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Origin of biomaterials!
Natural
selec,on
creates
new
material
designs
by
incremental
altera,on
to
genes
(and
by
extension
other
molecules)
Molecular
diversity
is
dependent
on
established
design
solu,ons
Cannot
go
backwards
or
transfer
informa,on
across
species
Therefore,
there
is
a
limited
set
of
biopolymers
and
inorganic
materials
used
by
biology
These
are
combined
in
dierent
ways
to
get
new
func,on
Polysaccharides
Lipids
Proteins!
Structure!
Linear polymer consisting of 20 different possible amino acids! Sequence specic! Monodisperse! Polymer folding leads to dened 3D shape determined by linear sequence!
Function!
Highly specic biochemical recognition! Dynamic structures! Catalysis!
Amino acids!
R OH H2N O
N H O R
ribosomal transla,on
R H N
N H
L--amino acids
Most naturally occurring amino acids have (L) stereochemistry! Peptide bond = amide bond!
Stable to hydrolysis polymers do not degrade spontaneously! Rigid limited exibility for entire chain!
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Protein biosynthesis! Intracellular process! Translated from genetic code! High sequence specicity!
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Polypeptide conformation!
All
19
other
amino
acids
Gly
parallel
an,parallel
Tertiary structure!
point muta,on
Polysaccharides!
Make up a large por,on of animal and plant ,ssues Main role in many ,ssues is to retain water
4
HO HO
6 5 3 2
enzymes
1
OH
OH
GLUCOSE
glycosyl bond
General
proper,es
of
polysaccharides
Hydrophilic
(Many
H-bonding
interac,ons,
some,mes
electrosta,c
with
modica,ons)
May
be
monomeric
or
have
a
MW
of
many
MDa
More
rigid
than
alipha,c
polymers
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
OH
O
O HO HO OH
HO OH OH
OH O HO HO O H
glucose (-D-glucopyranose)
OH
galactose (-D-galactopyranose)
mannose
OH
OH
O HO HO NH OH O
HO HO OH OH O O
OH O OH CH3 OH OH
N-acetylglucosamine (2-acetamido-2-deoxy--D-glucose)
glucuronic acid
rhamnose
Carbohydrate bonding!
OH OH O HO HO OH
OH O O
HO
OH
Glycosyl
bond
has
rota,on
exibility
in
2
direc,ons
May
be
or
depending
on
sugar
bond
orienta,on
Mnemonic
is
shaped
like
a
sh
(downward
orienta,on
as
drawn;
is
for
bird
(upward
bond
orienta,on
as
drawn)
Many
opportuni,es
for
H-bonds,
but
they
must
compete
with
water,
leading
to
more
conforma,onal
states
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Examples of polysaccharides!
cellulose chi,n
hyaluronic acid
alginate
Function!
Structural materials (space llers)! Gels (water retention)! Hard materials (chitin shells)!
Polysaccharide functionalization!
OH O HO HO NH O OH O O HO O NH OH
OH O NH2 HO HO NH2 OH O O OH
Basic treatment
HO
Chi,n
O Cl
OH O HO HO OH OH O O HO OH OH
Chitosan
O OH
OH
O O HO HO OH O O O HO OH OH
chloroace,c acid
HO
Cellulose
Carboxymethyl cellulose
Ionizable
groups
make
polymer
water
soluble
Amine
and
carboxylate
groups
allow
for
further
chemical
func,onaliza,on
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Unnatural sugars!
Examples of bioceramics!
Mollusk shells
bone
Ceramics!
Atoms
in
polymers
have
more
degrees
of
freedom
Stress
can
go
into
altering
polymer
conforma,on
Higher
strains
are
accommodated
by
unfolding
of
polymer
chains
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Interatomic distance
Atoms held rigidly in place Interatomic distance = 0.1 0.2 nm Maximum strain = <1%
Origin = equilibrium interatomic distance Linear on either side Asrac,ve forces in bond balance applied force How can this be extended to macroscopic size scales?
Radius, R
Entropic springs!
How
much
force
(f)
is
required
to
maintain
the
polymer
with
a
par,cular
radius
(R)
?
ENTROPY:
If
every
joint
is
freely
rota,ng,
there
are
an
innite
number
of
values
for
the
vector
R
By
applying
an
external
force,
some
of
those
values
are
not
available.
By
making
the
polymer
more
extended,
increasing
order
is
introduced
to
the
system
The
drop
in
entropy
associated
with
extending
the
polymer
chain
causes
the
polymer
chain
itself
to
apply
a
counter
force.
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Viscoelastic theory!
Denition of strain!
lo
l
eC
=
l lo
May
be
expressed
as
a
number
(0.005)
or
as
a
percentage
(0.5%)
STRAIN
=
Increase
in
length
per
unit
of
star,ng
length
This
makes
for
a
good
es,mate
if
l
<
0.1lo
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Denition of stress!
applied force
f = Ao
cross-sec,onal area
Stress-strain curve!
stress
Modulus
(s,ness)
Ul,mate
breaking
stress
(strength)
Ul,mate
breaking
strain
(extensibility)
E =
e
strain
Strain (unitless)
Stress
rubber
Strain
STRESS
elas,c-plas,c
visco-elas,c
STRAIN
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Stress
Strain
= Ee
Stress
1 e1 2 e2 m
Em
Ev 1 e1
2 e2 v
Stress-relaxation experiment!
In
a
stress
relaxa,on
expt,
length
is
held
constant
and
force
is
monitored
over
,me
1 e1 2 e2 m
Em
1 dt 1
1 = Eme1
2 = mde2/dt
Em
e1 dt
2 m
de2 dt
Therefore,
adding
the
two
equa,ons
together
we
get: d dt 1 Em + m = de1 dt + de2 dt = detotal dt
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Stress-relaxation experiment!
In
a
stress
relaxa,on
expt,
length
is
held
constant
and
force
is
monitored
over
,me
1 e1 2 e2 m
Em
d dt But,
1 Em
m detotal dt
detotal dt
= 0
Therefore: d dt integrate 1 Em + m = 0
= o exp(-Emt/m)
-Em m
dt
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!
Stress-relaxation experiment!
= o exp(-Emt/m)
In
a
stress
relaxa,on
experiment,
stress
decays
exponen,ally
over
,me
= o exp(-t/)
Creep test!
In
a
creep
test,
a
constant
force
is
applied
to
the
material
and
the
change
in
deforma,on
is
monitored
over
,me
Ev 1 e1
2 e2 v
e = eo exp(-t/)
More accurate models can be constructed from more complicated combina,ons of springs and dashpots
,me
eo
STRAIN For Hookean (elas,c) materials, stress varies linearly with strain
1 = Eme1
,me
eo
STRAIN For Hookean (elas,c) materials, stress varies linearly with strain
STRAIN For viscoelas,c materials, there is a phase shin between measured stress and applied strain
2 = mde2/dt
For viscous materials, maximum stress is achieved at the highest strain rate
=
loss
angle
an
indicator
of
viscoelas,c
character
=
90o
completely
viscous
=
0o
completely
elas,c
0o
<
<
90o
viscoelas,c
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!