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= Gcat Gu Gc = Gcat

Glucose reacts with hemoglobin to


form glycosylated hemoglobin, which
can be used to monitor the
A1c test effectiveness of treatments for
diabetes, a condition characterized by
high levels of blood glucose.

Above these temperatures they


are liquid crystals, i.e.,
Above these temperatures (Tm)
organized structures that have
membranes are...
the properties of a liquid within
each plane.

Acetaldehyde <--> [Alcohol


dehydrogenase......Zn2+] <-->
Ethanol Metal Ion

Catalysis type

A proton is transferred between


the enzyme and the substrate:
Acid-base catalysis
Acid catalysis
Base catalysis
The activity of an enzyme using
The activity of an enzyme using
acid-base catalysis is pH
acid-base catalysis is ____ sensitive.
sensitive.

All N-linked oligosaccharides All N-linked oligosaccharides


have in common a have in common a
Pentasaccharide core Pentasaccharide core

alpha RE inhibited
=(Km + [S])-[S] /Km
v=

Amino acid hydrophobicity plot


Amino acid hydrophobicity plot
for bacteriorhodopsin, showing
for bacteriorhodopsin, showing
that the membrane-spanning
that the membrane-spanning
helical regions are highly
helical regions are highly
___hydropjilic/phobic____, about 20
hydrophobic, about 20 a.a. long
a.a. long

___________ __________ analogs are much Transition state analogs are


more potent inhibitors than much more potent inhibitors
____________ analogs. than substrate analogs.
A special type of epimer, differs
only in its configuration at the
Anomer hemiacetal or hemiketal carbon,
also called the
anomeric carbon

Anomer: a special type of


epimer, differs only in its
Anomer: configuration at the hemiacetal
or hemiketal carbon, also called
the anomeric carbon

The anomeric carbon of a sugar The anomeric carbon of a sugar


can be linked to the nitrogen atom can be linked to the nitrogen
of an amine to form an ___- atom of an amine to form an N-
_______________ bond glycosidic bond

Apoenzyme + cofactor(s) = holoenzyme

________________ are proteins attached


to a particular type of
Proteoglycans
polysaccharide called
glycosaminoglycans.
The basis for ring formation is the The basis for ring formation is the
fact that an aldehyde can react fact that an aldehyde can react with
with an ________ to form a _______________. an alcohol to form a hemiacetal.

Similarly, a ketone can react with Similarly, a ketone can react with an
alcohol to form a hemiketal
an alcohol to form a ___________

Beat-D-Acetylgalactosamine
(GalNAc)

Below their characteristic Below their characteristic


transition temperatures (Tm) transition temperatures (Tm)
membranes are ___-______ ___________. membranes are gel-like solids.

Bent structures: optimal for energy storage

Beta-L-Fucose
...the more enhancement in
The bigger the Gcat value....
enzyme catalyzed reaction rate.

Bilayer formation is a Bilayer formation is a


consequence of the ___________________ consequence of the amphipathic
nature of glycerophospholipids nature of glycerophospholipids
and sphingolipids. and sphingolipids.

Binding sites are inherently


Binding sites are inherently chiral because they are
___a/chiral______ because they are composed of chiral amino acids
composed of...... which form asymmetrical
binding sites

Biological membranes are Biological membranes are


composed of _________ with different composed of lipids with
degrees of ____________ and different different degrees of saturation
_____________. This contributes to the and different lengths. This
disorder we see in the membrane contributes to the disorder we
interior. see in the membrane interior.

The bond formed between the


anomeric carbon of a sugar and
the hydroxyl oxygen atom of an
alcohol is called an __-___________ The bond formed between the anomeric carbon of a sugar and
bond the hydroxyl oxygen atom of an alcohol is called an O- glycosidic
bond
_____________ bonds determine Glycosidic bonds determine
polysaccharide structure polysaccharide structure

Carb Empirical formula: (CH2O)n

A carbohydrate group can be A carbohydrate group can be


____________ attached to a protein to covalently attached to a protein
form a glycoprotein to form a glycoprotein

Carbohydrates can be linked to


Carbohydrates can be linked to
proteins through the side chain
proteins through the side chain of
of Asparagine (N-linked) or
_____________ (_____-linked) or
Serine/Threonine (O-linked)
___________/_________ (__-linked) residues
residues

Carbonic Anhydrase
..... by interacting with the
A catalyst decreases the
reacting molecules such that
activation energy of a reaction. It
they are more likely to assume
does so by...
the transition state.

