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summer biochemistry jonklaas > glycolysis > Flashcards

glycolysis Flashcards

1
Q

what is the way to harness energy? what bonds do we need to break

A

CC,CH, COH

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2
Q

in prokkary. where does glycolysis happen

A

in the cytosol

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3
Q

in euk. where does glycolysis happen

A

in the cytosol

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4
Q

where does the krebs/etc/ ox phos happen

A

in the mitochondria

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5
Q

in glycolysis you have to oxidize Cs to what

A

release energy and capture some of the energy as NADH

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6
Q

use energy in glycolysis to make what compounds

A

1,3 BPG and PEp

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7
Q

what is the first step in glycolysis and what enzyme is used

A

glucose turns to G6p with hexokinase enzyme

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8
Q

what is the second step

A

G6p turns to F6p with phosphoglucoisomerase

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9
Q

all steps involving ATP plus enolase need what

A

Mg+2

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10
Q

what is the purpose of Mg+2

A

metal ion cat. (charge shielding)
- cofactor that stabilizes ATP

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11
Q

what is hexokinase

A

adds a phosphate to glucose and it is highly exergonic
- control point

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12
Q

hexokinase has what type of fit

A

induced fit

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13
Q

how many calories do carbs have

A

4 kcal/g

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14
Q

how does Mg+2 aid in metal ion charge sheilding

A

makes the gamma phosphorous more accessible for nucleophillic attack

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15
Q

enzyme movmen tplaces ATP where

A

in close proximity to 6’ch2OH and excludes water from the active site

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16
Q

what are some key points about phosphoglucose isomerase

A

the rxn reversible
GABC
occurs through enediol intermediate

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17
Q

what are the main points of phosphofructokinase

A
  • irreversible meaning you can’t go backwh
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18
Q

what is the main control point

A

phosphofructokinase 1

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19
Q

what does aldolase do

A

lyase removes DHap to give a double bond
- the rxn is reversible

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20
Q

what are some main points of triose phosphate isomerase

A
  • reversible
  • GABC
  • occurs through enediol intermediate
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21
Q

TIM mechanism involves what enediol intermediate

A

planar transition state analong

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22
Q

what binds to TIM 155 and makes it 100 times stronger than GAP of DHAP

A

phosphoglycohydroxamate

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23
Q

does equilibirum favor DHAP or GAP

A

DHAP bc GAP is consumed in the next step this draws the reaction to the right

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24
Q

what does the TIM TPI structure show

A

alpha beta barrel fold/motif

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25
Q

what structure is this

A

triosphosphate isomerase

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26
Q

what enzyme generates the first high energy intermediate and what does it use

A

GAP3DH ( glyceraldehyde-3-phosphate dehydrogenase)
- uses inorganic phosphate Pi

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27
Q

what type of enzymes are redox enxymes

A

redox enzymes

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28
Q

what transfer do dehygrogenases do

A

hyride transfer w/ help of a redox factor

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29
Q

GAP3DH or GAPDH generates how many NADH + H+ per glucose

A

2

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30
Q

how many energy electrons are stored in NADH

A

2

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31
Q

why is nadh important to the etc

A

it can charge etc and make more atp by ox phos

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32
Q

what element is similar chemically to phosphorous (P) and can subsitutute for P in biochemical reactions

A

arsenic

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33
Q

what is the relationship between arsenic and atp

A

arsenic can disrupt atp productino through several mechanisms

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34
Q

anhydrides contain what

A

stored chemical energy

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35
Q

what is the first atp generation step

A

phosphoglycerate kinase
- does substrate level phosphorylation

36
Q

pgk is similar to what enzyme

A

hexokinase bc of inducted fit

37
Q

which reactions are thermodynamically and physically coupled

A

GAPDH and phosphoglycerate kinase

38
Q

what residue does phosohoglycerate mutase have in its active site

A

phosphohistidine phospho-his residue

39
Q

enolase is classified as what

A

lyase and its reversible

40
Q

since enolase is a lyase what does it do

A

removes H2O to give a DB

41
Q

what is considered the usain bolt of high energy compounds

A

phosphoenol pyruvate bc it has a high standard free energy hydrolysis

42
Q

loss of what from 2-pg causes a redistriubution of energy within pep

A

loss of water and it increases the delta g hydrolysis of the phosphate form from -16kj to -61.9 kj

