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1.
Chem Rev ; 2024 Jul 22.
Artículo en Inglés | MEDLINE | ID: mdl-39038231

RESUMEN

Neuromorphic computing and artificial intelligence hardware generally aims to emulate features found in biological neural circuit components and to enable the development of energy-efficient machines. In the biological brain, ionic currents and temporal concentration gradients control information flow and storage. It is therefore of interest to examine materials and devices for neuromorphic computing wherein ionic and electronic currents can propagate. Protons being mobile under an external electric field offers a compelling avenue for facilitating biological functionalities in artificial synapses and neurons. In this review, we first highlight the interesting biological analog of protons as neurotransmitters in various animals. We then discuss the experimental approaches and mechanisms of proton doping in various classes of inorganic and organic proton-conducting materials for the advancement of neuromorphic architectures. Since hydrogen is among the lightest of elements, characterization in a solid matrix requires advanced techniques. We review powerful synchrotron-based spectroscopic techniques for characterizing hydrogen doping in various materials as well as complementary scattering techniques to detect hydrogen. First-principles calculations are then discussed as they help provide an understanding of proton migration and electronic structure modification. Outstanding scientific challenges to further our understanding of proton doping and its use in emerging neuromorphic electronics are pointed out.

2.
Nat Mater ; 22(7): 848-852, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-37106132

RESUMEN

Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 s state to hybridized Li-s/Ti-d orbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.


Asunto(s)
Electrólitos , Litio , Suministros de Energía Eléctrica , Ingeniería , Programas Informáticos
3.
Nano Lett ; 22(15): 6062-6068, 2022 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-35862274

RESUMEN

Recent reports of superconductivity at KTaO3 (KTO) (110) and (111) interfaces have sparked intense interest due to the relatively high critical temperature as well as other properties that distinguish this system from the more extensively studied SrTiO3 (STO)-based heterostructures. Here, we report the reconfigurable creation of conducting structures at intrinsically insulating LaAlO3/KTO(110) and (111) interfaces. Devices are created using two distinct methods previously developed for STO-based heterostructures: (1) conductive atomic-force microscopy lithography and (2) ultralow-voltage electron-beam lithography. At low temperatures, KTO(110)-based devices show superconductivity that is tunable by an applied back gate. A one-dimensional nanowire device shows single-electron-transistor (SET) behavior. A KTO(111)-based device is metallic but does not become superconducting. These reconfigurable methods of creating nanoscale devices in KTO-based heterostructures offer new avenues for investigating mechanisms of superconductivity as well as development of quantum devices that incorporate strong spin-orbit interactions, superconducting behavior, and nanoscale dimensions.

4.
Acc Chem Res ; 54(15): 3039-3049, 2021 Aug 03.
Artículo en Inglés | MEDLINE | ID: mdl-34297550

RESUMEN

ConspectusThe redox reaction pathway is crucial to the sustainable production of the fuels and chemicals required for a carbon-neutral society. Our society is becoming increasingly dependent on devices using batteries and electrolyzers, all of which rely on a series of redox reactions. The overall properties of oxide materials make them very well suited for such electrochemical and catalytic applications due to their associated cationic redox properties and the static site-adsorbate interactions. As these technologies have matured, it has become apparent that defect-driven redox reactions, defect-coupled diffusion, and structural transformations that are both time- and rate-dependent are also critical materials processes. This change in focus, considering not only redox properties but also more complex, dynamic behaviors, represents a new research frontier in the molecular sciences as they are strongly linked to device operation and degradation and lie at the heart of various phenomena that take place at electrochemical interfaces. Fundamental studies of the structural, electronic, and chemical transformation mechanisms are key to the advancement of materials and technological innovations that could be implemented in various electrochemical systems.In this Account, we focus on recent studies and advances in characterizing and understanding the dynamic redox evolution and structural transformations that take place in model perovskites and layered oxides under reactive conditions and correlate them with degradation mechanisms and operations in electrolyzers and batteries. We show that the dynamic evolution of oxygen vacancies and cationic migration in the surface or bulk occurs at the solid-liquid interface, using a combination of different synchrotron-based X-ray spectroscopies and scattering probes. Detailed redox-structure-reactivity correlation studies show how defects and diffusion processes can be tailored to drive various physical and chemical transformations in electrolyzers and batteries. We also highlight a strong correlation between oxygen redox reactivity and structural reorganization in both model thin films and particles, helping to bridge the gap between fundamental studies of the reaction mechanism and device applications. On the basis of these findings, we discuss strategies to probe and tune the redox reactivity and structural stability of the redox-active oxide interphase toward devising efficient pathways for energy and chemical harvesting.

