An immunocytokine consisting of a TNFR2 agonist and TNFR2 scFv enhances the expansion of regulatory T cells through TNFR2 clustering.

Regulatory T cells (Tregs) are lymphocytes that play a central role in peripheral immune tolerance. Tregs are promising targets for the prevention and suppression of autoimmune diseases, allergies, and graft-versus-host disease, and treatments aimed at regulating their functions are being developed. In this study, we created a new modality consisting of a protein molecule that suppressed excessive immune responses by effectively and preferentially expanding Tregs. Recent studies reported that tumor necrosis factor receptor type 2 (TNFR2) expressed on Tregs is involved in the proliferation and activation of Tregs. Therefore, we created a functional immunocytokine, named TNFR2-ICK-Ig, consisting of a fusion protein of an anti-TNFR2 single-chain Fv (scFv) and a TNFR2 agonist TNF-α mutant protein, as a new modality that strongly enhances TNFR2 signaling. The formation of agonist-receptor multimerization (TNFR2 cluster) is effective for the induction of a strong TNFR2 signal, similar to the TNFR2 signaling mechanism exhibited by membrane-bound TNF. TNFR2-ICK-Ig improved the TNFR2 signaling activity and promoted TNFR2 cluster formation compared to a TNFR2 agonist TNF-α mutant protein that did not have an immunocytokine structure. Furthermore, the Treg expansion efficiency was enhanced. TNFR2-ICK-Ig promotes its effects via scFv, which crosslinks receptors whereas the agonists transmit stimulatory signals. Therefore, this novel molecule expands Tregs via strong TNFR2 signaling by the formation of TNFR2 clustering.

Molecular Understanding of the Distinction between Adhesive Failure and Cohesive Failure in Adhesive Bonds with Epoxy Resin Adhesives.

In the development of adhesives, an understanding of the fracture behavior of the bonded joints is inevitable. Two typical failure modes are known: adhesive failure and cohesive failure. However, a molecular understanding of the cohesive failure process is not as advanced as that of the adhesive failure process. In this study, research was developed to establish a molecular understanding of cohesive failure using the example of a system in which epoxy resin is bonded to a hydroxyl-terminated self-assembled monolayer (SAM) surface. Adhesive failure was modeled as a process in which an epoxy molecule is pulled away from the SAM surface. Cohesive failure, on the other hand, was modeled as the process of an epoxy molecule separating from another epoxy molecule on the SAM surface or breaking of a covalent bond within the epoxy resin. The results of the simulations based on the models described above showed that the results of the calculations using the model of cohesive failure based on the breakdown of intermolecular interactions agreed well with the experimental results in the literature. Therefore, it was suggested that the cohesive failure of epoxy resin adhesives is most likely due to the breakdown of intermolecular interactions between adhesive molecules. We further analyzed the interactions at the adhesive failure and cohesive failure interfaces and found that the interactions at the cohesive failure interface are mainly accounted for by dispersion forces, whereas the interactions at the adhesive failure interface involve not only dispersion forces but also various chemical interactions, including hydrogen bonds. The selectivity between adhesive failure and cohesive failure was explained by the fact that varying the functional group density affected the chemical interactions but not the dispersion forces.

Effects of Curing Agents on the Adhesion of Epoxy Resin to Copper: A Density Functional Theory Study.

Epoxy resins are widely used adhesives in industrial fields. To use epoxy resin as an adhesive, it is necessary to mix the epoxy resin with a hardener. Hardeners have various functional groups and skeletons, and the properties of epoxy resins vary depending on the hardener. Although the adhesion of epoxy resins has been extensively studied using density functional theory (DFT) calculations, few studies have evaluated the effect of hardener molecules. Therefore, in this study, DFT calculations of adhesion energies and bonding structures on Cu (111) and Cu2O (111) surfaces are performed for model molecules of adducts of epoxy resin with hardeners having various functional groups and skeletons to evaluate the influence of the hardeners on the adhesion of epoxy resin to the metal surface. The adhesion energy to the Cu (111) surface is governed by the energy due to dispersion forces. Hardeners of the thiol type, which contain relatively heavy sulfur atoms, and hardeners with aromatic rings, displaying high planarity, enable the entire molecule to approach the metal surface, resulting in a relatively high adhesion strength. The calculations for the Cu2O (111) surface show the adhesion strength is more strongly influenced by interactions such as hydrogen bonds between the surface and adhesive molecules than by dispersion forces. Therefore, in adhesion to Cu2O (111), the benzylamine-epoxy adduct with hydrogen bonding and OH-π interactions with the surface, in addition to having a relatively flexible framework, shows a high adhesion strength.

