Abstract: Synthesis protocols for anisotropic CuInX2 (X = S, Se, Te)-based heteronanocrystals (HNCs) are scarce due to the difficulty in balancing the reactivities of multiple precursors and the high solid-state diffusion rates of the cations involved in the CuInX2 lattice. In this work, we report a multistep seeded growth synthesis protocol that yields colloidal wurtzite CuInS2/ZnS dot core/rod shell HNCs with photoluminescence in the NIR (∼800 nm). The wurtzite CuInS2 NCs used as seeds are obtained by topotactic partial Cu+ for In3+ cation exchange in template Cu2–xS NCs. The seed NCs are injected in a hot solution of zinc oleate and hexadecylamine in octadecene, 20 s after the injection of sulfur in octadecene. This results in heteroepitaxial growth of wurtzite ZnS primarily on the Sulfur-terminated polar facet of the CuInS2 seed NCs, the other facets being overcoated only by a thin (∼1 monolayer) shell. The fast (∼21 nm/min) asymmetric axial growth of the nanorod proceeds by addition of [ZnS] monomer units, so that the polarity of the terminal (002) facet is preserved throughout the growth. The delayed injection of the CuInS2 seed NCs is crucial to allow the concentration of [ZnS] monomers to build up, thereby maximizing the anisotropic heteroepitaxial growth rates while minimizing the rates of competing processes (etching, cation exchange, alloying). Nevertheless, a mild etching still occurred, likely prior to the onset of heteroepitaxial overgrowth, shrinking the core size from 5.5 to ∼4 nm. The insights provided by this work open up new possibilities in designing multifunctional Cu-chalcogenide based colloidal heteronanocrystals.

Abstract: Substitutional doping is a potentially powerful technique to control the properties of nanocrystal (NC) superlattices (SLs). However, not every NC can be substituted into any lattice, as the NCs have to be close in size and shape, limiting the application of substitutional doping. Here we show that this limitation can be overcome by employing ligands of various size. We show that small NCs with long ligands can be substituted into SLs of big NCs with short ligands. Furthermore, we show that shape differences can also be overcome and that cubes can substitute spheres when both are coated with long ligands. Finally, we use the NC effective ligand size, softness, and effective overall size ratio to explain observed doping behaviors.

Abstract: By focusing electrons on probes with a diameter of 50 pm, aberration-corrected scanning transmission electron microscopy (STEM) is currently crossing the border to probing subatomic details. A major challenge is the measurement of atomic electric fields using differential phase contrast (DPC) microscopy, traditionally exploiting the concept of a field- induced shift of diffraction patterns. Here we present a simplified quantum theoretical interpretation of DPC. This enables us to calculate the momentum transferred to the STEM probe from diffracted intensities recorded on a pixel array instead of conventional segmented bright- field detectors. The methodical development yielding atomic electric field, charge and electron density is performed using simulations for binary GaN as an ideal model system. We then present a detailed experimental study of SrTiO3 yielding atomic electric fields, validated by comprehensive simulations. With this interpretation and upgraded instrumentation, STEM is capable of quantifying atomic electric fields and high-contrast imaging of light atoms.

Abstract: A sound theoretical rationale for the design of a magnetic nanocarrier capable of magnetic capture in vivo after intravenous administration could help elucidate the parameters necessary for in vivo magnetic tumor targeting. In this work, we utilized our long-circulating polymeric magnetic nano carriers, encapsulating increasing amounts of superparamagnetic iron oxide nanoparticles (SPIONs) in a biocompatible oil carrier, to study the effects of SPION loading and of applied magnetic field strength on magnetic tumor targeting in CT26 tumor-bearing mice. Under controlled conditions, the in vivo magnetic targeting was quantified and found to be directly proportional to SPION loading and magnetic field strength. Highest SPION loading, however, resulted in a reduced blood circulation time and a plateauing of the magnetic targeting. Mathematical modeling was undertaken to compute the in vivo magnetic, viscoelastic, convective, and diffusive forces acting on the nanocapsules (NCs) in accordance with the Nacev-Shapiro construct, and this was then used to extrapolate to the expected behavior in humans. The model predicted that in the latter case, the NCs and magnetic forces applied here would have been sufficient to achieve successful targeting in humans. Lastly, an in vivo murine tumor growth delay study was performed using docetaxel (DTX)-encapsulated NCs. Magnetic targeting was found to offer enhanced therapeutic efficacy, and improve mice survival compared to passive targeting at drug doses of ca. 5-8 mg, of DTX/kg. This is,, to our knowledge, the first study that truly bridges the gap between preclinical experiments and clinical translation in the field of magnetic drug targeting.

