Effects of network junctions and defects on the crystallization of model poly(ethylene glycol) networks.

Polymer crystallization drastically changes the physical properties of polymeric materials. However, the crystallization in polymer networks has been little explored. This study investigated the crystallization behavior of a series of poly(ethylene glycol) (PEG) networks consisting of well-defined branched precursors. The PEG networks were prepared by drying gels synthesized at various conditions. The PEG networks showed slower crystallization with lower final crystallinity than uncrosslinked PEGs with amine end groups. Surprisingly, the effect of network formation was not as significant as that of the relatively bulky end-groups introduced in the uncrosslinked polymer. The molecular weight of the precursor PEG, or equivalently the chain length between neighboring junctions, was the primary parameter that affected the crystallization of the PEG networks. Shorter network chains led to lower crystallization rates and final crystallinity. This effect became less significant as the network chain length increased. On the other hand, the spatial and topological defects formed in the gel synthesis process did not affect the crystallization in the polymer networks at all. The crystallization in the polymer networks seems insensitive to these mesoscopic defects and can be solely controlled by the chain length between junctions.

Antimicrobial surface processing of polymethyl methacrylate denture base resin using a novel silica-based coating technology.

OBJECTIVES: This study investigated the surface characteristics of denture base resin coatings prepared using a novel silica-based film containing hinokitiol and assessed the effect of this coating on Candida albicans adhesion and growth. METHODS: Silica-based coating solutions (control solution; CS) and CS containing hinokitiol (CS-H) were prepared. C. albicans biofilm formed on denture base specimens coated with each solution and these uncoated specimens (control) were analyzed using colony-forming unit (CFU) assay, fluorescence microscopy, and scanning electron microscopy (SEM). Specimen surfaces were analyzed by measuring the surface roughness and wettability and with Fourier-transform infrared (FT-IR) and proton nuclear magnetic resonance (1H NMR). Stability of coated specimens was assessed via immersion in water for 1 week for each group (control-1w, CS-1w, and CS-H-1w) followed by CFU assay, measurement of surface roughness and wettability, and FT-IR. RESULTS: CS-H and CS-H-1w contained significantly lower CFUs than those present in the control and control-1w, which was also confirmed via SEM. Fluorescence microscopy from the CS-H group identified several dead cells. The values of surface roughness from coating groups were significantly less than those from the control and control-1w. The surface wettability from all coating groups exhibited high hydrophobicity. FT-IR analyses demonstrated that specimens were successfully coated, and 1H NMR analyses showed that hinokitiol was incorporated inside CS-H. CONCLUSIONS: A silica-based denture coating that incorporates hinokitiol inhibits C. albicans growth on denture. CLINICAL RELEVANCE: We provide a novel antifungal denture coating which can be helpful for the treatment of denture stomatitis.

Surface Functionalization of Non-Woven Fabrics Using a Novel Silica-Resin Coating Technology: Antiviral Treatment of Non-Woven Fabric Filters in Surgical Masks.

Masks are effective for preventing the spread of COVID-19 and other respiratory infections. If antimicrobial properties can be applied to the non-woven fabric filters in masks, they can become a more effective countermeasure against human-to-human and environmental infections. We investigated the possibilities of carrying antimicrobial agents on the fiber surfaces of non-woven fabric filters by applying silica-resin coating technology, which can form silica-resin layers on such fabrics at normal temperature and pressure. Scanning electron microscopy and electron probe microanalysis showed that a silica-resin layer was formed on the fiber surface of non-woven fabric filters. Bioassays for coronavirus and quantitative reverse transcription-polymerase chain reactions (RT-PCR) revealed that all antimicrobial agents tested loaded successfully onto non-woven fabric filters without losing their inactivation effects against the human coronavirus (inhibition efficacy: >99.999%). These results indicate that this technology could be used to load a functional substance onto a non-woven fabric filter by vitrifying its surface. Silica-resin coating technology also has the potential of becoming an important breakthrough not only in the prevention of infection but also in various fields, such as prevention of building aging, protection of various cultural properties, the realization of a plastic-free society, and prevention of environmental pollution.