Maintenance of biological
cellulose, chitin function
structure

Cellulose fibrils are formed by Cellulose fibrils are formed by


____________ chains that interact with parallel chains that interact with
one another by ______________ bonds. one another by hydrogen bonds.

Cellulose, the other major Cellulose, the other major


polysaccharide found in plants, polysaccharide found in plants,
serves a ________________ role. serves a structural role.

Short chain length and the


________ chain length and the
presence of cis double bonds
presence of _____ _____________ ___________
enhances the fluidity of fatty
enhances the fluidity of fatty acids.
acids.
Cholesterol has a ___________,
Bulky, rigid structure disrupts
_____________ structure that disrupts
regular fatty acid chain packing
regular fatty acid chain packing in
in membranes
membranes.

Cholesterol is a metabolic
Cholesterol is a metabolic
precursor of all steroid
precursor of all __________ hormones.
hormones.

Cholesterol is an important Cholesterol is an important


component of membrane, component of membrane,
especially plasma membranes. especially plasma membranes
They account for ________ mole%) (30-40 mole%)

Chondroitin 6-Sulfate

...peptide bonds following large


Chymotrypsin hydrolyzes...
hydrophobic side chains.
Cis polyunsaturated fatty acids
Cis polyunsaturated fatty acids are
are essential components of our
essential components of our diets
diets because we cannot
because....
synthesize them.

Citrate interacts asymmetrically Citrate interacts asymmetrically


with the enzyme and therefore with the enzyme and therefore
only one stereoisomer product is only one stereoisomer product
formed. is formed.

Coenzymes are chemically Coenzymes are chemically


____________ during catalysis and must modified during catalysis and
be ___________. must be regenerated.

Coenzymes are Derived


Nutritional Sources (Vitamins)
From...

Coenzymes that are not


permanently bound are cosubstrates
termed_____________.
*may be metal ions or organic
molecules
Cofactors
* provide chem
groups/reactivities not available
among amino acid R groups

Collagen can form ________ ___________, Collagen can form triple helix,
which provides structure and which provides structure and
tensile strength tensile strength

Competitive inhibition RE Km and


Vmax

Competitive Inhibitors Affect...

only Km

Cosubstrates
...on or off the enzyme.
regenerate...
Covalent bond in Covalent
transient
catalysis is __(how lasting)___

E & S become linked in a


Covalent bond @ 1+ points -
Covalent catalysis
>provide chem that speeds up
rxn

Nucleophile: a group that has a


lone pair electron that can be
Covalent catalysts in biochemistry
used for bond formation with a
are often ___________________
electron- poor group
(electrophile)

D configuration: the OH of the D configuration: the OH of the


highest numbered chiral carbon is highest numbered chiral carbon
on the _________ is on the right

Dermatan Sulfate
The designation means that
The designation means that the
the hydroxyl group is on the
hydroxyl group is on the ____________
opposite side of the ring from
side of the ring from the CH2OH
the CH2OH

Diastereomers: having two or


Diastereomers: more asymmetric centers, not
mirror images

The difference in free energy Gibbs free energy of activation


between the transition state and or simply the activation energy,
the substrate is called the... symbolized by G,

Double bonds in FA are almost Double bonds in FA are almost


always __(trans/cis)____ always cis

Effect of pH on Carbonic
as pH increases
Anhydrase Activity
Eicosanoids are all C___
20
compounds.

Enantiomers: contain
Enantiomers: asymmetric centers, mirror
images of each other

Acid-base catalysis

Enzymatic catalysis proceeds by


Covalent catalysis

one or more of the following


Metal ion catalysis

mechanisms
Electrostatic stabilization

(give 6)
Preferential binding to the transition
state

Proximity and orientation effect

3-D cleft or pocket

A small part of the total volume of the protein

Enzyme active site common unique microenvironment

features: (give 5) Substrate/transition state binds to enzyme active site by


multiple weak interactions

Specificity of binding depends on the precisely defined


arrangement of atoms in the active site.

