Colorimetric and fluorescent probe for detection of nanomolar lysine in aqueous medium

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Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2016 Colorimetric and fluorescent probe for detection of nanomolar lysine in aqueous medium Susanta Adhikari a *, Avijit Ghosh a, Sandip Mandal b, Subhajit Guria a, Prajna Paramita Banerjee c, Ansuman Chatterjee c and Debasis Das b* a Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009, West Bengal, India b Department of Chemistry, The University of Burdwan, Burdwan 713104, West Bengal, India c Department of Zoology, Visva Bharati University, Santiniketan, West Bengal, India INDEX page no. General information....(s-2) Calculation of detection limits... (S-3) 1 H, 13 C NMR and mass spectra of the compounds......(s-4)-(s-11) Table S-1 Crystal data and structure refinement for THBPY (CCDC No. 1409304)... (S-12)-(S-15) Figure S-7 Visible color changes of THBPY (10 µm) in DMSO HEPES buffer)... (S-16) Figure S-8 Effect of ph on the emission intensity of THBPY and [THBPY- Lys] (S-16) Figure S-9 HRMS spectrum of [THBPY- Lys] in methanol Figure S-10 Change in absorbance of [THBPY+ butyl amine] complex (S-17) (S-18) Figure S-11 Change in absorbance of THBPY (10µM) upon addition of butyl amine 1,5- diaminopentane, 6-amino hexanoic acid, ethelenediamine (S-19) Figure S-12 Change in fluorescence of THBPY (10µM) upon addition of butyl amine, 1,5- diaminopentane, 6-amino hexanoic acid and ethylenediamine (S-19) Figure S-13 Reversibility of absorbance of [THBPY+ Lys] adduct in DMSO HEPES buffer ---- - (S-20) S-1

Figure S-14 Reversibility of fluorescence of [THBPY-Lys] adduct in DMSO HEPES buffer... (S-20) Figure S-15 HRMS spectrum after H 2 O 2 treatment of [THBPY+ Lys] adduct... (S-21) Figure S-16 Changes in the emission profile of compound 3 upon addition of Lys.. ( S-21) Figure S-17 Change in the absorbance of compound 3 upon addition of Lys Figure S-18 Changes in the emission profile of compound-4 upon addition of Lys... (S-22) (S-22) Figure S-19 Changes in the absorbance of compound-4 upon addition of butyl amine 1,5- diaminopentane and 6-amino hexanoic acid complex... (S-23) Table S-2 Frontier molecular orbitals (MOs) of THBPY and energy levels of the MOs (S-23) Table S-3 Frontier molecular orbitals (MOs) of THBPY+ Lys (neutral) and the energy levels of MOs (S-24) Table S-4 Frontier molecular orbitals (MOs) of THBPY+ Lys (cationic) and the energy levels of MOs (S-25) Figure S-20 Selected MOs of THBPY, [THBPY + cysteine], [THBPY + homo cysteine]... (S-26) Cell imaging & cytotoxicity...(s-27) General information Reagents and solvents were purchased from commercial suppliers and used as received. 1 H and 13 C NMR spectra were recorded on a Bruker Avance III HD (300 MHz) spectrometer. Chemical shifts were reported in parts per million (ppm), and the residual solvent peak was used as an internal reference: proton (chloroform δ 7.26), carbon (chloroform δ 77.16) or tetramethylsilane (TMS δ 0.00) was used as a reference. Multiplicity was indicated as follows: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), dd (doublet of doublet), bs (broad S-2

singlet). Coupling constants were reported in Hertz (Hz). High resolution mass spectra were obtained on a Micromass/Q-Toff. micro TM spectrometer. IR spectra were measured on Thermo Scientific Nicolet 380 instrument. For thin layer chromatography (TLC), Merck precoated TLC plates (Merck 60 F254) were used, and compounds were visualized with a UV light at 254 nm. Further visualization was achieved by staining with iodine. Flash chromatography separations were performed on SRL 230-400 mesh silica gel. Measurement of fluorescence quantum yield For determination of the fluorescence quantum yields (Φ fl ), of BODIPY dye we used a Perkin- Elmer instrument, with fluorescein in 0.1 M NaOH as a fluorescence standard (fluorescence quantum yield of 0.85 in 0.1 N NaOH). Fluorescence quantum yields (Φ fl ) were obtained by the following equation Φ fl sample = Φ fl standard Abs standard Σ[F sample ] / Abs sample Σ[F standard ] Where F denotes fluorescence intensity at each wavelength and Σ [F] was calculated by summation of fluorescence intensity. 1 solvent Absorbance Fluorescence Quantum maximum maximum yield (%) CH 2 Cl 2 504 517 80 Methanol 503 515 68 Equation used for calculating detection limit (DL) DL = CL CT; where CL = conc. of ligand; CT = conc. of Lys at which fluorescence enhanced. Thus, DL = 1 10-6 0.001 µm = 0.001 10-6 µm. S-3

