Electronic Interaction of Epoxy Resin with Copper at the Adhered Interface.

A better understanding of the aggregation states of adhesive molecules in the interfacial region with an adherend is crucial for controlling the adhesion strength and is of great inherent academic interest. The adhesion mechanism has been described through four theories: adsorption, mechanical, diffusion, and electronic. While interfacial characterization techniques have been developed to validate the aforementioned theories, that related to the electronic theory has not yet been thoroughly studied. We here directly detected the electronic interaction between a commonly used thermosetting adhesive, cured epoxy of diglycidyl ether of bisphenol A (DGEBA) and 4,4'-diaminodiphenylmethane (DDM), and copper (Cu). This study used a combination of density functional theory (DFT) calculations and femtosecond transient absorption spectroscopic (TAS) measurements as this epoxy adhesive-Cu pairing is extensively used in electronic device packaging. The DFT calculations predicted that π electrons in a DDM molecule adsorbed onto the Cu surface flowed out onto the Cu surface, resulting in a positive charge on the DDM. TAS measurements for the Cu/epoxy multilayer film, a model sample containing many metal/adhesive interfaces, revealed that the electronic states of excited DDM moieties at the Cu interface were different from those in the bulk region. These results were in good accordance with the prediction by DFT calculations. Thus, it can be concluded that TAS is applicable to characterize the electronic interaction of adhesives with metal adherends in a nondestructive manner.

Quiet standing and anteroposterior limits of stability in adolescents and young adults with bilateral spastic cerebral palsy.

Stance stability in individuals with bilateral spastic cerebral palsy (BSCP) in various standing postures including the quiet standing (QS) and limits of stability (LoS) has been widely studied. However, the relationships between the QS and LoS remain unclear. This study aimed to determine the relationships between the positions and postural sway in the QS and anteroposterior LoS in individuals with BSCP. It included 27 adolescents and young adults with BSCP (BSCP group) and 27 adolescents and young adults without disability (control group). The position of center of pressure in the anteroposterior direction (CoPy position) and the path length of center of pressure (CoP path length) during the QS and the anterior and posterior LoS (A-LoS and P-LoS, respectively) were measured using a force platform. The CoPy positions in the A-LoS and P-LoS in the BSCP group were limited compared with those in the control group. In the BSCP group, the more anterior the CoPy position in the QS, the more anterior (i.e., limited) it was in the P-LoS. Although the CoP path length in the QS was larger in the BSCP group, those in the A-LoS and P-LoS were larger in the control group. The BSCP group also showed that the more anterior the CoPy position or the longer the CoP path length in the QS, the more decreased the anteroposterior LoS range was. Therefore, assessing various standing postures, including QS and anteroposterior LoS, is important to manage balance impairments in individuals with BSCP.

Absolute local conformation of poly(methyl methacrylate) chains adsorbed on a quartz surface.

Polymer chains at a buried interface with an inorganic solid play a critical role in the performance of polymer nanocomposites and adhesives. Sum frequency generation (SFG) vibrational spectroscopy with a sub-nanometer depth resolution provides valuable information regarding the orientation angle of functional groups at interfaces. However, in the case of conventional SFG, since the signal intensity is proportional to the square of the second-order nonlinear optical susceptibility and thereby loses phase information, it cannot be unambiguously determined whether the functional groups face upward or downward. This problem can be solved by phase-sensitive SFG (ps-SFG). We here applied ps-SFG to poly(methyl methacrylate) (PMMA) chains in direct contact with a quartz surface, shedding light on the local conformation of chains adsorbed onto the solid surface. The measurements made it possible to determine the absolute orientation of the ester methyl groups of PMMA, which were oriented toward the quartz interface. Combining ps-SFG with all-atomistic molecular dynamics simulation, the distribution of the local conformation and the driving force are also discussed.

Enhanced ionic conductivity in block copolymer electrolytes through interfacial passivation using mixed ionic liquids.

