Improvement in Cohesive Properties of Adhesion Systems Using Movable Cross-Linked Materials with Stress Relaxation Properties.

A strong, tough, and stable adhesion system used in various environments must be developed. A long-lasting adhesion system should effectively perform in the following five aspects: adhesion strength, toughness, energy dissipation property, self-restoration property, and creep resistance property. However, these properties are difficult to balance using conventional adhesives. Here, a new topological adhesion system using single-movable cross-network (SC) materials [SC(DMAAm) Adh] was designed. 3-(Trimethoxysilyl) propyl acrylate was used as the anchor, N,N-dimethyl acrylamide (DMAAm) was used as the main chain monomer, and γ-cyclodextrin (γ-CD) units acted as movable cross-links. The movable cross-links provided SC(DMAAm) Adh with energy dissipation properties, thereby improving its toughness. The γ-CD units also acted as bulky stoppers that provided a high adhesion strength and self-restoration properties. Moreover, the combination of the movable cross-links and bulky stoppers provided creep resistance to SC(DMAAm) Adh. The performance of the adhesion systems under different mobilities of the polymer chains was examined by adjusting the water content. In proper water-containing states, all mechanical properties of SC(DMAAm) Adh were better than those of the adhesion systems using homopolymers [P(DMAAm) Adh] and polymers with covalent cross-linking points [CP(DMAAm) Adh].

Enhancement of the mechanical properties of organic-inorganic hybrid elastomers by introducing movable and reversible crosslinks.

Organic-inorganic materials have been widely utilized in various fields as multifunctional materials. Poly(dimethyl siloxane) (PDMS), a typical inorganic polymer, has industrially appealing functions, such as transparency, biocompatibility, and gas permeability; however, it has poor mechanical properties. We incorporated organic-inorganic hybrid elastomers (PDMS-γCD-AAl⊃P(EA-HEMA) (x)) with movable crosslinks, and we utilized hydrogen bonds as reversible crosslinks. The organic polymer poly ethyl acrylate-r-hydroxy ethyl methacrylate (P(EA-HEMA)) penetrated the cavity of triacetylated γ-cyclodextrin (γCD), which was introduced into the side chains of PDMS, and it compounded with PDMS at the nanoscale. Structural studies involving visual and X-ray scattering measurements revealed that movable crosslinks improved the compatibility levels of PDMS and acrylate copolymers. However, macroscopic phase separation occurred when the number of reversible crosslinks increased. Furthermore, studies on the mobility levels of acrylate copolymers and movable crosslinks indicated that the relaxation behaviour of PDMS-γCD-AAl⊃P(EA-HEMA) (x) changed with changing numbers of reversible crosslinks. Introducing reversible crosslinks improved the Young's modulus and toughness values. The movable and reversible crosslinks between the organic and inorganic polymers contributed to the high elongation properties. The design of PDMS-γCD-AAl⊃P(EA-HEMA) (x) incorporated cooperatively movable and reversible crosslinks to achieve high compatibility of immiscible polymers and to control the mechanical properties.

Highly Stretchable Stress-Strain Sensor from Elastomer Nanocomposites with Movable Cross-links and Ketjenblack.

Practical applications like very thin stress-strain sensors require high strength, stretchability, and conductivity, simultaneously. One of the approaches is improving the toughness of the stress-strain sensing materials. Polymeric materials with movable cross-links in which the polymer chain penetrates the cavity of cyclodextrin (CD) demonstrate enhanced strength and stretchability, simultaneously. We designed two approaches that utilize elastomer nanocomposites with movable cross-links and carbon filler (ketjenblack, KB). One approach is mixing SC (a single movable cross-network material), a linear polymer (poly(ethyl acrylate), PEA), and KB to obtain their composite. The electrical resistance increases proportionally with tensile strain, leading to the application of this composite as a stress-strain sensor. The responses of this material are stable for over 100 loading and unloading cycles. The other approach is a composite made with KB and a movable cross-network elastomer for knitting dissimilar polymers (KP), where movable cross-links connect the CD-modified polystyrene (PSCD) and PEA. The obtained composite acts as a highly sensitive stress-strain sensor that exhibits an exponential increase in resistance with increasing tensile strain due to the polymer dethreading from the CD rings. The designed preparations of highly repeatable or highly responsive stress-strain sensors with good mechanical properties can help broaden their application in electrical devices.

