Concentrated suspensions of Brownian and non-Brownian particles display distinctive rheological behavior highly dependent on shear rate and shear stress. Cornstarch suspensions, composed of starch particles from corn plants, served as a model for concentrated non-Brownian suspensions, demonstrating discontinuous shear thickening (DST) and dynamic shear jamming (SJ). However, starch particles from other plant sources have not yet been investigated, despite their different sizes and shapes.
View Article and Find Full Text PDFSci Technol Adv Mater
October 2024
As an alternative to conventional plastic dishes, the interface between water-immiscible hydrophobic fluids, such as perfluorocarbons and silicones, permits cell adhesion and growth. Thus, it is expected to replace the petroleum-derived products in a sustainable society. However, most hydrophobic fluids are cytotoxic, which limits the range of mechanical and chemical cues exposed to the cells.
View Article and Find Full Text PDFConcentrated particle suspensions exhibit rheological behavior, such as discontinuous shear thickening (DST) and dynamic shear jamming (SJ), which affect applications such as soft armors. Although the origin of this behavior in shear-activated particle-particle interactions has been identified, the effect of chemical factors, especially the role of liquids, on this behavior remains unexplored. Hydrogen bonding in suspensions has been proposed to be essential for frictional contacts between particles, and therefore, most studies on DST and SJ have focused on aqueous and protic organic media with a definite hydrogen bonding ability.
View Article and Find Full Text PDFThis study reports the reversible solubility switching of a polymer triggered by non-phototoxic visible light. A photochromic polymerizable azobenzene monomer with four methoxy groups at the ortho-position (mAzoA) was synthesized, exhibiting reversible photoisomerization between trans- and cis-states using green (546 nm) and blue light (436 nm). Free radical copolymerization of hydrophilic dimethylacrylamide (DMAAm) with mAzoA produced a light-responsive random copolymer (P(mAzoA-r-DMAAm)) that shows a reversible photochromic reaction to visible light.
View Article and Find Full Text PDFIon gels, polymer networks swollen by ionic liquids, are expected to be applied to wearable devices that are tolerant to repeated stretching. High strength and excellent stretchability was achieved due to the numerous physical cross-links with abundant polymer chain entanglements in addition to a small number of immobile chemical cross-links, even though the ion gel was prepared by a facile methodology.
View Article and Find Full Text PDFIn sharp contrast to conventional solid/hydrogel platforms, water-immiscible liquids, such as perfluorocarbons and silicones, allow the adhesion of mammalian cells via protein nanolayers (PNLs) formed at the interface. However, fluorocarbons and silicones, which are typically used for liquid cell culture, possess only narrow ranges of physicochemical parameters and have not allowed for a wide variety of cell culturing environments. In this paper, it is proposed that water-immiscible ionic liquids (ILs) are a new family of liquid substrates with tunable physicochemical properties and high solvation capabilities.
View Article and Find Full Text PDFThe non-canonical photoisomerization-induced phase separation of an azobenzene-bearing polymer is found. The polymer composed of acrylate-based azobenzene (AzoAA) and N,N-dimethylacrylamide (DMA), namely poly(AzoAA-r-DMA), phase separates under visible light-induced cis-to-trans isomerization at high molecular weight, whereas the phase separation is realized under UV light-induced trans-to-cis isomerization at low molecular weight. Conventionally, the origin of photoisomerization-induced phase separation is believed to arise from the difference in polarity between the apolar trans and polar cis states; thereby the direction of phase changes, either to separate or dissolute, is uniquely determined by the polarity changes during the isomerization of azobenzene.
View Article and Find Full Text PDFIon gels are an emerging class of polymer gels in which a three-dimensional polymer network swells with an ionic liquid. Ion gels have drawn considerable attention in various fields such as energy and biotechnology owing to their excellent properties including nonvolatility, nonflammability, high ionic conductivity, and high thermal and electrochemical stability. Since the first report on ion gels (published ∼30 years ago), diverse functional ion gels exhibiting impressive physicochemical properties have been reported.
