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The development of efficient and low-cost catalysts is essential for photocatalysis; however, the intrinsically low photocatalytic efficiency as well as the difficulty in using and recycling photocatalysts in powder morphology greatly limit their practical performance. Herein, we describe quasi-homogeneous photocatalysis to overcome these two limitations by constructing ultrastiff, hierarchically porous, and photoactive aerogels of conjugated microporous polymers (CMPs). The CMP aerogels exhibit low density but high stiffness beyond 105 m2 s-2, outperforming most low-density materials. Extraordinary stiffness ensures their use as robust scaffolds for scaled photocatalysis and recycling without damage at the macroscopic level. A challenging but desirable reaction for direct deaminative borylation is demonstrated using CMP aerogel-based quasi-homogeneous photocatalysis with gram-scale productivity and record-high efficiency under ambient conditions. Combined terahertz and transient absorption spectroscopic studies unveil the generation of high-mobility free carriers and long-lived excitonic species in the CMP aerogels, underlying the observed superior catalytic performance.
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This study explores the opto-mechanical response of cholesteric liquid crystal elastomers (CLCEs) subjected to uniaxial stretching along the x-axis, perpendicular to their helical z-axis. A definitive crossover is observed in the strain (εx) dependencies of various optical and mechanical properties, such as the transmission spectra, degree of mesogen orientation, Poisson's ratios, and tensile stress. At low strains, CLCEs exhibit a blue shift in the selective reflection band due to a reduction in the helical pitch, accompanied by a decrease in reflection selectivity for circularly polarized light. Beyond a certain critical strain further pitch alterations halt. This strain regime is marked by substantial anisotropic lateral contractions without any z-axis contraction, as indicated by a Poisson's ratio (µxz) of zero. Within this intermediate strain regime, local directors predominantly reorient towards the x-direction within the xy-plane, resulting in a quasi-plateau of tensile stress. Approaching a higher critical strain a complete loss of reflective selectivity occurs. Past this threshold, while the mechanical responses resemble those of isotropic conventional rubber, they retain a periodic structure albeit without phase chirality. These observed features are accounted for by the Mao-Terentjev-Warner model, especially when the network anisotropy parameter is adjusted to match the critical strain magnitude associated with the cessation of selective reflection.
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Porous liquids (PLs) are attractive materials because of their capability to combine the intrinsic porosity of microporous solids and the processability of liquids. Most of the studies focus on the synthesis of PLs with not only high porosity but also low viscosity by considering their transportation in industrial plants. However, a gap exists between PLs and solid adsorbents for some practical cases, where the liquid characteristics and mechanical stability without leakage are simultaneously required. Here, we fill in this gap by demonstrating a new concept of pore-networked gels, in which the solvent phase is trapped by molecular networks with accessible porosity. To achieve this, we fabricate a linked metal-organic polyhedra (MOPs) gel, followed by exchanging the solvent phase with a bulky liquid such as ionic liquids (ILs); the dimethylformamide solvent trapped inside the as-synthesized gel is replaced by the target IL, 1-butyl-3-methylimidazolium tetrafluoroborate, which in turn cannot enter MOP pores due to their larger molecular size. The remaining volatile solvents in the MOP cavities can then be removed by thermal activation, endowing the obtained IL gel (Gel_IL) with accessible microporosity. The CO2 capacities of the gels are greatly enhanced compared to the neat IL. The exchange with the IL also exerts a positive influence on the final gel performances such as mechanical properties and low volatility. Besides ILs, various functional liquids are shown to be amenable to this strategy to fabricate pore-networked gels with accessible porosity, demonstrating their potential use in the field of gas adsorption or separation.
