Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification

Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials.</p

Optical energies of AllnN epilayers

Optical energy gaps are measured for high-quality Al1−xInxN-on-GaN epilayers with a range of compositions around the lattice match point using photoluminescence and photoluminescence excitation spectroscopy. These data are combined with structural data to determine the compositional dependence of emission and absorption energies. The trend indicates a very large bowing parameter of 6 eV and differences with earlier reports are discussed. Very large Stokes' shifts of 0.4-0.8 eV are observed in the composition range 0.13<x<0.24, increasing approximately linearly with InN fraction despite the change of sign of the piezoelectric fiel

A Thalamic Reticular Circuit for Head Direction Cell Tuning and Spatial Navigation.

As we navigate in space, external landmarks and internal information guide our movement. Circuit and synaptic mechanisms that integrate these cues with head-direction (HD) signals remain, however, unclear. We identify an excitatory synaptic projection from the presubiculum (PreS) and the multisensory-associative retrosplenial cortex (RSC) to the anterodorsal thalamic reticular nucleus (TRN), so far classically implied in gating sensory information flow. In vitro, projections to TRN involve AMPA/NMDA-type glutamate receptors that initiate TRN cell burst discharge and feedforward inhibition of anterior thalamic nuclei. In vivo, chemogenetic anterodorsal TRN inhibition modulates PreS/RSC-induced anterior thalamic firing dynamics, broadens the tuning of thalamic HD cells, and leads to preferential use of allo- over egocentric search strategies in the Morris water maze. TRN-dependent thalamic inhibition is thus an integral part of limbic navigational circuits wherein it coordinates external sensory and internal HD signals to regulate the choice of search strategies during spatial navigation

Recent emission channeling studies in wide band gap semiconductors

We present results of recent emission channeling experiments on the lattice location of implanted Fe and rare earths in wurtzite GaN and ZnO. In both cases the majority of implanted atoms are found on substitutional cation sites. The root mean square displacements from the ideal substitutional Ga and Zn sites are given and the stability of the Fe and rare earth lattice location against thermal annealing is discussed

Influence of O and C co-implantation on the lattice site of Er in GaN

The lattice location of low-dose implanted Er in GaN, GaN:O, and GaN:C was investigated using the emission channeling technique. The conversion electrons emitted by the probe isotope $^{167m}$Er give direct evidence that the majority (~90%) of Er atoms are located on substitutional Ga sites for all samples. Annealing up to 900 °C does not change these fractions, although it reduces the Er root-mean-square (rms) displacements. The only visible effect of oxygen or carbon doping is a small increase in the rms displacements with respect to the undoped sample

Formation of ultrathin Ni germanides : solid-phase reaction, morphology and texture

The solid-phase reaction of ultrathin (<= 10 nm) Ni films with different Ge substrates (single-crystalline (100), polycrystalline, and amorphous) was studied. As thickness goes down, thin film texture becomes a dominant factor in both the film's phase formation and morphological evolution. As a consequence, certain metastable microstructures are epitaxially stabilized on crystalline substrates, such as the epsilon-Ni5Ge3 phase or a strained NiGe crystal structure on the single-crystalline substrates. Similarly, the destabilizing effect of axiotaxial texture on the film's morphology becomes more pronounced as film thicknesses become smaller. These effects are contrasted by the evolution of germanide films on amorphous substrates, on which neither epitaxy nor axiotaxy can form, i.e. none of the (de) stabilizing effects of texture are observed. The crystallization of such amorphous substrates however, drives the film breakup

Stability studies of Hg implanted YBa2_{2}Cu3_{3}O6+x_{6+x}

High quality YBa$_{2}$Cu$_{3}$O$_{6+x}$ (YBCO) superconducting thin films were implanted with the radioactive $^{197m}$Hg (T$_{1/2}$ = 24 h) isotope to low fluences of 10$^{13}$ atoms/cm$^{2}$ and 60 keV energy. The lattice location and stability of the implanted Hg were studied combining the Perturbed Angular Correlation (PAC) and Emission Channeling (EC) techniques. We show that Hg can be introduced into the YBCO lattice by ion implantation into unique regular sites. The EC data show that Hg is located on a highly symmetric site on the YBCO lattice, while the PAC data suggests that Hg occupies the Cu(1) site. Annealing studies were performed under vacuum and O$_{2}$ atmosphere and show that Hg starts to diffuse only above 653 K

Stability and diffusion of Hg implanted YBa2_{2}Cu3_{3}O6+x_{6+x}

The radioactive isotope $^{197m}$Hg was implanted at 60 keV with low fluences (10$^{13}$ ions/cm$^{2}$ ) into YBa$_{2}$Cu$_{3}$O$_{6+x}$ (YBCO) superconducting thin films at ISOLDE/CERN. We report on the Hg dynamics and stability inside the YBCO lattice as a function of annealing temperature up to 890 K in vacuum or O$_{2}$ atmosphere. The perturbed angular correlation (PAC) technique was used for probing the Hg behavior at the atomic scale, while by monitoring the sample's activity in situ the Hg outdiffusion was studied. We found that Hg ions occupy unique lattice sites and that Hg should be bound to two apical oxygens. Hg diffusion occurs only for annealing temperatures above 653 K, in vacuum. The Hg migration energy was estimated to be EM = 1.58 $\pm$ 0.15 eV

Damage and strain in epitaxial GexSi1–x films irradiated with Si

The damage and strain induced by irradiation of both relaxed and pseudomorphic GexSi1–x films on Si(100) with 100 keV 28Si ions at room temperature have been studied by MeV 4He channeling spectrometry and x-ray double-crystal diffractometry. The ion energy was chosen to confine the major damage to the films. The results are compared with experiments for room temprature Si irradiation of Si(100) and Ge(100). The maximum relative damage created in low-Ge content films studied here (x=10%, 13%, 15%, 20%, and 22%) is considerably higher than the values obtained by interpolating between the results for relative damage in Si-irradiated single crystal Si and Ge. This, together with other facts, indicates that a relatively small fraction of Ge in Si has a significant stabilizing effect on the retained damage generated by room-temperature irradiation with Si ions. The damage induced by irradiation produces positive perpendicular strain in GexSi1–x, which superimposes on the intrinsic positive perpendicular strain of the pseudomorphic or partially relaxed films. In all of the cases studied here, the induced maximum perpendicular strain and the maximum relative damage initially increase slowly with the dose, but start to rise at an accelerated rate above a threshold value of ~0.15% and 15%, respectively, until the samples are amorphized. The pre-existing pseudomorphic strain in the GexSi1–x film does not significantly influence the maximum relative damage created by Si ion irradiation for all doses and x values. The relationship between the induced maximum perpendicular strain and the maximum relative damage differs from that found in bulk Si(100) and Ge(100)