We present a strategic approach for enhancing the ionic conductivity of block copolymer electrolytes. This was achieved by introducing mixed ionic liquids (ILs) with varying molar ratios, wherein the imidazolium cation was paired with either tetrafluoroborate (BF4) anion or bis(trifluoromethylsulfonyl)imide (TFSI) anion. Two polymer matrices, poly(4-styrenesulfonate)-b-polymethylbutylene (SSMB) and poly(4-styrenesulfonyl (trifluoromethanesulfonyl)imide)-b-polymethylbutylene (STMB), were synthesized for this purpose. All the SSMB and STMB containing mixed ILs showed hexagonal cylindrical structures, but the type of tethered acid group significantly influenced the interfacial properties. STMB electrolytes demonstrated enhanced segregation strength, which was attributed to strengthened Coulomb and hydrogen bonding interactions in the ionic domains, where the ILs were uniformly distributed. In contrast, the SSMB electrolytes exhibited increased concentration fluctuations because the BF4 anions were selectively sequestered at the block interfaces. This resulted in the effective confinement of imidazolium TFSI along the ionic domains, thereby preventing ion trapping in dead zones and facilitating rapid ion diffusion. Consequently, the SSMB electrolytes with mixed ILs demonstrated significantly improved ionic conductivities, surpassing the expected values based on the arithmetic average of the conductivities of each IL, whereas the ionic conductivity of the STMB was aligned with the expected average. The methodology explored in this study holds great promise for the development of solid-state polymer electrolytes.

Neutron Reflectometry Analysis of Condensed Water Layer Formation at a Solid Interface of Epoxy Resins Under High Humidity.

Water absorbed by epoxy resins from a humid atmosphere considerably influences their structure and properties. Examining the effects of absorbed water on epoxy resins at their interfaces with solid substrates is crucial because of their adhesive applications in various fields. The spatial distribution of absorbed water in epoxy resin thin films under high humidity was investigated in this study by neutron reflectometry. Water molecules were found to accumulate at the SiO2/epoxy resin interface after exposure at a relative humidity of 85% for 8 h. The formation of an ∼1-nm-thick condensed water layer was observed, and the thickness of this layer varied with curing conditions of epoxy systems. Furthermore, water accumulation at the interface was noted to be affected by high-temperature and high-humidity environments. The formation of the condensed water layer is presumed to be related to the features of the polymer layer near the interface. The construction of the interface layer of epoxy resin would be affected by the interface constraint effect on the cross-linked polymer chain during the curing reaction. This study provides essential information for understanding the factors influencing the accumulation of water at the interface in epoxy resins. In practical applications, the process of improving the construction of epoxy resins near the interface would be a reasonable solution to resist water accumulation in the interface.

Cap analogs with a hydrophobic photocleavable tag enable facile purification of fully capped mRNA with various cap structures.

Starting with the clinical application of two vaccines in 2020, mRNA therapeutics are currently being investigated for a variety of applications. Removing immunogenic uncapped mRNA from transcribed mRNA is critical in mRNA research and clinical applications. Commonly used capping methods provide maximum capping efficiency of around 80-90% for widely used Cap-0- and Cap-1-type mRNAs. However, uncapped and capped mRNA possesses almost identical physicochemical properties, posing challenges to their physical separation. In this work, we develop hydrophobic photocaged tag-modified cap analogs, which separate capped mRNA from uncapped mRNA by reversed-phase high-performance liquid chromatography. Subsequent photo-irradiation recovers footprint-free native capped mRNA. This approach provides 100% capping efficiency even in Cap-2-type mRNA with versatility applicable to 650 nt and 4,247 nt mRNA. We find that the Cap-2-type mRNA shows up to 3- to 4-fold higher translation activity in cultured cells and animals than the Cap-1-type mRNA prepared by the standard capping method.

A Biomechanical Simulation of Forearm Flexion Using the Finite Element Approach.

