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basic principles governing energy manipulation in cells
1) molecules are degraded or synthesized stepwize in a series of reactions (metabolic pathways)
2) ATP is the nergy currency of life
3) ATP can be formed by the oxidation of carbon fuels
4) although many reactions occur inside a cell, there are limited number of reaction types involving particulat intermediates that are common to all metabolic pathways
5) metabolic pathways are highly regulated
10
glucose is metabolized to pyruvate in ___ linked reactions
lactate; acetyl CoA
under anaerobic conditions, pyruvate is metabolized to ____ and, under aerobic conditions, to _____
CO2
the glucose derived carbon atoms of acetyl CoA are subsequently oxidized to ___
catabolic and anabolic
metabolic pathways can be divided into two types:
catabolic pathway
combust fuels to synthesize ATP
anabolic pathways
use ATP and reducing power to synthesize large biomolecules
1) the individual reactions must be specific
2) the pathway in total must be thermodynamically favorable
in order to construct a metabolic pathway, two criteria must be met:
coupling it to a more favorable reaction
a thermodynamically unfavorable reaction in a pathway can be made to occur by _____
hydrolysis of ATP
is exergonic because the triphosphate unit contains two phasophoanhydride bonds that are unstable
energy
___released on ATP hydrolysis is used to power a host of cellular functions
ATP
the structure of this consist of adenine, a ribose, and a triphosphate unit
Pa , PB , Py
the inner most phosphorus atom of ATP is designated ___, the middle one ____, and the outermost one ____.
ATP
is an energy coupling agent
1) charge repulsion (4 negative charges)
2) resonance stabilization makde ATP a high energy phosphoryl transfer group
3) increase in entropy
4) stabilization by hydration
ATP has a high phosphoryl transfer potential because of four key factors:
creatine phosphate
a quick source of energy; enough ATP for less than a second
oxidation of fuel, molecules, or photosynthesis
ADP to ATP
motion, active transport, biosyntheses, signal amplification
ATP to ADP
recycled
ATP must constantly be ___ to provide energy to power the cell
oxidation-reduction reaction or redox reaction
an oxidation reaction must be coupled with ractions that gain electrons (reduced)
oxidized
the carbon atoms in fuels are ____ to yield CO2, and the electrons are ultimately accepted by oxygen to form H2O
free energy
the more reduced a carbon is the more ____ is released upon oxidation
ATP synthesis
compounds with high phosphoryl transfer potential can couple carbon oxidation to ____
catabolism
is capturing the energy of carbon oxidation as ATP
oxidation
____of the carbon atom may form a compound with high phosphoryl transfer potential that can then be use to synthesize ATP
high phosphoryl transfer potential
oxidation of the carbon atom may form a compound with ____ that can be then used to synthesize ATP
activated carriers
are kinetically stable in the absence of specific catalysts; the metabolism of activated groups is accomplished with a small number of carriers
vitamins
ATP is an activated carrier of phosphoryl groups. other activated carriers are common in iochemistry, and often they are derived from _____
Nicotinamide adenine dinucleotide (NAD+) and flavin adenine dinucleotide (FAD)
carry activated electrons derived from the oxidation of fuels
nicotinamide adenine dinucleotide (NAD+)
is a prominent carrier of high energy electrons derived from the vitamin niacin (nicotinamide); reduced to NADH (accepts 2 electrons and 1 proton)
flavin adenine dinucleotide (FAD)
this electron carrier consists of the vitamin riboflavin and an ADP unit; accepts 2 electrons and 2 protons
NAD
accepts high energy electrons during cellular respiration to become NADH. it is involved in all stages of respiration; involved in cellular respiration processes throughout the cell inclusinfing glycolysis and the Krebs cycle
FAD
accepts high energy electrons during the Krebs cycle to become FADH2; primarily involved in the Krebs cycle, which occurs in the mitochondria
each reduced NADH molecule
is eventually used to produce more ATP in the electron trnasport chain, yielding a higher amount of energy
eahc reduced FADH2 molecule
is also used to produced ATP but it is oxidized later in the electron transport chain, resulting in a lower energy yield
higher; lower
NAD has a ____ redox potential, which allows it to carry more energy. FAD has a _____ redox potential which makes it suitable for metabolic steps that requires less energy
