Orderly Arranged Fluorescence Dyes as a Highly Efficient Chemiluminescence Resonance Energy Transfer Probe for Peroxynitrite

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1 Supporting Information: Orderly Arranged Fluorescence Dyes as a Highly Efficient Chemiluminescence Resonance Energy Transfer Probe for Peroxynitrite Zhihua Wang, Xu Teng and Chao Lu* State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing , China. Fax/Tel.: E mail: luchao@mail.buct.edu.cn. This Supporting Information includes: (1) Figure S1 and Figure S2 schematic diagram of the CL setup; (2) Figure S3 powder XRD patterns of NO 3 LDHs, and SDS LDHs, TEM images of NO 3 LDHs and SDS LDHs, normalized fluorescence spectrum of sediments obtained by centrifuging calcein on the surface of SDS LDHs, and pictures of sediments obtained by centrifuging calcein on the surface of SDS LDHs under visible light and ultraviolet light at 254 nm; (3) Figure S4 structures of anionic surfactant SDS molecule and calcein fluorescence dye molecule; (4) Figure S5 the adsorption time of calcein on the surface of SDS LDHs; (5) Figure S6 fluorescence spectra of calcein@sds solution mixed with different concentrations of OH, and fluorescence spectra of the collapsed calcein@sds solution (a holding time of 60 min) mixed with different concentrations of OH; (6) Figure S7 CL intensity from the reaction of calcein@sds solution with different concentrations of ClO ; (7) Figure S8 normalized CL spectrum ONOO system mixed with calcein@sds solution, and normalized fluorescence spectrum of calcein solution; (8) Figure S9 normalized CL spectrum of ONOOH *, and absorption spectrum of calcein@sds solution; (9) Figure S10 CL intensity from the reaction of uranine@sds solution with different ROS. Inset: absorption spectrum of uranine@sds solution; (10) Figure S11 detection of ONOO from SIN 1; (11) Table S1 comparison of zeta potential values for SDS LDHs and calcein assembled SDS LDHs; (12) Table S2 optimum experimental conditions for the CL determination of 10 µm ONOO ; (11) Table S3 tolerance limit of various coexistent substances on the determination of 10 µm ONOO. S-1

2 Figure S1. Schematic diagram of the CL setup. a, 0.02 M H 2 O M HCl at 1.6 ml/min; b, 10 µm NaNO 2 at 1.6 ml/min; c, 0.1 M NaOH at 0.8 ml/min; d, calcein or calcein@sds solution; P, peristaltic pump; V, six-way injection valve; W, waste; PMT, photomultiplier tube. S-2

3 Figure S2. Schematic diagram of the CL setup. a, sample or spiked sample solution at 0.8 ml/min; b, solution; P, peristaltic pump; V, six-way injection valve; W, waste; PMT, photomultiplier tube. S-3

4 1 2 Figure S3. (A) Powder XRD patterns of (1) NO 3 LDHs, and (2) SDS LDHs. Inset: TEM images of NO 3 LDHs and SDS LDHs; (B) Normalized fluorescence spectrum of sediments obtained by centrifuging calcein on the surface of SDS LDHs. Inset: pictures of sediments obtained by centrifuging calcein on the surface of SDS LDHs under visible light (left) and ultraviolet light at 254 nm (right). S-4

5 Figure S4. Structures of anionic surfactant SDS molecule and calcein fluorescence dye molecule. S-5

6 Figure S5. Effect of the adsorption time of calcein on the surface of SDS LDHs on the CL intensity. The concentrations of calcein and SDS for each solution were 1.0 mm and 0.1 M, respectively. The concentration of ONOO was 10 µm. The colloidal solution was acidified with 1.0 M HCl. S-6

7 Figure S6. (A) Fluorescence spectra of solution mixed with different concentrations of OH. (a) 0 mm, (b) 1 mm, (c) 10 mm, (d) 100 mm; (B) fluorescence spectra of the collapsed calcein@sds solution (a holding time of 60 min) mixed with different concentrations of OH. (a) 0 mm, (b) 1 mm, (c) 10 mm, (d) 100 mm. S-7

8 Figure S7. CL intensity from the reaction of solution with different concentrations of ClO. The concentrations of calcein and SDS were 1.0 mm and 0.1 M, respectively. The colloidal solution was acidified with 1.0 M HCl. S-8

9 Figure S8. (A) Normalized CL spectrum ONOO system mixed with solution; (B) normalized fluorescence spectrum of calcein solution. The concentrations of calcein and SDS were 1.0 mm and 0.1 M, respectively. The concentration of ONOO was 0.01 M. The colloidal solution was acidified with 1.0 M HCl. S-9

10 Figure S9. (A) Normalized CL spectrum of ONOOH * ; (B) Absorption spectrum of calcein@sds solution. The concentrations of calcein and SDS were 1.0 mm and 0.1 M, respectively. The colloidal solution was acidified with 1.0 M HCl. ONOOH * was prepared by 0.07 M acidified H 2 O 2 and 0.1 M NaNO 2. S-10

11 Figure S10. CL intensity from the reaction of solution with different ROS. Inset: absorption spectrum of solution. The concentrations of 1 O 2, H 2 O 2, OH, O 2 and ClO were 1.0 mm. The concentration of ONOO was 0.5 mm. The concentrations of uranine and SDS were 1.0 mm and 0.1 M, respectively. The colloidal solution was acidified with 1.0 M HCl. S-11

12 Figure S11. Detection of ONOO from SIN 1. The concentration of SIN 1 was 5 mm. S-12

13 Table S1 Comparison of zeta potential values for SDS LDHs and calcein assembled SDS LDHs. SDS LDHs Sample calcein assembled SDS LDHs Zeta Potential (mv) mv mv S-13

14 Table S2 Optimum experimental conditions for the CL determination of 10 µm ONOO. Parameter Range studied Optimum Concentration of HCl (mm) Concentration of H 2 O 2 (mm) Concentration of NaOH (mm) Concentration of calcein (mm) Flow rate for HCl-H 2 O 2 or NaNO 2 (ml/min) Flow rate for NaOH (ml/min) S-14

15 Table S3 Tolerance limit of various coexistent substances on the determination of 10 µm ONOO. Tolerance (mm) Coexistent substances 10 Glucose (3 7 mm) a 5 K + (2 4 mm), Mg 2+ (1 3 mm), Ca 2+ (1 3 mm), Ac - (2 4 mm), bilirubin (14 22 µm) 1 S 2- - (30 60 µm), NO 3 (1 10 µm), SO 2-4 (1 4 µm), C 2 O 2-4 (1 4 µm), H 2 PO - 4 (10 50 µm) 0.5 Pb ( µm), HPO 4 (10 60 µm), I - (1 5 µm), Al 3+ (2 5 µm), Cr 3+ ( µm), glutamine (1 4 µm), homocysteine (3 6 µm), uric acid ( µm) 0.1 Fe 3+ (20 25 µm), Cu 2+ (2 4 µm), PO 3-4 (20 50 µm), ascorbic acid (50 80 µm), cysteine (7 50 µm) a Values in brackets means the common concentration ranges of the interfering compounds in mouse blood plasma. S-15

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