Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (La3+, Nd3+, Sm3+, Gd3+)
Abstract
:1. Introduction
2. Results and Discussion
2.1. Harzianic Acid
2.2. Coordination Properties of Harzianic Acid toward La3+, Nd3+, Sm3+ and Gd3+
2.3. Ecotoxicity Tests on Raphidocelis subcapitata, Daphnia magna, and Aliivibrio fischeri
3. Materials and Methods
3.1. Reagents and Their Analysis
3.2. HPLC–MS Q-TOF Analyses
3.3. Preparation of Test Solutions for CD and UV–Vis Spectrophotometric Measurements
3.4. Ecotoxicity Tests
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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Ion | Observed m/z of Main Isotopic Peak | Formula | Exact Mass |
---|---|---|---|
Harzianic acid + La(ClO4)3 | |||
[H2L + H]+ | 366.1921 | C19H28NO6 | 366.1917 |
[H2L + Na]+ | 388.1730 | C19H27NO6Na | 388.1736 |
[H2L − H + La + ClO4]+ | 602.0315 | C19H26NO6LaClO4 | 602.0309 |
[H2L + La + 2ClO4]+ | 701.9867 | C19H27NO6La(ClO4)2 | 701.9872 |
[2H2L − 2H + La]+ | 867.2592 | C38H52N2O12La | 867.2584 |
Harzianic acid + NdCl3 | |||
[H2L + H]+ | 366.1908 | C19H28NO6 | 366.1917 |
[H2L + Na]+ | 388.1728 | C19H27NO6Na | 388.1736 |
[2H2L − 2H + Nd]+ | 870.2597 | C38H52N2O12Nd | 870.2602 |
Harzianic acid + Sm(ClO4)3 | |||
[H2L + H]+ | 366.1926 | C19H28NO6 | 366.1917 |
[H2L + Na]+ | 388.1741 | C19H27NO6Na | 388.1736 |
[2H2L − 2H + Sm]+ | 880.2716 | C38H52N2O12Sm | 880.2718 |
Harzianic acid + GdCl3 | |||
[H2L + H]+ | 366.1921 | C19H28NO6 | 366.1917 |
[H2L + Na]+ | 388.1730 | C19H27NO6Na | 388.1736 |
[2H2L − 2H + Gd]+ | 886.2765 | C38H52N2O12Gd | 886.2761 |
Element | O.P., cm | Dataset | ||
---|---|---|---|---|
La | 0.995 | 3.82(2.88); 3.64(3.31); 3.55(4.22); 3.49(7.37); 3.45(7.76); 3.42(8.00); 3.38(8.12) | 1 | Figure 3A (orange) |
1.992 | 3.99(2.88); 3.86(3.20); 3.76(3.83); 3.74(4.62); 3.71(6.48); 3.68(7.34) | 1 | Figure 3A (blue) | |
Nd | 1.000 | 23.3(2.84); 21.5(4.44); 21.2(6.36); 20.8(7.31); 20.5(7.79); 20.1(8.11); 19.7(8.59) | 0.2 | Figure 3B (orange) |
1.935 | 8.26(2.76); 7.78(3.26); 7.60(3.81); 7.54(4.57); 7.46(6.90); 7.42(7.32); 7.37(7.62); 7.04(9.71) | 0.2 | Figure 3B (blue) | |
Sm | 1.051 | 3.01(2.91); 2.85(3.76); 2.81(5.59); 2.80(6.30); 2.79(6.81); 2.78(7.29); 2.74(7.86); 2.69(8.24) | 1 | Figure 3C (orange) |
2.02 | 8.04(2.94); 7.85(3.17); 7.65(3.71); 7.59(4.12); 7.55 (4.83) | 1 | Figure 3C (blue) | |
Gd | 1.00 | 6.44(3.55); 6.36(3.94); 6.32(5.06); 6.26 (6.81); 6.23(7.39) | 1 | Figure 3D (orange) |
1.99 | 4.57(3.18); 4.41(4.23); 4.35(7.39); 4.25(9.62) | 1 | Figure 3D (blue) |
Ln3+ | Reaction | log (Formation Constant), log βpq ± σ |
---|---|---|
La3+ | La3+ + L2− ⇌ LaL+ La3+ + 2 L2− ⇌ LaL2− | 6.26 ± 0.04 17.46 ± 0.04 |
Nd3+ | Nd3+ + L2− ⇌ NdL+ Nd3+ + 2 L2− ⇌ NdL2− | 7.89 ± 0.04 15.48 ± 0.04 |
Sm3+ | Sm3+ + L2− ⇌ SmL+ Sm3+ + 2 L2− ⇌ SmL2− | 8.07 ± 0.02 13.66 ± 0.03 |
Gd3+ | Gd3+ + L2− ⇌ GdL+ Gd3+ + 2 L2− ⇌ GdL2− | 9.15 ± 0.07 14.14 ± 0.07 |
Organism | Compound | EC10 (µM) | EC50 (µM) |
---|---|---|---|
A. fischeri | Harzianic acid | >3.5 | >3.5 |
Gadolinium | 1.5 (0.7–2.6) | 2.6 (1.4–4.0) | |
R. subcapitata | Harzianic acid | 0.7 (0.4–0.9) | 1.2 (0.8–1.9) |
Gadolinium | 0.0 (0.0–0.1) | 3.5 (1.4–8.3) | |
D. magna | Harzianic acid | 0.7 (0.3–1.1) | 1.2 (0.7–2.2) |
Gadolinium | 0.0 (0.0–1.3) | 1.1 (0.0–14) |
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De Tommaso, G.; Salvatore, M.M.; Siciliano, A.; Staropoli, A.; Vinale, F.; Nicoletti, R.; DellaGreca, M.; Guida, M.; Salvatore, F.; Iuliano, M.; et al. Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (La3+, Nd3+, Sm3+, Gd3+). Molecules 2022, 27, 1959. https://doi.org/10.3390/molecules27061959
De Tommaso G, Salvatore MM, Siciliano A, Staropoli A, Vinale F, Nicoletti R, DellaGreca M, Guida M, Salvatore F, Iuliano M, et al. Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (La3+, Nd3+, Sm3+, Gd3+). Molecules. 2022; 27(6):1959. https://doi.org/10.3390/molecules27061959
Chicago/Turabian StyleDe Tommaso, Gaetano, Maria Michela Salvatore, Antonietta Siciliano, Alessia Staropoli, Francesco Vinale, Rosario Nicoletti, Marina DellaGreca, Marco Guida, Francesco Salvatore, Mauro Iuliano, and et al. 2022. "Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (La3+, Nd3+, Sm3+, Gd3+)" Molecules 27, no. 6: 1959. https://doi.org/10.3390/molecules27061959