Temperature-dependent effects

•  Crystallization: is the process by which, upon cooling, an ordered

solid phase (crystalline) is produced from a liquid
•  Melting: is the reverse process that occurs when a polymer is
heated goes from a solid to a liquid - large volume change

•  Glass transition: when amorphous or noncrystallizable polymers

that, when cooled from a liquid melt become rigid solids yet retain
disordered structures that is characteristic of liquid state – small
volume change

•  In semi-crystalline polymers, crystalline regions experience melting

whereas amorphous regions experience glass transition

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  1    
 Melting & Glass Transition Temperatures
Melting and glass transition require
movement or re-arrangement of
molecules
Tg increase with increasing chain stiffness
(reduced chain flexibility)

Chain stiffness increased by presence of

1.  Bulky sidegroups
2.  Polar groups or sidegroups
3.  Chain double bonds and aromatic
chain groups

Tm affected by
- chain stiffness
- crystallinity (higher crystallinity, higher Tm)
- Regularity of repeat unit arrangements
- Degree of branching
- Molecular weight (higher MW, higher Tm)
fewer chain ends which can move
Adapted from Fig. 15.18, Callister & Rethwisch 8e.

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  2    
 Natural Polymers
Hydrogels

Prof. Wendy Liu

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  3    
 Classes of natural polymers

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  4    
 Some common natural polymers

Yannas,  Natural  Materials,  Biomaterials  Science,  2004  

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  5    
 Why natural polymers?

Advantages Disadvantages
•  Naturally occurring, so the host •  Can still be immunogenic,
is prepared to recognize the especially depending on the
molecules source
•  Can have biological function •  Processing is often difficult,
on a molecular scale, rather often decompose at high
than have appropriate temperatures – can’t process
macroscopic properties (ie. like a thermoplastic
mechanical properties) •  Batch to batch variation,
depends on the source

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  6    
 Collagen
•  Gly-XY where X is usually
proline and Y is usually
hydroxyproline
•  Fiber structure confers
mechanical strength
•  Binds to fibronectin, which
confers cell adhesion

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  7    
 Collagen synthesis

Figure 19-66 Molecular Biology of the Cell (© Garland Science 2008)

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  8    
 Elastin

•  Large number of
hydrophobic amino acids
– valine

•  Presence of covalent
crosslinks
–  Lysyl oxidase crosslink at
lysine residues

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  9    
 Silk

109  Pa  

BME111   Design  
OmeneGo   of  Biomaterials  
and  Kaplan,   Science  2010   Spring  2015      April  16    Lecture  6  Slide  10    
 Molecular structure of silk

Jin  and  Kaplan,  Nature  2003  

•  Two structural proteins

–  Fibroin proteins which form micelles have beta-sheet “crystalline regions”, mostly
hydrophobic
–  Sericin proteins (hydrophilic) which glue together the fibroin micelles
•  Extrusion process – drawing in the gland causes elongation and shearing

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  11    
 Macromolecules containing protein and
carbohydrate

•  Proteoglycan – mainly carbohydrate, modified with some proteins

•  (In contrast to glycoproteins – mainly proteins, modified with
carbohydrates )
•  Hydroxyl function groups are reactive sites to form chains,
carbohydrates attached at serine or threonine residues of proteins

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  12    
 Aggrecan
•  Bottle brush structure
•  Found in cartilage
•  Resists compression

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  13    
 Other polysaccharide biomaterials

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  14    
 Polysacharides derived from plants or other
animals
Alginate  –  from  seaweed  

ChiOn/chitosan  –  from  the  shells  of  shell  fish  (crab/shrimp/lobster),  from  

exoskeleton  of  arthropods      

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  15    
 Hydrogels

•  A crosslinked water-swollen polymer network

•  Applications:
–  Poly(hema) – soft contact lens, other ophthalmological devices
–  Biosensors or membranes – good transport properties
–  Carriers for drug delivery

•  Two types of crosslinking:

–  Chemical crosslinking – covalent bonds
–  Physical crosslinking – entanglements, crystallites or weak
associations such as hydrogen bonds or vdW interactions

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  16    
 Chemical (covalent) hydrogels
Polyhydroxyethylmethacrylate  (poly(HEMA))    

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  17    
Hydrogel network
structure
•  Ideal macromolecular network
•  Network with multifunctional
junctions
•  Entanglements
•  Defects – unreacted
functionality or loops

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  18    
 Hydrogel polymerization schemes
•  Direct reaction of linear or branched polymer with a difunctional
small molecular weight crosslinking agent

•  Copolymerization of one or more monomer with one multifunctional

(3 or more functional groups) monomer

•  Interpenetrating gels – form the first network, then swollen in a

second monomer, which is reacted to form an interpenetrating
network

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  19    
 Physical hydrogels: polyelectrolyte
hydrogels

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  20    
 Hydrogel characteristics
•  Swelling ratio or volume degree of swelling Q

Q = volume of polymer in swollen, wet state

volume of polymer in dry state

–  Degree of swelling influences solute diffusion, surface properties, mechanical

properties

•  Molecular weight between crosslinks MC

•  Crosslinking density rho = 1/(vMc) where v is the specific volume or
volume/mass

BME111  Design  of  Biomaterials  Spring  2015      April  16    Lecture  6  Slide  21