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We revisit the classical results that the fracture energy density (Wb) of strain crystallizing (SC) elastomers exhibits an abrupt change at a characteristic value () of initial notch length (c0) in tensile edge-crack tests. We elucidate that the abrupt change of Wb reflects the transition in rupture mode between the catastrophic crack growth without a significant SIC effect at c0 > and the crack growth like that under cyclic loading (dc/dn mode) at c0 < as a result of a pronounced SIC effect near the crack tip. At c0 < , the tearing energy (G) was considerably enhanced by hardening via SIC near the crack tip, preventing and postponing catastrophic crack growth. The fracture dominated by the dc/dn mode at c0 < was validated by the c0-dependent G characterized by G = (c0/B)1/2/2 and the specific striations on the fracture surface. As the theory expects, coefficient B quantitatively agreed with the result of a separate cyclic loading test using the same specimen. We propose the methodology to quantify the tearing energy enhanced via SIC (GSIC) and to evaluate the dependence of GSIC on ambient temperature (T) and strain rate (î¡). The disappearance of the transition feature in the Wb-c0 relationships enables us to estimate definitely the upper limits of the SIC effects for T (T*) and î¡ (î¡*). Comparisons of the GSIC, T*, and î¡* values between natural rubber (NR) and its synthetic analog reveal the superior reinforcement effect via SIC in NR.
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We investigate the yielding under shear for dilute poly(N-isopropyl acrylamide-co-fumaric acid) (PNIPAM-FAc) colloidal gels obtained above the volume phase transition temperature. In this temperature range, the microgel suspensions form colloidal gels due to hydrophobic interparticle interactions under appropriate pH and ionic strength conditions. Step-strain tests revealed that yielding occurs when the applied strain exceeds a specific threshold, requiring a finite, stress-independent delay time (tD). This is distinct from previous findings on delayed yielding in other colloidal gels, where tD decreases with increasing stress. In the start-up shear tests, yield strain (γy) at a higher strain rate (î¢) increases with escalating î¢, while γy at lower î¢ remains constant. This characteristic γy-î¢ relationship is successfully explained by a simple model using the stress-independent tD value without an adjustable fitting parameter. The distinctive yielding behavior, underscored by a stress-independent tD, is expected to originate from strain-induced macroscopic phase separation into a dense colloidal gel and water, observable separately from rheological measurements.
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Hypercrosslinked polymers (HCPs), amorphous microporous three-dimensional networks based on covalent linkage of organic building blocks, are a promising class of materials due to their high surface area and easy functionalization; however, this type of material lacks processability due to its network rigidity based on covalent crosslinking. Indeed, the development of strategies to improve its solution processability for broader applications remains challenging. Although HCPs have similar three-dimensionally crosslinked networks to polymer gels, HCPs usually do not form gels but insoluble powders. Herein, we report the synthesis of HCP gels from a thermally induced polymerization of a tetrahedral monomer, which undergoes consecutive solubilization, covalent bond formation, colloidal formation, followed by their aggregation and percolation to yield a hierarchically porous network. The resulting gels feature concentration-dependent hierarchical porosities and mechanical stiffness. Furthermore, these HCP gels can be used as a platform to achieve molecular-level hybridization with a two-dimensional polymer during the HCP gel formation. This method provides functional gels and corresponding aerogels with the enhancement of porosities and mechanical stiffness. Used in column- and membrane-based molecular separation systems, the hybrid gels exhibited a separation of water contaminants with the efficiency of 97.9 and 98.6% for methylene blue and KMnO4, respectively. This result demonstrated the potentials of the HCP gels and their hybrid derivatives in separation systems requiring macroscopic scaffolds with hierarchical porosity.
