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1.
Nano Lett ; 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-39405088

RESUMEN

Copper (Cu) has been considered as the most promising catalyst for the electrochemical conversion of CO2 to multicarbon (C2+) products. However, insufficient coverage of the *CO intermediate on the C2+ formation Cu(100) facet largely hinders the C-C coupling process and thus the C2+ conversion efficiency. Herein, we developed an epitaxial growth strategy to generate highly tensile-strained Cu(100) facets via the epitaxial growth of hexagonal boron nitride (hBN) on Cu(100) facets to promote *CO coverage for efficient CO2 to C2+ conversion. The highest ∼6% tensile strain on the Cu(100) facets was obtained by lattice mismatch between the Cu(100) and hBN(002) facets. Theory calculations indicated that tensile-strained Cu(100) facets deliver a notable d-band center upshift to enhance *CO adsorption. As a result, the obtained highly tensile-strained Cu(100) facets enabled an 8-fold improvement of *CO coverage and thus a 83.4% C2+ Faradaic efficiency at 1.2 A cm-2 in strongly acidic electrolyte (pH = 1).

2.
Int J Mol Sci ; 25(19)2024 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-39408788

RESUMEN

ß-amyloid (Aß) peptides form self-organizing fibrils in Alzheimer's disease. The biologically active, toxic Aß25-35 fragment of the full-length Aß-peptide forms a stable, oriented filament network on the mica surface with an epitaxial mechanism at the timescale of seconds. While many of the structural and dynamic features of the oriented Aß25-35 fibrils have been investigated before, the ß-strand arrangement of the fibrils and their exact orientation with respect to the mica lattice remained unknown. By using high-resolution atomic force microscopy, here, we show that the Aß25-35 fibrils are oriented along the long diagonal of the oxygen hexagon of mica. To test the structure and stability of the oriented fibrils further, we carried out molecular dynamics simulations on model ß-sheets. The models included the mica surface and a single fibril motif built from ß-strands. We show that a sheet with parallel ß-strands binds to the mica surface with its positively charged groups, but the C-terminals of the strands orient upward. In contrast, the model with antiparallel strands preserves its parallel orientation with the surface in the molecular dynamics simulation, suggesting that this model describes the first ß-sheet layer of the mica-bound Aß25-35 fibrils well. These results pave the way toward nanotechnological construction and applications for the designed amyloid peptides.


Asunto(s)
Silicatos de Aluminio , Péptidos beta-Amiloides , Microscopía de Fuerza Atómica , Simulación de Dinámica Molecular , Fragmentos de Péptidos , Péptidos beta-Amiloides/química , Péptidos beta-Amiloides/metabolismo , Silicatos de Aluminio/química , Fragmentos de Péptidos/química , Fragmentos de Péptidos/metabolismo , Amiloide/química , Humanos , Conformación Proteica en Lámina beta
3.
Nano Lett ; 2024 Oct 02.
Artículo en Inglés | MEDLINE | ID: mdl-39356826

RESUMEN

Monocrystalline chalcogenide thin films in freestanding forms are very much needed in advanced electronics such as flexible phase change memories (PCMs). However, they are difficult to manufacture in a scalable manner due to their growth and delamination challenges. Herein, we report a viable strategy for a wafer-scale epitaxial growth of monocrystalline germanium telluride (GeTe) membranes and their deterministic integrations onto flexible substrates. GeTe films are epitaxially grown on Ge wafers via a tellurization reaction accompanying a formation of confined dislocations along GeTe/Ge interfaces. The as-grown films are subsequently delaminated off the wafers, preserving their wafer-scale structural integrity, enabled by a strain-engineered spalling method that leverages the stress-concentrated dislocations. The versatility of this wafer epitaxy and delamination approach is further expanded to manufacture other chalcogenide membranes, such as germanium selenide (GeSe). These materials exhibit phase change-driven electrical switching characteristics even in freestanding forms, opening up unprecedented opportunities for flexible PCM technologies.

