Metal chelation by a plant lignan, secoisolariciresinol diglucoside
Flavia Fucassi, Adam Heikal, Lyuba I. Mikhalovska, Guy Standen, Iain U. Allan, Sergey V. Mikhalovsky and Peter J. Cragg*
Journal of Inclusion Phenomena and Macrocyclic Chemistry
Supplementary Information
Figure S1. Linear response of SDG as the Na+ adduct.
Figure S2. Determination of background Na+ concentration
Figure S3. Typical mass spectrum for SDG which appears as its Na+ adduct at 709.3139 amu, expected at 709.2684 amu (error below 0.01%)
Figure S4. Typical mass spectrum for [SDG(-glucose)·Ca]+
Figure S5. Typical mass spectrum for [SDG·Ni]+
Figure S6. Typical mass spectrum for [SDG·Cu]+
Figure S7. Typical mass spectrum for [SDG·Fe]+
Figure S8. Typical mass spectrum for [SDG·Ag]+
Figure S9. Typical mass spectrum for [SDG·Pb]+
Figure S10. HPLC trace of flax hull extract in water
Table S1. Molecular simulation data from molecular mechanics (MMFF) and semiempirical (PM6) simulations.
Table S2. Binding data from molecular mechanics (MMFF) and semiempirical (PM6) simulations.
Figure S1. Linear response of SDG as the Na+adduct
Figure S2. Determination of background Na+ concentration
Figure S3. Typical mass spectrum for SDG which appears as its Na+ adduct at 709.3139 amu, expected at 709.2684 amu (error below 0.01%)
Figure S4. Typical mass spectrum for [SDG(-glucose)·Ca]+
Keq= {relative intensity at 563 (SDG-glucose-·Ca2+)/relative intensity at 709 (SDG·Na+)} x {[Na+back]/[Ca2+ini]}
= {(15101/3005)·(6.5 x 10-5/1.82 x 10-5)}
=17.95
Figure S5. Typical mass spectrum for [SDG·Ni]+
Keq={relative intensity at 744 (SDG-·Ni2+)/relative intensity at 709 (SDG·Na+)} x {[Na+back]/[Ni2+ini]}
= {(2722/3995)·(6.5 x 10-5/1.82 x 10-5)}
=2.43
Figure S6. Typical mass spectrum for [SDG·Cu]+
Keq={relative intensity at 749 (SDG-·Cu2+)/relative intensity at 709 (SDG·Na+)} x {[Na+back]/[Cu2+ini]}
= {(4745/2828)·(6.5 x 10-5/1.82 x 10-5)}
=5.99
Figure S7. Typical mass spectrum for [SDG·Fe]+
Keq={relative intensity at 741 (SDG-·Fe2+)/relative intensity at 709 (SDG·Na+)} x {[Na+back]/[Fe2+ini]}
= {(4939/8165)·(6.5 x 10-5/1.82 x 10-5)}
=2.16
Figure S8. Typical mass spectrum for [SDG·Ag]+
Keq={relative intensity at 793 (SDG-·Ag)/relative intensity at 709 (SDG·Na+)} x {[Na+back]/[Ag+ini]}
= {(988/2291)·(6.5 x 10-5/1.82 x 10-5)}
=1.54
Figure S9. Typical mass spectrum for [SDG·Pb]+
Keq={relative intensity at 893 (SDG-·Pb2+)/relative intensity at 709 (SDG·Na+)} x {[Na+back]/[Pb2+ini]}
= {(14129/10227)·(6.5 x 10-5/1.82 x 10-5)}
=4.93
Note: the major peaks and relative intensities for [SDG·Pb]+ were analysed and found to be in good agreement with the expected values.
Predicted:891.2840 (53%), 892.2860 (57%), 893.2882 (100%) and 894.2918 (40%)
Found:891.2452 (46%), 892.2466 (42%), 893.2474 (100%) and 894.2508 (35%)
1
Figure S10. HPLC trace of flax hull extract in water, diluted 10 times from stock solution (RT 16.85 min.). Mobile phase: water containing 1:1 v/v 15% acetonitrile/methanol, increasing to 25% after 10 min.; injection volume 20µl; detection wavelength 280 nm.