Figure S-1 1 H NMR spectrum of DFTH in CDCl 3 Figure S-2 13 C spectrum of DFTH in CDCl 3 S-4

Figure S-3 HRMS spectrum of DFTH in methanol Figure S-4 1 H NMR spectrum of THBPY in CDCl 3 S-5

Figure S-5 13 C NMR spectrum of THBPY in CDCl 3 Figure S-6 HRMS spectrum of THBPY in methanol S-6

Figure S-7 Color changes of THBPY (10 µm) in DMSO HEPES buffer (0.01 M, ph 7.4) (1: 9, v/v) media upon gradual addition of Lys from 0.05 to 5000.0 µm (bare eye, top) and under UV light for Lys 0.005 µm to 1000 µm (bottom). S-7

Figure S-8 Effect of ph on the emission intensity of THBPY and [THBPY-Lys] adduct Figure S-9 Change in absorbance of THBPY upon addition of butyl amine in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4) S-8

Figure S-10 Changes in absorbance of THBPY (10 µm) upon addition of 1,5-diaminopentane, 6-amino hexanoic acid and ethylenediamine (50 µm) in DMSO HEPES buffer, 1: 9, v/v, 0.01 M, ph 7.4. Figure S-11 Changes in fluorescence of THBPY (10 µm) upon addition of butyl amine, 1,5- diaminopentane, 6-amino hexanoic acid, ethelenediamine (50 µm) in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4). S-9

Figure S-12 Reversibility of absorbance of [THBPY+ Lys] adduct (50 µm) in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4) upon addition of 10,100 µm H 2 O 2 solutions. Figure S-13 Reversibility of fluorescence spectrum of the [THBPY+ Lys] adduct (10 µm) in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4) upon addition of 20,100 µm H 2 O 2 solutions. S-10

Figure S-14 HRMS spectrum of the solution of [THBPY+ Lys] adduct after treatment of H 2 O 2. Figure S-15 1 H NMR spectrum of 1 in CDCl 3 S-11

Figure S-16 13 C NMR spectrum of 1 in CDCl 3 Figure S-17 1 H NMR spectrum of 2 in CDCl 3 S-12

Figure S-18 13 C NMR spectrum of 2 in CDCl 3 Figure S-19 1 H NMR spectrum of 3 in CDCl 3 S-13

Figure S-20 13 C NMR spectrum of 3 in CDCl 3 Figure S-21 1 H NMR spectrum of 4 in DMSO-d 6 S-14

Figure S-22 13 C NMR spectrum of 4 in DMSO-d 6 Figure S-23 Changes in the absorbance of 3 (10 µm) upon addition of Lys (50 µm) in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4). S-15

Figure S-24 Changes in the emission profile of 3 (10 µm) upon addition of Lys (50 µm) in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4). Figure S-25 Changes in emission profile of 4 (10 µm) upon addition of Lys (50 µm) in DMSO HEPES buffer (1: 9, v/v, 0.01 M, ph 7.4). S-16

Figure S-26 Change in absorbance of 4 (10 µm) upon addition of butyl amine 1,5- diaminopentane, 6-amino hexanoic acid (50 µm in DMSO HEPES buffer, 1: 9, v/v, 0.01 M, ph 7.4). Table S-1 Crystal data and structure refinement for THBPY (CCDC No. 1409304) Bond lengths (Å) (B1)-(F1) 1.380(3) (F1)-(B1) 1.380(3) (B1)-(F2) 1.402(4) (F2)-(B1) 1.402(4) (B1)-(N2) 1.545(4) (N2)-(B1) 1.545(4) (B1)-(N1) 1.552(4) (N1)-(B1) 1.552(4) (N2)-(C8) 1.409(4) (C8)-(N2) 1.409(4) (N2)-(C10) 1.344(3) (C10)-(N2) 1.344(3) (N1)-(C6) 1.409(4) (C6)-(N1) 1.409(4) (N1)-(C2) 1.340(3) (C2)-(N1) 1.340(3) (C7)-(C8) 1.389(3) (C8)-(C7) 1.389(3) (C7)-(C6) 1.406(3) (C6)-(C7) 1.406(3) (C7)-(C14) 1.494(4) (C14)-(C7) 1.494(4) (C8)-(C12) 1.437(3) (C12)-(C8) 1.437(3) (C6)-(C4) 1.416(3) (C4)-(C6) 1.416(3) (C12)-(C13) 1.499(4) S-17

