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Test 2 Cards Schempke
Eek
215
Biochemistry
Graduate
02/21/2011

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Term
Synthesis or degradation of molecules involves a change in what?
Definition
Energy
Term
Thermodynamics
Definition
Study of the energy changes
Term
What determines direction of a reaction?
Definition
Free energy, delta G (G prod-Greact)
Term
Gibbs Free Energy equation
Definition
DeltaG=DeltaH -TDeltaS
Term
DeltaG' (o)
Definition
Under very artificial conditions
25 degreesC,
All reactants/product @ [1M]
ph=7
Term
What is Delta G' useful for?
Definition
When comparing 2 or 3 reactions
Term
If energy cannot be created or destroyed, what happens when - free energy?
Definition
Released in the form of heat or work
Term
Delta G an also =
Definition
Q+W (heat+work)
Term
Work can be
Definition
Motion, formation, [gradient], chemical work, etc.
Term
Second law of thermodynamics
Definition
For any reaction or process, then enropy of the universe increases
Term
Entropy Equations
Definition
DeltaSuniv=Sfinal-Sinitial (>0)
DeltaSuniv=DeltaSsystem+DeltaSsurrounding
Term
According to the second law of thermodynamics, can cells decrease their entropy?
Definition
Yes, only if their surroundings increase entropy by a greater extent
Term
What drives diffusion by concentration gradient?
Definition
Entropy
Term
If gibbs free energy is -
Definition
Energy decreases, favorable reaction, spontaneous.
Exergonic reaction
Term
Gibbs free energy is +
Definition
Energy is absorbed by the reaction,
+ deltaG
Endergonic reaction
Doesn't occur
Term
Does a -33 reaction proceed faster than a -16 reaction?
Definition
Not necessarily, just know it is spontaneous
Term
DeltaG and the equilibrium constant:
Definition
DeltaG=DeltaG'+RTln([C]^c[D]^d)/([A]^a[B]^b)
Term
What is deltaG @ equilibrium?
Definition
Term
DeltaG'=
Equation
Definition
RT*lnKeq
Term
The farther the reaction is from equilibrium, what is deltaG?
Definition
Low, (larger A,B values)
Term
Values of deltaG and deltaG' when system NOT @ equilibrium?
Definition
Not equal. Farther from equilibrium = more - reaction
Term
Coupled reactions
Definition
Occur simultaneously
One endergonic and exergonic
Term
What "drives" coupled reactions?
Definition
Negative -G of summed reactions.
Term
What compounds can transfer phosphate's?
Definition
Compound w/ more - deltag(hydrolysis) can transfer to a one w/ more +
Term
What compounds (specific) can add P+ADP=ATP
Definition
PEP, 1,3 BPG, Phosphocreatine,and phosphoarg
Term
What compounds CANT (specific) can add P+ADP=ATP
Definition
Glucose 1 P; Glucose 6 P; Glycerol 3 P
Term
High energy compounds and phosphate transfer
Definition
Want to transfer Pi; down hill
Term
Low energy compounds and phosphate transfer
Definition
Don't donate phosphate, uphill
Term
What provides free energy to drive most endergonic reactions?
Definition
Hydrolysis of ATP->ADP+P
Term
What is the primary energy currency of cells?
Definition
ATP
Term
Catabolism
Definition
Degredation of nutrients, releases energy which is captured and stored as ATP
Term
What happens in catabolism?
Definition
releases energy which is captured and stored as ATP
Term
Anabolism
Definition
Building up of nutrients (biosynthesis) ; Uses energy of ATP to do transport and mechanical work
Term
What happens during anabolism?
Definition
Uses energy of ATP to do transport and mechanical work
Term
Metabolism definition
Definition
Set of all reaction used by living organism to break down molecules necessary for energy (catabolism) and synthesize biomolecules from simple precursors (anabolism)
Term
What type of reaction is catabolism?
Definition
Exergonic
Term
What is characteristic of catabolism?
Definition
Oxidation, Hydrolysis, and conversion of biomolecules ->CO2, H20, and NH3 (urea)
Term
Energy released from oxidation is stored how?
