Supporting Information
Synthesis, Characterization and Cellular Localization of
Cytotoxic Constitutional Organometallic Isomers of
Rhenium Delivered on a Cyanocobalmin Scaffold.
Giuseppe Santoro,a Theodora Zlateva,b Albert Ruggi, a Luca Quaroni†b and Fabio
Zobi*a
a Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg,
Switzerland. Fax: (+41) 044 635 6802; Tel: (+41) 044 635 4623; E-mail: fabio.zobi@unifr.ch
b Paul Scherrer Institute, Swiss Light Source, 5232, Villigen-PSI
†Current address, Functional Genomic Center, ETH/University of Zürich,
Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
List of Figures
Figure 1S. Comparison of IR spectra of 1 (top) and 2. Note the shift in frequency of the νC≡N band at 2175 cm-1 for 1 indicative of a Co-CN-Re conjugate.
Figure 2S. 1H-COSY spectrum of 1 in the 7.7-9.2 ppm region. Figure 3S. Peak labels for NMR assignments of complexes 1 and 2.
Figure 4S. UV-Vis spectra of complexes 1 (black), 2 (red) and vitamin B12 in MeOH.
Figure 5S. Normalized emission spectra of 1 (black) and 2 (red) in MeOH. λexc = 400 nm.
Figure 6S. IR spectra of single 3T3 cell during accumulation of 2. Time Interval: 2 min between points. Left: uncorrected. Right: baseline corrected (unsupervised rubberband method). Red circle indicates the initial slow phase of accumulation, followed by a steep increase in rate about 60 min after exposure.
Figure 7S-8S. IR maps of the A1 carbonyl stretching vibration at 2028 cm-1 (7S) and of the lipid absorption at 2852 cm-1 (8S) with experimental scale of the integrated intensity of the 2nd
derivative.
Figure 9S. Pixel maps of a 3T3 fibroblast incubated with 2 (300 μM concentration).
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Figure 1S. Comparison of IR spectra of 1 (top) and 2. Note the shift in frequency of the νC≡N band at 2175 cm-1 for 1 indicative of a Co-CN-Re conjugate.
18 17 N 19 3 2 1 N 4 8 7 6 N 9 5 13 12 11 N 10 35 53 30 31 32 26 27 60 61 55 48 49 50 41 42 43 37 38 Co 25 H 54 46 47 36 56 57 O HN B5 B6 B7 B8 B9 B4 N B2 N B10 B11 R1 R2 R3 R4 O HO O P O Pr2 Pr1 H Pr3 R5 O O O 16 14 15 R 20
a
b
d
c
e
f
g
O H2N O NH2 O NH2 O NH2 O NH2 O H2N 62 O 63 PY1 PY2 N PY2 PY1 Phen 5 Phen 6 N Phen 3 Phen 4 N Phen 1 Phen 2 Re OC OC CO300 400 500 600 0.3 0.6 0.9 A b so rp tio n (A b s.) Wavelength (nm)
Figure 4S. UV-Vis spectra of complexes 1 (black), 2 (red) and vitamin B12 in MeOH.
510 610 710 In tensi ty ( a . u. ) Wavelength (nm)
Figure 6S. IR spectra of single 3T3 cell during accumulation of 2. Time Interval: 2 min between points. Left: uncorrected. Right: baseline corrected (unsupervised rubberband method). Red circle indicates the initial slow phase of accumulation, followed by a steep increase in rate about 60 min after exposure.
Figure 7S. IR map of the A1 carbonyl stretching vibration at 2028 cm-1 with the experimental scale of the integrated intensity of the 2nd derivative.
Figure 8S. IR map of the lipid absorption at 2852 cm-1 with experimental scale of the integrated intensity of the 2nd derivative.
Figure 9S. Optical images of a 3T3 fibroblast incubated with 2 (300 μM concentration). Left: top and bottom inserts show pixel images reconstructed from mapping the intensities of the 2nd derivative of the lipid absorption at 2852 cm-1 and the A1 carbonyl stretching vibration at
2028 cm-1 respectively. The scale represents relative units of 2nd derivative of absorbance with
the left scale referring to the top insert. Nc = cell nuclear area identified as previously described. Right: same cell with maxima of reconstructed integrated pixel intensities (same scale as to the left with minima set to -0.0001 and -0.0003 for the 2852 cm-1 and the 2028 cm-1
vibration respectively) of the 2nd derivative of the same lipid absorption and the A1 stretching