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Space Size-Dependent Transformation of Tetraphenylethylene Carboxylate Aggregates by Ice Confinement

  • Akihisa Miyagawa
    Akihisa Miyagawa
    Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
  • Makoto Harada
    Makoto Harada
    Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
  • Gaku Fukuhara
    Gaku Fukuhara
    Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
    JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
  • , and 
  • Tetsuo Okada*
    Tetsuo Okada
    Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
    *Phone/Fax: +81-3-5734-2612. E-mail: [email protected]
    More by Tetsuo Okada
Cite this: J. Phys. Chem. B 2020, 124, 11, 2209–2217
Publication Date (Web):February 25, 2020
https://doi.org/10.1021/acs.jpcb.9b11345
Copyright © 2020 American Chemical Society
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Abstract

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Tetraphenylethylene carboxylate (TPEC) aggregates are transformed by ice confinement, which is controlled by the initial concentration of sucrose employed as a cryoprotectant and temperature. The freezing of aqueous sucrose leads to the formation of micro- or nanoliquid phase confined in ice. Aggregation-induced emission (AIE) of tetraphenylethylene carboxylate (TPEC) in the ice-confined space is explored using fluorescence spectroscopy and lifetime measurements. The characteristics of AIE in the ice-confined space strongly depend on the initial sucrose concentration and temperature, which determine the size of the liquid phase. The AIE of TPEC in the ice-confined space can be classified into three regimes in terms of spectroscopic features. Loosely packed J aggregates of TPEC are formed in the microliquid phase (>2 μm). The fluorescence intensity increases, and the wavelength is hypsochromically shifted with a decrease in the size of the space, indicating that the molecular arrangement in the aggregate depends on the space size. The fluorescence lifetimes indicate polydisperse, loosely packed aggregation. No further change in aggregate structure is observed once the liquid phase size is decreased to ∼2 μm, and a spectroscopically identical structure is maintained upon further reduction of the space size to ∼0.5 μm. The molecular arrangement in the aggregate is independent of the space size in this regime. However, when the size of the space becomes smaller than ∼0.5 μm, the aggregate structure again starts to change into a more tightly packed aggregate and a hypsochromic shift of the fluorescence wavelength occurs again. The fluorescence lifetime indicates monodispersed aggregation in this submicrospace.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcb.9b11345.

  • NMR spectra for TPA-COOH and TPAC; absorption spectrum of TPEC in sucrose and tris buffer; freezing point depression curve for the sucrose/water system, and estimation of the freezing point depression curve in the subeutectic temperature range; relationship between l and VFCS; temperature change of fluorescence spectra of TPEC in sucrose solution; fluorescence spectrum of TPEC in tris buffer; fluorescence spectrum of TPEC crystal; excitation spectra of TPEC in the FCS at various T; repeated measurements of fluorescence spectra between −6 and −21 °C; fluorescence spectra of TPEC in the FCS for csucini= 50, 100, and 150 mM (PDF)

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Cited By


This article is cited by 3 publications.

  1. Tomoya Muto, Makoto Harada, Gaku Fukuhara, Tetsuo Okada. Ice Confinement-Induced Solubilization and Aggregation of Cyanonaphthol Revealed by Fluorescence Spectroscopy and Lifetime Measurements. The Journal of Physical Chemistry B 2020, 124 (18) , 3734-3742. https://doi.org/10.1021/acs.jpcb.0c01451
  2. Qingrui Fan, Linhai Li, Han Xue, Heng Zhou, Lishan Zhao, Jie Liu, Junqiang Mao, Shuwang Wu, Shizhong Zhang, Chenyang Wu, Xueming Li, Xin Zhou, Jianjun Wang. Precise Control Over Kinetics of Molecular Assembly: Production of Particles with Tunable Sizes and Crystalline Forms. Angewandte Chemie 2020, 132 (35) , 15253-15258. https://doi.org/10.1002/ange.202003922
  3. Qingrui Fan, Linhai Li, Han Xue, Heng Zhou, Lishan Zhao, Jie Liu, Junqiang Mao, Shuwang Wu, Shizhong Zhang, Chenyang Wu, Xueming Li, Xin Zhou, Jianjun Wang. Precise Control Over Kinetics of Molecular Assembly: Production of Particles with Tunable Sizes and Crystalline Forms. Angewandte Chemie International Edition 2020, 59 (35) , 15141-15146. https://doi.org/10.1002/anie.202003922

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