(C13)-(C12) 1.499(4) (C12)-(C11) 1.373(4) (C11)-(C12) 1.373(4) (C10)-(C9) 1.493(5) (C9)-(C10) 1.493(5) (C10)-(C11) 1.396(4) (C11)-(C10) 1.396(4) (C4)-(C3) 1.381(4) (C3)-(C4) 1.381(4) (C4)-(C5) 1.505(4) (C5)-(C4) 1.505(4) (C2)-(C3) 1.402(5) (C3)-(C2) 1.402(5) (C2)-(C1) 1.500(5) (C1)-(C2) 1.500(5) (C9)-(H9A) 0.961 (H9A)-(C9) 0.961 (C9)-(H9B) 0.96 (H9B)-(C9) 0.96 (C9)-(H9C) 0.96 (H9C)-(C9) 0.96 (C13)-(H13A) 0.96 (H13A)-(C13) 0.96 (C13)-(H13B) 0.959 (H13B)-(C13) 0.959 (C13)-(H13C) 0.96 (H13C)-(C13) 0.96 (C3)-(H3) 0.93 (H3)-(C3) 0.93 (C5)-(H5A) 0.961 (H5A)-(C5) 0.961 (C5)-(H5B) 0.959 (H5B)-(C5) 0.959 (C5)-(H5C) 0.96 (H5C)-(C5) 0.96 (C11)-(H11) 0.93 (H11)-(C11) 0.93 (C1)-(H1A) 0.96 (H1A)-(C1) 0.96 (C1)-(H1B) 0.96 (H1B)-(C1) 0.96 (C1)-(H1C) 0.961 (H1C)-(C1) 0.961 (C16)-(C15) 1.375(4) (C15)-(C16) 1.375(4) (C16)-(C17) 1.404(5) (C17)-(C16) 1.404(5) (C16)-(C21) 1.518(4) (C21)-(C16) 1.518(4) (C19)-(C18) 1.415(4) (C18)-(C19) 1.415(4) (C19)-(C14) 1.390(4) (C14)-(C19) 1.390(4) (C19)-(C20) 1.507(4) (C20)-(C19) 1.507(4) (C18)-(C17) 1.413(4) (C17)-(C18) 1.413(4) (C18)-(C24) 1.454(5) (C24)-(C18) 1.454(5) (C15)-(H15) 0.929 (H15)-(C15) 0.929 (C15)-(C14) 1.409(4) (C14)-(C15) 1.409(4) (C17)-(O2) 1.353(4) (O2)-(C17) 1.353(4) (C24)-(H24) 0.93 (H24)-(C24) 0.93 (C24)-(O1) 1.233(4) (O1)-(C24) 1.233(4) (C20)-(H20A) 0.96 (H20A)-(C20) 0.96 (C20)-(H20B) 0.96 (H20B)-(C20) 0.96 (C20)-(H20C) 0.96 (H20C)-(C20) 0.96 S-18

