Supporting Information. Design and synthesis of a novel colorimetric fluorescent probe for

Transcription

1 Electronic upplementary Material (EI) for ew Journal of Chemistry. This journal is The Royal ociety of Chemistry and the Centre ational de la Recherche cientifique 2019 upporting Information Design and synthesis of a novel colorimetric fluorescent probe for selective detection of sulfur dioxide in H-Y5Y neuroblastoma cells and its application in Traditional Chinese Medicines Lili Yang a,b, Mofan Liu a,b, Kangjia heng a,b, Xiaolu Li a,b, Junli Du a,b, Yaoyao ing a,b, Xiaoqing Wang c, Jianli Li c,yongmin Zhang a,b,d and haoping Wu a,b * a chool of Pharmacy; Key Laboratory of Resource Biology and Biotechnology in Western China (orthwest University), Ministry of Education; Biomedicine Key Laboratory of haanxi Province, orthwest University, Xi an , China b Joint International Laboratory of Glycobiology and Medicinal Chemistry, orthwest University, Xi an, haanxi , China c Key Laboratory of ynthetic and atural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials cience, orthwest University, Xi'an, haanxi , P. R. China d orbonne Université, Institut Parisien de Chimie Moléculaire, CR UMR 8232, 4 place Jussieu, Paris, France * Tel.: ; Fax: E_mail: wushaoping@nwu.edu.cn CTET 1. Recent progress in the development of fluorescent probes for the detection of Calculation of the detection limit of probe DTCC. 3. The calculation of fluorescence quantum yield about probe DTCC. 4. The optical properties of DTCC in different organic solvents. 5. The characterization data of the intermediate and probe DTCC. 6. Proposed reaction mechanism of detecting DFT optimized structures. 8. Cytotoxicity experiment. 9. Detection and analysis of sulfur dioxide residue in Traditional Chinese Medicines.

2 1. Recent progress in the development of fluorescent probes for the detection of 3 2- Ref Probe structures λ ex /λ em LD (M) [1] 550 / ensing ph ranges Response Time Biological imaging application 3~9 30 s MCF-7 cells [2] 585 / ~8 Less than HeLa Cells min 3 [3] H I 428 / MCF-7 cells [4] Br 490 / ~ s Hela cells, MCF-7 cells [5] H CH 377 / ~9.0 within seconds HE-2 cells [6] C C C 482 / ~ min HeLa cells and 10-8 HepG2 cells [7] 490 / ~ min [8] 510 / ~ s A549 cells and zebrafish [9] 510 / min - F B F 10-8 [10] 410 / min HeLa cells Et / 590

3 ur work H 385 / Less than 10 s HeLa cells 2. Calculation of the detection limit of probe DTCC 3 LD= k Where σ is the standard deviation of the blank measurement, k is the slope between the fluorescence intensity and concentration 2-3 (0~100 µm). The fluorescence intensity of DTCC was measured by eleven times and the standard deviation of the blank measurement was achieved. The calculated LD of probe DTCC are showed in Table 1. Probe DTCC LD/µM 0.23 Table 1 The calculated detection limit for probe DTCC. 3. The calculation of fluorescence quantum yield about probe DTCC The quantum yield (Ф) of DTCC denotes the fluorescence quantum yield. It was measured at room temperature referenced to fluorescein in aqueous solution of 0.1 M sodium hydroxide, which has a quantum yield of We calculated the fluorescence quantum yield of DTCC in different organic solvents. The results were shown in Table 2. olvent CH 2 2 DMF DM EtH CH 3 C Ф f Table 2 The calculated the fluorescence quantum yield for DTCC in different organic solvents. Ф was quantum yield of fluorescein; A X and A indicated the absorption intensity of the sample and the standard at the excitation wavelength, respectively; F X and F for the sample and the standard fluorescence integral area; n was refractive index of the solvent; ubscript s and x was the standard and unknown samples,

4 respectively. A F n X X F(X) F ( ) AX F n 2 4. The optical properties of DTCC in different organic solvents The optical properties of DTCC in different organic solvents included the maximum absorption wavelength (λ abs ) Molar absorption coefficient (ε max ) Emission wavelength tokes shift. The calculation results are shown in Table 3. We could get that there was a large tokes shift for DTCC. olvent λ abs / ε max /M -1 cm -1 λ em / Φ F(X) tokes shift cm -1 EtH CH DMF DM CH 3 C Table 3 The optical properties of DTCC in different organic solvents. Fig. 1 Time-dependent absorption changes of free probe (10 μm) and probe (10 μm) with 3 2- (100 μm) in Hepes buffer (10 mm, ph 7.4, containing 20% CH 3 C, 25 ) solution.

