A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
Sonication-assisted nonpolar-antisolvent approach to produce cellulose suspensions, disaggregated by a nonpolar-antisolvent with orthogonal Kamlet-Taft acidity/basicity: Roles of net-basicity and cosolvency
Tekijät: Domínguez, Sergio E.; Novikov, Alexander S.; Kornilov, Dmitry A.; Vuolle, Antti; Meriläinen, Mia; Beltrán, Hiram Isaac
Kustantaja: Elsevier BV
Julkaisuvuosi: 2025
Lehti:: Ultrasonics Sonochemistry
Artikkelin numero: 107465
Vuosikerta: 120
ISSN: 1350-4177
eISSN: 1873-2828
DOI: https://doi.org/10.1016/j.ultsonch.2025.107465
Verkko-osoite: https://doi.org/10.1016/j.ultsonch.2025.107465
Rinnakkaistallenteen osoite: https://research.utu.fi/converis/portal/detail/Publication/500425869
This work reports a simple sonication-assisted approach to produce diluted (0.5 mg/mL) suspensions of cellulose in the non-functionalizing nonpolar-antisolvent tetrahydrofuran (THF), which has a purely basic character (null Kamlet-Taft acidity parameter, α = 0), by using it as medium to sonicate microcrystalline cellulose (MCC) at 40 kHz/70 Watts. The suspensions are obtained because of the high reactivity of the amorphous regions within MCC and its capability to behave as a (Turbak) acid, together with the low viscosity and surface tension of THF, and most importantly because of the positive 0.55 net-basicity of THF, comparable to that of ionic liquids (ILs) or deep eutectic solvents (DESs) used to dissolve cellulose in polar conditions. This was demonstrated by chloroform (CHCl3), which cannot generate suspensions despite having similar values of viscosity, surface tension and molar volume than THF, however having a null basicity parameter, β = 0. (Complementary computational qualitative analyses using model molecules & conditions also show thermodynamic favorability of THF over CHCl3). FTIR suggest a decrease of around 5 % in the crystallinity of cellulose after sonication in THF, while DLS show that adding CHCl3 to the suspension in THF promotes disaggregation despite the THF-CHCl3 has a smaller net-basicity than THF, thus demonstrating cosolvency (instead of cononsolvency). (Complementary Langmuir trough experiments at the surface of water also demonstrate disaggregation because of CHCl3 instead of moisture). Despite the THF-CHCl3 pair has been used previously to analyze the supramolecular properties of different polymers, this work uses it to analyze disaggregation in two antisolvents. This approach could constitute a platform to perform studies of dissolution/regeneration under null polarity, using proper probes (e.g. ILs or DESs), substrates and matrices.
Ladattava julkaisu This is an electronic reprint of the original article. |  |
Julkaisussa olevat rahoitustiedot:
Sergio E. Domínguez acknowledges the Mexican National Council for Science and Technology (CONACyT) for the scholarship №. 310828. From the University of Turku are acknowledged Pia Damlin for donating MCC and facilitating access to the DLS instrument; and also Ermei Mäkiläa and Martti Kaasalainen for their support such instrument. From Malvern Instruments Ltd. to Michael Kaszuba because of his technical support in regard to the use and interpretation of the DLS instrument, and also for suggesting the respective experimental/analytical approach. From Universidad Autónoma Metropolitana are acknowledged Sergio Revah Moiseev and José Campos Terán for giving access to the Langmuir trough instrument.
Alexander S. Novikov is grateful to the RUDN University Scientific Projects Grant System, project № 021342-2-000.
Dmitry A. Kornilov is grateful to Eurasian Scientific and Educational Center (No. TsPD-ML-4/RF-23) and the Ministry of Science and Higher Education of the Russian Federation (No. FZWU-2023-0002)
