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Metabolism > Glycolysis, glucose and pyruvate > Flashcards

Glycolysis, glucose and pyruvate Flashcards

1
Q

What makes glucose a good fuel

A
  • rich in potential energy (-2,840 Kj/mol)
  • can be stored as polymer while keeping low cytosolic osmolarity
  • readily available
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2
Q

M3

Diff names for PPP

A

phosphogluconate pathway, hexose monophosphate shunt

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3
Q

M3

What is NADPH used for?

A

Reductive biosynthesis

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4
Q

M3

What cells undergo constitutive glycolysis

A

RBC’s, renal medula, brain, sperm

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5
Q

M3

What is fermentation

A

general term for the anaerobic degradation of glucose or other organic nutrients to obtain energy, conserved as ATP.

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6
Q

M3

What happens in the 2nd step of glycolysis?

A

Phosphohexose isomerase converts G-6-P to F-6-P.

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7
Q

M3

What happens in step 4 of glycolysis?

A

F-1,6-B is converted to glyceraldehyde-3-phosphate and dihydroxyacetone-3-phosphate

Enzyme: aldolase

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8
Q

M3

What molecule is converted to g-3-P in the 5th step of glycolysis?

A

Dihydroxyacetone phosphate

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9
Q

M3

What is g-3-p converted to And what are its other by products and the enzyme involved

A
  • Makes 1,3- Bisphophoglycerate
  • enzyme: G-3-P dehydrogenase -

makes NADH and from NAD - phosphorylates molec. Using Pi

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10
Q

M3

What is the first substrate level phosphorylation rxn in glycolysis

A
  • 1,3- Bisphophoglycerate to 3-Bisphophoglycerate
  • enzyme: phosphoglycerate kinase
  • ADP–> ATP
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11
Q

M3

What happens after the first substrate level phosphorylation rxn of glycolysis

A
  • 3-phosphoglycerate is mutated to 2-phosphoglycerate -
  • Enzyme: phosphoglycerate mutase
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12
Q

M3

What does a mutase do?

A

Moves phosphate group

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13
Q

M3

What does an isomerase do?

A

It rearranges the carbon structure

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14
Q

M3

What happens after the phosphate group is moved in glycolysis?

A
  • 2-phosphoglycerate is reacted to form phosphoenol pyruvate
  • enzyme: enolase
  • releases H2O
  • OH group on carbon 3 is removed
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15
Q

what are the 3 types of pathways

A
  • Linear (product of rxns aresubstrates for subsequent rxns)
  • Closed Loop (intermediates recycled)
  • Spiral (same set of enzymes used repeatedly)
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16
Q

what are 3 dietary sources of energy? list percentages and cal per gram

A

carbs = 40% 4 cal/g

Fat = 40 % 9 cal/g

Proteins = 20% 4 cal/g

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17
Q

List 3 genral concepts of Digestion and Absorbtion

A

1) Food must be broken down into “absorbable”
components before any utilization is possible

2) Only monosaccharides are absorbed, thus complex
materials must be broken down to monosaccharides

3) Breakdown of complex carbohydrates or proteins
into monomer units involves hydrolysis; no other
reaction is required

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18
Q

What kind of molecules provide enegy?

A

Oxidizable substrates

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19
Q

complete oxidation of glucose to CO2 yields how much energy

A

686 kcal/mol

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20
Q

reactions in calorimeter yield what

A

heat

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21
Q

How is energy of digestibles harnessed

A

by tranducing it to ATP, which stores it as chemical energy

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22
Q

one molecule of glucose reacts with how many O2’s?

A

6

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23
Q

glucose and the other substrate make what? how many of these molecules are made per glucose?

A

CO2 and H2O

6 of each

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24
Q

what 3 pathways does glycolysis lead to?

under what conditions?

what is their final product?

