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1 Electronic Supplementary Material (ESI) for ew Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre ational de la Recherche Scientifique 217 Signalling probes appended with two rhodamine derivatives: Inter-component preferences, Fe(III)-ion selective fluorescence responses and bio-imaging in plant species Debajani Mallick a,b, Biswonath Biswal a, M. Thirunavoukkarasu c, Roshnara Mohanty c, Bamaprasad Bag a,b, * a Colloids and Materials Chemistry Department, b Academy of Scientific and Innovative Research, c Environment and Sustainability Department, CSIR-Institute of Minerals and Materials Technology, P..: R.R.L., Bhubaneswar , disha, India. bpbag@immt.res.in Supplementary Information SP1

2 5 λ ex(35) Fluo. Int.(/E6, arb.units) λ ex(4) λ ex(45) λ ex(5) 1+Fe(III) Fig. S1: Fluorescence spectral pattern of 1 in presence of Fe(III) ion in EtH H 2 (1:1 v/v,.1m PBS) medium on excitation at various wavelength. [1] = 1µM, [Fe(III)] = 5 µm, em. and ex. b.p. = 5 nm, RT. Fig. S2: Photograph of change in colour of the solution of 1 in EtH H 2 (1:1 v/v,.1m PBS) medium on addition of various metal ions; added metal ions (from left to right: blank, a(i), K(I), Ca(II), Mn(II), Fe(II), Fe(III), Co(II), i(ii), Cu(II), Zn(II), Ag(I), Cd(II), Hg(II) and Pb(II) Fluo. Int. (I 55 /I ) a(i) K(I) Ca(II) Mn(II) Fe(II) Fe(III) Co(II) i(ii) Zn(II) Cd(II) Ag(I) Pb(II) Hg(II) Metal ions added Fig. S3: Fluorescence enhancement factor (I 55 /I ) of 1 in presence of various metal ions. [1] = 1µM, [M(I/II/III)] = 1 µm, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT, EtH. SP2

3 Abs. enhancement (ε/ε ) (a) a(i) K(I) Mn(II) Fe(II) Fe(III) Co(II) λ = 53 nm λ = 557 nm Added metal ions i(ii) Cu(II) Zn(II) Ag(I) Cd(II) Pb(II) Hg(II) Cr(III) Fluo. enhancement factor (I/I ) a(i) K(I) Mn(II) Fe(II) Fe(III) Co(II) i(ii) Cu(II) Added metal ions λ =55nm λ =58nm Zn(II) Ag(I) Cd(II) Pb(II) Hg(II) Cr(III) Fig. S4: (a) Absorption enhancement factor (ε/ε ) and (b) Fluorescence enhancement factor (I 55 /I ) of 2 in presence of various metal ions in EtH-H 2 (1:1 v/v,.1m PBS) medium. Abs: [2] = 1µM, [M(I/II/III)] = 25 µm; Fluorescence: [2] = 1µM, [M(I/II/III)] = 5 µm; λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. (b) A A eq. [Fe(III)] Abs. eq Fig. S5: Absorption titration spectra of 1 as a function of added Fe(III) ion. The spectra were recorded 3h after addition of solutions of metal ions to that of probes. [1] = 6.6 µm. The increase in A 557 peak in comparison to A 525 peak in the spectra shows coordination pattern of Rho-B component becomes predominant over Rho-6G component over time. SP3

4 3 F 584 Fluo. Int. (/E6, arb. units) F eq. [Fe(III)] eq Wavelength (nm) Fig. S6: Fluorescence titration spectra of 1 as a function of added Fe(III) ion. The spectra were recorded 3h after addition of solutions of metal ions to that of probes. The increase in F 58 peak in comparison to F 55 peak in the spectra shows coordination pattern of the probe s Rho-B component becomes predominant over Rho-6G component over time. [1] = 1µM, λ ex = 5 nm, em. and ex. b.p. = 5 nm, RT (A-A ) 53.3 Abs [Fe(III)], M 1 eq. Fe(III) eq Fig. S7: Absorption titration spectra of 2(1µM) as a function of added Fe(III) ion in EtH- H 2 (1:1v/v,.1M PBS) medium. Inset: Absorption intensity change (A-A ) at 53 nm versus added concentration of Fe(III) ion. SP4

