Impact of the Three-Dimensional Arrangements of Polyhydroxylated Crosslinkers on the Resulting Properties of Chitosan-Based Hydrogels
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Preparation of Glucaric, Mannaric, and Mucic Acid Salts
2.2.1. Obtention of Glucaric Acid as Its Monopotassium Salt
2.2.2. Obtention of Mannaric Acid as Its Sodium Salt
2.2.3. Obtention of Disodium Galactarate
2.3. Preparation of Crosslinked Chitosans
2.3.1. General Procedure
2.3.2. Specific Details Involved in the Reaction of the Crosslinkers with Chitosan
- Chitosan/Glucaric acid derivative preparation (Ch/GlcA)
- Chitosan/mannaric acid derivative preparation (Ch/ManA)
- Chitosan/mucic acid derivative preparation (Ch/MucA)
2.4. Characterization Assays
2.4.1. Solubility Assays
2.4.2. Chemical Structural Analyses
2.4.3. Morphologic Studies
2.4.4. Determination of the Specific Surface Area
2.4.5. Thermogravimetric Analyses (TGA)
2.4.6. Hydrogel Characterization
- Oscillatory rheological experiments
- Swelling studies
- Differential scanning calorimetry (DSC) and fusion endotherms of water in hydrogels
2.5. Adsorption Studies
2.5.1. Influence of pH
2.5.2. Influence of Adsorbent Dosage
2.5.3. Kinetic Studies
2.5.4. Adsorption Isotherms
2.5.5. Regeneration and Reusability Studies
3. Results
3.1. Characterization of the Crosslinked Chitosans
3.2. Hydrogel Characterization
3.3. Adsorption Studies
3.3.1. Effect of pH
3.3.2. Effect of Adsorbent Dosage
3.3.3. Kinetic Studies
3.3.4. Adsorption Isotherm
3.3.5. Regeneration and Reusability Studies
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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[%] ± SD | ||||
---|---|---|---|---|
Ch | 30.0 ± 1.3 | 70.0 ± 1.3 | - | - |
Ch/GlcA | 30.0 ± 1.3 | 21.2 ± 4.9 | 31.8 ± 3.1 | 17.1 ± 4.8 |
Ch/ManA | 30.0 ± 1.3 | 24.7 ± 3.9 | 28.1 ± 3.8 | 17.3 ± 3.6 |
Ch/MucA | 30.0 ± 1.3 | 17.7 ± 3.7 | 36.2 ± 3.5 | 16.1 ± 4.1 |
BET Surface Area [m2 g−1] | |
---|---|
Ch | 1.25 ± 0.03 |
Ch/GlcA | 1.35 ± 0.03 |
Ch/ManA | 1.33 ± 0.03 |
Ch/MucA | 1.35 ± 0.03 |
Samples | Swelling [g H2O g−1 Dry Sample] | W [%] | Qendo (J/g) | Qendo/Qice | Non-Freezable Water | Freezable Water | ||
---|---|---|---|---|---|---|---|---|
Wnf (%) | g H2O g−1 Dry Sample | Wf (%) | g H2O g−1 Dry Sample | |||||
Ch/GlcA | 52 ± 3 | 98.1 ± 0.1 | 308 ± 3 | 0.92 ± 0.01 | 6 ± 1 | 3 ± 1 | 92 ± 1 | 49 ± 1 |
Ch/ManA | 38 ± 3 | 97.4 ± 0.2 | 287 ± 3 | 0.86 ± 0.01 | 11 ± 1 | 4 ± 1 | 86 ± 1 | 33 ± 1 |
Ch/MucA | 41 ± 3 | 97.6 ± 0.2 | 294 ± 3 | 0.88 ± 0.01 | 10 ± 1 | 4 ± 1 | 88 ± 1 | 37 ± 1 |
Ch | 24 ± 3 | 96.1 ± 0.4 | 305 ± 3 | 0.91 ± 0.01 | 5 ± 1 | 1 ± 1 | 91 ± 1 | 23 ± 1 |
Model | Parameters | Ch | Ch/GlcA | Ch/ManA | Ch/MucA |
---|---|---|---|---|---|
Pseudo-first-order model | k1 [min−1] | 0.011 ± 0.003 | 0.343 ± 0.023 | 0.393 ± 0.022 | 0.395 ± 0.045 |
qe [mg g−1] | 18.7 ± 2.0 | 82.1 ± 0.5 | 90.9 ± 0.4 | 79.1 ± 0.8 | |
