Unit Three Flashcards
what is a regulatory enzyme
regulatory enzymes increase or decrease catalytic activity in a biochemical mechanism in response to certain signals. Activities of regulatory enzymes are modified in a number of different ways: allosteric enzymes, reversible covalent modification, binding of separate regulatory proteins, removal of peptide segments by proteolytic cleavage
what kinetic behavior is displayed by regulatory enzymes?
How is ATCase regulated?
aspartate transcarbamoylase (ATCase) catalyzes the formation of carbamoyl aspartate. It is an allosteric enzyme made up of 12 subunits.
ATP: positive regulator: if ATP levels are high the cell is very metabolically active, high concentrations of ATP result in the R state. The effects of ATP overpower the effects of CTP
CTP: negative regulator: in high concentration of CTP, enzyme activity is low (T-state). In low concentrations of CTP enzyme activity is high (R-state)
what are positive and negative allosteric modulators
positive modulator: acts as an activator. These increase enzyme activity through a process called positive inhibition
negative modulator: act as inhibitors. Inactivates the enzyme in a process called negative feedback
how does covalent modification modulate enzyme activity
In covalent modification, a functional group is transferred from one molecule onto the enzyme or protein, thereby turning the enzyme either on or off. (phosphorylation)
what is a v modulator
a modulator that changes Vmax but K0.5 dremains constant
what is a K0.5 modulator
a modulator that changes K0.5 but Vmax remains constant
how is glycogen phosphorylase regulated and what type of modulation is present
controlled through the phosphorylation state. Glycogen phosphorylase is activated when it is phosphorylated (favors production of glucose 1-phosphate.)
Phosphorylase a: exists predominantly in the more active state (R state)
Phosphorylase b: exists predominantly in the less active state (T state)
phosphorylase kinase will convert phosphorylase b to phosphorylase a by phosphorylating certain serine amino acids, but energy input is needed for this.
when a cell has a low concentration of ATP compared to AMP, AMP acts as an allosteric activator of phosphorylase b. AMP will bind to it and shift the equilibrium towards the R state
what are zymogens (proenzyme)
inactive enzyme precursors that can be converted into active enzymes. The activation usually occurs via cleavage of peptide bonds. An energy source is NOT needed for the activation process
how does proteolytic modulation work? what does this look like on chymotrypsin?
Chymotrypsin originally synthesized as a zymogen in our pancreas (chymotrypsinogen). Trypsin cleaves a peptide bond, which creates pi-chymotrypsin. When pi-chymotrypsin reacts with another pi-chymotrypsin another peptide bond is cleaved, which creates chymotrypsin (active and ready to digest)
what is a kinase
an enzyme that catalyzes the transfer of a phosphate group from ATP to a specified molecule.
i.e. a kinase adds a phosphate group
what is phosphatase
a phosphatase is an enzyme that uses water to cleave a phosphoric acid monoester into a phosphate ion and an alcohol.
i.e. a phosphatase cleaves a phosphate group
what it is a proenzyme
any of a group of proteins that display no catalytic activity but are transformed within an organism into enzymes, especially those that catalyze reactions involving the breakdown of proteins.
what is a proprotein
an inactive protein that must have part of its sequence removed to become an active protein. e.g. proinsulin
what is the difference between and aldose and a ketose
Aldose: contains one aldehyde per molecule, they tend to isomerize into ketoses
Ketose: contains one ketone group per molecule. They can isomerize into aldoses only if the carbonyl group is at the end of the chain ( I think they have to be in the presence of a base). Contains less stereoisomers than aldoses
what is the difference between enantiomers, diastereomers, epimers, and anomers
enantiomers: mirror images
diastereomers: pairs of isomers that have opposite configurations at one or more chiral centers but they are NOT mirror images
epimers: two sugars that differ in configuration at only ONE chiral center
anomers: stereoisomers that differ in the configuration at the anomeric carbon
what is an anomer and what is the difference between alpha and beta
the anomeric carbon is when the former carbonyl oxygen becomes a hydroxyl group in the cyclization of a carbohydrate. If the hydroxyl group is on the opposite side (trans) of the ring the configuration is alpha. If it is cis of the ring as the CH2OH is it beta configuration
why is equatorial group distribution in a cyclic structure more abundant and how does this correlate to the carbohydrates most abundantly found in nature
All hydroxyl groups in beta-D-glucose are equatorial.
alpha-D-glucose has the anomeric hydroxyl in axial position (less stable)
The beta anomer predominates because all groups lie along the less hindered side (larger groups point away from each other leading to less steric hinderance)
what reaction leads to the formation of cyclic structures and the reaction for disaccharides/polymers
when aldehydes or ketones are attacked by alcohol the reaction forms the basis of cyclization of sugars
aldehydes form hemiacetals and ketones form hemiketals
what is the process for naming glycosidic links
1) Give configuration (a or B) of anomeric carbon joining first unit (left) to right unit
2) Name nonreducing residue first
3) use parentheses to indicate at which carbon the bond is connected on each saccharide
4) Name the second residue
what determines if something is a reducing sugar, what does this mean
A reducing sugar is one that has a free hemiacetal at the anomeric carbon or a free aldehyde/ketone that can react to reduce something else
what chemical changes can carbohydrates have, what is the effect of each modification
phosphorylation: oxidation for energy. Common in glycolydic pathway. It creates a weaker base and stronger leaving group
amination: Replaces a hydroxyl group with an amino group. This makes a better nucleophile
reduction of carbonyl carbon: Redox reaction that results in an alcohol
oxidation of aldehyde: results in aldonic acid
oxidation of primary alcohol: results in uronic acid
(know the difference between aldonic and uronic acid)
deoxy sugars: reduction of a hydroxyl group to hydrogen on second carbon (RNA –> DNA)
what sugars make lactose, sucrose, and maltose. What are the chemical differences between them?
Lactose is made by one galactose and glucose molecule
Sucrose is made by glucose and fructose
Maltose is made by two units of glucose
comparison table of all the polysacharides