43
Q

what is the secont atp generation step and what does it use

A

pyruvate kinase , substrate level phos

44
Q

what happens in the pyruvate kinase reaction

A
  • metal ion cat
  • phospho group transfer
  • pep transfers high energy phosphate to adp–> atp
  • slp
45
Q

what is the main function of pep

A

facilitates the generation of atp

46
Q

what is the net reactants of glycolysis

A

glucose+ 2ADP+ 2Pi+ 2NAD+

47
Q

what are the net products of glycolysis

A

2 pyruvate + 2ATP+ 2NADH+2H+ 2H2O

48
Q

is glycolysis anaerobic or aerobic

A

anaerobic meaning there is no O2 involved

49
Q

what catalysis does aldolase do

A

covalent catalysis

50
Q

what is commonly used in formation of schiff bases/imines

A

lysine

51
Q

what does aldolase provide

A

an alternate pathway through formation of a covalent adduct

52
Q

what residue is a nucleophille in aldolase

A

lysine 229 it atacks c=o of FBP

53
Q

what works as a gen base in aldolase

A

asp 33 to facilitate c3-c4
results in enamine and release of fap

54
Q

how can asp 33 work as a gen acid

A

protonates enamine to work iminium cation

55
Q

the hydrolysis of iminium cation releases what

A

DHAP

56
Q

since class 2 aldolases are found in fungi and algae and do not form a schiff base what cation is used

A

zn+2

57
Q

is class 2 aldolase less efficient or more efficient than class 1

A

less efficient

58
Q

what structures inhibit GAPDH and what does it do to glycolysis

A
  • iodoacetate/ iodoacetamide
  • Hg and heavy metals
    inhibits glycolysis
59
Q

what residue does GAPDH have

A

cysteine thiol groups

60
Q

in the GAPDH mechanism what acts a nuc and what does it form

A

cys thiol
forms thio-hemiacetal his as GB

61
Q

what does thiohemiacetal undergo

A

oxidation to acyl thioester by direct hydride transfer to NAD+

62
Q

inorganic Pi attacks what in GAPH

A

the thioester to form 1,3 BPG

63
Q

what are the 3 steps that are regulaed in glycolysis

A

1,3,20

63
Q

what are the main control points

A

hexokinase,pfk-1, pyruvate kinase

64
Q

in a diagram of glucose why is there branching

A

quick release of glucose units

65
Q

what are phosphatases

A

enzymes that remove phosphoryl groups

66
Q

phosphorylaiton can do what to enzyme activity

A

activate or inhibit it

67
Q

glycogen phosphorylase is controleed by what

A

reversible phosphorylation

68
Q

what regulation does glycogen phosphorylation have

A

allosteric regulation

69
Q

what is a negative heterotropic effector in glycogen phosphorylase

A

ATP

70
Q

what is a positive heterotropic effector in glycogen phosphorylase

A

AMP

71
Q

what is an allosteric inhibitor

A

mlcl that binds to an enzyme at a site other than the enzymes active site

72
Q

even though glycolysis is anerobic what has to be regenerated to sustain glycolysis

A

NAD+

73
Q

under aerobic glycolysis what is regenerated

A

NAD+ by etc/ox phos

74
Q

why does NAD+ have to be regenrated

A

for glycolyssis to continue so the fate of pyruvate depends on methods available to cell to do this

75
Q

what happens under anaerobic conditions

A

yeast and some bacteria convert pyruvate to ethanol and co2 to regenerate NADH–> NAD+

76
Q

what is the first step of alcoholic fermentation

A

pyruvate decarboxylase

77
Q

what does pyruv. carb. require

A

thiamine pyrophosphate (TPP) cofactor from vitamin b1(thiamine)
- from vitamin b1 thiamine

78
Q

what does TPP enable

A

decarboxylation of alpha keto acids

79
Q

deficiency in what vitamin leads to beri beri

A

vitamin b deficiency

80
Q

what is the purpose of coenzymes

A

transient carrier of specific functional groups they come from vitamins

81
Q

alcohol dehydrogenase requires what cofactor

A

ZN+2 cofactor

82
Q

since ethanol cannot be excreted it has to be

A

metabolized by ADH in the liver

83
Q

what happens if methanol was ingested

A

liver ADH converts to for,aldehyde

84
Q

what is the warburg effect

A

malignant tumors have glycolytic rates that are 200x higher than those of normal cells

85
Q

what is an isozyme

A

enzymes with the same reaction but differ in kinetics and regulation

86
Q
A

summer biochemistry jonklaas (14 decks)

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