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1 Supporting Information ph-regulated Optical Performances in Organic/Inorganic Hybrid: A Dual-Mode Sensor Array for Pattern Recognition-Based Biosensing Qing Yan, Xu-Yin Ding, Zi-Han Chen, Shi-Fan Xue, Xin-Yue Han, Zi-Yang Lin, Miao Yang, Guoyue Shi, Min Zhang* School of Chemistry and Molecular Engineering, Shanghai Key Laboratory for Urban Ecological Processes and Eco-Restoration, East China Normal University, 500 Dongchuan Road, Shanghai , China. Phone & Tel: ; mzhang@chem.ecnu.edu.cn Contents Synthesis of oleic acid (OA)-capped lanthanide-doped upcoversion nanoparticles (OA-Ln-UCNPs). Preparation of water-dispersible ligand-free lanthanide-doped upcoversion nanoparticles (Ln-UCNPs). Figure S1. FTIR spectra of OA-Ln-UCNPs and Ln-UCNPs. Figure S2. TEM images of OA-Ln-UCNPs and Ln-UCNPs. Figure S3. The upconversion fluorescence spectra of OA-Ln-UCNPs and Ln-UCNPs under the excitation of 980 nm. Figure S4. Investigation of zeta potential of Ln-UCNPs and TPPS. Figure S5. The upconversion fluorescence spectra of Ln-UCNPs in the range of 420~550 nm challenged with various concentration of TPPS in the buffers with ph at 4.0, 4.5, and 5.0, respectively. Figure S6. Long-term stability of the absorption intensity and the upconversion fluorescence intensity of TPPS/Ln-UCNPs at ph=4.0, 4.5, and 5.0. Figure S7. Time-course responses of the absorption intensity of TPPS/Ln-UCNPs in the presence of 10 µm ATP regulated by buffers with ph at 4.0, 4.5, and 5.0, respectively. Figure S8. Time-course responses of the upconversion fluorescence intensity of TPPS/Ln-UCNPs in the presence of 10 µm ATP regulated by buffers with ph at 4.0, 4.5, and 5.0, respectively. Figure S9. UV-vis absorbance and upconversion fluorescence response patterns and heat maps of the ph-regulated TPPS/Ln-UCNPs sensor array toward 20 µm PCs (ATP, ADP, AMP, CTP, CDP, CMP, GTP, GDP, GMP, UTP, UDP, UMP, PPi, and Pi), and 100 µm Cu 2+. Figure S10. UV-vis absorbance and upconversion fluorescence response patterns and heat maps of the ph-regulated TPPS/Ln-UCNPs sensor array toward various concentrations of ATP. Figure S11. Identification of PPi at various concentrations via the ph-regulated TPPS/Ln-UCNPs sensor array. Figure S12. UV absorbance and upconversion fluorescence response patterns and heat maps of the ph-regulated TPPS/Ln-UCNPs sensor array toward the mixture of ATP and CTP. Figure S13. UV absorbance and upconversion fluorescence response patterns, heat maps and canonical score plots of the ph-regulated TPPS/Ln-UCNPs sensor array toward the mixture of ATP and CTP. Table S1-S15. Mulliken charges in TPPS, ATP, ADP, AMP, CTP, CDP, CMP, GTP, GDP, GMP, UTP, UDP, UMP, PPi, and Pi. Table S16-S17. Identification of unknown PCs using the ph-regulated TPPS/Ln-UCNPs sensor array in UV-vis absorbance mode and in upconversion fluorescence mode. S-1

2 Synthesis of oleic acid (OA)-capped lanthanide-doped upcoversion nanoparticles (OA-Ln-UCNPs). Briefly, mmol of YCl 3 6H 2 O, 0.2 mmol of YbCl 3 6H 2 O, and mmol of TmCl 3 6H 2 O were mixed with 15 ml ODE and 6 ml OA in a 100 ml three-neck round-bottom flask. The resulting mixture was magnetically stirred and heated to 160 C for 30 min to form the lanthanide-oleate complexes and remove residual water and oxygen. Then the mixture was cooled to room temperature under a gentle flow of N 2 gas. After that, a solution of 4 mmol NH 4 F and 2.5 mmol NaOH dissolved in 10 ml methanol was added to the flask and the resulting mixture was heated to 50 C and vigorously stirred for 30 min. Then the slurry was slowly heated and kept at 100 C for 10 min to evaporating water and methanol. Subsequently, the reaction mixture was heated to 300 C in a nitrogen atmosphere and maintained for 60 min, and then cooled to room temperature naturally. The as-prepared OA-Ln-UCNPs were precipitated by adding ethanol and centrifuged, and re-dispersed in chloroform after three-time washing with chloroform/ethanol (1:1). Preparation of water-dispersible ligand-free lanthanide-doped upcoversion nanoparticles (Ln-UCNPs). In brief, the as-prepared OA-Ln-UCNPs (200 mg) were dispersed in 20 ml aqueous solution. The solution was acidified with 0.1 M HCl solution for maintaining the ph at 4. The carboxylate group of OA ligand was protonated during this reaction. After intensely agitated for 4 h, the reaction was completed. The aqueous solution was re-extracted with diethyl ether at least three times to remove the oleic acid and the combined organic extracts were re-extracted with water. Moreover, the combined water layers were re-extracted by diethyl ether. The ligand-free Ln-UCNPs in water layers were isolated by centrifugation after precipitation with acetone. Finally, Ln-UCNPs were readily dispersed in water for further use. Figure S1. FTIR spectra of OA-Ln-UCNPs (black curve) and Ln-UCNPs (red curve). S-2

