Polymer Characterization

Lecture 3: Polymeric Biomaterials. Part 2 – Advanced

Techniques for Analysis of Macromolecules

Lecturer:

Ivan Djordjevic, PhD (Materials)

Department of Biomedical Eng.
Faculty of Engineering,
University of Malaya

Tissue Engineering Lab (Block U)

Tel: 037967 7616
Email: ivan.djordjevic@um.edu.my
 Polymer Characterization

Objective:
- outline of the advanced methodologies for polymer characterisation
- relationship between designed polymer structure and impact on biomaterial
properties
- application of theoretical calculations for description of cross-linking density
and hydrogel systems

Outline:

 Analytical techniques
 Data interpretation
 Macromolecular structure
 Polymer Characterization
Monomers identification
 Polymer Characterization
Mass Spectrometry (MS)

http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/
MassSpec/masspec1.htm
Mass Spectrometry (MS) Polymer Characterization

- Conventional MS good for small molecules

- The most powerful analytical system:

combination of chromatography and mass spectrometry
(both GC-MS and HPLC-MS)

- Polymers, due to their size would produce

too many molecular fragments difficult for
interpretation
 Polymer Characterization
Time-of-Flight Mass Spectrometry (TOF-MS) Detector

Time-of-flight mass spectrometry (TOF-MS) is probably the simplest method of mass measurement to
conceptualise.

The inherent characteristics of TOF-MS are extreme sensitivity (all ions are detected), almost
unlimited mass range and speed of analysis (modern instruments can obtain full spectra in seconds).

This makes TOF-MS one of the most desirable methods of mass analysis.
 Polymer Characterization

Matrix-Assisted Laser Desorption Time-of-Flight Mass Spectrometry

(MALDI-TOF-MS)

NaI as an ionizing agent + MALDI matrix

Soft ionization technique used in mass spectrometry, allowing the analysis of biomolecules
(biopolymers such as DNA, proteins, peptides and sugars) and large organic molecules (such
as polymers, dendrimers and other macromolecules), which tend to be fragile and fragment
when ionized by more conventional ionization methods.
http://en.wikipedia.org/wiki/Matrix-assisted_laser_desorption/ionization
Exercize 1: MALDI ToF MS
interpretation Polymer Characterization

OD CA

Polyoctanediol Citrate (POC)

~ CA - (OD-CA)2 - OD ~

POC + Na Association and detection:

m/z of Polymer + 22 (from Na)

n=?
 Polymer Characterization
Fourier Transform Infra Red (FTIR) Spectroscopy

Infrared (IR) spectroscopy is often used to characterize the chemical

structure of polymers. Infrared spectra are obtained by passing
infrared radiation through the sample of interest .

Observing the wavelength of the absorption peaks. These peaks are

caused by the absorption of the radiation and its conversion into
specific motions, such as C–H stretching
Photo-acoustic, PA-FTIR spectroscopy Polymer Characterization

10 OD
5
0
10 CA
5
0
Absorbance

10 POC
5
0
10 PVA
5
0
10 PVA_CA
5
0
4000 3000 2000 1000
Wavenumbers (cm-1)

Appearance of peaks at 1730 cm-1 and 1200 cm-1 is attributed

to C = O and C – O stretching vibrations in ester groups of both
POC and PVA-CA scaffolds.
Octanediol (OD)
OH
OH OH

O O
O OH

Polyvinyl alcohol (PVA) Citric acid (CA)

 Polymer Characterization
Mechanical Tests and Rubber Elasticity Theory

n represents the number of active network

chain segments per unit volume (mol m-3);

Mc represents the molecular weight between

cross-links (g mol-1);

E0 represents Young’s modulus (MPa); R is the

universal gas constant (8.314 J mol-1 K-1);

T is the absolute temperature (T = 298 K) ;

ρ is the density.
 Polymer Characterization
Case 1: Polyoctanediol Citrate-Sebacate p(OCS)
CA CA
CA
SA OD

OD OD OD

p(O1C1S0) p(O1C0.75S0.25)
OD CA

SA OD OD

p(O1C0.5S0.5)
 Polymer Characterization
Swelling Experiment

H2O

Percentage swelling:

M0 and Mw represent the

disc masses in dry and
wet conditions
 Polymer Characterization
P(OCS): Swelling results

Swelling results closely related

to mechanical test results.

