Thermochemical Study of CH3NH3Pb(Cl1−xBrx)3 Solid Solutions

Hybrid organic–inorganic perovskite halides, and, in particular, their mixed halide solid solutions, belong to a broad class of materials which appear promising for a wide range of potential applications in various optoelectronic devices. However, these materials are notorious for their stability issues, including their sensitivity to atmospheric oxygen and moisture as well as phase separation under illumination. The thermodynamic properties, such as enthalpy, entropy, and Gibbs free energy of mixing, of perovskite halide solid solutions are strongly required to shed some light on their stability. Herein, we report the results of an experimental thermochemical study of the CH₃NH₃Pb(Cl_1−xBr_x)₃ mixed halides by solution calorimetry. Combining these results with molecular dynamics simulation revealed the complex and irregular shape of the compositional dependence of the mixing enthalpy to be the result of a complex interplay between the local lattice strain, hydrogen bonds, and energetics of these solid solutions.     

(Cr1−xAlx)N Coating Deposition by Short-Pulse High-Power Dual Magnetron Sputtering

The paper deals with the (Cr_1−xAl_x)N coating containing 17 to 54 % Al which is deposited on AISI 430 stainless steel stationary substrates by short-pulse high-power dual magnetron sputtering of Al and Cr targets. The Al/Cr ratio in the coating depends on the substrate position relative to magnetrons. It is shown that the higher Al content in the (Cr_1−xAl_x)N coating improves its hardness from 17 to 28 GPa. Regardless of the Al content, the (Cr_1−xAl_x)N coating manifests a low wear rate, namely (4.1–7.8) × 10⁻⁹ and (3.9–5.3) × 10⁻⁷ mm³N⁻¹m⁻¹ in using metallic (100Cr6) and ceramic (Al₂O₃) counter bodies, respectively. In addition, this coating possesses the friction coefficient 0.4–0.7 and adhesive strength quality HF1 and HF2 indicating good interfacial adhesion according to the Daimler-Benz Rockwell-C adhesion test.     

Functional anatomy of the hair follicle: The Secondary Hair Germ

The secondary hair germ (SHG)—a transitory structure in the lower portion of the mouse telogen hair follicle (HF)—is directly involved in anagen induction and eventual HF regrowth. Some crucial aspects of SHG functioning and ontogenetic relations with other HF parts, however, remain undefined. According to recent evidence (in contrast to previous bulge‐centric views), the SHG is the primary target of anagen‐inducing signalling and a source of both the outer root sheath (ORS) and ascending HF layers during the initial (morphogenetic) anagen subphase. The SHG is comprised of two functionally distinct cell populations. Its lower portion (originating from lower HF cells that survived catagen) forms all ascending HF layers, while the upper SHG (formed by bulge‐derived cells) builds up the ORS. The predetermination of SHG cells to a specific morphogenetic fate contradicts their attribution to the “stem cell” category and supports SHG designation as a “germinative” or a “founder” cell population. The mechanisms of this predetermination driving transition of the SHG from “refractory” to the “competent” state during the telogen remain unknown. Functionally, the SHG serves as a barrier, protecting the quiescent bulge stem cell niche from the extensive follicular papilla/SHG signalling milieu. The formation of the SHG is a prerequisite for efficient “precommitment” of these cells and provides for easier sensing and a faster response to anagen‐inducing signals. In general, the formation of the SHG is an evolutionary adaptation, which allowed the ancestors of modern Muridae to acquire a specific, highly synchronized pattern of hair cycling.     

Evoked phase synchronization between adjacent high-density electrodes in human scalp EEG: duration and time course related to behavior.

OBJECTIVE: Data from a previous event-related potential (ERP) study in visual-perceptual grouping [Nikolaev AR, van Leeuwen C. Flexibility in spatial and non-spatial feature grouping: an event-related potentials study. Brain Res Cogn Brain Res 2004;22:13-25] were re-analyzed to identify event-related dynamics of phase-synchronization. METHODS: In 20 Hz activity, uniform spreading of phase synchronization in closely spaced (approximately 2 cm) scalp electrodes appears and disappears spontaneously. The lengths of synchronized activity intervals and how they vary as a function of stimulus presentation were compared between task and control conditions. RESULTS: Synchronization reached a maximum in the task condition about 180 ms post-stimulus onset, coinciding with the peak N180 ERP marking the deployment of task-specific attention. Synchronized intervals were longer in the task than in the control condition. Long (above 80 ms) intervals occurred at a stable rate before and just after stimulus onset, but steeply decreased 200-400 ms afterwards. CONCLUSIONS: Perceptual tasks lead to longer synchronized intervals in early visual areas. Attention deployment resets the ongoing synchronization. Event-related activity, besides low-frequency ERP, consists of high-frequency short and long synchronized intervals corresponding to evoked bursts and ongoing oscillations, respectively. SIGNIFICANCE: High-density scalp recorded EEG revealed synchronization dynamics in a local, early visual area of cortex that can be interpreted as modulation of spontaneous ongoing task-related processes by attention.     