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.

Effect of Condensed Water at an Alumina/Epoxy Resin Interface on Curing Reaction.

The adhesion of epoxy adhesives to aluminum materials is an important issue in assembling parts for lightweight mobility. Aluminum surfaces typically possess an oxide layer, which readily adsorbs water. In this study, the aggregation states of water and its effect on the curing reaction were examined by placing a water layer between an amorphous alumina surface and a mixture of epoxy and amine components. This study used molecular dynamics simulations and density functional theory calculations. Before the reaction, water molecules strongly adsorbed onto the alumina surface, aggregating excess water. Some water diffused into the epoxy/amine mixture, accelerating the diffusion of unreacted substances. This led to faster reaction kinetics, particularly in proximity to the alumina surface. The adsorption of water molecules onto the alumina surface and the aggregation of excess water were similarly observed even after the curing process. Subsequently, the interaction between the alumina surface and various functional groups of the epoxy/amine mixture was evaluated before and after the reaction. Epoxy monomers had little interaction with the alumina surface before the reaction, whereas hydroxy groups formed by the ring-opening reaction of epoxy groups exhibited notable interaction. Conversely, sulfonyl and amino groups in amine compounds formed hydrogen bonds with OH groups on the alumina surface before the reaction. However, after the reaction, amino groups weakened their interaction with the alumina OH groups as they transformed from primary to tertiary during the curing reaction. Both epoxy and amine monomers/fragments similarly interacted with water molecules, both before and after the reaction. The insights gained from this study are expected to contribute to a better understanding of the impact of moisture absorption on the application of epoxy resins.

Coordination-Induced Trigger for Activity: N-Heterocyclic Carbene-Decorated Ceria Catalysts Incorporating Cr and Rh with Activity Induction by Surface Adsorption Site Control.

A coordination-induced trigger for catalytic activity is proposed on an N-heterocyclic carbene (NHC)-decorated ceria catalyst incorporating Cr and Rh (ICy-r-Cr0.19Rh0.06CeOz). ICy-r-Cr0.19Rh0.06CeOz was prepared by grafting 1,3-dicyclohexylimidazol-2-ylidene (ICy) onto H2-reduced Cr0.19Rh0.06CeOz (r-Cr0.19Rh0.06CeOz) surfaces, which went on to exhibit substantial catalytic activity for the 1,4-arylation of cyclohexenone with phenylboronic acid, whereas r-Cr0.19Rh0.06CeOz without ICy was inactive. FT-IR, Rh K-edge XAFS, XPS, and photoluminescence spectroscopy showed that the ICy carbene-coordinated Rh nanoclusters were the key active species. The coordination-induced trigger for catalytic activity on the ICy-bearing Rh nanoclusters could not be attributed to electronic donation from ICy to the Rh nanoclusters. DFT calculations suggested that ICy controlled the adsorption sites of the phenyl group on the Rh nanocluster to promote the C-C bond formation of the phenyl group and cyclohexenone.

Tripodal Triazatruxene Derivative as a Face-On Oriented Hole-Collecting Monolayer for Efficient and Stable Inverted Perovskite Solar Cells.

Hole-collecting monolayers have drawn attention in perovskite solar cell research due to their ease of processing, high performance, and good durability. Since molecules in the hole-collecting monolayer are typically composed of functionalized π-conjugated structures, hole extraction is expected to be more efficient when the π-cores are oriented face-on with respect to the adjacent surfaces. However, strategies for reliably controlling the molecular orientation in monolayers remain elusive. In this work, multiple phosphonic acid anchoring groups were used to control the molecular orientation of a series of triazatruxene derivatives chemisorbed on a transparent conducting oxide electrode surface. Using infrared reflection absorption spectroscopy and metastable atom electron spectroscopy, we found that multipodal derivatives align face-on to the electrode surface, while the monopodal counterpart adopts a more tilted configuration. The face-on orientation was found to facilitate hole extraction, leading to inverted perovskite solar cells with enhanced stability and high-power conversion efficiencies up to 23.0%.

Extraordinary Acceleration of an Electrophilic Reaction Driven by the Polar Surface of 2D Aluminosilicate Nanosheets.