Upper limb movement is vital in daily life. A biomechanical simulation of the forearm with consideration of the physiological characteristics of the muscles is instrumental in gaining deeper insights into the upper limb motion mechanisms. In this study, we established a finite element model of the forearm, including the radius, biceps brachii, and tendons. We simulated the motion of the forearm resulting from the contraction of the biceps brachii by using a Hill-type transversely isotropic hyperelastic muscle model. We adjusted the contraction velocity of the biceps brachii muscle in the simulation and found that a slower muscle contraction velocity facilitated forearm flexion. Then, we changed the percentage of fast-twitch fibers, the maximum muscle strength, and the neural excitation values of the biceps brachii muscle to investigate the forearm flexion of elderly individuals. Our results indicated that reduced fast-twitch fiber percentage, maximum muscle strength, and neural excitation contributed to the decline in forearm motion capability in elderly individuals. Additionally, there is a threshold for neural excitation, below which, motion capability sharply declines. Our model aids in understanding the role of the biceps brachii in forearm flexion and identifying the causes of upper limb movement disorders, which is able to provide guidance for enhancing upper limb performance.

An increase in relative contribution of compensatory postural adjustments during voluntary movement while standing in adolescents and young adults with bilateral spastic cerebral palsy.

Previous studies have revealed several deficits in anticipatory postural adjustments (APAs) during voluntary movements while standing in individuals with bilateral spastic cerebral palsy (BSCP). However, it remains unclear whether compensatory postural adjustments (CPAs) during movement increase to compensate for APA deficits. We investigated the anticipatory and compensatory activities of postural muscles during voluntary movement while standing in adolescents and young adults with BSCP. The study included seven participants with BSCP with level II on the Gross Motor Function Classification System (GMFCS), seven with BSCP with level III on the GMFCS, and fourteen healthy controls. The participants stood on a force platform and lifted a load under two weight conditions (light and heavy). The electromyographic activities of postural muscles were analyzed at time intervals typical for APAs and CPAs. The percentage of muscle activity in the CPA time epoch against the total muscle activity during the APA and CPA time epochs was higher in the two BSCP groups than in the control group. In the control group, a load-related modulation was observed only in the APA time epoch, whereas in the BSCP-II group, the load-related increase was observed in both the APA and CPA time epochs. No load-related modulations were observed in the BSCP-III group. These findings suggest that adolescents and young adults with BSCP exhibit an increase in the relative contribution of CPAs during voluntary movement and that there exist severity-related differences in the modulation of APAs and CPAs.

Kinetics of the interfacial curing reaction for an epoxy-amine mixture.

A better understanding of the chemical reaction between epoxy and amine compounds at a solid interface is crucial for the design and fabrication of materials with appropriate adhesive strength. Here, we examined the curing reaction kinetics of epoxy phenol novolac and 4,4'-diaminodiphenyl sulfone at the outermost interface using sum-frequency generation spectroscopy, and X-ray and neutron reflectivity in conjunction with a full atomistic molecular dynamics simulation. The reaction rate constant was much larger at the quartz interface than in the bulk. While the apparent activation energy at the quartz interface obtained from an Arrhenius plot was almost identical to the bulk value, the frequency factor at the quartz interface was greater than that in the bulk. These results could be explained in terms of the densification and orientation of reactants at the interface, facilitating the encounter of the reactants present.

Enhanced Glass Transition Temperature of Thin Polystyrene Films Having an Underneath Cross-Linked Layer.

Due to the importance of the interface in the segmental dynamics of supported macromolecule ultrathin films, the glass transition temperature (Tg) of polystyrene (PS) ultrathin films upon solid substrates modified with a cross-linked PS (CLPS) layer has been investigated. The results showed that the Tg of the thin PS films on a silica surface with a ∼5 nm cross-linked layer increased with reducing film thickness. Meanwhile, the increase in Tg of the thin PS films became more pronounced with increasing the cross-linking density of the layer. For example, a 20 nm thick PS film supported on CLPS with 1.8 kDa of cross-linking degree exhibited a ∼35 and ∼50 K increase in Tg compared to its bulk and that on neat SiO2 substrate, respectively. Such a large Tg elevation for the ultrathin PS films was attributed to the interfacial aggregation states in which chains diffused through nanolevel voids formed in the cross-linked layer to the SiO2-Si surface. In such a situation, the chains were topologically constrained in the cross-linked layer with less mobility. These results offer us the opportunity to tailor interfacial effects by changing the degree of cross-linking, which has great potential application in many polymer nanocomposites.

Complete Chemical Synthesis of Minimal Messenger RNA by Efficient Chemical Capping Reaction.

