Supporting Information for Advanced Functional Materials, adfm.200601202 Wiley-VCH 2007 69451 Weinheim, Germany
[Supporting Information] Optical Sensor Based on Nanomaterial for the Selective Detection of Toxic Metal Ion ** By Soo Jin Lee, Ji Eun Lee, Joobeom Seo, Il Yun Jeong, Shim Sung Lee,* and Jong Hwa Jung* Table of Contents: Title and table of contents S1 Scheme S1. Chemical Structure of 5 S2 Figure S1. TEM images with electron energy-loss spectroscopy (EELS) of (A) SNT, and (B) SNT-1. S3 Figure S2. Thermogravimetric analysis data of SNT-1 S4 Figure S3. Thermogravimetric analysis data of SSP-1 S5 Figure S4. SEM image of SSP-1 S6 Figure S5. Solid UV-VIS spectra of SNT-1 in the presence of (a) Hg(Br) 2 and (b) Hg(Br) 2 +NaNO 3 in water S7 Figure S6. Crystal structure of [Hg(5)(NO 3 ) 2 ] S8 Crystallographic Structure Determination S9 Table S1. Crystal and Experimental Data S10 Figure S7. TEM images with electron energy-loss spectroscopy (EELS) of Hg 2+ -loaded SNT-1 S11 Figure S8. Chromatograms of Hg 2+ a) before and b) after extraction by SNT-1 S12 Figure S9. Solid UV-VIS spectra of SNT-1 glass plate with various concentrations of Hg(NO 3 ) 2. (B) Standard calibration curve of the change in absorbance of SNT-1 glass plate as function of Hg(NO 3 ) 2 S13 Figure S10. Plot of the ph dependence data of the optical absorbance of SNT-1 in aqueous Hg 2+ solution S14 References. S15 Prof. J. H. Jung, Prof. S. S. Lee, Dr. J. Seo, S. J. Lee, J.-E. Lee Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Chinju 660-701, Korea E-mail: jonghwa@gnu.ac.kr Dr. I. Y. Jeong Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, Jeongeup 580-185, Korea S 1
O S H N 5 O S Scheme S1. Chemical Structure of 5. S 2
Figure S1. TEM images with electron energy-loss spectroscopy (EELS) of (A) SNT, and (B) SNT-1. (a) Zero-loss image, (b) silicon component, (c) oxygen component, (d) carbon component. and (e) nitrogen component. S 3
100 Weight (%) 80 60 87.5 % 0 200 400 600 800 Temperature ( o C) Figure S2. Thermogravimetric analysis data of SNT-1. S 4
100 Weight (%) 80 95.8 % 60 200 400 600 800 1000 Temperature ( o C ) Figure S3. Thermogravimetric analysis data of SSP-1. S 5
Figure S4. SEM image of SSP-1. S 6
1.4 a 1.2 b Absorbance 1.0 0.8 0.6 0.4 0.2 0.0 300 400 500 600 700 Wavelength(nm) Figure S5. Solid UV-VIS spectra of SNT-1 in the presence of (a) Hg(Br) 2 and (b) Hg(Br) 2 +NaNO 3 in water. S 7
Figure S6. Molecular structure of [Hg(5)(NO 3 ) 2 ]. Hydrogen atoms and noncoordinating solvents are omitted. Ellipsoids are drawn at the 30 % probability level. Selected bond lengths (Å) and angles ( ): Hg-S1 2.563(2), Hg-S2 2.576(2), Hg-N1 2.421(7), Hg-O3 2.481(7), Hg-O4 2.798(9), Hg-O6 2.797(8), Hg-O7 2.339(7), N1-Hg-O3 176.7(2), N1-Hg-O4 135.4(2), N1-Hg-O6 88.6(3), N1-Hg-S1 80.3(2), N1-Hg-S2 81.6(2), S1-Hg-S2 140.0(1), O3- Hg-O4 47.2(3), O3-Hg-O6 88.0(3), O3-Hg-S1 102.4(2), O3-Hg-S2 97.2(2), O4-Hg-O6 126.1(3), O4-Hg-S1 85.4(2), O4-Hg-S2 83.1(2), O6-Hg-S1 140.8(2), O6-Hg-S2 73.5(2), O7- Hg-N1 105.5(3), O7-Hg-O3 72.4(3), O7-Hg-O4 118.5(3), O7-Hg-O6 47.3(3), O7-Hg-S1 99.7(2), O7-Hg-S2 119.4(2), O1-C-C-O2-57.3( 1.2), S1-C-C-N1 61.00(9), N1-C-C-S2-60.2(1.0). S 8
