Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity
Abstract
:1. Introduction
2. Results and Discussion
2.1. FT-IR Spectroscopy
2.2. 1H NMR and ROESY Spectra
2.3. Thermal Stability
2.4. DSC Analysis
2.5. Rheological Properties
2.5.1. Flow Curves
2.5.2. Dynamic Oscillatory Measurements
2.5.3. Effect of Temperature
2.6. Antibacterial and Antifungal Activities
2.7. Evaluation of Biocompatibility
3. Conclusions
4. Experimental Part
4.1. Materials
4.2. Preparation of Aqueous HPC-NADES Gel Solutions
4.3. Measurements
4.3.1. Antimicrobial Susceptibility Tests
4.3.2. MTS Assay
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Abbreviation
NADES | Natural Deep Eutectic Solvents | HBD | Hydrogen-Bond Donor |
HPC | Hydroxypropyl cellulose | HBA | Hydrogen-Bond Acceptor |
LCST | Lower Critical Solution Temperature | HGF | Human Gingival Fibroblast |
ChCl | Choline chloride | DSC | Differential Scanning Calorimetry |
U | Urea | TGA | Thermogravimetric analysis |
CA | Citric acid | DTG | Differential thermogravimetric analysis |
LA | Lactic acid | FT-IR | Fourier-Transform Infrared |
Gly | Glycerol | NMR | Nuclear Magnetic Resonance |
References
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Sample | HPC-NADES (Dry State) | HPC-NADES (in Solution) | ||
---|---|---|---|---|
EH (kJ) | R(Å) | EH (kJ) | R(Å) | |
HPC | 27.832 | 2.753 | 15.318 | 2.792 |
HPC-ChCl-U 17% | 20.401 (N-H) | 2.717 (N-H) | 14.885 (N-H) | 2.851 (N-H) |
22.151 (O-H) | 2.769 (O-H) | 20.281 (O-H) | 2.776 (O-H) | |
HPC-ChCl-U 29% | 20.552 (N-H) | 2.714 (N-H) | 15.860 (N-H) | 2.827 (N-H) |
22.366 (O-H) | 2.770 (O-H) | 20.568 (O-H) | 2.775 (O-H) | |
HPC-ChCl-Gly 17% | 21.863 | 2.771 | 20.065 | 2.777 |
HPC-ChCl-Gly 29% | 20.281 | 2.776 | 20.136 | 2.776 |
HPC-ChCl-LA17% | 19.633 | 2.778 | 19.921 | 2.777 |
HPC-ChCl-LA 29% | 18.482 | 2.782 | 19.489 | 2.778 |
HPC-ChCl-CA 17% | 18.770 | 2.781 | 18.627 | 2.782 |
HPC-ChCl-CA 29% | 16.397 | 2.788 | 18.770 | 2.781 |
Original NADES | in dry state | in solution | ||
ChCl-U | 21.006 (N-H) | 2.703 (N-H) | 16.623 (N-H) | 2.808 (N-H) |
23.373 (O-H) | 2.766 (O-H) | 21.001 (O-H) | 2.774 (O-H) | |
ChCl-Gly | 24.092 | 2.764 | 22.150 | 2.770 |
ChCl-LA | 22.798 | 2.768 | 20.424 | 2.775 |
ChCl-CA | 21.575 | 2.772 | 18.771 | 2.781 |
Sample | Stages, °C | Tmax a, °C | Δw b, % |
---|---|---|---|
ChCl-CA 100% | I 36.8–121.6 | 61.7 | 6.8 |
II 171.7–200.9 | 191.6 | 40.9 | |
III 225.5–277.2 | 262.5 | 41.2 | |
IV 307.8–419.0 | 364.3 | 3.2 | |
ChCl-Gly 100% | I 109.7–176.9 | 128.0 | 5.5 |