View Article and Find Full Text PDFA new class of ion gels, termed ultrahigh molecular weight (UHMW) gels, formed by physical entanglement of ultrahigh molecular weight polymers in ionic liquids, are synthesised using facile one step radical polymerisation with significantly low initiator conditions, and exhibit superior mechanical characteristics such as stretchability, recyclability, and room temperature self-healing ability. In this study, UHMW gels are synthesised using various combinations of monomer and IL structures, and the effect of their chemical structures on the physicochemical properties of UHMW gels are thoroughly investigated. UHMW polymers are prepared for all combinations of ILs and monomers used in this study, indicating the wide applicability of this fabrication strategy.
View Article and Find Full Text PDFA mixture of poly(benzyl methacrylate) (PBnMA) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Cmim][NTf]) exhibits lower-critical-solution-temperature (LCST)-type phase separation. An investigation combining magic-angle spinning NMR spectroscopy and small-angle scattering was performed to gain new insights into the interaction between PBnMA and the ionic liquid. The molecular mobility and the solute-solvent interaction in the system were investigated using H high-resolution magic-angle spinning NMR.
View Article and Find Full Text PDFHighly stretchable and self-healing polymer gels formed solely by physical entanglements of ultrahigh-molecular weight (UHMW) polymers were fabricated through a facile one-step process. Radical polymerization of vinyl monomers in ionic liquids under very low initiator concentration conditions produced UHMW polymers of more than 10 g/mol with nearly 100% yield, resulting in the formation of physically entangled transparent polymer gels. The UHMW gels showed excellent properties, such as high stretchability, high ionic conductivity, and recyclability.
View Article and Find Full Text PDFGlassy magnetic behavior has been observed in a wide range of crystalline magnetic materials called spin glass. Here, we report spin glass behavior in a structural glass of a magnetic ionic liquid, C4mimFeCl. Magnetization measurements demonstrate that an antiferromagnetic ordering occurs at T = 2.
View Article and Find Full Text PDFMechanics of the extracellular matrix (ECM) exhibit changes during many biological events. During disease progression, such as cancer, matrix stiffening or softening occurs due to crosslinking of the collagen matrix or matrix degradation through cell-secreted enzymes. Engineered hydrogels have emerged as a prime in vitro model to mimic such dynamic mechanics during disease progression.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2020
Various biological behaviors are fueled by "respiration", which is an example of catabolism. So far, we have reported various self-oscillating soft materials exhibiting bioinspired dynamic movements. These autonomous polymer systems are driven by the Belousov-Zhabotinsky (BZ) reaction, which is analogous to the tricarboxylic acid (TCA) cycle that is an integral part of respiration.
View Article and Find Full Text PDFWe report the solvation structure of a lower critical solution temperature (LCST)-type thermoresponsive polymer in a solvate ionic liquid (SIL, i.e., an ionic liquid comprising solvate ions) to elucidate the predominant interaction for the dissolution of the thermoresponsive polymer in SIL at low temperatures.
View Article and Find Full Text PDFMechanical cues of cellular microenvironments can modulate cell functions including cell spreading and differentiation. Most studies of cellular functions are performed using a solid substrate, and it is thought that cells cannot spread on fluid substrates because of rapid relaxation, which cannot resist against actomyosin-based cell contractility. Here, the spreading and growth of anchorage-dependent cells such as human mesenchymal stem cells at the liquid interface between a perfluorocarbon fluid and the culture medium are observed.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2018
An autonomous swelling-deswelling oscillation of polymer gels in a hydrated protic ionic liquid (PIL) as a proton source for the Belousov-Zhabotinsky (BZ) reaction is presented. Methylammonium hydrogen sulfate ([maH ][HSO ]) was employed as the PIL because it provides stable redox oscillation in the BZ reaction. Due to the significantly higher pK for [maH ][HSO ] than those for conventional proton sources for the BZ reaction, chemomechanical oscillation can be expected under weaker acidic conditions.
