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Nanoparticle supercrystals (NPSCs) are of great interest as materials with emergent properties. Different types of intermolecular forces, such as van der Waals interaction and hydrogen bonding, are present in the NPSCs fabricated to date. However, the limited structural stability of such NPSCs that results from the weakness of these intermolecular forces is a challenge. Here, we report a spontaneous formation of NPSCs driven by covalent bonding interactions, a type of intramolecular force much stronger than the above-mentioned intermolecular forces. A model solution-phase anhydride reaction is used to form covalent bonds between molecules grafted on the surface of gold nanoparticles, resulting in three-dimensional NPSCs. The NPSCs are very stable in different solvents, in dried conditions, and at temperatures as high as 160 °C. In addition to this, the large library of covalent-bond-forming reactions available and the low cost of reactants make the covalent bonding approach highly versatile and economical.
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Cortisol is an endogenous glucocorticoid (GC) and primary stress hormone that regulates a wide range of stress responses in humans. The adverse effects of cortisol on the skin have been extensively documented but the underlying mechanism of cortisol-induced signaling is still unclear. In the present study, we investigate the effect of cortisol on collagen type I expression and the effect of AP collagen peptides, collagen tripeptide-rich hydrolysates containing 3% glycine-proline- hydroxyproline (Gly-Pro-Hyp, GPH) from the fish skin, on the cortisol-mediated inhibition of collagen type I and the cortisol-induced signaling that regulates collagen type I production in human dermal fibroblasts (HDFs). We determine that cortisol downregulates the expression of collagen type I. AP collagen peptides or GC receptor (GR) inhibitors recover the cortisol-mediated inhibition of collagen type I and GR activation. AP collagen peptides or GR inhibitors also prevent the cortisol-dependent inhibition of transforming growth factor (TGF)-ß signaling. AP collagen peptides or GR inhibitors are effective in the prevention of collagen type I inhibition mediated by cortisol in senescent HDFs and reconstituted human skin models. Taken together, GR signaling might be responsible for the cortisol-mediated inhibition of TGF-ß. AP collagen peptides act as GR-mediated signaling blockers, preventing the cortisol-dependent inhibition of collagen type I. Therefore, AP collagen peptides have the potential to improve skin health.
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Anti-Inflamatórios/farmacologia , Colágeno Tipo I/metabolismo , Fibroblastos/efeitos dos fármacos , Hidrocortisona/farmacologia , Oligopeptídeos/farmacologia , Animais , Linhagem Celular , Derme/citologia , Derme/efeitos dos fármacos , Derme/metabolismo , Fibroblastos/citologia , Fibroblastos/metabolismo , Peixes , Humanos , Transdução de Sinais/efeitos dos fármacos , Fator de Crescimento Transformador beta/metabolismoRESUMO
Nanoparticle superlattices (NPSLs) are of great interest as materials with designed emerging properties depending on the lattice symmetry as well as composition. The symmetry transition of NPSLs depending on environmental conditions can be an excellent ground for making new stimuli-responsive functional materials. Here, we report a spherical micelle-assisted method to form exceptionally ordered NPSLs which are inherently sensitive to environmental conditions. Upon mixing functionalized gold nanoparticles (AuNPs) with a nonionic surfactant spherical micellar solution, NPSLs of different symmetries such as NaZn13, MgZn2, and AlB2-type are formed depending on the size ratio between micelles and functionalized AuNPs and composition. The NPSLs formed by the spherical micelle-assisted method show thermally reversible order-order (NaZn13-AlB2) and order-disorder (MgZn2-isotropic) symmetry transitions, which are consistent with the Gibbs free energy calculations for binary hard-sphere model. This approach may open up new possibilities for NPSLs as stimuli-responsive functional materials.