Water-Content-Dependent Switching of the Bending Behavior of Photoresponsive Hydrogels Composed of Hydrophilic Acrylamide-Based Main Chains and Hydrophobic Azobenzene.

Photoresponsiveness is a promising characteristic of stimulus-responsive materials. Photoresponsiveness can be achieved by incorporating photoresponsive molecules into polymeric materials. In addition, multiple-stimuli-responsive materials have attracted scientists' interest. Among the numerous multiple-stimuli-responsive materials, moisture- and photoresponsive materials are the focus of this report. These stimuli-responsive materials responded to the stimuli synergistically or orthogonally. Unlike most stimulus-responsive materials utilizing moisture and light as stimuli, the materials studied herein switch their photoresponsiveness in the presence of moisture. Appropriate copolymers consisting of hydrophilic acrylamide-based monomers for the main chain and hydrophobic azobenzene moieties switched their bending behaviors at 6-9 wt% water contents. At water contents lower than 6 wt%, the polymeric materials bent away from the light source, while they bent toward the light source at water contents higher than 10 wt%. At a low water content, the bending behaviors can be described on the molecular scale. At a high water content, the bending behavior requires consideration of the phase scale, not only the molecular scale. By controlling the balance between hydrophilicity and hydrophobicity, the switching behavior was achieved. This switching behavior may inspire additional strategies for the application of polymeric material as actuators.

Leaf-Inspired Host-Guest Complexation-Dictating Supramolecular Gas Sensors.

We report unique conductive leaf-inspired (in particular, stomata-inspired) supramolecular gas sensors in which acetylated cyclodextrin derivatives rule the electric output. The gas sensors consist of polymers bearing acetylated cyclodextrin, adamantane, and carbon black. Host-guest complexes between acetylated cyclodextrin and adamantane corresponding to the closed stomata realize a flexible polymeric matrix. Effective recombination of the cross-links contributes to the robustness. As gas sensors, the supramolecular materials detect ammonia as well as various other gases at 1 ppm in 10 min. The free acetylated cyclodextrin corresponding to open stomata recognized the guest gases to alter the electric resistivity. Interestingly, the conductive device failed to detect ammonia gases at all without acetylated cyclodextrin. The molecular recognition was studied by molecular dynamics simulations. The gas molecules existed stably in the cavity of free acetylated cyclodextrin. These findings show the potential for developing wearable gas sensors.

Inherent seizure susceptibility in patients with antihistamine-induced acute symptomatic seizure: a resting-state EEG analysis.

We compared neural activities and network properties between the antihistamine-induced seizures (AIS) and seizure-free groups, with the hypothesis that patients with AIS might have inherently increased neural activities and network properties that are easily synchronized. Resting-state electroencephalography (EEG) data were collected from 27 AIS patients and 30 healthy adults who had never had a seizure. Power spectral density analysis was used to compare neural activities in each localized region. Functional connectivity (FC) was measured using coherence, and graph theoretical analyses were performed to compare network properties between the groups. Machine learning algorithms were applied using measurements found to be different between the groups in the EEG analyses as input features. Compared with the seizure-free group, the AIS group showed a higher spectral power in the entire regions of the delta, theta, and beta bands, as well as in the frontal areas of the alpha band. The AIS group had a higher overall FC strength, as well as a shorter characteristic path length in the theta band and higher global efficiency, local efficiency, and clustering coefficient in the beta band than the seizure-free group. The Support Vector Machine, k-Nearest Neighbor, and Random Forest models distinguished the AIS group from the seizure-free group with a high accuracy of more than 99%. The AIS group had seizure susceptibility considering both regional neural activities and functional network properties. Our findings provide insights into the underlying pathophysiological mechanisms of AIS and may be useful for the differential diagnosis of new-onset seizures in the clinical setting.