5.
Phys Rev Lett ; 129(23): 235701, 2022 Dec 02.
Artículo en Inglés | MEDLINE | ID: mdl-36563221

RESUMEN

Understanding the behavior of defects in the complex oxides is key to controlling myriad ionic and electronic properties in these multifunctional materials. The observation of defect dynamics, however, requires a unique probe-one sensitive to the configuration of defects as well as its time evolution. Here, we present measurements of oxygen vacancy ordering in epitaxial thin films of SrCoO_{x} and the brownmillerite-perovskite phase transition employing x-ray photon correlation spectroscopy. These and associated synchrotron measurements and theory calculations reveal the close interaction between the kinetics and the dynamics of the phase transition, showing how spatial and temporal fluctuations of heterointerface evolve during the transformation process. The energetics of the transition are correlated with the behavior of oxygen vacancies, and the dimensionality of the transformation is shown to depend strongly on whether the phase is undergoing oxidation or reduction. The experimental and theoretical methods described here are broadly applicable to in situ measurements of dynamic phase behavior and demonstrate how coherence may be employed for novel studies of the complex oxides as enabled by the arrival of fourth-generation hard x-ray coherent light sources.

6.
Nature ; 534(7606): 231-4, 2016 06 09.
Artículo en Inglés | MEDLINE | ID: mdl-27279218

RESUMEN

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

7.
Clin Exp Dermatol ; 47(10): 1853-1856, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35546559

RESUMEN

Full-body skin examinations (FBSEs) involve examination of the patient's skin from head to toe, and may be uncomfortable for some patients. While many patients prefer same-sex providers for pelvic, genital and rectal exams, desire for same-sex providers for FBSEs is not well characterized. This may be further magnified when FBSE is performed by medical trainees. We surveyed 566 subjects using Amazon Mechanical Turk (AMT), an online crowdsourcing platform, to assess the public's willingness to receive FBSEs based on the sex and/or gender and the level of training of the healthcare provider (HCP). The overall willingness by all respondents to undergo FBSE performed by a dermatologist, dermatology resident and medical student was 84.3%, 77.5% and 65.7%, respectively, if the HCP was the same sex/gender, compared with 60.6%, 54.8% and 45.7% if the HCP was a different sex/gender (P < 0.001). In our cohort, unwillingness for FBSEs was greater if the patient was female, if the HCP was a different gender/sex from the patient and if the HCP was a medical student.


Asunto(s)
Neoplasias Cutáneas , Estudiantes de Medicina , Femenino , Humanos , Examen Físico , Piel , Neoplasias Cutáneas/diagnóstico , Encuestas y Cuestionarios
8.
S D Med ; 74(8): 363-366, 2021 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-34461001

RESUMEN

Methotrexate therapy has evolved over the years to become a fundamental component in the management of rheumatoid arthritis and psoriasis. Liver toxicity remains an ever-present concern when prescribing methotrexate. As such, methotrexate liver toxicity monitoring guidelines have been developed independently by rheumatologists and dermatologists. The main differentiating factor between the dermatology and rheumatology guidelines is risk stratification. Dermatology guidelines are largely based off of the presence or absence of hepatoxicity risk factors (alcohol usage, obesity, type II diabetes, among other) while the rheumatology guidelines do not emphasize this distinction. Thus, the aim of this review is to identify why these screening guidelines differences exist and discuss if the differences in stratification and screening are valid. We will also briefly examine alternatives to the current gold standard hepatoxicity screening test: the liver biopsy.


