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Glycolipid
-sugar containing lipid derived from sphingosine -sugar residues attached via linkage at 1-OH group of sphingosine -one sugar: cerebroside -two or more: gangliosides
Facilitated Diffusion
- proteins facilitate net movement of solutes only in thermodynamically favorable direction - proteins display measurable affinity for transported solute - saturable - graph looks like x=y^2
Passive Diffusion
- transported species moves across membrane in thermo. favored direction w/o help of specific transport system or protein
Ways proteins interact with membrane bilayer
- bind to surfaces of integral proteins - transverse the lipid bilayer - interact with the hydrocarbon region of the bilayer - tightly anchor themselves to the membrane via covalently attached lipid molecule
Hydrolase
- enzyme that speeds up process of hydrolysis -cleave by addition of water -ex: chymotrypisin, trypsin 3.4.21.4
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Induced fit model
Feedback inhibition
inhibition of allosteric enzyme by the end product of the pathway controlled by the enzyme
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Red box: first order
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Noncompetitive Inhibition - inhibitor and substrate can bind simultaneously to enzyme at different bonding sites -works by decreasing overall # of active enzymes bound to substrate -cannot be overcome by increase in substrate concentration ESI complex
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Uncompetitive Inhibition - inhibitor binds only to enzyme-substrate complex - inhibitors' binding site created only when enzyme binds substrate - cannot be overcome by addition of more substrate - ex. Round Up - ES complex. then ESI complex
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Competitive Inhibition - inhibitor resembles substrate and binds to active site of enzyme - substrate prevented from binding - diminishes rate of cataylsis by reducing proportion of enzyme molecules bound to a substrate -relieved by increase in substrate concentration
Hemoglobin's oxygen binding properties affected by:
- change in concentration of hydrogen ions - pH -increased concentration of 2,3- biphosphoglycerate
carbonic anhydrase
- catalyst to rxn of carbon dioxide with water to form carbonic acid - occurs inside red blood cell
Melting point of fatty acid determined by:
- # van der Waals interactions between hydrocarbon chains - chain length - # of methylene groups
Lower melting temp correlates with
more fluidity
Fatty Acids
- Stored for fuel as triacylglycerides - found in linear, branched, and cyclic forms - mostly with even number of carbons
Fatty acids are:
- stored for fuel as triacylglycerides - found in linear, branched, and cyclic forms - even number of carbons
Enzymes
- proteins, RNA - catalyze metabolic rxns - may use cofactors - form metabolic pathways - have substrate and rxn specificity - present in small amounts (not consumed by rxn) - Integrate metabolic (ana/catbolic) fcns - regulated: sensor of cell needs
What enzymes do
- provide alternate pathway of lower activation energy - does not change free energy of reactants and products
Oxidoreductase
redox rxns
transferases
transfer of functional groups between molecules
lyases
modifies double bonds
isomerases
move groups within molecule
ligases
join two molecules by ATP cleavage
Phospholipids
- oriented in membrane in tail-to-tail fashion - within each bilayer membrane, phospholipid comp of inner and outer leaflets is difference - main component of membranes - composed of three components: -backbone (gylcerol or sphingosine) -two fatty acid chains -phosphorylated a…
Active Transport
transported species moves in therm. unfavored direction (low to high) - energy required - pump
Catalytic Power
ratio of enzyme catalyzed rate to uncatalyzed rate
Antiporter
- transport system in which a molecule is carried across a membrane in the direction opposite that of an ion, which in turn is pumped back across the membrane through a pump linked to ATP hydrolysis - secondary
Cholesterol is component/precursor of:
-Vitamin D - Glucocorticoids - membranes of intracellular organelles - animal cell membranes
Cholesterol Derivatives
-5 Families of Steroid hormones -androgens -estrogens -progestins -gulcocorticoids -mineralocorticoids -Bile acids (assist in absorption of dietary lipids) -Vitamin D
Strategy by which catalysts work
increase probability of product formation
Concerted Model
- allosteric regulation that requires all subunits to be in the same state
allosteric enzyme
- enzyme having multiple active sites as well as distinct regulatory sites that controls the flux of biochemicals through a metabolic pathway - regulation of catalytic activity is by environmental signals, including the final product of the metabolic pathway regulated by the enzyme
Some Hemoglobin Stuff
- hemoglobin displays cooperative behavior - myoglobin and hemoglobin bind oxygen in heme groups - hemoglobin binds oxygen cooperatively - hydrogen ions and CO2 promote dissociation of oxygen from hemoglobin
homotropic effect
disruption of the T<-> R equilibruim by substrates
heterotrophic effect
disruption of T<-> R equilibrium by regulators
Why is super market meat red?
