Coordination-enabled one-step assembly of. ultrathin, hybrid microcapsules with. weak ph-response

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1 Supporting Information Coordination-enabled one-step assembly of ultrathin, hybrid microcapsules with weak ph-response Chen Yang,, Hong Wu,, Xiao Yang,, Jiafu Shi*,,, Xiaoli Wang,, Shaohua Zhang, and Zhongyi Jiang*,, Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin , China; School of Environmental Science and Engineering, Tianjin University, Tianjin , China; Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin , China. *Corresponding author: Prof. Zhongyi Jiang Prof. Jiafu Shi S1

2 Table S1 The effect of charge and radius of the metal ions on the stability of the coordination compound Notes: Atomic number Element Coordination Ionic radius (nm) 2 Ch arg e radius 12 Mg (II) Al (III) Ca (II) Sc (III) Ti (IV) V (III) Cr (III) Mn (II) (hs) Fe (III) (hs) Fe (II) (hs) Co (II) (hs) Co (III) (hs) Ni (II) Cu (II) Zn (II) Ga (III) As (III) Sr (II) Y (III) Zr (IV) In (III) a. The data of ionic radius came from website ( that was hosted by the Atomistic Simulation Group in the Materials Department of Imperial College. b. hs represents high spin. c. Metal ions with stable high oxidation state (i.e., Ti IV, Fe III, Cr III ) could coordinate with catechol primarily through tris- coordination state. The divalent metal ions (i.e., Cu II, Ni II, Cr II ) could coordinate with catechol only through mono- and bis- coordination state. 1-2 S2

3 Table S2 Ti and TA concentrations in the feeds and in the products Molar ratio of Molar ratio of Molar ratio of Final c TA /(mm) Final c Ti /(mm) TA to Ti (in the feed) C (inta) to Ti (in the product) TA to Ti (in the product) Note i : i ii 1:10 iii 12.29:1 1: i : :1 1: ii 1: ii 1:1 5.51:1 1: :10 iii :10 iii 3.13:1 1:24.28 Cannot obain microcapsules Can obtain microcapsules as shown in Figure S3a-b Can obtain microcapsules as shown in Figure S3c-d Cannot obain microcapsules Can obtain microcapsules as shown in Figure S3e-f Cannot obain microcapsules Can form precipitates as shown in Figure S3g-h Can form numerous :10 iii 3.49:1 1:21.78 precipitates as shown in Figure S3i-j i. Superscript i denoted as group "i" that has the same concentration of TA in the feed. ii. Superscript ii denoted as group "ii" that has the same concentration of Ti-BALDH in the feed. iii. Superscript iii denoted as group "iii" that has the same molar ratio of TA and Ti-BALDH in the feed. S3

4 Figure S1 The EDS result of the TA-Ti IV microcapsules. S4

5 100 Weight remain % Temperature ( o C) Figure S2 The TGA curve of the TA-Ti IV microcapsules. S5

6 a) c) e) g) i) b) d) f) h) j) Figure S3 The SEM imgages of the TA-Ti IV product (microcapsule/precipitate) by changing the concentrations of TA and Ti. (a, b) c TA =0.240 mm, c Ti =2.400 mm. (c, d) c TA =2.400 mm, c Ti =2.400 mm. (e, f) c TA =0.240 mm c Ti = mm. (g, h) c TA = mm c Ti = mm. (I, j) c TA = mm c Ti = mm. S6

7 PSS- CaC 3 Ti IV TA EDTA - - H + H + ph < 3 3 ph 11 ph > 11 vs. - H + 3 < ph < 6 7 < ph < 9 Figure S4 The fabrication process of the TA-Ti IV microcapsules and the probable structure of TA-Ti IV and TA-Fe III coordination states at different ph values. Ti,, C, H, Fe atoms are represented by blue, red, gray, white, purple spheres, respectively. The remainder of TA molecule is represented by yellow sticks. S7

8 H Ti Ti H Figure S5 Probable chemical structure of TA-Ti IV cooridination compounds under alkaline condition. S8

9 Ti Figure S6 Probable chemical structure of TA-Ti IV cooridination compounds under neutral condition. S9

10 H H H H Ti Ti Figure S7 Probable chemical structure of TA-Ti IV cooridination compounds under acid condition. S10

11 H H H-bond H H H -H +,-e or -H. -H + H e H 1 1 Figure S8 eaction scheme of the auto-oxidation of catechol to quinone. 3 S11

12 H 1 2 -NH 2 Michael Addition Shif f Bases H H N- 2 1 NH- 2 Figure S9. Probable reaction scheme of the Michael addition and Schiff base reaction S12

13 eference 1. Sever, M. J.; Wilker, J. J., Visible absorption spectra of metal-catecholate and metal-tironate complexes. Dalton Trans. 2004, Sever, M. J.; Wilker, J. J., Absorption spectroscopy and binding constants for first-row transition metal complexes of a DPA-containing peptide. Dalton Trans. 2006, Quideau, S.; Deffieux, D.; Douat-Casassus, C.; Pouysegu, L., Plant polyphenols: chemical properties, biological activities, and synthesis. Angew Chem Int Ed Engl 2011, 50, Kutyrev, A. A.; Moskva, V., Nucleophilic reactions of quinones. ussian Chemical eviews 1991, 60, (1), Klein,. F.; Bargas, L. M.; Horak, V.; Navarro, M., Spontaneous rearrangement in Corey's reaction. Tetrahedron letters 1988, 29, Bittner, S., When quinones meet amino acids: chemical, physical and biological consequences. Amino acids 2006, 30, S13