Asunto(s)
Artritis Reumatoide , Enfermedad Hepática Inducida por Sustancias y Drogas , Diabetes Mellitus Tipo 2 , Psoriasis , Artritis Reumatoide/diagnóstico , Artritis Reumatoide/tratamiento farmacológico , Enfermedad Hepática Inducida por Sustancias y Drogas/diagnóstico , Enfermedad Hepática Inducida por Sustancias y Drogas/epidemiología , Enfermedad Hepática Inducida por Sustancias y Drogas/etiología , Consenso , Humanos , Metotrexato/efectos adversos , Psoriasis/diagnóstico , Psoriasis/tratamiento farmacológico
9.
Epilepsia ; 61(7): 1503-1514, 2020 07.
Artículo en Inglés | MEDLINE | ID: mdl-32484924

RESUMEN

OBJECTIVE: To determine the role of aquaporin-4 (AQP4) in posttraumatic epileptogenesis using long-term video-electroencephalographic (vEEG) recordings. Here, differences in EEG were analyzed between wild-type (WT) and AQP4 knockout (KO) mice and between mice with and without posttraumatic epilepsy (PTE). METHODS: WT and AQP4 KO mice were subjected to a single controlled cortical impact traumatic brain injury (TBI) in the frontal cortex, and vEEG was recorded in the ipsilateral hippocampus at 14, 30, 60, and 90 days postinjury (dpi). Intrahippocampal electrical stimulation was also used to assess electrographic seizure threshold and electrographic seizure duration (ESD). RESULTS: The mean seizure frequency per day for WT mice was 0.07 ± 0.07, 0.11 ± 0.07, 0.26 ± 0.13, and 0.12 ± 0.10 at 14, 30, 60, and 90 dpi, respectively. The mean seizure frequency per day for AQP4 KO mice was 0.45 ± 0.27, 0.29 ± 0.12, and 0.26 ± 0.19 at 14, 30, and 60 dpi, respectively. The mean seizure duration was 15 ± 2 seconds and 24 ± 3 seconds for WT and AQP4 KO mice, respectively. The percentage of mice that developed PTE were 28% and 37% for WT and AQP4 KO mice, respectively. Power spectral density (PSD) analysis revealed alterations in EEG frequency bands between sham and TBI in both genotypes. Additionally, PSD analysis of spontaneous recurrent seizures revealed alterations in delta power between genotypes. Morlet wavelet analysis detected heterogeneity in EEG seizure subtypes and dynamic EEG power patterns after TBI. Compared with AQP4 KO mice, a significant increase in ESD was observed in WT mice at 14 dpi. SIGNIFICANCE: Posttraumatic seizures (PTSs) may be modulated by the astrocyte water channel AQP4. Absence of AQP4 increases the number of spontaneous seizures, increases seizure duration, and alters EEG power patterns of PTSs.


Asunto(s)
Acuaporina 4/deficiencia , Lesiones Traumáticas del Encéfalo/metabolismo , Lesiones Traumáticas del Encéfalo/fisiopatología , Epilepsia Postraumática/metabolismo , Epilepsia Postraumática/fisiopatología , Animales , Electroencefalografía/métodos , Masculino , Ratones , Ratones Noqueados , Grabación en Video/métodos
10.
J Drugs Dermatol ; 19(12): 1192-1198, 2020 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-33346521