Enzyme catalyzed reaction: restriction


of _____________ and _______________ _______________ restriction of translational and
of reacting groups at the enzyme active
rotational motions of reacting
site lessens the ________________ penalty for
transition state formation because the
groups ... entropic penalty ....
mobilities of the reactants are ______________ lower to begin with.
to begin with.
An enzyme does not affect G
of the reaction. It can only lower
Enzyme impact on activation energy and allows the
G reaction to reach equilibrium
faster than it would in the
absence of a catalyst.

Higher RXN rate


Enzymes are Better Than Most
Milder RXN conditions
Chemical Catalysts because
Greater RXN Specificity
give 4
Can be regulated

Enzymes are proteins that


Enzymes are__________ that catalyze
catalyze chemical reactions
chemical reactions inside the cell.
inside the cell.

Enzymes preferentially stabilize


transition state to achieve rate
the ___________ ___________ to achieve
enhancement
_______ __________

Enzyme stabilizes the transition


Enzyme stabilizes the transition
state by close complementarity
state by close complementarity in
in shape and charge between
_________ and ________ between the
the active site and the transition
active site and the transition state.
state.
Epimers: differing in
Epimers: configuration at a single
asymmetric center

EPO is what type of hormone :a glycoprotein hormone

Erythropoietin is secreted by Secreted by kidneys and


___________ and stimulates the stimulates the production of red
production of ____ _______ _______. blood cells

Fat is suited for its roles in Fat is suited for its roles in
metabolic energy storage metabolic energy storage
because its carbon atoms are because its carbon atoms are
highly reduced highly reduced

Fatty acid carbon atoms are


Fatty acid carbon atoms are
usually numbered beginning
usually numbered beginning with
with the carboxyl terminal
the......
carbon atom.
These fatty acids are precursors to These fatty acids are precursors
a variety of _______________ and appear to a variety of hormones and
to offer some protection from appear to offer some protection
____________ _________ disease. from coronary heart disease.

Unsaturated fatty acids contain


______________ fatty acids contain one
one or more cis C-C double
or more cis C-C double bonds,
bonds, whereas saturated fatty
whereas ________________ fatty acids
acids contain no C-C double
contain no C-C double bonds.
bonds.

The fluidity of fatty acids The fluidity of fatty acids


________________ as the chain length decreases as the chain length
increases and the number of cis increases and the number of cis
double bonds decreases. double bonds decreases.

Formation of glycosidic bonds is


Formation of glycosidic bonds is
catalyzed by
catalyzed by _____________________
glycosyltransferases

The free energy of activation for a The free energy of activation for
reaction is related to the _______ a reaction is related to the rate
____________. constant.
Fructose forms both __________ and Fructose forms both pyranose
______________ rings and furanose rings

Furanose form predominates in Furanose form predominates in


many fructose __________ many fructose derivatives

GalNAc: N-acetyl- galactosamine N-acetyl- galactosamine

Glycan: Generic term for


Glycan: oligosaccharides and
polysaccharides

glycoprotein function Cell adhesion


glycosaminoglycans function Joint lubrication

Glycosphingolipids have___________ Glycosphingolipids have glycans


attached to sphingosine attached to sphingosine

Glycosylation greatly increases Glycosylation greatly increases


the ___________ of the proteome. the complexity of the proteome.

Heparin (GlcNAc)
an anticoagulant that binds to antiprothrombin
III and inhibits blood clotting

the effects of nonsubstrate


molecules on allosteric enzymes
Heterotropic effects:
(such as CTP and ATP on
ATCase)
Reactions with same G may
How can RXNs with same G have have different activation energy,
different rates therefore proceed at different
rates.

Hyaluronate

In acidic form: abundant in synovial fluid of joints and


vitreous humor of the eye; biological lubricant

The hydrophobic interior of a


The hydrophobic interior of a
bilayer is in constant motion
bilayer is in constant motion due
due to rotations about C-C
to...
bonds in the aliphatic tails.

_________________, includes
cerebrosides (contain one sugar)
and gangliosides, common in the Glycosphingolipids
membranes of brain and nerve
cells

Individual lipid molecules


Individual lipid molecules undergo
undergo rapid lateral diffusion
rapid ___________ diffusion in a bilayer.
in a bilayer. Hence the lipid
Hence the lipid bilayer is
bilayer is considered a two-
considered a two-dimensional
dimensional fluid, or liquid
fluid, or liquid crystal.
crystal.
Both the enzyme and the
induced fit models of enzyme substrate change shape upon
catalysis: substrate binding, this is called
induced fit.

