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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2024, Vol. 18 Issue (12) : 155    https://doi.org/10.1007/s11705-024-2501-6
Reversible heat-set four-phase transitions of gel1-to-sol1-to-gel2-to-sol2 in binary hydrogels
Mengjiao Liang, Wenwen Cao, Yaodong Huang()
Key Laboratory of Systems Bioengineering (Ministry of Education), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
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Abstract

A class of supramolecular binary hydrogels is formed from dodecylamine or tridecylamine and sparing carboxylic acids (with amine/acid molar ratio ≥ 18). These hydrogels exhibit a remarkable thermally reversible four-phase transition. On heating, they transition from gel one (G1)-to-sol one (Sol1), then to gel two (G2)-to-sol two (Sol2). On cooling, they revert from Sol2-to-G2-to-Sol1-to-G1. Additionally, several G1 and G2 hydrogels undergo thermally reversible gel-to-gel phase transitions, which are reflected by translucent-opaque and opaque-translucent changes in their appearance. The nature of the four-phase transformation was analyzed using a range of techniques. Scanning electron microscopy images confirmed that the fibers of the opaque hydrogel at high temperatures were considerably larger than those of its translucent counterpart at low temperatures. Fluorescence emission spectra demonstrated that higher temperatures, higher amine/acid ratios, and greater acid hydrophobicity increased the hydrophobic interactions. Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopic analyses confirmed the existence of hydrogen-bonding interactions and aggregation in the hydrogels. X-ray diffraction profiles indicated that the hydrogels adopt lamellar structures. The findings advance our current understanding of the phase transition of supramolecular gels and facilitate the constitution of binary or multicomponent gels, providing a practical way to create new smart functional materials.
Keywords binaryhydrogels      dodecylamine      tridecylamine      gel1-to-sol1-to-gel2-to-sol2 phase transition      gel-to-gel phase transition     
Corresponding Author(s): Yaodong Huang   
Just Accepted Date: 17 July 2024   Issue Date: 27 September 2024
 Cite this article:   
Yaodong Huang,Wenwen Cao,Mengjiao Liang. Reversible heat-set four-phase transitions of gel1-to-sol1-to-gel2-to-sol2 in binary hydrogels[J]. Front. Chem. Sci. Eng., 2024, 18(12): 155.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2501-6
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I12/155
  Scheme1 Carboxylic acids used in this study.
Item G1 Sol1 G2 Sol2
DDAM
1A TG1 (? 33) 35–41 OG2 (43–58) ? 60
2A OG1 (? 34) 36–42 OG2 (44–58) ? 60
DPDA TG1 (? 33) 35–46 TG2 (48–54)OG2 (55–63) ? 65
3A TG1 (? 33) 35–47 TG2 (49–52)OG2 (53–63) ? 65
4A TG1 (? 33) 35–42 TG2 (44–47)OG2 (48–58) ? 60
5A TG1 (? 33) 35–44 TG2 (46–48)OG2 (49–60) ? 62
6A TG1 (? 33) 35–45 TG2 (47–52)OG2 (53–63) ? 65
7A TG1 (? 34) 35–41 TG2 (43–50)OG2 (51–60) ? 62
8A TG1 (? 34) 36–41 TG2 (43–48)OG2 (49–60) ? 61
9A TG1 (? 34) 36–41 TG2 (43–47)OG2 (48–58) ? 60
10A TG1 (? 35) 37–45 OG2 (47–63) ? 65
11A TG1 (? 32) 34–44 TG2 (46–50)OG2 (51–61) ? 62
12A TG1 (? 33) 35–45 TG2 (47–50)OG2 (51–64) ? 66
13A TG1 (? 33) 35–45 TG2 (47–51)OG2 (52–67) ? 69
14A TG1 (? 31) 33–45 TG2 (47–52)OG2 (53–63) ? 65
TDAM
1A TG1 (? 35)OG1 (37–53) ? 55 n.e. n.e.
2A OG1 (? 55) ? 57 n.e. n.e.