5 Abs Blank K(I) Mn(II) Fe(III) i(ii) Zn(II) Ag(I) Hg(II) a(i) Ca(II) Fe(II) Co(II) Cu(II) Cd(II) Pb(II) (a) Fluo. int. (/E6, arb. units) (b) Blank a(i) K(I) Ca(II) Mn(II) Fe(II) Fe(III) Co(II) i(ii) Cu(II) Zn(II) Cd(II) Ag(I) Pb(II) Hg(II) Fig S8: (a): Absorption and (b) fluorescence spectra of 1 in presence of metal ions in MeC H 2 (9:1 v/v, PBS,.1M) medium. λ ex = 47 nm, em. and ex b. p. = 5 nm, RT. The spectral pattern in different solvent/binary mixture medium shows that Fe(III) ion exhibited optimal absorption and fluorescence spectral responses in 1 among various metal ions due to higher probe-metal interaction irrespective of solvent condition (those investigated here). SP5

6 Abs (A 525 ) Equation y = A2 + (A1-A2)/(1 + exp((x-x)/dx)) Adj. R-Square.9925 Value Standard Error B A B A B x B dx (a) Ln([Fe(III)]).12.1 (b) Abs. (A 556 ) Model -- Equation y = A2 + (A1-A2)/(1 + exp((x-x)/dx)) Red. Chi S-qr E-5 Adj. R-Square Value Standard Error B A B A B x B dx Ln([Fe(III)]) Fig. S9: on-linear regression plot of complex 1-Fe(III) for determination of association constant (Ka). The absorption data taken at (a) 525nm and (b) 556 nm from the titration of 1 as a function of added Fe(III) ion. SP6

7 14 Fluo. Int. (arb. units, /E6) x1-6 2.x1-6 3.x1-6 4.x1-6 [Fe(III)] (a) Fluo. Int. (arb. units, /E6) Equation y = A2 + (A1-A2)/(1 + exp((x-x)/dx)) Adj. R-Squa Value ln (Fe(III)) Standard Error B A E B A E E6 B x B dx Fig. S1: on-linear regression plot of complex 1-Fe(III) for determination of association constant (Ka) through fluorescence titration. (a) The fluorescence intensity data taken at 55 nm (a) as a function of added Fe(III) ion or (b) ln(fe(iii)). [1] = 1µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. (b) SP7

8 (A-A ) (a) Equation Reduced Chi-S qr y = A2 + (A1-A2)/(1 + exp((x-x)/dx)) E-4 Adj. R-Square.9962 Value Standard Error A-A A A-A A A-A x A-A dx Ln [Fe(III)] (b) I 55 (/E6, arb. units) Equation Reduced Chi- Sqr y = A2 + (A1-A2)/(1 + exp((x-x)/dx)) E1 Adj. R-Square Value Standard Erro B A B A E B x B dx Ln [Fe(III)] Fig. S11: on-linear regression plot of change in (a) absorption at 53nm and (b) fluorescence at 55nm of 2 on addition of Fe(III) determination of association constant (Ka). Abs: [2] = 1µM, Fluorescence: [2] = 1µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. SP8

9 8 (a) 3 (b) (A-A ) Equation Adj. R-Square y = A1*exp(-x/t1) + y Value Standard Error Aq.-EtH y E-5 Aq.-EtH A E-5 Aq.-EtH t Time(s) (A-A ) Equation y = A1*exp(-x/t1) + y Adj. R-Square Value Standard Error Aq. EtH y Aq. EtH A Aq. EtH t Time (s) 12 (c).16 (d) (A-A ) Equation Adj. R-Square.9968 y = A1*exp(-x/t1) + y Time(s) Value Standard Error EtH y E-5 EtH A E-5 EtH t (A-A ) Equation y = A1*exp(-x/t1) + y Adj. R-Squ Value Standard Error A-A y E-4 A-A A E-4 A-A t Time (s) Fig S12: Change in absorption at (a) 525nm(A 525 ), (b) 557nm(A 557 ) in 1(5M) on equimolar Fe(III) ion addition as a function of time(s) in EtH H 2 (1:1 v/v, PBS,.1M) medium. (c) The same(a 525 ) when carried out in EtH medium. [1] = [Fe(III)] = 5 µm. (d) Change in absorption(a 525 ) in 1(1M) on addition of Fe(III) as a function of time(s) in EtH H 2 (1:1v/v, PBS,.1M) medium, [1] = [Fe(III)] = 1 µm. The non-linear regression fit (A = A e -kt ) of first-order kinetics at desired time interval determines of rate constant (k)..1 8 Abs λ obs = 53nm Mole fraction of added Fe(III) Fig S13: Absorbance of 2 as a function of mole fraction of added Fe(III) ion for determination of complexation stoichiometry. SP9

