Supporting Information

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1 Supporting Information Of Tetraphenylethene crosslinked thermo-sensitive microgels via acylhydrazone bond: Aggregation-induced emission in nano-confined environment and the cononsolvency effect Jinqiao Xue, a,1 Wei Bai, a,1 Hanyi Duan, a Jingjing Nie, b Binyang Du,* a Jing Zhi Sun,* a Ben Zhong Tang* c a MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science & Engineering, Zhejiang University, Hangzhou 327, China b Department of Chemistry, Zhejiang University, Hangzhou 327, China c Department of Chemistry, Division of Life Science, Division of Biomedical Engineering, Institute for Advanced Study, and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China *Corresponding authors. duby@zju.edu.cn, sunjz@zju.edu.cn, tangbenz@ust.hk. 1 Those authors contributed equally. S1

2 h i,j b a f g c,d e b a * h a b c d e g * i,j f Chemical shift (ppm) Figure S1. 1 H NMR spectrum of AH monomer in DMSO-d 6. The solvent peaks were labelled with asterisks. (Solvent existing: DMSO and H 2 O) 1 H NMR ( MHz, DMSO-d 6 ): 1.87 ppm ( s, 3H, -C(-CH 3 )=CH 2 ), 3.64 ppm ( m, 2H, -OCH 2 CH(OH)-CH 2 - ), 3.93 ppm ( m, 1H, -OCH 2 CH(OH)-CH 2 - ), 4.9 ppm ( d, 2H, -OCH 2 CH(OH)-CH 2 - ), 5.54 ppm ( d, 2H, -NH-NH 2 ), 5.68 ppm ( t, 1H, -OOCC(CH3)=CHH ) 6.6 ppm ( s,1h, -OOCC(CH 3 )=CHH ), 7.71 ppm and 8.69 ppm ( q, 4H, -C 5 H 4 N + (Cl - )- ). S2

3 314. Relative Abundance m/z Figure S2. ESI-MS spectrum of AH monomer. ESI-MS (m/z): [M+Cl] - :349.9, [M-H] - :314., [M-H 2 O-H] - :296., [M-NHNH 2 ] - : * a b c * * * Chemical shift (ppm) Figure S3. 1 H NMR spectrum of TPE-4ALD in DMSO-d 6. The solvent peaks were labelled with asterisks. (Solvent existing: DMSO, H 2 O, and THF) 1 H NMR ( MHz, DMSO-d 6 ): 7.27 ppm (d, J = 8.2 Hz, 8H, -C 6 H 4 -CHO), 7.74 ppm (d, J = 8.3 Hz, 8H, -C 6 H 4 -CHO), 9.91 ppm (s, 4H, -C 6 H 4 -CHO). S3

4 tan17117_3 37 (31) Cn (Cen,4, 9., Ar); Sb (15,1. ); Sm (SG, 2x3.); Cm (33:) TOF LD % m/z Figure S4. HRMS spectrum of TPE-4ALD. [M] + : Calcd , Found Table S1. Viscosities of the water/organic mixtures with various χ water s measured by Ubbelohde viscometer a χ water Solvent Water/DMF Water/methanol Water/ethanol Water/THF Water/DMSO a measured at 25 o C. The unit of viscosity is cp. S4

5 A Absorbance (a.u.) a b c AH monomer TPE-4ALD N-AH-TPE nanogels B Absorbance (a.u.) nm Abs=.49*CTPE-4ALD-.11 R 2 = CTPE-4ALD ( µm ) Figure S5. (A) UV-visible spectra of (a) AH monomer dissolved in DMF (b) TPE-4ALD dissolved in DMF and (c) N-AH-TPE nanogels re-dispersed in DMF. (B) The standard calibration UV-visible curve of TPE-4ALD in DMF. Figure S6. CLSM image of N-AH-TPE nanogels. λ ex = 5 nm, [TPE-4AH] =.243 µm S5

6 a (a.u.) b 1. (a.u.) in solvent mixture adding ions.3 rt 5 rt 5 rt 5 rt Temperature ( o C) Figure S7. (a) Relative FL intensities at maximum emission wavelengths of TPE-4ALD as a function of temperature in three temperature jumps. (b) FL spectra of TPE-4ALD in a mixture of methanol, ethanol, DMF, DMSO, THF, and water (black curve). The volume fraction of each organic solvent was 5% and the volume fraction of water was 75 %. FL spectra of TPE-4ALD in THF/H 2 O (1/9 by volume) mixture with the presence of KBr, KBF4, KPF6, KTFS, and KTFSI salts (red curve). The final concentration of each salt was set as 1 mm water/dmf Wavelength of Peak (nm) Figure S8. Plots of emission intensities at maximum fluorescent emission wavelengths and the maximum fluorescent emission wavelengths of N-AH-TPE nanogels in water/dmf mixed solvents with various water fractions χ water. λ ex = 3 nm. [TPE-4AH] = 2.43 µm. The measured temperature was 25 o C. S6