Site-specific chemical modification of mRNA can improve its translational efficiency and stability. For this purpose, it is desirable to develop a complete chemical synthesis method for chemically modified mRNA. The key is a chemical reaction that introduces a cap structure into the chemically synthesized RNA. In this study, we developed a fast and quantitative chemical capping reaction between 5'-phosphorylated RNA and N7-methylated GDP imidazolide in the presence of 1-methylimidazole in the organic solvent dimethyl sulfoxide. It enabled quantitative preparation of capping RNA within 3 h. We prepared chemically modified 107-nucleotide mRNAs, including N6-methyladenosine, insertion of non-nucleotide linkers, and 2'-O-methylated nucleotides at the 5' end and evaluated their effects on translational activity in cultured HeLa cells. The results showed that mRNAs with non-nucleotide linkers in the untranslated regions were sufficiently tolerant to translation and that mRNAs with the Cap_2 structure had higher translational activity than those with the Cap_0 structure.

Laser slice thinning of GaN-on-GaN high electron mobility transistors.

As a newly developed technique to slice GaN substrates, which are currently very expensive, with less loss, we previously reported a laser slicing technique in this journal. In the previous report, from the perspective of GaN substrate processing, we could only show that the GaN substrate could be sliced by a laser and that the sliced GaN substrate could be reused. In this study, we newly investigated the applicability of this method as a device fabrication process. We demonstrated the thinning of GaN-on-GaN high-electron-mobility transistors (HEMTs) using a laser slicing technique. Even when the HEMTs were thinned by laser slicing to a thickness of 50 mm after completing the fabrication process, no significant fracture was observed in these devices, and no adverse effects of laser-induced damage were observed on electrical characteristics. This means that the laser slicing process can be applied even after device fabrication. It can also be used as a completely new semiconductor process for fabricating thin devices with thicknesses on the order of 10 mm, while significantly reducing the consumption of GaN substrates.

Effect of Oligomer Segregation on the Aggregation State and Strength at the Polystyrene/Substrate Interface.

The interfacial strength of polystyrene (PS) with and without PS oligomers in contact with a glass substrate was examined to determine the relationship between the interfacial aggregation state and adhesion. The shear bond strength and adsorbed layer thickness of neat PS exhibited a similar dependence on the thermal annealing time: they increased to constant values within almost the same time. This implies that the adhesion of the polymer is closely related to the formation of an adsorbed layer at the adhesion interface. Nevertheless, in the case of PS with a small amount of oligomer, the shear bond strength decreased, while the adsorbed layer thickness was almost the same as that of neat PS. Based on the results of interfacial analyses, we propose that the interfacial segregation of the oligomer reduced the entanglement between the interfacial free chains in the adsorbed layer and the bulk chains.

Change in local conformation of polymer chains at film surface attached to solid surface.

Adhesion is a molecular event where polymer chains contact with a material surface to form an interfacial layer. To obtain a better understanding of the adhesion on a molecular scale, we herein examined the conformational change of polystyrene (PS) chains at the film surface after contacting with hydrophobic or hydrophilic surfaces using sum-frequency generation (SFG) spectroscopy. Chains altered their local conformations with a quartz surface more quickly than a hydrophobic alkyl-functionalized one. A full-atomistic molecular dynamics simulation showed that these results, which were coupled with the contact process of PS chains with the solid surface, could be explained in terms of the Coulomb interaction between them.

The role of the molecular weight of the adsorbed layer on a substrate in the suppressed dynamics of supported thin polystyrene films.

The adsorbed layer on a solid surface plays a crucial role in the dynamics of nanoconfinement polymer materials. However, the influence of the adsorbed layer is complex, and clarifying this influence on the dynamics of confined polymers remains a major challenge. In this paper, SiO2-Si substrates with various thicknesses and adsorbed layers of PS with various molecular weights were used to reveal the effect of the adsorbed layer on the corresponding segmental dynamics of the supported thin PS films. Strongly suppressed segmental dynamics of thin PS films were observed for the films supported on thicker adsorbed layers or prepared using higher molecular weight. Neutron reflectivity revealed that the overlap region thickness between the adsorbed layer and the top overlayer increased with increasing thickness and molecular weight of the adsorbed layer, both of which correlate well with the distance over which the polystyrene dynamics were depressed by the adsorbed layer. The results show that the influencing distance of the adsorbed layer is related to the overlap zone formed between the adsorption layer and the upper thin film. The effect of the adsorbed layer molecular weight can be ascribed to the fact that large loops and long tails in the adsorbed layer result in stronger interpenetrations and entanglements between polymer chains in the adsorbed layer and in the overlayer, causing a stronger substrate effect and suppression of the segment dynamics of the supported thin PS films.