A

pyruvate fermentation to ethanol and CO2 in yeast; under hypoxic or anaerobic conditions

pyruvate to LActate in anaerobic conditions (vigorously contracting muscle, erythrocytes, in other cells and some microoganisms)

to acetyl CoA, CO2 and NADH via PDH in aerobic conditions

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25
Q

what is the role of glycolysis in muscles

A

production of lactic acid under anaerobic conditions; regenerate NAD+ to drive glycolysis forward; lactate released into bloodstream and delivered to liver where it is converted to glucose

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26
Q

role of glycolysis in liver

A

major function to
maintain blood glucose levels;
excess glucose converted to
fatty acids – adipose tissue,
or to glycogen

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27
Q

role of glycolysis in RBCs

A

since they lack
mitochondria, glycolysis is
essential for energy production;
lactate is end product

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28
Q

role of glycolysis in the brain

A

glucose is aerobically
catabolized to CO2 and H2O;
reducing equivalents in NADH
delivered to mitochondria

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29
Q

what are the 4 uses of glucose

A

1) a storage form (glycogen),
2) energy source (ultimate conversion to CO2)
3) source of metabolic intermediates and electrons
4) precursor of all other sugars found in mammals

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30
Q

what does glucose membrane transport depend on and where?

A

Transport of glucose may be hormone-dependent

(insulin in muscle) or not (liver)

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31
Q

what cells use glucose exclusively or nearly exclusively?

A

brain cells and RBC’s

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32
Q

how many grams of glucose does the brain need per day?

A

120 g

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33
Q

what are the dietary sources of glucose

A
  • milk: lactose
  • fruits: glucose, fructose, higher sugars
  • table sugar: sucrose
  • vegetables: starches
  • roughage: cellulose, etc
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34
Q

why is maintanence of glucose levels important and how is it maintained?

A

1) Since the brain is heavily dependent on glucose under
normal conditions, maintenance of blood glucose levels is
very important

2) Nearly continual process utilizing both storage forms
(glycogen) and de novo synthesis (gluconeogenesis)
from non-carbohydrate sources (primarily amino acids)

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35
Q

what happens after glucose is split to glyceraldehyde

A

it is rearranged to pyruvate (and then lactate or ethanol)

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36
Q

how many ATP and NADH are generated per molecule of glucose?

A

2 ATP and 2 NAH

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37
Q

what is the fate of NADH in aerobic conditions?

A

it is reoxidized with Oxygen as teh final electron acceptor

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38
Q

what is the formula for glycolysis

A

Glucose+2ADP+2NAD++2Pi -> 2pyruvate+2ATP+2NADH+2H++2H20

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39
Q

what cells carry out glycolysis

A

Essentially all cells carry out glycolysis

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40
Q

what aspect of glycolysis differs in the different cells

A

the rate of the reactions

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41
Q

what the 2 functions of glycolysis

A
  1. generate ATP
  2. make pyruvate for TCA cycle to reduce glucose to CO2 and H2O
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42
Q

NAME THE 2 PHASES

A

1) Preparatory phase: investment of 2 ATP to
utilize a single glucose molecule as fuel

2) Payoff phase: Yields 4 ATP and 2 NADH
per glucose molecule

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43
Q

what are the advantages of phosphorylation

A

1) Transport: cells have transport systems on
membranes for fuel molecules such as glucose;
phosphorylated glucose is no longer recognized
by glucose transport system; trapped in cell

2) Binding: To allow strong highly specific
interaction between enzymes and substrates;
phosphate provides large electrically charged
functional group

3) Synthesis of ATP: substrate level phosphorylation
- phosphate group is directly transferred
to ADP from substrate to make ATP

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44
Q

in the first reaction of glycolysis:

what are the , substrates/products, cofactors, delta G,

what is a result of the phosphorylation of glucose

A
  • glucose is phosphorylated on C-6
  • requires a Mg2+: ATP complex
  • phosphorylation retains glucose in the cell

Enzyme: hexokinase

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45
Q

what is the 1st priming reaction of glycolysis

A

the first one

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46
Q

what is the shape of the intermediate in the 1st rxn of glycoslysis

A

trigonal bipyramid

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47
Q

what do different hexokinases phosphorylate

A

Phosphorylates hexoses such as glucose,
fructose, and mannose

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48
Q

what are the main forms of hexokinases?

what cells are they in?

which on is responsible for DM?

A

Two major forms: hexokinase (all cells, types
I, II, and III) & glucokinase (liver,pancreatic
β-cells;type IV; mutated in diabetes mellitus)

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49
Q

what is the Km of hexokinase I and why is it significant

what is the conc. of glucose in the blood normally

A

Km for hexokinase is 0.1 mM; ensures that its
activity is independent of blood glucose
concentration (4 - 5 mM)

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50
Q

what is the Km for glucokinase?

why is this significant?

A

Km for glucokinase is 10 mM; only turns on
when cell is rich in glucose; ensures its
activity is dependent on blood glucose levels

Glucokinase functions when glucose levels are
high to sequester glucose in the liver.

