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Abstract: The deep oxidation of dimethylamine (DMA) was studied over Pt/Al2O3 catalysts with small (1nm) and large (7.8–15.5nm) Pt crystallite sizes. The turnover frequency (TOF) was higher for the large than for the small Pt crystallites, indicating that the reaction is structure sensitive. Two kinetic models were used to interpret the obtained results, i.e., the Mars van Krevelen and a mechanism based on the adsorption of oxygen and adsorption of dimethylamine on different active sites were employed. Both models showed that the activation energy for the oxygen chemisorption rate constant (k o) decreased with increasing of Pt crystallite size and that the activation energy for the surface reaction rate constant (k i) was independent of the Pt crystallite size. The structure sensitivity may be explained by differences in the reactivity of the oxygen adsorbed on these Pt crystallites. The Mars van Krevelen model fits the TOF values very well at concentrations of DMA higher than 1500ppm, while in the lower concentrations region, the model under predicts the experimental data. The model based on the adsorption of oxygen and DMA on different active sites fits the experimental data quite well over the whole temperature and concentration range. The fitted values of the Henry adsorption constant are independent of the Pt crystallite size. [Copyright &y& Elsevier]

Abstract: The influence of low loadings of MnO x on the catalytic activity for n-hexene and CO oxidation over highly dispersed Pt on alumina catalysts has been investigated. The applied deposition–precipitation method allows Mn to be deposited on the Pt containing egg-shell volume. The catalyst samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and selective CO chemisorption. Platinum influences the dispersion of deposited MnO x . The dispersion of the MnO x phase is higher on Pt containing samples than on Al2O3. The Pt decoration by Mn is reflected by a low CO uptake and the Pt oxidation state (Pt2+). The addition of Mn lowers the catalytic activity for CO oxidation. This is attributed to a change of the Pt sites such that adsorption of CO is less favorable. The activity of the catalysts in the oxidation of n-hexane showed a significant improvement with addition of MnO x . A light-off shift by about 40°C was observed. This improvement is attributed to the formation of Mn–Pt oxide like species that primarily weakens the Pt–O bond. [Copyright &y& Elsevier]

The phase transformation and crystallization kinetics of amorphous Al78W22 thin films under isothermal and isochronal conditions was examined by continuous in situ electrical resistance measurements. Sample preparation was performed by magnetron co-deposition. The resistivity of the samples was monitored during isothermal annealing at 803, 813, and 823 K, i.e. at temperatures at which the crystalline phase starts to develop. The temperature dependence of the resistivity ?(T?) was estimated from the isochronal measurements, while the volume fraction of the crystalline phase ?(x,t) was established by using the isothermal measurements and general two-phase resistivity models for this system. Combinations of these two approaches were used to model the variation of the resistivity during the cooling cycles. The activation energy for crystallization and the reaction order were determined within the framework of the JMA theory. The results indicate that the crystallization mechanism is a diffusion-controlled process with quenched-in nuclei during non-isothermal heating, whereas it is a diffusion-controlled process with steady-state nucleation during isothermal heating. [ABSTRACT FROM AUTHOR]

We report on structural properties and charge trapping in [(Ge+SiO2)/SiO2]×2 films deposited by magnetron sputtering on a periodically corrugated-rippled substrate and annealed in vacuum and forming gas. The rippled substrate caused a self-ordered growth of Ge quantum dots, while annealing in different environments enabled us to separate charge trapping in quantum dots from the trapping at the dot-matrix and matrix-substrate interfaces. We show that the charge trapping occurs mainly in Ge quantum dots in the films annealed in the forming gas, while Si-SiO2 interface trapping is dominant for the vacuum annealed films. [ABSTRACT FROM AUTHOR]

We demonstrate the production of a well ordered three-dimensional array of Ge quantum dots in amorphous silica matrix. The ordering is achieved by ion beam irradiation and annealing of a multilayer film. Structural analysis shows that quantum dots nucleate along the direction of the ion beam used for irradiation, while the mutual distance of the quantum dots is determined by the diffusion properties of the multilayer material rather than the distances between traces of ions that are used for irradiation. [ABSTRACT FROM AUTHOR]

