Supplemental Table S2. Results of the Refinement of the EXAFS Spectra of Plant Samples

Supplemental table S2. Results of the refinement of the EXAFS spectra of plant samples using the DL-Excurve program: alternative fitting for testing the presence of biomineralisation (Cu(II)-phosphates, Cu(II)oxalate and Cu(II)-oxides) that was found in the T.caerulescens samples in our companion paper. The data of EXAFS samples were taken from the experiments of the second series, in the first series no EXAFS samples were taken (see methods for details).EF = Fermi energy, defines the threshold for the EXAFS spectra (Rehr and Albers, 2000).FI = Fit index.

se = Mathematical standard errors of the refinement (two sigma level). The error of the EXAFS approach as such is higher, this is revealed by the differences between samples of the same type.

remarks / Sample incl. number of individual plants used to prepare it / Number / Type of ligands per shell
(± 2 sigma standard deviation) / Distance
(± 2 sigma standard deviation)
[Å] / i2
(± 2 sigma standard deviation)
[Å2] / EF
(± 2 sigma standard deviation)
[eV] / FI
No significant contributions of metal-metal or metal-phosphorus interactions / eSCu,
1st refinement / 0.4 (±0.1) S
5.5 (±0.4) O
0.1 (±0.5) NA / 2.459(±0.020)
1.949(±0.004) *
1.949(±0.004) * / 0.008 (±0.001) *
0.008 (±0.001) *
0.008 (±0.001) * / -12.7 (±0.4) / 0.176
No significant contributions of metal-metal or metal-phosphorus interactions / eSCu,
2nd refinement,
best fit of series / 3.7 (±0.5) O
2.2 (±0.5) NA / 1.953(±0.003) *
1.953(±0.003) * / 0.008 (±0.001) *
0.008 (±0.001) * / -12.0 (±0.4) / 0.177
alternative refinement with different start parameters. Results are more reasonable! / eSCu
3rd refinement / 0.0 (±0.1) S
3.8 (±0.5) O
2.0 (±0.6) NA / 2.28 #
1.952(±0.004) *
1.952(±0.004) *
#: fixed in refinement / 0.008 (±0.001) *
0.008 (±0.001) *
0.008 (±0.001) * / -12.1 (±0.4) / 0.177
eECu / 3.9 (±0.4) O
0.0 (±0.1) NA / 1.914(±0.004) *
1.914(±0.004) * / 0.004 (±0.003) *
0.004 (±0.003) * / -8.3 (±0.9) / 1.127
No significant contributions of metal-metal or metal-phosphorus interactions / sECu / 4.8 (±0.5) O
0.9 (±0.5) NA / 1.940(±0.004) *
1.940(±0.004) * / 0.008 (±0.001) *
0.008 (±0.001) * / -10.6 (±0.4) / 0.149
No significant contributions of metal-metal or metal-phosphorus interactions / sSCu / 4.4 (±0.4) O
1.1 (±0.5) NA / 1.942(±0.003) *
1.942(±0.003) * / 0.009 (±0.001) *
0.009 (±0.001) * / -10.7 (±0.4) / 0.150

*1, *2, *: Values were constrained to be identical for these contributions. Deviations from this simplification do not improve the model significantly. Afac was set to 0.75; For nicotianamine (NA) the structural model obtained in the refinement of the model complex has been used, keeping the metal carbon distances constant and defining their Debye-Waller factors to 120% of the corresponding first shell value.