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A facile and green synthesis method for mesoporous gold sponges has been developed, which involves a simple mixing of a very small amount of thiolated-poly(ethylene glycol) (SH-PEG) and citrate-covered gold nanoparticles (Au NPs) in aqueous solution at room temperature. While SH-PEG molecules have been widely used as biocompatible hydrophilic capping agents for Au NPs for stable dispersion in aqueous solution, here they are used as destabilizing agents. When SH-PEG molecules are mixed with citrate-covered Au NPs at the molar ratio ranging from 3 to 20 (SH-PEG/Au NP), mesoporous gold sponges with randomly interconnected 3D network structures are formed within 2 to 3 h. This is driven by the destabilization of negatively charged citrate molecules on Au NPs by a small number of SH-PEG molecules bonded on the particle surface, which results in the decrease in zeta potential and thus the assembly of Au NPs into porous sponges. The use of very low concentration of SH-PEG (ca. 20-200 nM) in aqueous solution at room temperature makes the method highly eco-friendly as well as results in high-purity as-synthesized gold sponges (98.7 wt %). The mesoporous gold sponges fabricated with the present method exhibit a high SERS activity, making them highly applicable for sensitive SERS detection of molecules.
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We have investigated the distributions of individually isolated and hydrophilically functionalized single-walled carbon nanotubes (p-SWNTs) in the Pluronic L121-water system at the reverse hexagonal phase using small-angle X-ray scattering (SAXS) and contrast-matched small-angle neutron scattering (SANS) measurements. As the p-SWNT-L121-water system is transitioned from the lamellar phase to the reverse hexagonal phase with temperature, p-SWNTs which were selectively distributed in the polar layers of the lamellar structure become selectively distributed in the cylindrical polar cores of the reverse hexagonal structure, forming a hexagonal array of p-SWNTs. This was clearly confirmed by the contrast-matched SANS measurements. The selective distribution of p-SWNTs in the reverse hexagonal phase is driven by the selective affinity of p-SWNTs to the polar domains of the block copolymer system. The method demonstrated in this study provides a new route for fabricating ordered SWNT superstructures and may be applicable for inorganic 1D nanoparticles such as semiconducting, metallic and magnetic nanorods which are of great interest.
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We report a highly ordered intercalated hexagonal binary superlattice of hydrophilically functionalized single-walled carbon nanotubes (p-SWNTs) and surfactant (C12 E5 ) cylindrical micelles. When p-SWNTs (with a diameter slightly larger than that of the C12 E5 cylinders) were added to the hexagonally packed C12 E5 cylindrical-micellar system, p-SWNTs positioned themselves in such a way that the free-volume entropies for both p-SWNTs and C12 E5 cylinders were maximized, thus resulting in the intercalated hexagonal binary superlattice. In this binary superlattice, a hexagonal array of p-SWNTs is embedded in a honeycomb lattice of C12 E5 cylinders. The intercalated hexagonal binary superlattice can be highly aligned in one direction by an oscillatory shear field and remains aligned after the shear is removed.
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Micelas , Nanotubos de Carbono/química , Interações Hidrofóbicas e Hidrofílicas , Modelos Moleculares , Tensoativos/químicaRESUMO
The Zn element precipitates during aging in the Al-Zn binary alloy. Increased Zn content and prolonged aging leads to discontinuous Zn precipitation. The addition of 2 wt% Cu to the Al-43 wt%Zn alloy accelerates this discontinuous precipitation, resulting in decreased thickness of Zn layers and inter-distance between them. This acceleration is attributed to the influence of Cu solutes on the Zn phase, thereby reducing the interface energy between Zn precipitates and the Al matrix. The Al-Zn-Cu alloy demonstrates exceptional behavior during tensile tests, displaying a simultaneous increase in tensile strength and ductility alongside an 75 % reduction in area at room temperature drawing. Notably, despite the drawn beyond uniform deformation limit, there is an observed increase in total elongation. Our demonstration highlights this phenomenon, attributing it to the sustained coherent interface between the Zn layer and the Al matrix, as well as the uninterrupted continuity of Zn layers during drawing.
