Supporting Information. Magnetic Iron Oxide Nanoparticle Seeded Growth of. Nucleotide Coordinated Polymers

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1 Supporting Information Magnetic Iron xide anoparticle Seeded Growth of ucleotide Coordinated Polymers Hao Liang,* a,b BiwuLiu, b QipengYuan a and Juewen Liu* b a State key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, China. lianghao@mail.buct.edu.cn b Department of Chemistry and Waterloo Institute for anotechnology, University of Waterloo, Waterloo, Canada. liujw@uwaterloo.ca; Fax: ; Tel: ext S 1

2 AMP remained in the supernatant (%) on-reacted AMP Precipitant weight ph Precipitant weight (g) Figure S1. Precipitant weight and the remaining AMP percentage in the supernatant after centrifugation of the product from Fe 3+ (5 mm) reacting with AMP (5 mm) in HEPES buffers (25 mm) of different ph. The indicated ph values on the x-axis were the actual ph of the final mixture. AMP remained in the supernatant (%) on-reacted AMP Precipitant weight [acl] (mm) Precipitant weight (g) Figure S2. Precipitant weight and the remaining AMP percentage in the supernatant after centrifugation of the product from Fe 3+ (5 mm) reacting with AMP (5 mm) in HEPES buffer (25 mm, ph 7.6) in the presence of various acl concentrations. The actual ph values were ph 6.3. S 2

3 A 2 B 25 2 umber (%) 15 1 umber (%) Diameter (nm) Diameter (nm) C 2 D 25 2 umber (%) 1 umber (%) Diameter (nm) Diameter (nm) Figure S3. Dynamic light scattering analysis of particle size distribution of Fe 3+ /AMP (A), Fe 3+ /GMP (B), Fe 3+ /CMP (C), and Fe 3+ /TMP (D). The measurements were carried out in HEPES buffer (ph 7.6, 1mM) with a concentration of.2 mg/ml of the particles at 25 C. Table S1. Average particle sizes and -potential of Fe 3+ /nucleotide CPs in ph 7.6 HEPES buffer (1mM). Fe 3+ /AMP Fe 3+ /GMP Fe 3+ /CMP Fe 3+ /TMP Average diameter 637±28 347±4 436±11 461±13 (nm) Zeta-potential (mv) -33.3± ± ± ±1. S 3

4 - Adenosine 5 monophosphate (AMP) - P P - - H H Guanosine 5 monophosphate (GMP) H H H 2 H H P - H H 2 H Cytidine 5 monophosphate (CMP) P - H H H Thymidine 5 monophosphate (TMP) Figure S4. Chemical structures of the four kinds of nucleoside monophosphates used in this work. The contents of iron and phosphorus analyzed by ICP An ICP-ES 21DV instrument (PerkinElmer, USA) was used for element analysis of phosphorus and iron. The Fe 3+ /AMP sample (1.5 mg) was digested with 1 ml H3 followed by microwave treatment. The resulting solutions were diluted with deionized water to a final volume of 5 ml. Two kinds of standard solutions: phosphorus standard solution and multi-element standard solutions, were prepared at 5 mg/l and 1 mg/l, respectively. The samples were analyzed with blanks and both standard solutions. The ICP-ES instrument conditions are shown in Table S2. Table S2. ICP instrument conditions. forward power (W) 13 plasma gas flow rate (L/min) 15 auxiliary gas flow rate (L/min).2 nebulizer gas flow rate (L/min).8 peristaltic pump flow rate (ml/min) 1.5 S 4

5 The contents of iron and phosphorus in the formed Fe 3+ /AMP CPs analyzed by ICP are shown in Table S3. According to the analysis results, it can be concluded that the molar ratio of Fe 3+ and AMP was about 1:1 in this coordination polymer. Table S3. The contents of iron and phosphorus in the formed Fe 3+ /AMP CPs analyzed by ICP. umber of trial Average Fe (mmol/l) ±.3 P (mmol/l) ±.16 Figure S5. TEM micrographs of Fe 3+ /AMP (A), Fe 3+ /GMP (B), Fe 3+ /CMP (C), and Fe 3+ /TMP (D). S 5

6 Figure S6. Photographs showing the samples of Cu2+ (5mM) reacted with AMP (5 mm) in the presence of Fe34 Ps (.2 mg/ml). After magnet attraction, some Fe34 Ps escaped from the Cu2+/AMP CPs, and the light blue Cu2+/AMP precipitants were observed. Figure S7.TEM micrographs of Fe3+/AMP CPs coated on other nanomaterials: (A) silica; (B) carboxyl latex beads; (C) amidine latex beads; (D) AuPs. S 6

7 1. Absorbance (a.u.) Time (min) Figure S8. Kinetics of ABTS (.25 mm) oxidization by H22 (1 mm) in the presence of Fe34 (.56 mg/ml) in acetate buffer (ph 4., 25 mm). Table S4. The sequences and modifications of DA used in this work. DA names FAM-A15 FAM-C15 FAM-T15 Random DA Sequences (from 5 to 3 ) and modifications FAM-AAA AAA AAAAAAAAA FAM-CCC CCC CCCCCCCCC FAM-TTT TTT TTTTTTTTT FAM-ACG CAT CTG TGA AGA GAA CCT GGG Table S5. -potential of Fe34 or Fe34@Fe 3+ /AMP at various ph s of acetate buffer. anoparticles ph -potential (mv) Fe ±1.6 Fe 3+ /AMP CPs ±.6 Fe34@Fe 3+ /AMP CPs ±.4 Fe34@Fe 3+ /AMP CPs ±.4 Fe34@Fe 3+ /AMP CPs ±1.1 S 7

8 Figure S9. Encapsulated weights and encapsulation ratio of Gx by 3+ /AMP complexes at various initial free Gx concentrations in HEPES buffer (ph 8., 25 mm). The amount of 3+ /AMP used was 2.2 mg/ml. Glucose detection of fruit samples by Fe 3+ /AMP A piece of fresh watermelon (5 g) was ground by a juice extractor, and about 1 g of watermelon juice was centrifuged at 12, rpm for 5 min (Figure S1). The supernatant (2 μl) was added to 16 μl acetate buffer (ph 4) containing 1 μl the suspension of the Gx&Fe34@Fe 3+ /AMP complexes and 1 μl ABTS (1 mm). After 1 h incubation at room temperature, the solution was centrifuged at 1, rpm for 5 min. The absorbance of the supernatant at 415 nm was measured. For HPLC, the watermelon juice after centrifuged was filtered through a.22 μm membrane filter. 1 μl of this filtered sample was injected into HPLC using anh2 column (4.6 mm 15 mm, 5 μm, Inertsil TM ), and column oven temperature was maintained at 35 C. Glucose was detected by refractive index using a Hitachi differential refractometer. The mobile phase was 75% acetonitrile in water, and the flow rate was 1 ml/min. All the samples were tested for three times. The glucose contents of watermelon juice samples by two methods are shown in Table S6. Table S6. The contents of glucose in the extracted watermelon juice analyzed by the Gx&Fe34@Fe 3+ /AMP CP sensor and by HPLC. Methods Glucose content (mg/g) Gx&Fe34@Fe 3+ /AMP CPs 51.8 ±.4 HPLC 47.2 ± 2.5 S 8

9 Figure S1. Photographs showing the watermelon juice after centrifugation (A) and the supernatant analyzed by 3+ /AMP CPs (B). S 9