Polymorphic Forms of Valinomycin Investigated by NMR Crystallography
Abstract
:1. Introduction
2. Results
2.1. General Considerations
2.2. The Triclinic Polymorph
2.3. The Monoclinic Polymorph
2.4. The “Symmetric” Structural Motif
2.5. The “Propeller” Structural Motif
3. Discussion
4. Materials and Methods
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Residue | H-Bonding Scheme | Corresponding {13C/15N/1H} NMR Chemical Shift (in ppm) | Dihedral Angle (in Degrees) | |||||
---|---|---|---|---|---|---|---|---|
CO | Cα | Namid | Hamid | Hα | φ | ψ | ||
D-Hyv1 | a ← d4 (a ← d4) | 170.2 (171.0) | 76.6 (75.1) | – | – | 5.8 (6.2) | −2 (−7) | +94 (+102) |
D-Val2 | d → a11, a ← d6 (d → a11, a ← d6) | 176.4 (175.9) | 60.7 (58.5) | 123 (114) | 9.2 (8.6) | 3.7 (4.8) | −124 (−135) | +65 (+64) |
L-Lac3 | none (none) | 166.8 (166.3) | 74.9 (75.6) | – | – | 5.5 (5.2) | −11 (−11) | −68 (−68) |
L-Val4 | d → a1 (d → a1) | 171.7 (172.3) | 54.2 (53.8) | 113 (112) | 9.1 (8.3) | 5.7 (5.9) | +68 (+76) | −109 (−107) |
D-Hyv5 | a ← d8 (a ← d8) | 168.4 (169.6) | 78.0 (78.3) | – | – | 6.1 (6.3) | −6 (−11) | +153 (+142) |
D-Val6 | d → a2 (d → a2) | 173.7 (173.7) | 60.2 (61.1) | 117 (116) | 7.5 (8.0) | 3.7 (3.7) | −130 (−129) | +57 (+62) |
L-Lac7 | a ← d10 (a ← d10) | 171.8 (171.8) | 70.3 (70.0) | – | – | 6.1 (6.0) | +9 (+9) | −96 (−96) |
L-Val8 | d → a5, a ← d12 (d → a5, a ← d12) | 177.9 (177.7) | 61.5 (61.7) | 120 (120) | 9.3 (9.5) | 4.0 (3.9) | +128 (+129) | −68 (−65) |
D-Hyv9 | none (none) | 166.1 (166.3) | 83.4 (83.2) | – | – | 5.7 (5.6) | +3 (+4) | +82 (+81) |
D-Val10 | d → a7 (d → a7) | 173.1 (173.3) | 55.2 (54.6) | 115 (116) | 8.5 (8.6) | 5.6 (5.9) | −66 (−66) | +106 (+104) |
L-Lac11 | a ← d2 (a ← d2) | 171.3 (170.5) | 72.9 (72.5) | – | – | 6.7 (6.2) | +26 (+21) | −161 (−159) |
L-Val12 | d → a8 (d → a8) | 173.7 (173.5) | 60.8 (61.1) | 116 (115) | 8.5 (8.2) | 4.0 (3.7) | +128 (+125) | −68 (−68) |
Residue | H-Bonding Scheme | Corresponding {13C/15N/1H} NMR Chemical Shift (in ppm) | Dihedral Angle (in Degrees) | |||||
---|---|---|---|---|---|---|---|---|
CO | Cα | Namid | Hamid | Hα | φ | ψ | ||
D-Hyv1 | a ← d4 | 168.9 | 76.2 | – | – | 6.3 | −7 | +142 |
D-Val2 | d → a10 | 172.7 | 61.4 | 116 | 7.2 | 3.7 | −130 | +59 |
L-Lac3 | a ← d6 | 171.5 | 71.1 | – | – | 6.1 | +9 | −96 |
L-Val4 | d → a1, a ← d8 | 177.7 | 61.1 | 119 | 9.6 | 4.0 | +127 | −67 |
D-Hyv5 | none | 165.8 | 82.7 | – | – | 5.7 | +2 | +81 |
D-Val6 | d → a3 | 172.7 | 54.8 | 115 | 8.5 | 5.6 | −68 | +106 |
L-Lac7 | a ← d10 | 170.0 | 70.3 | – | – | 6.3 | +22 | −155 |
L-Val8 | d → a4 | 173.2 | 61.5 | 115 | 7.9 | 3.6 | +128 | −67 |
D-Hyv9 | a ← d12 | 171.2 | 74.2 | – | – | 6.0 | −3 | +95 |