4.
ACS Nano ; 2024 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-39417602

RESUMEN

The p-n junction, a widely studied semiconductor material structure, offers only limited improvements in photoelectrochemical (PEC) efficiency. Herein, a three-dimensional (3D) p-n junction h-Ta3N5@CoN featuring a stable chestnut shell hollow sphere structure and photothermal effect was synthesized by using an epitaxial growth strategy. The fine fibers within the sphere induce Rayleigh scattering, which scatters unabsorbed light, thereby enabling secondary absorption and enhancing light utilization. The quantum confinement effects generated by CoN fine fibers, which are sized in a few nanometers, inhibit the recombination of electron-hole pairs. Moreover, the lattice matching between Ta3N5 and CoN allows for smoother movement of carriers and nonradiative relaxation phonons along the lattice, thereby enhancing the transport of both carriers and heat. The obtained h-Ta3N5@CoN/FTO p-n junction photoanode, under near-infrared (NIR) auxiliary irradiation, demonstrates a photocurrent of 8.71 mA cm-2 at 1.23 VRHE. Moreover, the h-Ta3N5@CoN+NIR/FTO photoanode can sustain operation for 168 h, which, to my knowledge, surpasses the operational durations of all other Ta3N5-based photoanodes. This study synthesizes three-dimensional hollow chestnut shell photothermal p-n heterojunctions through an epitaxial growth strategy, endowing the material with a more efficient carrier separation and photothermal transfer efficiency.

5.
Artículo en Inglés | MEDLINE | ID: mdl-39455411

RESUMEN

Epitaxially grown lanthanide metal-organic frameworks (Ln MOFs) exhibit multicolor and characteristic Ln emission with sharp emission bands, which are of great value in the field of information security and anti-counterfeiting. Epitaxial growth of Ln MOFs is generally achieved by solvothermal or hydrothermal methods, which suffer from challenges such as high reaction temperature and long growth time. Here, we report the fast epitaxial growth of multicolor lanthanide MOFs by an ultrasonic method at room temperature. The TbSmSQ shows a core-shell type structure with the Tb ion in the core and Sm in the shell within one crystal and exhibits the characteristic emission lines of Tb and Sm, respectively. The nonporous structure and large distance between lanthanide ions effectively avoid the influence of solvent vapor on the intensity and color of luminescence emission. Its application as photonic barcodes has been studied. This work demonstrates the feasibility of epitaxial growth of multicolor Ln MOFs by the ultrasonic method and its value for anti-counterfeiting and information security applications.

6.
Artículo en Inglés | MEDLINE | ID: mdl-39431596

RESUMEN

Lead halide perovskite single crystals (LHPSC) are promising for room-temperature γ-ray spectroscopy in radiation detection. While MA(CH3NH3)-based LHPSCs are the most straightforward and cost-effective to synthesize from solution, their performance in γ-ray spectroscopy is hindered by significant noise and ion migration at high bias, which degrades their energy resolution (ER). The work introduced an n-type/intrinsic/n-type photodiode incorporating passivation layers of MA-based LHPSCs, grown through solution-process epitaxial growth. This single-polarity device demonstrated an outstanding ER of 3.6% for 662 keV γ-ray photons. Overall, this work provides useful information for developing room-temperature γ-ray detectors based on solution-processed lead halide perovskites.

7.
ACS Nano ; 2024 Sep 12.
Artículo en Inglés | MEDLINE | ID: mdl-39263972

RESUMEN

The epitaxial growth of wafer-scale two-dimensional (2D) semiconducting transition metal dichalcogenides (STMDCs) single crystals is the key premise for their applications in next-generation electronics. Despite significant advancements, some fundamental factors affecting the epitaxy growth have not been fully uncovered, e.g., interface coupling strength, adlayer-substrate lattice matching, substrate step-edge-guiding effects, etc. Herein, we develop a model system to tackle these issues concurrently, and realize the epitaxial growth of wafer-scale monolayer tungsten disulfide (WS2) single crystals on the Au(111) substrate. This epitaxial system is featured with good adlayer-substrate lattice matching, obvious step-edge-guiding effect for the unidirectionally aligned nucleation/growth, and relatively weaker interfacial interaction than that of monolayer MoS2/Au(111), as evidenced by the evolution of a uniform Moiré pattern and an intrinsic band gap, according to on-site scanning tunneling microscopy/spectroscopy (STM/STS) characterizations and density functional theory calculations. Intriguingly, the unidirectionally aligned monolayer WS2 domains along the Au(111) steps can behave as ultrasensitive templates for surface-enhanced Raman scattering detection of organic molecules, due to the obvious charge transfer occurred at substrate step edges. This work should hereby deepen our understanding of the epitaxy mechanism of 2D STMDCs on single-crystal substrates, and propel their wafer-scale production and applications in various cutting-edge fields.