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51
Q

which hexokinase is inhibited by G-6-P

A 
Hexokinase (not glucokinase) is allosterically
 inhibited by (product) glucose-6-P
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52
Q

why phosphoryl group is transfered by hexokinase and to what atom?

A

Hexokinase transfers the γ-phosphoryl grp of ATP to the oxygen
atom at C-6 of glucose, producing glucose 6-P and ADP

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53
Q

name the 2nd reaction of glycolysis

A

Enzyme:Phosphohexose isomerase

• Interconverts glucose 6-phosphate and fructose 6-phosphate.

Mg2+ cofactor

54
Q

what enzymes have a dimer structure?

A

hexokinase, phosphohexose isomerase

55
Q

what is the structure of the substrates of phosphohexose isomerase?

A

• Uses open chain structure as substrate

• Interconversion proceeds through a cis-enediol
intermediate; with the enzyme present the energy
barriers around enediol are lowered enough to speed
the interconversion.

56
Q

Reaction 3 of glycolysis

enzyme, cofactors, delta G knot

A
  • PFK-1
  • Cofactors: ATP, Mg2+
  • makes F-1,6- Bisphosphate from β-D-fructose-6-phosphate
  • The second priming reaction, first committed step
57
Q

what is the major control point in glycolysis?

A

PFK-1’s rxn

58
Q

what is the structure of PFK-1 and what are the two states it can exist in

what stabilizes these states?

A

• PFK is a homotetramer that can exist in two
states, R-state and T-state

• F-6-P stabilizes the R state, while ATP
stabilizes the T state and inhibits PFK

59
Q

what are the effect of ATP, citrate and AMP on PFK-1

A
  • ATP inhibits, AMP reverses inhibition
  • Citrate is also an allosteric inhibitor
60
Q

what effect does fructose 2,6 bisphosphate have on PFK1?

in what tissues?

A

• Fructose-2,6-bisphosphate is allosteric
activator in liver; prevents inhibition by ATP

61
Q

what happens to PFk 1 in low energy or high energy status

A
  • Low energy status: PFK increases activity
  • High energy status: PFK decreases activity
62
Q

what disease does PFK deficiency lead to?

what kind disease is it? what is the genetic component?

A 
Tauri disease (glycogen
 storage disease IV)- autosomal recessive disorder
63
Q

what is the 4th rxn of glycolysis

enzyme, cofactors, substrate/products

what is notable about this rxn

A
  • aldolase
  • no cofactors noted
  • F-1,6-BP to G-3-P (C4-C6) and Dihydroxyacetone phosphate (DHAP) (C1-C3)
64
Q

what kind of cleavage happens in rxn 4 of glycolysis

A

Hexose cleaved to form two trioses; aldol cleavage

65
Q

what kind of intermediate does aldolase’s rxn proceed through?

A

Schiff-base intermediate

66
Q

what is a precursor to triacylglycerols

A

DHAP (or DHA?)

67
Q

5th reaction of glycolysis

A

Triose Phosphate Isomerase (TPI)

-Conversion of DHAP to G-3-P by TPI;
maintains steady state [G-3-P]; reversible

no cofactors

68
Q

What kind of intermediates does teh second phase of glycolysis yield?

what are they?

A

• Second phase involves two very high
energy phosphate intermediates • .
– 1,3 BPG
– Phosphoenolpyruvate

69
Q

Rxn 6 of glycolysis

enzyme, cofactors, substrates/products

A

Glyceraldehyde-3P-Dehydrogenase

G-3P + Pi –> 1,3- bisphosphoglycerate

yields 1 NADH +H+

70
Q

what molecule is in the active site of G-3-P

A

cystine

71
Q

what part of the rxn by Glyceraldehyde-3P-Dehydrogenase is reversible

A

formation of first intermediate with high phosphoryl group
transfer potential 1,3-BPG

72
Q

what intermediates does G3P dehydrogenase form

A

a thiohemiacetal and then a thioester with C1 of GAP

73
Q

how many hydrogens are formed by G3P dehydrogenase?

A

2 hydrogens formed, one from C1 and the other from the phosphate

74
Q

what carbon does NAD+ accept a hydride ion from?

why is this important?

