Computational and Experimental Investigations of Osmium-Rich Borides Hf2MOs5B2 (M = Mn, Fe, Co): From Spin Glass to Room-Temperature Magnetic Behaviors.

The metal borides, Hf2MOs5B2 (M = Mn, Fe, Co), which are the first Os-rich quaternary variants of the prolific Ti3Co5B2 structure type, were investigated computationally and experimentally. In their crystal structures, osmium builds a network of prisms, in which the other elements are located. The magnetic M elements are found in face-connected Os8 square prisms leading to M-chains with intra- and interchain distances of about 3.0 and 6.5 Å, respectively. Density functional theory (DFT) showed that magnetic ordering is hugely favored for M = Mn and Fe but only slightly favored for M = Co. Experimental investigations then confirmed and extended the DFT predictions as a metamagnetic behavior was found for the M = Mn and Fe phases, whereby the antiferromagnetic interactions (TN = 19 and 90 K) found at low magnetic fields change to ferromagnetic at higher fields. A very broad transition (TN = 45 K) is found for M = Co, suggesting spin-glass behavior for this phase. For M = Fe, a hard-magnet hysteresis at 5 K is found with a 40 kA/m coercivity, and even at room temperature, a significant hysteresis is found. This study paves the way for the discovery of Os-based magnets in this structure type and other intermetallics.

Hetero-trimetallic complexes comprising bridging boryl and borylene ligands: an experimental and theoretical study.

In an effort to explore the coordination chemistry of the coordinative sulfur centers in arachno-ruthenaborane [(Cp*Ru)2(B3H8)(CS2H)] (arachno-1), we have thermolyzed arachno-1 with group-6 metal carbonyls [M(CO)5·THF] (M = Cr, Mo and W). The reaction of arachno-1 with [Cr(CO)5·THF] resulted in the formation of hetero-trimetallic triply bridging borylene [(Cp*Ru)2(µ-CO)(µ3-CH2S2-κ2S':κ2S''){Cr(CO)3}(µ3-BH)] (2), bridging boryl-borylene [(Cp*Ru)2(µ-CO){(µ3-BH(CH2S2)-κ2B:κ2S':κ1S'')}{Cr(CO)3}(µ3-BH)] (3), and sulfido bridged hetero-trimetallic complex [(Cp*Ru)2(µ-CO)3{Cr(CO)3}(µ3-S)] (4). In 2, one side of Ru2Cr-triangle features a µ3-BH ligand while the other side is quadruply bridged by a methanedithiolato ligand in an unsymmetrical fashion. Unlike 2, in complex 3, one side of the Ru2Cr-triangle has a µ3-BH ligand while the opposite side is bridged by a boryl ligand BH(CH2S2) in an unsymmetrical way (µ3-κ2:κ2:κ1) to the metal centers. Interestingly, when the similar reactions of arachno-1 were performed with heavier group-6 metal carbonyls [M(CO)5·THF] (M = Mo and W), it led to the formation of methanedithiolato bridged hetero-trimetallic chain complexes, [{Cp*Ru(CO)}2(µ-CO)2(µ3-CH2S2-κ2S':κ2S''){M(CO)2}] (5, M = Mo; 6, M = W) and sulfido-bridged hetero-trimetallic complexes [(Cp*Ru)2(µ-CO)3{M(CO)3}(µ3-S)] (7, M = Mo; 8, M = W), analogous to 4. In complexes 5 and 6, a Ru2M-chain is symmetrically bridged by a methanedithiolato ligand. On the other hand, in complexes 4, 7, and 8, a sulfido ligand coordinates to two ruthenium and one group-6 metal atoms in µ3-fashion. All the complexes have been characterized by 1H NMR, 13C NMR, UV-vis, IR spectroscopy, and mass spectrometry and their structural architectures have been unambiguously established by single crystal X-ray diffraction studies. In addition, theoretical investigations provided valuable insights into their electronic structures and bonding properties.

Enhancing Intrinsic Magnetic Hardness by Modulating Antagonistic Interactions in the Rare-Earth-Free Magnetic Solid Solution Hf2 Fe1-δ Ru5-x Irx+δ B2.