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Polímeros , Geles/química , Polimerizacion , Polímeros/química , PorosidadRESUMEN
Supramolecular hydrogels utilizing host-guest interactions (HG gels) exhibit large deformability and pronounced viscoelasticity. The inclusion complexes between ß-cyclodextrin (host) and adamantane (guest) units on the water-soluble polymers form transient bonds. The HG gels show significant stress relaxation with finite equilibrium stress following the step strain. The stress relaxation process reflects the detachment dynamics of the transient bonds which sustain the initial stress, while the finite equilibrium stress is preserved by the permanent topological cross-links with a rotaxane structure. Nonlinear stress relaxation experiments in biaxial stretching with various combinations of two orthogonal strains unambiguously reveal that time and strain effects on stress are not separable. The relaxation is accelerated for a short time frame (<102 s) with an increase in the magnitude of strain, whereas it is retarded for a longer time window with an increase in the anisotropy of the imposed biaxial strain. The time-strain inseparability in the HG gels is in contrast to the simple nonlinear viscoelasticity of a dual cross-link gel with covalent and transient cross-links in which the separability was previously validated by the same assessment. We currently interpret that the significant susceptibility of the detachment dynamics to the deformation type results from the structural characteristics of the HG gels, i.e., the host and guest moieties covalently connected to the network chains, the considerably low concentrations (<0.1 M) of these moieties, and the slidability of the permanent rotaxane cross-links.
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Out-of-equilibrium patterns arising from diffusion processes are ubiquitous in nature, although they have not been fully exploited for the design of artificial materials. Here, we describe the formation of phototriggered out-of-equilibrium patterns using photoresponsive peptide-based nanofibers in a self-sorting double network hydrogel. Light irradiation using a photomask followed by thermal incubation induced the spatially controlled condensation of peptide nanofibers. According to confocal images and spectroscopic analyses, metastable nanofibers photodecomposed in the irradiated areas, where thermodynamically stable nanofibers reconstituted and condensed with a supply of monomers from the nonirradiated areas. These supramolecular events were regulated by light and diffusion to facilitate the creation of unique out-of-equilibrium patterns, including two lines from a one-line photomask and a line pattern of a protein immobilized in the hydrogel.
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Hidrogeles/química , Nanofibras/química , Péptidos/química , Hidrogeles/síntesis química , Estructura Molecular , Tamaño de la Partícula , Procesos FotoquímicosRESUMEN
In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA) and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption, and 1H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.
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Coloides/química , Geles/química , Estructuras Metalorgánicas/química , Arilsulfonatos/química , Arilsulfonatos/efectos de la radiación , Coloides/síntesis química , Módulo de Elasticidad , Geles/síntesis química , Luz , Estructuras Metalorgánicas/síntesis química , Polimerizacion/efectos de la radiación , Porosidad , Ácido Trifluoroacético/químicaRESUMEN
The equilibrium nonlinear stress-stretch relationships for a monodomain main-chain nematic elastomer (MNE) are investigated by varying the angle between the stretching and initial director axes (θ0). Angle θ0 has pronounced effects on the ultimate elongation as well as on the width of the low stress plateau regime (Λp) during director rotation, whereas θ0 has no appreciable effect on the plateau stress (σp). In the stretching normal to the initial director (θ0 = 90°), the plateau end exceeds 200% strain. At oblique angles of 90° > θ0≥ 35°, Λp decreases with decreasing θ0, whereas the definite plateau regime vanishes at θ0 < 24°. Wide-angle X-ray scattering and polarized optical microscopy measurements reveal that the director rotates uniformly in the biased direction for the MNE of θ0°âª 90°, whereas directors rotating clockwise and counterclockwise are coexistent for θ0 = 90°. Over the entire plateau regime, the MNEs exhibit pure shear deformation characterized by a Poisson's ratio of zero in the direction of the rotation axis. The Λp for the corresponding polydomain NE (PNE) undergoing a transition to the monodomain alignment is smaller than that of the MNE of θ0 = 90°, while the σp values for both NEs are almost similar. The semi-soft elasticity concept satisfactorily explains the effects of θ0 on Λp, and the Λp value of the PNE, using a single anisotropy parameter which is evaluated from the degree of thermally induced deformation of MNEs.
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Activated hepatic stellate cells (HSCs) play a central role in fibrillary collagen production, the primary cause of liver fibrosis. Although it is known that primary cultured HSCs are activated by plastic culture dish stiffness, HSC activation and quiescent-state-reversion mechanisms are still unclear. In this study, we used cultured normal rat HSCs on 3.2 kPa collagen normal liver stiffness equivalent gel, to determine whether high glucose or high succinate conditions induce HSC activation, and examined whether activated HSCs reverted to a quiescent state when suppressed by GPR91 antagonists or TGF-ß1 receptor inhibitors. We measured the gene expression levels of α-SMA and type I collagen HSC activation markers using real-time PCR. Our data indicated that high glucose conditions induced HSC activation, and showed that under continuous high glucose exposure HSC activation progressed. A GPR91 antagonist, 2 d, and a TGF-ß1 receptor inhibitor, SB525334, suppressed the Col1α mRNA expression level of these activated HSCs. Similarly, under extended high succinate exposure, 2 d and SB525334 reduced Col1α mRNA expression levels of activated HSCs. From the above, we determined that even though HSCs had already been activated by high glucose or succinate conditions which persisted after activation, the GPR91 antagonist and the TGF-ß1 receptor inhibitor were able to reduce the production of type I collagen from activated HSCs.
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Colágeno/metabolismo , Glucosa/metabolismo , Células Estrelladas Hepáticas/efectos de los fármacos , Imidazoles/farmacología , Quinoxalinas/farmacología , Receptores Acoplados a Proteínas G/antagonistas & inhibidores , Factor de Crecimiento Transformador beta/antagonistas & inhibidores , Animales , Células Cultivadas , Células Estrelladas Hepáticas/metabolismo , Células Estrelladas Hepáticas/patología , Cirrosis Hepática/tratamiento farmacológico , Cirrosis Hepática/metabolismo , Cirrosis Hepática/patología , Masculino , Ratas Sprague-Dawley , Receptores Acoplados a Proteínas G/metabolismo , Ácido Succínico/metabolismo , Factor de Crecimiento Transformador beta/metabolismoRESUMEN
Steady-state flow and elastic behavior is investigated for the moderately concentrated binary suspensions of soft microgels (pastes) with chemically dissimilar surfaces, and various degrees of size- and stiffness disparities. The pastes of poly(N-isopropyl acrylamide) (N) and poly(N-isopropyl methacrylamide) (NM) microgels with different values of yield strain γc (γNc > γNMc) are employed as the components. For the single microgel pastes (φ ≈ 1 where φ is apparent volume fraction), the values of γc are governed by the chemical species of constituent polymer in microgel surface whereas γc is insensitive to cross-link density and particle size. We demonstrate that the binary N/NM pastes with large size disparity (RN/NM = DN/DNM < 0.26 where D is the microgel diameter) at low φN (φN: weight fraction of small N microgels) exhibit the peculiarities in several rheological aspects, i.e., the two-step yielding in steady-state flow, and their values of γc and equilibrium shear modulus (G0) being equivalent to those of the single large NM microgel paste. These peculiarities are attributed to the characteristic packing resulting from large size disparity in which all or almost of the small N microgels tend to be accommodated in the gap between the large NM microgels even in moderately concentrated state. This characteristic packing substantially masks the contribution of the small N microgels at low φN, explaining the φN-independent G0 and γc as well as the first yielding governed solely by the large NM microgels. The second yielding results from the emerged contribution of the small N microgels expelled out from the gap by the positional rearrangements after the first yielding. The binary homo-N/N pastes with the similarly large size disparity at low φsmall also exhibit the φsmall-independent values of G0, but they show one-step yielding, indicating that the two-step yielding requires not only sufficiently large size disparity but also chemical dissimilarity (different values of γc) between the two components.
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Living cells exhibit sophisticated functions because they contain numerous endogenous stimuli-responsive molecular systems that independently and cooperatively act in response to an external circumstance. On the other hand, artificial soft materials containing multiple stimuli-responsive molecular systems are still rare. Herein, we demonstrate a unique multicomponent hydrogel composed of a self-sorting double network prepared through a post-assembly fabrication (PAF) protocol. The PAF protocol allowed the construction of a well-ordered hydrogel with a dual-biomolecule response to two important biomolecules (adenosine triphosphate (ATP) and sarcosine). Such a hydrogel could not be prepared through a one-step mixing protocol. The resultant multicomponent hydrogel responded to ATP and sarcosine through gel-sol transition behavior programmed in an AND logic gate fashion. Finally, we applied the multicomponent hydrogel to the controlled release of an antibody.
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The dynamics of colloidal gel particle suspensions, i.e., microgel suspensions, has been investigated by dynamic light scattering (DLS) over a wide concentration range from the (I) dilute (φ < φcp) to the (II) intermediate (φ ≈ φcp) and (III) high concentration regions (φ â« φcp), where φ and φcp are the volume fraction of the gel particles in the suspension and the random close packing fraction, φcp ≈ 0.64, respectively. The time-intensity correlation function exhibited a distinct change with increasing φ, i.e., from ergodic behaviour (region I and II) to nonergodic behaviour (region III). A mode transition from translational (region I) to cooperative diffusion (the so-called gel mode) (region II) was also observed due to the soft and deformable nature of the microgels. Different from the dynamics of hard colloidal glass suspensions, the gel mode remained even at φ â« φcp. By using the ensemble-averaged time-correlation function, IE, we quantify the relationship between φ and their dynamics, and show that the soft microgels are deswollen in the densely packed state.
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Anisotropy of strain-induced internal damage in tough double network (DN) hydrogels is characterized by a sequence of two tensile experiments. Firstly, the virgin DN gels are subjected to a single biaxial loading-unloading cycle using various combinations of the two maximum strains λx,m and λy,m in the x- and y-directions (λx,m ≥ λy,m). Secondly, the rectangular subsamples, which are cut out from the unloaded specimens so that the long axis can have an angle (θ) relative to the larger pre-strain (x-)axis, are stretched uniaxially along the long axis. Directional internal damage caused by various types of pre-stretching is evaluated by comparing the loading curves of the virgin gels and the subsamples with various θ. The modulus reduction (ΔEθ) and strain-energy reduction (Dθ) are characterized as functions of λx,m, λy,m and θ. The anisotropy of damage increases with the anisotropy of imposed pre-strain field as well as λx,m, which is also observed in the anisotropic re-swelling behavior of the subsamples. The damage and the extensibility of the subsamples with θ = 0° increase with λy,m, and the damage of the subsamples with θ = 90° significantly increases with λx,m. These results reveal the presence of a pronounced damage cross-effect: a finite portion of the chain fractures in the first brittle network in one direction is caused by loading in the other orthogonal direction. This feature is in contrast to the very modest damage cross-effect in the silica reinforced elastomers, which show apparently similar stress-softening behavior but with a different origin. The strong damage cross-effect is a key feature of the internal fracture mechanism of the tough DN gels.
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Hidrogeles/química , Estrés Mecánico , Anisotropía , Ensayo de Materiales , Soporte de PesoRESUMEN
Despite the tremendous efforts devoted to the structural analysis of hydrogel microspheres (microgels), many details of their structures remain unclear. Reported in this study is that thermoresponsive poly(N-isopropyl acrylamide) (pNIPAm)-based microgels exhibit not only the widely accepted core-shell structures, but also inhomogeneous decanano-sized non-thermoresponsive spherical domains within their dense cores, which was revealed by temperature-controlled high-speed atomic force microscopy (TC-HS-AFM). Based on a series of experiments, it is concluded that the non-thermoresponsive domains are characteristic for pNIPAm microgels synthesized by precipitation polymerization, and plausible structures for microgels prepared by other polymerization techniques are proposed.
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Porous molecular cages have a characteristic processability arising from their solubility, which allows their incorporation into porous materials. Attaining solubility often requires covalently bound functional groups that are unnecessary for porosity and which ultimately occupy free volume in the materials, decreasing their surface areas. Here, a method is described that takes advantage of the coordination bonds in metal-organic polyhedra (MOPs) to render insoluble MOPs soluble by reversibly attaching an alkyl-functionalized ligand. We then use the newly soluble MOPs as monomers for supramolecular polymerization reactions, obtaining permanently porous, amorphous polymers with the shape of colloids and gels, which display increased gas uptake in comparison with materials made with covalently functionalized MOPs.