Comparison of reorganization of the somatosensory system in rats that sustained forelimb removal as neonates and as adults

Studies of sensory pathways in several species indicate that the extent and form of reorganization resulting from deafferentation early in life vs. adulthood are not the same. The reasons for such differences are not well understood. To gain further insight into age-dependent mechanisms of reorganization, this study compared the consequences of neonatal vs. adult forelimb amputation in rats at multiple levels of the sensory pathway, including primary somatosensory cortex, brainstem, and dorsal root ganglia. At the cortical level, the average area of the functional forelimb-stump representation from rats amputated as adults was significantly smaller (P < 0.05) than that of neonatally amputated rats (4.3 +/- 1.3 mm(2) vs. 6.6 +/- 1.5 mm(2), respectively). At the brainstem level, neonatally amputated rat cuneate neurons possessed the following responsivities: 20% stump responsive, 40% responsive to both stump and hindlimb, 30% responsive to another body region, and 10% unresponsive. In contrast, cuneate neurons of adult amputated rats were 70% stump responsive, 2% responsive to both stump and hindlimb, and 30% unresponsive. A significantly (P < 0.001) greater percentage of the C(6)-C(8) dorsal root ganglia neurons of adult amputated rats were unresponsive to peripheral stimulation vs. neurons from neonatally amputated rats (48% vs. 16%, respectively). These results indicate that the reorganization that occurs in response to forelimb amputation at birth vs. adulthood is distinctly different at each of these levels of the dorsal column-medial lemniscal pathway. Possible mechanisms to account for these differences are considered.     

Supramolecular D⋯A-layered structures based on germanium complexes with 2,3-dihydroxynaphthalene and N,N′-bidentate ligands

The concept of using redox-active ligands, which has become extremely widespread in organometallic chemistry, is often considered from ‘their effect on the metal center properties’ point of view and ‘how to modify the ligands’. In this paper, we present the reverse side of this effective approach – a dramatic change of redox properties of ligands under the influence of a redox-inert metal. Germanium derivatives based on 2,3-dihydroxynaphthalene (1) and N,N′-bidentate ligands, namely 2,2′-bipyridine (2) and 1,10-phenanthroline (3), were obtained and characterized by CV, UV-vis spectroscopy, DFT calculations and in the case of 3 X-ray diffraction. It was shown that the HOMO of the complexes is almost completely located on the naphthalene fragment while the LUMO is on the N,N-ligands. At the same time, there are no boundary molecular orbitals on the germanium atom, but it forms the axial part of the molecule holding two opposite motifs together. Moreover, it sharply affects the level of HOMO and LUMO. Derivatives 2 and 3 are more easily oxidized compared to 2,3-dihydroxynaphthalene by 0.31–0.34 V (7–8 kcal mol⁻¹) and are more easily reduced compared to N,N-donors by 1.08–1.15 V (25–26.5 kcal mol⁻¹). All this together makes it possible to form a system with a narrow HOMO/LUMO gap (∼2 eV). The crystal structure of 3 consists of alternating monomolecular easily oxidizing and easily reducing layers formed due to intermolecular interactions, in particular π-stacking. In addition, in contrast to 1 that starts to decompose noticeably at the temperatures from 200 °C, 2 and 3 have an extremely high thermal stability. They remain stable with no signs of decomposition and melting up to 400 °С. We believe that this approach to the formation of the supramolecular structure may present prospects for obtaining new functional materials.

The concept of using redox-active ligands is often considered from ‘their effect on the metal center properties’ point of view. We present the reverse side of this approach – change of redox properties of ligands under the influence of metal.     

Albumin-associated free fatty acids induce macropinocytosis in podocytes

Podocytes are specialized epithelial cells in the kidney glomerulus that play important structural and functional roles in maintaining the filtration barrier. Nephrotic syndrome results from a breakdown of the kidney filtration barrier and is associated with proteinuria, hyperlipidemia, and edema. Additionally, podocytes undergo changes in morphology and internalize plasma proteins in response to this disorder. Here, we used fluid-phase tracers in murine models and determined that podocytes actively internalize fluid from the plasma and that the rate of internalization is increased when the filtration barrier is disrupted. In cultured podocytes, the presence of free fatty acids (FFAs) associated with serum albumin stimulated macropinocytosis through a pathway that involves FFA receptors, the Gβ/Gγ complex, and RAC1. Moreover, mice with elevated levels of plasma FFAs as the result of a high-fat diet were more susceptible to Adriamycin-induced proteinuria than were animals on standard chow. Together, these results support a model in which podocytes sense the disruption of the filtration barrier via FFAs bound to albumin and respond by enhancing fluid-phase uptake. The response to FFAs may function in the development of nephrotic syndrome by amplifying the effects of proteinuria.     

Autoimmunity as the consequence of a spontaneous mutation in Rasgrp1

A mouse strain was identified with a recessive genetic lesion, which spontaneously developed a lymphoproliferative autoimmune syndrome exhibiting features of systemic lupus erythematosus. Positional mapping of the disease-associated locus revealed a lesion in Rasgrp1 that prevented the translation of the RasGRP1 protein. T cells from these mice failed to activate Ras or proliferate vigorously following antigen encounter and showed defects in positive selection. Peripheral RasGRP1lag T cells spontaneously adopted a memory phenotype and were able to transfer disease to lymphopenic recipient mice. CD4+ T cells accumulated in the lymphoid tissues of older RasGRP1lag mice and were resistant to activation-induced cell death. RasGRP1lag B cells were functionally normal, but activated B cells were detected in older mice, as were autoantibodies directed against self-antigens. Our findings indicate that Ras signaling pathways are required to maintain T cell tolerance and to prevent autoimmune disease.