In glycogen, two chains of glucose molecules


In glycogen, two chains of glucose
joined by ___-___,___-glycosidic bond are linked
molecules joined by -1,4-glycosidic bond
by an ___-___,____- glycosidic bond to create a
are linked by an -1,6- glycosidic bond to
branch point.
create a branch point. Such an -1,6-
glycosidic bond forms at approximately
Such an __-___,___-glycosidic bond forms at
every 10 glucose units, making the glycogen
approximately every ___ glucose units, making
a highly branched molecule.
the glycogen a highly branched molecule.

Uncompetitive Inhibitors Have


__________________Inhibitors Have
Identical Effects on Vmax and
Identical Effects on Vmax and KM
KM

In polyunsaturated fatty acids In polyunsaturated fatty acids


multiple double bonds ___(are/are multiple double bonds are not
not)____ conjugated. conjugated.

An integral membrane protein


An integral membrane protein
orients only in one direction in
orients only in ....
the membrane.
Intermembrane region of Intermembrane region of
membrane proteins presents membrane proteins presents
apolar amino acids (shown in apolar amino acids (shown in
green) toward the fatty acyl tails green) toward the fatty acyl tails
of phospholipids of phospholipids

___________ is an unbranched polymer


of glucose residues joined by -1,4 Cellulose
linkages.

_______________ is a very large,


branched polymer of glucose and
glycogen
serves as a storage form of
glucose

Amylopectin is branched and


______________ is branched and has
has about one bond -1,6
about one bond -1,6 linkage for
linkage for every 30 -1,4
every 30 -1,4 linkages (so it is a
linkages (so it is a less branched
less branched form of glycogen).
form of glycogen).

________ is crucial for Carbonic


Zn2+ is crucial for CA function
Anhydrase function
___________________ _______ is the major Arachidonic acid is the major
precursor of several classes of precursor of several classes of
signaling molecules: prostaglandins, signaling molecules: prostaglandins,
prostacyclins, thromboxanes, prostacyclins, thromboxanes,
leukotrienes and lipoxins. They are leukotrienes and lipoxins. They are
known as _________________ because they are known as eicosanoids because they
all C20 compounds. are all C20 compounds.

_____________ is unbranched and Amylose is unbranched and


consists of glucose residues in - consists of glucose residues in
1,4 linkage. -1,4 linkage.

k= k = AeG/RT

Keratan Sulfate

Km apparent = Km (1+([I]/K) = Km
...is the Michaelis constant, it is the substrate concentration at which
velocity is half-maximal (Vmax)

...indicative of how efficiently an enzyme selects its substrate. KM is


often used as an approximation of enzyme's substrate dissociation

Km is...
constant, i.e., a measure of an enzyme's affinity for a substrate

...unique for each enzyme-substrate pair and therefore good for


comparing:

Activities of different enzymes on the same substrate


An enzyme's ability to recognize different substrates

L configuration: the OH of the


L configuration: the OH is on the
highest numbered chiral carbon is
left
on the _______

Lineweaver-Burke plot
1/Vmax
when x = 0, y =

Lineweaver-Burke plot
-1/Km
when y = 0, x =

Lipids and many membrane Lipids and many membrane


proteins are constantly in proteins are constantly in lateral
______________ motion, a process motion, a process called lateral
called _____________ diffusion. diffusion.
Lipids containing unsaturated Lipids containing unsaturated
chains are much more fluid chains are much more fluid
compared to compared to
saturated ones. This has important saturated ones. This has
consequences for biological important consequences for
membranes. biological membranes.

The lower the KM value, the


The lower the KM value, the better the enzyme binds to the
substrate

Made of disaccharide repeating


units containing a derivative of an
Glycosaminoglycans
amino sugar (glucosamine or
galactosamine)

_______________ makes up as much as


Glycosaminoglycan
95% of the biomolecule by weight

Many _______________ ______________ Many peripheral membrane


_____________ are bound to the proteins are bound to the
surfaces of integral proteins, on surfaces of integral proteins, on
either the cytosolic or the either the cytosolic or the
extracellular side of the extracellular side of the
membrane. membrane.
___________________ mediate the
adhesion of cells to the
extracellular matrix and bind Proteoglycans
factors that stimulate cell
proliferation

The membrane is an The membrane is an overall


overall___________ _____________ state at liquid crystalline state at
physiological temperatures. physiological temperatures.

