Table S1: Fluorescence lifetimes of proteins in presence of ZnO nanoparticles at pH ~ 7.0 (λex =295 nm, λem =340 nm) (only the maximum concentrations of ZnO used are shown) Sample 1 f1 2 f2 3 (ns) 0 1.34 0.29 4.85 0.36 0.05 0.18 0.13 0.17 4.15 5.29 x 10-5 1.12 0.28 4.64 0.39 0.06 0.17 0.10 0.16 4.07 0 1.72 0.32 5.30 0.46 15.81 0.12 0.22 0.10 8.94 5.29 x 10-5 1.64 0.34 5.15 0.43 15.69 0.12 0.22 0.11 8.95 (ns) f3 4 Conc. of ZnO (M) (ns) f4 (ns) <> (ns) HMb HRP The fourth exponential decay: I (, t) = a1exp (-t / 1) + a2 exp (-t / 2) + a3exp (-t / 3) + a4exp (-t / 4). fi = aii / ( j ajj). Average fluorescence lifetime, <τ> = ∑ai τi2 / ∑ ai τi (see text) Table S 2a: Determination of binding constants K, number of binding sites n and the different thermodynamic parameters of HMb-ZnO complex at different temperatures Temperature (K) n log K K(M-1) R2 G0 (kcal mol-1) 291 1.02 4.08 1.2 x104 0.999 -2.37 298 1.00 3.88 7.6 x103 0.999 -2.29 308 0.98 3.70 5.0 x103 0.999 -2.22 H0 (kcal mol-1) (±0.11) S0 (cal mol-1K-1) (±0.24) - 6.83 -15.22 Table S 2b: Determination of binding constants K, number of binding sites n and the different thermodynamic parameters of HRP-ZnO complex at different temperatures Temperature (K) n log K K(M-1) R2 G0 (kcal mol-1) 291 1.02 3.87 7.4 x103 0.999 -5.20 298 1.04 3.80 6.3 x103 0.999 -5.14 308 1.07 3.80 6.3 x103 0.998 -5.09 H0 (kcal mol-1) (±0.11) S0 (cal mol-1K-1) (±0.24) - 8.37 -10.83 FIG. S1: The fluorescence decay profiles associated with impulse response function (faster decay) of HMb (concentration ~ 3x10-5 M) (λex ~ 295 nm, λem ~ 340 nm) in buffer solution in absence and presence (two decays overlap with each other) of ZnO nanoparticles. (χ2 ~ 1.12) FIG. S2: The fluorescence decay profiles associated with impulse response function (faster decay) of HRP (concentration ~ 2x10-5 M) (λex ~ 295 nm, λem ~ 340 nm) in buffer solution in absence and presence (two decays overlap with each other) of ZnO nanoparticles. (χ2 ~ 1.12) 308K 298K 291K -0.6 291K 298K 308K -0.6 log [(F0-F)/ F] log [(F0-F)/ F] -0.3 -0.9 -1.2 -0.9 -1.2 -1.5 -1.5 -5.2 -5.0 -4.8 -4.6 log Q Fig. S3 -4.4 -4.2 -1.8 -5.2 -5.0 -4.8 -4.6 log Q -4.4 Fig. S4 FIG. S3: log [(F0-F)/F] vs. log [Q] plots in case of HMb–ZnO nanomaterial complex at different temperatures. FIG. S4: log [(F0-F)/F] vs. log [Q] plots in case of HRP–ZnO nanomaterial complex at different temperatures. -4.2 (A) (B) (C) (D) (E) (F) (G) (H) (I) (J) Fig. S5 FIG. S5: AFM Topographic images of the (A) HMb where the scan area is 3 μm × 3 μm, (B) HMb in 3D image view, (C) HMb- ZnO nanoparticles complex where the scan area is 3 μm × 3 μm, (D) HMb- ZnO nanoparticles complex in 3D image view, (E) HMb- ZnO nanoparticles complex where the scan area is1 μm × 1 μm, (F) the height analysis of ZnO nanoparticle of HMb- ZnO nanoparticles complex where the scan area is1 μm × 1 μm, (G) HRP, (H) HRP in 3D image view, (I) HRP - ZnO nanoparticles complex, (J) HRP ZnO nanoparticles complex in 3D image view taken under tapping mode in air.
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