We report on a method for the determination of ion track radii, formed in amorphous materials by ion-beam irradiation. The method is based on the addition to an amorphous matrix of a small amount of foreign atoms, which easily diffuse and form clusters when the temperature is sufficiently increased. The irradiation causes clustering of these atoms, and the final separations of the formed clusters are dependent on the parameters of the ion-beam. Comparison of the separations between the clusters that are formed by ions with different properties in the same type of material enables the determination of ion-track radii. [ABSTRACT FROM AUTHOR]

Abstract: Germanium Quantum Dots (Ge QDs) were formed in SiO2 by RT magnetron sputtering co-deposition of Ge and SiO2 and subsequent annealing. Films were deposited in the form of alternating (Ge+SiO2) layers (40:60 molar ratio) and pure SiO2 layers, serving as spacers. Grazing incidence small angle x-ray scattering (GISAXS) was applied for structural characterization of the QDs synthesized in the SiO2 amorphous matrix. The chemical composition and phase of the QDs were determined by Raman spectroscopy, and the spatial distribution and concentration of the Ge atoms by Rutherford Backscattering. The 2D GISAXS patterns, besides giving information on the layered structure, were used to reveal the onset of the synthesis of Ge QDs in SiO2 and to determine the average size and shape of QDs. It has been shown that the insertion of spacer SiO2 layers between (Ge+SiO2) layers transforms the 3D growth of Ge QDs into a preferentially 2D growth, within each 7 nm thick (Ge+SiO2) layer. This resulted in a considerably smaller average size of Ge QDs in the layered films. The synthesis of well crystallized, moderately sized, spherical Ge QDs was achieved by post-deposition annealing in the 700–800 ∘C range. [Copyright &y& Elsevier]

Changes in the extracellular matrix of pulmonary arteries (PAs) are a key aspect of vascular remodeling in pulmonary hypertension (PH). Yet, our understanding of the alterations affecting the proteoglycan (PG) family remains limited. We sought to investigate the expression and spatial distribution of major vascular PGs in PAs from healthy individuals and various PH groups (chronic obstructive pulmonary disease: PH-COPD, pulmonary fibrosis: PH-PF, idiopathic: IPAH). PG regulation, deposition, and synthesis were notably heightened in IPAH, followed by PH-PF, with minor alterations in PH-COPD. Single-cell analysis unveiled cell-type and disease-specific PG regulation. Agrin expression, a basement membrane PG, was increased in IPAH, with PA endothelial cells (PAECs) identified as a major source. PA smooth muscle cells (PASMCs) mainly produced large-PGs, aggrecan and versican, and small-leucine-like proteoglycan (SLRP) biglycan, whereas the major PGs produced by adventitial fibroblasts were SLRP decorin and lumican. In IPAH and PF-PH, the neointima-forming PASMC population increased the expression of all investigated large-PGs and SLRPs, except fibroblast-predominant decorin (DCN). Expression of lumican, versican, and biglycan also positively correlated with collagen 1α1/1α2 expression in PASMCs in patients with IPAH and PH-PF. We demonstrated that transforming growth factor-beta (TGF-β) regulates versican and biglycan expression, indicating their contribution to vessel fibrosis in IPAH and PF-PH. We furthermore show that certain circulating PG levels display a disease-dependent pattern, with increased decorin and lumican across all patient groups, while versican was elevated in PH-COPD and IPAH and biglycan reduced in IPAH. These findings suggest unique compartment-specific PG regulation in different forms of PH, indicating distinct pathological processes. NEW & NOTEWORTHY Idiopathic pulmonary arterial hypertension (IPAH) pulmonary arteries (PAs) displayed the greatest proteoglycan (PG) changes, with PH associated with pulmonary fibrosis (PH-PF) and PH associated with chronic obstructive pulmonary disease (PH-COPD) following. Agrin, an endothelial cell-specific PG, was solely upregulated in IPAH. Among all cells, neo-intima-forming smooth muscle cells (SMCs) displayed the most significant PG increase. Increased levels of circulating decorin, lumican, and versican, mainly derived from SMCs, and adventitial fibroblasts, may serve as systemic indicators of pulmonary remodeling, reflecting perivascular fibrosis and neointima formation.

