Supporting Information

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1 Supporting Information Adenosine-Related Compounds as an Enhancer for Peroxidase-Mimicking Activity of Nanomaterials: Application to Sensing of Heparin Level in Human Plasma and Total Sulfated Glycosaminoglycan Content in Synthetic Cerebrospinal Fluid Jyun-Guo You a, Yen-Ting Wang a and Wei-Lung Tseng* a,b a Department of Chemistry, National Sun Yat-sen University, Kaohsiung City, 804, Taiwan b School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Kaohsiung City, 807, Taiwan Correspondence: Department of Chemistry, National Sun Yat-sen University, 70 Lienhai Rd., Kaohsiung 80424, Taiwan, R.O.C. * tsengwl@mail.nsysu.edu.tw. Phone: Fax: S-1

2 Figure S1. Effects of (A) ADP, (B) AMP, (C) ADP, and (D) ADP on the peroxidase-like acitivty of (A) citrate-capped Au NPs, (B) bare Fe 3 O 4 NPs, (C) BSA-AuNCs, and (D) citrate-capped Pt NPs. The nanomaterials were incubated with adenosine analogues in Tris-HCl (10 mm, ph 7.0) for 0.5 h. The concentrations of NPs, adenosine analogue, AUR, and H 2 O 2 are 1 mg/ml, mm, 5 µm, and 2.5 mm, respectively. The error bars are standard deviations measured from three independent experiments. S-2

3 Figure S2. Double reciprocal plot of the activities of (A) citrate-capped Au NPs (black square) and ADP-Au NPs (red circle), (B) citrate-capped Pt NPs (black square) and ADP-modified Pt NPs (red circle), (C) BSA-AuNCs (black square) and ADP-modified BSA-AuNCs (red circle), and (D) Fe 3 O 4 NPs (black square) and AMP-modified Fe 3 O 4 NPs (red circle). S-3

4 Figure S3. Fluorescence spectra obtained from the mixing of (A) citrate-capped Au NPs and ADP, (B) citrate-capped Pt NPs and ADP, (C) BSA-AuNCs and ADP, and (D) Fe 3 O 4 NPs and AMP for 10 min, followed by the incubation of H 2 O 2 and AU in Tris-HCl (10 mm, ph 7.5). The arrow indicates the signal changes with increases in AUR concentration. S-4

5 Figure S4. Fluorescence intensity (590 nm) of the oxidized AUR obtained from the use of unmodified, GMP-modified, CMP-modified, and AMP-modified Fe 3 O 4 NPs as catalysts. Fe 3 O 4 NPs were incubated with monophosphate nucleotides in Tris-HCl buffer (10 mm, ph 7.0) for 0.5h. The concentrations of NPs, monophosphate nucleotide, AUR, and H 2 O 2 are 1 mg/ml, 0.1 mm, 5 µm, and 2.5 mm, respectively. The error bars are standard deviations measured from three independent experiments. S-5

6 Figure S5. TEM images of (A) ADP-Au NPs, (B) surfen and ADP-AuNPs, and (C) surfen-adp-au NPs and heparin. The concentrations of ADP-Au NPs, surfen, and heparin are 1 nm, 500 nm, and 100 nm, respectively. S-6

7 Figure S6. DLS spectra of (A) ADP-Au NPs, (B) surfen and ADP-AuNPs, and (C) surfen-adp-au NPs and heparin. The concentrations of ADP-Au NPs, surfen, and heparin are 1 nm, 500 nm, and 100 nm, respectively. S-7

8 Figure S7. Relative fluorescence intensity [(I F - I F0 )/I F0 ] at 590 nm obtained from the addition of (a) heparin, (b) CO 2-3, (c) NO - 3, (d) Cl -, (e) SO 2-4, (f) P 2 O 4-7, (h) bovine serum albumin, (i) human serum albumin, (j) aspartic acid, (k) aspartic acid, (l) uric acid, (m) citric acid, (n) ascorbic acid, and (o) glutathione. The surfen-adp-au NPs probe (500 nm surfen and 1 nm ADP-Au NPs) was incubated with 5 nm analytes in Tris-HCl (10 mm, ph 7.5) for 0.5 h. The error bars are standard deviations measured from three independent experiments. S-8

9 Figure S8. Fluorescence spectra obtained by the addition nm heparin to the proposed system. Inset: a plot of the value of (I F - I F0 )/I F0 versus the concentration of heparin. The surfen-adp-au NPs probe (50 µm surfen and 1 nm ADP-Au NPs) was incubated with heparin in Tris-HCl buffer (10 mm, ph 7.5) for 0.5 h. The error bars represent the standard deviation based on three independent measurements. S-9

