Functional Group Mapping by Electron Beam Vibrational Spectroscopy from Nanoscale Volumes.

Vibrational spectroscopies directly record details of bonding in materials, but spatially resolved methods have been limited to surface techniques for mapping functional groups at the nanoscale. Electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope presents a route to functional group analysis from nanoscale volumes using transmitted subnanometer electron probes. Here, we now use vibrational EELS to map distinct carboxylate and imidazolate linkers in a metal-organic framework (MOF) crystal-glass composite material. Domains <100 nm in size are observed using vibrational EELS, with recorded spatial resolution <15 nm at interfaces in the composite. This nanoscale functional group mapping is confirmed by correlated EELS at core ionization edges as well as X-ray energy dispersive spectroscopy for elemental mapping of the metal centers of the two constituent MOFs. These results present a complete nanoscale analysis of the building blocks of the MOF composite and establish spatially resolved functional group analysis using electron beam spectroscopy for crystalline and amorphous organic and metal-organic solids.

Intracellular Biodegradation of Ag Nanoparticles, Storage in Ferritin, and Protection by a Au Shell for Enhanced Photothermal Therapy.

Despite their highly efficient plasmonic properties, gold nanoparticles are currently preferred to silver nanoparticles for biomedical applications such as photothermal therapy due to their high chemical stability in the biological environment. To confer protection while preserving their plasmonic properties, we allied the advantages of both materials and produced hybrid nanoparticles made of an anisotropic silver nanoplate core coated with a frame of gold. The efficiency of these hybrid nanoparticles (Ag@AuNPs) in photothermia was compared to monometallic silver nanoplates (AgNPs) or gold nanostars (AuNPs). The structural and functional properties of AuNPs, AgNPs, and Ag@AuNPs were investigated in environments of increasing complexity, in water suspensions, in cells, and in tumors in vivo. While AgNPs showed the greatest heating efficiency in suspension (followed by Ag@AuNPs and AuNPs), this trend was reversed intracellularly within a tissue-mimetic model. In this setup, AgNPs failed to provide consistent photothermal conversion over time, due to structural damage induced by the intracellular environment. Remarkably, the degraded Ag was found to be stored within the iron-storage ferritin protein. By contrast, the Au shell provided the Ag@AuNPs with total Ag biopersistence. As a result, photothermal therapy was successful with Ag@AuNPs in vivo in a mouse tumor model, providing the ultimate proof on Au shell's capability to shield the Ag core from the harsh biological environment and preserve its excellent heating properties.

Real-space localization and quantification of hole distribution in chain-ladder Sr3Ca11Cu24O41 superconductor.

Understanding the physical properties of the chain-ladder Sr3Ca11Cu24O41 hole-doped superconductor has been precluded by the unknown hole distribution among chains and ladders. We use electron energy-loss spectrometry (EELS) in a scanning transmission electron microscope (STEM) at atomic resolution to directly separate the contributions of chains and ladders and to unravel the hole distribution from the atomic scale variations of the O-K near-edge structures. The experimental data unambiguously demonstrate that most of the holes lie within the chain layers. A quantitative interpretation supported by inelastic scattering calculations shows that about two holes are located in the ladders, and about four holes in the chains, shedding light on the electronic structure of Sr3Ca11Cu24O41. Combined atomic resolution STEM-EELS and inelastic scattering calculations is demonstrated as a powerful approach toward a quantitative understanding of the electronic structure of cuprate superconductors, offering new possibilities for elucidating their physical properties.

Can magneto-plasmonic nanohybrids efficiently combine photothermia with magnetic hyperthermia?

Multifunctional hybrid-design nanomaterials appear to be a promising route to meet the current therapeutics needs required for efficient cancer treatment. Herein, two efficient heat nano-generators were combined into a multifunctional single nanohybrid (a multi-core iron oxide nanoparticle optimized for magnetic hyperthermia, and a gold branched shell with tunable plasmonic properties in the NIR region, for photothermal therapy) which impressively enhanced heat generation, in suspension or in vivo in tumours, opening up exciting new therapeutic perspectives.

Magnetic nanopantograph in the SrCu2(BO3)2 Shastry-Sutherland lattice.

