Unit Three Flashcards

1
Q

what is a regulatory enzyme

A

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

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2
Q

what kinetic behavior is displayed by regulatory enzymes?

A
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3
Q

How is ATCase regulated?

A

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)

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4
Q

what are positive and negative allosteric modulators

A

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

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5
Q

how does covalent modification modulate enzyme activity

A

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)

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6
Q

what is a v modulator

A

a modulator that changes Vmax but K0.5 dremains constant

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7
Q

what is a K0.5 modulator

A

a modulator that changes K0.5 but Vmax remains constant

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8
Q

how is glycogen phosphorylase regulated and what type of modulation is present

A

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

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9
Q

what are zymogens (proenzyme)

A

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

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10
Q

how does proteolytic modulation work? what does this look like on chymotrypsin?

A

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)

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11
Q

what is a kinase

A

an enzyme that catalyzes the transfer of a phosphate group from ATP to a specified molecule.

i.e. a kinase adds a phosphate group

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12
Q

what is phosphatase

A

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

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13
Q

what it is a proenzyme

A

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.

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14
Q

what is a proprotein

A

an inactive protein that must have part of its sequence removed to become an active protein. e.g. proinsulin

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15
Q

what is the difference between and aldose and a ketose

A

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

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16
Q

what is the difference between enantiomers, diastereomers, epimers, and anomers

A

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

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17
Q

what is an anomer and what is the difference between alpha and beta

A

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

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18
Q

why is equatorial group distribution in a cyclic structure more abundant and how does this correlate to the carbohydrates most abundantly found in nature

A

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)

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19
Q

what reaction leads to the formation of cyclic structures and the reaction for disaccharides/polymers

A

when aldehydes or ketones are attacked by alcohol the reaction forms the basis of cyclization of sugars
aldehydes form hemiacetals and ketones form hemiketals

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20
Q

what is the process for naming glycosidic links

A

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

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21
Q

what determines if something is a reducing sugar, what does this mean

A

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

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22
Q

what chemical changes can carbohydrates have, what is the effect of each modification

A

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)

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23
Q

what sugars make lactose, sucrose, and maltose. What are the chemical differences between them?