Abstract: Hyperbolic polaritons exhibit large photonic density of states and can be collimated in certain propagation directions. The majority of hyperbolic polaritons are sustained in man-made metamaterials. However, natural-occurring hyperbolic materials also exist. Particularly, natural in-plane hyperbolic polaritons in layered materials have been demonstrated in MoO3 and WTe2, which are based on phonon and plasmon resonances respectively. Here, by determining the anisotropic optical conductivity (dielectric function) through optical spectroscopy, we predict that monolayer black phosphorus naturally hosts hyperbolic exciton-polaritons due to the pronounced in-plane anisotropy and strong exciton resonances. We simultaneously observe a strong and sharp ground state exciton peak and weaker excited states in high quality monolayer samples in the reflection spectrum, which enables us to determine the exciton binding energy of similar to 452 meV. Our work provides another appealing platform for the in-plane natural hyperbolic polaritons, which is based on excitons rather than phonons or plasmons.

Abstract: We illustrate the potential of advanced transmission electron microscopy for the characterization of a new class of soft porous materials: metal@Zn4O(bdc)3 (metal@MOF-5; bdc = 1,4-benzenedicarboxylate). By combining several electron microscopy techniques (transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and electron tomography) and by carefully reducing the electron dose to avoid beam damage, it is possible to simultaneously characterize the MOF-5 framework material and the loaded metal nanoparticles. We also demonstrate that electron tomography can be used to accurately determine the position and distribution of the particles within the MOF-5 framework. To demonstrate the implementation of these microscopy techniques and what kind of results can be expected, measurements on gas-phase-loaded metal−organic framework materials Ru@MOF-5 and Pd@MOF-5 are presented.

Abstract: This study aims at sensing in situ reactive oxygen and nitrogen species (RONS) and specifically superoxide anion (O-2(center dot-)) in aqueous buffer solutions exposed to cold atmospheric plasmas (CAPs). CAPs were generated by ionizing He gas shielded with variable N-2/O-2 mixtures. Thanks to ultramicroelectrodes protected against the high electric fields transported by the ionization waves of CAPs, the production of superoxide and several RONS was electrochemically directly detected in liquids during their plasma exposure. Complementarily, optical emissive spectroscopy (OES) was used to study the plasma phase composition and its correlation with the chemistry in the exposed liquid. The specific production of O-2(center dot-), a biologically reactive redox species, was analyzed by cyclic voltammetry (CV), in both alkaline (pH 11), where the species is fairly stable, and physiological (pH 7.4) conditions, where it is unstable. To understand its generation with respect to the plasma chemistry, we varied the shielding gas composition of CAPs to directly impact on the RONS composition at the plasma-liquid interface. We observed that the production and accumulation of RONS in liquids, including O(2)(center dot-)depends on the plasma composition, with N-2-based shieldings providing the highest superoxide concentrations (few 10s of micromolar at most) and of its derivatives (hundreds of micromolar). In situ spectroscopic and electrochemical analyses provide a high resolution kinetic and quantitative understanding of the interactions between CAPs and physiological solutions for biomedical applications.

Abstract: Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)(2)] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)(3)] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)(4)]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.

Abstract: Analysis of the structural parameters of phases that adopt brownmillerite-type structures suggests the distribution of the different complex ordering schemes adopted within this structure type can be rationalized by considering both the size of the separation between the tetrahedral layers and the tetrahedral chain distortion angle. A systematic study using structural data obtained from La1−xAxMnO2,5 (A = Ba, Sr, Ca,) phases, prepared by the topotactic reduction of the analogous La1−xAxMnO3 perovskite phases, was performed to investigate this relationship. By manipulating the A-cation composition, both the tetrahedral layer separation and tetrahedral chain distortion angle in the La1−xAxMnO2,5 phases were controlled and from the data obtained a ¡°structure map¡± of the different brownmillerite variants was plotted as a function of these structural parameters. This map has been extended to include a wide range of reported brownmillerite phases showing the structural ideas presented are widely applicable. The complete structural characterization of La1−xAxMnO2,5 0.1 ¡Ü x ¡Ü 0.33, A = Ba; 0.15 ¡Ü x ¡Ü 0.5 A = Sr, and 0.22 ¡Ü x ¡Ü 0.5 A = Ca is described and includes compositions which exhibit complex intralayer ordered structures and Mn2+/Mn3+ charge ordering.

