An unexpected highly selective mononuclear zinc complex for adenosine diphosphate (ADP)

Transcription

1 This journal is The Royal Society of Chemistry 213 Supplementary Information for An unexpected highly selective mononuclear zinc complex for adenosine diphosphate (ADP) Lei Shi, Ping Hu, Yanliang Ren and Guoqiang Feng* Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China ormal University, Wuhan 4379, P.R. China, 1. General Experimental Details. Starting materials were purchased from commercial suppliers and were used without further purification. ucleotides AMP, ADP and ATP were purchased at the highest purity available. All solvents were purified by the most used methods before use. 2-[4-(2-hydroxyethyl)-1-piperazinyl]-ethanesulfonic acid (HEPES) was used to prepare buffer solution and all solutions were prepared with using distilled water that had been passed through a Millipore-Q ultrapurification system. MR spectra were measured on Varian Mercury 4 and 6 instruments, operating at 4 or 6 MHz for 1 H MR and 1 or 15 MHz for 13 C MR. IR spectra were recorded on a Perkin-Elmer Spectrum BX FT-IR spectrophotometer as KBr pellets and were reported in cm -1. Fluorescent spectra were recorded on an Agilent Cary Eclipse fluorescence spectrophotometer, respectively. 2. Synthesis of ZnL 1

2 This journal is The Royal Society of Chemistry 213 Synthesis of 1: The 9-(aminomethyl)anthracene (.14 g,.5 mmol) was dissolved in 3 ml of CH 3 OH and then the 2,6-pyridinedicarboxaldehyde (.34 g,.25 mmol) was added. The mixture was stirred at room temperature. After about 3 minutes, yellow precipitate generated gradually. The reaction mixture was further stirred for another 4 h, and then the reaction was cooled to. The yellow solid was collected on a filter and washed with CH 3 OH. Further dried in a vacuum afforded 1 as a yellow solid (81 mg, yield 63.1%). Mp: C. 1 H MR (6 MHz, CDCl 3 ): δ 8.46 (s, 2H, CH=), 8.22 (d, J = 8.9 Hz, 4H, ArH), 8.13 (s, 2H, ArH), 8.2 (d, J = 8.4 Hz, 4H, ArH), 7.89 (d, J = 7.9 Hz, 2H, PyH), 7.66 (s, 1H, PyH), 7.46 (dd, J = 17.7, 8. Hz, 8H, ArH), 5.89 (s, 4H, 2CH 2 ). 13 C MR (1 MHz, CDCl 3 ): δ , , , , 13.73, 129.1, 128.7, , , , 124.2, , IR (KBr, cm -1 ): 349, 2868, 1639, 1565, 145, 134, 1317, 126, 989, 95, 881, 728. MS (EI): (M +, 3%), ((M-anthracene-CH 2 ) +, 28%), (anthracene-ch + 2, 1%). Synthesis of L: To a stirring solution of 1 (6 mg,.12 mmol) in a mixture of CH 3 OH (2 ml) and CHCl 3 (5 ml) was slowly added.3 g abh 4 in portions at C. The mixture was stirred at C for 1 h and then warmed to room temperature and stirred for 3 h. The solvent was evaporated and H 2 O (4 ml) was added. The formed solid was collected on a filter and washed with H 2 O. Dried under vacuum afforded L as a yellow solid (5 mg, yield 81%). Mp: C. 1 H MR (4 MHz, CDCl 3 ): δ 8.37 (s, 2H, ArH), 8.3 (d, J = 8.1 Hz, 4H, ArH), (m, 4H, ArH), 7.59 (t, J = 7.7 Hz, 1H, PyH), (m, 8H, ArH), 7.19 (d, J = 7.7 Hz, 2H, PyH), 4.79 (s, 4H, 2CH 2 ), 4.13 (s, 4H, 2CH 2 ). 13 C MR (1 MHz, CDCl 3 ) δ , , , ,13.39, 129.1, , 126.8, , , 12.86, 55.42, IR (KBr, cm -1 ): 3452, 349, 2852, 1622, 159, 145, 1425, 1329, 889, 733. MS (EI): (M +, 2%), ((M-anthracene-CH 2 ) +, 2%), (anthracene-ch + 2, 1%). HR-MS (ESI) m/z calcd. for C 37 H [M + H] , found Synthesis of ZnL: The Compound L (1.34 mg,.2 mmol) was dissolved in 1 ml of CHCl 3, and then 1 ml Zn(O 3 ) 2 solution (2 mm) was added. After about 1 minutes, yellow precipitate generated gradually. The yellow solid was collected on a filter and washed with cold CH 3 OH. And then it was dried under vacuum to afford ZnL as a yellow solid (1.7 mg, yield 76%). Mp: C. 1 H MR (4 MHz, d 6 -DMSO): δ 8.77 (s, 2H, ArH), 8.43 (s, 4H, ArH), 8.24 (s, 4H, ArH), 7.88 (s, 1H, PyH), 7.69 (d, J = 33.3 Hz, 8H, ArH), 7.3 (s, 2H, PyH), 5.7 (s, 4H, 2CH 2 ), 4.39 (s, 2H, 2H), 3.81 (s, 4H, 2CH 2 ). 13 C MR (1 MHz, CDCl 3 ): δ 153.9, 14.95, , 13.36, , , , , , , 122.1, 49.31, IR (KBr, cm -1 ): , 35.96, , , , , , , ESI-MS: ([ZnL-2O - 3 +OH - ] + ). Elemental analysis (%) Calcd. for C 37 H 31 5 O 6 Zn. H 2 O: C, 61.29; H, 4.59;, Found: C, 6.93; H, 4.75;,