8.
Materials (Basel) ; 17(17)2024 Aug 28.
Artículo en Inglés | MEDLINE | ID: mdl-39274651

RESUMEN

Beta-phase gallium oxide (ß-Ga2O3) is a cutting-edge ultrawide bandgap (UWBG) semiconductor, featuring a bandgap energy of around 4.8 eV and a highly critical electric field strength of about 8 MV/cm. These properties make it highly suitable for next-generation power electronics and deep ultraviolet optoelectronics. Key advantages of ß-Ga2O3 include the availability of large-size single-crystal bulk native substrates produced from melt and the precise control of n-type doping during both bulk growth and thin-film epitaxy. A comprehensive understanding of the fundamental growth processes, control parameters, and underlying mechanisms is essential to enable scalable manufacturing of high-performance epitaxial structures. This review highlights recent advancements in the epitaxial growth of ß-Ga2O3 through various techniques, including Molecular Beam Epitaxy (MBE), Metal-Organic Chemical Vapor Deposition (MOCVD), Hydride Vapor Phase Epitaxy (HVPE), Mist Chemical Vapor Deposition (Mist CVD), Pulsed Laser Deposition (PLD), and Low-Pressure Chemical Vapor Deposition (LPCVD). This review concentrates on the progress of Ga2O3 growth in achieving high growth rates, low defect densities, excellent crystalline quality, and high carrier mobilities through different approaches. It aims to advance the development of device-grade epitaxial Ga2O3 thin films and serves as a crucial resource for researchers and engineers focused on UWBG semiconductors and the future of power electronics.

9.
Angew Chem Int Ed Engl ; 63(40): e202405132, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-39223903

RESUMEN

By integrating TiO2 with rare earth upconversion nanocrystals (NaREF4), efficient energy transfer can be achieved between the two subunits under near-infrared (NIR) excitation, which hold tremendous potential in the fields of photocatalysis, photodynamic therapy (PDT), etc. However, in the previous studies, the combination of TiO2 with NaREF4 is a non-epitaxial random blending mode, resulting in a diminished energy transfer efficiency between the NaREF4 and TiO2. Herein, we present a fluorine doping-mediated epitaxial growth strategy for the synthesis of TiO2-NaREF4 heteronanocrystals (HNCs). Due to the epitaxial growth connection, NaREF4 can transfer energy through phonon-assisted pathway to TiO2, which is more efficient than the traditional indirect secondary photon excitation. Additionally, F doping brings oxygen vacancies in the TiO2 subunit, which further introduces new impurity energy levels in the intrinsic band gap of TiO2 subunit, and facilitates the energy transfer through phonon-assisted method from NaREF4 to TiO2. As a proof of concept, TiO2-NaGdF4 : Yb,Tm@NaYF4@NaGdF4 : Nd@NaYF4 HNCs were rationally constructed. Taking advantage of the dual-model up- and downconversion luminescence of the delicately designed multi-shell structured NaREF4 subunit, highly efficient photo-response capability of the F-doped TiO2 subunit and the efficient phonon-assisted energy transfer between them, the prepared HNCs provide a distinctive nanoplatform for bioimaging-guided NIR-triggered PDT.