The first hematopoietic stem and progenitor cells (HSPCs) emerge in the Aorta-Gonad-Mesonephros (AGM) region of the mid-gestation mouse embryo. However, the precise nature of their supportive mesenchymal microenvironment remains largely unexplored. Here, we profiled transcriptomes of laser micro-dissected aortic tissues at three developmental stages and individual AGM cells. Computational analyses allowed the identification of several cell subpopulations within the E11.5 AGM mesenchyme, with the presence of a yet unidentified subpopulation characterized by the dual expression of genes implicated in adhesive or neuronal functions. We confirmed the identity of this cell subset as a neuro-mesenchymal population, through morphological and lineage tracing assays. Loss of function in the zebrafish confirmed that Decorin, a characteristic extracellular matrix component of the neuro-mesenchyme, is essential for HSPC development. We further demonstrated that this cell population is not merely derived from the neural crest, and hence, is a bona fide novel subpopulation of the AGM mesenchyme., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2024. Published by The Company of Biologists Ltd.)

Pituitary xanthogranulomatomas (XG) are a rare pathological entity caused by accumulation of lipid laden macrophages and reactive granuloma formation usually triggered by cystic fluid leakage or hemorrhage. Our aim was to compare clinical characteristics and presenting features of patients with secondary etiology of XG and those with no identifiable founding lesion (primary -"pure" XG) in order to gain new insights into this rare pituitary pathology. In a retrospective review of 714 patients operated for sellar masses, at tertiary center, we identified 16 (2.24%) with histologically confirmed diagnosis of pituitary XG over the period of 7 years (2015-2021). Patients were further analyzed according to XG etiology: "pure"- XG (n = 8) with no identifiable founding lesion were compared to those with histological elements of pituitary tumor or cyst - secondary XG (n = 8). We identified 16 patients (11 male), mean age 44.8 ± 22.3 years, diagnosed with pituitary XG. Secondary forms were associated with Ratke's cleft cyst (RCC, n = 2) and pituitary adenoma (PA, n = 6). The most common presenting features in both groups were hypopituitarism (75%), headache (68.5%) and visual disturbances (37.5%). Predominance of male sex was noted (males 68.75%, females 31.25%), especially in patients with primary forms. Patients with primary pituitary XG were all males (p = 0.0256) and more frequently affected by panhypopituitarism (87.5% vs. 25%, p = 0.0406) compared to patients with secondary causes. Hyperprolactinemia was noted in pituitary tumor group with secondary etiology only (p = 0.0769). Majority of lesions were solid on magnetic resonance imaging - MRI (81.25%). Distinct clinical phenotype was observed dependent on the etiology of XG.

Deposition of basement membrane components, such as collagen IVα5, is associated with altered endothelial cell function in pulmonary hypertension. Collagen IVα5 harbors a functionally active fragment within its C-terminal noncollageneous (NC1) domain, called pentastatin, whose role in pulmonary endothelial cell behavior remains unknown. Here, we demonstrate that pentastatin serves as a mediator of pulmonary endothelial cell dysfunction, contributing to pulmonary hypertension. In vitro, treatment with pentastatin induced transcription of immediate early genes and proinflammatory cytokines and led to a functional loss of endothelial barrier integrity in pulmonary arterial endothelial cells. Mechanistically, pentastatin leads to β1-integrin subunit clustering and Rho/ROCK activation. Blockage of the β1-integrin subunit or the Rho/ROCK pathway partially attenuated the pentastatin-induced endothelial barrier disruption. Although pentastatin reduced the viability of endothelial cells, smooth muscle cell proliferation was induced. These effects on the pulmonary vascular cells were recapitulated ex vivo in the isolated-perfused lung model, where treatment with pentastatin-induced swelling of the endothelium accompanied by occasional endothelial cell apoptosis. This was reflected by increased vascular permeability and elevated pulmonary arterial pressure induced by pentastatin. This study identifies pentastatin as a mediator of endothelial cell dysfunction, which thus might contribute to the pathogenesis of pulmonary vascular disorders such as pulmonary hypertension. NEW & NOTEWORTHY This study is the first to show that pentastatin, the matrikine of the basement membrane (BM) collagen IVα5 polypeptide, triggers rapid pulmonary arterial endothelial cell barrier disruption, activation, and apoptosis in vitro and ex vivo. Mechanistically, pentastatin partially acts through binding to the β1-integrin subunit and the Rho/ROCK pathway. These findings are the first to link pentastatin to pulmonary endothelial dysfunction and, thus, suggest a major role for BM-matrikines in pulmonary vascular diseases such as pulmonary hypertension.