beginning; further along
NAD is oxidized at the ____ of the electron transport chain. FAD if oxidized ____ in the the electron transport chain
Nicotinamide adenine dinucleotide phosphate (NADH+)
is an activated carrier of electrons for reductive biosynthesis (fatty acid synthesis)
Coenxyme A (CoA-SH)
is an activated carrier of acyl groups such as the acetyl group; the transfer of the acyl group is exergonic because the thioester is unstable
vitamin A
roles in vision, growth, reproduction
deficiency: night blindness, cornea damage, damage to respiratory and gastrointestinal tracts
vitamin C (ascorbate)
antioxidant
deficiency: Scurvy
scurvy
swollen and bleeding gums, subdermal hemorrhaging
vitamin D
regulation of calcium and phosphate metabolism
deficiency: rickets (children): skeltal deformities, impaired growth; Osteomalacia (adults): soft, bending bones
vitamin E
antioxidant
deficiency: lesions in muscles and nerves (rare)
vitamin K
blood coagulation
deficiency: subdermal hemorrhaging
homeostasis
a stable biochemical environment, is maintained by careful regulation of biocheical processes
1) the amount of enzymes present
2) the catalytic activity of enzymes
3) the accessiility of substrates
3 regulatory control are especially prominent for homeostasis:
gene transcription
the quantity of enzyme present can be regulated at the level of ____
catayltic activity
is regulated allosterically through feedback inhibition or by covalent modification
hormones
coordinate metabolic activity, often by insitgating the covalent modification of allosteric enzymes
eninephrine
breakdown glycogen to glucose for energy (muscle)
glucagon
glucose relase from glycogen (liver)
opposing reactions
may occur in different cellular compartments (fatty acid synthesis and degradation)
metabolism
regulating the flu of substrates between compartments is used to regulate _____
glucose
a prominent fuel in all life forms because it may have been available for primitive biochemical system because it can form under prebiotic conditions; the msot stable haxose; a low tendency to nonenzymatically glycosylate proteins
formaldehyde
is the source of glucose
first stage of glycolysis
glucose is trapped, destabilized, and cleaved into two interconvertible 3C molecules, generated by the cleavage of 6C fructose (phosphorylation, isomerization, phosphorylation)
stage two of glycolysis
the 3C units are oxidized to pyruvate, generating ATP (oxidation reaction, ATP formation, ATP formation)
hexokinase
this enzyme is used for the first step of glycolysis; phosphorylates glucose to trap it in the cell
phosphoglucose isomerase
this enzyme is used for the second step of glycolysis; reversible reaction that converts glucose 6-phosphate to fructose 6-phosphate; important because without the conversion glucose 6-phosphate will not be able ot be cleaved into two 3 carbon sugars
phosphofructokinase (PFK)
this enzyme is used for the third step of glycolysis; adds a second phosphate to form fructose 1,6-bisphosphate to trap in it the fructose form; creates a symmetrical structure that can split into two; irreversible reaction
aldolase
this enzyme is used for the fourth step of glycolysis; cleaves the 6C to two 3C sugars one an aldose (GAP) and the other a ketose(DHAP)
triose phosphate isomerase
DHAP and Gap are isomers and this enzyme can change them to one or the other
1,3,BPG (1,3-Bisphosphoglycerate)
oxidation of GAP forms a high phosphoryl compound
glyceraldehyde 3-phosphate dehydrogenase
this enzyme is used for the fifth step of glycolysis; a compound with high phosphoryl transfer potential, 1,3-Biophosphoglycerate, is generated by the oxidation of GAP in a reaction catalyzed by this
would not occur
if the oxidation reaction and acyl phosphate formation are not couple, then ____
thioester intermediate
couples the oxidation and acyl formation which lowers the activation energy
substrate level phosphorylation
transfer a phosphate from a substrate to ADP (ex. formation of ATP from the high energy phosphoyl group 1,3-BPG)
oxidation reduction reaction
ATP is generated from phosphenolpyruvate conversion to pyruvate (phosphate is rearranged)
GLucose + 2Pi + 2ADP + 2NAD+ → 2 pyruvate + 2ATp + 2NADH + 2H+ + 2 H2O
the net reaction for glycolysis:
2; 4; 2
in glycolysis ___ ATP are used and ___ ATP are made which makes the net ATP ____
lactate
acetyl CoA → futher oxidation
Actealdehyde → ethanol
what three forms can pyruvate turn into?
