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summer biochemistry jonklaas > glycolysis > Flashcards

glycolysis Flashcards

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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
what structure is this
triosphosphate isomerase
26
what enzyme generates the first high energy intermediate and what does it use
GAP3DH ( glyceraldehyde-3-phosphate dehydrogenase) - uses inorganic phosphate Pi
27
what type of enzymes are redox enxymes
redox enzymes
28
what transfer do dehygrogenases do
hyride transfer w/ help of a redox factor
29
GAP3DH or GAPDH generates how many NADH + H+ per glucose
2
30
how many energy electrons are stored in NADH
2
31
why is nadh important to the etc
it can charge etc and make more atp by ox phos
32
what element is similar chemically to phosphorous (P) and can subsitutute for P in biochemical reactions
arsenic
33
what is the relationship between arsenic and atp
arsenic can disrupt atp productino through several mechanisms
34
anhydrides contain what
stored chemical energy
35
what is the first atp generation step
phosphoglycerate kinase - does substrate level phosphorylation
36
pgk is similar to what enzyme
hexokinase bc of inducted fit
37
which reactions are thermodynamically and physically coupled
GAPDH and phosphoglycerate kinase
38
what residue does phosohoglycerate mutase have in its active site
phosphohistidine phospho-his residue
39
enolase is classified as what
lyase and its reversible
40
since enolase is a lyase what does it do
removes H2O to give a DB
41
what is considered the usain bolt of high energy compounds
phosphoenol pyruvate bc it has a high standard free energy hydrolysis
42
loss of what from 2-pg causes a redistriubution of energy within pep
loss of water and it increases the delta g hydrolysis of the phosphate form from -16kj to -61.9 kj
43
what is the secont atp generation step and what does it use
pyruvate kinase , substrate level phos
44
what happens in the pyruvate kinase reaction
- metal ion cat - phospho group transfer - pep transfers high energy phosphate to adp--> atp - slp
45
what is the main function of pep
facilitates the generation of atp
46
what is the net reactants of glycolysis
glucose+ 2ADP+ 2Pi+ 2NAD+
47
what are the net products of glycolysis
2 pyruvate + 2ATP+ 2NADH+2H+ 2H2O
48
is glycolysis anaerobic or aerobic
anaerobic meaning there is no O2 involved
49
what catalysis does aldolase do
covalent catalysis
50
what is commonly used in formation of schiff bases/imines
lysine
51
what does aldolase provide
an alternate pathway through formation of a covalent adduct
52
what residue is a nucleophille in aldolase
lysine 229 it atacks c=o of FBP
53
what works as a gen base in aldolase
asp 33 to facilitate c3-c4 results in enamine and release of fap
54
how can asp 33 work as a gen acid
protonates enamine to work iminium cation
55
the hydrolysis of iminium cation releases what
DHAP
56
since class 2 aldolases are found in fungi and algae and do not form a schiff base what cation is used
zn+2
57
is class 2 aldolase less efficient or more efficient than class 1
less efficient
58
what structures inhibit GAPDH and what does it do to glycolysis
- iodoacetate/ iodoacetamide - Hg and heavy metals inhibits glycolysis
59
what residue does GAPDH have
cysteine thiol groups
60
in the GAPDH mechanism what acts a nuc and what does it form
cys thiol forms thio-hemiacetal his as GB
61
what does thiohemiacetal undergo
oxidation to acyl thioester by direct hydride transfer to NAD+
62
inorganic Pi attacks what in GAPH
the thioester to form 1,3 BPG
63
what are the 3 steps that are regulaed in glycolysis
1,3,20
63
what are the main control points
hexokinase,pfk-1, pyruvate kinase
64
in a diagram of glucose why is there branching
quick release of glucose units
65
what are phosphatases
enzymes that remove phosphoryl groups
66
phosphorylaiton can do what to enzyme activity
activate or inhibit it
67
glycogen phosphorylase is controleed by what
reversible phosphorylation
68
what regulation does glycogen phosphorylation have
allosteric regulation
69
what is a negative heterotropic effector in glycogen phosphorylase
ATP
70
what is a positive heterotropic effector in glycogen phosphorylase
AMP
71
what is an allosteric inhibitor
mlcl that binds to an enzyme at a site other than the enzymes active site
72
even though glycolysis is anerobic what has to be regenerated to sustain glycolysis
NAD+
73
under aerobic glycolysis what is regenerated
NAD+ by etc/ox phos
74
why does NAD+ have to be regenrated
for glycolyssis to continue so the fate of pyruvate depends on methods available to cell to do this
75
what happens under anaerobic conditions
yeast and some bacteria convert pyruvate to ethanol and co2 to regenerate NADH--> NAD+
76
what is the first step of alcoholic fermentation
pyruvate decarboxylase
77
what does pyruv. carb. require
thiamine pyrophosphate (TPP) cofactor from vitamin b1(thiamine) - from vitamin b1 thiamine
78
what does TPP enable
decarboxylation of alpha keto acids
79
deficiency in what vitamin leads to beri beri
vitamin b deficiency
80
what is the purpose of coenzymes
transient carrier of specific functional groups they come from vitamins
81
alcohol dehydrogenase requires what cofactor
ZN+2 cofactor
82
since ethanol cannot be excreted it has to be
metabolized by ADH in the liver
83
what happens if methanol was ingested
liver ADH converts to for,aldehyde
84
what is the warburg effect
malignant tumors have glycolytic rates that are 200x higher than those of normal cells
85
what is an isozyme
enzymes with the same reaction but differ in kinetics and regulation
86

summer biochemistry jonklaas (14 decks)

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