5 5. The characterization data of the intermediate and probe DTCC compound TADARD CARB PARAMETER WU_MRLAB f1 (ppm) Fig. 2 1 H-MR spectrum of intermediate 1 in CD 3. compound2-2dmso TADARD CARB PARAMETER WU_MRLAB dmso H H 3 C H 3 C f1 (ppm) Fig. 3 1 H-MR spectrum of intermediate 2 in DM-d 6.

6 0.0 compound3 TADARD CARB PARAMETER WU_MRLAB H 800 H 3 C H 3 C f1 (ppm) Fig. 4 1 H-MR spectrum of intermediate 3 in CD 3. Fig. 5 1 H-MR spectrum of probe DTCC in DM-d 6.

7 Fig C-MR spectrum of probe DTCC in DM-d 6. Fig. 7 HRM of probe DTCC. 6. Proposed reaction mechanism of detecting 3 2- Fig. 8 Proposed reaction mechanism of detecting 3 2-.

8 7. DFT optimized structures Fig. 9 Density functional theory optimized structures of DTCC and compound DTCC Cytotoxicity experiment The cell viability (%) was assessed using the following equation: Cell viability (%) = T/C 100%, where T is the D 450 value of experience group and C is the control group of D 450 (optical density) value. D 450 value of each repeated wells are given as mean ± standard deviation (D) Fig. 10 Cytotoxicity assays of probe DTCC at different concentrations (0 µm, 5 µm, 10 µm, 15 µm, 20 µm) for H-Y5Y neuroblastoma cells. 9. Detection and analysis of sulfur dioxide residue in Traditional Chinese Medicines Pharmacopoeia method The Pharmacopoeia methods for detecting residual sulfur dioxide in Traditional Chinese Medicines including acid-base titration, ion chromatography and so on. Currently, the most commonly used method is acid-base titration, but the operation

9 process is cumbersome and complicated. The herbal medicines are treated by distillation in water, then the sulfite substance in the sample are converted into sulfur dioxide derivatives by acid treatment, and introduced into an absorption bottle containing hydrogen peroxide with a nitrogen flow, which are oxidized to sulfate ion by hydrogen peroxide, and finally determined by acid-base titration method to calculate the residue of sulfur dioxide remaining in the TCMs. Fluorescence method Compared with the methods in pharmacopoeia, fluorescent method has been extensively used as promising detection tools due to their simple operation, high sensitivity and selectivity, fast response as well as strong anti-interference and spatial resolution. The sample could be treated simply by grinding into powder, then ultrasonic-extracted with H 2 :CH 3 C:H (1:1:0.05) for 20 min at room temperature and filtered. 10 μm DTCC probes were added into the filtrate, fluorescence intensity was measured and calculated the residue of sulfur dioxide according to the linear relationship. References 1 Y.-F. Wang, Q.-T. Meng, R. Zhang, H.-M. Jia, C.-P. Wang and Z.-Q. Zhang, J. Lumi., 2017, 192, Q. Zhang, Y. Zhang,.-. Ding, H.-Y. Zhang, G.-Q. Feng, ens. Actuators B, 2015, 211, L.-J. Tang, P. He, X.-M. Yan, J.-Z. un, K.-L. Zhong and.-h. Hou, ens. Actuators B, 2017, 247, H.-D. Li, X. Zhou, J.-L. Fan,. Long, J.-J. Du and J.-Y. Wang, ens. Actuators B, 2018, 254, X. Liu, Q. Yang, W. Chen, L. Mo,. Chen and J. Kang, rg. Biomol. Chem., 2015, 13, M.-F. Huang, L.-. Chen, J.-Y. ing, W.-L. Wu, X.-D. He and J.-Y. Miao, ens. Actuators B., 2018, 261,

10 7 X. Ma, C.-X. Liu, Q.-L. han, G.-H. Wei, D.-B. Wei, Y.-G. Du, ens. Actuators B., 2013, 188, Y. Yue, F. Huo, P. ing, Y. Zhang, J. Chao, X. Meng and C. Yin, J. Am. Chem. oc., 2017, 139, X. Gu, C. Liu, Y.-C. Zhu and Y.-Z. Zhu, J. Agric. Food Chem., 2011, 59, H. Tian, J. Qian, Q. un, C. Jiang, R. Zhang and W. Zhang, Analyst., 2014, 139,