(C21)-(H21) 0.981 (H21)-(C21) 0.981 (C21)-(C23) 1.520(5) (C23)-(C21) 1.520(5) (C21)-(C22) 1.528(4) (C22)-(C21) 1.528(4) (O2)-(H2) 0.82 Bond angles ( o ) (F1)-(B1)-(F2) 108.9(2) (F1)-(B1)-(N2) 111.3(2) (F1)-(B1)-(N1) 111.3(2) (F2)-(B1)-(N2) 109.2(2) (F2)-(B1)-(N1) 109.4(2) (N2)-(B1)-(N1) 106.6(2) (B1)-(N2)-(C8) 125.4(2) (B1)-(N2)-(C10) 126.2(2) (C8)-(N2)-(C10) 108.3(2) (B1)-(N1)-(C6) 125.5(2) (B1)-(N1)-(C2) 126.5(3) (C6)-(N1)-(C2) 108.0(2) (C8)-(C7)-(C6) 121.5(2) (C8)-(C7)-(C14) 118.6(2) (C6-(C7)-(C14) 119.9(2) (N2)-(C8)-(C7) 120.6(2) (N2)-(C8)-(C12) 107.4(2) (H2)-(O2) 0.82 (C23)-(H23A) 0.96 (H23A)-(C23) 0.96 (C23)-(H23B) 0.96 (H23B)-(C23) 0.96 (C23)-(H23C) 0.96 (H23C)-(C23) 0.96 (C7)-(C8)-(C12) 132.1(2) (N1)-(C6)-(C7) 119.8(2) (N1)-(C6)-(C4) 108.0(2) (C7)-(C6)-(C4) 132.1(3) (C8-(C12)-(C13) 129.7(2) (C8)-(C12)-(C11) 105.8(2) (C13)-(C12)-(C11) 124.5(3) (N2)-(C10)-(C9) 121.8(3) (N2)-(C10)-(C11) 109.0(3) (C9)-(C10)-(C11) 129.2(3) (C6)-(C4)-(C3) 106.1(3) (C6)-(C4)-(C5) 128.7(3) (C3)-(C4)-(C5) 125.3(3) (N1)-(C2)-(C3) 109.1(3) (N1)-(C2)-(C1) 122.7(3) (C3)-(C2)-(C1) 128.2(3) (C10)-(C9)-(H9A) 109.4 (C22)-(H22A) 0.96 (H22A)-(C22) 0.96 (C22)-(H22B) 0.959 (H22B)-(C22) 0.959 (C22)-(H22C) 0.96 (H22C)-(C22) 0.96 (C10)-(C9)-(H9B) 109.5 (C10)-(C9)-(H9C) 109.5 (H9A)-(C9)-(H9B) 109.5 (H9A)-(C9)-(H9C) 109.5 (H9B)-(C9)-(H9C) 109.5 (C12)-(C13)-(H13A) 109.4 (C12)-(C13)-(H13B) 109.5 (C12)-(C13)-(H13C) 109.4 (H13A)-(C13)-(H13B)109.5 (H13A)-(C13)-(H13C)109.5 (H13B)-(C13)-(H13C)109.6 (C4)-(C3)-(C2) 108.8(3) (C4)-(C3)-(H3) 125.6 (C2)-(C3)-(H3) 125.6 (C4)-(C5)-(H5A) 109.5 (C4)-(C5)-(H5B) 109.5 (C4)-(C5)-(H5C) 109.5 S-19

(H5A)-(C5)-(H5B) 109.4 (H5A)-(C5)-(H5C) 109.4 (H5B)-(C5)-(H5C) 109.5 (C12)-(C11)-(C10) 109.5(3) (C12)-(C11)-(H11) 125.2 (C10)-(C11)-(H11) 125.2 (C2)-(C1)-(H1A) 109.5 (C2)-(C1)-(H1B) 109.5 (C2)-(C1)-(H1C) 109.5 (H1A)-(C1)-(H1B) 109.5 (H1A)-(C1)-(H1C) 109.4 (H1B)-(C1)-(H1C) 109.4 (C15)-(C16)-(C17) 116.7(2) (C15)-(C16)-(C21) 123.6(2) (C17)-(C16)-(C21) 119.7(2) (C18)-(C19)-(C14) 118.0(2) (C18)-(C19)-(C20) 121.6(2) (C14)-(C19)-(C20) 120.4(2) (C19)-(C18)-(C17) 120.5(2) (C19)-(C18)-(C24) 120.6(3) (C17)-(C18)-(C24) 118.8(3) (C16)-(C15)-(H15) 118.3 (C16)-(C15)-(C14) 123.5(2) (H15)-(C15)-(C14) 118.2 (C16)-(C17)-(18) 121.3(3) (C16)-(C17)-(O2) 117.5(3) (C18)-(C17)-(O2) 121.1(3) (C7)-(C14)-(C19) 121.0(2) (C7)-(C14)-(C15) 119.0(2) (C19)-(C14)-(C15) 119.9(2) (C18)-(C24)-(H24) 117.7 (C18)-(C24)-(O1) 124.6(3) (H24)-(C24)-(O1) 117.7 (C19)-(C20)-(H20A) 109.5 (C19)-(C20)-(H20B) 109.4 (C19)-(C20)-(H20C) 109.5 (H20A)-(C20)-(H20B)109.5 (H20A)-(C20)-(H20C)109.5 (H20B)-(C20)-(H20C)109.5 (C16)-(C21)-(H21) 107.6 (C16)-(C21)-(C23) 113.4(3) (C16)-(C21)-(C22) 110.0(3) (H21)-(C21)-(C23) 107.6 (H21)-(C21)-(C22) 107.6 (C23)-(C21)-(C22) 110.4(3) (C17)-(O2)-(H2) 109.4 (C21)-(C23)-(H23A) 109.5 (C21)-(C23)-(H23B) 109.5 (C21)-(C23)-(H23C) 109.5 (H23A)-(C23)-(H23B)109.4 (H23A)-(C23)-(H23C)109.5 (H23B)-(C23)-(H23C)109.5 (C21)-(C22)-(H22A) 109.4 (C21)-(C22)-(H22B) 109.5 (C21)-(C22)-(H22C) 109.5 (H22A)-(C22)-(H22B)109.5 (H22A)-(C22)-(H22C)109.4 (H22B)-(C22)-(H22C)109.5 S-20