Definition
NADH, NADPH, ATP
Term
What type of reaction is anabolism?
Definition
Endergonic
Term
What characterizes anabolism?
Definition
Reduction, Hydration, Conversion of small molecules to complex biomolecules
Term
How is energy for anabolism supplied?
Definition
NADH, NADPH, ATP
Term
Different forms of metabolic pathways:
Definition
Cyclic; linear; Spiral; Reversible
Term
Overall DeltaG (for multi-step)
Definition
Sum of delta G for each step
Term
What could multiple steps mean for energy?
Definition
Small amounts of free energy change in each step. More feasible biological systems.
Term
Good example of many steps, small change:
Definition
Ethanol->Acetyl CoA
Term
Ehtanol oxidized to acetyl reaction
Definition
Ethanol->Acetaldyhyde->Acetate->Acetyl CoA
Term
What oxidizes nutrients in catabolism?
Definition
NAD+; FAD+
Term
NADH and FADH2 in catabolism
Definition
Reduced factors
Store energy
Term
What happens when reduced cofactors are oxidized?
Definition
Released energy is used to form ATP
Term
What are small molecules converted to in anabolism?
Definition
Larger, more energy rich products
Term
What supplies energy to anabolism?
Definition
ATP
Term
Reducing equivalents in anabolism?
Definition
NADPH
Term
NAD/NADH ratio
Definition
100/1
NAD+ Necessary for catabolism
Term
NADP/NADPH
Definition
1/100
NADPH necessary for anabolism
Term
ATP/(ADP+AMP) Ratio
Definition
4/1
ATP required for anabolism and other energy requiring rxns
Term
Major carb pathway:
Definition
Glucose->Phosphoenolpyruvate->2pyruvate->Acetyl CoA-> Citric acid cycle.
Term
Is glucose->phosphoenolPyruvate reaversible?
Definition
Yes. Depending on the needs of the cell
Term
Gluconeogenesis
Definition
Synthesis of glucose
Term
Where does gluconeogenesis occur?
Definition
Liver cells only
Term
What cells can convert glucose->cycle?
Definition
All cells
Term
What cells use energy as an energy source?
Definition
All cells
Term
What cell can ONLY use glucose as an energy source?
Definition
RBC-only glucose
Neuron- prefer glucose; can use others
Term
Glycolysis
Definition
Anaerobic oxidation of glucose to give two molecules of pyruvate and chemical energy in the form of ATP and NADH
Term
GLycolysis Reaction
Definition
Glucose+ 2ATP+ 2P+ 2NAD+->
2 pyruvate+2ATP+ 2NADH+ H2O+ 2H+
Term
What type of reaction is glycolysis?
Thermodynamicly and Oxygen requirement
Definition
Exergonic
Anerobic
Term
What helps make glucose more reactive in glycolysis?
Definition
ATP
Term
Stages 1 and 2 of glycolysis?
Definition
Energy input
Energy output
Term
How is energy released in glycolysis stage 2?
Definition
As G3P converted to pyruvate.
Term
What is the 1st step of glycolysis?
Definition
Glucose+ATP->Glucose 6 phosphate+ADP
Term
Why is glucose converted to glucose 6 phosphate?
Definition
Glucose 6 phosphate cannot get out of the cell
Term
What enzyme catalyzes Glucose->Glucose 6 phos?
Definition
Hexokinase; glucokinase
Term
What is the second step of glycolysis?
Definition
Glucose 6 phos==Fructose 6 phos
Term
What is the enzyme for the second step of glycolysis?
Definition
Glucose 6 phosphate isomerase
Term
Step 3 of glycolysis
Definition
Add another phospho group to molecule
Fructose 6 phos-> Fructose 1,6 biphos
Term
Enzyme for 3rd step of glycolysis?
Definition
Fructo-kinase 1
Term
What is the committed step in stage 1 of glycolysis?
Definition
3rd step.Fructose 1,6 Bisphos is formed
Term
What regulates PFK-1?