3 Figure S2. TEM images of (a) OA-Ln-UCNPs and (b) Ln-UCNPs. Figure S3. The upconversion fluorescence spectra of OA-Ln-UCNPs (blue curve) and Ln-UCNPs (red curve) under the excitation of 980 nm. Figure S4. Investigation of zeta potential of Ln-UCNPs and TPPS. S-3

4 Figure S5. The upconversion fluorescence spectra of Ln-UCNPs in the range of 420~550 nm challenged with various concentration of TPPS in the buffers with ph at 4.0 (a), 4.5 (c), and 5.0 (e), respectively; Plots of the changes in upconversion fluorescence intensity at 480 nm versus concentrations of TPPS in the buffers with ph at 4.0 (b), 4.5 (d), and 5.0 (f), respectively. Figure S6. Long-term stability of the absorption intensity (a-c) and the upconversion fluorescence intensity (d-e) of TPPS/Ln-UCNPs at ph=4.0, 4.5, and 5.0. S-4

5 Figure S7. Time-course responses of the absorption intensity of TPPS/Ln-UCNPs in the presence of 10 µm ATP regulated by buffers with ph at 4.0 (a), 4.5 (b), and 5.0 (c), respectively. Figure S8. Time-course responses of the upconversion fluorescence intensity of TPPS/Ln-UCNPs in the presence of 10 µm ATP regulated by buffers with ph at 4.0 (a), 4.5 (b), and 5.0 (c), respectively. S-5

6 Figure S9. (a) UV-vis absorbance and (d) upconversion fluorescence response patterns of ph-regulated TPPS/Ln-UCNPs sensor array toward 20 µm PCs (ATP, ADP, AMP, CTP, CDP, CMP, GTP, GDP, GMP, UTP, UDP, UMP, PPi, and Pi), and 100 µm Cu 2+. Heat maps derived from the (b) UV-vis absorbance and (e) upconversion fluorescence response patterns of ph-regulated TPPS/Ln-UCNPs sensor array toward 20 µm PCs indicated, and 100 µm Cu 2+. Canonical score plots for (c) UV-vis absorbance and (f) upconversion fluorescence response patterns obtained with ph-regulated TPPS/Ln-UCNPs sensor array toward 20 µm PCs indicated, and 100 µm Cu 2+. S-6

patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward

Heat maps derived from (b) UV-vis absorbance and (d)

Identification of PPi at various concentrations via the

(a) UV-vis absorbance and (e) upconversion fluorescence response

Heat maps derived from (b) UV-vis absorbance and (f)

7 Figure S10. (a) UV-vis absorbance and (c) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward various concentrations of ATP. Heat maps derived from (b) UV-vis absorbance and (d) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward various concentrations of ATP. Figure S11. Identification of PPi at various concentrations via the ph-regulated TPPS/Ln-UCNPs sensor array. (a) UV-vis absorbance and (e) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward various concentrations of PPi. Heat maps derived from (b) UV-vis absorbance and (f) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward S-7

8 various concentrations of PPi. Canonical score plot for (c) UV-vis absorption response patterns and (g) upconversion fluorescence response patterns obtained with the ph-regulated TPPS/Ln-UCNPs sensor array toward different concentrations of PPi. Plots of PC1 vs the concentrations of PPi in (d) UV-vis absorption mode and (h) upconversion fluorescence mode. Figure S12. (a) UV absorbance and (c) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward the mixture of ATP and CTP. Heat maps derived from (b) UV-vis absorbance and (d) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward the mixture of ATP and CTP. S-8