Scheme S-1 Synthesis of [THBPY- Lys] adduct (complex-1) Figure S-27 HRMS spectrum of [THBPY- Lys] adduct in methanol. S-21

Scheme S-2 Reversibility of [THBPY- Lys] adduct in presence of hydrogen peroxide Table S-2 Frontier molecular orbitals (MOs) of THBPY and the energy levels of the MOs are shown (in a.u). Calculations are based on ground state geometry by DFT at the B3LYP/6-31G/level using Gaussian 09 Frontier orbital Energy (a.u.) Energy optimised geometry LUMO+1-0.0498 S-22

LUMO -0.0985 HOMO -0.2084 HOMO-1-0.2410 Table S-3 Frontier molecular orbitals (MOs) of THBPY-lysine (neutral) and the energy levels of the MOs are shown (in a.u). Calculations are based on ground state geometry by DFT at the B3LYP/6-31G/level using Gaussian 09. S-23

Frontier orbital Energy (a.u.) Energy optimised geometry LUMO+1 0.0565 LUMO -0.0738 HOMO -0.1253 S-24

HOMO-1-0.1433 Table S-4 Frontier molecular orbitals (MOs) of THBPY-lysine (cationic) and the energy levels of the MOs are shown (in a.u). Calculations are based on ground state geometry by DFT at the B3LYP/6-31G/level using Gaussian 09. Frontier orbital Energy (a.u.) Energy optimized geometry LUMO+1 0.0613 LUMO -0.08011 S-25

HOMO -0.1415 HOMO-1-0.1612 Figure S-28 Selected MOs of THBPY, [THBPY + cysteine], [THBPY + homo cysteine], (not to scale; isovalue = 0.02). S-26

Cytotoxicity assay In vitro cytotoxicity was measured by using the colorimetric methyl thiazolyltetrazolium (MTT) assay against MDA-MB 231 cells. Cells were seeded into 24-well tissue culture plate in presence of 500 µl Dulbecco s modified eagle medium (DMEM) supplemented with 10% fetal bovine serum (FBS) and 1% penicillin/streptomycin at 37 ºC temperature and 5 % CO 2 atmosphere for overnight and then incubated for 12h in presence of THBPY at different concentrations (10-100 µm). Then cells were washed with PBS buffer and 500 µl supplemented DMEM medium was added. Subsequently, 50 µl 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide MTT (5 mg/ml) was added to each well and incubated for 4h. Next, violet formazan was dissolved in 500 μl of sodium dodecyl sulfate solution in water/dmf mixture. The absorbance of solution was measured at 570 nm using microplate reader. The cell viability was determined by assuming 100 % cell viability for cells without MDA-MB 231 cells. 100 Cell Viability (%) 80 60 40 20 0 10 25 50 75 Concentration ( M) 100 Figure S-29 Cell viability of THBPY at different concentration against MDA-MB 231 cells after 12h incubation. Ref: (1) Xu, J.; Li, Q.; Yue, Y.; Guo, Y.; Shao, S. Biosens. Bioelectron. 2014, 56, 58 63. S-27

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