10 Fluo. Int. (/E5, arb. units) Equation y = a + b*x Adj. R-Squ Value Standard Error D Intercept E D Slope E E11 2.E-8 4.E-8 6.E-8 8.E-8 [Fe(III)] Fig. S14: Linear regression to the plot of fluorescence intensity (I F /I ) of 1 (1μM) as a function of concentration of Fe(III) added. (S/ = 5), [1] = 1µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. Fluo. int.(i-i ), /E6, arb.units) Equation y = a + b*x Adj. R-Square.9738 Value Standard Error I-I Intercept I-I Slope E E [Fe(III)](µM) Fig. S15: Linear regression to the plot of fluorescence intensity (I F -I ) 55 of 2(1μM) as a function of concentration of Fe(III) added. (S/ = 5), [2] = 1µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. SP1

11 Table ST1: Comparison in sensitivity among few rhodamine based probes towards detection of Fe(III) ion. o. Probe Sensitivity, LD References µm Y. Wang, H. Chang, W. Wu, X. Zhaoa, Y. Yang, Z. Xu, Z. H. Xu and L. Jia. Sens. Actuat. B, 217,239, 6. S H H 2 H H 2.1µM X. Li, Y. Yin, J. Deng, H. Zhong, J. Tang, Z. Chen, L.Yang and L. -J. Ma. Talanta, 216, 154, H.396µM X. Bao, X. Cao, X. ie, Y. Xu, W. Guo, B. Zhou, L. Zhang, H. Liao and T. Pang, Sens. Actuat. B, 215, 28, Y P P P Y = H 4.8 μm R. Kagit, M. Yildirim,. zay, S. Yesilot and H. za. Inorg. Chem., 214, 53, H Y 5 R X R R = X = H 2 H 2 H H 2 (a) H 2 (b) (a).3 µm (b) 1.2 µm (a) Y. Du, M. Chen, Y. Zhang, F. Luo, C. He, M. Li and X. Chen, Talanta, 213, 16, 261. (b) Y. Ding, H. Zhu, X. Zhang, J.-J. Zhu and C. Burda, Chem. Commun., 213, 49, Probe 1 11nM Work in this manuscript 7 Probe 2.16µM Work in this manuscript SP11

12 .95.9 Fluo. Int. ratio (I 58 /I 55 ) E+ 5.E-8 1.E-7 1.5E-7 2.E-7 [Fe(III)] Fig. S16: the plot of fluorescence intensity ratio [(I F /I ) 58 /(I F /I ) 55 ] of 1 (1μM) as a function of concentration of Fe(III) added. (S/ = 5), [1] = 1µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. 1.x1 4 8.x1 3 Photon counts 6.x1 3 4.x Fe(III) 2.x Time(t, ns) Fig S17: Time-resolved fluorescence exponentially fitted decay profile of 1 alone and in presence of Fe(III) ion in EtH-H 2 (1:1 v/v,.1m PBS) medium. SP12

13 Table ST 2: Data of the fitted decay profile of 1 and [1+Fe(III)] Fluo. Int. (/E6, arb. units) [1+Fe(III)] [1+Fe(III)]+Iodide [1+Fe(III)]+Carbonate [1+Fe(III)]+Acetate [1+Fe(III)]+Chloride [1+Fe(III)]+Phosphate [1+Fe(III)]+Thiocyanate [1+Fe(III)]+Sulphate [1+Fe(III)]+EDTA [1+Fe(III)]+Acetate Fig. S18: Fluorescence spectra of [1-Fe(III)] in-situ complex in presence of various anions and counter reagents. : [1] = 1µM, [Fe(III)] = 5µM, [anion] = 1 µm, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. SP13

14 Abs. (a) EtH-H 2 (varied propertions, v/v) 9:1 8:2 7:3 6:4 5:5 4:6 3:7 2:8 1: Abs. (b) (EtH-H 2 varied propertions, v/v) 9:1 8:2 7:3 6:4 5:5 4:6 3:7 2:8 1: Fe(III) Fig. S19: Absorption spectra of 2 (a) alone and (b) in presence of Fe(III) in varied proportion of a EtH-H 2 binary mixture (v/v) as solvent medium. [2] = M, [Fe(III)] = M. Fluo. Int.(/E5, arb. units) (a) EtH-H 2 (varied propertions, v/v) 9:1 8:2 7:3 6:4 5:5 4:6 3:7 2:8 1: Fluo. Int.(/E5, arb. units) EtH-H 2 binary mixture varied propertions (v/v) 9:1 8:2 7:3 6:4 5:5 4:6 3:7 2: :9 2+Fe(III) Fig. S2: Fluorescence spectra of 2 alone (a) and (b) in presence of Fe(III) in varied proportion of a EtH-H 2 binary mixture (v/v) as solvent medium. [2] = M, [Fe(III)] = M, λ ex = 48 nm, emission and excitation band pass = 5nm, RT. The error in fluorescence output (for 3 measurements) is < 1 % for ligand and < 5% for the complex. (b) SP14