A

from C1 and is reduced to NADH (NAD+
must be regenerated to sustain the forward reaction

75
Q

rxn 7 of glycolysis

A

1,3 bisphosphoglycerate + ADP –> 3- Phosphoglycerate + ATP

enzyme: phosphoglycerate kinase (PGK)

no cofactos noted

76
Q

Deficiencies in Phosphoglycerate Kinase (PGK) lead to what

A

haemolytic anemia,
myopathy, central nervous system disorder, growth retardation

77
Q

rxn 8 of glycolysis

A

Phosphoglycerate Mutase

interconverts 3-phosphoglycerate and 2-phosphoglycerate

Mg2+

78
Q

Phosphoglycerate Mutase PGAM deficinecies lead to

A

muscle dysfunction with exercise
intolerance and muscle breakdown

79
Q

Phosphoglycerate Mutase rxn involves

A

• involves formation of 2,3-bisphosphoglycerate via transient
phosphorylation of a histidine residue of the enzyme.

80
Q

Rxn 9 of glycolysis

A

Enolase

converts 2-phosphoglycerate to phosphoenolpyruvate (PEP).

relases H20

no cofactors noted

81
Q

Rxn 10 of glycolysis

A

Pyruvate Kinase

-transfers a phosphate from phosphoenolpyruvate to ADP,
producing pyruvate and ATP

no cofactors noted

82
Q

what inhibits and what activates Pyruvate kinase

A
  • Allosterically activated by AMP, F-1,6-biP (feed-forward activation)
  • Allosterically inhibited by ATP and acetyl-CoA
83
Q

interconversion of pyruvate is called.

what forms does it interconvert between

A

tautomerization

enol and keto forms

• Enolpyruvate is formed first that is rapidly converted to pyruvate

-PEP is the second compound with high phosphoryl group potential

-pyruvate kinase transfers this phosphate to ADP in rxn with
large negative G’o

84
Q

lactic acid fermentation rxn

A

lactate dehydrogenase

pyruvate–> L-lactate

G= -25 kj/mol

location: cytosol

regenarates NAD+ under anaeronic conditions

85
Q

what is fermentation

A

processes that extract energy from
metabolic fuel without changing concentration of
NAD+ and NADH

86
Q

Can NADH be transported to into the mitochondria?

A

not directly

87
Q

in what cells is the cori cycle important?

where is lactate circulated back to?

A
  • Lactate made in muscle under anaerobic conditions
  • major product in erythrocytes
  • Lactate is circulated back to liver to reform glucose
88
Q
A
89
Q

what is the first rxn in ethanol fermentation

A

pyruvate to acetaldehyde

pyruvate decarboxylase

cofactors: Mg, TPP

90
Q

what is teh 2nd rxn in ethanol fermentation

A

acetaldehyde to ethanol

alcohol dehydrogenase

Cofactors: NADH +H+

yields: NAD+

91
Q

what are teh GLUT transporters in hepatocytes

A

• GLUT 1, GLUT 2 - hepatocytes (plasma membrane)

92
Q

what is the glucose transporter int he brain

A

• GLUT 3 - brain neurons (plasma membrane)

93
Q

Where are GLUT 4 transporters found

A

• GLUT 4 - muscle, adipose tissue (in intracellular
vesicles and move to plasma membrane in response
to insulin signal from pancreatic β cells)

94
Q

type 1 DM is lacking what cells

A

• Type 1 Diabetes Mellitus - have too few β cells

95
Q

what happens to the blood glucose levels in type 1 DM and why?

what do muscle and fat tissue use when they cant access glucose? what energy molecules are formed as a result?

A

• Cells unable to take up glucose — abnormally high
levels of glucose in blood (hyperglycemia)

• Muscle and fat tissue use fatty acids (triacylglycerol)
as principal fuel —breakdown products are
converted to “ketone bodies” — ketoacidosis

96
Q

what happens to the rate of glucose uptake in tumor cells?

what changes happen as a result?