Magnetic materials having competing, i.e., frustrated, interactions can display magnetism prolific in intricate structures, discrete jumps, plateaus, and exotic spin states with increasing applied magnetic fields. When the associated elastic energy cost is not too expensive, this high potential can be enhanced by the existence of an omnipresent magnetoelastic coupling. Here we report experimental and theoretical evidence of a nonnegligible magnetoelastic coupling in one of these fascinating materials, SrCu2(BO3)2 (SCBO). First, using pulsed-field transversal and longitudinal magnetostriction measurements we show that its physical dimensions, indeed, mimic closely its unusually rich field-induced magnetism. Second, using density functional-based calculations we find that the driving force behind the magnetoelastic coupling is the CuOCu superexchange angle that, due to the orthogonal Cu(2+) dimers acting as pantographs, can shrink significantly (0.44%) with minute (0.01%) variations in the lattice parameters. With this original approach we also find a reduction of ∼ 10% in the intradimer exchange integral J, enough to make predictions for the highly magnetized states and the effects of applied pressure on SCBO.

Detecting non-bridging oxygens: non-resonant inelastic X-ray scattering in crystalline lithium borates.

Probing the local environment of low-Z elements, such as oxygen, is of great interest for understanding the atomic-scale behavior in materials, but it requires experimental techniques allowing it to work with versatile sample environments. In this paper, the local environment of lithium borate crystals is investigated using non-resonant inelastic X-ray scattering (NRIXS) at energy losses corresponding to the oxygen K-edge. Large variations of the spectral features are observed close to the edge onset in the 535-540 eV energy range when varying the Li2O content. Calculations allow identification of contributions associated with bridging oxygen (BO) and non-bridging oxygen (NBO) atoms. The main result resides in the observed core-level shift of about 1.7 eV in the spectral signatures of the BO and NBO. The clear signature at 535 eV in the O K-edge NRXIS spectrum is thus an original way to probe the presence of NBOs in borates, with the great advantage of making possible the use of complex environments such as a high-pressure cell or high-temperature device for in situ measurements.

Bonding and structure of a reconstructed (001) surface of SrTiO3 from TEM.

The determination of the atomic structure and the retrieval of information about reconstruction and bonding of metal oxide surfaces is challenging owing to the highly defective structure and insulating properties of these surfaces. Transmission electron microscopy (TEM) offers extremely high spatial resolution (less than one ångström) and the ability to provide systematic information from both real and reciprocal space. However, very few TEM studies have been carried out on surfaces because the information from the bulk dominates the very weak signals originating from surfaces. Here we report an experimental approach to extract surface information effectively from a thickness series of electron energy-loss spectra containing different weights of surface signals, using a wedge-shaped sample. Using the (001) surface of the technologically important compound strontium titanate, SrTiO(3) (refs 4-6), as a model system for validation, our method shows that surface spectra are sensitive to the atomic reconstruction and indicate bonding and crystal-field changes surrounding the surface Ti cations. Very good agreement can be achieved between the experimental surface spectra and crystal-field multiplet calculations based on the proposed atomic surface structure optimized by density functional calculations. The distorted TiO(6-x) units indicated by the proposed model can be viewed directly in our high-resolution scanning TEM images. We suggest that this approach be used as a general method to extract valuable spectroscopic information from surface atoms in parallel with high-resolution images in TEM.

Three-dimensional atomic structure of metastable nanoclusters in doped semiconductors.

Aberration-corrected scanning transmission electron microscopy is used to determine the atomic structure of nanoclusters of cerium dopant atoms embedded in silicon. By channeling electrons along two crystallographic orientations, we identify a characteristic zinc-blende chemical ordering within CeSi clusters coherent with the silicon host matrix. Strain energy limits the size of these ordered arrangements to just above 1 nm. With the local order identified, we then determine the atomic configuration of an individual subnanometer cluster by quantifying the scattering intensity under weak channeling condition in terms of the number of atoms. Analysis based on single-atom visualization also evidences the presence of split-vacancy impurity complexes, which supports the hypothesis of a vacancy-assisted formation of these metastable CeSi nanophases.

Binary nanoparticle superlattices in the semiconductor-semiconductor system: CdTe and CdSe.

We report binary nanoparticle superlattices obtained by self-assembly of two different semiconductor quantum dots. Such a system is a means to include two discretized, quantum-confined, and complimentary semiconductor units in close proximity, for purposes of band gap matching and/or energy transfer. From a range of possible structures predicted, we observe an exclusive preference for the formation of Cuboctahedral AB13 and AB5 (isostructural with CaCu5) obtained in the system of 8.1 nm CdTe and 4.4 nm CdSe nanoparticles. For this system, a possible ionic origin for the formation of structures with lower packing densities was ruled out on the basis of electrophoretic mobility measurements. To understand further the principles of superlattice formation, we constructed space-filling curves for binary component hard spheres over the full range of radius ratio. In addition, the pair interaction energies due to core-core and ligand-ligand van der Waals (VDW) forces are estimated. The real structures are believed to form under a combined influence of entropic driving forces (following hard-sphere space filling principles) and the surface (due to ligand-ligand VDW).