lactate
is acidic so the muscle cells do not keep it for long (the liver helps out)
lactate
pyruvate gets turned into this with lactate dehydrogenase And NADH (which turns into NAD+); is anaerobic
acetyl CoA
pyruvate get turned into this with the addition of O2 and release of CO2; is aerobic and can go through further oxidation
acetaldehyde
pyruvate gets turned into this through alcoholic fermination from pyruvate decarboxylase (TPP) and the release of CO2; is aerobic
ethanol
pyruvategets turned into this after it is turned into acetaldehyde through alcohol dehydrogenase and NADH with the release of NAD+
physiological condition, tissues, and organisms
the fate of glucose is varies with _____
decarboxylase
whrn some form of carbon comes out of a reaction
alcoholic fermentations
are the means of oxidizing NADH; the conversion of glucose into two molecules of ethanol
thiamine (vitamine B)
is a compoenent of the coenzymes thiamine pyrophosphate (TPP), which is used in decarboxylation reactions (pork and legumes are good sources of this)
NADH
____generated by glyceraldehyde 3-phosphate dehydrogenase is oxidized by alchol dehydrogenase, regenerating NAD+
reoxidized to NAD+
the NADH produced by the glyceraldehyde 3-phosphate dehydrogenase reaction must be ____ for the glycolytic pathway to continue.
alcohol dehydrogenase
in alcoholic fermentation, ____ oxidizes NADH and generates ethanol
lactate dehydrogenase
NADH can also be oxidized by converting pyruvate to lactate in a reaction catalyzed by _____
lactic acid fermentation
the conversion of glucose into 2 molecules of lactate
glucose + 2Pi + 2ADP → 2lactate + 2ATP + 2H2O
lactic acid and regenerate NAD+
in lactic acid fermentation, lactate dehydrogenase oxidizes NADH to produce____-
glycolytic intermediates
fructose from table sugar or high-fructose corn sytrup and galatose from milk sugar are converted into this
fructose and galatose
these sugars convert to metabolites of the glycolytic pathway
phosphofructokinase (PFK)
fructose leads to type II diabetes because of the manner in which fructose in processed in the liver, the key regulatory eneryme of glycolysis is by-passed/ not regulated
fats
excess acetyl CoA synthesized and converted to ___
galactose-glucose conversion pathway
galatose is converted into glucose 6 phosphate by the _____ which begins with the phosphotylation of galatose by galactokinase
galactose
is highly toxic if transferse is missing
galactosemia
results if galactose 1-phosphate uridyl transferase activity is deficient; symptons include failure to thrive, jaundice, and liver enlargment that can lead to cirrhosis; cataracts may form
cataracts
a clouding of the lends due to water accumulation, form because the galatose is converted into galactitol
galactitol
is osmotically active and causes water to diffuse inot lens; poorly metabolized
phosphorylated and metabolized
notice all sugars are ____ by entry into the glycolytic pathway
reducatse enzyme
high levels of glucose present in the lends of the eye causes the lens to swell which affects clarity of vision. ____ reduces glucose into sorbitol (polyol pathway) that causes the lends to become less clear and more opaque (leads to cataract formation)
lactase
a deficiency of this casues lactose intolerance
lactose intolerance
when lactose can not be broken down into galactose and glucose wht lactic acid ferments by bacteria which draws the water in the intestine