Effects of perspective switching and utilitarian thinking on moral judgments in a sacrificial dilemma among healthcare and non-healthcare students.

During the COVID-19 pandemic, healthcare professionals have often faced moral challenges, which required them to choose between endorsing self- or other-sacrifice for the greater good. Drawing on the altruistic rationalization hypothesis and trait-activation theory, this study investigates (a) whether healthcare students' endorsement of utilitarian solutions to sacrificial moral dilemmas varies when they are confronted with the minority group, majority group, or third-person perspective on the given dilemma and (b) whether individual differences in utilitarian thinking, as measured by the Oxford Utilitarianism Scale (both instrumental harm and impartial beneficence), predict endorsement of utilitarian solutions to moral dilemmas. The study population was divided into a group of healthcare students and a group of non-healthcare students. It was found that the members of both groups expressed a stronger pro-utilitarian position when making moral dilemma judgments from a majority perspective than from the two other perspectives. However, a difference was observed with healthcare students being more reluctant to endorse the utilitarian action than their non-healthcare counterparts in the self-in-majority context. The instrumental harm component was a significant predictor of utilitarian judgments in the healthcare group, but impartial beneficence significantly predicted utilitarian judgments in the non-healthcare group in the self-in-majority context. Supplementary Information: The online version contains supplementary material available at 10.1007/s12144-023-04380-z.

A Transformable and Bulky Methacrylate Monomer That Enables the Synthesis of an MMA-nBA Alternating Copolymer: Sequence-Dependent Self-Healing Properties.

In this study, we designed a methacrylate molecule with an alkyl-substituted trichloro salicylic acid pendant as a transformable bulky monomer to enable the synthesis of an alternating copolymer of methyl methacrylate (MMA) and n-butyl acrylate (nBA). The adamantyl-substituted methacrylate monomer (1-Ad) showed very low homopolymerization propensity in radical polymerizations, but afforded the alternating copolymer with nBA via copolymerization. The 1-Ad units in the resultant copolymer were quantitatively and selectively transformed into MMA via transesterification with methanol to yield the alternating copolymer of MMA and nBA. Its alternating sequence was clearly demonstrated by a structural analysis via 13 C NMR spectroscopy as well as the low reactivity ratios for the 1-Ad and nBA pair. Finally, we verified the superior self-healing ability of the alternating copolymer compared to that of the corresponding 1 : 1 statistical copolymer.

Simultaneous control of the mechanical properties and adhesion of human umbilical vein endothelial cells to suppress platelet adhesion on a supramolecular substrate.

The demand for artificial blood vessels to treat vascular disease will continue to increase in the future. To expand the application of blood-compatible poly(2-methoxyethyl acrylate) (pMEA) to artificial blood vessels, control of the mechanical properties of pMEA is established using supramolecular cross-links based on inclusion complexation of acetylated cyclodextrin. The mechanical properties, such as Young's modulus and toughness, of these pMEA-based elastomers change with the amount of cross-links, maintaining tissue-like behavior (J-shaped stress-strain curve). Regardless of the cross-links, the pMEA-based elastomers exhibit low platelet adhesion properties (approximately 3% platelet adherence) compared with those of poly(ethylene terephthalate), which is one of the commercialized materials for artificial blood vessels. Contact angle measurements imply a shift of supramolecular cross-links in response to the surrounding environment. When immersed in water, hydrophobic supramolecular cross-links are buried within the interior of the materials, thereby exposing pMEA chains to the aqueous environment; this is why supramolecular cross-links do not affect the platelet adhesion properties. In addition, the elastomers exhibit stable adhesion to human umbilical vein endothelial cells. This report shows the potential of combining supramolecular cross-links and pMEA.

Multi-energy dissipation mechanisms in supramolecular hydrogels with fast and slow relaxation modes.