Abstract: The graphene-metal contact is very important for optimizing the performance of graphene based electronic devices. However, it is difficult to probe the properties of the graphene/metal interface directly via transport measurements in traditional graphene lateral devices, because the dominated transport channel is graphene, not the interface. Here, we employ the Au/graphene/Au vertical and lateral hybrid structure to unveil the metal-graphene interface properties, where the transport is dominated by the charge carriers across the interface. The magnetoresistance (MR) of Au/monolayer graphene/Au and Au/stacked two-layered graphene/Au devices is measured and modulated by gate voltage, demonstrating that the interface is a device. The gate-tunable MR is identified from the graphene lying on the SiO2 substrate and underneath the top metal electrode. Our unique structures couple the in-plane and out-of-plane transport and display linear MR with small amplitude oscillations at low temperatures. Under a magnetic field, the electronic coupling between the graphene edge states and the electrode leads to the appearance of quantum oscillations. Our results not only provide a new pathway to explore the intrinsic transport mechanism at the graphene/metal interface but also open up new vistas of magnetoelectronics.

Abstract: We review the energy spectrum and transport properties of several types of one-dimensional superlattices (SLs) on single-layer and bilayer graphene. In single-layer graphene, for certain SL parameters an electron beam incident on an SL is highly collimated. On the other hand, there are extra Dirac points generated for other SL parameters. Using rectangular barriers allows us to find analytical expressions for the location of new Dirac points in the spectrum and for the renormalization of the electron velocities. The influence of these extra Dirac points on the conductivity is investigated. In the limit of δ-function barriers, the transmission T through and conductance G of a finite number of barriers as well as the energy spectra of SLs are periodic functions of the dimensionless strength P of the barriers, Graphic, with vF the Fermi velocity. For a KronigPenney SL with alternating sign of the height of the barriers, the Dirac point becomes a Dirac line for P = π/2+nπ with n an integer. In bilayer graphene, with an appropriate bias applied to the barriers and wells, we show that several new types of SLs are produced and two of them are similar to type I and type II semiconductor SLs. Similar to single-layer graphene SLs, extra Dirac points are found in bilayer graphene SLs. Non-ballistic transport is also considered.

Abstract: Pb cations in PbS quantum rods made from CdS quantum rods by successive complete cationic exchange reactions are partially re-exchanged for Cd cations. Using STEM-HAADF, we show that this leads to the formation of unique multiple dot-in-rod PbS/CdS heteronanostructures, with a photoluminescence quantum yield of 4555%. We argue that the formation of multiple dot-in-rods is related to the initial polycrystallinity of the PbS quantum rods, where each PbS crystallite transforms in a separate PbS/CdS dot-in-dot. Effective mass modeling indicates that electronic coupling between the different PbS conduction band states is feasible for the multiple dot-in-rod geometries obtained, while the hole states remain largely uncoupled.

Abstract: The aggregation of insoluble amyloid beta (Aβ) peptides in the brain is known to trigger the onset of neurodegenerative diseases, such as Alzheimer’s disease. In spite of the massive number of investigations, the underlying mechanisms to destabilize the Aβ aggregates are still poorly understood. Some studies indicate the importance of oxidation to destabilize the Aβ aggregates. In particular, oxidation induced by cold atmospheric plasma (CAP) has demonstrated promising results in eliminating these toxic aggregates. In this paper, we investigate the effect of oxidation on the stability of an Aβ pentamer. By means of molecular dynamics simulations and umbrella sampling, we elucidate the conformational changes of Aβ pentamer in the presence of oxidized residues, and we estimate the dissociation free energy of the terminal peptide out of the pentamer form. The calculated dissociation free energy of the terminal peptide is also found to decrease with increasing oxidation. This indicates that Aβ pentamer aggregation becomes less favorable upon oxidation. Our study contributes to a better insight in one of the potential mechanisms for inhibition of toxic Aβ peptide aggregation, which is considered to be the main culprit to Alzheimer’s disease.