Type-II Red Phosphorus: Wavy Packing of Twisted Pentagonal Tubes.

Elemental phosphorus exhibits fascinating structural varieties and versatile properties. The unique nature of phosphorus bonds can lead to the formation of extremely complex structures, and detailed structural information on some phosphorus polymorphs is yet to be investigated. In this study, we investigated an unidentified crystalline phase of phosphorus, type-II red phosphorus (RP), by combining state-of-the-art structural characterization techniques. Electron diffraction tomography, atomic-resolution scanning transmission electron microscopy (STEM), powder X-ray diffraction, and Raman spectroscopy were concurrently used to elucidate the hidden structural motifs and their packing in type-II RP. Electron diffraction tomography, performed using individual crystalline nanowires, was used to identify a triclinic unit cell with volume of 5330 Å3 , which is the largest unit cell for elemental phosphorus crystals up to now and contains approximately 250 phosphorus atoms. Atomic-resolution STEM imaging, which was performed along different crystal-zone axes, confirmed that the twisted wavy tubular motif is the basic building block of type-II RP. Our study discovered and presented a new variation of building blocks in phosphorus, and it provides insights to clarify the complexities observed in phosphorus as well as other relevant systems.

Spin-flip-driven anomalous Hall effect and anisotropic magnetoresistance in a layered Ising antiferromagnet.

The influence of magnetocrystalline anisotropy in antiferromagnets is evident in a spin flip or flop transition. Contrary to spin flops, a spin-flip transition has been scarcely presented due to its specific condition of relatively strong magnetocrystalline anisotropy and the role of spin-flips on anisotropic phenomena has not been investigated in detail. In this study, we present antiferromagnet-based functional properties on an itinerant Ising antiferromagnet Ca0.9Sr0.1Co2As2. In the presence of a rotating magnetic field, anomalous Hall conductivity and anisotropic magnetoresistance are demonstrated, the effects of which are maximized above the spin-flip transition. Moreover, a joint experimental and theoretical study is conducted to provide an efficient tool to identify various spin states, which can be useful in spin-processing functionalities.

Understanding of Active Sites and Interconversion of Pd and PdO during CH4 Oxidation.

Pd-based catalysts are widely used in the oxidation of CH4 and have a significant impact on global warming. However, understanding their active sites remains controversial, because interconversion between Pd and PdO occurs consecutively during the reaction. Understanding the intrinsic active sites under reaction conditions is critical for developing highly active and selective catalysts. In this study, we demonstrated that partially oxidized palladium (PdOx) on the surface plays an important role for CH4 oxidation. Regardless of whether the initial state of Pd corresponds to oxides or metallic clusters, the topmost surface is PdOx, which is formed during CH4 oxidation. A quantitative analysis using CO titration, diffuse reflectance infrared Fourier-transform spectroscopy, X-ray diffraction, and scanning transmission electron microscopy demonstrated that a surface PdO layer was formed on top of the metallic Pd clusters during the CH4 oxidation reaction. Furthermore, the time-on-stream test of CH4 oxidation revealed that the presence of the PdO layer on top of the metallic Pd clusters improves the catalytic activity. Our periodic density functional theory (DFT) calculations with a PdOx slab and nanoparticle models aided the elucidation of the structure of the experimental PdO particles, as well as the experimental C-O bands. The DFT results also revealed the formation of a PdO layer on the metallic Pd clusters. This study helps achieve a fundamental understanding of the active sites of Pd and PdO for CH4 oxidation and provides insights into the development of active and durable Pd-based catalysts through molecular-level design.

Behavior of magnetoelectric hysteresis and role of rare earth ions in multiferroicity in double perovskite Yb2CoMnO6.

Double-perovskite multiferroics have been investigated because alternating orders of magnetic ions act as distinct magnetic origins for ferroelectricity. In Yb2CoMnO6, the frustrated antiferromagnetic order emerging at TN = 52 K induces ferroelectric polarization perpendicular to the c axis through cooperative O2- shifts via the symmetric exchange striction. In our detailed measurements of the magnetoelectric properties of single-crystalline Yb2CoMnO6, we observe full ferromagnetic-like hysteresis loops that are strongly coupled to the dielectric constant and ferroelectric polarization at various temperatures below TN. Unlike Lu2CoMnO6 with non-magnetic Lu3+ ions, we suggest the emergence of additional ferroelectric polarization along the c axis below the ordering temperature of magnetic Yb3+ ions, TYb ≈ 20 K, based on the spin structure established from recent neutron diffraction experiments. While the proposed description for additional ferroelectricity, ascribed to the symmetric exchange striction between Yb3+ and Co2+/Mn4+ magnetic moments, is clearly given, anomalies of dielectric constants along the c axis are solely observed. Our interesting findings on magnetoelectric hysteresis and the possible development of additional ferroelectricity reveal notable characteristics of double perovskites and provide essential guidance for the further examination of magnetoelectric functional properties.

