New Haloterpenes from the Marine Red Alga Laurencia papillosa: Structure Elucidation and Biological Activity
Abstract
:1. Introduction
2. Results and Discussion
2.1. Working up and Structure Identification
2.1.1. Aplysiolic Acid
2.1.2. 7-Acetyl-aplysiol
2.1.3. Aplysiol-7-one
2.1.4. 11,14-Dihydroaplysia-5,11,14,15-tetrols
2.1.5. 5-epi-Maneolactone
2.2. Biological Activities
3. Materials and Methods
3.1. General Procedures
3.2. Collection and Taxonomy of the Marine Alga
3.3. Extraction and Isolation of the Bioactive Constituents
3.4. Antimicrobial Assay
3.5. Ab Initio Calculations
3.6. Crystal Structure Determination of 7-acetylaplysiol (2) and 5-epi-maneolactone (6)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Author Statement
Abbreviations
References
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Aplysiolic Acid (1) | 7-Acetyl-aplysiol (2) | Aplysiol-7-one (3) | Dihydroaplysiatetrol (5a) | 5-epi-Maneolactone (6) | |
---|---|---|---|---|---|
Appearance | colorless solid | colorless solid | colorless solid | colorless oil | colorless solid |
Rf | 0.26 a | 0.28 b | 0.39 b | 0.30 a | 0.50 b |
Anisaldehyde/ sulfuric acid | pink, turning later to violet | pink, turning later to violet | pink, turning later to violet | pink, turning later to violet | brownish gray |
Molecular formula | C13H19BrO3 | C14H21BrO2 | C12H17BrO2 | C20H33BrO4 | C12H11ClO3 |
(+)-ESIMS: m/z (%) | 323/325 [M + Na]+ (100:95.4), 623/625/627 [2M + Na]+, (10:31:10) | 296/298 [M + Na]+ (88:100), 569 [2M + Na]+ | 439/441 [M + Na]+ (100:97), 855/857/859 [2M + Na]+, (20:57:19) | 261/263 [M + Na]+ (100:31), 499 [2M + Na]+ (4) | |
(−)-ESIMS: m/z (%) | 301/303 [M − H]– (100:90.5), 603/605/607 [2M − H]–(37:57:21) | 335/337/339 [M + Cl]− (69:100:25) | 461/463 [M + 2Na − 3H]− (100:97), 831/833/855 [2M − H]–, (25:52:27) | ||
(+)-ESIHRMS: (m/z) | 323.0615 [M + Na]+ (calc. 323.0617 for C14H21BrNaO2), 625.1326 [2M + Na]+ (calc. 625.1327 for C28H42Br2NaO4) | 439.1454 [M + Na]+ (calc. 439.1454 for C20H33BrO4Na) | 261.0299 [M + Na]+ (calc. 261.0289 for C12H11ClO3Na) | ||
(−)-ESIHRMS (m/z) | 301.0441 [M − H]- (calc. 301.0444 for C13H18BrO3) | 335.0418 [M + H]– (calc. 335.0418 for C14H21BrClO2) | |||
IR (KBr) ν cm−1 | 3259, 2361, 2182, 1782, 1592, 1358, 1160, 1018, 895, 841, 794, 665 | ||||
[α]20D (MeOH) | −34.8 (c, 0.13) | −55.4 (c, 0.24) | − 31.9 (c, 0.12) | −155.8 (c, 0.26) |
Nr. | 1 | 2 | 3 | |||
---|---|---|---|---|---|---|
δC | δH (J in Hz) | δC | δH (J in Hz) | δC | δH (J in Hz) | |
1 | 62.9 | 4.72 (dd, 12.4, 4.7) | 63.2 | 4.69 (dd, 12.3, 4.7) | 61.5 | 4.67 (dd, 12.7, 4.5) |
2 | 33.9 | 2.20 (m), 2.13 (m) | 33.9 | 2.15 (m), 2.08 (m) | 34.0 | 2.24 (m), 2.09 (m) |
3 | 32.5 | 2.70 (dddd, 13.5, 9.6, 5.7, 2.1)2.15 (m) | 32.5 | 2.11 (m), 2.67 (tdt, 13.0, 5.6, 2.0) | 32.1 | 2.64 (ddd, 13.6, 5.0, 2.8), 2.17 (ddd, 13.6, 5.0, 2.0) |