RESUMEN

Certain dermatologic conditions and drugs used for their treatment are associated with uveitis, a vision-threatening group of inflammatory eye diseases. Dermatologists may therefore be the first healthcare providers to recognize the presence of uveitis in certain patients and can help ensure morbidity is minimized. Posterior uveitis in particular, which may manifest as insidious, painless vision loss, may first be identified by a careful review of systems by a dermatologist. Understanding uveitis and its associations with certain skin findings and drugs will help enable identification and triage of patients in need of ophthalmic care. An overview of uveitis is provided, including its epidemiology, etiologies, classification, presenting signs and symptoms, general management, and complications. Next, dermatologic diseases that may be associated with uveitis are reviewed with a focus on how uveitis is most likely to present. Lastly, drugs used by dermatologists and less common dermatologic diseases associated with uveitis are reviewed. Multidisciplinary management is necessary for patients with both skin disease and ocular complications such as uveitis. Dermatologists’ recognition of uveitis in patients may reduce time to referral and improve patient outcomes. J Drugs Dermatol. 2020;19(12): doi:10.36849/JDD.2020.5165.


Asunto(s)
Fármacos Dermatológicos/efectos adversos , Enfermedades de la Piel/tratamiento farmacológico , Uveítis/diagnóstico , Dermatólogos/organización & administración , Humanos , Oftalmología/organización & administración , Grupo de Atención al Paciente/organización & administración , Derivación y Consulta/organización & administración , Factores de Riesgo , Enfermedades de la Piel/complicaciones , Factores de Tiempo , Triaje/organización & administración , Uveítis/epidemiología , Uveítis/etiología
11.
Ann Oncol ; 30(4): 575-581, 2019 04 01.
Artículo en Inglés | MEDLINE | ID: mdl-30753274

RESUMEN

BACKGROUND: Previous data suggest that the immune microenvironment plays a critical role in human epidermal growth factor receptor 2 (HER2) -positive breast cancer; however, there is little known about the immune profiles of small HER2-positive tumors. In this study, we aimed to characterize the immune microenvironment of small HER2-positive breast cancers included in the Adjuvant paclitaxel and trastuzumab for node-negative, HER2-positive breast cancer (APT) trial and to correlate the immune markers with pathological and molecular tumor characteristics. PATIENTS AND METHODS: The APT trial was a multicenter, single-arm, phase II study of paclitaxel and trastuzumab in patients with node-negative HER2-positive breast cancer. The study included 406 patients with HER2-positive, node-negative breast cancer, measuring up to 3 cm. Exploratory analysis of tumor infiltrating lymphocytes (TIL), programmed death-ligand 1 (PD-L1) expression (by immunohistochemistry), and immune gene signatures using data generated by nCounter PanCancer Pathways Panel (NanoString Technologies, Seattle, WA), and their association with pathological and molecular characteristics was carried out. RESULTS: Of the 406 patients, 328 (81%) had at least one immune assay carried out: 284 cases were evaluated for TIL, 266 for PD-L1, and 213 for immune gene signatures. High TIL (≥60%) were seen with greater frequency in hormone-receptor (HR) negative, histological grades 2 and 3, as well in HER2-enriched and basal-like tumors. Lower stromal PD-L1 (≤1%) expression was seen with greater frequency in HR-positive, histological grade 1, and in luminal tumors. Both TIL and stromal PD-L1 were positively correlated with 10 immune cell signatures, including Th1 and B cell signatures. Luminal B tumors were negatively correlated with those signatures. Significant correlation was seen among these immune markers; however, the magnitude of correlation did not indicate a monotonic relationship between them. CONCLUSION: Immune profiles of small HER2-positive breast cancers differ according to HR status, histological grade, and molecular subtype. Further work is needed to explore the implication of these findings on disease outcome. CLINICAL TRIAL REGISTRATION: clinicaltrials.gov identifier: NCT00542451.