7 A DMF/water B Figure S9. (A) Fluorescent emission spectra and (B) Plots of emission intensities at maximum fluorescent emission wavelengths of N-AH-TPE nanogels in DMF/water mixed solvents with various water molar fractions χ water. λ ex = 3 nm. [TPE-4AH] = 2.43 µm. The measured temperature was 25 o C A water/ethanol B water/methanol C water/thf D water/dmso Figure S1. Fluorescent emission spectra of N-AH-TPE nanogels in (A) water/ethanol, (B) water/methanol, (C) water/thf, and (D) water/dmso mixed solvents with various water molar fractions χ water, respectively. λ ex = 3 nm. [TPE-4AH] = 2.43 µm. The measured temperature was 25 o C. S7

8 A C water/ethanol water/thf 53 B Wavelength of Peak (nm) Wavelength of Peak (nm) D water/methanol water/dmso Wavelength of Peak (nm) Wavelength of Peak (nm) Figure S11. Plots of emission intensities at maximum emission wavelengths and maximum emission wavelengths of N-AH-TPE nanogels in (A) water/ethanol, (B) water/methanol, (C) water/thf, and (D) water/dmso mixed solvents with various water molar fractions χ water, respectively. λ ex = 3 nm. [TPE-4AH] = 2.43 µm. The measured temperature was 25 o C. S8

9 A B C water/thf water/ethanol water/dmso Relative Hydrodynamic Diameter Figure S12. Plots of relative FL intensities at maximum emission wavelengths (black solid curves) and relative hydrodynamic diameters (blue sold curves) of N-AH-TPE nanogels in (A) water/ethanol, (B) water/thf, and (C) water/dmso mixed solvents with various water molar fractions χ water, respectively. The emission intensities and hydrodynamic diameters of N-AH-TPE nanogels in pure water were taken as the reference states. λ ex = 3 nm. [TPE-4AH] = 2.43 µm. The measured temperature was 25 o C. S9

10 A heating B cooling 25 o C 27 o C 29 o C 3 o C 31 o C 32 o C 33 o C 34 o C 35 o C 36 o C 37 o C 38 o C 39 o C o C 41 o C 42 o C 43 o C 44 o C 45 o C 46 o C 47 o C 48 o C 5 o C 25 o C 27 o C 29 o C 3 o C 31 o C 32 o C 33 o C 34 o C 35 o C 36 o C 37 o C 38 o C 39 o C o C 41 o C 42 o C 43 o C 44 o C 45 o C 46 o C 47 o C 48 o C 5 o C Figure S13. FL emission spectra of N-AH-TPE nanogel aqueous suspensions in the (A) heating and (B) cooling processes, respectively. λ ex = 3 nm. [TPE-4AH] = 2.43 µm. S1

11 cycle1-heating cycle1-cooling cycle2-heating cycle2-cooling Temperature ( o C) Figure S14. Relative FL intensities at maximum emission wavelengths of N-AH-TPE microgel as a function of temperature in two successive heating-cooling cycles. S11

12 A [Br - ] mm.1 mm.2 mm.3 mm.4 mm.5 mm.6 mm.7 mm.8 mm.9 mm.1 mm B [BF4- ] mm.1 mm.2 mm.3 mm.4 mm.5 mm.6 mm.7 mm.8 mm.9 mm.1 mm [TFS C - ] mm.1 mm.2 mm.3 mm.4 mm.5 mm.6 mm.7 mm.8 mm.9 mm.1 mm D [PF6- ] mm.1 mm.2 mm.3 mm.4 mm.5 mm.6 mm.7 mm.8 mm.9 mm.1 mm [TFSI E - ] mm.1 mm.2 mm.3 mm.4 mm.5 mm.6 mm.7 mm.8 mm.9 mm.1 mm Figure S15. FL emission spectra of N-AH-TPE nanogel aqueous suspensions with various concentrations of (A) KBr, (B) KBF4, (C) KTFS, (D) KPF6, and (E) KTFSI. λ ex = 3 nm. [TPE-4AH] = 7.29 µm. S12