Tunable magnetization steps in mixed valent ferromagnet Eu2CoMnO6.

Magnetic properties can be manipulated to enhance certain functionalities by tuning different material processing parameters. Here, we present the controllable magnetization steps of hysteresis loops in double-perovskite single crystals of Eu2CoMnO6. Ferromagnetic order emerges below TC ≈ 122 K along the crystallographic c axis. The difficulty in altering Co2+ and Mn4+ ions naturally induces additional antiferromagnetic clusters in this system. Annealing the crystals in different gas environments modifies the mixed magnetic state, and results in the retardation (after O2-annealing) and bifurcation (after Ar-annealing) of the magnetization steps of isothermal magnetization. This remarkable variation offers an efficient approach for improving the magnetic properties of double-perovskite oxides.

Highly nonlinear magnetoelectric effect in buckled-honeycomb antiferromagnetic Co4Ta2O9.

Strongly correlated materials with multiple order parameters provide unique insights into the fundamental interactions in condensed matter systems and present opportunities for innovative technological applications. A class of antiferromagnetic honeycomb lattices compounds, A4B2O9 (A = Co, Fe, Mn; B = Nb, Ta), have been explored owing to the occurrence of linear magnetoelectricity. From our investigation of magnetoelectricity on single crystalline Co4Ta2O9, we discovered strongly nonlinear and antisymmetric magnetoelectric behavior above the spin-flop transition for magnetic fields applied along two orthogonal in-plane directions. This observation suggests that two types of inequivalent Co2+ sublattices generate magnetic-field-dependent ferroelectric polarization with opposite signs. The results motivate fundamental and applied research on the intriguing magnetoelectric characteristics of these buckled-honeycomb lattice materials.

Anisotropic and nonlinear magnetodielectric effects in orthoferrite ErFeO3 single crystals.

In rare-earth orthoferrites, strongly correlated order parameters have been thoroughly investigated, which aims to find multiple functionalities such as multiferroic or magnetoelectric properties. We have discovered highly anisotropic and nonlinear magnetodielectric effects from detailed measurements of magnetoelectric properties in single-crystalline orthoferrite, ErFeO3. Isothermal dielectric constant varies in shapes and signs depending on the relative orientations between the external electric and magnetic fields, which may be ascribed to the spin-phonon couplings. In addition, a dielectric constant with both electric and magnetic fields along the c axis exhibits two symmetric sharp anomalies, which are closely relevant to the spin-flop transition, below the ordering temperature of Er3+ spins, TEr = 3.4 K. We speculate that the magnetostriction from the exchange couplings between Er3+ and Fe3+ magnetic moments would be responsible for this relationship between electric and magnetic properties. Our results present significant characteristics of the orthoferrite compounds and offer a crucial guide for exploring suitable materials for magnetoelectric functional applications.

The effects of therapeutic exercise using PNF on the size of calcium deposits, pain self-awareness, and shoulder joint function in a calcific tendinitis patient: a case study.

[Purpose] The purpose of this case study was to identify the effects of independent and intensive therapeutic exercise using Proprioceptive neuromuscular facilitation on the size of calcium deposits, pain self-awareness, and shoulder joint function in a patient with calcific tendonitis. [Subject and Methods] The subject was a 42-year-old female patient with calcific tendonitis and acute pain who had difficulty with active movement and problems with general function. The independent and intensive Proprioceptive neuromuscular facilitation exercise was applied for 40 min twice a day five times a week for two weeks for a total of 20 times. An X-ray, the visual analog scale, a simple shoulder test, the Constant-Murley Scale, and passive range of motion was used to evaluate the patient's change. [Results] The size of the calcium deposit, the visual analog scale score, and the simple shoulder test score decreased. The Constant-Murley Scale score and the passive range of motion were increased. [Conclusion] The results of this study suggested that intensive and independent therapeutic short-term exercise without any other exercise reduced pain and produced positive effects in shoulder function in a patient with the calcific tendonitis, which could confirm the importance of therapeutic exercise in the treatment of calcific tendonitis.