Asunto(s)
Protocolos de Quimioterapia Combinada Antineoplásica/uso terapéutico , Biomarcadores de Tumor/metabolismo , Neoplasias de la Mama/inmunología , Receptor ErbB-2/metabolismo , Microambiente Tumoral/inmunología , Anciano , Antígeno B7-H1/metabolismo , Biomarcadores de Tumor/inmunología , Mama/inmunología , Mama/patología , Mama/cirugía , Neoplasias de la Mama/mortalidad , Neoplasias de la Mama/patología , Neoplasias de la Mama/terapia , Quimioterapia Adyuvante/métodos , Supervivencia sin Enfermedad , Femenino , Estudios de Seguimiento , Humanos , Estimación de Kaplan-Meier , Mastectomía , Persona de Mediana Edad , Paclitaxel/uso terapéutico , Trastuzumab/uso terapéutico , Carga Tumoral/inmunología
12.
Chemistry ; 25(5): 1249-1259, 2019 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-30338571

RESUMEN

The rational design of fluorescent nucleoside analogues is greatly hampered by the lack of a general method to predict their photophysics, a problem that is especially acute when base pairing and stacking change fluorescence. To better understand these effects, a series of tricyclic cytidine (tC and tCO ) analogues ranging from electron-rich to electron-deficient was designed and synthesized. They were then incorporated into oligonucleotides, and photophysical responses to base pairing and stacking were studied. When inserted into double-stranded DNA oligonucleotides, electron-rich analogues exhibit a fluorescence turn-on effect, in contrast with the electron-deficient compounds, which show diminished fluorescence. The magnitude of these fluorescence changes is correlated with the oxidation potential of nearest neighbor nucleobases. Moreover, matched base pairing enhances fluorescence turn-on for the electron-rich compounds, and it causes a fluorescence decrease for the electron-deficient compounds. For the tCO compounds, the emergence of vibrational fine structure in the fluorescence spectra in response to base pairing and stacking was observed, offering a potential new tool for studying nucleic acid structure and dynamics. These results, supported by DFT calculations, help to rationalize fluorescence changes in the base stack and will be useful for selecting the best fluorescent nucleoside analogues for a desired application.

13.
Rep Prog Phys ; 81(3): 036502, 2018 03.
Artículo en Inglés | MEDLINE | ID: mdl-29368693

RESUMEN

For over 70 years, ferroelectric materials have been one of the central research topics for condensed matter physics and material science, an interest driven both by fundamental science and applications. However, ferroelectric surfaces, the key component of ferroelectric films and nanostructures, still present a significant theoretical and even conceptual challenge. Indeed, stability of ferroelectric phase per se necessitates screening of polarization charge. At surfaces, this can lead to coupling between ferroelectric and semiconducting properties of material, or with surface (electro) chemistry, going well beyond classical models applicable for ferroelectric interfaces. In this review, we summarize recent studies of surface-screening phenomena in ferroelectrics. We provide a brief overview of the historical understanding of the physics of ferroelectric surfaces, and existing theoretical models that both introduce screening mechanisms and explore the relationship between screening and relevant aspects of ferroelectric functionalities starting from phase stability itself. Given that the majority of ferroelectrics exist in multiple-domain states, we focus on local studies of screening phenomena using scanning probe microscopy techniques. We discuss recent studies of static and dynamic phenomena on ferroelectric surfaces, as well as phenomena observed under lateral transport, light, chemical, and pressure stimuli. We also note that the need for ionic screening renders polarization switching a coupled physical-electrochemical process and discuss the non-trivial phenomena such as chaotic behavior during domain switching that stem from this.

14.
J Am Chem Soc ; 139(4): 1372-1375, 2017 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-28080035

RESUMEN

Most fluorescent nucleoside analogues are quenched when base stacked and some maintain their brightness, but there has been little progress toward developing nucleoside analogues that markedly increase their fluorescence upon duplex formation. Here, we report on the design and synthesis of a new tricyclic cytidine analogue, 8-diethylamino-tC (8-DEA-tC), that responds to DNA duplex formation with up to a 20-fold increase in fluorescent quantum yield as compared with the free nucleoside, depending on neighboring bases. This turn-on response to duplex formation is the greatest of any reported nucleoside analogue that can participate in Watson-Crick base pairing. Measurements of the quantum yield of 8-DEA-tC mispaired with adenosine and, separately, opposite an abasic site show that there is almost no fluorescence increase without the formation of correct Watson-Crick hydrogen bonds. Kinetic isotope effects from the use of deuterated buffer show that the duplex protects 8-DEA-tC against quenching by excited state proton transfer. These results, supported by DFT calculations, suggest a rationale for the observed photophysical properties that is dependent on duplex integrity and the electronic structure of the analogue.