Membrane proteins are free to Membrane proteins are free to


diffuse ___________ in the lipid matrix diffuse laterally in the lipid
unless restricted by special matrix unless restricted by
interactions. special interactions.

Membranes are structurally and Membranes are structurally and


functionally functionally asymmetric. The
__symmetric/asymmeteric____. The outer
outer and inner surfaces of all
and inner surfaces of all known
biological membranes have
known biological membranes
___same/different___ _____________and have different components and
different _________________ activities. different enzymatic activities.

Membrane-spanning regions
Membrane-spanning regions may
may be -barrels (top) or -
be______________ or ____________________
helices (bottom)
Membrane-spanning regions may Membrane-spanning regions
be -barrels (____top/bottom____) or may be -barrels (top) or -
-helices (top/bottom) helices (bottom)

Metabolism, storage and


generation of energy (glucose, ...
glycogen, starch)

Mediating oxidation-reduction
Promoting reactivity of other
Metal ion catalysis
groups through
electrostatic effects.

Michaelis-Menten equation
Vmax[S] / KM +[S]
v0 =

Mixed inhibition RE Km and


Vmax
Mixed Inhibitors Can Variably
Mixed Inhibitors Affect
Affect Vmax and KM

Mixed Inhibitors (noncompetitive)


vo

Monosaccharide: Simple sugars


Monosaccharide: and derivatives with 3 to 9
carbon atoms

Monosaccharides are joined to Monosaccharides are joined to


Alcohols and Amines through Alcohols and Amines through
__________ Bonds Glycosidic Bonds

Monosaccharides are __________ or Monosaccharides are aldehydes


__________ with multiple (2 or more) or ketones with multiple (2 or
_________ groups more) hydroxyl groups
The nicotinamide ring of NAD+
The nicotinamide ring of NAD+ Serves as an oxidizing agent by
Serves as an __________ agent accepting two electrons and a
by...... proton (formally a hydride ion,
H-)

Noncom inhibition RE Km and


Vmax

Non-rotatable ____________ bonds Non-rotatable double bonds


introduce ___________. These limit introduce bends. These limit
formation of ___________ contacts formation of VDW contacts
between the aliphatic chains. This between the aliphatic chains.
_____up/down________ the melting This lowers the melting point of
point of the fatty acid. the fatty acid.

Oligosaccharide: Compound
formed by linking several
Oligosaccharide:
monosaccharides together
(example, disaccharide, with 2)

Organic cofactors are also


coenzymes
termed___________
Osteoarthritis can result from
Osteoarthritis can result from the
the proteolytic degradation of
____________ degradation of aggrecan
aggrecan and collagen in the
and collagen in the cartilage
cartilage

The overall free energy change The overall free energy change
for a reaction is related to the for a reaction is related to the
_________ __________. equilibrium constant.

The overall transition temperature The overall transition


of a bilayer increases with the temperature of a bilayer
______________ and _____________ __ increases with the length and
____________ of the fatty acid chains it degree of saturation of the fatty
contains. acid chains it contains.

3 mannose
Pentasaccharide core consist of
_#__ ______________ and _#_ _______________ and
residues
2 N-acetylglucosamine residues

Pentoses and Hexoses Cyclize to Pentoses and Hexoses Cyclize to


form ___________ and _________________ form Furanose and Pyranose
Rings Rings
A peripheral membrane protein
A peripheral membrane protein is
is invariably located on only one
invariably located on only...
particular face of the membrane.

Permanently associated
coenzymes are prosthetic groups
termed_________________.

Phosphate esters

phosphatidic acid

Phosphatidylcholine
Phosphatidylethanolamine

Phosphatidyl Inositol

Phosphatidylserine

Polysaccharide: Polymer formed


from multiple saccharide units;
Polysaccharide:
may be homopolysaccharide or
heteropolysaccharide

Polysaccharides play vital roles in


__________ __________ and in maintaining
energy storage.......structural
the _____________ integrity of an
organism.
The properties of fatty acids are The properties of fatty acids are
dependent on chain __________ and dependent on chain length and
degree of _______________. degree of unsaturation.