Radj2 | 0.8632 | 0.9951 | 0.9970 | 0.9891 | |
RMSE | 42.7 | 1.6 | 1.4 | 2.4 | |
AIC | 24.3 | 18.9 | 14.3 | 27.6 | |
Pseudo-second-order model | k2 [g mg−1 min−1] | 6.6·10−4 ± 2.5·10−4 | 0.012 ± 0.001 | 0.013 ± 0.002 | 0.013 ± 0.002 |
qe [mg g−1] | 20.4 ± 2.3 | 83.9 ± 0.6 | 93.0 ± 0.4 | 81.3 ± 0.6 | |
Radj2 | 0.8594 | 0.9966 | 0.9986 | 0.9960 | |
RMSE | 43.9 | 1.4 | 1.4 | 1.4 | |
AIC | 24.6 | 14.3 | 6.7 | 15.6 |
Adsorption Isotherm Model | Adsorbent | ||||
---|---|---|---|---|---|
Equation | Parameters | Ch | Ch/GlcA | Ch/ManA | Ch/MucA |
Langmuir | qmax [mg g−1] | 18.2 ± 5.3 | 82.9 ± 0.9 | 93.8 ± 1.3 | 79.2 ± 1.4 |
kL [L mg−1] | 0.659 ± 2.438 | 18.0 ± 1.14 | 7.08 ± 0.49 | 37.72 ± 3.80 | |
Radj2 | 0.2929 | 0.9975 | 0.9966 | 0.9941 | |
RMSE | 8.6 | 1.7 | 2.1 | 2.4 | |
AIC | 41.8 | 18.7 | 22.1 | 23.9 | |
Freundlich | kFre [mg g−1 (mg L−1)−1/n] | 15 ± 12 | 60.2 ± 5.0 | 63.7 ± 5.8 | 60.4 ± 5.0 |
n | 0.036 ± 0.211 | 0.102 ± 0.026 | 0.128 ± 0.032 | 0.084 ± 0.024 | |
Radj2 | 0.2794 | 0.8890 | 0.8767 | 0.8692 | |
RMSE | 8.7 | 11.0 | 12.8 | 11.3 | |
AIC | 41.9 | 45.2 | 47.4 | 45.6 | |
Dubinin–Radushkevich | qD-R [mg g−1] | 18.4 ± 4.2 | 83.0 ± 1.2 | 91.6 ± 1.7 | 80.0 ± 1.8 |
kD-R [mol2 J−2] | 0.009 ± 0.017 | 3.4·10−5 ± 1.9·10−6 | 6.3·10−5 ± 4.3·10−6 | 2.1·10−5 ± 1.9·10−6 | |
E [J mol−1] | 7.5 | 121.3 | 89.1 | 154.3 | |
Radj2 | 0.4399 | 0.9954 | 0.9933 | 0.9890 | |
RMSE | 8.4 | 2.2 | 3.0 | 3.3 | |
AIC | 41.4 | 22.8 | 27.0 | 28.3 | |
Frumkin | a [g mg−1 min−1] | 4.06 ± 0.71 | 3.3 ± 9.4 | 2.8 ± 4.4 | 2.9 ± 5.0 |
KFru [mg g−1] | 0.001 ± 0.79 | 0.038 ± 0.70 | 0.068 ± 0.56 | 0.041 ± 0.40 | |
Radj2 | −0.2108 | −0.2709 | 0.6569 | 0.5857 | |
RMSE | 44.9 | 22.8 | 8.9 | 14.3 | |
AIC | 64.9 | 55.4 | 42.2 | 48.9 |
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Díaz Bukvic, G.; Ojeda Henriquez, M.; Rodríguez Vannini, A.B.; Fidalgo, M.M.; Salvay, A.G.; Rossi, E.; Errea, M.I. Impact of the Three-Dimensional Arrangements of Polyhydroxylated Crosslinkers on the Resulting Properties of Chitosan-Based Hydrogels. Polysaccharides 2024, 5, 358-379. https://doi.org/10.3390/polysaccharides5030023
Díaz Bukvic G, Ojeda Henriquez M, Rodríguez Vannini AB, Fidalgo MM, Salvay AG, Rossi E, Errea MI. Impact of the Three-Dimensional Arrangements of Polyhydroxylated Crosslinkers on the Resulting Properties of Chitosan-Based Hydrogels. Polysaccharides. 2024; 5(3):358-379. https://doi.org/10.3390/polysaccharides5030023
Chicago/Turabian StyleDíaz Bukvic, Gema, Martin Ojeda Henriquez, Agustín Brandon Rodríguez Vannini, María Marta Fidalgo, Andrés Gerardo Salvay, Ezequiel Rossi, and María Inés Errea. 2024. "Impact of the Three-Dimensional Arrangements of Polyhydroxylated Crosslinkers on the Resulting Properties of Chitosan-Based Hydrogels" Polysaccharides 5, no. 3: 358-379. https://doi.org/10.3390/polysaccharides5030023