3 This journal is The Royal Society of Chemistry H 2 O Fig. S1. 1 H MR and 13 C MR of 1 in CDCl 3. 3

4 This journal is The Royal Society of Chemistry H H L H H L Fig. S2. 1 H MR and 13 C MR of L in CDCl 3. 4

5 This journal is The Royal Society of Chemistry 213 H Zn 2+ H ZnL (in d 6 -DMSO) (a) 1 H MR of ZnL in d 6 -DMSO H Zn 2+ H ZnL (in CDCl 3 ) (b) 1 H MR of ZnL in CDCl 3 5

6 This journal is The Royal Society of Chemistry H Zn 2+ H ZnL (c) 13 C MR of ZnL in CDCl 3. ZnL L H H Zn 2+ H OH - 2 O Chemical Formula: C 37 H 34 3 O 2 Zn + Molecular Weight: (d) ESI-Mass spectrum of ZnL in CDCl 3. Fig. S3. 1 H MR, 13 C MR and ESI-Mass spectrum of ZnL 6

7 This journal is The Royal Society of Chemistry Fluorescent studies using DMSO and THF as co-solvent ZnL + ADP ZnL ZnL + AMP ZnL + ATP Wavelength (nm) (a) DMSO/H 2 O = 1/ ZnL + ADP ZnL ZnL + AMP ZnL + ATP Wavelength (nm) (b) THF/H 2 O = 1/3 Fig. S4. The fluorescent spectra changes of ZnL (1 μm) upon addition of two equiv of ADP, AMP, ATP. (a) in an aqueous HEPES buffer solution (1 mm, ph = 7.2, DMSO/H 2 O = 1/3, v/v) at 25 C. (b) in an aqueous HEPES buffer solution (1 mm, ph = 7.2, THF/H 2 O = 1/3, v/v) at 25 C. λ ex = 38 nm. 7

8 This journal is The Royal Society of Chemistry Fluorescent studies for ATP with ZnL (a) Fluroscent Intensity [ATP] I/I (416nm) K d =.168 M R 2 = [ATP] M (b) [ATP]/([ATP]+[ZnL]) I -I (416nm) Fig. S5. (a) Fluorescent titration of complex ZnL (1 μm) upon the addition of ATP. Insert: The fluorescence intensity changes at 416 nm of ZnL upon addition of ADP, solid lines are generated by curve fitting of the data using a 1:1 binding mode. (b) Job s plot examined between ZnL and ATP, [ZnL] + [ATP] = 1 μm. All the spectra were measured in an aqueous HEPES buffer solution (1 mm, ph = 7.2, containing 25% DMF, v/v) at 25 C. 5. Fluorescent studies for PPi with ZnL (a) Fluroscent Intensity [PPi] I/I (416nm) Kd =.7 M R 2 = [PPi] M (b) I -I (416nm) [PPi]/([PPi]+[ZnL]) Fig. S6. (a) Fluorescent titration of complex ZnL (1 μm) upon the addition of PPi. Insert: The fluorescence intensity changes at 416 nm of ZnL upon addition of PPi, solid lines are generated by curve fitting of the data using a 1:1 binding mode. (b) Job s plot examined between ZnL and PPi, [ZnL] + [PPi] = 1 μm. All the spectra were measured in an aqueous HEPES buffer solution (1 mm, ph = 7.2, containing 25% DMF, v/v) at 25 C. 8

