input of ATP, sugar splitting rxn for which sequence is named, oxidative events that generate NADH, and two specific steps at which the rxn sequence is coupled to ATP generation |
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Glycolysis Phase 1: Preparation and Cleavage |
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Definition
net result of the 1st 3 reactions is to convert an unphosphorylated molecule (glucose) into a doubly phosphorylated molecule called fructose 1, 6-bisphosphate
requires transfer of 2 phosphate groups from ATP to glucose, one on each terminal carbon
ATP hydrolysis provides driving force that renders phosphorylation rxn strongly exergonic making it irreversible
glucose is phosphorylated and phosphoester bond is formed |
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Glycolysis Phase 2: Oxidation of ATP Generation |
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glyceraldehyde-3-phosphate oxidized to corresponding three-carbon acid
3-phosphoglycerate is highly exergonic and drives the next 2 steps |
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Glycolysis Phase 3: Pyruvate Formation and ATP Generation
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phosphoester bond converted to phosphoenol bond
increase in amount of free energy release upon hydrolysis involves rearrangement of internal energy within molecule |
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2 molecules of ATP initially invested and 2 formed per molecule of glucose
glucose+2NAD+ + 2ADP +2Pi---->
2pyruvate +2NADH+2H+2ATP |
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dependent upon availability of oxygen
oxygen:undergoes further oxidation to a molecule called acetyl coenzyme A when oxygen is present which can be further oxidized to produce over 30 molecules of ATP per glucose
no oxygen: pyruvate is reduced and lactate/ethanol is formed |
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Definition
generate by direct transfer of electrons from NADH to carbonyl group of pyruvate reducing it to the hydroxyl group of lactate
reaction is reversible
major energy-yielding pathway in many anaerobic bacteria
used to produce cheese, yogurt, and muscles during periods of strenous exercise
glucose +2ADP +2Pi --> 2 lactate + 2ATP |
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pyruvate loses a carbon atom as carbon dioxide to form a 2 carbon compound called acetaldehyde
used by yeast cells in baking, brewing, and winemaking
2pyruvate + 2NADH + 4H--> 2ethanol +2CO2+2NAD+ |
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Fermentation taps only a fraction of the substrate's free energy, but conserves that energy efficiently |
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Definition
no external electron acceptor is involved and no net oxidation occurs
around 93% of free energy of glucose is still present in the 2 lactate molecules and only about 7% of the free energy potentially available from glucose was obtained during fermentation |
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alternative substrates for glycolysis |
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alternative substrates often converted to intermediates in main pathway for glucose catabolism |
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other sugars and glycerol are also catabolized by glycolytic pathway |
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sucrose(table sugar): disaccharide consisting of glucose and fructose
lactose (sugar in milk): consists of glucose and galactose
disaccharides are hydrolyzed into their component monosaccharides which are then converted to a glycolytic intermediate
phosphorylated pentoses are used in glycolytic pathways after being converted to hexose phosphates |
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overall energy yield for glucose is greater by 1 molecule of ATP when it is catabolized from polysaccharide level than when it is catabolized with the free sugar as a starting substrate |
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process of glucose synthesis or the process by which cells synthesize glucose from 3-carbon and 4-carbon precursors that are usually not carbs
consumes 6 ATP molecules per glucose synthesized |
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gluconeogenesis: bypass reactions (alternative rxns that can circumvent the 3 steps that were irreversible in glycolysis) |
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Steps 1-3: bypassed by hydrolytic reaction that liberates inorganic phosphate
Step 10: bypassed by a two reaction sequence in which carbon dioxide is added to pyruvate and the carboxyl group is removed to form PEP
*consumes 6 ATP molecules per glucose synthesized |
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regulation of glycolysis and gluconeogenesis |
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Definition
important to keep glycolysis and gluconeogenesis from proceeding simultaneously in the same cell
spatial regulation: pathways operate in separate cells
temporal regulation: operate at different times within the same cell |
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involves interconversion of an enzyme between 2 forms: 1 is catalytically active and the other 1 is catalytically inactive
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key enzymes of glycolysis |
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hexokinase, pyruvate kinase |
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key enzymes of gluconeogenesis |
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activators indicated by +
inhibitors indicated by - |
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fructose-2,6-biphosphate is an important regulator of glycolysis and gluconeogenesis |
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most important regulator
synthesis of F2,6BP is catalyzed by a separate form called phosphofructokinase-2 (PFK-2)
it activates glycolytic enzyme and inhibits gluconeogenic enzymes which in turn affects the F2,6BP concentration by inactivating the glycolytic activity and stimulating the gluconeogenic activity |
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roles for glycolytic enzymes |
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Definition
regulation of apoptosis: process of programmed cell death
act as transcriptional regulators or transriptional activators |
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