Swelling Behavior of Carboxymethylcellulose Hydrogels in Relation to Cross-Linking, pH, and Charge

Density

 carboxymethylcellulose (CMC) Hydrogels 2.5%, 25%, 50%, and 100% @ CMPJ cross-linked
 The polymer was sulfated by sulfur trioxide pyridine complex (SO3-Py).
 Water uptake parameters: cross-linking, pH, and sulfation.
 FT-IR was used at different pH to evidence the hydrogen bonds and the correlation between
water uptake properties and the chemical composition of the gels.

CMC: highly water-soluble, and emulsifying agent.

Hydrogels carrying protonable groups respond to external stimuli (pH, T, and ionic strength) by shrinking
or water uptake.

CMC’s FT-IR spectroscopy:

 1620 cm-1: COO- stretching

 1400 cm-1: COO- bending
 hydrogen bonding (between OH and COO-group) widened bands.
 1450 cm-1: CH2 absorptions
 1330 cm-1: CH absorptions
 1200 to 1000 cm-1: sugar ring absorption (Broad bands from 1200 to 1000 cm-1)

Water Uptake Measurements:

Water uptake and weighting measurements were taken from small bags of Nylon enclosed in a water-
permeable net and immersed for 24 hours. The bags were then removed from the solvent, pressed
gently with tissue paper to remove excess solvent, weigh and return to the medium. This process
continued from the starting weight (W d ) until the gels attained a constant final weight (W ¿ ¿ s)¿.

W s−W d
Water uptake= 100
Wd
Hydrogen bonds in CMC hydrogels affect pH-dependent water uptake.

FT-IR Characterization:

 The spectra of gels at different pH elucidated the role of hydrogen bonds in gel water uptake.

 Characteristic absorption due to C=O vibration of the protonated carboxylic groups involved in
hydrogen bond formation shifted from 1740 to 1720 cm-1.

 The spectra of the 100% cross-linked gel did not show pH dependence.
  The introduction of sulfated groups caused a more drastic reduction in hydrogen-bond formation
in the gels.

Conclusion:

 The different water uptake behavior of CMC-based hydrogels cross-linking was governed by H-
bond formation.
 Carboxylic groups (COOH) had two principal effects on water uptake:
o when fully protonated (COOH), they formed several hydrogen bonds which reduced
the water uptake of the gels;
o when ionized (COO-), they produced electrostatic repulsion which opened the
network and increased water uptake of the gels.
 The synergistic effect of negative charges and hydrogen bonds explains water uptake behavior in
the intermediate pH range.
 Sulfation of CMC hydrogels reduced the number of hydrogen bonds, opened the network, and
increased water uptake because the extra negative charges caused electrostatic repulsion
between chains.
 The influence of H bonds and water uptake on the hydrophilic groups can be observed by
comparing CMC-based hydrogels with the corresponding hyaluronic acid-based hydrogel.