Shape-memory alloys capable of a superelastic stress-induced phase transformation and a high displacement actuation have promise for applications in micro-electromechanical systems for wearable healthcare and flexible electronic technologies. However, some of the fundamental aspects of their nanoscale behaviour remain unclear, including the question of whether the critical stress for the stress-induced martensitic transformation exhibits a size effect similar to that observed in confined plasticity. Here we provide evidence of a strong size effect on the critical stress that induces such a transformation with a threefold increase in the trigger stress in pillars milled on [001] L2 single crystals from a Cu-Al-Ni shape-memory alloy from 2 μm to 260 nm in diameter. A power-law size dependence of n = -2 is observed for the nanoscale superelasticity. Our observation is supported by the atomic lattice shearing and an elastic model for homogeneous martensite nucleation.
Reticular chemistry has boosted the design of thousands of metal and covalent organic frameworks for unlimited chemical compositions, structures, and sizable porosities. The ability to generate porous materials at will on the basis of geometrical design concepts is responsible for the rapid growth of the field and the increasing number of applications derived. Despite their promising features, the synthesis of targeted homo-and heterometallic titanium−organic frameworks amenable to these principles is relentlessly limited by the high reactivity of this metal in solution that impedes the controlled assembly of titanium molecular clusters. We describe an unprecedented methodology for the synthesis of heterometallic titanium frameworks by metal-exchange reactions of MOF crystals at temperatures below those conventionally used in solvothermal synthesis. The combination of hard (titanium) and soft (calcium) metals in the heterometallic nodes of MUV-10(Ca) enables controlled metal exchange in soft positions for the generation of heterometallic secondary building units (SBUs) with variable nuclearity, controlled by the metal incorporated. The structural information encoded in the newly formed SBUs drives an MOF-to-MOF conversion into bipartite nets compatible with the connectivity of the organic linker originally present in the crystal. Our simulations show that this transformation has a thermodynamic origin and is controlled by the terminations of the (111) surfaces of the crystal. The reaction of MUV-10(Ca) with first-row transition metals permits the production of crystals of Co,Ni,Zn) and MUV-102(Cu), heterometallic titanium MOFs isostructural with archetypical solids such as MIL-100 and HKUST. In comparison to de novo synthesis, this metal-induced topological transformation provides control over the formation of hierarchical micro-/mesopore structures at different reaction times and enables the formation of heterometallic titanium MOFs not accessible under solvothermal conditions at high temperature, thus opening the door for the isolation of additional titanium heterometallic phases not linked exclusively to trimesate linkers.
SiO2 and TiO2 thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO2–Au and TiO2–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO2‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO2 films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.
In the last decade there has been profuse research efforts exploring the uses of iron oxide particles in nanomedicine. To a great extent, the efficiency of magnetic iron oxide nanoparticles for biomedical applications and the nanoparticles fate depend on how the nanoparticle surface interfaces with the proteins in a physiological environment. It is well reported how ungoverned protein corona can be detrimental for cellular uptake and targeting efficiency and how it can modify the nanoparticles biodistribution. Novel strategies are emerging to achieve enhanced and more reproducible performances of engineered nanoparticles with a custom-built protein corona. Here we report on a generalized protocol to preform a monolayer of human serum albumin (HSA) on superparamagnetic iron oxide nanoparticles (SPIONs) of different sizes. The resulting molecular structure is described by molecular dynamics simulations of the hybrid nanoconjugates. The number of proteins forming the corona and their disposition as a monolayer on the particle surface predicted by molecular simulations is in agreement with the results obtained from dynamic light scattering and electronic microscopy analysis. Moreover, by tryptophan fluorescence quenching, we determine a strong interaction between the SPIONs and the HSA endorsing the robustness of the proteinnanoparticles conjugates in this system. Besides, the effect of the HSA corona on the SPIONs efficiency as magnetic resonance imaging (MRI) contrast agents in water, human serum and in saline medium has been evaluated. The protein corona did not affect the efficiency of the SPIONs as T 2 contrast agents but reduce their efficiency as T 1. In addition, we observed a greater stability for HSA-SPIONs nanoconjugates in saline and in acid media preventing nanoparticle dissolution in extreme gastric conditions.
Manipulation of the exciton emission rate in nanocrystals of lead halide perovskites (LHPs) was demonstrated by means of coupling of excitons with a hyperbolic metamaterial (HMM) consisting of alternating thin metal (Ag) and dielectric (LiF) layers. Such a coupling is found to induce an increase of the exciton radiative recombination rate by more than a factor of three due to the Purcell effect when the distance between the quantum emitter and HMM is nominally as small as 10 nm, which coincides well with the results of our theoretical analysis. Besides, an effect of the coupling-induced long wavelength shift of the exciton emission spectrum is detected and modeled. These results can be of interest for quantum information applications of single emitters on the basis of perovskite nanocrystals with high photon emission rates.
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