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Collagen-derived dipeptides and tripeptides have various physiological activities. In this study, we compared the plasma kinetics of free Hyp, peptide-derived Hyp, Pro-Hyp, cyclo(Pro-Hyp), Hyp-Gly, Gly-Pro-Hyp, and Gly-Pro-Ala after ingestion of four different collagen samples: AP collagen peptide (APCP), general collagen peptide, collagen, and APCP and γ-aminobutyric acid (GABA) combination. Each peptide was measured by high-performance liquid chromatography and triple quadrupole mass spectrometer. We found that, among all the peptides that were analyzed, only Gly-Pro-Hyp was significantly increased after ingestion of APCP compared with that of general collagen peptides and collagen. In addition, ingestion of the APCP and GABA combination improved the absorption efficiency of Gly-Pro-Ala. Finally, we reveal that Gly-Pro-Hyp was effective for preventing H2O2-induced reduction in extracellular matrix (ECM)-related genes, COL1A, elastin, and fibronectin, in dermal fibroblasts. Taken together, APCP significantly enhances the absorption of Gly-Pro-Hyp, which might act as an ECM-associated signaling factor in dermal fibroblasts, and the APCP and GABA combination promotes Gly-Pro-Ala absorption. Clinical Trial Registration number: UMIN000047972.
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Colágeno , Fibroblastos , Peróxido de Hidrogênio , Peptídeos , Absorção Fisiológica , Colágeno/administração & dosagem , Colágeno/química , Ingestão de Alimentos , Fibroblastos/metabolismoRESUMO
Nonmelanoma skin cancer is one of the most frequently occurring cancers in the United States. Chronic exposure to UVB irradiation is a major cause of this cancer. Daidzein, along with genistein, is a major isoflavone found in soybeans; however, little is known about the chemopreventive effects of daidzein and its metabolites in UVB-induced skin cancer. Here, we found that 7,3',4'-trihydroxyisoflavone (THIF), a major metabolite of daidzein, effectively inhibits UVB-induced cyclooxygenase 2 (COX-2) expression through the inhibition of NF-κB transcription activity in mouse skin epidermal JB6 P+ cells. In contrast, daidzein had no effect on COX-2 expression levels. Data from Western blot and kinase assays showed that 7,3',4'-THIF inhibited Cot and MKK4 activity, thereby suppressing UVB-induced phosphorylation of mitogen-activated protein kinases. Pull-down assays indicated that 7,3',4'-THIF competed with ATP to inhibit Cot or MKK4 activity. Topical application of 7,3',4'-THIF clearly suppressed the incidence and multiplicity of UVB-induced tumors in hairless mouse skin. Hairless mouse skin results also showed that 7,3',4'-THIF inhibits Cot or MKK4 kinase activity directly, resulting in suppressed UVB-induced COX-2 expression. A docking study revealed that 7,3',4'-THIF, but not daidzein, easily docked to the ATP binding site of Cot and MKK4, which is located between the N- and C-lobes of the kinase domain. Collectively, these results provide insight into the biological actions of 7,3',4'-THIF, a potential skin cancer chemopreventive agent.
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Regulação Neoplásica da Expressão Gênica , Glycine max/metabolismo , Isoflavonas/química , Isoflavonas/farmacologia , MAP Quinase Quinase 4/metabolismo , MAP Quinase Quinase Quinases/metabolismo , Neoplasias Induzidas por Radiação/prevenção & controle , Proteínas Proto-Oncogênicas/metabolismo , Neoplasias Cutâneas/prevenção & controle , Animais , Ciclo-Oxigenase 2/metabolismo , Camundongos , Camundongos Endogâmicos ICR , NF-kappa B/metabolismo , Extratos Vegetais/farmacologia , Transdução de Sinais , Raios UltravioletaRESUMO
Ni-22Fe-22Cr-6Al metallic foam, prepared using a thermomechanical treatment and alloying elements, was studied via transmission electron microscopy (TEM) in order to clarify the relationship between the mechanical properties and the nanoscale microstructural characteristics. Due to the unique porous structure of the metallic foam, TEM specimens were prepared using an embedding-process-assisted-ion-milling technique and a focused-ion-beam method. The Cr-, Fe- and Al-clustered regions around the surface of the metallic foam were investigated using elemental maps. The Ni(3)Al (γ') precipitates, which can affect the mechanical properties of the Ni-Fe-Cr (γ) matrix, were characterized in the metallic foam.