Star-Polymer-DNA Gels Showing Highly Predictable and Tunable Mechanical Responses.

Dynamically crosslinked gels are appealing materials for applications that require time-dependent mechanical responses. DNA duplexes are ideal crosslinkers for building such gels because of their excellent sequence addressability and flexible tunability in bond energy. However, the mechanical responses of most DNA gels are complicated and unpredictable. Here, a DNA gel with a highly homogeneous gel network and well predictable mechanical behaviors is demonstrated by using a pair of star-polymer-DNA precursors with presimulated DNA sequences showing the two-state transition. The melting curve analysis of the DNA gels reveals the good correspondence between the thermodynamic potentials of the DNA crosslinkers and the presimulated values by DNA calculators. Stress-relaxation tests and dissociation kinetics measurements show that the macroscopic relaxation time of the DNA gels is approximately equal to the lifetime of the DNA crosslinkers over 4 orders of magnitude from 0.1-2000 s. Furthermore, a series of durability tests find the DNA gels are hysteresis-less and self-healable after the applications of repeated temperature and mechanical stimuli. These results demonstrate the great potential of star-polymer-DNA precursors for building gels with predictable and tunable viscoelastic properties, suitable for applications such as stress-response extracellular matrices, injectable solids, and soft robotics.

In Situ Neutron Reflectometry Analysis of Interfacial Structure Formation between Phenolic Resin and Silica during Curing.

The structural formation mechanism of phenolic resin-silica interfaces was investigated in situ by neutron reflectometry during curing. There was a 4 nm thick novolac resin adsorption layer on the silica surface before curing. The curing reaction of the novolac resin with hexamethylenetetramine (HMTA) increased the coherent neutron scattering length density of the resin due to the cure shrinkage accompanied by the volatilization of ammonia, which is a byproduct of HMTA decomposition. As curing proceeded at 180 °C, the thickness of the bulk layer increased despite the cure shrinkage, and the thickness of the interfacial layer decreased from 4 to 1 nm. This is attributed to the diffusion of decomposed HMTA fragments generated in the bulk layer into the interfacial novolac adsorption layer during diffusion throughout the bulk layer, incorporating the upper part of the interfacial layer reacting with the fragment into the bulk layer. On the other hand, the fragments could not diffuse into the tightly bound immobile segments of novolac resin in direct contact with the silica surface, retaining the 1-2 nm thick interfacial layer in the cured resin. This structural formation mechanism caused interfacial cross-link inhomogeneity in the cured resin on the silica surface.

Structural changes in pH-responsive gelatin/hydroxypropyl methylcellulose phthalate blends aimed at drug-release systems.

The present study aimed to investigate the thermal- and pH-dependent gelation behavior of gelatin/HPMCP blends using ultraviolet (UV) spectrophotometry, viscoelasticity, and dynamic light scattering (DLS). We found that the release of lisinopril from gelatin/HPMCP gels can be inhibited at low pH. UV spectrophotometric analysis showed that pH had a significant effect on the transparency of aqueous HPMCP systems and gelatin/HPMCP gels. The viscoelastic patterns of gelatin/HPMCP at pH 4.6 considerably differed from those of gelatin/HPMCP at pH 5.2 and 6.0. DLS measurements showed that HPMCP molecules in low concentrations underwent strong aggregation below pH 4.8. Such HPMCP aggregation induces a physical barrier in the matrix structures of the gelatin/HPMCP gels, which inhibits the drug release at pH 1.2. This hydrogel delivery system using polymer blends of gelatin/HPMCP can be used in oral gel formulations with pH-responsive properties.

Neutralization and Salt Effect on the Structure and Mechanical Properties of Polyacrylic Acid Gels under Equivolume Conditions.