Definition
Allosteric effectors
Term
Reaction @ PFK-1
Definition
Irreversible
Term
Glycolysis step 4
Definition
Fructose 1,6 Bisphos cleaved to form Dihydroxy-acetone and glyceraldehyde
Term
Step 4 of glycolysis begins what?
Definition
First step of energy out stage
Term
Enzyme in fourth step of glycolysis?
Definition
Aldose
Term
Glycolysis Step 5
Definition
Interconversion of dihydroxyacetone to glyceraldehyde (from previous)
Term
Enzyme for step 5 of glycolysis
Definition
Triose phosphate isomerase
Term
What happens after step 5?
Definition
2 glyceraldehyde molecules.
Each reaction happens 2 times :)
Term
Reaction 6 of glycolysis (overall)
Definition
phosphorylate G3P to form 1,3 Bisphosphoglycerate
Term
What enzyme is used in step 6 of glycolysis?
Definition
Glyceraldehyde 3 phosphate dehydrogenase
Term
What two things happen in reaction 6 of glycolysis?
Definition
Phosphorylation and Electron oxidation
Term
Detail Reaction 6 of glycolysis?
Definition
G3p+NAD+H2O->3 phosphoglycerate +NADH -43
3 phosphoglycerate + P->1,3 bisphosphoglycerate (+49.3)
Term
What does G3P stand for?
Definition
Glyceraldehyde 3 phosphate formed in 4/5
Term
Step 7 of glycolysis?
Definition
1,3 bisphosphoglycerate->3 phosphoglycerate
Term
What happens for the first time in reaction 7?
Definition
Transfer of a high energy phosphoryl group
ADP->ATP
Term
What is the enzyme for reaction 7?
Definition
Phosphoroglycerate kinase
Term
Glycolysis step 8
Definition
Intramolecular phosphoryl group transfer
3 phosphoglycerate->2phosphoglycerate
Term
Enzyme for reaction 8 of glycolysis?
Definition
Phosphoglycerate mutase
Term
Glycolysis step 9
Definition
Dehydration to form energy rich ester
2 phosphoglycerate->phosphoenol pyruvate
Term
Reaction 9 enzyme?
Definition
Enolase
Term
Glycolysis step 10
Definition
Transfer of a high energy P group to ADP to yield ATP
Phosphoenol pyruvate->Pyruvate
Term
Enzyme of reaction 10 of glycolysis
Definition
Pyruvate kinase
Term
Fates of pyruvate:
Definition
Conterted to ethanol (yeasts, alc. ferm)
Lactate (in RBC and anaerobic musc.)
Oxaloacetate (TXA- substrate for gluconeogenesis)
Term
Energy of pyruvate
Definition
High energy
Term
What can cells with mitochondria do to pyruvate?
Definition
Extract energy from it by converting it to acetyl CoA
Term
Pyruvate fermintation reaction:
Definition
Pyruvate->L-lactate via lactate dehydrogenase
Converts NADH->NAD
Term
Where does pyruvate fermentation occur?
Definition
Cells w/ no mitochondria.
Ex. RBC or anaerobically muscle cells
Term
Where does NADH->NAD usually occur?
Definition
Mitochondria (ox/phos)
Term
Why does lactic acid make muscles sure?
Definition
Acidic, inflammation
Term
What converts pyruvate to ethanol?
Definition
Yeasts
Term
How do yeasts convert pyruvate -> ehtanol
Definition
Pyruvate decarboxylase->Acetyl aldehyde
Alcohol dehydrogenase ->ethanol
Term
Where is pyruvate decarboxylase found?
Definition
Only in bacteria and yeasts, if we had it we could hold our breath and get drunk ;)
Term
How do you make 2,3 BPG for RBC?
Definition
You take 1,3 BPG from step 6 and you use enzyme BPG mutase and get 2,3 BPG
Term
ATP production of glycolysis (Stage 1, Stage2)
Definition
2 steps in stage 1 use ATP
gluctose->Glucose 6 phos
Fructose 6 p->1,6 bisphos
2 steps produce ATP in stage 3
Glycerate 1,3 bisP to 3-P glycerate
PEP to pyruvate
Net result=2 ATP/glucose
Term
Which steps of glycolysis are irreversible?