Reversible cross-links by non-covalent bonds have been widely used to produce supramolecular hydrogels that are both tough and functional. While various supramolecular hydrogels with several kinds of reversible cross-links have been designed for many years, a universal design that would allow control of mechanical and functional properties remains unavailable. The physical properties of reversible cross-links are usually quantified by thermodynamics, dynamics, and bond energies. Herein, we investigated the relationship between the molecular mobility and mechanical toughness of supramolecular hydrogels consisting of two kinetically distinct reversible cross-links via host-guest interactions. The molecular mobility was quantified as the second-order average relaxation time (〈τ〉w) of the reversible cross-links. We discovered that hydrogels combining fast (〈τ〉w = 1.8 or 18 s) and slowly (〈τ〉w = 6.6 × 103 or 9.5 × 103 s) reversible cross-links showed increased toughness compared to hydrogels with only one type of cross-link because relaxation processes in the former occurred with wide timescales.

Learning goal orientation and promotive voice: A moderated mediation model.

Drawing on the broaden-and-build theory and trait-activation theory, this study investigates the mediating effect of thriving at work on the relationship between learning goal orientation (LGO) and promotive voice behavior, as well as the moderating effect of intrinsic career growth (ICG) on the relationship between employees' LGO and thriving at work. Using the two-wave design with a 4-month time lag involving 279 employees, the results demonstrate that employees' LGO is positively associated with promotive voice behavior by thriving at work. Furthermore, ICG moderates the relationship between LGO and thriving at work. ICG also moderates the mediating effect of thriving at work on the relationship between LGO and promotive voice behavior, such that the mediating effect is only significant when employees perceive high ICG.

Practical Approaches to Apply Ultra-Thick Graphite Anode to High-Energy Lithium-Ion Battery: Carbonization and 3-Dimensionalization.

Lithium-ion batteries with ultra-thick electrodes have high energy density and low manufacturing costs because of the reduction of the inactive materials in the same battery volume. However, the partial usage of the full capacity and the low rate capability are caused by poor ionic and electronic conduction. In this work, the effects of two approaches, such as electrode binder carbonization by heat treatment and 3-dimensionalization by the laser structuring of ultra-thick graphite anodes to lithium-ion batteries for high energy density, are investigated. During the heat treatment, the polyvinylidene fluoride (PVDF) binder is carbonized to form fluorinated graphitic carbons, thereby increasing the number of lithium-ion storage sites and the improvement of the electrode capacity by 14% (420 mAh g-1 and 20 mAh cm-2). Further, the carbonization improves the rate capability by 31% at 0.1 C by simultaneously reducing the ionic and electronic resistances. Furthermore, after the laser structuring of the carbonized electrode, the areal discharge capacity increases to 50% at the increasing current rates, resulting from drastically improved ionic conduction. In addition to the electrochemical characteristics, these two approaches contribute considerably to the fast wetting of the electrolyte into the ultra-thick electrode. The carbonization and laser structuring of the ultra-thick graphite anodes are practical approaches for high-energy batteries to overcome the thickness limitation.

Synergetic improvement in the mechanical properties of polyurethanes with movable crosslinking and hydrogen bonds.

Polyurethane (PU) materials with movable crosslinking were prepared by a typical two-step synthetic process using an acetylated γ-cyclodextrin (TAcγCD) diol compound. The soft segment of PU is polytetrahydrofuran (PTHF), and the hard segment consists of hexamethylene diisocyanate (HDI) and 1,3-propylene glycol (POD). The synthesized PU materials exhibited the typical mechanical characteristics of a movable crosslinking network, and the presence of hydrogen bonds from the urethane bonds resulted in a synergistic effect. Two kinds of noncovalent bond crosslinking increased the Young's modulus of the material without affecting its toughness. Fourier transform infrared spectroscopy and X-ray scattering measurements were performed to analyze the effect of introducing movable crosslinking on the internal hydrogen bond and the microphase separation structure of PU, and the results showed that the carbonyl groups on TAcγCD could form hydrogen bonds with the PU chains and that the introduction of movable crosslinking weakened the hydrogen bonds between the hard segments of PU. When stretched, the movable crosslinking of the PU materials suppressed the orientation of polymer chains (shish-kebab orientation) in the tensile direction. The mechanical properties of the movable crosslinked PU materials show promise for future application in the industrial field.