Asunto(s)
Flúor , Rayos Infrarrojos , Fotoquimioterapia , Titanio , Titanio/química , Flúor/química , Humanos , Nanopartículas/química , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/síntesis química , Imagen Óptica , Gadolinio/química , Animales , Fluoruros
10.
ACS Nano ; 18(34): 22958-22964, 2024 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-39136292

RESUMEN

Artificial two-dimensional (2D) moiré superlattices provide a platform for generating exotic quantum matter or phenomena. Here, an epitaxial heterostructure composed of bilayer Bi(111) and an Fe3GeTe2 substrate with a zero-twist angle is acquired by molecular beam epitaxy. Scanning tunneling microscopy and spectroscopy studies reveal the spatially tailored Kondo resonance and interfacial magnetism within this moiré superlattice. Combined with first-principles calculations, it is found that the modulation effect of the moiré superlattice originates from the interfacial orbital hybridization between Bi and Fe atoms. Our work provides a tunable platform for strong electron correlation studies to explore 2D artificial heavy Fermion systems and interface magnetism.

11.
J Phys Condens Matter ; 36(46)2024 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-39111342

RESUMEN

The final structure and properties of layers grown by epitaxy techniques are determined in the very early stage of the process. This review describes one-dimensional models for epitaxial growth, emphasizing the basic theoretical concepts employed to analyze nucleation and aggregation phenomena in the submonolayer regime. The main findings regarding the evolution of quantities that define the properties of the system, such as monomer and island densities, and the associated island size, gap length, and capture zone distributions are discussed, as well as the analytical tools used to evaluate them. This review provides a concise overview of the most widely used algorithms for simulating growth processes, discusses relevant experimental results, and establishes connections with existing theoretical studies.

12.
Small ; : e2405322, 2024 Aug 18.
Artículo en Inglés | MEDLINE | ID: mdl-39155418

RESUMEN

Anode materials for sodium ion batteries (SIBs) are confronted with severe volume expansion and poor electrical conductivity. Construction of assembled structures featuring hollow interior and carbon material modification is considered as an efficient strategy to address the issues. Herein, a novel template-assisted epitaxial growth method, ingeniously exploiting lattice matching nature, is developed to fabricate hollow ordered architectures assembled by SnO2 nanorods. SnO2 nanorods growing along [100] direction can achieve lattice-matched epitaxial growth on (110) plane of α-Fe2O3. Driven by the lattice matching, different α-Fe2O3 templates possessing different crystal plane orientations enable distinct assembly modes of SnO2, and four kinds of hollow ordered SnO2@C nanorods arrays (HONAs) with different morphologies including disc, hexahedron, dodecahedron and tetrakaidecahedron (denoted as Di-, He-, Do-, and Te-SnO2@C) are achieved. Benefiting from the synergy of hollow structure, carbon coating and ordered assembly structure, good structural integrity and stability and enhanced electrical conductivity are realized, resulting in impressive sodium storage performances when utilized as SIB anodes. Specifically, Te-SnO2@C HONAs exhibit excellent rate capability (385.6 mAh·g-1 at 2.0 A·g-1) and remarkable cycling stability (355.4 mAh·g-1 after 2000 cycles at 1.0 A·g-1). This work provides a promising route for constructing advanced SIB anode materials through epitaxial growth for rational structural design.

13.
Nanomaterials (Basel) ; 14(15)2024 Jul 25.
Artículo en Inglés | MEDLINE | ID: mdl-39120353

RESUMEN

Morphology plays a crucial role in defining the optical, electronic, and mechanical properties of halide perovskite microcrystals. Therefore, developing strategies that offer precise control over crystal morphology during the growth process is highly desirable. This work presents a simple scheme to simultaneously grow distinct geometries of cesium lead bromide (CsPbBr3) microcrystals, including microrods (MR), microplates (MP), and microspheres (MS), in a single chemical vapor deposition (CVD) experiment. By strategically adjusting precursor evaporation temperatures, flux density, and the substrate temperature, we surpass previous techniques by achieving simultaneous yet selective growth of multiple CsPbBr3 geometries at distinct positions on the same substrate. This fine growth control is attributed to the synergistic variation in fluid flow dynamics, precursor substrate distance, and temperature across the substrate, offering regions suitable for the growth of different morphologies. Pertinently, perovskite MR are grown at the top, while MP and MS are observed at the center and bottom regions of the substrate, respectively. Structural analysis reveals high crystallinity and an orthorhombic phase of the as-grown perovskite microcrystals, while persistent photonic lasing manifests their nonlinear optical characteristics, underpinning their potential application for next-generation photonic and optoelectronic devices.