Definition
1,3,10
Significantly negative delta G values
Term
Overall glycolysis is endergonic or exergoinic?
Definition
Exergonic
Term
Where are the primary sites of regulation in glycolysis?
Definition
Irreversible reactions. 1,3,10
Term
Regulation of glycolysis
Definition
3 allosteric enzymes
Hexokinase
PFK-1
Pyruvate Kinase
Term
Hexokinase
Definition
Step 1
Inhibitor is Glucose 6 phos, ATP
No activator
Term
PFK-1
Definition
Step 3
Activated by F2,5 bp, AMP
Inhibitied by Citrate, ATP
Term
Pyruvate kinase
Definition
Step 10
Activated by F,1-6 BP, AMP
Inhibitied by Acetyl CoA; ATP
Term
What can generate acetyl CoA?
Definition
Many nutrients
Protein, Triglyceride, Glycogen
Term
Where does oxidation of acetyl CoA occur?
Definition
Mitochondria
Term
What does oxidation of acetyl CoA provide?
Definition
Vast majority of energy for aerobic cells
Term
PDH
Definition
Pyruvate Dehydrogenase
Term
What does pyruvate dehydrogenase do?
Definition
Takes pyruvate->Acetyl
Reduces NAD->NADH also
Term
Required cofactors for PDH
Definition
Thiamine pyrophosphate (TPP)
Lipoamine
FAD/FADH2
Coenzyme A (carries acetyl)
NAD/NADH (carries reducing equivalent)
Term
Coenzyme A contains what subgroups
Definition
2 mercaptoethylamine, Pantothenate, ADP w/ 3' phosphate group.
Term
How is CoA often written, why?
Definition
As CoA-SH. All the chemistry happens @ SH group
Term
Where is the high energy bond in acetyl CoA?
Definition
Thio-ester bond which connects the two structures
Term
Role of Coenzyme A?
Definition
Carries acetyl group
Term
Role of NAD in PDH cofactors?
Definition
Carries reducing equivalents
Term
Purpose of TPP as a PDH cofactor?
Definition
Chemistry takes place at the R group.
A possible R group, hydroxy ethyl, comes from pyruvate
Term
Function of Lipoamide as a PDH cofactor?
Definition
2 carbon fragment transferred here. Oxidation reaction. Reduced agent if Flavin (FAD->FADH2)
2 forms
Term
Lipoamide oxidized form?
Definition
Disulfide bond
Term
Lipoamide Reduced form?
Definition
SH bond
Term
FAD as cofactor for PDH?
Definition
Reduces to FADH2 as the oxidation reaction occurs @ the lipoamide. Puts enzayme back into reduced form
Term
What are the 3 enzymes present in the reaction cataylzed by PDH?
Definition
PDH
Dihyrolipoamide Acetyl transferase
Dihyrolipoamide dehydrogenase
Term
What is the structure of pyruvate referred to as?
Definition
Alpha Keto acid
Term
What is the function of NAD in PDH?
Definition
Takes enzyme back to origonal form by reducing FADH->FAD
Term
UQH2/U2 is similar to what?
Definition
NADH2/NAD
Term
UQ and NAD motility
Definition
Diffusable redox reactions
Term
FAD FMN motility?
Definition
Enzyme bound. Non mobile
Term
Difference between UQ and NAD?
Definition
UQ-insoluble. Only some membranes
NAD- soluble.
Term
When FAD/FADH2 oxidized?
Definition
FADH2
Term
NADH/NAD oxidized/reduced??
Definition
Reduced is NADH (NADPH)
Oxidized is NAD (NADP)
Term
Where does glycolysis occur?
Definition
Cytosol of most cells
Term
First step of TCA cycle?
Definition
Pyruvate->Acetyl
Term
Where do products of PDH go?
Definition
Mitochondria, cannot leave there
Term
Product that leaves mitochondria just before start of TCA cycle?
