Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

A cost-scaling algorithm for minimum-cost node-capacitated multiflow problem

Mathematical Programming - Many practical integer programming problems involve variables with one or two-sided bounds. Dunkel and Schulz (A refined Gomory–Chvátal closure for polytopes...     

Rhodium‐Catalyzed Stitching Polymerization of 1,5‐Hexadiynes and Related Oligoalkynes

A new mode of polymerization, rhodium‐catalyzed stitching polymerization, has been developed for the synthesis of π‐conjugated polymers with bridged repeating units from nonconjugated 1,5‐hexadiynes containing both terminal and internal alkyne moieties as monomers. The polymerization proceeded smoothly with a high degree of stitching efficiency under mild conditions, and 1,5,9‐decatriyne and 1,5,9,13‐tetradecatetrayne monomers could also be employed. The present polymerization strategy would be particularly beneficial for the synthesis of polymers consisting of a repeating unit that is difficult to prepare as a stable monomer because it does not require the use of a preformed bridged π‐conjugated monomer.     

Structural,Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO_2.67 (Ba₃Co₃O₈□₁) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10⁻⁴ S cm⁻¹ is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–y, confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts.     

An Anti CuO2‐type Metal Hydride Square Net Structure in Ln2M2As2Hx (Ln=La or Sm,M=Ti,V, Cr,or Mn)

Using a high pressure technique and the strong donating nature of H⁻, a new series of tetragonal La₂Fe₂Se₂O₃‐type layered mixed‐anion arsenides, Ln₂M₂As₂H_x, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x≈3). In these compounds, an unusual M₂H square net, which has anti CuO₂ square net structures accompanying two As³⁻ ions, is sandwiched by (LaH)₂ fluorite layers. Notably, strong metal–metal bonding with a distance of 2.80 Å was confirmed in La₂Ti₂As₂H_2.3, which has metallic properties. In fact, these compounds are situated near the boundary between salt‐like ionic hydrides and transition‐metal hydrides with metallic characters.     

Diffuse mode bifurcation of soil causing convection-like shear investigated by group-theoretic image analysis

Diffuse mode bifurcation of soil under plane-strain compression test is shown, by means of an image analysis based on group-theoretic bifurcation theory, to trigger convection-like shear and to precede shear band formation. First digital photos of Toyoura sand specimens are processed by PIV (particle image velocimetry) to gather digitized images of deformation. Next bifurcation from a uniform state is detected by expanding these images into the double Fourier series and finding a predominant harmonic diffuse bifurcation mode based on that theory. This harmonic bifurcation mode, which is the mixture of a few harmonic functions, expresses complex convection-like shear. Last bifurcation from a non-uniform state is detected by decomposing each image into a few images with different symmetries to extract non-harmonic diffuse bifurcation modes. Diffuse modes of bifurcation, which hitherto were hidden behind predominant uniform compressive deformation, have thus been made transparent by virtue of the group-theoretic image analysis proposed. A possible course of deformation suggested herein is the evolution of diffuse mode bifurcation with a convection-like bifurcation mode breaking uniformity and symmetry, followed by the formation of shear bands through localization.     

Electron Temperatures and Electron Densities in Microwave Helium Discharges with Pressures Higher than 0.1 MPa

We adopted laser Thomson scattering for measuring the electron density and the electron temperature of microwave plasmas produced in helium at the pressures higher than the atmospheric pressure. The electron density decreased while we observed the increase in the electron temperature with the pressure. These are reasonable results by considering the decrease in the reduced electric field, the dominant loss of electrons via three‐body recombination with helium as the third body, and the production of electrons with medium energy via heavy particle collisions at the high gas pressure. The temporal variation of the electron temperature had the rise and the fall time constants of approximately 10 ns. The rapid heating and cooling of the electron temperature are due to the fast energy transfer from electrons to helium because of the high collision frequency in the high‐pressure discharge. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Generalized sensitivity and probabilistic analysis of buckling loads of structures

The imperfection sensitivity law by Koiter played a pivotal role in the early stage of research on initial post-buckling behaviors of structures, but seems somewhat overshadowed by numerical approaches in the computer age. In this paper, to make this law consistent with practical application, the law is extended to implement the influence of a number of imperfections, and the second-order (minor) imperfections are considered, in addition to the first-order (major) imperfections considered in the Koiter law. Explicit formulas are presented to be readily applicable to the numerical evaluation of imperfection sensitivity. A procedure to describe the probabilistic variation of critical loads is presented for the case where initial imperfections of structures are subject to a multivariate normal distribution; the formula for the probability density function of critical loads is derived by considering up to the second-order imperfections. The validity and usefulness of the present procedure are demonstrated through the application to truss structures.     

Cyclically symmetric hyperbolic spatial graphs in 3-manifolds

The aims of this paper is to prove that every closed connected orientable 3-manifold with an orientation-preserving periodic diffeomorphism contains infinitely many, setwise invariant, spatial graphs whose exteriors are hyperbolic 3-manifolds.