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Ligas/química , Microscopia Eletrônica de Transmissão/instrumentação , Microscopia Eletrônica de Transmissão/métodos , Simulação por Computador , Processamento de Imagem Assistida por Computador/métodosRESUMO
We report direct observation of controlled and reversible switching of magnetic domains using static (dc) electric fields applied in situ during Lorentz microscopy. The switching is realized through electromechanical coupling in thin film Fe(0.7)Ga(0.3)/BaTiO(3) bilayer structures mechanically released from the growth substrate. The domain wall motion is observed dynamically, allowing the direct association of local magnetic ordering throughout a range of applied electric fields. During application of approximately 7-11 MV/m electric fields to the piezoelectric BaTiO(3) film, local magnetic domains rearrange in the ferromagnetic Fe(0.7)Ga(0.3) layer due to the transfer of strain from the BaTiO(3) film. A simulation based on micromagnetic modeling shows a magnetostrictive anisotropy of 25 kPa induced in the Fe(0.7)Ga(0.3) due to the strain. This electric-field-dependent uniaxial anisotropy is proposed as a possible mechanism to control the coercive field during operation of an integrated magnetoelectric memory node.
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Magnetismo , Nanopartículas/química , Nanotecnologia/métodos , Campos Eletromagnéticos , Nanotecnologia/instrumentaçãoRESUMO
PURPOSE: The objective of this study was to assess the impact of healthcare benefits on adherence to positive airway pressure (PAP) therapy in obstructive sleep apnea (OSA) patients. METHODS: Medical records of OSA patients at the Veterans Health Service Medical Center were retrospectively reviewed. OSA patients were assigned to two groups as the date of prescribing PAP: after (=Group A) and before (=Group B) July 1, 2018 when PAP therapy starts to be included in healthcare insurance coverage for OSA patients in South Korea. PAP adherence was compared over a 3-month period between the two groups; subjective improvement after therapy was evaluated using the Epworth Sleepiness Scale (ESS) and Pittsburgh Sleep Quality Index scores. In addition, we evaluated a number of OSA patients who chose to start PAP therapy without healthcare benefit (from July 2018 to December 2018). RESULTS: Each of the 50 patients in the Group A and B exhibited PAP adherence rates of 82% and 26%, respectively (P < .001). Age did not affect PAP adherence in the Group A. The mean apnea-hypopnea index (from 36.7 to 1.34, P < .001) and ESS (from 7.6 to 5.6, P = .004) scores of patients in the Group A had significantly improved within the first three months. Twenty-three (23 out of 334, 6.9%) OSA patients did not have any healthcare insurance, but they medically needed PAP therapy. However, only one of the 23 patients began PAP treatment. CONCLUSION: Short-term PAP adherence significantly improved after PAP therapy was included in healthcare insurance coverage.
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Pressão Positiva Contínua nas Vias Aéreas , Apneia Obstrutiva do Sono , Atenção à Saúde , Humanos , Cooperação do Paciente , Modalidades de Fisioterapia , Estudos Retrospectivos , Apneia Obstrutiva do Sono/terapiaRESUMO
BACKGROUND: A few studies have reported the use of middle ear implants (MEIs) in older adults. OBJECTIVES: To evaluate the audiologic outcomes and postoperative complications of MEIs in older adults. METHODS: This retrospective study reviewed audiologic data and medical records from a single referral centre. We identified 34 patients aged ≥65 years who underwent middle ear implantation using the Vibrant SoundbridgeTM device. Preoperative audiometric testing and postoperative aided audiometric testing were performed to evaluate the functional hearing gain at 1 year postoperatively. Patients were divided into 2 groups depending on whether they underwent explantation because of poor hearing benefit. RESULTS: Follow-up duration ranged from <1 to 5.3 years. The functional gain with MEIs significantly improved relative to the preoperative air conduction thresholds at 0.5, 1, 2, and 4 kHz. Eight patients underwent explantation and 7 lost their external audio processor devices. Those who removed their implants because of the poor hearing (group 1) showed significantly worse hearing thresholds at 1 kHz and speech discrimination scores than the others (group 2). CONCLUSIONS AND SIGNIFICANCE: MEIs for auditory rehabilitation can provide improved speech recognition and significant functional gains in older adults. Patients must be given appropriate preoperative explanations regarding the expected outcomes.