To increase chemical reaction rates, general solutions include increasing the concentration/temperature and introducing catalysts. In this study, the rate constant of an electrophilic metal coordination reaction is accelerated 23-fold on the surface of layered aluminosilicate (LAS), where the reaction substrate (ligand molecule) induces dielectric polarization owing to the polar and anionic surface. According to the Arrhenius plot, the frequency factor (A) is increased by almost three orders of magnitude on the surface. This leads to the conclusion that the collision efficiency between the ligands and metal ions is enhanced on the surface due to the dielectric polarization. This is surprising because one side of the ligand is obscured by the surface, so the collision efficiency is expected to be decreased. This unique method to accelerate the chemical reaction is expected to expand the range of utilization of LASs, which are chemically inert, abundant, and environmentally friendly. The concept is also applicable to other metal oxides which have polar surfaces, which will be useful for various chemical reactions in the future.

Elucidating the Effects of Chemisorbed Water Molecules on the Adhesive Interactions of Epoxy Resin to γ-Alumina Surfaces.

The adhesion mechanism of epoxy resin to the γ-alumina (110) surface was investigated using first-principles density functional theory (DFT). Aluminum materials are lightweight and are used in a wide range of industrial fields. Its surface is oxidized to alumina, and the stable surface is known as the γ-alumina (110) surface. The coverage of hydroxy groups by chemisorbed water molecules on this surface varied depending on the pretreatment temperature. In this study, we investigated the adhesive interactions of epoxy resin on four alumina surfaces with different densities of surface hydroxy groups (0, 3, 6, and 9 OH/nm2) and have discussed their effects. At each interface, the energy curves of the vertically displaced epoxy resin were calculated and the adhesive forces were estimated by differentiating these curves. As the coverage of the surface hydroxy groups increased from 0 to 6 OH/nm2, the adhesive strength gradually decreased. However, the adhesive strength at 9 OH/nm2 was relatively large and almost equal to that at 3 OH/nm2. This inverse volcano-type behavior was analyzed via the decomposition of adhesive forces and the crystal orbital Hamilton population (COHP). The decomposition of adhesive forces into DFT and dispersion components revealed that the inverse volcano-type behavior is derived from the DFT component, and the interfacial interactions owing to the DFT component are accompanied by charge transfer. These were investigated using a COHP analysis, which revealed that this behavior was caused by changes in the activity of the aluminum atoms on the surface and surface reconstruction by chemisorbed water molecules. It is noteworthy that the adhesive strength for 9 OH/nm2 was only 6.9% lower than that for 0 OH/nm2 wherein the chemisorbed water molecules were completely removed from the surface. These results are expected to provide a guideline for the adhesion of epoxy resin to aluminum materials.

Hückel Molecular Orbital Analysis for Stability and Instability of Stacked Aromatic and Stacked Antiaromatic Systems.

Face-to-face stacking of aromatic compounds leads to stacked antiaromaticity, while that of antiaromatic compounds leads to stacked aromaticity. This is a prediction with a long history; in the late 2000s, the prediction was confirmed by high-precision quantum chemical calculations, and finally, in 2016, a π-conjugated system with stacked aromaticity was synthesized. Several variations have since been reported, but essentially, they are all the same molecule. To realize stacked aromaticity in a completely new and different molecular system and to trigger an extension of the concept of stacked aromaticity, it is important to understand the origin of stacked aromaticity. The Hückel method, which has been successful in giving qualitatively correct results for π-conjugated systems despite its bold assumptions, is well suited for the analysis of stacked aromaticity. We use this method to model the face-to-face stacking systems of benzene and cyclobutadiene molecules and discuss their stacked antiaromaticity and stacked aromaticity on the basis of their π-electron energies. By further developing the discussion, we search for clues to realize stacked aromaticity in synthesizable molecular systems.

Characterization of a TNFR2-Selective Agonistic TNF-α Mutant and Its Derivatives as an Optimal Regulatory T Cell Expander.