Definition
Acetyl CoA
Term
What is the primary use of NADH?
Definition
Energy Production
Term
What is the primary use of acetyl CoA
Definition
Energy Production
Term
How is the activity of the PDH controlled?
Definition
By availability of pyruvate;
rate of product use (energy status of the cell)
Term
How is energy status of the cell determined?
Definition
NADH/NAD ratio (High=High energy)
ATP/ADP ratio (high= high energy)
Term
NADH and ATP are
Definition
Directly linked. High NADH=High ATP
Term
How is PDH activity regulated?
Definition
Allosteric regulation
Phosphorylation
Term
What does acetyl CoA have negative feedback on?
Definition
Dihydroliponamide acetyltransferase
Term
In regulation of PDH what does NADH have negative feedback on?
Definition
Dihydrolipoamide dehydrogenase
Term
in regulation of PDH what does NAD have positive feedback on?
Definition
Dihydrolioamide dehydrogenase
Term
In regulation of PDH what does HS-CoA have feedbackon?
Definition
Positive feedback, Dihydroliponamde acetyltransferase.
Term
What do you have lots of if you are starved for energy?
Definition
NAD+
Term
What type of metabolic pathway is the TCA cycle?
Definition
Cyclic
Term
How does the TCA cycle form citrate?
Definition
Combining acetyl CoA and oxaloacetate
Term
What reduction reactions happen in the TCA cycle?
Definition
3NAD+->NADH
Uq->UQH2
GDP->GTP
Term
In what organisms is the TCA cycle found?
Definition
Mostly aerobic organisms
Term
Mutations in the TCA cycle?
Definition
Few known, but they indicate critical function.
Term
Citrate re-arranges when?
Definition
After it's formed to make isocitrate
Term
What happens to isocitrate in TCA cycle?
Definition
It is oxidized to alpha keto glutarate
Term
What oxidizes isocitrate?
Definition
Isocitrase dehyrogenase
Term
Where does the first CO2 come off in the TCA cycle?
Definition
After oxidation of isocitrate.
Term
When does the second oxidation reaction occur?
Definition
4. alpha keto glutarate->Succinyl CoA
Term
Alphaketoglutarate is oxidized and combines w/ what?
Definition
CoA group. Forms succinyl CoA
Term
Alphaketohydrogenase is similar to what?
Definition
PDH.
Same cofactors. B/c molecules are same class.
Term
Where does second carbon leave?
Definition
@ second oxidation. Oxidation of alphaketoglutarate
Term
Thio-ester bond in succinyl coA?
Definition
High energy bond, just like acetyl
Term
What is hydrolysis of thio-ester bond associated with in the TCA cycle?
Definition
High energy bond. Forms energy for GDP->GTP
Term
Substrate level phosphorylation in TCA cycle?
Definition
GDP->GTP
Term
What reaction does succinyl CoA undergo in TCA cycle?
Definition
Succinyl CoA synthetase oxidizes it.
FAD as cofactor
Term
What is cofactor of Succinate dehydrogenase complex in TCA cycle?
Definition
FAD as cofactor
Term
What does succinyl CoA synthetase do?
Definition
Succinyl CoA -> Succinate
Via substrate level phosphorylation
Release Hs-CoA
Term
Succinate dehydrogenase complex in TCA cycle?
Definition
Succinate->Fumarate
Term
Fumarase in TCA cycle?
Definition
Fumarate-> L-maleate
Term
Maleate dehydrogenase in TCA cycle?
Definition
Maleate -> Oxaloacetate
Oxidation. NOT decarboxylation
Term
What happens to the reduced cofactors of the TCA cycle?
Definition
They enter the ox/phos pathway
Term
Why does NADH goes to ETC?
Definition
To get oxidized back to NAD, so the TCA cycle can function
Term
Final reactions of ETC?
Definition
H2O and water?
Term
If no oxygen present, what happens to ETC?
Definition
No function
NADH can't get oxidized back to NAD
Term
What is the TCA cycle coupled to?
Definition
ETC
Term
Exergonic reactions of TCA cycle?
