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Lecture 4
Biomaterials Surfaces: Chemistry
Like metallic implants, some polymers used in biomaterials applications
are susceptible to chemical reactions that lead to degradation through
hydrolysis. In many cases, a polymer is specifically chosen for its ability
to degrade in vivo.
Polymer Hydrolysis
Polymer hydrolysis involves the scission of susceptible molecular
groups by reaction with H
2
O.
May be acid, base or enzyme catalyzed
Not surface-limited if water penetrates bulk
a) Molecular & Structural Factors Influencing Hydrolysis
Bond Stability
Hydrophobicity: hydrophobicity hydrolysis
MW & architecture: higher MW hydrolysis
Morphology
crystallinity hydrolysis
porosity hydrolysis
T
g
: less mobility hydrolysis
Bond Stability
Susceptible linkages at bonds where resonance stabilized intermediates
are possible
O O
Esters: R-
C
-O-R +H
2
O R-
C
-OH +HO-R

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Example 1: poly(lactide-co-glycolide)
Properties: rapid degradation, amorphous, T
g
~45-55C
Uses: bioresorbable sutures, controlled release matrices,
tissue engineering scaffolds
O O
(-O-CH(CH
3
)-
C
-)
x
-r-(-O-CH
2
-
C
-)
y
lactic acid glycolic acid
Example 2: polyethylene terephthalate (Dacron)
Properties: very slow hydrolysis, semicrystalline, T
g
~69C
Uses: vascular grafts, arterial patches, heart pumps
O
O
[-O C
C
O- CH
2
- CH
2
-]
N
base-catalyzed polyester hydrolysis:
OH

O
R
C

OR

O
O
R R
+ HOR +OH

C C
OH
O
R
H H
O
OH

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acid-catalyzed polyester hydrolysis:
H
+
X

O
R
+
OR
H X
H H

O
O
R
C
OR
H H
O
OH X
O
C
R
O
+
C
R
O
R
H
H
+ HOR
H
3
O
+
X
OH
O O
Amides: R-C -NH-R +H
2
O R-C-OH +H
2
N-R
amide or peptide linkage,
also found in proteins!
O O
Example: Nylon 6,6 (-NH-(CH
2
)
6
-NH-
C
-(CH
2
)
4
-
C
-)
N
poly(hexamethylene adipamide)
Properties: ~9% H
2
O uptake, semicrystalline, T
g
~50C
Uses: removable sutures, prosthetic joints
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O O O O
Anhydrides: R-
C
-O-
C
-R +H
2
O R-C-OH +HO-
C
-R
O O
Example: poly(sebacic acid anyhydride) (-(CH
2
)
8
-C -O-
C
-)
N
Properties: rapid degradation (surface-based)
Uses: drug delivery matrices
Ethers: R-O-R +H
2
O R-CH
2
-OH +HO-CH
2
-R
Example: polyethylene oxide (PEO) (-CH
2
-O-CH
2
-)
N
Properties: water soluble, semicrystalline, T
g
~-60C
Uses: hydrogels, protein-resistant coatings
O O
Urethanes: R-NH-
C
-O-R +H
2
O R-NH-
C
-OH +HO-R
Example: polyether urethane
O O
[(-(CH
2
)
4
-O-)
x
C -NH CH
2
NH
C
-O-]
N
[hard block]
Properties: soft block of SPU Biomer, slow hydrolysis
Uses: pacemaker lead sheaths & connectors
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O O
Ureas: R-NH-
C
-NH-R +H
2
O R-NH-
C
-OH +H
2
N-R
O O
Carbonates: R-O-
C
-O-R +H
2
O R-O-
C
-OH +HO-R
Rates of Hydrolysis: anhydride >ester >amide >ether
Stable Polymer Chemistries:
Olefins
e.g., UHMWPE: joint cup liners
Halogenated hydrocarbons
e.g., PVC: catheters; PTFE: vascular grafts
Siloxanes
e.g., PDMS: soft tissue prostheses
Sulfones
e.g., PSf: renal dialysis membranes
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b) Biological Factors Influencing Hydrolysis
pH variations
inflammation/infection pH, catalyzes hydrolysis
Hydrolasesenzymes that catalyze hydrolytic reactions
Proteolases: catalyze hydrolysis of peptide bonds
Esterases: catalyze hydrolysis of ester bonds
Produced by phagocytic cells
c) Influence of Hydrolysis on In Vivo Performance
Loss of structural integrity
e.g., i) polyester urethanes: rapid degradation in orthopedic
reconstructions (no longer used)
ii) PET fibers: deterioration after long periods in
cardiovascular applications
Toxicity/mutagenicity
e.g., i) segmented polyurethanes (SPUs): suspected
tumorigenicity of degradation products
ii) cyanoacrylates (soft tissue adhesive):
hydrolysis generates formaldehyde