DPDA OG1 (? 43) 45–52 OG2 (54–64) ? 66
3A TG1 (? 43) 45–49 OG2 (51–63) ? 65
4A TG1 (? 42) 44–46 OG2 (48–61) ? 63
5A TG1 (? 39) 41–47 OG2 (49–63) ? 65
6A TG1 (? 44) 46–50 OG2 (52–63) ? 65
7A TG1 (? 41)OG1 (43–54) ? 56 n.e. n.e.
8A TG1 (? 41)OG1 (43–56) ? 58 n.e. n.e.
9A TG1 (? 41)OG1 (42–53) ? 55 n.e. n.e.
10A n.e. n.e. n.e. n.e.
11A TG1 (? 42) 43–48 OG2 (50–64) ? 65
12A TG1 (? 42) 44–49 OG2 (51–63) ? 65
13A TG1 (? 41) 43–50 OG2 (52–61) ? 63
14A TG1 (? 40) 42–54 OG2 (56–59) ? 61
Tab.1  Phase transitions and temperatures (°C) of the hydrogels formed with DDAM or TDAM and different carboxylic acidsa)
Fig.1  Thermally reversible four-phase transition of the hydrogel formed from DDAM (2.0 mmol), 3A (0.1 mmol), and H2O (1 mL).
Fig.2  DSC thermograms of the hydrogels from (a) DDAM/3A, (b) DDAM/7A, and (c) DDAM/11A. The molar ratios of DDAM to acids are all 30:1 and the amine contents are all 2 mmol·mL–1.
Fig.3  Plots of phase-transition temperatures against the molar ratios of DDAM/3A at a heating rate of 2 °C·min–1 in a water bath. The amine content was 2 mmol·mL–1.
Fig.4  Fluorescence spectra of sols with 1 × 10?6 mol·L–1 pyrene. (a) DDAM:3A = 20:1 at 25 °C and 10 °C; (b) DDAM:3A = 20:1, 25:1, 30:1, 35:1, and 40:1 at 25 °C; (c) DDAM:8A = 20:1, DDAM:10A = 20:1, at 25 °C. The amine content was 2 mmol·mL–1 in all cases.
Fig.5  SEM images of the xerogels prepared from hydrogels of (a) DDAM/3A at room temperature, (b) DDAM/3A at 50 °C, (c) DDAM/3A at 58 °C, (d) DDAM/5A at room temperature, (e) DDAM/5A at 46 °C, (f) DDAM/5A at 56 °C, (g) DDAM/11A at room temperature, (h) DDAM/11A at 48 °C, and (i) DDAM/11A at 58 °C. The molar DDAM/acid ratios were all 30:1.
Fig.6  FTIR spectra of 3A, OG2, TG1, and DDAM. The xerogels of TG1 and OG2 were prepared from hydrogels of DDAM/3A (molar ratio 30:1) at 20 and 60 °C, respectively. All the samples for FTIR were prepared as KBr pellets.
Fig.7  UV absorption of hydrogel TG1 and different sols. The DDAM content of the sols was 0.1 mmol·mL–1 and the 3A concentrations were 0.0025, 0.0033, 0.004, and 0.005 mmol·mL–1 (from top to down). The DDAM content of TG1 was 2 mmol·mL–1 and the 3A concentration was 0.1 mmol·mL–1.
Fig.8  XRD profiles of the xerogels prepared from hydrogels of (a) TG1 and OG2 of DDAM/3A (molar ratio 30:1), (b) TG1 and OG2 of DDAM/5A (molar ratio 50:1), (c) OG1 and OG2 of DDAM/2A (molar ratio 30:1), and (d) TG1s of DDAM/11A and DDAM/14A (molar ratio 30:1). All the G1 xerogels were prepared at room temperature and the OG2 xerogels were obtained at 56 °C.
  Scheme2 Schematic representation of the heat-set Gel1-to-Sol1-to-Gel2-to-Sol2 phase transition.
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