10 Figure S9. Fluorescence spectra obtained by the addition nm to the proposed system. Inset: a plot of the value of (I F - I F0 )/I F0 versus the concentration of DS. The surfen-adp-au NPs probe (500 nm surfen and 1 nm ADP-Au NPs) was incubated with DS in Tris-HCl buffer (10 mm, ph 7.5) for 0.5 h. The error bars represent the standard deviation based on three independent measurements. S-10

11 Figure S10. Fluorescence spectra obtained by the addition nm HS to the proposed system. Inset: a plot of the value of (I F - I F0 )/I F0 versus the concentration of HS. The surfen-adp-au NPs probe (500 nm surfen and 1 nm ADP-Au NPs) was incubated with HS in Tris-HCl buffer (10 mm, ph 7.5) for 0.5 h. The error bars represent the standard deviation based on three independent measurements. S-11

12 Table S1. Comparison of the present probe with recently reported sensors for heparin. Sensor LOD Linear Range Ref. (nm) (nm) Pyrene derivative to Silole derivative to Poly(fluorine-alt-benzothiadiazole) derivative N.A to Adenosine-based molecular beacon 3 10 to A 20 and coralyne 4 10 to Functionalized silica nanoparticles 2000 N.A. 6 Polyfluorene derivative N.A. 30 to Phloxine B/polyethyleneimine to Copolymer-based sensor N.A. 30 to Graphene oxide/supercharged fluorescent protein N.A. 2.7 to Trypsin-stabilized gold nanoclusters 2 5 to Glutathione-capped gold nanoclusters /cetyltrimethylammonium bromide to Rhodamine B-modified polyethyleneimine graphene oxide complex to Bovine serum albumin-stabilized gold nanoclusters/amino-functionalized graphene to oxide hybrids Red-emitting fluorophore N.A to Diversity oriented fluorescence library approach N.A. 100 to Water-soluble AIE-based fluorescent probe 80 0 to Amphiphilic ph-responsive AIEgen to Surfen-assembled graphene oxide to Surfen CdTe quantum dots-coated amphiphilic thiophene copolymers to S-12

13 CdTe quantum dots-coated amphiphilic thiophene copolymers to Amine-functionalised pyrene derivatives N.A to Metal Organic Framework Nanosheets to Tetraphenylethene-based fluorescent probe to ADP-modified citrate-capped Au NPs to 9 and 100 to This 600 study a N.A, not available. References (1) Dai, Q.; Liu, W.; Zhuang, X.; Wu, J.; Zhang, H.; Wang, P. Ratiometric Fluorescence Sensor Based on a Pyrene Derivative and Quantification Detection of Heparin in Aqueous Solution and Serum. Anal. Chem. 2011, 83, (2) Wang, M.; Zhang, D.; Zhang, G.; Zhu, D. The Convenient Fluorescence Turn-on Detection of Heparin with a Silole Derivative Featuring an Ammonium Group. Chem. Comm. 2008, (3) Kan-Yi, P.; Bin, L. Conjugated Polyelectrolytes as Light-Up Macromolecular Probes for Heparin Sensing. Adv. Funct. Mater. 2009, 19, (4) Kuo, C.-Y.; Tseng, W.-L. Adenosine-Based Molecular Beacons as Light-up Probes for Sensing Heparin in Plasma. Chem. Comm. 2013, 49, (5) Hung, S.-Y.; Tseng, W.-L. A Polyadenosine Coralyne Complex as a Novel Fluorescent Probe for The Sensitive and Selective Detection of Heparin in Plasma. Biosens. Bioelectron. 2014, 57, (6) Estela, C.; Pilar, C.; Dolores, M. M.; Ramón, M.-M.; Félix, S.; Juan, S. Selective Chromofluorogenic Sensing of Heparin by using Functionalised Silica Nanoparticles Containing Binding Sites and a Signalling Reporter. Chem. Eur. J. 2009, 15, (7) Pu, K.-Y.; Liu, B. A Multicolor Cationic Conjugated Polymer for Naked-Eye Detection and Quantification of Heparin. Macromolecules 2008, 41, (8) Ling, Y.; Gao, Z. F.; Zhou, Q.; Li, N. B.; Luo, H. Q. Multidimensional Optical Sensing Platform for Detection of Heparin and Reversible Molecular Logic Gate Operation Based on the Phloxine B/Polyethyleneimine System. Anal. Chem. 2015, 87, S-13

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