The effects of neutralization and salt on the structure and mechanical properties of polyacrylic acid (PAA) gels under equivolume conditions were investigated by small-angle X-ray scattering (SAXS) measurements and tensile tests. We attained the equivolume condition by immersing a piece of PAA gel sample in an ion reservoir containing linear PAA, NaOH, and NaCl at prescribed concentrations (post-ion-tuning). The volume fraction of the linear polymer was set to be the same as that of the gel so as to satisfy the iso-osmotic pressure at the reference state. Various types of reservoirs were prepared by adding NaOH and/or NaCl with different concentrations to the reference reservoir, followed by immersing a PAA gel piece. In the SAXS measurements, a scattering peak appeared, and the scattering intensity at q = 0 decreased by neutralization, while the addition of salt increased the scattering intensity. On the other hand, Young's modulus measured with the tensile test decreased with neutralization; however, it scarcely changed with the addition of salt. The newly developed equivolume post-ion-tuning technique may serve as a new standard scheme to study polyelectrolyte gels.

Effect of Nonlinear Elasticity on the Swelling Behaviors of Highly Swollen Polyelectrolyte Gels.

Polyelectrolyte gels exhibit swelling behaviors that are dependent on the external environment. The swelling behaviors of highly charged polyelectrolyte gels can be well explained using the Flory-Rehner model combined with the Gibbs-Donnan effect and Manning's counterion condensation effect (the FRGDM model). This study investigated the swelling properties of a series of model polyelectrolyte gels, namely tetra-polyacrylic acid-polyethylene glycol gels (Tetra-PAA-PEG gels), and determined the applicability of the FRGDM model. The swelling ratio (Vs/V0) was well reproduced by the FRGDM model in the moderate swelling regime (Vs/V0 < 10). However, in the high swelling regime (Vs/V0 > 10), the FRGDM model is approx. 1.6 times larger than the experimental results. When we introduced the finite extensibility to the elastic free energy in the FRGDM model, the swelling behavior was successfully reproduced even in the high swelling regime. Our results reveal that finite extensibility is one of the factors determining the swelling equilibrium of highly charged polyelectrolyte gels. The modified FRGDM model reproduces well the swelling behavior of a wide range of polyelectrolyte gels.

Microphase separation of stimuli-responsive interpenetrating network microgels investigated by scattering methods.

Polymer stimuli-responsive microgels find their use in various applications. The knowledge of its internal structure is of importance for further improvement and expanding the scope. Interpenetrating network (IPN) microgels may possess a remarkable feature of strongly non-uniform inner architecture, even microphase separation, in conditions of a selective solvent. In this research, we, for the first time, use a combination of static light scattering (SLS) and small-angle X-ray scattering (SAXS) techniques to collect the structure factors of aqueous dispersions of poly(N-isopropylacrylamide)-polyacrylic acid IPN microgels on the broad scale ofqvalues. We study the influence of solvent quality on microgel conformations and show that in a selective solvent, such a system undergoes microphase separation: the sub-network in a poor solvent conditions forms dense small aggregates inside the large swollen sub-network in a good solvent. We propose the microstructured sphere model for the IPN microgel structure factor interpretation and perform additional analysis and verification through coarse-grained molecular dynamics computer simulations.

Nanostructure and thermoresponsiveness of poly(N-isopropyl methacrylamide)-based hydrogel microspheres prepared via aqueous free radical precipitation polymerization.

Thermoresponsive hydrogel microspheres (microgels) are smart materials that quickly respond to external stimuli, and their thermoresponsiveness can be tuned by varying the constituent chemical species. Although uniformly sized microgels can be prepared via aqueous free radical precipitation polymerization, the nanostructure of the obtained microgels is complex and remains unclear so far. In the present study, the nanostructure and thermoresponsiveness of poly(N-isopropyl methacrylamide) (pNIPMAm)-based microgels, which have a volume-transition temperature of ∼43 °C, were evaluated mainly using temperature-controllable high-speed atomic force microscopy. These observations, which are characterized by high spatio-temporal resolution, revealed that the pNIPMAm microgels have a peculiar heterogeneous structure, for example a core-shell and non-thermoresponsive nanostructure in the core region, that originates from the precipitation polymerization process. Furthermore, it was found that the adsorption concentration of the microgels on the substrate is one of the keys for controlling their thermoresponsiveness. These findings can be expected to advance the design of new materials such as thermoresponsive nanosheets and stimuli-responsive coatings.