D-Val10 | d → a7, a ← d2 | 176.5 | 59.3 | 122 | 9.0 | 4.0 | −125 | +66 |
L-Lac11 | none | 166.9 | 73.6 | – | – | 5.5 | −11 | −77 |
L-Val12 | d → a9 | 171.7 | 54.1 | 113 | 8.9 | 5.8 | +74 | −105 |
Residue | H-Bonding Scheme | Corresponding {13C/15N/1H} NMR Chemical Shift (in ppm) | Dihedral Angle (in Degrees) | |||||
---|---|---|---|---|---|---|---|---|
CO | Cα | Namid | Hamid | Hα | φ | ψ | ||
D-Hyv1 | a ← d4 | 170.3 | 75.9 | – | – | 5.8 | +1 | +101 |
D-Val2 | d → a11 | 173.2 | 60.8 | 122 | 9.0 | 4.2 | −123 | +66 |
L-Lac3 | a ← d6 | 172.5 | 72.3 | – | – | 5.4 | −17 | −79 |
L-Val4 | d → a1 | 171.3 | 58.8 | 115 | 9.5 | 4.1 | +107 | −78 |
D-Hyv5 | a ← d8 | 169.9 | 77.4 | – | – | 6.4 | −8 | +114 |
D-Val6 | d → a3 | 169.7 | 59.0 | 121 | 9.0 | 4.3 | −101 | +83 |
L-Lac7 | a ← d10 | 170.4 | 69.4 | – | – | 6.2 | +8 | −125 |
L-Val8 | d → a5 | 170.8 | 59.2 | 119 | 9.8 | 4.3 | +106 | −80 |
D-Hyv9 | a ← d12 | 170.3 | 75.5 | – | – | 6.2 | +3 | +115 |
D-Val10 | d → a7 | 174.4 | 60.1 | 122 | 9.4 | 4.0 | −128 | +64 |
L-Lac11 | a ← d2 | 171.3 | 71.8 | – | – | 5.2 | −18 | −76 |
L-Val12 | d → a9 | 171.2 | 59.7 | 114 | 8.9 | 3.9 | +118 | −70 |
Residue | H-Bonding Scheme | Corresponding {13C/15N/1H} NMR Chemical Shift (in ppm) | Dihedral Angle (in Degrees) | |||||
---|---|---|---|---|---|---|---|---|
CO | Cα | Namid | Hamid | Hα | φ | ψ | ||
D-Hyv1 | none | 167.1 | 79.0 | – | – | 6.4 | 0 | +104 |
D-Val2 | d → a11 | 173.0 | 52.2 | 101 | 9.0 | 6.1 | −177 | +125 |
L-Lac3 | a ← d6 | 171.9 | 70.9 | – | – | 7.3 | +19 | −146 |
L-Val4 | none | 173.5 | 59.9 | 113 | 7.2 | 4.6 | +116 | 72 |
D-Hyv5 | none | 165.5 | 80.0 | – | – | 6.3 | −4 | +10 |
D-Val6 | d → a3 | 174.5 | 53.7 | 100 | 8.5 | 6.5 | −170 | +121 |
L-Lac7 | a ← d10 | 171.3 | 70.1 | – | – | 7.0 | +35 | −142 |
L-Val8 | none | 174.2 | 68.6 | 113 | 6.9 | 4.7 | +122 | −70 |
D-Hyv9 | none | 166.4 | 80.2 | – | – | 6.1 | +3 | +88 |
D-Val10 | d → a7 | 172.5 | 53.4 | 99 | 8.3 | 6.0 | −177 | +121 |
L-Lac11 | a ← d2 | 168.8 | 71.9 | – | – | 7.0 | +25 | −137 |
L-Val12 | none | 172.3 | 58.5 | 112 | 6.7 | 4.4 | +110 | −72 |
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Czernek, J.; Brus, J. Polymorphic Forms of Valinomycin Investigated by NMR Crystallography. Int. J. Mol. Sci. 2020, 21, 4907. https://doi.org/10.3390/ijms21144907
Czernek J, Brus J. Polymorphic Forms of Valinomycin Investigated by NMR Crystallography. International Journal of Molecular Sciences. 2020; 21(14):4907. https://doi.org/10.3390/ijms21144907
Chicago/Turabian StyleCzernek, Jiří, and Jiří Brus. 2020. "Polymorphic Forms of Valinomycin Investigated by NMR Crystallography" International Journal of Molecular Sciences 21, no. 14: 4907. https://doi.org/10.3390/ijms21144907