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Seminar on Mechanism of Biodegradation of Polymers

Keyur Vasava

Contents Introduction to polymers Definition of biodegradation Eg. of biodegradation Biodegradation mechanism Erosion mechanism Biodegradation of some polymers Factors affecting polymer degradation Factors that accelerate polymer degradation References Introduction Of Polymers Polymers are very large molecules comprising of repeating units of small molecules, the monomer. The monomers can be linked together to generate linear, branched or cross-linked polymers. The biodegradable polymers can be defined as polymers comprised of monomers linked to one another through functional groups & have unstable linkages in the backbone. The biodegradable polymers should be biocompatible, biosorbable and bifunctional.

Definition of Biodegradation The term BIODEGRADATION is often used to denote degradation occuring in the biological environment. A better definition is Gradual breakdown of a material mediated by a specific biological activity.

Biodegradable Polymers Used for Medical Applications Natural polymers Fibrin Collagen Chitosan Gelatin Hyaluronan Synthetic polymers PLA, PGA, PLGA, Polyorthoesters Poly(dioxanone) Poly(anhydrides) Poly(trimethylene carbonate) Polyphosphozenes ... Why Do We Prefer Synthetic Ones? Predictable lot-to-lot uniformity Free from concerns of immunogenicity Reliable source of raw materials

POLYMER
PGA PLA (L form) PLA (DL form) PLGA

DEGRADATION RATE
2-3 months > 2 years 12-16 months 1-6 months

Eg. Of Biodegradation
Carbonyl bond to

A.
O R1 C X R2 H2O R1

O N S
O C OH

+ HX

R2

Where X= O, N, S
O R1 C O R2

O R1 C NH R2

O R1 C S R2

Ester

Amide

Thioester

B.
R1 X

O C X' R2

H 2O R1 X

O C OH

HX'

R2

Where X and X= O, N
O

O
R1 NH C NH R2

R1

R2

Carbonate

Urea
O R1 C OH O

C.

O R1 C X

O C R2

H 2O

+
O

HX

R2

Where X = N, O
O R1 C NH O C R2 R1 O O C R2 C

Imide

Anhydride

Biodegradable Functional Groups


H C H

O C H H

Acetal:

H 2O R' R OH

+
OH

R'

OH

OH

OH O C OH
H H 2O

Hemiacetal:
Ether
R

C C OH OH C
H C H O

OH C

C H2O C OH OH C
H R C H

+ H2O C OH C==O H
H OH

C H

R'

R'

C H H

OH

Nitrile Phosphonate

H R C C R N

H2 O R

H C C H 2N R O

H 2O R

C C HO

R O

O H2 O RO P OR'' OR' R OH

+ HO
H R C H

P OR''

OH

+ HO

R'

Polycyanocrylate
R

H C H

CN C C O

H C H

CN H 2O C C O R'

CN C C O

H C H OH

CN

C C O

R'

OR''

OR'''

OR''

OR'''

Biodegradation Generally, polymer degradation occurs in 2 phases: 1. In first phase, water penetrates the bulk of the device & attacks the chemical bonds in the amorphous phase leading to conversion of long polymer chains into shorter water-soluble fragments. 2. In second phase, there is a rapid loss of polymer mass due to enzymatic attack & fragment metabolism. More specifically, degradation can be divided in 4 steps: 1) water sorption 2) reduction of mechanical properties 3) reduction of molar mass 4) weight loss

Biodegradation Mechanism
Enzymatic degradation Here, biodegradation of polymers takes place by enzymes.. Enzymes like hydroxylase, oxygenase and various colonic bacterial enzymes like galactoronidase, etc. play a significant role in the polymer biodegradation.

b) Hydrolysis (depend on main chain structure: anhydride > ester > carbonate)

Degradation by Erosion Surface erosion (poly (ortho) esters and Sample is eroded from the surface Mass loss is faster than the ingress of water into the bulk 2. Bulk erosion (PLA, PGA, PLGA, PCL) Degradation takes place throughout the whole of the sample Ingress of water is faster than the rate of degradation polyanhydrides)

Polymer Degradation by Erosion

Eg. Of Erodible Matrices


(a)

Surface-eroding system

(b)

Bulk-eroding system

Bioerosion can be classified into 2 main types as follows: 1. Type erosion: High molecular weight, water insoluble macromolecules are converted in to small, water soluble molecules by a hydrolytic cleavage of labile bonds in the polymer backbone. The development of a useful system mandates that all degradation products be completely nontoxic. 2. Type II erosion:

In systems based on type II erosion, water-insoluble macromolecules are converted to water-soluble macromolecules by hydrolysis, ionization, or protonation of a pendant group. Because no backbone cleavage takes place, the solubilization does not result in any significant change in molecular weight.

Biodegradation of PCL

Biodegradation of polyphosphozenes

Polyphosphozenes

Excreted

Metabolism

Factors Influence the Degradation Behavior Chemical Structure and Chemical Composition: Linear polymer chain structure is less degraded than branched structure because of less no. of entanglements than branched structure. If polymer is composed of more hydrophilic groups, then it is more degraded by hydrolysis. Distribution of repeat units: If polymer has long monomers, then it decreases polymer strength due to decrease in no. of entanglements per chain, hence more biodegraded, while short monomers increase polymer strength.

Molecular Weight: Low mol.wt. polymers are more degraded by microbes, as they are taken in by microbial cells, attached to coenz.A and metabolized within microbes. Too large polymers have difficulty in entering the microbial cells.

Polydispersity: Some polymers have different sequence and no. of monomers, which leads to diferent mass. This phenomenon is called polydispersity. It indirectly affects degradation by affecting molecular weight. Presence of Ionic groups: Presence of opposite ionic groups lead to attraction between monomers which increase strength of polymer, hence polymer is less degraded.

Presence of absorbed or adsorbed compounds: If water, ions, etc. are present as absorbed or adsorbed compounds, then they cause more degradation.

Morphology: If polymer is crystalline, then it is less degraded than amorphous, because only amorphous phase is accessible to permeants like water and susceptible to attack. Storage History: If polymers have stored in environment where fungi, bacteria and their enzymes are present, then they consume polymers as food substances and thus, degradation increases at such place. Target Site: At target site, if more bacteria are present, then degradation is faster , eg. colonic site. Size: If polymer has small size, then larger surface is in contact with biological environment, hence, more degradation. Factors That Accelerate Polymer Degradation More hydrophilic end groups. Less crystallinity. More porosity. Smaller device size.

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