Mechanical properties of temperature-responsive gels containing ethylene glycol in their side chains.

The mechanical properties of temperature-responsive and biocompatible poly(oligo-ethylene glycol methyl ether methacrylate)-based gels were investigated using dynamic viscoelasticity measurements so as to find applications in tissue and biomedical engineering. The gels were copolymerized using two ethylene glycol methacrylate monomers with diethylene glycol side chains: diethylene glycol methacrylate (MeO2MA), which contains two ethylene oxide units, and oligo-ethylene glycol methyl ether methacrylate (OEGMA) with either four or five ethylene oxide units. The storage (G') and loss (G'') moduli of these gels exhibit unique temperature-responsive behavior and depend on the copolymerization ratio. In MeO2MA-rich gels, phase separation occurred with increasing temperature, resulting in a significant increase in G' and the disappearance of the frequency dependence of G''. Although phase separation of OEGMA-rich gels was also observed with increasing temperature, it resulted in only a slight increase in the storage modulus due to the steric hindrance of the side chain. The mechanical properties of these gels are thus found to be strongly affected by a slight difference in the number of ethylene oxide groups in their side chains.

Examination of cross-calibration and concentration linearity with quantitative gallium-67 single-photon emission computed tomography: phantom experiment.

We evaluated whether scattered radiation should be considered for cross-calibration and concentration linearity with quantitative gallium-67 (67Ga) single-photon emission computed tomography (SPECT). The scanned data from cylinder and spherical phantoms were used. They were reconstructed using ordered subset expectation maximization with resolution recovery, scatter, and computed tomography (CT)-based attenuation correction. The standardized uptake values (SUVs) of the cylinder phantom SPECT/CT images were calculated using system planar sensitivity with and without scatter correction, and the results were compared with the theoretical value. To determine concentration linearity, the relationship between the measured SUVs in three different spherical phantoms was evaluated. SUVs calculated by system planar sensitivity without scatter correction were closer to the theoretical values. Furthermore, the 37-mm sphere showed proper radioactive linearity. Our study suggests the utility of the SUV for 67Ga SEPCT/CT. Nevertheless, additional studies are required.

Versatile whole-organ/body staining and imaging based on electrolyte-gel properties of biological tissues.

Whole-organ/body three-dimensional (3D) staining and imaging have been enduring challenges in histology. By dissecting the complex physicochemical environment of the staining system, we developed a highly optimized 3D staining imaging pipeline based on CUBIC. Based on our precise characterization of biological tissues as an electrolyte gel, we experimentally evaluated broad 3D staining conditions by using an artificial tissue-mimicking material. The combination of optimized conditions allows a bottom-up design of a superior 3D staining protocol that can uniformly label whole adult mouse brains, an adult marmoset brain hemisphere, an ~1 cm3 tissue block of a postmortem adult human cerebellum, and an entire infant marmoset body with dozens of antibodies and cell-impermeant nuclear stains. The whole-organ 3D images collected by light-sheet microscopy are used for computational analyses and whole-organ comparison analysis between species. This pipeline, named CUBIC-HistoVIsion, thus offers advanced opportunities for organ- and organism-scale histological analysis of multicellular systems.

Quantification for the Mixing of Polymers on Microspheres in Waterborne Latex Films.