14.
Molecules ; 29(13)2024 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-38999114

RESUMEN

Molecular beam epitaxy (MBE) is a powerful tool in modern technologies, including electronic, optoelectronic, spintronic, and sensoric applications. The primary factor determining epitaxial heterostructure properties is the growth mode and the resulting atomic structure and microstructure. In this paper, we present a novel method for growing epitaxial layers and nanostructures with specific and optimized structural and magnetic properties by assisting the MBE process using electromagnetic and mechanical external stimuli: an electric field (EF), a magnetic field (MF), and a strain field (SF). The transmission of the external fields to the sample is realized using a system of specialized sample holders, advanced transfers, and dedicated manipulators. Examples of applications include the influence of MFs on the growth and anisotropy of epitaxial magnetite and iron films, the use of EFs for in situ resistivity measurements, the realization of in situ magneto-optic measurements, and the application of SFs to the structural modification of metal films on mica.

15.
Nano Lett ; 24(29): 8887-8893, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-38984749

RESUMEN

The synthesis of transition metal nitrides nanocrystals (TMNs NCs) has posed a significant challenge due to the limited reactivity of nitrogen sources at lower temperatures and the scarcity of available synthesis methods. In this study, we present a novel colloidal synthesis strategy for the fabrication of Cu3N nanorods (NRs). It is found that the trace oxygen (O2) plays an important role in the synthesis process. And a new mechanism for the formation of Cu3N is proposed. Subsequently, by employing secondary lateral epitaxial growth, the Cu3N-Cu2O heteronanostructures (HNs) can be prepared. The Cu3N NRs and Cu3N-Cu2O HNs were evaluated as precursor electrocatalysts for the CO2 reduction reaction (CO2RR). The Cu3N-Cu2O HNs demonstrate remarkable selectivity and stability with ethylene (C2H4) Faradaic efficiency (FE) up to 55.3%, surpassing that of Cu3N NRs. This study provides innovative insights into the reaction mechanism of colloidal synthesis of TMNs NCs and presents alternative options for designing cost-effective electrocatalysts to achieve carbon neutrality.

16.
J Colloid Interface Sci ; 675: 721-730, 2024 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-38996702

RESUMEN

The lack of compactness in heterojunction interfaces and poor charge separation is a great challenge in developing high-efficiency heterojunction photocatalysts. Herein, a novel Bi4Ti3O12-BiPO4 heterojunction was successfully prepared for the first time by epitaxial growth of BiPO4 on the surface of Bi4Ti3O12 nanosheets. The optimized Bi4Ti3O12-BiPO4-0.5 increased the NO oxidation efficiency to 73.05%, surpassing pure Bi4Ti3O12 (63.45%) and BiPO4 (8.35%). Experiments and theoretical calculations indicated that the closely contacted heterointerface between BTO and BPO promoted the generation of the built-in electric field, which led to the formation of the Z- scheme transfer pathway for the photogenerated carriers. Therefore, the separation of photogenerated carriers was facilitated while retaining high redox potential, generating more ·O2- and ·OH to participate in NO oxidation. Furthermore, the adsorption of NO and O2 was enhanced by introducing BiPO4, further improving the photocatalytic NO oxidation performance. This work emphasizes the critical role of heterointerface in accelerating charge transfer, providing a basis for the design and construction of tightly contacted heterojunction photocatalysts.