The quinary members in the solid solution Hf2 Fe1-δ Ru5-x Irx+δ B2 (x=1-4, VE=63-66) have been investigated experimentally and computationally. They were synthesized via arc-melting and analyzed by EDX and X-ray diffraction. Density functional theory (DFT) calculations predicted a preference for magnetic ordering in all members, but with a strong competition between ferro- and antiferromagnetism arising from interchain Fe-Fe interactions. The spin exchange and magnetic anisotropy energies predicted the lowest magnetic hardness for x=1 and 3 and the highest for x=2. Magnetization measurements confirm the DFT predictions and demonstrate that the antiferromagnetic ordering (TN =55-70 K) found at low magnetic fields changed to ferromagnetic (TC =150-750 K) at higher fields, suggesting metamagnetic behavior for all samples. As predicted, Hf2 FeRu3 Ir2 B2 has the highest intrinsic coercivity (Hc =74 kA/m) reported to date for Ti3 Co5 B2 -type phases. Furthermore, all coercivities outperform that of ferromagnetic Hf2 FeIr5 B2 , indicating the importance of AFM interactions in enhancing magnetic anisotropy in these materials. Importantly, two members (x=1 and 4) maintain intrinsic coercivities in the semi-hard range at room temperature. This study opens an avenue for controlling magnetic hardness by modulating antagonistic AFM and FM interactions in low-dimensional rare-earth-free magnetic materials.

Voice Pathologies and the General Population's Perception.

OBJECTIVES: To examine how the general population perceives voice pathology based on subjective qualities. STUDY DESIGN: Descriptive, cross-sectional, survey-based study. METHODS: This is an IRB-approved Qualtrics survey on Amazon MTurk for respondents ages 18 and older. Ten subjects with voice pathologies supplied voice recordings of the Rainbow Passage to be assessed by the respondents. Respondents then assessed the voice conditions on perceived qualities of intelligence, leadership ability, and employability. One-way analysis of variance (ANOVA) and Dunnett's multiple comparison test with Sidak correction compared the mean scores of the samples (alpha = 0.05). RESULTS: A total of 1754 responses were included in the final dataset. The female control voice was scored as more likely to be a Fortune 500 leader as well as more intelligent, friendly, attractive, and employable when compared to the female vocal fry and muscle tension dysphonia (MTD) recordings (P < 0.0001). Conversely, the male MTD was the only male pathology that received a significantly lower score on friendliness, attractiveness, Fortune 500 leader status and employability than the male control (P = 0.0102, P = 0.0007, P = 0.0338, and P = 0.0039, respectively). CONCLUSIONS: This study demonstrates the more critical appraisal of voice pathologies of female patients compared to their male counterparts. People with voice disorders are perceived as being less successful, a disadvantage to potential leadership and career opportunities.

Metal-Mediated Directional Capping of Rod-Packing Metal-Organic Frameworks.

Two new rod-packing metal-organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn2+ with a stronger Lewis acidic Co2+ , leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.

Identification of raw as a regulator of glial development.

Glial cells perform numerous functions to support neuron development and function, including axon wrapping, formation of the blood brain barrier, and enhancement of synaptic transmission. We have identified a novel gene, raw, which functions in glia of the central and peripheral nervous systems in Drosophila. Reducing Raw levels in glia results in morphological defects in the brain and ventral nerve cord, as well as defects in neuron function, as revealed by decreased locomotion in crawling assays. Examination of the number of glia along peripheral nerves reveals a reduction in glial number upon raw knockdown. The reduced number of glia along peripheral nerves occurs as a result of decreased glial proliferation. As Raw has been shown to negatively regulate Jun N-terminal kinase (JNK) signaling in other developmental contexts, we examined the expression of a JNK reporter and the downstream JNK target, matrix metalloproteinase 1 (mmp1), and found that raw knockdown results in increased reporter activity and Mmp1 levels. These results are consistent with previous studies showing increased Mmp levels lead to nerve cord defects similar to those observed upon raw knockdown. In addition, knockdown of puckered, a negative feedback regulator of JNK signaling, also causes a decrease in glial number. Thus, our studies have resulted in the identification of a new regulator of gliogenesis, and demonstrate that increased JNK signaling negatively impacts glial development.