Cascading One-Pot Synthesis of Biodegradable Uronic Acid-Based Surfactants from Oligoalginates, Semi-Refined Alginates, and Crude Brown Seaweeds
Abstract
:1. Introduction
2. Results
2.1. Preparation of Starting Materials
2.2. Synthesis from Oligoalginates
2.2.1. Synthesis from Oligomannuronate (OM)
2.2.2. Synthesis from Oligoguluronate (OG)
2.2.3. Synthesis from Oligoalginate (OAlg)
2.3. Synthesis from Semi-Refined Alginate (s-r Alg)
2.4. Synthesis from Crude Brown Seaweeds
2.5. Physico-Chemical Properties of Anionic and Non-Ionic Surfactant Compositions Derived from Oligoalginates, Semi-Refined Alginates, and Crude Brown Seaweed
2.5.1. Measurements of Air-Water Interfacial Behavior
H-C12 Derivatives from OM, OG, OAlg, and s-r Alg
H–C8 Surfactant Composition from Crude Seaweed
2.5.2. Ecotoxicity Studies
2.5.3. Biodegradability Studies
3. Discussion
4. Materials and Methods
4.1. Chemistry
4.2. Physico-Chemistry
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Description | Method | Result | Units | |
---|---|---|---|---|
Oligomannuronate (OM) | Solids | Constant weight at 103 °C | 95.6 | %dry/crude |
Mineral matter | 12 h, 550 °C | 31.9 | %dry/crude | |
Ratio (M/G) | By calculation, 1H NMR | 2.7 | ||
DP | By calculation | 4.0 | ||
Oligoguluronate (OG) | Solids | Constant weight at 103 °C | 100.0 | %dry/crude |
Mineral matter | 12 h, 550 °C | 26.3 | %dry/crude | |
Ratio (M/G) | By calculation, 1H NMR | 0.04 | ||
DP | By calculation | 30.0 | ||
Oligoalginate (OAlg) | Solids | Constant weight at 103 °C | 90.1 | %dry/crude |
Mineral matter | 12 h, 550 °C | 44.3 | %dry/crude | |
Ratio (M/G) | By calculation, 1H NMR | 1.4 | ||
DP | By calculation | 12.7 | ||
Semi-refined alginates (s-r Alg) | Solids | Constant weight at 103 °C | 94.9 | %dry/crude |
Mineral matter | 12 h, 550 °C | 47.0 | %dry/crude | |
Mannuronic and guluronic content | Methanolysis | 29.2 | %dry/crude | |
Glucose content | Methanolysis | 10.9 | %dry/crude | |
Xylose content | Methanolysis | <0.5 | %dry/crude | |
Fucose content | Methanolysis | 2.1 | %dry/crude | |
Ratio (M/G) | By calculation, 1H NMR | 2.6 |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
1α (Man) | 4.91 (d) | 1.7 | α-Pyranose | 52 |
2α (Man) | 4.97 (s) | - | α-Furanose | 7 |
3α (Man) | 5.05 (d) | 2.0 | α-Lactone | 11 |
3β (Man) | 5.03 (d) | 4.6 | β-Lactone | 13 |
4α (Gul) | 4.95 (d) | 4.4 | α-Lactone | 5 |
4β (Gul) | 5.06 (s) | - | β-Lactone | 5 |
5β (Gul) | 4.91 (s) | - | β-Furanose | 3 |
MSA (n eq) | ||||
---|---|---|---|---|
Compounds | 1.7 | 2.2 | 2.6 | 4.7 |
1α | 183 mg (yld = 33%) | 132 mg (yld = 24%) | 150 mg (yld = 27%) | 69 mg (yld = 12%) |
2α, 3α,β, 4α,β, 5β | 126 mg | 118 mg | 117 mg | 31 mg |
6 | 57 mg | 166 mg | 148 mg | 380 mg |
Entries | DodOH (n’ eq) | MSA (n eq) | 7α | 8α, 9α,β, 10α,β, 11α,β, 12β |
---|---|---|---|---|
1 a | 16 | 2 | 229 mg (yld = 24%) | 153 mg |
2 | 4 | 1 | 240 mg (yld = 25%) | 168 mg |
3 | 4 | 0.5 | 200 mg (yld = 21%) | 184 mg |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
7α (Man) | 4.92 (d) | 1.7 | α-Pyranose | 48 |
8α (Man) | 4.97 (s) | - | α-Furanose | 9 |
9α (Man) | 5.05 (d) | 2.0 | α-Lactone | 5 |
9β (Man) | 5.03 (d) | 4.5 | β-Lactone | 22 |
10α (Gul) | 4.95 (d) | 4.5 | α-Lactone | 3 |
10β (Gul) | 5.07 (s) | - | β-Lactone | 3 |
11β (Gul) * | n.d. | n.d. | β-Pyranose | 5 |
12β (Gul) | 4.91 (s) | - | β-Furanose | 6 |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
13α (Man) | 4.80 (d) | 2.1 | α-Pyranose | 47 |
9α (Man) | 5.00 (d) | 1.6 | α-Lactone | 4 |
9β (Man) | 4.96 (d) | 3.8- | β-Lactone | 12 |
14β (Gul) | 4.62 (d) | 8.3 | β-Pyranose | 4 |
10α (Gul) | 4.92 (d) | 4.4 | α-Lactone | 9 |