Crystallographic Structure Determination: All data were collected on a Bruker Smart diffractometer equipped with a graphite monochromated Mo Kα (λ = 0.71073 Å) radiation source and a CCD detector. The 45 frames of two dimensional diffraction images were collected and processed to obtain the cell parameters and orientation matrix. The first 50 frames were retaken after complete data collection. The crystal showed no significant decay. The frame data were processed to give structure factors using the SAINT. S1 The structure was solved by direct methods and refined by full matrix least squares methods on F 2 for all data using SHELXTL software. S2 The nonhydrogen atoms were refined anisotropically. O5, O6 and C21 show relatively large thermal displacement parameters; attempts to resolve the atoms as partial occupancy could not be done sensibly. The final difference Fourier map show ghost peaks close to heavy atoms. The hydrogen atoms were placed in calculated positions and refined with a riding model with U iso constrained to be 1.2 times U eq of the parent atom. S 9
Table S1. Crystal and Experimental Data Formula: C 21 H 26.5 HgN 3.5 O 8 S 2 Formula weight = 720.67 Crystal system: Monoclinic Space group: C2/c Z = 8 a = 23.2346(18) Å b = 9.7680(7) Å β = 114.2290(10) c = 24.4789(18) Å V = 5066.2(7) Å 3 D calc = 1.890 g/cm 3 No. of reflections used = 6035 [R int = 0.0627] 2θ max = 56.56 with Mo K α R = 0.0495, wr = 0.1139 [I>2σ(I)] R= 0.1055, wr = 0.1435 [all data] Absorption correction: Empirical SADABS Measurement: Bruker SMART CCD system Program system: SHELXTL Structure determination: direct method Refinement: Full-matrix least-squares on F 2 S 10
Figure S7. TEM images with electron energy-loss spectroscopy (EELS) of Hg 2+ -loaded SNT- 1. (a) Zero-loss image, (b) silicon component, (c) oxygen component, (d) carbon component. (e) nitrogen component, and (f) mercury component. S 11
15 a) 10 Intensity 5 0 b) 0 2 4 6 8 10 12 14 Time (minutes) Figure S8. Ion chromatograms of Hg 2+ a) before and b) after extraction by SNT-1. S 12
3 A (g) 2 B (f) (e) Absorbance 2 (d) Absorbance 1 1 (c) (b) (a) 0 400 500 600 700 Wavelength(nm) 0 0.0 0.2 0.4 0.6 0.8 1.0 [Hg(NO 3 ) 2 ] / mm. Figure S9. (A) Solid UV-VIS spectra of SNT-1 with various concentration of Hg(NO 3 ) 2 : (a) 0.0 mm, (b) 0.10 mm, (c) 0.22 mm, (d) 0.45 mm, (e) 0.60 mm, (f) 0.75 mm, and (g) 0.90 mm. (B) Standard calibration curve of the change in absorbance of SNT-1 glass plate as function of Hg(NO 3 ) 2. Data are shown at a probe wavelength of 550 nm S 13
1.0 0.8 A 542 0.6 0.4 2 3 4 5 6 7 8 9 10 11 ph units Figure S10. Plot of the ph dependence data of the optical absorbance of SNT-1 in aqueous Hg 2+ solution. S 14
References (S1) Bruker, SMART and SAINT: Area Detector Control and Integration Software Ver. 5.0; Bruker Analytical X-ray Instruments: Madison, Wisconsin, 1998. (S2) Bruker, SHELXTL: Structure Determination Programs Ver. 5.16; Bruker Analytical X- ray Instruments: Madison, Wisconsin, 1998. S 15