Although tremendous efforts have been devoted to the structural analysis and understanding of the toughness of latex films, in which soft elastomer microspheres are interpenetrated, a method to quantitatively analyze the mixing of polymer chains at the microsphere surface, i.e., delocalization of hydrophilic charged group on the polymer chains by aging, has not yet been established. In this study, small-angle X-ray scattering was applied to characterize latex films by assuming a pseudo-two-phase system, which consists of an average-electron density microsphere core and a high-electron density interphase between the microsphere interfaces due to localized charged groups. The thus obtained parameter, i.e., the characteristic interfacial thickness (tinter), quantitatively reflects the degree of mixing of polymer chains on the microsphere surface. We found that tinter is strongly correlated to the fracture energy of the latex films. The proposed analysis method for the microscopic mixing of polymers on the microsphere surface in the film can thus be expected to shed light on design guidelines for industrial latex films and on the understanding of the mechanical properties of such films.

A Simple and Versatile Method for the Construction of Nearly Ideal Polymer Networks.

Polymer networks usually contain numerous inhomogeneities that deteriorate their physical properties and should be eliminated to create reliable, high-performance materials. A simple method is introduced for the production of nearly ideal networks from various vinyl polymers through controlled polymerization and subsequent crosslinking. Monodisperse star polymers with bromide end groups were synthesized by atom-transfer radical polymerization and end-linked with dithiol linkers using thiol-bromide chemistry. This simple procedure formed nearly ideal polymer networks, as revealed from elasticity of the formed gel and model conjugation reactions involving linear polymers. The versatility of this method was demonstrated by preparing networks of common vinyl polymers, including polyacrylates, polymethacrylate, and polystyrene. This method can be used to prepare multiple functional nearly ideal gels and elastomers and to explore fundamental aspects of polymer networks.

Concentration dependence of the dynamics of microgel suspensions investigated by dynamic light scattering.

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 ≫ 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 ≫ 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.

Non-Thermoresponsive Decanano-sized Domains in Thermoresponsive Hydrogel Microspheres Revealed by Temperature-Controlled High-Speed Atomic Force Microscopy.

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.

Hydrogel Microellipsoids that Form Robust String-Like Assemblies at the Air/Water Interface.

Soft colloidal particles such as hydrogel microspheres assemble at air/water or oil/water interfaces, where the soft colloids are highly deformed and their surface polymer chains are highly entangled with each other. Herein, we report the formation of robust one-dimensional, string-like colloidal assemblies through self-organization of hydrogel microspheres with shape anisotropy at the air/water interface of sessile droplets. Shape-anisotropic hydrogel microspheres were synthesized via two-step polymerization, whereby a hydrogel shell was formed onto preformed rigid microellipsoids. The shape anisotropy of the hydrogel microspheres was confirmed by transmission electron microscopy and high-speed atomic force microscopy as well as by light-scattering measurements. The present findings are crucial for the understanding of natural self-organization phenomena, where "softness" influences microscopic assembled structures such as those of Nostoc bacteria.

Chiral crystal-like droplets displaying unidirectional rotational sliding.

The self-assembly of organic molecules into supramolecular materials with structural ordering beyond the nanometre scale is challenging. Here, we report the spontaneous self-assembly of a chiral discotic triphenylene derivative into millimetre-sized droplets. The structure of the droplets is characterized by high positional and orientational ordering and a three-dimensional integrity similar to that of single crystals. Notwithstanding, these assemblies slide when placed on a vertical substrate demonstrating their fluid nature. X-ray imaging shows that during the sliding process the internal crystal-like structure is maintained and that the droplets undergo clockwise or counterclockwise unidirectional rotation, depending on the chirality of their molecular components. Rheological measurements suggest that this rotational behaviour might result from the distinct yield stress between the (R)- and (S)-enantiomers. Overall, our findings demonstrate that molecular chirality can determine the movement direction of a supramolecular structure, thus expanding the fundamental understanding of the structure and dynamics of soft materials.

Viscoelastic change of block copolymer ion gels in a photo-switchable azobenzene ionic liquid triggered by light.

A photo-switchable ionic liquid solvent bearing an azobenzene moiety induced a viscoelastic change of block copolymer ion gels by light. ABA triblock copolymers having poly(phenethyl methacrylate) and poly(benzyl methacrylate) as A blocks exhibited opposite photoinduced rheological responses although they had only a tiny structural difference in the alkyl chain length.