Table S1. Molecular simulation data from molecular mechanics (MMFF) and semiempirical (PM6) simulations.
PM6 simulation / MMFF simulationH
(kJmol-1) / G
(kJmol-1) / E
(kJmol-1)
SDG / -1014.2 / -1288.2 / 844.9
H2O / -178.5 / -234.6 / -227.2
H3O+ / 669.4 / 611.5 / 590.3
[Ca(H2O)6]2+ / -34.3 / -183.3 / -943.9
[Pb(H2O)6]2+ / 928.8 / 773.7 / 213.1
[Cu(H2O)6]2+ / 550.5 / 406.9 / -1134.7
[Fe(H2O)6]2+ / 664.5 / 517.3 / -1106.7
[Ni(H2O)6]2+ / 592.6 / 458.6 / -209.3
[Ag(H2O)6]+ / 511.1 / 373.3 / -212.6
[SDG∙Ca] / -944.4 / -1288.9 / -903.8
[SDG∙Pb] / -654.6 / -940.8 / -1070.8
[SDG∙Cu] / -563.9 / -849.6 / -1137.4
[SDG∙Fe] / -700.6 / -983.8 / -1100.9
[SDG∙Ni] / -350.0 / -637.3 / 1045.3
[SDG∙Ag] / -1135.3 / -1418.6 / 962.3
[SDG∙Ca]+ / -365.0 / -652.6
[SDG∙Pb]+ / -130.0 / -419.4
[SDG∙Cu]+ / -1.3 / -288.9
[SDG∙Fe]+ / -180.2 / -461.
[SDG∙Ni]+ / 259.9 / 6.2
[SDG∙Ag]+ / -22.4 / -257.8
[SDG∙Ca]2+ / 521.6 / 231.6
[SDG∙Pb]2+ / 703.2 / 411.7
[SDG∙Cu]2+ / 973.5 / 685.2
[SDG∙Fe]2+ / 715.0 / 431.0
[SDG∙Ni]2+ / 1122.9 / 830.2
Table S2. Binding data from molecular mechanics (MMFF) and semiempirical (PM6) simulations.
Formation of: / PM6 simulation / MMFF simulationΔH
(kJmol-1) / ΔG
(kJmol-1) / ΔE
(kJmol-1)
{[SDG∙Ca]2+∙6H2O} / 499.1 / 295.5 / -2171.0
{[SDG∙Pb]2+∙6H2O} / -282.4 / -481.4 / -3491.7
{[SDG∙Cu]2+∙6H2O} / 366.2 / 158.9 / -2210.7
{[SDG∙Fe]2+∙6H2O} / -6.3 / -205.7 / -2201.6
{[SDG∙Ni]2+∙6H2O} / 473.5 / 252.2 / -953.5
{[SDG∙Ag]+∙6H2O} / -1703.2 / -1911.3 / -1033.2
{[SDG∙Ca]+∙H3O+∙5H2O} / 460.4 / 257.4
{[SDG∙Pb]+∙H3O+∙5H2O} / -267.7 / -466.4
{[SDG∙Cu]+∙H3O+∙5H2O} / 239.3 / 30.9
{[SDG∙Fe]+∙H3O+∙5H2O} / -50.6 / -252.3
{[SDG∙Ni]+∙H3O+∙5H2O} / 494.4 / 274.3
{[SDG∙Ag]∙H3O+∙5H2O} / -855.3 / -784.7
{[SDG∙Ca]∙2H3O+∙4H2O} / 788.9 / 407.2
{[SDG∙Pb]∙2H3O+∙4H2O} / 115.6 / -141.7
{[SDG∙Cu]∙2H3O+∙4H2O} / 584.6 / 316.6
{[SDG∙Fe]∙2H3O+∙4H2O} / 333.9 / 71.7
{[SDG∙Ni]∙2H3O+∙4H2O} / 756.4 / 476.9
1