Regulatory T cells (Tregs) are a subpopulation of lymphocytes that play a role in suppressing and regulating immune responses. Recently, it was suggested that controlling the functions and activities of Tregs might be applicable to the treatment of human diseases such as autoimmune diseases, organ transplant rejection, and graft-versus-host disease. TNF receptor type 2 (TNFR2) is a target molecule that modulates Treg functions. In this study, we investigated the role of TNFR2 signaling in the differentiation and activation of mouse Tregs. We previously reported the generation of a TNFR2-selective agonist TNF mutant, termed R2agoTNF, by using our unique cytokine modification method based on phage display. R2agoTNF activates cell signaling via mouse TNFR2. In this study, we evaluated the efficacy of R2agoTNF for the proliferation and activation of Tregs in mice. R2agoTNF expanded and activated mouse CD4+CD25+ Tregs ex vivo. The structural optimization of R2agoTNF by internal cross-linking or IgG-Fc fusion selectively and effectively enhanced Treg expansion in vivo. Furthermore, the IgG-Fc fusion protein suppressed skin-contact hypersensitivity reactions in mice. TNFR2 agonists are expected to be new Treg expanders.

Frontier Orbital Views of Stacked Aromaticity.

Recent studies have theoretically and experimentally demonstrated that antiaromatic molecules with 4n π electrons exhibit stacked aromaticity according to π-π stacking when arranged in a face-to-face manner. However, the mechanism of its occurrence has not been clearly studied. In this study, we investigated the mechanism of stacked aromaticity using cyclobutadiene. When the antiaromatic molecules are stacked in a face-to-face manner, the orbital interactions between the degenerate singly occupied molecular orbitals (SOMOs) of the monomer unit cause a larger energy gap between the degenerate highest-occupied molecular orbitals (HOMOs) and the lowest-unoccupied molecular orbitals (LUMOs) of the dimer. However, the antiaromatic molecules are more stable in less symmetric conformations, mainly because of pseudo-Jahn-Teller distortions. In the case of cyclobutadiene, the two SOMOs of the monomer unit split into HOMO and LUMO because of the bond alternation. When the molecules are stacked in a face-to-face manner, the HOMO-LUMO gap of the dimer is smaller than that of the monomer due to the interactions between the HOMOs and LUMOs of the two monomer units. When the monomer units are within a specific distance of each other, the HOMO and LUMO of the dimer, which correspond to antibonding and bonding between the units, respectively, are interchanged. This alternation of molecular orbitals may result in an increase in the bond strength between the monomer units, exhibiting stacked aromaticity. We demonstrated that it is possible to control the distance exhibited by stacked aromaticity by engineering the HOMO-LUMO gap of the monomer units.

Oxidative Addition of Methane and Reductive Elimination of Ethane and Hydrogen on Surfaces: From Pure Metals to Single Atom Alloys.

Oxidative addition of CH4 to the catalyst surface produces CH3 and H. If the CH3 species generated on the surface couple with each other, reductive elimination of C2H6 may be achieved. Similarly, H's could couple to form H2. This is the outline of nonoxidative coupling of methane (NOCM). It is difficult to achieve this reaction on a typical Pt catalyst surface. This is because methane is overoxidized and coking occurs. In this study, the authors approach this problem from a molecular aspect, relying on organometallic or complex chemistry concepts. Diagrams obtained by extending the concepts of the Walsh diagram to surface reactions are used extensively. C-H bond activation, i.e., oxidative addition, and C-C and H-H bond formation, i.e., reductive elimination, on metal catalyst surfaces are thoroughly discussed from the point of view of orbital theory. The density functional theory method for structural optimization and accurate energy calculations and the extended Hückel method for detailed analysis of crystal orbital changes and interactions play complementary roles. Limitations of monometallic catalysts are noted. Therefore, a rational design of single atom alloy (SAA) catalysts is attempted. As a result, the effectiveness of the Pt1/Au(111) SAA catalyst for NOCM is theoretically proposed. On such an SAA surface, one would expect to find a single Pt monatomic site in a sea of inert Au atoms. This is desirable for both inhibiting overoxidation and promoting reductive elimination.

Theoretical Study on the Contribution of Interfacial Functional Groups to the Adhesive Interaction between Epoxy Resins and Aluminum Surfaces.