4 | 148.5 | 148.6 | 147.7 | |||
5 | 76.2 | 76.3 | 79.6 | |||
6 | 34.1 | 2.04 (dd, 13.8, 12.8), 1.83 (m) | 33.1 | 1.65 (ddd, 14.0, 3.9, 1.3), 1.91 (m) | 48.5 | 2.86 (d, 14.6), 2.38 (m) |
7 | 38.2 | 2.94 (tt, 12.9, 4.1) | 46.3 | 2.90 (tt, 12.7, 4.0) | 209.9 | |
8 | 23.5 | 1.90 (m), 1.66 (m) | 23.4 | 1.80 (m), 1.45 (m) | 37.5 | 2.41 (m) |
9 | 32.0 | 1.77 (m) | 32.2 | 1.74 (m) | 33.3 | 2.08 (m) |
10 | 43.0 | 43.0 | 43.4 | |||
11 | 181.0 | 211.8 | 110.9 | 4.94 (d, 2.0), 4.74 (d, 1.5) | ||
12 | 14.8 | 0.96 (s) | 14.7 | 0.89 (s) | 14.8 | 1.18 (s) |
13 | 110.2 | 4.90 (dd, 2.0, 1.0), 4.81 (d, 1.5) | 110.0 | 4.86 (m), 4.79 (t, 1.3) | ||
14 | - | 28.3 | 2.13 (s) |
Nr. | 5a | Epimer 5b | ||
---|---|---|---|---|
δC | δH (J in Hz) | δC | δH (J in Hz) | |
1 | 65.23 | 4.72 (m) | 65.23 | 4.72 (m) |
2 | 35.61 | 2.14 (m), 2.10 (m) | 35.61 | 2.13 (m), 2.08 (m) |
3 | 33.69 | 2.77 (m), 2.12 (m) | 33.69 | 2.77 (m), 2.09 (m) |
4 | 151.64 | 151.61 | ||
5 | 77.28 | 77.27 | ||
6 | 32.75 | 1.66 (m), 1.75 (m) | 32.75 | 1.66 (m), 1.73 |
7 | 43.48 | 1.95 (m) | 43.65 | 1.95 (m) |
8 | 22.22 | 1.33, 1.67 (m) | 22.93 | 1.33, 1.60 (m) |
9 | 34.03 | 1.68 (m) | 33.96 | 1.67 (m) |
10 | 44.17 | 44.17 | ||
11 | 75.39 | 75.38 | ||
12 | 139.83 | 5.79 (d, 16.3) | 140.46 | 5.77 (d, 15.6) |
13 | 128.08 | 5.74 (dd, 15–16, 6–7) | 127.95 | 5.71 (dd, 15–16, 6–7) |
14 | 80.33 | 3.85 (m) | 80.39 | 3.86 (m) |
15 | 73.69 | 73.66 | ||
16 | 25.97 | 1.15 (s) | 26.07 | 1.15 (s) |
17 | 25.11 | 1.15 (s) | 25.16 | 1.16 (s) |
18 | 26.30 | 1.27 (s) | 26.22 | 1.27 (s) |
19 | 15.21 | 0.89 (s) | 15.21 | 0.891 (s) |
20 | 109.15 | 4.84 (s), 4.74 (s) | 109.17 | 4.83 (s), 4.75 (s) |
Nr. | δC | δH (J in Hz) |
---|---|---|
1 | 86.5 | 3.36 (dd, 2.4, 1.0) |
2 | 78.2 | |
3 | 113.8 | 5.71 (ddd, 10.5, 2.5, 0.5) |
4 | 139.2 | 6.01 (ddd, 10.5, 9.5, 1.1) |
5 | 55.3 | 4.81 (m) |
6 | 52.9 | 2.83 (dddd, 12.1, 10.4, 4.1, 1.7) |
7 | 80.0 | 4.83 (m) |
8 | 33.9 | 2.11 (d,18.0), 2.02 (m) |
9 | 78.9 | 4.85 (m) |
10 | 84.1 | 5.36 (td, 5.0, 0.9) |
11 | 42.9 | 2.71 (ddd, 10.2, 5.1, 0.8) |
12 | 173.5 |
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Shaaban, M.; Abou-El-Wafa, G.S.E.; Golz, C.; Laatsch, H. New Haloterpenes from the Marine Red Alga Laurencia papillosa: Structure Elucidation and Biological Activity. Mar. Drugs 2021, 19, 35. https://doi.org/10.3390/md19010035
Shaaban M, Abou-El-Wafa GSE, Golz C, Laatsch H. New Haloterpenes from the Marine Red Alga Laurencia papillosa: Structure Elucidation and Biological Activity. Marine Drugs. 2021; 19(1):35. https://doi.org/10.3390/md19010035
Chicago/Turabian StyleShaaban, Mohamed, Ghada S. E. Abou-El-Wafa, Christopher Golz, and Hartmut Laatsch. 2021. "New Haloterpenes from the Marine Red Alga Laurencia papillosa: Structure Elucidation and Biological Activity" Marine Drugs 19, no. 1: 35. https://doi.org/10.3390/md19010035