Mc represents the molecular

weight between cross-links

According to Table 3:

a=?
b=?
c=? CA OD OD OD

SA CA
 Polymer Characterization
Hydrolytic (in vitro) Degradation of Biopolymers

Samples in phosphate buffer saline (PBS) solution on 37°C: simulated physiological conditions

Percentage degradation reported as:

[(M0 – Md) / Md] x 100 %

M0 is a sample mass prior to degradation and Md is a sample mass after drying to

a constant weight.

Tests are performed in the time scale from 1 to 6 months. Each experiment is performed on
samples after degradation periods: mechanical properties, structure (spectroscopy) and
analysis of degradation products

Degradation products can be analysed with cromatography-mass spectrometry hybrid

analytical systems (HPLC-MS) capable of low concentration detection.
 P(OCS): In vitro degradation results and
Polymer Characterization
molecular structure (from FTIR)

Broad bands centred at 3440 cm-1 and 3295

cm-1 are assigned to hydrogen-bonded
hydroxyl groups stretching vibration and the
O–H vibration (νO-H) of the hydrogen bonded
carboxyl groups from CA segment, respectively.

CA
OD OD

SA OD
CA

According to FTIR results:

a=?
b=?
c=?
 Polymer Characterization
Case 2: Polydiol Citrates PDC

n = 6; polyhexanediol citrate (PHC)

n = 8; polyoctanediol citrate (POC)

n = 10; polydecanediol citrate (PDC)

n = 12; polydodecanediol citrate (PDDC)

n n
Polymer Characterization
 Polymer Characterization

n n
 Polymer Characterization
Case 2: Polydiol Citrates PDC degradation

n n
 Polymer Characterization
Case 2: POC mechanical properties as a function of reaction condition
 Polymer Characterization
Hydrogels
Multi-functional
junction
Hydrogels are water-swollen,
cross-linked polymeric
structures

Cross-links: Ideal macromolecular

-covalent bonds - produced by network
the simple reaction of one or
more comonomers
- physical cross-links from
entanglements Physical cross-links
- association bonds such as
Hydrogen bonds or strong van
der Waals interactions between Unreacted
chains crystallites bringing functional group
together two or more Chain loops
macromolecular chains.

Ratner, Hoffman, Schoen and lemons. Biomaterials Science: An

Introduction to Materials in Medicine. Academic Press 1996.

Hydrogels
Based on the method of preparation,
They may be:
(i) homopolymer hydrogels,
(ii) copolymer hydrogels,
(iii) multipolymer hydrogels,
(iv) interpenetrating polymeric hydrogels.
Polymer Characterization
Based on their ionic charges,
hydrogels may be classified as;
(i) neutral hydrogels,
(ii) anionic hydrogels,
(iii) cationic hydrogels,
(iv) ampholytic hydrogels.
Based on physical structural features
of the system, they can be classified as:
(i) amorphous hydrogels,
(ii) semicrystalline hydrogels,
(iii) hydrogen-bonded or complexation
structures.
Peppas, N.A., Hilt, J.Z., Khademhosseini, A., Langer, R.
Hydrogels in Biology ind Medicine: From Molecular
Principles to Bionanotechnology.
Advanced Materials 18, 1345-1360 (2006).
 Polymer Characterization
Hydrogel swelling

Hydrogels are prepared by swelling cross-linked Flory (1953) developed the initial theory of the swelling
structures in water or biological fluids. Water or of cross-linked polymer gels using a Gaussian
aqueous solutions may be present during the initial distribution of the polymer chains.
preparation of the cross-linked structure.

The physical behavior of hydrogels is dependent on

their equilibrium and dynamic swelling behavior in
water, since upon preparation they must be brought in
contact with water to yield the final, swollen network
structure.
 Polymer Characterization
Hydrogels and Elastomers
Rubber elasticity theory and determination of Molecular weight between cross-links MC

E0 = Young’s modulus (MPa);

The Flory-Huggins theory

 Polymer Characterization
References

Peppas, N.A., Hilt, J.Z., Khademhosseini, A., Langer, R. Hydrogels in Biology ind
Medicine: From Molecular Principles to Bionanotechnology. Advanced Materials 18,
1345-1360 (2006).

Ratner, Hoffman, Schoen and lemons. Biomaterials Science: An Introduction to

Materials in Medicine. Academic Press 1996.

Ivan Djordjevic, Namita Roy Choudhury, Naba Dutta and Sunil Kumar. Synthesis
and characterization of novel citric acid-based polyester elastomers, Polymer, 2009;
(50): 1682-1691.