Prediction of the Delamination at the Steel and CFRP Interface of Hybrid Composite Part.

The purpose of this study was to predict the adhesive behavior of steel and carbon-fiber-reinforced plastic (CFRP) hybrid parts based on the cohesive zone model (CZM). In this study, the steel sheet and CFRP were joined by epoxy resin in the CFRP prepreg during the curing process, which could generate delamination at their interface because of the springback of steel or the thermal contraction of the CFRP. First, double cantilever beam (DCB) and end-notched flexure (ENF) tests were performed to obtain various adhesion properties such as the critical energy release rate of mode I, mode II (GI, GII), and critical stress (σmax). A finite element (FE) simulation was performed to predict delamination using CZM, which was also used to describe the interfacial behavior between the steel sheet and the CFRP. Finally, a U-shape drawing test was performed for the steel/CFRP hybrid parts, and these results were compared with analytical results.

Extremely Rapid Self-Healable and Recyclable Supramolecular Materials through Planetary Ball Milling and Host-Guest Interactions.

The host-guest interaction as noncovalent bonds can make polymeric materials tough and flexible based on the reversibility property, which is a promising approach to extend the lifetime of polymeric materials. Supramolecular materials with cyclodextrin and adamantane are prepared by mixing host polymers and guest polymers by planetary ball milling. The toughness of the supramolecular materials prepared by ball milling is approximately 2 to 5 times higher than that of supramolecular materials prepared by casting, which is the conventional method. The materials maintain their mechanical properties during repeated ball milling treatments. They are also applicable as self-healable bulk materials and coatings, and they retain the transparency of the substrate. Moreover, fractured pieces of the materials can be re-adhered within 10 min. Dynamic mechanical analysis, thermal property measurements, small-angle X-ray scattering, and microscopy observations reveal these behaviors in detail. Scars formed on the coating disappear within a few seconds at 60 °C. At the same time, the coating shows scratch resistance due to its good mechanical properties. The ball milling method mixes the host polymer and guest polymer at the nano level to achieve the self-healing and recycling properties.

Silver Nanowire/Colorless-Polyimide Composite Electrode: Application in Flexible and Transparent Resistive Switching Memory.

Improving the performance of resistive switching memories, while providing high transparency and excellent mechanical stability, has been of great interest because of the emerging need for electronic wearable devices. However, it remains a great challenge to fabricate fully flexible and transparent resistive switching memories because not enough research on flexible and transparent electrodes, for their application in resistive switching memories, has been conducted. Therefore, it has not been possible to obtain a nonvolatile memory with commercial applications. Recently, an electrode composed of a networked structure of Ag nanowires (AgNWs) embedded in a polymer, such as colorless polyimide (cPI), has been attracting increasing attention because of its high electrical, optical, and mechanical stability. However, for an intended use as a transparent electrode and substrate for resistive switching memories, it still has the crucial disadvantage of having a limited surface coverage of conductive pathways. Here, we introduce a novel approach to obtain a AgNWs/cPI composite electrode with a high figure-of-merit, mechanical stability, surface smoothness, and abundant surface coverage of conductive networks. By employing the fabricated electrodes, a flexible and transparent resistive memory could be successfully fabricated.

The effects on postural control and low back pain according to the types of orthoses in chronic low back pain patients.

[Purpose] This study investigated how types of lumbosacral orthoses applied to patients with chronic lumbar pain affect postural control and low back pain. [Subjects and Methods] Ten subjects were randomly selected and allocated to each a group wearing soft lumbosacral orthoses and a group wearing rigid lumbosacral orthoses. They wore the lumbosacral orthoses for 4 weeks. Pain index and postural control were measured on the first day of wearing lumbosacral orthoses and 4 weeks later. Pain index was evaluated using a visual analogue scale, and postural control was measured using a Balance measurement system. The measurements examined included the overall balance index, anteroposterior balance index, and mediolateral balance index. [Results] There were statistically meaningful within-group differences in all variables, the visual analogue scale, overall balance index, anteroposterior balance index, and mediolateral balance index, in the group wearing soft lumbosacral orthoses. There were meaningful differences in visual analogue scale, overall balance index, and mediolateral balance index in the group wearing rigid lumbosacral orthoses. Furthermore, there was a meaningful difference in anteroposterior balance index between the group wearing soft lumbosacral orthoses and the group wearing rigid lumbosacral orthoses. [Conclusion] The results of the present study showed that wearing soft lumbosacral orthoses was more effective than wearing rigid lumbosacral orthoses.