To ensure the quality and reliability of products bonded by epoxy resin adhesives, elucidation of the microscopic adhesion mechanism is essential. The adhesive interaction and bonding strength between epoxy resins and hydroxylated γ-alumina (001) surfaces were investigated by using a combined molecular dynamics (MD) and density functional theory (DFT) study. The curing reaction of an epoxy resin consisting of diglycidyl ether of bisphenol A (DGEBA) and 4,4'-diaminodiphenyl sulfone (DDS) was simulated. The resin structure was divided into fragmentary structures to study the interaction of each functional group with the alumina surface using DFT calculations. From the characteristics of the adhesive structures and the calculated adhesion energies, it was found that the fragments forming hydrogen bonds with hydroxy groups on the alumina surface resulted in large adhesion energies. On the other hand, the fragments adsorbed on the alumina surface via dispersion interactions resulted in small adhesion energies. The adhesion forces evaluated from the Hellmann-Feynman force calculations indicated the significant contribution of the hydroxy groups and benzene ether moieties derived from DGEBA to the adhesive stress of the DGEBA/DDS epoxy resin. The direction of hydrogen bonding between the epoxy resin and the surface and the difference in geometry at the interface between the donor and acceptor of hydrogen bonding played a central role in maintaining the adhesive strength during the failure process of the adhesive interface.

Shear adhesive strength between epoxy resin and copper surfaces: a density functional theory study.

Adhesive strength varies greatly with direction; various adhesion tests have been conducted. In this study, the shear and tensile adhesive strength of epoxy resin for copper (Cu) and copper oxide (Cu2O) surfaces were estimated based on quantum chemical calculations. Here, density functional theory (DFT) calculations with dispersion correction were used. In the tensile process, the entire epoxy resin is peeled off vertically, whereas in the shear process, a force parallel to the adhesive surface is applied. Then, a bending moment acts on the adhesive layer, and a total force (stress) inclined at an angle θ with respect to the adherend surface is applied to the adhesive interface. We computed adhesive stress-displacement curves for each θ exhaustively and discussed the changes. When θ equals 90°, it corresponds to a tensile process. As θ decreases from 90°, the shear adhesive stress on both surfaces decreases slowly. When θ is less than 30°, the constraint to the surface causes periodic changes in the adhesive stress curves. The constraint to the Cu2O surface is especially strong, and this change is large. This periodicity is similar to the stick-slip phenomenon in tribology. To further understand the shear adhesive forces, force decomposition analysis was performed, revealing that the periodicity of the adhesive stress originates from the DFT contribution rather than the dispersion one. The procedure proposed in this study for estimating shear adhesive strength is expected to be useful in the evaluation and prediction of adhesive and adherend properties.

Graph-theoretical exploration of the relation between conductivity and connectivity in heteroatom-containing single-molecule junctions.

In this study, we employ the Sachs graph theory to formulate the conduction properties of a single-molecular junction consisting of a molecule in which one carbon atom of an alternant hydrocarbon is replaced with a heteroatom. The derived formula includes odd and even powers of the adjacency matrix, unlike the graph of the parental structure. These powers correspond to odd- and even-length walks. Furthermore, because the heteroatom is represented as a self-loop of unit length in the graph, an odd number of passes of the self-loop will change the parity of the length of the walk. To confirm the aforementioned effects of heteroatoms on conduction in an actual sample, the conduction behavior of meta-connected molecular junctions consisting of a heterocyclic six-membered ring, whose conductive properties have already been experimentally determined, was analyzed based on the enumerated number of walks.

Structural optimization of a TNFR1-selective antagonistic TNFα mutant to create new-modality TNF-regulating biologics.

Excessive activation of the proinflammatory cytokine tumor necrosis factor-α (TNFα) is a major cause of autoimmune diseases, including rheumatoid arthritis. TNFα induces immune responses via TNF receptor 1 (TNFR1) and TNFR2. Signaling via TNFR1 induces proinflammatory responses, whereas TNFR2 signaling is suggested to suppress the pathophysiology of inflammatory diseases. Therefore, selective inhibition of TNFR1 signaling and preservation of TNFR2 signaling activities may be beneficial for managing autoimmune diseases. To this end, we developed a TNFR1-selective, antagonistic TNFα mutant (R1antTNF). Here, we developed an R1antTNF derivative, scR1antTNF-Fc, which represents a single-chain form of trimeric R1antTNF with a human IgG-Fc domain. scR1antTNF-Fc had properties similar to those of R1antTNF, including TNFR1-selective binding avidity, TNFR1 antagonistic activity, and thermal stability, and had a significantly extended plasma t1/2in vivo In a murine rheumatoid arthritis model, scR1antTNF-Fc and 40-kDa PEG-scR1antTNF (a previously reported PEGylated form) delayed the onset of collagen-induced arthritis, suppressed arthritis progression in mice, and required a reduced frequency of administration. Interestingly, with these biologic treatments, we observed an increased ratio of regulatory T cells to conventional T cells in lymph nodes compared with etanercept, a commonly used TNF inhibitor. Therefore, scR1antTNF-Fc and 40-kDa PEG-scR1antTNF indirectly induced immunosuppression. These results suggest that selective TNFR1 inhibition benefits the management of autoimmune diseases and that R1antTNF derivatives hold promise as new-modality TNF-regulating biologics.