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The density of threaded ring molecules (fCD) in polyrotaxane (PR) chains has pronounced effects on the strain-induced swelling of PR gels where the cross-linked ring molecules are slidable along the network strands. The equilibrium Poisson's ratio (µ∞), which is a measure of the strain-induced volume change, for the PR gel increases with an increase in elongation (λ) at moderate λ but becomes a constant value () at sufficiently large λ. When the modulus exceeds a threshold value (Ec), the λ dependence of µ∞ disappears due to the loss of the slidability of the cross-links. The fraction fCD significantly influences the values of and Ec. When fCD is sufficiently small (<14%), (≈0.25) agrees with the values of µ∞ for the classical gels in good solvents. When fCD is high (>25%), varies over a wide range (0.22 < < 0.33) depending on fCD and the cross-link concentration in a complicated way. The modulus Ec at fCD = 25% is more than twice as high as that at fCD = 5% due to the finite contribution of the larger amount of uncross-linked ring molecules via combinatorial entropy in the axial polymers. The origin of the markedly small values of µ∞ (less than 0.1) at small λ is also considered on the basis of the magnitude of the accompanying force reduction caused by the slidable function of the cross-links.
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Dense suspensions of temperature (T)-sensitive poly(N-isopropyl acrylamide) (N) and poly(N-isopropyl methacrylamide) (NM) microgel mixtures with different volume transition temperatures (T and T, respectively; T < T) exhibit a characteristic T-dependent viscoelasticity due to T-induced changes in the type of interparticle interaction as well as the volume fraction of each gel. In the range of T < T, where the swollen microgels with repulsive interparticle interactions are densely packed, the equilibrium modulus (G) decreases upon heating due entirely to the packing effect, i.e., a reduction in the total volume fraction of the microgels (φ). At T > T where the attractive interparticle interactions between dehydrated and hydrophobic microgels emerge, the suspensions show solid-like elastic properties due to the network-like flocculation of the shrunken microgels (colloidal gelation), even when φ becomes considerably lower than the threshold for randomly close packing. The T-dependence of G shows a minimum at a characteristic temperature (TB; TB > T) due to the competition between the repulsive interparticle interactions from the packing effect and electrostatic force, and the attractive interactions from the hydrophobicity. The TB in N/NM mixture suspensions shifts to a higher value with a decrease in N content in the mixtures (XN), accompanied by a discontinuous-like change at a specific value of XN (XN*). The TB at every value of XN agrees approximately with the temperature where the total volume fraction of the attractive hydrophobic microgels is 0.3 regardless of microgel type (N or NM). The discontinuous-like variation in TB at XN* reflects the change in the network-like flocculation particles, from only attractive N microgels in the high XN regime, to the attractive N and NM microgel mixtures in the moderate XN regime. The requirement of the repulsive electrostatic force with an appropriate strength for the stability of the network-like flocculation is also demonstrated using the PNIPAM-co-fumaric acid (NF) microgel suspensions at various pH.
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We investigate the thermal bending behavior of liquid crystal gels with hybrid alignment (H-LCGs) accompanied by volume change in isotropic and nematic solvents. The curvature (r-1) of H-LCGs in each solvent markedly depends on the temperature (T) in the nematic state including the reversal of the bending direction, as in the case of the corresponding elastomers in the dry state (H-LCE). The thermal bending of three systems-H-LCGs in isotropic and nematic solvents and H-LCE-differs significantly in several aspects including the T range where r-1 depends on T and the total variation of r-1. The differences in these features among the three systems result from the differences in the magnitude as well as the T-dependence of the nematic order (S), which is correlated with the T-induced volume change. We demonstrate that the T-dependence of the reduced curvature in each system is satisfactorily described by a combination of linear bending theory and the anisotropic Gaussian network model using the corresponding S-T data.