Supporting Information for A Mixed Crystal Lanthanide Zeolite-like Metal-Organic Framework as a Fluorescent Indicator for Lysophosphatidic Acid, a Cancer Biomarker Shi- Yuan Zhang,, Wei Shi, *, Peng Cheng, and Michael J. Zaworotko *, Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, P. R. China Department of Chemical & Environmental Science, Materials and Surface Science Institute, University of Limerick, Limerick, Republic of Ireland Table of Contents Experimental Section S2-S3 Crystallographic data (Table S1) S4 PXRD patterns (Figure S1) S5 TGA plots (Figure S2) S5 Photoluminescence graphs and plots (Figures S3-S17) S6-S15 Lifetime measurements (Figure S18 and Table S2) S16 S1
Experimental Section Materials and Methods. All reagents were commercially available and were used without further purification. Powder X-ray diffraction measurements were recorded on a Rigaku D/Max-2500 X-ray diffractometer using Cu-Kα radiation. Thermal analyses (N 2 atmosphere, heating rate of 1.5 C/min) were carried out in a Labsys NETZSCH TG 209 Setaram apparatus. ICP-AES was measured by ICP-9000(N+M) (USA Thermo Jarrell-Ash Corp). The fluorescence spectra were measured on Aglient Cary Eclipse fluorescence spectrophotometer with temperature probes and mix accessory. Lifetime was recorded on fluorescence spectrometer F900, Edinburgh Instruments Ltd. Synthesis of Tb-ZMOF. A mixture of Tb(NO 3 ) 3 6H 2 O (90 mg, 0.2 mmol), H 2 bpdc (50 mg, 0.2 mmol), CH 3 OH (5 ml) and CHCl 3 (5 ml) was sealed in a 23 ml teflon-lined stainless steel vessel and heated at 80 C for 2 days, and then cooled to room temperature. Colorless transparent polyhedral crystals were obtained as a pure phase, washed by chloroform and methanol, and dried at room temperature. Synthesis of Eu-ZMOF. Eu-ZMOF was synthesized in the similar way as Tb-ZMOF, except that Eu(NO 3 ) 3 6H 2 O (90 mg, 0.2 mmol) was used instead of Tb(NO 3 ) 3 6H 2 O. Synthesis of MZMOF-1. MZMOF-1 was synthesized in the similar way as Tb-ZMOF, except that Tb(NO 3 ) 3 6H 2 O (90 mg, 0.2 mmol) and Eu(NO 3 ) 3 6H 2 O (45 mg, 0.1 mmol) were used instead of Tb(NO 3 ) 3 6H 2 O. Synthesis of MZMOF-2. MZMOF-2 was synthesized in the similar way as Tb-ZMOF, except that Tb(NO 3 ) 3 6H 2 O (68 mg, 0.15 mmol) and Eu(NO 3 ) 3 6H 2 O (68 mg, 0.15 mmol) were used instead of Tb(NO 3 ) 3 6H 2 O. Synthesis of MZMOF-3. MZMOF-3 was synthesized in the similar way as Tb-ZMOF, except that Tb(NO 3 ) 3 6H 2 O (45 mg, 0.1 mmol) and Eu(NO 3 ) 3 6H 2 O (90 mg, 0.2 mmol) were used instead of Tb(NO 3 ) 3 6H 2 O. S2
X-ray Structure Determination. The crystallographic data were collected by an Oxford Supernova Single Crystal Diffractometer equipped with graphite monochromatic Mo Kα radiation (λ = 0.71073 Å). Structures were solved by direct methods with SHELXS program and refined by full-matrix least-squares techniques against F 2 with the SHELXL program package. 1 All non-hydrogen atoms were refined anisotropically, and hydrogen atoms were located and refined isotropically. The contribution of disordered solvent molecules was treated as a diffuse using the Squeeze procedure in PLATON. 2 The resulting new HKL4 files were used to further refine the structures. (1) Sheldrick, G. Acta Cryst. 2008, A64, 112. (2) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7. Photoluminescence Experiment. The samples of Tb-ZMOF, Eu-ZMOF and MZMOFs were well grinded into powder before use. The standard suspensions (0.03 mg/ml) were prepared by introducing each sample into 500 ml volumetric flask with vigorously agitation using ultrasound for 20 min. Then 2 ml standard suspension was transferred to a cuvette. The luminescent spectrum of the suspension was measured on Aglient Cary Eclipse fluorescence spectrophotometer at 25 C with continuous stirring. The spectrum excited at 300 nm was recorded from 450 to 700 nm. Different amount of analytes was added into the suspension and agitated for additional 1 min before measurement. Fluorescent Lifetime Measurements. The suspension of MZMOF-1 (2 ml, 0.03 mg/ml) was excited at 300 nm and the lifetime was recorded at 546 and 613 nm on an Edinburgh FLS 900 spectrometer, respectively. Then 0.5 and 1 ml LPA (0.10 mm) was transferred to the suspension and the corresponding lifetime was monitored. Same procedure was applied to MZMOF-2 and MZMOF-3. S3