Prosthetic Groups
...must occur on the enzyme.
regeneration.....

The proteoglycan ________ and the The proteoglycan aggrecan and


protein _________ are key the protein collagen are key
components of cartilage components of cartilage

Proximity and orientation of


..... the entropic penalties to
substrates and reacting groups in
G
enzyme active sites reduces ......

Pyranose form predominates in Pyranose form predominates in


fructose _______ ___ ____________ fructose free in solution
R3 groups are ________________, also R3 groups are hydrophilic, also
called ________ _________ of lipids. When called head group of lipids.
R3 is H, this structure is When R3 is H, this structure is
____________________. phosphatidic acid.

The rapid lateral movement of The rapid lateral movement of


membrane proteins has been membrane proteins has been
visualized by means of _______________ visualized by means of
_________________. fluorescence spectroscopy.

Reactants in enzyme are called . substrates

RE Carbonic Anhydrase: Histidine


protonshuttle
acts as a

RE Carbonic Anhydrase: Zn2+


H2O pKa
decreases
RE Chymotrypsin: Aspartate the histidine and renders it a
orients the better proton acceptor.

a proton from Ser195,


RE Chymotrypsin: His57 removes generating a highly reactive
alkoxide ion.

RE Chymotrypsin: The alkoxide ion the peptide bond of the


attacks substrate.

RE FA: Carbon atoms 2 and 3 are Carbon atoms 2 and 3 are also
also referred to as __ and __, referred to as and ,
respectively. respectively.

RE FA:The methyl carbon atom is


The methyl carbon atom is often
often called the ____________ (__)
called the omega () carbon.
carbon.
RE FA: The positions of double The positions of double bonds
bonds are indicated with the are indicated with the symbol ,
symbol ______, with with

9 indicates a double bond


RE FA:9 indicates a double bond
between carbon atoms 9 and
between carbon atoms ____ and ____.
10.

RE Glycerophospholipid: Derived Derived from glycerol-3-


from _____________________ by _______________ phosphate by esterification at
at C_ and C_ positions with fatty C1 and C2 positions with fatty
acids. acids.

RE Glycerophospholipid: Fatty
Fatty acid at C2 usually has an
acid at C_ usually has an
unsaturated C16 or C20 chain.
unsaturated C__ or C__ chain.

RE Glycerophospholipid:
Saturated C16 or C18 fatty acids
Saturated C__ or C___ fatty acids
usually occur at position C1.
usually occur at position C___.
RE Glycosaminoglycans: At least
one of the sugars in the repeating
negatively charged
unit has a _______________ charged
carboxylate or sulfate group

RE RXN Coordinate:

Locate Transition state, G &


G.

The ring forms are energetically The ring forms are energetically
more ________ than the open chain more stable than the open chain
forms forms

Siliac Acid

Some amino acid side chains can Some amino acid side chains
act as acid-base catalyst, can act as acid-base catalyst,
depending on their _____________ depending on their protonation
__________ in the protein. state in the protein.
Some peripheral membrane proteins Some peripheral membrane proteins
are bound to membranes primarily by are bound to membranes primarily by
electrostatic and hydrogen-bond electrostatic and hydrogen-bond
interactions with the head groups of interactions with the head groups of
lipids. These polar interactions can be lipids. These polar interactions can
disrupted by adding salts or by be disrupted by adding salts or by
changing the pH. changing the pH.

Sphingolipids are built on the Sphingolipids are built on the


______________ _______________ ________________, amino alcohol sphingosine,
rather than glycerol. rather than glycerol.

Straight chains: optimal for structure

Substrate Binding Specificity


Shape, charge, polarity and
involves what 4 complimentary
hydrophobic complementarity
qualities between
between substrate/transition
substrate/transition state and
state and binding site.
binding site.

Sucrose, lactose and maltose are


common dietary components. They are ........by enzymes (sucrase,
cleaved into their respective lactase and maltase,
component monosaccharides by respectively) located on the
enzymes....(name 3).... located on the outer surfaces of epithelial cells
________________of _____________cells lining the lining the small intestine.
__________ ____________.
A suspension of phospholipids
A suspension of phospholipids can
can form liposomes: closed,
form ____________________: closed, self-
self-sealing solvent- filled
sealing solvent- filled vesicles that
vesicles that are bound a single
are bound a single bilayer.
bilayer.