- cooking denatures the globin, Fe2+ becomes Fe3+, turning brown - carbon monoxide is added to meat to keep it red
Bohr
hydrogen ions and carbon dioxide promote release of oxygen
heterotrophic regulators of oxygen binding by hemoglobin
- carbon dioxide - H+
Membrane formation
Driving force: -water's tendency to H-bond -hydrophobic effect
Lipids
-water insoluble molecules but highly soluble in organic solvents -have polar and non-polar end (amphipathic) -Several Fcns: -energy storage -membrane component -signal transduction pathway -hormones
Five Classes of Lipids
-Fatty acids: fuel, building blocks of membranes; can be saturated/unsaturated -Triacylglycerol: storage form of fatty acids, major source of glycerol -Phospholipids: main component of membranes -Glycolipids: important membrane constituents -Steriods: Polycylic
Cis-Unsaturated Fatty Acids
always naturally occurring in cis formation
Fatty acids esterification
Fatty acids stored as triacylglycerols in which three fatty acids are esterified to one molecule of glycerol
Triacylglycerols
Major energy reserve -most natural plant and animal fat
Why Triacylglycerols good fuel reserve?
-richer in energy (more reduced) than carbohydrates -Tg can be stored more efficiently -Tg aggregates are inert; no risk of undesired chem rxns w/ other cell comp. -provide enough storage for 2 weeks
Membrane Lipids
Phopholipids -Glycolipids -Cholesterol
Sphingosine
amino alcohol containing long unsaturated hydrocarbon chain
Lipid Anchors
-Palmitoyl Group -Farnesyl Group -Glycosylphosphatidylinsotiol anchor
Eukaryotic Membranes
-Membranes serve as boundaries that maintain division of labor in cell -Actively involved in cellular processes -permeability barriers -establish compartments
Characteristics of Membranes
-sheet like structures -composed of lipids and proteins -membrane lipids small amphipathic molecules -proteins serve to mitigate impermeability of membranes -noncovalent assemblies -asymmetric -fluid structures
Membrane formation
Driving force: -water's tendency to H-bond -hydrophobic effect
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endergonic
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exergonic
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facilitated diffusion
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passive diffusion
FRAP fluorescence recovery after photobleaching
- cell surface fluoresces because of labeled surface component - fluorescent molecules of small part of surface are bleached by intense light pulse - fluorescence intensity recovers as bleached molecules diffuse out of region and unbleached diffuse in -rate of recover depends on diffus…
Proteases
large class of enzymes that catalyze protein breakdown cleave by hydrolysis
Catalytic Triad
- Serine 195 - Histidine 57 - Aspartate 102
His residue
positions Ser side chain & polarize hydroxyl group for deprotonation
In presence of substrate, His:
accepts proton from Ser hydroxyl group
His 57 acts as
general base catalyst
Withdrawal of proton from hydroxyl group
alkoxide ion
Asp orients His to make better proton acceptor via
H-bonding electrostatic effects
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Effect of heat on enzyme: increases then eventually sharply decreases
covalent catalysis
active site contains nucleophile briefly covalently modified
general acid base catalysis
molecule (not water) donates or accepts proton
metal ion catalysis
metal ions function as electrophilic catalyst
catalysis by approximation and orientation
enzyme brings two substrates together in orientation that facilitates catalysis
Enzymatic activity and T
increases with increase in temp
pH dependence
due to presence of ionizable R groups
Irreversible Inhibitors
group specific affinity labels suicide inhibitors
apoenzyme
enzyme without its cofactor
holoenzyme
complete catalytically active enzyme
two main types of cofactors
Coenzymes and metals
Hutchinson Gilford disease
mutation of lamin, a protein causing
glycosphingolipid
ceramide, fatty acid, amide
sphingomyelin
myelin (neural) sheath
The low incidence of protein or lipid flip-flop in a membrane preserves
membrane asymmetry
affinity inversely proportional to
Km
multiple substrate enzymes
sequential and double
affinity label
substrate analogue specifically binds to active site resembles substrate
Bohr effect..again
lower pH or high pressure - release of O2 from oxy heomglobin
Sickle cell anemia
substitution of valine reside for glutamic acid residue at B6 position
Tense
deoxyhemoglobin
Relaxed
oxyhemoglobin
Glycerolphospholipid
1,2- diacylglycerol and phosphate group component of membranes member of phospholipid
unsaturation
lowers melting point
high lysine content
ionic; hydrophobic
Triacylglycerols again
more energy upon oxidation
FRAP measures
increase in fluorescence
Vmax attained when
all enzyme is bound to substrate zero order (top of graph)
same y-int
competitive
same slope
uncompetitive
same x-int
noncompetitive
Transition state analogue
not: stable chemically and structurally similar molecules to transition state
negative allosteric effect
decrease in cooperativity of substrate
positive allosteric effect
increase in cooperativity of substrate
Difference in myoglobin and hemoglobin
hemoglobin exhibits cooperative binding of O2 while myoglobin does not

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