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Auxiliares de Audição , Perda Auditiva/reabilitação , Prótese Ossicular , Fatores Etários , Idoso , Idoso de 80 Anos ou mais , Audiometria , Limiar Auditivo , Feminino , Perda Auditiva/diagnóstico , Humanos , Masculino , Prótese Ossicular/efeitos adversos , Estudos Retrospectivos , Percepção da Fala , Resultado do TratamentoRESUMO
The stratum corneum (SC) is the outermost layer of the epidermis and plays an important role in maintaining skin moisture and protecting the skin from the external environment. Ceramide and natural moisturizing factor (NMF) are the major SC components that maintain skin moisture. In this study, we investigated whether the oral intake of enzymatically decomposed AP collagen peptides (APCPs) can improve skin moisture and barrier function by assessing changes in the ceramide and NMF contents in the SC after APCP ingestion with the aim to develop a skin functional food. Fifty participants orally ingested APCP (1000 mg) or placebo for 12 weeks, and then, skin hydration and skin texture were evaluated. SC samples were collected to analyze skin scaling, ceramide, and NMF contents. Participants in the APCP group exhibited improved skin moisture content by 7.33% (p = 0.031) and roughness by -4.09% (p = 0.036) when compared with those in the placebo group. NMF content; the amounts of amino acids (AA), including glycine and proline; and AA derivatives were significantly increased in the APCP group (31.98 µg/mg protein) compared to those in the placebo group (-16.01 µg/mg protein) (p = 0.006). The amounts of total ceramides and ceramide subclasses were significantly higher in the APCP group than in the placebo group (p = 0.014). In conclusion, our results demonstrate that APCP intake improves skin moisture and increase the ceramide and NMF contents in the SC, thereby enhancing the skin barrier function.
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Água Corporal/metabolismo , Ceramidas/metabolismo , Colágeno/administração & dosagem , Colágeno/farmacologia , Suplementos Nutricionais , Ingestão de Alimentos/fisiologia , Epiderme/metabolismo , Adulto , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Perda Insensível de Água/efeitos dos fármacosRESUMO
The composites and thin films comprising individual single-walled carbon nanotubes with a polymer coating (p-CNTs) have been prepared and their electromagnetic responses have been studied in a wide range from low-frequency (25-107 Hz) up to the infrared region. In spite of the high volume fraction of the nanotubes (up to 3.3%), the polymer coating prevents direct p-CNT contacts and the formation of the percolation network in those composites, so that p-CNTs interact only via the electromagnetic coupling. Thereby it is an ideal model system to verify experimentally the fundamental issues related to carbon nanotube electromagnetics, such as the influence of inter-tube electron tunneling on the localized plasmon resonance in the terahertz range, or the infrared absorption enhancement of polymer molecules attached to the nanotube surface. Along with addressing the fundamentals, applied carbon nanotube electromagnetics got insights important for the applications of p-CNT based composites as dielectric media in the terahertz regime. In particular, we found that the real part of the permittivity of the p-CNT film in the terahertz range is rather competitive, i.e. 8-13, however the loss tangent is not so small (0.4-0.6) as has been predicted. The way to increase p-CNT terahertz performance is also discussed.
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We have synthesized new blue light emitting random copolymers, poly(9,9'-n-dioctylfluorene-co-2,2',6,6'-tetraoctyloxybiphenyl-3,3'-diyl)s (PFTOBPs), via Ni(0)-mediated coupling reactions. The PL emission peaks of the resulting copolymers closely resembled those of the polyfluorene (PF) homopolymer. The EL devices fabricated using these copolymers exhibited highly pure blue emission with approximate 1931 CIE coordinates of (0.15, 0.15) at 1000 cd/m2. The maximum brightnesses ranged from 2000 to 12000 cd/m2 with maximum efficiencies from 0.53 to 0.97 cd/A. The efficiencies were found to increase as the fraction of TOBP in the copolymers was increased, which may result the inhibition of exciton quenching that is produced by the introduction of the highly twisted and bulky TOBP moieties into the copolymers.
