Electronic upplementary Material (EI) for Photochemical & Photobiological ciences. This journal is The Royal ociety of Chemistry and wner ocieties 214 upplementary Information elective and sensitive fluorescence-shift probes based on two dansyl groups for mercury(ii) ion detection Li-Jun Ma,* Jialun Liu, Lefang Deng, Meili Zhao, Zhifu Deng, Xutian Li, Jian Tang and Liting Yang Table of contents Pages Fig. 1 Job s plot and binding constant of 2 and Hg 2+... 2 Fig. 2 Job s plot and binding constant of 1 and Hg 2+... 2 Fig. 3 The ph influence on the selectivity of compound 2.........3 Fig. 4 The ph influence on the selectivity of compound 1.........3 Fig. Reversibility study of 1 and 2 with EDTA......4 Fig. 6 Atomic numbering of 1...... Table. 1 Hydrogen chemical shifts (δ, in ppm) for 1 and its complex with Hg (II).... Fig. 7 The 1 H MR spectra of 1 with addition of Hg 2+ in MeH-d 4 :D 2 (2:1, V/V)....6 Fig. 8 Proposed coordination model for 1-Hg 2+...7 Fig. 9 The EI-M spectra of 2 and 2+Hg( 3 ) 2...8 Fig. 1 Atomic numbering of 2...9 Table. 2 Hydrogen chemical shifts (δ, in ppm) for 2 and its complex with Hg (II)......9 Fig. 11 The 1 H MR spectra of 2 with addition of Hg 2+ in MeH-d 4 :D 2 (7:2, V/V).....1 Fig. 12 Proposed coordination model for 2-Hg 2+...11
8 6 (A) 1.8 1. 1.2 (B) I-I 4 2 [ Hg 2+ ] /1-6 M.9.6.3..1.2.3.4..6.7.8.9 1. [Hg] 2+ /( [2]+[Hg] 2+ )...2.4.6.8 1. ( I-I ) /( I MAX -I ) Fig.1 (A) Fluorescence intensity changes of peak at 498 nm of 2 and Hg 2+ with a total concentration of 2. M in ah 2 P 4 /a 2 HP 4 buffered solution (methanol- 1%, ph 6.), indicating a 2:1 stoichiometric ration of 2: Hg 2+ (λ ex = 34 nm, λ em = 498 nm). (B) Estimation of binding constant for 2 and Hg 2+, the plot was calculated based on the equation and a 2:1 binding model (λ ex = 34 nm, λ em = 498 nm) 12 1 (A) 6 (B) I-I 7 I /(I-I ) 4 3 2 2..1.2.3.4..6.7.8.9 1. [ Hg 2+ ] /( [1]+[ Hg 2+ ] ) 1..x1 1.x1 6 1.x1 6 2.x1 6 [Hg 2+ ] -1 /M Fig.2 (A) Fluorescence intensity changes of peak at 498 nm of 1 and Hg 2+ with a total concentration of 2. M in ah 2 P 4 /a 2 HP 4 buffered solution (methanol- 2%, ph 6.), indicating a 1:1 stoichiometric ration of 1: Hg 2+ (λ ex = 34 nm, λ em = 498 nm). (B) Estimation of binding constant for 1 and Hg 2+, the plot was calculated based on the equation and a 2:1 binding model (λ ex = 34 nm, λ em = 498 nm) The ph influence on the selectivity of compound 1 and 2-2 -
( a ) ( a ) Intensity 1 8 6 4 2 4 4 6 6 7 Wavelength/nm ph. 8. 4. 7.. 6. Peak hift/nm 4 4 3 3 2 2 1 1 4... 6. 6. 7. 7. 8. 8. ph Fig.3 (a) Fluorescence spectra of 2 (. M) in ah 2 P 4 /a 2 HP 4 buffered solution (Methanol-1 %) under different ph value excitated at 34 nm (without the addition of Hg( 3 ) 2 ); (b) Fluorescence spectra of 2 (. M) in ah 2 P 4 /a 2 HP 4 buffered solution (Methanol-1 %) under different ph value excitated at 34 nm. The blue-shift of maximum emission peak upon addition of. M Hg( 3 ) 2. 3 3 Intensity 2 2 1 1 ph 8. 6. 7... 4. Peak hift/nm 3 2 2 1 1 4 4 6 6 7 Wavelength/nm 4... 6. 6. 7. 7. 8. 8. ph Fig.4 (a) Fluorescence spectra of 1 (. M) in ah 2 P 4 /a 2 HP 4 buffered solution (Methanol-2 %) under different ph value excitated at 34 nm (without the addition of HgCl 2 ); (b) Fluorescence spectra of 2 (. M) in ah 2 P 4 /a 2 HP 4 buffered solution (Methanol-2 %) under different ph value excitated at 34 nm. The blue-shift of maximum emission peak upon addition of. M Hg( 3 ) 2. Reversibility study of 1 and 2 with EDTA -3 -