Asunto(s)
Citidina/análogos & derivados , ADN/química , Fluorescencia , Citidina/química , Enlace de Hidrógeno , Cinética , Conformación de Ácido Nucleico , Teoría Cuántica
15.
Acc Chem Res ; 49(5): 966-73, 2016 05 17.
Artículo en Inglés | MEDLINE | ID: mdl-27149528

RESUMEN

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±Î´/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.


Asunto(s)
Óxidos/química , Catálisis , Estructura Molecular , Propiedades de Superficie
16.
Phys Rev Lett ; 118(9): 097601, 2017 Mar 03.
Artículo en Inglés | MEDLINE | ID: mdl-28306309

RESUMEN

Ferroelectric-dielectric superlattices consisting of alternating layers of ferroelectric PbTiO_{3} and dielectric SrTiO_{3} exhibit a disordered striped nanodomain pattern, with characteristic length scales of 6 nm for the domain periodicity and 30 nm for the in-plane coherence of the domain pattern. Spatial disorder in the domain pattern gives rise to coherent hard x-ray scattering patterns exhibiting intensity speckles. We show here using variable-temperature Bragg-geometry x-ray photon correlation spectroscopy that x-ray scattering patterns from the disordered domains exhibit a continuous temporal decorrelation due to spontaneous domain fluctuations. The temporal decorrelation can be described using a compressed exponential function, consistent with what has been observed in other systems with arrested dynamics. The fluctuation speeds up at higher temperatures and the thermal activation energy estimated from the Arrhenius model is 0.35±0.21 eV. The magnitude of the energy barrier implies that the complicated energy landscape of the domain structures is induced by pinning mechanisms and domain patterns fluctuate via the generation and annihilation of topological defects similar to soft materials such as block copolymers.

17.
Nanotechnology ; 28(9): 095704, 2017 Mar 03.
Artículo en Inglés | MEDLINE | ID: mdl-28135207

RESUMEN

The polarity in ZnO nanowires is an important issue since it strongly affects surface configuration and reactivity, nucleation and growth, electro-optical properties, and nanoscale-engineering device performances. However, measuring statistically the polarity of ZnO nanowire arrays grown by chemical bath deposition and elucidating its correlation with the polarity of the underneath polycrystalline ZnO seed layer grown by the sol-gel process represents a major difficulty. To address that issue, we combine resonant x-ray diffraction (XRD) at Zn K-edge using synchrotron radiation with piezoelectric force microscopy and polarity-sensitive chemical etching to statistically investigate the polarity of more than 107 nano-objects both on the macroscopic and local microscopic scales, respectively. By using high temperature annealing under an argon atmosphere, it is shown that the compact, highly c-axis oriented ZnO seed layer is more than 92% Zn-polar and that only a few small O-polar ZnO grains with an amount less than 8% are formed. Correlatively, the resulting ZnO nanowires are also found to be Zn-polar, indicating that their polarity is transferred from the c-axis oriented ZnO grains acting as nucleation sites in the seed layer. These findings pave the way for the development of new strategies to form unipolar ZnO nanowire arrays as a requirement for a number of nanoscale-engineering devices like piezoelectric nanogenerators. They also highlight the great advantage of resonant XRD as a macroscopic, non-destructive method to simultaneously and statistically measure the polarity of ZnO nanowire arrays and of the underneath ZnO seed layer.