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Compostos de Bifenilo/química , Cristalização/métodos , Fluorenos/química , Iluminação/métodos , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Semicondutores , Iluminação/instrumentação , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Nanotecnologia/métodos , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Synthesis of binary nanoparticle superlattices has attracted attention for a broad spectrum of potential applications. However, this has remained challenging for one-dimensional nanoparticle systems. In this study, we investigate the packing behavior of one-dimensional nanoparticles of different diameters into a hexagonally packed cylindrical micellar system and demonstrate that binary one-dimensional nanoparticle superlattices of two different symmetries can be obtained by tuning particle diameter and mixing ratios. The hexagonal arrays of one-dimensional nanoparticles are embedded in the honeycomb lattices (for AB2 type) or kagome lattices (for AB3 type) of micellar cylinders. The maximization of free volume entropy is considered as the main driving force for the formation of superlattices, which is well supported by our theoretical free energy calculations. Our approach provides a route for fabricating binary one-dimensional nanoparticle superlattices and may be applicable for inorganic one-dimensional nanoparticle systems.Binary mixtures of 1D particles are rarely observed to cooperatively self-assemble into binary superlattices, as the particle types separate into phases. Here, the authors design a system that avoids phase separation, obtaining binary superlattices with different symmetries by simply tuning the particle diameter and mixture composition.
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Cast-Al alloys that include a high amount of the second element in their matrix have comparatively high strength but low ductility because of the high volume fraction of strengthening phases or undesirable inclusions. Al-Zn alloys that have more than 30 wt% Zn have a tensile strength below 300 MPa, with elongation under 5% in the as-cast state. However, we found that after substitution of 2% Zn by Cu, the tensile strength of as-cast Al-Zn-Cu alloys was 25% higher and ductility was four times higher than for the corresponding Al-35% Zn alloy. Additionally, for the Al-43% Zn alloy with 2% Cu after 1 h solution treatment at 400 °C and water quenching, the tensile strength unexpectedly reached values close to 600 MPa. For the Al-33% Zn alloy with 2% Cu, the tensile strength was 500 MPa with 8% ductility. The unusual trends of the mechanical properties of Al-Zn alloys with Cu addition observed during processing from casting to the subsequent solution treatment were attributed to the precipitation of Zn in the Al matrix. The interface energy between the Zn particles and the Al matrix decreased when using a solution of Cu in Zn.
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The precipitation strengthening of Cu alloys inevitably accompanies lowering of their electric conductivity and ductility. We produced bulk Cu alloys arrayed with nanofibers of stiff intermetallic compound through a precipitation mechanism using conventional casting and heat treatment processes. We then successfully elongated these arrays of nanofibers in the bulk Cu alloys to 400% of original length without breakage at room temperature using conventional rolling process. By inducing such an one-directional array of nanofibers of intermetallic compound from the uniform distribution of fine precipitates in the bulk Cu alloys, the trade-off between strength and conductivity and between strength and ductility could be significantly reduced. We observed a simultaneous increase in electrical conductivity by 1.3 times and also tensile strength by 1.3 times in this Cu alloy bulk compared to the conventional Cu alloys.
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The development of Cu-based alloys with high-mechanical properties (strength, ductility) and electrical conductivity plays a key role over a wide range of industrial applications. Successful design of the materials, however, has been rare due to the improvement of mutually exclusive properties as conventionally speculated. In this paper, we demonstrate that these contradictory material properties can be improved simultaneously if the interfacial energies of heterogeneous interfaces are carefully controlled. We uniformly disperse γ-Al2O3 nanoparticles over Cu matrix, and then we controlled atomic level morphology of the interface γ-Al2O3//Cu by adding Ti solutes. It is shown that the Ti dramatically drives the interfacial phase transformation from very irregular to homogeneous spherical morphologies resulting in substantial enhancement of the mechanical property of Cu matrix. Furthermore, the Ti removes impurities (O and Al) in the Cu matrix by forming oxides leading to recovery of the electrical conductivity of pure Cu. We validate experimental results using TEM and EDX combined with first-principles density functional theory (DFT) calculations, which all consistently poise that our materials are suitable for industrial applications.