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LECTURE 2: Molecular raw materials and mechanical properties!

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Molecular raw materials!


Proteins Ceramics

Polysaccharides

Lipids

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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!

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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!

Naturally occurring amino acids!

Hydrophobic Non-polar (ionizable) Polar (non-ionizable)

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!

Unnatural amino acids!


Hacking the gene,c code Unnatural AAs have been incorporated in vivo Selec,ve func,onaliza,on Photolabile groups Glycosyla,on Tracking dyes

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Polypeptide conformation!
All 19 other amino acids Gly

Hollmover, et al. Acta Crystallographica D 2002 58 (5) 768-776

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Secondary structure: alpha helix!


3.6 amino acids per turn, right handed helix! ! 36 amino acid a-helix has 10 turns and is 5.4 nm long! ! Helix propensi,es of the amino acids are as follows (kcal/ mol): Ala = 0 Leu = 0.21 Arg = 0.21 Met = 0.24 Lys = 0.26 Gln = 0.39 Glu = 0.40 Ile = 0.41 Trp = 0.49 Ser = 0.50 Tyr = 0.53 Phe = 0.54 Val = 0.61 His = 0.61 Asn = 0.65 Thr = 0.66 Cys = 0.68 Asp = 0.69 Gly = 1 (Pace, et al. Biophys. J. 1998 75 422-427)
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Secondary structure: beta-sheet!


Pleated structure! May be parallel or an,parallel -sheet propensi,es : Thr > Ser > Glu > Val > Phe > Tyr > Ala May be parallel or an,parallel

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Secondary structure: beta-sheets!

parallel

an,parallel

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Tertiary structure!

Green Fluorescent Protein (mostly -sheet)

Hemoglobin (mostly -helix)

Fibrin (mixture of -helix and -sheet)

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Proteins are Evolutionary Materials!


Polypep,de sequence is directly related to DNA instruc,ons, which can change!

point muta,on

Homologous recombina,on alterna,ve splicing


ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Polysaccharides!

Make up a large por,on of animal and plant ,ssues Main role in many ,ssues is to retain water

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Polysaccharides made up of sugars!


Anomeric posi3on
OH

4
HO HO

6 5 3 2

enzymes
1
OH

OH

GLUCOSE

glycosyl bond

STARCH (-1,4-linked glucose)

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!

Naturally occurring sugars!


OH
HO OH

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

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Polysaccharide properties! Structure!


Polydisperse! Limited options for exploring sequence space !

Function!
Structural materials (space llers)! Gels (water retention)! Hard materials (chitin shells)!

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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!

We are not limited to naturally occurring func,onal groups on polysaccharides

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Examples of bioceramics!

Mollusk shells

Sea urchin spine Egg shells

bone

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Ceramics!

2 main types of inorganic biomaterials: Calcium-based Silica-based

Conch shell (aragonite CaCO3)

Key features: Metabolically cheap High s,ness Templated by organic molecules


Diatom (silica SiO2)
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Deforming materials Deforming molecules!


Why are crystalline materials generally hard and polymeric materials generally son? Deforming a bulk material is only accomplished by altering the spacing or packing of its cons,tuent molecules Atoms in crystalline materials cannot move with respect to each other stress is readily transferred throughout the crystal lapce Strain is limited to movement of atoms within the lapce

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!

How do materials respond to deformation?!


Interatomic force TENSION

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?

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Polymer conformation - The random walk!


For an ideal polymer of length L, made up of many freely jointed segments:

Contour length, L R ~ L1/2

Radius, R

The conforma,on of the polymer can be referred to as a random walk:

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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!

What do we mean when we say a materials is:!


Stiff?! Strong?! Tough?! Resilient?!
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Denition of strain!
lo

Cauchy strain (a.k.a. conven,onal, nominal, or engineering strain)

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

has units of force/unit area (N/m2 or Pa)

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Stress-strain curve!
stress
Modulus (s,ness) Ul,mate breaking stress (strength) Ul,mate breaking strain (extensibility)

E =

e
strain

Modulus (same units as stress - Pa)


Stress, (Pa)

Strain (unitless)

Energy absorbed by material before breaking (toughness)

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Stress-strain behavior of materials!


steel

Stress

rubber

Strain

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Idealized types of material behavior!


elas,c plas,c

STRESS

elas,c-plas,c

visco-elas,c

STRAIN
ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Springs and dashpots!


Hookean region material behaves like a spring Elas,c you get back the energy you put into the system Material will return to its ini,al form

Stress

Hookes spring model F = kx

Strain

= Ee

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Springs and dashpots!


Non-Hookean region Non-elas,c component of material can be modeled as a dashpot Energy you put in is dissipated by viscous material

Stress

Dashpot Stress on material is propor,onal to the change in posi,on and viscosity

= (de/dt) Strain where = viscosity


ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Most biomaterials are viscoelastic!


Viscoelas,c materials can be modeled with Maxwell or Voigt models

1 e1 2 e2 m

Em

Ev 1 e1

2 e2 v

Maxwell (use for stress-relaxa,on expt)

Voigt (use for creep test expt)

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
1 dt 1

1 = Eme1

2 = mde2/dt

Em

e1 dt

2 m

de2 dt

Maxwell (use for stress-relaxa,on expt)

However, 1 = 2 = AND etotal = e1 + e2

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

Maxwell (use for stress-relaxa,on expt)

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

Therefore, let = (m/Em) be a characteris,c ,me constant

= o exp(-t/)

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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

Using arguments similar to those used for the stress-relaxa,on test:

Voigt (use for creep test expt)

e = eo exp(-t/)

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

More sophisticated models of viscoelasticty!


Because of their deciencies, the Voigt and Maxwell models alone are usually not comprehensive enough to represent most real materials

More accurate models can be constructed from more complicated combina,ons of springs and dashpots

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Dynamic tests (Hookean)!


The most prac,cal method to assess the viscoelas,city of most biological materials is with a dynamic experiment
Applied strain Measured stress

eo STRESS and STRAIN o

,me

This is the response expected from a Hookean material

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Dynamic responses (Hookean)!


o STRESS

eo

STRAIN For Hookean (elas,c) materials, stress varies linearly with strain

1 = Eme1

For Hookean (elas,c) materials, stress varies linearly with strain

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Dynamic tests (viscous)!


The most prac,cal method to assess the viscoelas,city of most biological materials is with a dynamic experiment
Applied strain Measured stress

eo STRESS and STRAIN o

,me

This is the response expected from a viscous material

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

Dynamic responses (viscous)!


o STRESS STRESS o eo

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!

ES228: Biomaterials! Lecture 2 Slides! Spring 2013!

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