15 .6 Abs. (a) 1 ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 Abs..6 (b) 1+Fe(III) ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph Fluo. Int (/E6, arb. units) (c) 1 ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 Fluo. Int. (/E6, arb. units) (d) 1+Fe(III) ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph Fig. S21: Absorption (a and b) and fluorescence(c and d) spectra of 1(a and c) and 1+Fe(III) (b and d) respectively as a function of varying ph in the acidic region. Conditions: EtH H 2 (1:1 v/v), Abs: [1] = 1µM, [Fe(III)] = 2µM, Fluorescence: [1] = 1µM, [Fe(III)] = 5µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT. s SP15

16 .6 Abs. (a) 2 ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph Abs. (b) 2 + Fe(III) ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph (c) 5 (d) Fluo. Int. (/E6, arb.unit) ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph 8 Fluo. Int.(/E6, arb. units) Fe(III) ph 1 ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph Fig. S22: Absorption (a and b) and fluorescence(c and d) spectra of 2(a and c) and 2+Fe(III) (b and d) respectively as a function of varying ph in the acidic region. Conditions: EtH H 2 (1:1 v/v), Abs: [2] = 1µM, [Fe(III)] = 25µM, Fluorescence: [1] = 1µM, [Fe(III)] = 5µM, λ ex = 5 nm, em. and ex. b. p. = 5 nm, RT (A 53 ) Abs.3.1 1(A 525 ) Fig. S23: Comparison of absorption intensities of 1 and 2 as a function of varying ph in the acidic region. Inset: photograph of 2 in EtH H 2 (1:1 v/v) at different ph. ph SP16

17 T(%, arb. units) 1+Fe(III) Complex 1 Fig S24: Wavenumber (cm -1 ) FTIR spectrum of 1 and [1+Fe(III)] complex T(%) cm cm -1 2-Fe(III) complex 2 Fig S25: Wavenumber(cm -1 ) FTIR spectrum of 2 and [2+Fe(III)] complex SP17

18 Fig S26: ESI-MS spectrum of complex (1+Fe(III)). Fig S27: ESI-MS spectrum of 1 (M w : ). SP18

19 Fig S28: 1 HMR spectrum of 1(CDCl 3 ). Fig S29: 13 C-MR spectrum of 1(CDCl 3 ). SP19

20 Fig S3: 1 HMR spectrum of 2(CDCl 3 ). Fig S31: 13 C-MR spectrum of 2(CDCl 3 ). SP2

21 Fig S32: HR-MS spectrum of 2 (M w : 887). Fig. S33: Fluorescence microscopic images of cross section of root tissues of G. Pteridifolia treated with Fe(III) at varying proportions(a) control, (b)1 ppm, (c) 2ppm (d) 3ppm followed by treatment with 1(5 ppm). The bright (orange) emission inferred to Fe(III) deposition on xylem cells. SP21

22 Fig. S34: Fluorescence microscopic images of the cross section of root tissues of G. Pteridifolia treated with both Fe(III) ions and 1 at (a) 15mins and (b) after 24h. Fig. S35: Microscopic images of the cross section of root tissues of G. Pteridifolia treated with both Fe(III) ions and 1 at (a) 15mins and (b) after 24h, showing the colour of 1-Fe(III) complexes. SP22

23 Fig. S36: Microscopic images of the cross section of root tissues of G. Pteridifolia treated with Fe(III) ions at varying concentrations (a) 1ppm, (b)2 ppm, (c) 25ppm and (d) 3ppm followed by 1 showing the colour contrast of 1-Fe(III) complexes. Fig. S37: Fluorescence microscopic images of cross section of stem tissues of G. Pteridifolia treated with Fe(III) ion followed by treatment with 1(5 ppm). The bright (orange) emission inferred to Fe(III) deposition on xylem cells. SP23