Two-Dimensional Cellular Patterning on a Polymer Film Based on Interfacial Stiffness.

The mechanical properties in the outermost region of a polymer film strongly affect various material functions. We here propose a novel and promising strategy for the two-dimensional regulation of the mechanical properties of a polymer film at the water interface based on an inkjet drawing of silica nanoparticles (SNPs) underneath it. A film of poly(2-hydroxyethyl methacrylate) (PHEMA), which exhibits excellent bioinertness properties at the water interface, was well fabricated on a substrate with a pattern of SNPs. X-ray photoelectron spectroscopy and atomic force microscopy confirmed that the surface of the PHEMA film was flat and chemically homogeneous. However, the film surface was in-plane heterogeneous in stiffness due to the presence of the underlying SNP lines. It was also noted that NIH/3T3 fibroblast cells selectively adhered and formed aggregates on the areas under which an SNP line was drawn.

Local orientation of chains at crystal/amorphous interfaces buried in isotactic polypropylene thin films.

A better understanding of the aggregation states of polymer chains in thin films is of pivotal importance for developing thin film polymer devices in addition to its inherent scientific interest. Here we report the preferential orientation of the crystalline lamellae for isotactic polypropylene (iPP) in spin-coated films by grazing incidence of wide-angle X-ray diffraction in conjunction with sum frequency generation vibrational spectroscopy, which provides information on the local conformation of chains at crystal/amorphous interfaces buried in a thin film. The crystalline orientation of iPP, which formed cross-hatched lamellae induced by lamellar branching, altered from a mixture of edge-on and face-on mother lamellae to preferential face-on mother lamellae with decreasing thickness. The orientation of methyl groups at the crystal/amorphous interfaces in the interior region of the iPP films changed, accompanied by a change in the lamellar orientation.

Smart-cut-like laser slicing of GaN substrate using its own nitrogen.

We have investigated the possibility of applying lasers to slice GaN substrates. Using a sub-nanosecond laser with a wavelength of 532 nm, we succeeded in slicing GaN substrates. In the laser slicing method used in this study, there was almost no kerf loss, and the thickness of the layer damaged by laser slicing was about 40 µm. We demonstrated that a standard high quality homoepitaxial layer can be grown on the sliced surface after removing the damaged layer by polishing.

Mobility gradients yield rubbery surfaces on top of polymer glasses.

Many emerging materials, such as ultrastable glasses1,2 of interest for phone displays and OLED television screens, owe their properties to a gradient of enhanced mobility at the surface of glass-forming liquids. The discovery of this surface mobility enhancement3-5 has reshaped our understanding of the behaviour of glass formers and of how to fashion them into improved materials. In polymeric glasses, these interfacial modifications are complicated by the existence of a second length scale-the size of the polymer chain-as well as the length scale of the interfacial mobility gradient6-9. Here we present simulations, theory and time-resolved surface nano-creep experiments to reveal that this two-scale nature of glassy polymer surfaces drives the emergence of a transient rubbery, entangled-like surface behaviour even in polymers comprised of short, subentangled chains. We find that this effect emerges from superposed gradients in segmental dynamics and chain conformational statistics. The lifetime of this rubbery behaviour, which will have broad implications in constraining surface relaxations central to applications including tribology, adhesion, and surface healing of polymeric glasses, extends as the material is cooled. The surface layers suffer a general breakdown in time-temperature superposition (TTS), a fundamental tenet of polymer physics and rheology. This finding may require a reevaluation of strategies for the prediction of long-time properties in polymeric glasses with high interfacial areas. We expect that this interfacial transient elastomer effect and TTS breakdown should normally occur in macromolecular systems ranging from nanocomposites to thin films, where interfaces dominate material properties5,10.