A

-tumor cells:
glucose uptake and
glycolysis proceed
10x faster than in
normal cells

-hypoxic conditions

-change to dependence
in glycolysis
for ATP generation

-tolerance to low pH

97
Q

how to tumor cells adapt to use glycolysis primarily

A
  • tolerance to low pH
  • inc. expression of

1) glycolytic enzymes
2) glucose transporters
GLUT1,3

98
Q

tetrameric enzymes of glycolysis

A

G-3-P Dehydrogenase, triose phosphate isomerase (PFK-1 is homotetramer)

99
Q

what type of reaction happens in rxn 6 of glycolysis

A

coupled oxidation and phosphorylation

100
Q

what is the delta G of the rxn catalyzed by G3P dehydrogenase

A

6.3 kj/mol

101
Q

which glycolysis rxn are noted to be at or near equilibrium

A

rxn 6

102
Q

what is used to push rxn 6 of glycolysis

A

• C1 phosphoryl group has high group transfer potential,used to phosphorylate ADP to ATP in next step of glycolysis

103
Q

what donates the phosphate in rxn 6 of glycolysis

A

inorganic phosphate (Pi)

104
Q

what happens to the NADH formed in rxn 6 of glycolysis

A

• NADH generated in this reaction is reoxidized by respiratory electron transport chain (which generates more ATP)

105
Q

what is the delta G of the rxn catalyzed by phosphoglycerate kinase (PGK)

A

-18.5 kj/mol

106
Q

what is dephosphorylated by phosphoglycerate kinase

A

1,3-bisphosphoglycerate

107
Q

In what rxn is substrate level phosphorylation done

A

1,3 bisphosphoglycerate + ADP –> 3- Phosphoglycerate + ATP ; enzyme: phosphoglycerate kinase (PGK)

108
Q

what part of the substrate donate the phosphoryl group for the 1st substrate level phosphorylation

A

the carboxyl group of 1,3-phosphoglycerate (PGA)

109
Q

how many ATP’s per molecule of glucose is made during substrate level phosphorylation rxns

A

2

110
Q

what rxns of glycolysis lack cofactors (noted in the syllabus)

A

phosphoglycerate kinase rxn, enolase rxn, pyruvate kinase rxn, triose phosphate isomerase rxn, aldolase rxn

111
Q

what rxns of glycolysis require ATP

A

hexokinase rxn, PFK-1 rxn

112
Q

what rxns of glycolysis have Mg2+ as cofactors

A

phosphoglycerate mutase rxn, PFK-1 rxn, hexokinase rxn

113
Q

what is the delta G of phosphoclycerate mutase rxn

A

4.4 kj/mol

114
Q

where is the phosphoryl group move in phosphoglycerate mutase rxn. Is this reversible?

A

C3 to C2; it is reversible

115
Q

delta G of Enolase rxn

A

7.5

116
Q

what kind of rxn is catalyszed by enolase? what is released by enolase rxn? Is it reversible?

A

dehydration; H20 ; revesible rxn

117
Q

compare the energy content of 2-Phosphoglycerate and phosphoenolpyruvate

A

simlar energy content

118
Q

what is the purpose of enolase

A

rearrages 2- phosphoglycerate to PEP to a form from which more energy can be released via hydrolysis

119
Q

what does release of H2O from 2-phosphoglycerate do

A

converts the phosphate group to a very high potential energy (energy gain)

120
Q

delta G of pyruvate kinase rxn

A

-31.4 kj/mol; Large, negative ΔG; essentially irreversible

121
Q

what is the 2nd substrate level phosphorylation rxn

A

PEP + ADP –> Pyruvate + ATP ; Pyruvate kinase (no cofactors)

122
Q

what kind of molecules does triose phosphate isomerase convert

A

ketose to aldose isomerization

123
Q

delta G of tiose phosphate isomerase (TPI)

A

7.5; reversible

124
Q

what is the most efficient enzyme known? Why?

A

triose phosphate isomeraze; Kcat/Km is near diffusion limit

125
Q

delta G knot for aldolase

A

23.8 kj/mol; Near-equilibrium rxn; reversible

126
Q

what carbon is first G3P made from and what carbons is dihydroxyacetone phosphate made from?

A

C4-C6; C1-C3

127
Q

what is the 2nd priming rxn of glycolysis

A

PFK-1 rxn

128
Q

delat G of PFK-1

A

• large -ΔG (-14.2) means PFK is highly regulated; irreversible

129
Q

what kind of rxn in 2nd step of glycolysis

A

aldose to ketose isomerization

130
Q

delta G knot for phosphohexose isomerase

A

• 1.7 KJ/mol; Near-equilibrium rxn (reversible); direction depends on levels of substrate and product

131
Q

delta g knot for hexokinase

A

-16.7; large negative ΔG’o makes this reaction irreversible

132
Q

what enxyme requires ATP:Mg2+ complex

A

hexokinase rxn

Metabolism (8 decks)

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