II 228.2–318.9 | 296.3 | 92.5 | |
ChCl-LA 100% | I 74.5–143 | 89.1 | 4.87 |
II 171.3–232.9 | 206.1 | 14.5 | |
III 232.9–315.0 | 284.6 | 78.1 | |
ChCl-U 100% | I 127.9–223.2 | 179.0 | 10.9 |
II 223.2–269.3 | 237.0 | 24.8 | |
III 269.3–320.8 | 280.7 | 62.4 | |
HPC | I 26.7–122.7 | 72.6 | 6.7 |
II 306.3–399.7 | 374.0 | 85.1 | |
ChCl-CA 17% | I 157.3–177.2 | 162.8 | 8.9 |
II 194.4–216.2 | 210.4 | 16.6 | |
III 236.6–282.7 | 260.5 | 18.2 | |
IV 328.2–391.6 | 369.5 | 51.8 | |
ChCl-Gly 17% | I 43.5–120.4 | 90.8 | 17.2 |
II 249.3–301.5 | 277.3 | 47.8 | |
III 334.7–398.6 | 382.2 | 31.9 | |
ChCl-LA 17% | I 61.6–143.3 | 89.8 | 9.48 |
II 231.4–280.0 | 261.6 | 27.3 | |
III 301.3–396.3 | 372.2 | 55.8 | |
ChCl-U 17% | I 36.3–121.6 | 88.0 | 12.8 |
II 184.3–259.1 | 214.0 | 14.4 | |
III 259.1–298.2 | 270.5 | 39.6 | |
IV 298.2–404.3 | 380.1 | 25.7 | |
ChCl-CA 29% | I 69.7–135.5 | 90.0 | 3.4 |
II 135.5–156.8 | 147.2 | 4.95 | |
III 191.7–216.8 | 210.1 | 28.8 | |
IV 238.5–285.3 | 266.1 | 23.0 | |
V 320.7–391.6 | 368.9 | 35.3 | |
ChCl-Gly 29% | I 55.5–126.9 | 95.8 | 15.9 |
II 249.7–287.0 | 278.2 | 31.1 | |
III 287.0–303.5 | 295.0 | 26.7 | |
IV 303.5–393.7 | 366.7 | 20.6 | |
ChCl-LA 29% | I 40.9–125.8 | 79.8 | 12.1 |
II 223.3–281.1 | 264.4 | 40.2 | |
III 298.5–398.6 | 374.2 | 42.3 | |
ChCl-U 29% | I 38.9–116.6 | 83.7 | 15.5 |
II 182.1–247.5 | 206.9 | 13.5 | |
III 254.6–292.6 | 269.4 | 57.3 | |
IV 334.9–402.9 | 377.6 | 8.4 |
Sample | Activation Energy (kJ/mol)/ln A/Order of Reaction | |||
---|---|---|---|---|
Coats–Redfern | Flynn–Wall | Van Krevelen | Urbanovici–Segal | |
ChCl-CA 100% | II 367.1/92.13/1.7 | 356.2/90.35/1.7 | 382.2/96.0/1.7 | 354.9/88.8/1.5 |
III 211.2/43.69/1.3 | 209.0/43.26/1.3 | 233.0/48.72/1.4 | 214.2/44.43/1.3 | |
ChCl-Gly 100% | 163.98/30.17/1.1 | 164.5/30.32/1.1 | 182.8/34.2/1.1 | 165.67/30.6/1.1 |
ChCl-LA 100% | 96.8/16.31/0.9 | 100.2/17.38/0.9 | 120.8/21.74/1.0 | 96.1/16.18/0.8 |
ChCl-U 100% | 51.3/4.86/0.1 | 55.8/6.84/0.0 | 70.4/9.42/0.4 | 53.4/5.55/0.2 |
HPC | 222.2/36.71/1.1 | 221.1/36.53/1.1 | 251.3/42.23/1.2 | 224.0/37.1/1.1 |
ChCl-CA 17% a | 305.7/53.15/1.4 | 300.6/52.37/1.4 | 337.8/59.25/1.5 | 309.3/53.89/1.4 |
ChCl-Gly 17% a | 235.8/39.55/1.4 | 234.3/39.3/1.4 | 263.7/44.84/1.5 | 239.9/40.37/1.4 |
ChCl-LA 17% a | 160.4/25.64/1.3 | 156.8/24.96/1.2 | 178.6/29.09/1.3 | 157.2/25.0/1.2 |
ChCl-U 17% a | 186.6/30.47/1.4 | 187.4/30.67/1.4 | 213.9/35.7/1.5 | 189.8/31.16/1.4 |
ChCl-CA 29% a | 192.4/31.60/1.2 | 192.8/31.70/1.2 | 214.0/35.65/1.2 | 194.4/32.03/1.2 |