View Article and Find Full Text PDFHere, we report a facile methodology to control the sol-gel transition temperature () of a physically cross-linked hydrogel by blending two kinds of ABC triblock terpolymers. Well-defined triblock terpolymers including thermosensitive -isopropylacrylamide (NIPAAm), ABC1, and ABC2, were prepared by sequential reversible addition-fragmentation chain transfer polymerization. The chemical structure as well as the molecular weight of the A and B blocks for both polymers are identical, whereas the C blocks are different.
View Article and Find Full Text PDFIonic liquids (ILs), solely composed of cations and anions, are regarded as a novel class of promising liquids, potentially applicable to energy devices, reaction media, separation materials, etc. ILs have also attracted great attention as new media for molecular self-assembly, capable of producing novel soft materials with unique features never observed for conventional soft materials containing organic and aqueous solvents. In this review, we focus on recent developments in block copolymer (BCP) self-assembly in ILs.
View Article and Find Full Text PDFAlkyl-methyl-imidazolium ionic liquids CnmimX (n: alkyl-carbon number, X: anion) have short-range layer structures consisting of ionic and neutral (alkylchain) domains. To investigate the temperature dependences of the interlayer, interionic group, and inter-alkylchain correlations, we have measured the neutron diffraction (ND) of C16mimPF, C9.5mimPF, and C8mimPF in the temperature region from 4 K to 470 K.
View Article and Find Full Text PDFTwo complementary thermoreversible ABC triblock copolymers containing either phenylboronic acids with low pK values or galactosyl groups in the hydrophilic B blocks are synthesized by sequential reversible addition-fragmentation chain transfer polymerization and subsequent modification of the functional groups. Both ABC triblock copolymers undergo reversible sol-to-gel transitions upon temperature change and form physically cross-linked hydrogels under physiological conditions. Furthermore, the spontaneous adhesion of these thermoreversible hydrogels via the formation of boronic esters between the phenylboronic acid and galactosyl groups under physiological conditions is realized for the first time.
View Article and Find Full Text PDFHerein, we develop a photocurable ABA triblock copolymer-based ion gel, which can be converted from a thermally processable, physically crosslinked ion gel to a thermally and mechanically stable, chemically crosslinked ion gel photoinduced dimerization. The A block consists of a random copolymer of -isopropylacrylamide and a coumarin-containing acrylate monomer, while the B block consists of an ionic liquid-philic poly(ethylene oxide). Due to the upper critical solution temperature-type phase behavior of the A block, the ABA triblock copolymer undergoes gel-to-sol transitions in a hydrophobic ionic liquid as the temperature is increased.
View Article and Find Full Text PDFWe report a lower critical solution temperature (LCST) behavior of binary systems consisting of poly(benzyl methacrylate) (PBnMA) and solvate ionic liquids: equimolar mixtures of triglyme (G3) or tetraglyme (G4) and lithium bis(trifluoromethanesulfonyl)amide. We evaluated the critical temperatures (Ts) using transmittance measurements. The stability of the glyme-Li complex ([Li(G3 or G4)]) in the presence of PBnMA was confirmed using Raman spectroscopy, pulsed-field gradient spin-echo NMR (PGSE-NMR), and thermogravimetric analysis to demonstrate that the complex was not disrupted.
View Article and Find Full Text PDFWe developed a novel type of block copolymer, named the self-oscillating block copolymer, which exhibits autonomous assembly and disassembly driven by the dissipative structures formed by the oscillatory Belousov-Zhabotinsky (BZ) reaction. In a catalyst-free BZ solution, this polymer undergoes autonomous structural changes following the periodic redox changes of a metal catalyst incorporated into the polymer side chain. However, until now, a detailed study of the relationship between the dynamic structural changes and polymer solution conditions has not been conducted.
View Article and Find Full Text PDFIn the field of polymer science, many kinds of polymeric material systems that show a sol-gel transition have been created. However, most systems are unidirectional stimuli-responsive systems that require physical signals such as a change in temperature. Here, we report on the design of a block copolymer solution that undergoes autonomous and periodic sol-gel transition under constant conditions without any on-off switching through external stimuli.
View Article and Find Full Text PDF