9 This journal is The Royal Society of Chemistry Fluorescent studies for citrate with ZnL (a) Fluroscent Intensity 4 [Citrate] Kd = M 3.9 R 2 = [Citrate] M I/I (416nm) (b) I -I (416nm) [Citrate]/([Citrate]+[ZnL]) Fig. S7. (a) Fluorescent titration of complex ZnL (1 μm) upon the addition of citrate. Insert: The fluorescence intensity changes at 416 nm of ZnL upon addition of citrate, solid lines are generated by curve fitting of the data using a 1:1 binding mode. (b) Job s plot examined between ZnL and citrate, [ZnL] + [citrate] = 1 μm. All the spectra were measured in an aqueous HEPES buffer solution (1 mm, ph = 7.2, containing 25% DMF, v/v) at 25 C. 7. Fluorescent titrations of ZnL with other anions Fluroscent Intensity [AMP] -1 M A [F - ] -1 M B [Cl - ] -1 M C [Br - ] -1 M D 9

10 This journal is The Royal Society of Chemistry [SO 2-4 ] -1 M E [ClO - 4 ] -1 M F [S 2 O 2-7 ] -1 M G [HCO - 3 ] -1 M Wavelength (nm) H [O - 3 ] -1 M I [ 3 - ] -1 M J [H 2 PO - 4 ] -1 M [PO 3-4 ] -1 M K L 1

11 This journal is The Royal Society of Chemistry [HPO 2-4 ] -1 M M [PhPi] -1 M Fig. S8. Fluorescent titration of complex ZnL (1 μm) upon the addition of other anions in an aqueous HEPES buffer solution (1 mm, ph = 7.2, containing 25% DMF, v/v) at 25 C. From A to : AMP, F, Cl, Br, SO 4 2, ClO4, S2 O 7 2, HCO3, O3, 3, H2 PO 4, PO4 3, HPO4 2, PhPi. 8. Job s plot for ADP and ZnL I-I (416nm) [ADP]/([ADP]+[ZnL]) Fig. S9. Job s plot examined between ZnL and ADP, [ZnL] + [ADP] = 1 μm. The spectra were measured in an aqueous HEPES buffer solution (1 mm, ph = 7.2, containing 25% DMF, v/v) at 25 C. 11

12 This journal is The Royal Society of Chemistry Mass spectrum of the mixture of ZnL and ADP H H Zn 2+ H 2 O - OH P P HO O O O O O OHOH Chemical Formula: C 47 H 45 8 O 1 P 2 Zn + Mass: 17 (a) % Calculated Mass (b) Fig. S1. (a) ESI-Mass spectrum of a mixture of ZnL + ADP in DMF/H 2 O. (b) Isotope distribution calculated for C 47 H 45 8 O 1 P 2 Zn MR studies 12

13 This journal is The Royal Society of Chemistry Fig. 11. (a) Partial 1 H MR spectra of ZnL (1 mm), ZnL (1 mm) with one equiv of ADP, and ADP (1 mm). (b) 31 P MR spectra of ADP (1 mm) and ADP (1 mm) with one equiv. of ZnL. MR solvents: 1% D 2 O in d 6 -DMSO. 11. DFT calculated interactions between AMP, ATP and ZnL (a) AMP 13

14 This journal is The Royal Society of Chemistry 213 (b) ATP Fig. S12. (a) Plot views of DFT calculated interactions between ZnL and AMP from different angles. (b) Plot views of DFT calculated interactions between ZnL and ATP from different angles. Hydrogen atoms are omitted for clarity. 14