ChCl-Gly 29% a | 108.1/15.57/1.1 | 112.6/16.78/1.1 | 122.6/18.36/1.1 | 111.2/16.26/1.1 |
ChCl-LA 29% a | 150.8/23.79/1.3 | 153.2/24.36/1.3 | 168.9/27.22/1.3 | 153.3/24.35/1.3 |
ChCl-U 29% a | 234.0/39.27/1.5 | 232.6/39.04/1.5 | 252.7/42.71/1.5 | 237.3/39.95/1.5 |
Sample | Tg, °C | Tm, °C | Sample | Tg, °C | Tm, °C |
---|---|---|---|---|---|
ChCl-CA 100% | −34.1 | - | ChCl-LA 100% | −64.7 | -a |
HPC-ChCl-CA 17% | −28.7; 13.9 | - | HPC-ChCl-LA 17% | −63.5;0.8; 28.2 | -b |
HPC-ChCl-CA 29% | −27.6; 9.9 | - | HPC-ChCl-LA 29% | −79.5; −14.5; 24.2 | - |
ChCl-Gly 100% | −96.2 | - | ChCl-U 100% | −73.7 | - |
HPC-ChCl-Gly 17% | −93.3; −5.5 | - | HPC-ChCl-U 17% | −44.8; −0.2; 28.1 | - |
HPC-ChCl-Gly 29% | −93.9; 23.7 | - | HPC-ChCl-U 29% | −45.7; 5.0; 23.5 | - |
HPC | 4.8 | 197.2 | - | - | - |
Sample | Bingham | Herschel-Bulkley | Vocadlo | Casson | τ0exp, Pa |
---|---|---|---|---|---|
HPC 14% | τ0 = 14.78; μ = 5.11; R = 0.999 | τ0 = 13.90; μ = 4.93; n = 0.97; R = 0.9997 | τ0 = 13.89; μ = 6.40; n = 0.96; R = 0.9999 | τ0 = 14.00; μ = 3.70; R = 0.9957 | 14.18 |
ChCl-Gly 29% | τ0 = 18.18; μ = 6.44; R = 0.99648 | τ0 = 15.00; μ = 6.49; n = 1.04; R = 0.98892 | τ0 = 7.81; μ = 34.06; n = 0.79; R = 0.99989 | τ0 = 5.77; μ = 5.38; R = 0.99964 | 10.62 |
ChCl-CA 29% | τ0 = 23.92;μ = 14.22; R = 0.99859 | τ0 =24.40; μ = 11.35; n = 1.09; R = 0.9902 | τ0 =11.74; μ = 30.10; n = 0.91; R = 0.99971 | τ0 = 6.67; μ = 12.29; R = 0.99974 | 13.70 |
ChCl-U 29% | τ0 = 12.07; μ = 8.72; R = 0.99848 | τ0 = 3.40; μ = 14.30; n = 0.88; R = 0.99998 | τ0 = 3.63; μ = 21.76; n = 0.88; R = 0.99998 | τ0 = 2.21; μ = 7.96; R = 0.99976 | 5.38 |
ChCl-LA 29% | τ0 = 10.55; μ = 2.31; R = 0.98363 | τ0 = 1.10; μ = 9.96; n = 0.66; R = 0.99994 | τ0 = 1.53; μ = 38.74; n = 0.65; R = 0.9999 | τ0 = 2.88; μ = 2.02; R = 0.9924 | 3.33 |
ChCl-CA 17% | τ0 = 79.95;μ = 12.57; R = 0.9961 | τ0 = 62.70; μ = 17.92; n = 0.97; R = 0.9912 | τ0 = 59.01; μ = 208.06; n = 0.71; R = 0.9996 | τ0 = 80.00; μ = 8.17; R = 0.9989 | 64.53 |
ChCl-Gly 17% | τ0 = 23.81;μ = 15.22; R = 0.9984 | τ0 = 11.50; μ = 17.18; n = 1.02; R = 0.9926 | τ0 = 8.87; μ = 39.49; n = 0.88; R = 0.9999 | τ0 = 23.00; μ = 13.59; R = 0.9998 | 11.68 |
ChCl-U 17% | τ0 = 28.67;μ = 12.17; R = 0.9998 | τ0 = 27.50; μ = 9.65; n = 1.09; R = 0.9936 | τ0 = 24.82; μ = 19.27; n = 0.94; R = 0.9999 | τ0 = 28.00; μ = 9.15; R = 0.9969 | 26.24 |
ChCl-LA 17% | τ0 = 24.38;μ = 13.99; R = 0.9998 | τ0 = 22.60; μ = 11.43; n = 1.09; R = 0.9944 | τ0 = 20.45; μ = 19.78; n = 0.95; R = 0.9999 | τ0 = 24.00; μ = 11.16; R = 0.9978 | 22.56 |
