Supplementary information for Induced CD of iron(ii) clathrochelates: sensing of the structural and conformational alterations of serum albumins

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1 Electronic Supplementary Material (ESI) for Metallomics. This journal is The Royal Society of Chemistry 218 Supplementary information for Induced CD of iron(ii) clathrochelates: sensing of the structural and conformational alterations of serum albumins Vladyslava Kovalska, *ab Marina Kuperman, a Mykhaylo Losytskyy, a Serhii Vakarov, bc Slawomir Potocki, d Sergiy Yarmoluk, a Yan Voloshin, e Oleg Varzatskii, bc Elzbieta Gumienna- Kontecka d* a Institute of Molecular Biology and Genetics, NASU, 1 Zabolotnogo St., 3143 Kyiv, Ukraine, v.kovalska@gmail.com b SC Princeton Biomolecular Research Labs, 2A Saperne pole St., 142, Kyiv, Ukraine c Institute of General and Inorganic Chemistry, 32/34 Palladin Av., 38 Kyiv, Ukraine d Faculty of Chemistry, University of Wroclaw, 14 F. Joliot-Curie St., -383 Wroclaw, Poland, elzbieta.gumienna-kontecka@chem.uni.wroc.pl e Nesmeyanov Institute of Organoelement Compounds RAS, 28 Vavilova St., , Moscow, Russia *corresponding author 1

2 fluorescence intensity, arb.un BSA + ortho-substituted isomer (1) = 28 nm Figure S1a. Fluorescence spectra (non-corrected for inner filter effect) of 3μM BSA solution in the presence of, 1, 2, 2., 3, 4, and 1 μm of ortho-substituted isomer (1) in mm Tris-HCl buffer, ph.9; λ ex = 28 nm. fluorescence intensity, arb.un BSA + meta-substituted isomer (2) = 28 nm Figure S1b. Fluorescence spectra (non-corrected for inner filter effect) of 3μM BSA solution in the presence of, 1, 2, 2., 3, 4, and 1 μm of meta -substituted isomer (2) in mm Tris-HCl buffer, ph.9; λ ex = 28 nm. 2

3 fluorescence intensity, arb.un BSA + para-substituted isomer (3) = 28 nm Figure S1c. Fluorescence spectra (non-corrected for inner filter effect) of 3μM BSA solution in the presence of, 1, 2, 2., 3, 4, and 1 μm of para-substituted isomer (3) in mm Tris-HCl buffer, ph.9; λ ex = 28 nm. fluorescence intensity, arb.un BSA + ortho-substituted isomer (1) = 29 nm Figure S1d. Fluorescence spectra (non-corrected for inner filter effect) of 3μM BSA solution in the presence of,., 1, 1., 2, 2., 3, 4., and μm of ortho-substituted isomer (1) in mm Tris-HCl buffer, ph.9; λ ex = 29 nm. 3

4 fluorescence intensity, arb.un BSA + meta-substituted isomer (2) = 29 nm Figure S1e. Fluorescence spectra (non-corrected for inner filter effect) of 3μM BSA solution in the presence of, 1, 2, 2., 3, 4, and 1 μm of meta -substituted isomer (2) in mm Tris-HCl buffer, ph.9; λ ex = 29 nm. 2 BSA + para-substituted isomer (3) fluorescence intensity, arb.un = 29 nm Figure S1f. Fluorescence spectra (non-corrected for inner filter effect) of 3μM BSA solution in the presence of,., 1, 1., 2, 2., 3, 4., and μm of para-substituted isomer (3) in mm Tris- HCl buffer, ph.9; λ ex = 29 nm. 4

5 4 HSA + ortho-substituted isomer (1) fluorescence intensity, arb.un = 28 nm Figure S1g. Fluorescence spectra (non-corrected for inner filter effect) of 3μM HSA solution in the presence of, 1, 2, 2., 4,, 1 and 1 μm of ortho-substituted isomer (1) in mm Tris-HCl buffer, ph.9; λ ex = 28 nm. 4 HSA + meta-substituted isomer (2) fluorescence intensity, arb.un = 28 nm Figure S1h. Fluorescence spectra (non-corrected for inner filter effect) of 3μM HSA solution in the presence of, 1, 2, 2., 4,, 1 and 1 μm of meta-substituted isomer (2) in mm Tris-HCl buffer, ph.9; λ ex = 28 nm.

6 fluorescence intensity, arb.un HSA + para-substituted isomer (3) = 28 nm Figure S1i. Fluorescence spectra (non-corrected for inner filter effect) of 3μM HSA solution in the presence of, 1, 2, 2., 4,, 1 and 1 μm of para-substituted isomer (3) in mm Tris-HCl buffer, ph.9; λ ex = 28 nm max, nm BSA + ortho-substituted isomer (1) meta-substituted isomer (2) para-substituted isomer (3) = 28 nm , M Figure S2a. Dependence of maximum wavelength (λ max ) of BSA fluorescence (λ ex = 28 nm) for 3μM BSA solution in the presence of -1 μm of ortho-substituted isomer (1), meta-substituted isomer (2) and para-substituted isomer (3) in mm Tris-HCl buffer, ph.9.

7 max, nm = 29 nm BSA + ortho-substituted isomer (1) meta-substituted isomer (2) para-substituted isomer (3) , M Figure S2b. Dependence of maximum wavelength (λ max ) of BSA fluorescence (λ ex = 29 nm) for 3μM BSA solution in the presence of - μm of ortho-substituted isomer (1), meta-substituted isomer (2) and para-substituted isomer (3) in mm Tris-HCl buffer, ph max, nm 3 38 = 28 nm HSA + ortho-substituted isomer (1) meta-substituted isomer (2) para-substituted isomer (3) , M Figure S2c. Dependence of maximum wavelength (λ max ) of HSA fluorescence (λ ex = 28 nm) for 3μM BSA solution in the presence of -1 μm of ortho-substituted isomer (1), meta-substituted isomer (2) and para-substituted isomer (3) in mm Tris-HCl buffer, ph.9.

8 F 2,2 2, 1,8 1, 1,4 1,2 1, = 29 nm ortho-substituted isomer (1) meta-substituted isomer (2) para-substituted isomer (3) Figure S3. Stern Volmer plots of HSA fluorescence quenching at and 29 nm by studied clathrochelates; F and F are the protein fluorescence intensities in absence and in presence of clathrochelates. Absorbance,,4,3,2,1, 4 clathrochelate 1 clathrochelate 2 clathrochelate 3 Figure S4. Absorption spectra of the clathrochelates

9 Ortho- (1) BSA ICD HSA ICD BSA fluorescence quenching F 18 3, 1 12, Meta- (2) F 3 3, 2 2, Para- (3) F ,, Figure S. ICD spectra of iron(ii) clathrochelates in the presence of BSA or HSA and plots of their quenching of BSA emission at different ph. 9

10 F 2,2 2, 1,8 1, 1,4 1,2 1, ph ortho- substituted isomer (1) meta- substituted isomer (2) para- substituted isomer (3) F ph Figure S. Stern Volmer plots of BSA fluorescence quenching by the iron(ii) clathrochelates at ph 3. and. 1