( a ) Intensity 2 17 1 12 1 7 2 2+Hg( 3 ) 2 2+Hg( 3 ) 2 +EDTA 2 4 4 6 6 Wavelength/nm Intensity 33 1+Hg( 3 ) 2 3 27 1 24 1+Hg( 3 ) 2 +EDTA 21 18 1 12 9 6 3 42 4 48 1 4 7 6 63 66 Wavelength/nm Fig. (a) Fluorescence spectra of 2 (. M) in ah 2 P 4 /a 2 HP 4 buffered solution (Methanol-1 %) upon addition of Hg( 3 ) 2 (2. M) and EDTA (2. M) at an excitation of 34 nm; (b) Fluorescence spectra of 1 (. M) in ah 2 P 4 /a 2 HP 4 buffered solution (Methanol-2 %) upon addition of Hg( 3 ) 2 (2. M) and EDTA (2. M) at an excitation of 34 nm. -4 -
7 3 2 4 1 6 1 1 9 1 3 1 4 1 1 2 1 8 1 9 1 7 1 8 1 6 MR date of 1 and 1-Hg 2+ H H Fig.6 Atomic numbering of 1 Table 1 Hydrogen chemical shifts (δ, in ppm) for 2 and its complex with Hg (II); atomic numbering is shown in Fig.6 1 1-Hg 2+ (2:1,m/m) 1-Hg 2+ (1:1,m/m) Δλ(ppm) Δλ(ppm) H3(1) 8.47-8.491 8.482-8.3 8.486-8.2.12.16-.11 H1(13) 8.224-8.246 8.441-8.463 8.46-8.482.217.241-.236 H6(19) 8.89-8.119 8.177-8.196 8.186-8.24.88-.77.97-.8 H2(14) H(17) 7.4-7.86 7.672-7.712 7.691-7.732.127-.126.146 H4(16) 7.221-7.239 7.33-7.3 7.76-7.9.312-.314.3-.36 H7(18) 2.89 3.1 3.81.242.272 H8(12) 2.17-2.1 2.9-2.624 2.94-2.628.73.77-.78 H9(11).933 1.17 1.19.84.8 H1.726.844.8.118.129 - -
( c ) ( a ) 8. 8. 7. 7. 6. 6... 4. 4. 3. 3. 2. 2. 1. 1.. ppm Fig.7 elected region of the 1 H MR spectra of (a) 1, (b)1/hg 2+ (2:1), (c) 1/Hg 2+ (1:1) in MeH-d 4 :D 2 (7:2, V/V). -6 -
H 3 C CH 3 H 3 C CH3 H + CH - Hg 2+ CH - - 3 - CH Hg 2+ CH - H 3 C CH 3 H + H 3 C CH 3 Fig. 8 Proposed coordination model for 1-Hg 2+ -7 -
( a ) 2 [ 2 ] + H g 2 + [ 2 + H + ] + [ 2 + a + ] + The EI-M spectra of 2 and 2+Hg( 3 ) 2 1 627.61 9 9 8 8 7 7 6 Relative Abundance 6 4 4 3 649.68 3 2 2 1 1 364.88 671.92 728.39 99.84 171.11 218.3 49.31 22.1 61.4 82.26 928.69 99.88 1 2 3 4 6 7 8 9 1 m/z 1 9 9 8 8 7 144.3 7 147.79 6 Relative Abundance 6 4 4 3 1446.14 1446.99 1449.61 14.96 149.83 1464.68 1468.9 1461.6 1477.9 1482.64 3 2 2 1 1442.9 147.44 1478.23 148.26 1 148.66 144 14 14 146 146 147 147 148 148 m/z Fig.9 The EI-M spectra of 2 in the absence (a) and presence (b) of Hg( 3 ) 2 in CH 3 H. -8 -
2 1 4 3 6 2 1 1 9 1 7 1 1 8 1 2 1 1 ( a ) 1 6 1 4 1 3 1 7 2 8 2 2 9 MR date of 2 and 2-Hg (II) H C CH 3 H Fig.1 Atomic numbering of 2 Table 2 Hydrogen chemical shifts (δ, in ppm) for 2 and its complex with Hg (II); atomic numbering is shown in Fig.1 2 2-Hg 2+ (:1,m/m) 2-Hg 2+ (2:1,m/m) δ 1 /ppm δ 2 /ppm H12 H7 8.244-8.24 8.4-8.414 8.463-8.437.16-.21.119-.233 H11 H8 7.62-7.61 7.761-7.716 7.779-7.734.19-.11.127-.133 H1 8.49-8.28 8.34-8.11 8.3-8.8 -.1--.17 -.19--.2 H9 7.339-7.32 7.631-7.61 7.672-7.62.292-.29.333-.332 H2 3.269 3.211 3.29 -.8 -.6 H18 3.383 3.448 3.43.6.7 H17 1.219 1.26 1.274.46. H16.678.74.743.62.6 H1.878.937.944.9.66 H14 2.47-2.39 2.17-2.436 3.31-3.439.47-.41.61-.44 H21 2.742 2.988 3.18.246.276 H3 7.189-7.17 7.6-7.487 7.47-7.28.317.38 H6 H1 8.12-8.12 8.196-8.177 8.26-8.188.76-.7.86-.86 H4 8.47-8.436 8.484-8.464 8.486-8.473.27-.28.29-.37 H22 2.871 3.97 3.126.226.2 H2 H 7.7-7.3 7.687-7.64 7.7-7.693.117-.124.23-.163-9 -
( c ) ( a ) 9 8 7 6 4 3 2 1 ppm Fig.11 elected region of the 1 H MR spectra of (a) 2, (b) 2/Hg 2+ (:1), (c) 2/Hg 2+ (2:1) in MeH-d 4 :D 2 (2:1, V/V). -1 -
H 3 C H + CH 3 H 3 C H + CH 3 HC - C CH 3 - Hg 2+ CH H 3 C C - - H 3 C H + CH 3 H3C CH3 H + Fig. 12 Proposed coordination model for 2-Hg 2+ -11 -