Thesugartobeaddedcomesin the
Thesugartobeaddedcomesin the
form of an activated sugar
form of an
nucleotide

Transfer of lipid across a bilayer is Transfer of lipid across a bilayer


__(rare or likely)___. is rare.

Transition-state analogs are good because they bind with high


enzyme inhibitors because affinity and block the active site

.....transient molecular structure


that is no longer the substrate
but is not yet the product. It is
The transition state is a.....
the least stable and least-
occupied structure along the
reaction path.
Two forms of
Amylose and Amylopectin
starch

Uncatalyzed reaction: formation


of the transition state decreases
disorder (entropy)because it...... ....decreases the mobility of the
This unfavorable change in reacting groups.
entropy contributes to the
reaction free energy barrier.

Uncompetitive Inhibition: Inhibitor


...S is bound.
does not bind until...

Uncompetitive Inhibition RE Km
and Vmax

Uncompetitive v o
Unglycosylated EPO has only
Unglycosylated EPO has only about 10% of the bioactivity of
about ______ of the bioactivity of the the glycosylated form because
glycosylated form because the...... the protein is rapidly removed
from the blood by the kidney

Unglycosylated Erythropoietin has


____ percent of bioactivity of 10
glycosylated form.

Unmodified monosaccharides can Unmodified monosaccharides


react with oxidizing agents can react with oxidizing agents
because they contain a free because they contain a free
____________ or ____________ group aldehyde or ketone group
(reducing sugars) (reducing sugars)

y=1/v
Using Lineweaver-Burke plot to
a=Km/Vmax
obtain value of KM and Vmax.
x=1/[S]
RE: y=ax+b give values
b=1/Vmax

vinhib = (%)Vmax=Vmax [S]/Km+[S]


constant under a certain enzyme
concentration [E]T
Vmax and [E]T
[E]T dependent.

theoretical maximal rate


Vmax is the ofthereaction,itisapproached,but
never achieved.

Water is absorbed on the Water is absorbed on the


_________________, attracted by the glycosaminoglycans, attracted
many __________ charges, to cushion by the many negative charges,
compressive forces, therefore to cushion compressive forces,
__________ serves as a shock therefore aggrecan serves as a
absorber. shock absorber.

We can apply the same We can apply the same nomenclature


nomenclature seen with glucose seen with glucose to the furanose
to the furanose ring form of ring form of fructose, except that
fructose, except that and refer and refer to the hydroxyl groups
to the _________ groups attached to attached to C-2, the anomeric carbon
atom.
C-__, the anomeric carbon atom.

w/ Enzyme: electrostatic and VDW interactions


transition state forms more ______________ and
____________ interactions with the enzyme than the
substrate(s) do. enthalpy

The resulting favorable change in energy


(_____________ in this case) lowers the transition
lowers the transition state free
state . energy barrier.
0.8xVmax = (Vmax.[S] / (KM + [S]))

0.8 = ([S] / (KM + [S]))


What value of [S], as a fraction of
KM, is required to reach 80% of 0.8x(KM +[S]) = [S]

Vmax? 0.8xKM = 0.2 [S]

[S] = 4xKM

When a symmetrical molecule .....the two equivalent groups


binds to an enzyme through at are no longer equivalent, this is
least 3 points.... called prochiral.

When cells marked with


fluorescently- labeled membrane
mix over time
proteins are induced to fuse, the
proteins gradually....

Enzyme binds to the transition state better than the


substrate.

By bringing the substrates into the active site, enzyme


Why enzymes are superior than reduces the entropy penalty of transition state formation.

chemical catalyst increases collision rate of reactants.

At active site , the substrates positioned in optimal


orientation increasing productive collisions.

-amylose forms
left-handed helix
a
means that the hydroxyl group
means that the hydroxyl group is
is on the same side as the
on the ___________ side as the CH2OH
CH2OH at the chiral center (For
at the chiral center (For D-sugars)
D-sugars)

Gibbs free energy of activation


G
or simply the activation energy

G impact RE determinating RXN


it does not determine direction
direction

Gcat is a measure
catalysis.
of

the free energy barrier has been


Gcat with positive value
reduced, i.e., catalysis has
indicates
occurred.
G defines rate enhancement

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