17.
ACS Nano ; 18(26): 17282-17292, 2024 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-38904992

RESUMEN

Epitaxial growth stands as a key method for integrating semiconductors into heterostructures, offering a potent avenue to explore the electronic and optoelectronic characteristics of cutting-edge materials, such as transition metal dichalcogenide (TMD) and perovskites. Nevertheless, the layer-by-layer growth atop TMD materials confronts a substantial energy barrier, impeding the adsorption and nucleation of perovskite atoms on the 2D surface. Here, we epitaxially grown an inorganic lead-free perovskite on TMD and formed van der Waals (vdW) heterojunctions. Our work employs a monomolecular membrane-assisted growth strategy that reduces the contact angle and simultaneously diminishing the energy barrier for Cs3Sb2Br9 surface nucleation. By controlling the nucleation temperature, we achieved a reduction in the thickness of the Cs3Sb2Br9 epitaxial layer from 30 to approximately 4 nm. In the realm of inorganic lead-free perovskite and TMD heterojunctions, we observed long-lived interlayer exciton of 9.9 ns, approximately 36 times longer than the intralayer exciton lifetime, which benefited from the excellent interlayer coupling brought by direct epitaxial growth. Our research introduces a monomolecular membrane-assisted growth strategy that expands the diversity of materials attainable through vdW epitaxial growth, potentially contributing to future applications in optoelectronics involving heterojunctions.

18.
Angew Chem Int Ed Engl ; 63(29): e202405878, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38713005

RESUMEN

Lattice mismatch significantly influences microscopic transport in semiconducting devices, affecting interfacial charge behavior and device efficacy. This atomic-level disordering, often overlooked in previous research, is crucial for device efficiency and lifetime. Recent studies have highlighted emerging challenges related to lattice mismatch in perovskite solar cells, especially at heterojunctions, revealing issues like severe tensile stress, increased ion migration, and reduced carrier mobility. This review systematically discusses the effects of lattice mismatch on strain, material stability, and carrier dynamics. It also includes detailed characterizations of these phenomena and summarizes current strategies including epitaxial growth and buffer layer, as well as explores future solutions to mitigate mismatch-induced issues. We also provide the challenges and prospects for lattice mismatch, aiming to enhance the efficiency and stability of perovskite solar cells, and contribute to renewable energy technology advancements.

19.
J Phys Condens Matter ; 36(34)2024 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-38813672

RESUMEN

Single-crystal magnetic nanostructures with well-defined shapes attract lots of interest due to their potential applications in magnetic and spintronic devices. However, development of methods allowing controlling their mutual crystallographic and geometric orientation constitutes a significant scientific challenge. One of the routes for obtaining such structures is to grow the materials epitaxially on naturally-structured supports, such as vicinal surfaces of single-crystal substrates. Iron oxides are among the most well-known magnetic materials which, depending on the phase, may exhibit ferro/ferri- or antiferromagnetic ordering. We have grown iron oxide nanowires on a Cu(410) single-crystal substrate faceted with molecular oxygen. Scanning tunneling microscopy and low energy electron diffraction revealed that the oxide grows in the [111] direction, along the step edges of the substrate and rotated by ±15° with respect to the [010] direction of copper atomic terraces (so that the the growing elongated structures are orientated parallel to each other). Notably, x-ray photoelectron spectroscopy confirmed that the nanowires represent the ferrimagneticγ-Fe2O3(maghemite) iron oxide phase, while micromagnetic simulations indicated that the wires are single-domain, with the easy magnetization axis orientated in-plane and along the long axis of the wire.

20.
Adv Mater ; 36(30): e2402855, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38683952

RESUMEN

Large-scale, high-quality, and uniform monolayer molybdenum disulfide (MoS2) films are crucial for their applications in next-generation electronics and optoelectronics. Epitaxy is a mainstream technique for achieving high-quality MoS2 films and is demonstrated at a wafer scale up to 4-in. In this study, the epitaxial growth of 8-in. wafer-scale highly oriented monolayer MoS2 on sapphire is reported as with excellent spatial homogeneity, using a specially designed vertical chemical vapor deposition (VCVD) system. Field effect transistors (FETs) based on the as-grown 8-in. wafer-scale monolayer MoS2 film are fabricated and exhibit high performances, with an average mobility and an on/off ratio of 53.5 cm2 V-1 s-1 and 107, respectively. In addition, batch fabrication of logic devices and 11-stage ring oscillators are also demonstrated, showcasing excellent electrical functions. This work may pave the way of MoS2 in practical industry-scale applications.

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