9 Figure S13. (a) UV absorbance and (d) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward the mixture of PPi and Pi. Heat maps derived from (b) UV-vis absorbance and (e) upconversion fluorescence response patterns of the ph-regulated TPPS/Ln-UCNPs sensor array toward the mixture of PPi and Pi. Canonical score plots for the ph-regulated TPPS/Ln-UCNPs sensor array toward mixtures of PPi and Pi with different molar ratios in (c) UV-vis absorption mode and (f) upconversion fluorescence mode. Table S1. Mulliken charges in TPPS (remove hydrogen). 1 C C C C C C C C C C C N C C C S-9

10 16 C C C C C C C C N C C C C C N C C C N C C C C C C C C C C C C C C S O O O S O O O S O O S-10

11 60 O S O O O Table S2. Mulliken charges in ATP (remove hydrogen). 1 P O P O O O O O N C N C C C N C N N C C C O C O O C O P O O O Table S3. Mulliken charges in ADP (remove hydrogen). S-11

12 1 N C N C C C N C N N C C C O C O O C O P O O O P O O O Table S4. Mulliken charges in AMP (remove hydrogen). S-12 1 N C N C C C N C N N C C C

13 14 O C O O C O P O O O Table S5. Mulliken charges in CTP (remove hydrogen). 1 C C C N C N O N C C C O C O O C O P O O O P O P O O O O O S-13

14 Table S6. Mulliken charges in CDP (remove hydrogen). 1 C C C N C N O N C C C O C O O C O P O O O P O O O Table S7. Mulliken charges in CMP (remove hydrogen). S-14 1 C C C N C N O N C C C O

15 13 C O O C O P O O O Table S8. Mulliken charges in GTP (remove hydrogen). S-15 1 O P O P O O O O O N C N C C C C N O N N C C C O C O C O O P O

16 36 O Table S9. Mulliken charges in GDP (remove hydrogen). 1 N C N C C C C N O N N C C C O C O C O O P O O O P O O O Table S10. Mulliken charges in GMP (remove hydrogen). S-16 1 N C N C C C C

17 8 N O N N C C C O C O C O O P O O O Table S11. Mulliken charges in UTP (remove hydrogen). S-17 1 C C C N C O O N C C C O C O O C O P O O O

18 26 P O O O P O O O Table S12. Mulliken charges in UDP (remove hydrogen). 1 C C C N C O O N C C C O C O O C O P O O O P O O O Table S13. Mulliken charges in UMP (remove hydrogen). S-18 1 C C C

19 4 N C O O N C C C O C O O C O P O O O Table S14. Mulliken charges in PPi. 1 O P O P O O O O O Table S15. Mulliken charges in phosphate. 1 O P O O O S-19

20 Table S16. Identification of unknown PCs using the ph-regulated TPPS/Ln-UCNPs sensor array in UV-vis absorbance mode. Sample (A 0 -A)/A 0 ph=4.0 ph=4.5 ph=5.0 Identification Verification ATP ATP ADP ADP AMP AMP CTP CTP CDP CDP CMP CMP GTP GTP GDP GDP GMP GMP UTP UTP UDP UDP UMP UMP PPi PPi Pi Pi Table S17. Identification of unknown PCs using the ph-regulated TPPS/Ln-UCNPs sensor array in upconversion fluorescence mode. Sample (F 0 -F)/F 0 ph=4.0 ph=4.5 ph=5.0 Identification Verification ATP ATP ADP ADP AMP AMP CTP CTP S-20

21 S CDP CMP CDP CMP GTP GDP GMP UTP UDP UMP PPi Pi GTP GDP GMP UTP UDP UMP PPi Pi

382 25,,, 4.2 g 96% m.p.139~140 ( [21] :138~139 ), (4- )-2,2 6,2 - (L), [17], 2.5 mmol 1-(2- )-, 2.5 mmol 1-(2- )-(4- ) -1-2,2 6,2 (25.0 mmol),

382 25,,, 4.2 g 96% m.p.139~140 ( [21] :138~139 ), (4- )-2,2 6,2 - (L), [17], 2.5 mmol 1-(2- )-, 2.5 mmol 1-(2- )-(4- ) -1-2,2 6,2 (25.0 mmol), 25 3 2009 3 CHINESE JOURNAL OF INORGANIC CHEMISTRY Vol.25 No.3 381~385 4-1 *,1 1 1,2 ( 1, 361005) ( 2, 361005) : -2,2 6,2 -,4 - -2,2 6,2 - (L), L (ZnL),, ZnL 1 1 2 1 2 1,ZnL : ; 4 - -2,2 6,2 - ; ; : O614.24