The effect of exercise types for rotator cuff repair patients on activities of shoulder muscles and upper limb disability.

[Purpose] This study investigated the effect on activities, shoulder muscle fatigue, upper limb disability of two exercise types performed by patients in the post- immobilization period of rotator cuff repair. [Subjects and Methods] The intervention program was performed by 20 patients from 6 weeks after rotator cuff repair. Ten subjects each were randomly allocated to a group performing open kinetic chain exercise and a group preforming closed kinetic chain exercise. Muscle activity and median frequency were measured by using sEMG and the Upper Extremity Function Assessment before and after conducting the intervention and changes in the results were compared. [Results] There was a significant within group increases in the activities of the shoulder muscles, except for the posterior deltoid. The median power frequencies (MFD) of the supraspinatus, infraspinatus and anterior deltoid significantly increased in the open kinetic chain exercise group, but that of the posterior deltoid decreased. There were significant differences in the changes in the upper limb disability scores of the two groups, in the shoulder muscle activities, except for that of the posterior deltoid, in the comparison of the change in the muscle activities of the two groups, and in the MDFs of all shoulder muscles. [Conclusion] The Median power frequencies of all these muscles after closed kinetic chain exercise increased indicating that muscle fatigue decreased. Therefore, research into exercise programs using closed kinetic chain exercises will be needed to establish exercise methods for reducing muscle fatigue.

Flexible ambipolar organic field-effect transistors with reverse-offset-printed silver electrodes for a complementary inverter.

We report ambipolar organic field-effect transistors and complementary inverter circuits with reverse-offset-printed (ROP) Ag electrodes fabricated on a flexible substrate. A diketopyrrolopyrrole-based co-polymer (PDPP-TAT) was used as the semiconductor and poly(methyl methacrylate) was used as the gate insulator. Considerable improvement is observed in the n-channel electrical characteristics by inserting a cesium carbonate (Cs2CO3) as the electron-injection/hole-blocking layer at the interface between the semiconductors and the electrodes. The saturation mobility values are 0.35 cm(2) V(-1) s(-1) for the p-channel and 0.027 cm(2) V(-1) s(-1) for the n-channel. A complementary inverter is demonstrated based on the ROP process, and it is selectively controlled by the insertion of Cs2CO3 onto the n-channel region via thermal evaporation. Moreover, the devices show stable operation during the mechanical bending test using tensile strains ranging from 0.05% to 0.5%. The results confirm that these devices have great potential for use in flexible and inexpensive integrated circuits over a large area.

Localized-surface-plasmon-enhanced multifunction silicon nanomembrane Schottky diodes based on Au nanoparticles.

Au nanoparticle (NP)-modified Si nanomembrane (Si NM) Schottky barrier diodes (SBDs) were fabricated by using a transfer-printing method to create pedestals using only one photomask on a flexible substrate. The transfer using the pedestals afforded a yield of >95% with no significant cracks. The plasmonic Au NPs can facilitate the improvement of the incident optical absorption. The Au NP-modified Si NM SBD exhibited enhanced photoresponse characteristics with an external quantum efficiency (η(EQE)) of 34%, a photosensitivity (P) of 27 at a voltage bias of -5 V, a light intensity of 1.2 W cm(-2), and a responsivity (R(ph)) of 0.21 A W(-1). Additionally, the mechanical bending characteristics of the device were observed while a compressive strain up to 0.62% was applied to the diode. The results suggest that the Au NP-modified Si NM SBD has great potential for use in multifunction devices as a strain sensor and photosensor.