Definition
Acetyl->Citrate
Isocitrate->Alphaketoglutarate
Alphaketoglutarate->Succinyl Coa
Term
Which reactions in the TCA cycle are irreversible?
Definition
1,3,4
Release CO2
Exergonic ones
Term
Which reactions are sites of regulation in TCA cycle?
Enzymes?
Definition
1,3,4
1.Citrate synthase
2.Isocitrate dehydrogenase
3.Alphaketoglutarate dehydrogenase complex
Term
What reactions drives the TCA cycle
Definition
1,3,4
Term
Other reactions we need to know:
Definition
5,6,8
Syccinyl-CoA synthetase
Succinate dehydrogenase complex
Malate dehydrogenase
Term
Succinate dehydrogenase Reaction
Definition
Oxidized succinate to fumerate
Complex 2 of the ETC
Term
Succinate dehydrogenase enzyme location
Definition
Membrane bound enzyme (inner membrane of the mitochondria)
Term
Succinate dehydrogenase enzyme function
Definition
Takes reducing equiv. of succinate->FAD->QH2
QH2 released. Donate e- to rest of ETC
Term
Thio-ester high energy bond in the succinyl CoA synthetase provides energy for what?
Definition
Substrate level phosphorylation
Term
Malate dehydrogenase DeltaG'
Definition
Positive
Term
What is Delta Gactual of Malate dehydrogenase in cell?
Definition
Close to zero because the NAD/NADH ratio is >>0.
Term
Overall Delta G' for TCA cycle?
Definition
-13.1 kcal/mol;-54.7 kj/mol
Term
Since the Delta G of TCA is negative what happens?
Definition
Releases energy as heat
Stores energy as NADH; FADH2; GTP
Term
What forms of energy storage are created by TCA cycle?
Definition
GTP; NADH; FADH2
Term
Other function of the TCA cycle?
Definition
Intermediates for TCA cycle can be used as precursors for other metabolic pathways.
Term
What substrates can be exported from TCA cycle?
Definition
Citrate
Alphaketoglutarate
Succinyl CoA
Axaloacetate (gluconeogenesis)
Term
What happens to TCA cycle when TCA cycle intermediates leave?
Definition
Depletes oxaloacetate.
Can eventually limit TCA cycle.
Term
If oxaloacetate is low enough that TCA cycle is limited, what kind of energy state is the cell in?
Definition
The cell is at a lower state of energy, so it doesn't need the TCA cycle. However, it can have a sudden need.
Term
What happens if the cell needs energy quickly and not enough oxaloacetate?
Definition
Run in reverse, to get oxaloacetate.
Most important reaction is the first one (pyruvate+co2) make oxaloacetate
Term
Pyruvate carboxylase
Definition
Catalyzes Pyruvate+Bicarb=oxaloacetate
Term
Anaplerotic Reaction
Definition
Reaction running in reverse to get necessary products to form reaction
Term
Most important Anaplerotic Reaction?
Definition
Pyruvate Carboxylase
Term
What stimulates pyruvate carboxylase reaction?
Definition
Acetyl CoA
Term
Where in the body can pyruvate carboxylase be found?
Definition
High levels in the liver and neruon mitochondria.
Term
Function of pyruvate carboxylase?
Definition
To decrease the number of intermediates in the TCA cycle to allow it to function @ maximum level.
Term
Regulation of TCA cycle
Definition
Primarily by the energy state of teh cell
NADH/NAD
ATP/ADP ratios= high=high energy (low reactivity)
Term
Glycolysis ATP numbers
Definition
7 total (5 NADH, 2 ATP)
Term
Pyruvate->Acetyl ATP
Definition
5 (2 NADH)
Term
TCA cycle
Definition
2 GDP/ATP;6nadh (15ATP)
2QH2=3 ATP
TOtal: 20 ATP (18NADH,2ATP)
Term
Total ATP from one Glucose
Definition
32
28 from NADH
Term
If the ETC is not working, how many ATP/glucose?
Definition
4
2 from glycolysis
2 from CAC
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