10β (Gul) | 4.98 (s) | - | β-Lactone | 9 |
15β (Gul) * | n.d. | n.d. | β-Furanose | 4 |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
13α (Man) | 4.80 (d) | 2.1 | α-Pyranose | 15 |
14β (Gul) | 4.62 (d) | 8.4 | β-Pyranose | 13 |
10α (Gul) | 4.92 (d) | 4.5 | α-Lactone | 26 |
10β (Gul) | 4.98 (s) | - | β-Lactone | 26 |
15β (Gul) * | n.d. | n.d. | β-Furanose | 21 |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
13α (Man) | 4.80 (d) | 2.1 | α-Pyranose | 23 |
9α (Man) * | n.d. | n.d. | α-Lactone | 4 |
9β (Man) | 4.95 (d) | 4.1- | β-Lactone | 9 |
14β (Gul) | 4.61 (d) | 8.2 | β-Pyranose | 9 |
10α (Gul) | 4.91 (d) | 4.5 | α-Lactone | 20 |
10β (Gul) | 4.97 (s) | - | β-Lactone | 20 |
15β (Gul) ** | n.d. | n.d. | β-Furanose | 9 |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
13α (Man) | 4.85 (d) | 2.0 | α-Pyranose | 23 |
9α (Man) * | n.d. | n.d. | α-Lactone | 5 |
9β (Man) | 4.95 (d) | 4.7- | β-Lactone | 13 |
14β (Gul) ** | n.d. | n.d. | β-Pyranose | 11 |
10β (Gul) | 5.03 (s) | - | β-Lactone | 20 |
17α (Fuc) | 4.83 (d) | 3.8 | α-Pyranose | 5 |
17β (Fuc) | 4.27 (d) | 7.7 | β-Pyranose | 8 |
18α (Fuc) | 4.75 (d) | 3.6 | α-Furanose | (+18β) 15 |
18β (Fuc) | 4.75 (d) | n.d. | β-Furanose | (+18α) 15 |
Compounds | δ H1 (ppm) (Multiplicity) | J1,2 (Hz) | Form | Composition (mol%) |
---|---|---|---|---|
19α (Man) | 4.82 (d) | 2.0 | α-Pyranose | 30 |
20β (Gul) | 4.64 (d) | 8.1 | β-Pyranose | 6 |
21α (Gul) | 4.93 (d) | 4.6 | α-Lactone | 5 |
22α (Fuc) | 4.78 (d) | 3.8 | α-Pyranose | 13 |
22β (Fuc) | 4.26 (d) | 7.8 | β-Pyranose | 9 |
23α (Fuc) | 4.72 (d) | 3.7 | α-Furanose | 9 |
23β (Fuc) | 4.75 (d) | 2.2 | β-Furanose | 28 |
Category Acute 1 (very toxic) | |
CL50 96 h (for the fish) | ≤1 mg L−1 and/or |
CE50 48 h (for the shellfish) | ≤1 mg L−1 and/or |
CEr50 72 h (for the seaweed) | ≤1 mg L−1 |
Category Acute 2 (toxic) | |
CL50 96 h (for the fish) | >1 but ≤10 mg L−1 and/or |
CE50 48 h (for the shellfish) | >1 but ≤10 mg L−1 and/or |
CEr50 72 h (for the seaweed) | >1 but ≤10 mg L−1 |
Category Acute 3 (poorly toxic) | |
CL50 96 h (for the fish) | >10 but ≤100 mg L−1 and/or |
CE50 48 h (for the shellfish) | >10 but ≤100 mg L−1 and/or |
CEr50 72 h (for the seaweed) | >10 but ≤100 mg L−1 |
Above 100 mg L−1, the substance is considered as non-toxic |
Test | Effect | Toxicological Descriptor * | SLES | H–C12 s-r Alg |
---|---|---|---|---|
Microalgae | Rate of growth | CEr50—72 h | 7.0 mg L−1 Toxic | 45.8 mg L−1 Poorly toxic |
Daphnia | Immobilization | CE50—24 h | 11.6 mg L−1 Poorly toxic | >100 mg L−1 Non-toxic |
Fish | Mortality | CL50—96 h | 11.2 mg L−1 Poorly toxic | 67.0 mg L−1 Poorly toxic |
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Pessel, F.; Noirbent, G.; Boyère, C.; Arnaud, S.P.; Wong, T.; Durand, L.; Benvegnu, T. Cascading One-Pot Synthesis of Biodegradable Uronic Acid-Based Surfactants from Oligoalginates, Semi-Refined Alginates, and Crude Brown Seaweeds. Molecules 2023, 28, 5201. https://doi.org/10.3390/molecules28135201
Pessel F, Noirbent G, Boyère C, Arnaud SP, Wong T, Durand L, Benvegnu T. Cascading One-Pot Synthesis of Biodegradable Uronic Acid-Based Surfactants from Oligoalginates, Semi-Refined Alginates, and Crude Brown Seaweeds. Molecules. 2023; 28(13):5201. https://doi.org/10.3390/molecules28135201
Chicago/Turabian StylePessel, Freddy, Guillaume Noirbent, Cédric Boyère, Sacha Pérocheau Arnaud, Tiphaine Wong, Laura Durand, and Thierry Benvegnu. 2023. "Cascading One-Pot Synthesis of Biodegradable Uronic Acid-Based Surfactants from Oligoalginates, Semi-Refined Alginates, and Crude Brown Seaweeds" Molecules 28, no. 13: 5201. https://doi.org/10.3390/molecules28135201