18.
Nano Lett ; 16(1): 534-42, 2016 Jan 13.
Artículo en Inglés | MEDLINE | ID: mdl-26652204

RESUMEN

The field of oxide electronics has benefited from the wide spectrum of functionalities available to the ABO3 perovskites, and researchers are now employing defect engineering in single crystalline heterostructures to tailor properties. However, bulk oxide single crystals are not conducive to many types of applications, particularly those requiring mechanical flexibility. Here, we demonstrate the realization of an all-oxide, single-crystalline nanomembrane heterostructure. With a surface-to-volume ratio of 2 × 10(7), the nanomembranes are fully flexible and can be readily transferred to other materials for handling purposes or for new materials integration schemes. Using in situ synchrotron X-ray scattering, we find that the nanomembranes can bond to other host substrates near room temperature and demonstrate coupling between surface reactivity and electromechanical properties in ferroelectric nanomembrane systems. The synthesis technique described here represents a significant advancement in materials integration and provides a new platform for the development of flexible oxide electronics.

19.
Rep Prog Phys ; 79(7): 076501, 2016 07.
Artículo en Inglés | MEDLINE | ID: mdl-27308889

RESUMEN

The interfaces of polar oxide heterostructures can display electronic properties unique from the oxides they border, as they require screening from either internal or external sources of charge. The screening mechanism depends on a variety of factors, including the band structure at the interface, the presence of point defects or adsorbates, whether or not the oxide is ferroelectric, and whether or not an external field is applied. In this review, we discuss both theoretical and experimental aspects of different screening mechanisms, giving special emphasis to ways in which the mechanism can be altered to provide novel or tunable functionalities. We begin with a theoretical introduction to the problem and highlight recent progress in understanding the impact of point defects on polar interfaces. Different case studies are then discussed, for both the high thickness regime, where interfaces must be screened and each interface can be considered separately, and the low thickness regime, where the degree and nature of screening can be manipulated and the interfaces are close enough to interact. We end with a brief outlook toward new developments in this rapidly progressing field.

20.
Psychol Med ; 45(1): 121-31, 2015 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-25055809

RESUMEN

BACKGROUND: Individuals with major depressive disorder (MDD) are characterized by maladaptive responses to both positive and negative outcomes, which have been linked to localized abnormal activations in cortical and striatal brain regions. However, the exact neural circuitry implicated in such abnormalities remains largely unexplored. METHOD: In this study 26 unmedicated adults with MDD and 29 matched healthy controls (HCs) completed a monetary incentive delay task during functional magnetic resonance imaging (fMRI). Psychophysiological interaction (PPI) analyses probed group differences in connectivity separately in response to positive and negative outcomes (i.e. monetary gains and penalties). RESULTS: Relative to HCs, MDD subjects displayed decreased connectivity between the caudate and dorsal anterior cingulate cortex (dACC) in response to monetary gains, yet increased connectivity between the caudate and a different, more rostral, dACC subregion in response to monetary penalties. Moreover, exploratory analyses of 14 MDD patients who completed a 12-week, double-blind, placebo-controlled clinical trial after the baseline fMRI scans indicated that a more normative pattern of cortico-striatal connectivity pre-treatment was associated with greater improvement in symptoms 12 weeks later. CONCLUSIONS: These results identify the caudate as a region with dissociable incentive-dependent dACC connectivity abnormalities in MDD, and provide initial evidence that cortico-striatal circuitry may play a role in MDD treatment response. Given the role of cortico-striatal circuitry in encoding action-outcome contingencies, such dysregulated connectivity may relate to the prominent disruptions in goal-directed behavior that characterize MDD.


Asunto(s)
Trastorno Depresivo Mayor/fisiopatología , Trastorno Depresivo Mayor/psicología , Adulto , Antidepresivos de Segunda Generación/uso terapéutico , Estudios de Casos y Controles , Citalopram/uso terapéutico , Cuerpo Estriado/fisiopatología , Trastorno Depresivo Mayor/diagnóstico , Trastorno Depresivo Mayor/tratamiento farmacológico , Femenino , Giro del Cíngulo/fisiopatología , Humanos , Imagen por Resonancia Magnética , Masculino , Persona de Mediana Edad , Motivación , Escalas de Valoración Psiquiátrica , Castigo , Análisis de Regresión , S-Adenosilmetionina/uso terapéutico , Resultado del Tratamiento
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