Competition between Hydrogen Bonding and Dispersion Force in Water Adsorption and Epoxy Adhesion to Boron Nitride: From the Flat to the Curved.

Hexagonal boron nitride (h-BN) is a material with excellent thermal conductivity and electrical insulation, used as an additive to various matrices. To increase the affinity of h-BN to them, hydrogen bonds should be formed at the interface. In reality, however, they are not formed; the N atoms are not capable of accepting hydrogen bonds due to the delocalization of their lone pair electrons over the B-N π bonds. To make it form hydrogen bonds, one may need to break the planarity of h-BN so that the orbital overlap in the B-N π bonds can be reduced. This idea is verified with first-principles calculations on the adsorption of a water molecule on hypothetical h-BN surfaces, the planarity of which is broken. One can do it in silico but not in vitro. BN nanotubes (BNNTs) are considered as a more realistic BN surface with nonplanarity. The hydrogen bond is shown to become stronger as the curvature of the tube increases. On the contrary, the strength of the dispersion force acting at the interface becomes weaker. In water adsorption, these two interactions are in competition with each other. However, in epoxy adhesion, the interaction due to dispersion forces is overwhelmingly stronger than that due to hydrogen bonding. The smaller the curvature of the surface, the smaller the distance between more atoms at the interface; thus, the interaction due to dispersion forces maximized.

Molecular Dynamics Study on the Thermal Aspects of the Effect of Water Molecules at the Adhesive Interface on an Adhesive Structure.

The presence of adsorbed water on hydrophilic solid surfaces should be taken into account, especially in humid environments. It significantly reduces the adhesive strength between the epoxy resin and the adherend surface. Here, the adhesion structure of interfacial water sandwiched between bisphenol A epoxy resin and a hydroxylated silica (001) surface is investigated with microsecond molecular dynamics simulations. Specifically, interfacial water layers with initial thicknesses of 7.5, 10, and 20 Å are modeled. The density curves of water and the diglycidyl ether of bisphenol A show that at room temperature, the surface of the silica with hydroxyl groups is completely covered with a thick layer of water. For water layers thinner than 10 Å, the density of epoxy resin on the silica surface increases when the system is heated and does not return to the original density when the system is cooled. Furthermore, calculation of the interaction energy revealed that the exclusion of water from the hydroxylated surface by epoxy resin during heating can contribute to the increase in the adhesive interaction between the epoxy resin and the silica surface with hydroxyl groups.

Theoretical Study on the Adhesion Interaction between Epoxy Resin Including Curing Agent and Plated Gold Surface.

In this study, the adhesive interaction between gold and epoxy resin is theoretically investigated. These materials make up crucial components of a wide range of electronic devices. The objectives of the study are (1) to elucidate the bonding mechanism between epoxy resin and a realistic gold surface, and (2) to obtain a device-design guideline for superior adhesion, thus reducing the bonding breakage that may potentially cause device failure. Die pad surfaces used in chip attachment methods for microelectronics are usually fabricated using an electrolytic plating technique. This technique involves ionic gold solutions like K[Au(CN)2]. The combined theoretical and experimental studies previously carried out by the authors have revealed that the CN- counteranion of the gold cation has a high affinity for gold and is likely to remain on the realistic gold surface generated by plating. However, the cyano group content on the surface of the plated gold is still unknown. Therefore, gold surfaces embedded with cyano groups with various coverages are constructed. The effect of the varying coverage of the cyano groups on the adhesion strength is inspected using first-principles density functional theory calculations. As the number of cyano groups on the surface increases, the direct interaction between the gold surface and the epoxy resin is hindered, but the hydroxy and amino groups in the epoxy resin and hardener form more hydrogen bonds with the cyano groups adsorbed on the surface. It is found that the surface with intermediate cyano coverage (about 33%) yields the highest adhesive strength.