Table S1 Crystal data and structure refinement details of Tb-ZMOF Tb-ZMOF formula C 12 H 6 TbN 3 O 7 fw 463.12 temp(k) 150(2) cryst system space group Cubic Pn-3n a (Å) 29.2095(7) V (Å 3 ) 24921.3(10) Z 48 Dc (g cm -3 ) 1.481 µ (mm -1 ) 3.434 F (000) 10560 R int 0.0747 GOF 0.945 R 1 (I>2σ(I)) 0.0737 wr 2 (all data) 0.1987 ρ max (e Å -3 ) 1.693 ρ min (eå -3 ) -0.745 S4
Figure S1. PXRD patterns of calculated Tb-ZMOF (cal-tb-zmof), as-synthesized Tb-ZMOF (as-tb-zmof), Eu-ZMOF (as-eu-zmof) and MZMOFs (as-mzmof-1, as-mzmof-2, and as-mzmof-3). Figure S2. TGA plots of as-synthesized Tb-ZMOF, Eu-ZMOF and MZMOFs. S5
Figure S3. Relative luminescence intensity changes of Tb-ZMOF (0.3 mg/ml) in the present of different analytes. The concentration of LPA, GPA, L-proline, urea, NaCl and glucose was 0.05, 0.05, 5, 7, 146, and 5.5 mm, respectively. H 2 O was used as pure phase. S6
Figure S4. Relative luminescence intensity changes of Eu-ZMOF (0.3 mg/ml) in the present of different analytes. The concentration of LPA, GPA, L-proline, urea, NaCl and glucose was 0.05, 0.05, 5, 7, 146, and 5.5 mm, respectively. H 2 O was used as pure phase. S7
Figure S5. Relative luminescence intensity changes of MZMOF-1 (0.3 mg/ml) in the present of different analytes. The concentration of LPA, GPA, L-proline, urea, NaCl and glucose was 0.05, 0.05, 5, 7, 146, and 5.5 mm, respectively. H 2 O was used as pure phase. S8
Figure S6. Relative luminescence intensity changes of MZMOF-2 (0.3 mg/ml) in the present of different analytes. The concentration of LPA, GPA, L-proline, urea, NaCl and glucose was 0.05, 0.05, 5, 7, 146, and 5.5 mm, respectively. H 2 O was used as pure phase. S9
Figure S7. Relative luminescence intensity changes of MZMOF-3 (0.3 mg/ml) in the present of different analytes. The concentration of LPA, GPA, L-proline, urea, NaCl and glucose was 0.05, 0.05, 5, 7, 146, and 5.5 mm, respectively. H 2 O was used as pure phase. S10
Figure S8. Fluorescence intensity changes of MZMOF-3 toward addition of 0.03 mm LPA in methanol solution. Figure S9. Fluorescence intensity changes of MZMOF-3 toward addition of 0.05 mm LPA in methanol solution. S11
Figure S10. Fluorescence intensity changes of MZMOF-3 toward addition of 0.10 mm LPA in methanol solution. Figure S11. Fluorescence intensity changes of MZMOF-3 toward addition of 0.13 mm LPA in methanol solution. S12
Figure S12. Integrated luminescence intensity changes of MZMOF-3 in methanol toward different concentrations of LPA. (a) 0.03 mm; (b) 0.05 mm; (c) 0.10 mm; (d) 0.13 mm LPA was added by aliquot volume (0.1 ml) to MZMOF-3 solution. (e) Integrated data points obtained from four individual measurements. (f) Linear fitting parameters of each plot. Figure S13. Fluorescence intensity changes (a) and integrated fluorescence intensity changes (b) of MZMOF-3 toward addition of 0.10 mm LPA in aqueous solution. S13
Figure S14. Fluorescence intensity changes of MZMOF-3 toward addition of a mixture of analytes in methanol. The mixture contains: LPA (0.0375 mm), L-proline (5 mm), urea (7 mm), NaCl (146 mm) and glucose (5.5 mm). Figure S15. Fluorescence intensity changes of MZMOF-3 toward addition of a mixture of analytes in methanol. The mixture contains: LPA (0.06 mm), L-proline (5 mm), urea (7 mm), NaCl (146 mm) and glucose (5.5 mm). S14
Figure S16. Fluorescence intensity changes of MZMOF-3 toward addition of a mixture of analytes in methanol. The mixture contains: LPA (0.075 mm), L-proline (5 mm), urea (7 mm), NaCl (146 mm) and glucose (5.5 mm). Figure S17. Integrated data points obtained from three individual titration measurements. The concentrations of analytes are shown in Figures S14-S16. S15
Figure S18. Lifetime for MZMOF-1 (a, b), MZMOF-2 (c, d) and MZMOF-3 (e, f) suspension samples in the absence (green) and presence of 0.5 ml (orange) and 1 ml (red) LPA (0.10 mm). Initial volume of each sample was 2 ml with the concentration of 0.03 mg/ml. Lifetime measurements were monitored at 546 and 613 nm upon 300 nm excitation, respectively. These data were fit to a single exponential (solid line). Table S2. Lifetime fitting results for MZMOFs in the absence and presence of LPA. Addition of LPA b / ml Lifetime c / ms 546 nm 613 nm MZMOF-1 a 0.5 938.96 1288.80 0 331.86 694.37 1 1035.04 1382.44 MZMOF-2 a 0.5 988.74 1094.23 0 887.93 453.54 1 1031.72 1305.66 MZMOF-3 a 0.5 735.83 867.08 0 1052.32 447.29 1 686.69 1074.19 a 2 ml of methanol suspension with concentration of 0.3 mg/ml. b 0.10 mm. c Excited at 300 nm. S16