Compounds | Diameter of Inhibition Zones (mm) | |||
---|---|---|---|---|
S. aureus ATCC 25923 | E. coli ATCC 25922 | Pseudomonas aeruginosa ATCC 27853 | C. albicans ATCC 90028 | |
ChCl-CA 29% | 20.30 ± 0.57 | 19.00 ± 0.00 | 0.00 | 17.50 ± 0.50 |
ChCl-Gly 29% | 0.00 | 0.00 | 0.00 | 0.00 |
ChCl-LA 29% | 16.00 ± 0.00 | 15.10 ± 0.05 | 0.00 | 18.30 ± 0.57 |
ChCl-U 29% | 10.10 ± 0.05 | 0.00 | 0.00 | 12.00 ± 0.00 |
ChCl-CA 100% | 29.00 ± 0.00 | 26.00 ± 0.00 | 30.00 ± 0.00 | 28.00 ± 0.00 |
ChCl-Gly 100% | 0.00 | 0.00 | 0.00 | 13.00 ± 0.00 |
ChCl-LA100% | 20.00 ± 0.00 | 23.00 ± 0.00 | 15.00 ± 0.00 | 21.10 ± 0.05 |
ChCl-U 100% | 12.00 ± 0.00 | 0.00 | 0.00 | 15.00 ± 0.00 |
Ciprofloxacin (5 µg/disc) | 26.70 ± 0.06 | 30.00 ± 0.00 | 32.00 ± 0.00 | * NT |
Fluconazol (25 µg/disc) | NT * | NT * | NT * | 28.00 ± 0.00 |
Voriconazol (1 µg/disc) | NT * | NT * | NT * | 32.50 ± 0.50 |
HPC-NADES Components | HPC-NADES Systems | |
---|---|---|
HPC-NADES 17% | HPC-NADES 29% | |
HPC | 1.36 g | 1.12 g |
ChCl-U 100% | 0.73 g choline chloride + 0.63 g urea (1:2 molar ratio) | 1.25 g choline chloride + 1.07 g urea (1:2 molar ratio) |
ChCl-Gly 100% | 0.58 g choline chloride + 0.77 g glycerol (1:2 molar ratio) | 1.00 g choline chloride + 1.32 g glycerol (1:2 molar ratio) |
ChCl-LA 100% | 0.83 g choline chloride + 0.53 g lactic acid (1:1 molar ratio) | 1.41 g choline chloride + 0.91 g lactic acid (1:1 molar ratio) |
ChCl-CA 100% | 0.57 g choline chloride + 0.78 g citric acid (1:1 molar ratio) | 0.98 g choline chloride + 1.34 g citric acid (1:1 molar ratio) |
water | 5.28 g | 4.56 g |
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Filip, D.; Macocinschi, D.; Balan-Porcarasu, M.; Varganici, C.-D.; Dumitriu, R.-P.; Peptanariu, D.; Tuchilus, C.G.; Zaltariov, M.-F. Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity. Gels 2022, 8, 666. https://doi.org/10.3390/gels8100666
Filip D, Macocinschi D, Balan-Porcarasu M, Varganici C-D, Dumitriu R-P, Peptanariu D, Tuchilus CG, Zaltariov M-F. Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity. Gels. 2022; 8(10):666. https://doi.org/10.3390/gels8100666
Chicago/Turabian StyleFilip, Daniela, Doina Macocinschi, Mihaela Balan-Porcarasu, Cristian-Dragos Varganici, Raluca-Petronela Dumitriu, Dragos Peptanariu, Cristina Gabriela Tuchilus, and Mirela-Fernanda Zaltariov. 2022. "Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity" Gels 8, no. 10: 666. https://doi.org/10.3390/gels8100666