A

Lactose is made by one galactose and glucose molecule

Sucrose is made by glucose and fructose

Maltose is made by two units of glucose

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24
Q

comparison table of all the polysacharides

A
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25
why is the storage of carbohydrates done in the polymeric form
polymerization prevents significant changes in concentration gradient of osmotic pressure.
26
what are 5 nucleosides and nucleotides
27
what are the structures of the 5 nucleotides and nucleosides
28
what nitrogenous bases can be found in DNA and which ones are in RNA
29
what happens to melting temperature in different solution conditions
30
what three things stabilize the double helix
1. Stacking of nitrogenous bases --> creates hydrophobic effect which contributes to 55% of the stability 2. Metal Cation 3. Hydrogen bonding with complementary nitrogenous base --> contributes 45% of the stablility
31
how are the polymers of nucleic acids are formed
phosphodiester linkages (please double check me on this I think its right but im not sure)
32
what are the fundamental principles or PCR
33
what does RNA have greater functional diversity and is less stable than DNA
because it has ribose rather than deoxyribose, meaning it has an extra OH group available for/more susceptible to hydrolysis (might want to double check me on this just off the dome -Ant)
34
how do you name the chemical bonds formed in nucleotides and nucleic acids
35
what are the main lipid categories
triacylglycerols (also known as triglycerides) phospholipids sterols
36
how do you name and draw fatty acids using delta and omega nomenclature
37
what are the general functions of omega-6 and omega-3 fatty acids in your body
omega 6: pro-inflammatory (e.g. eggs, canola oil) omega 3: anti inflammatory (e.g. fish, olive oil)
38
what are the building blocks of storage lipids
triglycerides are the storage lipids and they are comprised 3 fatty acids linked to glycerol via ester linkages
39
what are the definitions of fat and oil for storage lipids
fat : saturated oil : unsaturated
40
what are the advantages of storing energy in this form for storage lipids
Fatty acids carry more energy per carbon because they are more reduced. Fatty acids carry less water per gram because they are non polar. thus, fats are better for storage of energy compared to polysaccharides
41
what is the melting temp for storage lipids, predict and explain how fatty acid composition can change melting temp
melting point decreases as the chain length decreases melting point decreases as the number of 2x bonds increases (2x bonds easier to break in this case bc they take up more space and can’t be packed as tightly and thus don’t have as many h bonds/other intramolecular forces holding the chains together)
42
what are the different classifications of membrane lipids
phospholipids, sterols, glycolipids
43
what are the building blocks for different types of membrane lipids
Phospholipids: Glycerophospholipids and sphingolipids Glycolipids: Sphingolipids and Galactolipids (AKA sulfolipids) Sterols: polar head group, steroid nucleus (4 fused rings), alkyl side chain
44
how do different membrane lipids form and the effect of cholesterol on membrane fluidity
Glycer
45
what are sterols
A type of membrane lipid composed of a steroid nucleus (four fused rings) Contains a polar head (hydroxyl group) in the A ring of the tetracyclic structure Has various non polar alkyl side chains
46
what does cholesterol look like and what is its function
Cholesterol is a sterol so it has a tetracyclic structure with a polar (hydroxyl group) head in the A ring and a non polar alkyl side chain stemming from the D ring Sterols -modulate fluidity and permeability -thicken the plasma membrane to ______ Mammals obtain cholesterol from food or synthesize it de novo in the liver In most bacteria, sterols are not present
47
what is the function of sterols as hormones
- Metabolism control - Water and salt regulation - Sexual Development
48
what is the function of sterols as vitamins
When your body digests plant sterols instead of cholesterol, it removes some of the cholesterol as waste. This results in lower cholesterol levels and improved health. this is the best I can find
49
which vitamins are lipid soluble
A, D, K, E because they are soluble in organic solvents and are absorbed and transported in a manner similar to that of fats. They contain a polar structure that allows them to embed themselves within the membrane
50
what is the general function of vitamin K in our body
coenzyme involved in prothrombin activation, leading to blood clotting (deactivation of signaling cascade for blood clotting)
51
what is the general function of vitamin A in our body
hormone precursor aides in vision
52
what is the general function of vitamin D in our body
hormone precursor synthesized from cholesterol and regulates calcium metabolism
53
what is the general function of vitamin E in our body
it is found in membranes of our cells. Prevents oxidative damage to membranes of cells (antioxidants) Lipid soluble vitamin, contains non polar structure allowing it to embed itself in the membrane
54
structure and role of starch
a mixture of amylose and amylopectin main storage polysaccharide in plants forms a helical structure- we can use iodine to identify starches because it fits well between the helical structures
55
structure and role of amylose
unbranched polymer of glucose with alpha 1-4 linked residues one of the homopolysaccharides found in starch
56
structure, role, size, etc. of amylopectin
homopolysaccharide of glucose branch points with alpha 1-6 bonds occur every 24-30 residues one of the structures in starch
57
structure, role, size, etc. of glycogen
Type: homopolysaccharide Size: up to 50,000 monosaccharide units; molecular weight reaches several millions Role: energy storage in bacteria and animal cells form alpha 1-4 linked chains. There are branch points with alpha 1-6 links every 8-12 residues digestion takes places from every non-reducing end
58
structure, role, size, etc. of cellulose
linear homopolysaccharide of glucose (up to 15,000 monomers) Glucose monomers form beta 1-4 linked chains. The beta 1-4 linkage is why out body can't digest cellulose, lack enzyme to hydrolyze it. Hydrogen bonds form between adjacent monomers and there are additional H bonds between chains. Abundance of of H bonds with other carbs (not water) is what makes cellulose insoluble The structure is tough and water insoluble this makes it a difficult substrate to act upon most abundant polysaccharide in nature it does not contain many glycogens fungi, bacteria, and protozoa secrete cellulase, which allows them to use wood as source of glucose. Ruminants and termites live symbiotically with mircoorganisms that produce cellulase and are able to absorb the freed glucose into their bloodstreams
59
what are proteoglycans
type of glycoconjugate: sulfated glucosaminoglycans attached to a large rod-shaped protein in cell membrane the nature of the sugar is what differentiates this from a glycoprotein. They are negatively charged due to presence of sulfate and uronic acid groups function in cell to cell interaction and regulate cell growth soluble in extracellular environment but anchored to the molecule Syndecans: protein has a single transmembrane domain Glypicans: protein is anchored to a lipid membrane
60
what are glycoconjugates
a protein or lipid with small oligosaccharides attached (covalently attached) these include glycoproteins, glycolipids, and proteoglycans. Functions of the oligosaccharides include: Structural: - hydrophilic (protein surface) - limit conformations Reactivity: - Shield surface and affect reactivity Surface recognition: - label proteins - intracellular communication
61
what determines if a disaccharide/polysaccharide is alpha or beta?
If the left sugar is in alpha or beta conformation. When naming a disaccharide/polysaccharide, whether it is labeled as alpha or beta is dependent on what form the left most carb is in.
62
Make a comparison table for all the polysaccharides discussed in lecture. Table must include name of glycosidic bonds, type of polymer, function of polymer, where can they be found (nature and/or body). Table must include: homopolysaccharides, heteropolysaccharides, glycoconjugates.
63
what are the advantages of branched vs linear polymers in energy storage
Compared to a linear molecule, a branched-chain polymer has more termini for addition or hydrolysis of glucose units per unit volume of the polymer. Because there are more sites for enzymatic activity the body can digest it and gain energy faster and more easily --> good for maintaining equilibrium branched also allows for increased water solubility branching allows more energy storage while also taking up less room
64
allosteric control
can be positive or negative and it displays cooperativity. Enzyme binds to allosteric site. ATCase is allosteric
65
Reversible covalent modification
acitvity of enzyme is changed by covalently modifying the structure of the enzyme. Most common is addition of phosphoryl group on to enzyme
66
Proteolytic cleavage
enzymes that are produced in their inactive form are called zygomens or proenzymes. To activate these enzymes they are cleaved irreversibly by protease at specific sites on the peptide. They can be inactivated by the binding of an irreversible inhibitor
67
what are glycoproteins
a type of glycoconjugate: a protein with small oligosaccharides attached (covalently attached) typically found extracellularly (on the cell surface) but if it's found inside the cell it will be attached to the golgi apparatus these can help a proteins fold inside the cell or help signal where a protein is supposed to go carbohydrates play a role in protein-protein recognition. viral proteins are heavily glycosylated which helps them evade the immune system ex: mucins
68
what are glycolipids
type of glycoconjugate: lipids with covalently bound oligosaccharide part of plant and animal cell membranes ganglioside carbohydrate composition determines blood groups (blood type is based on what carbohydrate is attached to the glycolipid) found on extracellular region of membrane facilitate cellular recognition
69
hyaluronan (a glycosaminoglycan)
linear polymers of repeating disaccharide units, heteropolysaccharide. Role: structural: in vertebrates , extracellular matrix of skin and connective tissue, viscosity and lubrication in joints (forms meshwork with fibrous proteins to form extracellular matrix. May be linked to membrane of part of extracellular matrix. Regulation of cellular growth, migration, and division) Size: up to 100,000 monosaccharide units