Strongly confined quantum wire states in strained T-shaped GaAs/InAlAs structures

The confinement energy of T-shaped quantum wires (QWRs), which were fabricated by the cleaved edge overgrowth technique in a way that the QWRs form at the intersection of In_0.2Al_0.8As stressor layers and the overgrown (1 1 0) GaAs quantum well (QW), is examined using micro-photoluminescence spectroscopy. Photoluminescence (PL) signals from individual QWRs can be spatially resolved, since the strained films are separated by 1 μm wide Al_0.3Ga_0.7As layers. We find that due to the tensile strain being transmitted to the QW, the confinement energy of the QWRs rises systematically up to 40 meV with increasing thickness of the stressor layers. By reducing the excitation power to 0.1 μW the QWR PL emission occurs 48 meV redshifted with respect to the QW. All QWR peaks exhibit smooth lineshapes, indicating the absence of pronounced exciton localization.     

Electrical detection of coherent nuclear spin oscillations in phosphorus-doped silicon using pulsed ENDOR

We demonstrate the electrical detection of pulsed X-band electron nuclear double resonance (ENDOR) in phosphorus-doped silicon at 5 K. A pulse sequence analogous to Davies ENDOR in conventional electron spin resonance is used to measure the nuclear spin transition frequencies of the (31)P nuclear spins, where the (31)P electron spins are detected electrically via spin-dependent transitions through Si/SiO(2) interface states, thus not relying on a polarization of the electron spin system. In addition, the electrical detection of coherent nuclear spin oscillations is shown, demonstrating the feasibility to electrically read out the spin states of possible nuclear spin qubits.     

Sustainable challenges on the moon

For a permanently manned outpost on the moon – a moon village – a first holistic concept of a sustainable material flow has been established. From this context three dedicated topics have been investigated to more depth: Additive manufacturing (AM) of Al from disused space crafts, AM of structural elements with local resources, and resource extraction from regolith via thermal processes.     

Isomerizing Olefin Metathesis

Isomerizing olefin metathesis is currently undergoing a transformation from laboratory curiosity to powerful synthetic concept at the heart of orthogonal tandem catalysis. In this process, an isomerization catalyst continuously moves double bonds along carbon chains, while a metathesis catalyst scrambles the residues at the C−C double bonds. This cooperative action of two catalysts can be used to access single, defined products from a complex mixture of compounds. Alternatively, it enables the transformation of uniform starting materials into complex product blends with defined, tunable properties. This concept article highlights recent developments and potential applications of this fascinating reaction concept.     

Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

NMR offers many possibilities in chemical analysis, structural investigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity. Hyperpolarization techniques enhance NMR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the para-hydrogen's singlet state to create enhanced signals is of particular interest since it allows to produce molecular imaging agents within seconds. Herein, we present a strategy for signal enhancement of the carbonyl ¹³C in amino acids by using parahydrogen, as demonstrated for glycine and alanine. Importantly, the hyperpolarization step is carried out in water and chemically unmodified canonical amino acids are obtained. Our approach thus offers a high degree of biocompatibility, which is crucial for further application. The rapid sample hyperpolarization (within seconds) may enable the continuous production of biologically useful probes, such as metabolic contrast agents or probes for structural biology.     

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

The interplay between the self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room-temperature deposition of HATP onto pristine Cu(111), self-assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π–d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal–organic trimer, in which three HATP molecules were coordinated by Cu₃ clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)–Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal–organic bonds.     

High Blocking Temperature of Magnetization and Giant Coercivity in the Azafullerene Tb2@C79N with a Single‐Electron Terbium–Terbium Bond

The azafullerene Tb₂@C₇₉N is found to be a single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb?Tb bond. Relaxation of magnetization in Tb₂@C₇₉N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τ_QTM=16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped.     

Dextramabs: A Novel Format of Antibody-Drug Conjugates Featuring a Multivalent Polysaccharide Scaffold

Antibody-drug conjugates (ADCs) are multicomponent biomolecules that have emerged as a powerful tool for targeted tumor therapy. Combining specific binding of an immunoglobulin with toxic properties of a payload, they however often suffer from poor hydrophilicity when loaded with a high amount of toxins. To address these issues simultaneously, we developed dextramabs, a novel class of hybrid antibody-drug conjugates. In these architectures, the therapeutic antibody trastuzumab is equipped with a multivalent dextran polysaccharide that enables efficient loading with a potent toxin in a controllable fashion. Our modular chemoenzymatic approach provides an access to synthetic dextramabs bearing monomethyl auristatin as releasable cytotoxic cargo. They possess high drug-to-antibody ratios, remarkable hydrophilicity, and high toxicity in vitro.     

1,2,5,6-Tetrakis(guanidino)-Naphthalenes: Electron Donors,Fluorescent Probes and Redox-Active Ligands

New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps.