A New Method for Characterization of Natural Zeolites and Organic Nanostructure using Atomic Force Microscopy

In order to study and develop an economic solution to environmental pollution in water, a wide variety of materials were investigated. Natural zeolites emerge from that research as the best in class of this category. Zeolites are natural materials relatively abundant and non biodegradable, economic and good to perform processes of environmental remediation. This paper contains a full description of a new method to characterize superficial properties of natural zeolites of exotic provenience (Caribbean Islets) with atomic force microscopy (AFM). AFM works with the optical microscope simplicity and the high resolution typical of a transmission electron microscope (TEM). Structural information of mesoporous material is obtained using scanning and transmission electron microscopy (SEM and TEM), only if the sample is conductive, otherwise the sample has to be processed through the grafitation technique, but this procedure induces errors of topography. Therefore, the existing AFM method, to observe zeolite powders, is made in a liquid cell-head scanner, but this work puts in evidence and confirms that it is possible to use an ambient air-head scanner to obtain a new kind of microtopography. Once optimized, this new method allows investigating of organic micelles, very soft nanostructure, of cetyltriammonium bromide (CTAB) upon an inorganic surface such as natural zeolites. It is shown some correlation between SEM microphotographies and AFM 3D images

Insulin-like growth factor-1 is a negative modulator of glucagon secretion

Glucagon secretion involves a combination of paracrine, autocrine, hormonal, and autonomic neural mechanisms. Type 2 diabetes often presents impaired glucagon suppression by insulin and glucose. Insulin-like growth factor-I (IGF-1) has elevated homology with insulin, and regulates pancreatic β-cells insulin secretion. Insulin and IGF-1 receptors share considerable structure homology and function. We hypothesized the existence of a mechanism linking the inhibition of α-cells glucagon secretion to IGF-1. Herein, we evaluated the association between plasma IGF-1 and glucagon levels in 116 nondiabetic adults. After adjusting for age gender and BMI, fasting glucagon levels were positively correlated with 2-h post-load glycaemia, HOMA index and fasting insulin, and were negatively correlated with IGF-1 levels. In a multivariable regression, the variables independently associated to fasting glucagon were circulating IGF-1 levels, HOMA index and BMI, explaining 20.7% variation. To unravel the molecular mechanisms beneath IGF-1 and glucagon association, we investigated whether IGF-1 directly modulates glucagon expression and secretion in an in vitro model of α-cells. Our data showed that IGF-1 inhibits the ability of low glucose concentration to stimulate glucagon expression and secretion via activation of the phosphatidylinositol-3-kinase/Akt/FoxO1 pathway. Collectively, our results suggest a new regulatory role of IGF-1 on α-cells biological function

Determination of carbonyl compounds in exhaled breath by on-sorbent derivatization coupled with thermal desorption and gas chromatography-tandem mass spectrometry

A reliable method for the determination of carbonyl compounds in exhaled breath based on on-sorbent derivatization coupled with thermal desorption and gas chromatography-tandem mass spectrometry is described. The analytical performances were optimized for a mixture of C2-C9 aldehydes and C3-C9 ketones, particularly interesting for clinical applications, by using an internal standard and applying a 2^3 full factorial design. A volume of sample (250 ml) was loaded at 50 ml min-1 into a Tenax GR sorbent tube containing 130 nmol of O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride. All compounds showed a limit of detection lower than 200 pptv. The yield of the derivatization procedure was normalized by adding to the sample a known amount of 6D-acetone as an internal standard. This allowed halving the relative standard deviation to 10% and 15% for the mono-and di-carbonyl compounds, respectively, thus improving reliability. The optimized method was applied to the determination of carbonyl compounds in 12 breath samples collected from four patients suffering from heart failure during hospitalization

Comparison of sampling bags for the analysis of volatile organic compounds in breath

Nalophan, Tedlar and Cali-5-Bond polymeric bags were compared to determine the most suitable type for breath sampling and storage when volatile organic compounds are to be determined. Analyses were performed by thermal desorption gas chromatography mass spectrometry. For each bag, the release of contaminants and the chemical stability of a gaseous standard mixture containing eighteen organic compounds, as well as the CO2 partial pressure were assessed. The selected compounds were representative of breath constituents and belonged to different chemical classes (i.e. hydrocarbons, ketones, aldehydes, aromatics, sulfurs and esters). In the case of Nalophan, the influence of the surface-to-volume ratio, related to the bag's filling degree, on the chemical stability was also evaluated. Nalophan bags were found to be the most suitable in terms of contaminants released during storage (only 2-methyl-1,3-dioxalane), good sample stability (up to 24 h for both dry and humid samples), and very limited costs (about 1 for a 20 liter bag). The (film) surface-to-(sample) volume ratio was found to be an important factor affecting the stability of selected compounds, and therefore we recommended to fill the bag completely

Adipogenesis of skeletal muscle fibro/adipogenic progenitors is affected by the WNT5a/GSK3/β-catenin axis

Fibro/Adipogenic Progenitors (FAPs) are muscle-interstitial progenitors mediating pro-myogenic signals that are critical for muscle homeostasis and regeneration. In myopathies, the autocrine/paracrine constraints controlling FAP adipogenesis are released causing fat infiltrates. Here, by combining pharmacological screening, high-dimensional mass cytometry and in silico network modeling with the integration of single-cell/bulk RNA sequencing data, we highlighted the canonical WNT/GSK/β-catenin signaling as a crucial pathway modulating FAP adipogenesis triggered by insulin signaling. Consistently, pharmacological blockade of GSK3, by the LY2090314 inhibitor, stabilizes β-catenin and represses PPARγ expression abrogating FAP adipogenesis ex vivo while limiting fatty degeneration in vivo. Furthermore, GSK3 inhibition improves the FAP pro-myogenic role by efficiently stimulating, via follistatin secretion, muscle satellite cell (MuSC) differentiation into mature myotubes. Combining, publicly available single-cell RNAseq datasets, we characterize FAPs as the main source of WNT ligands inferring their potential in mediating autocrine/paracrine responses in the muscle niche. Lastly, we identify WNT5a, whose expression is impaired in dystrophic FAPs, as a crucial WNT ligand able to restrain the detrimental adipogenic differentiation drift of these cells through the positive modulation of the β-catenin signaling

Inter and intra-tumor heterogeneity of paediatric type diffuse high-grade gliomas revealed by single-cell mass cytometry

Paediatric-type diffuse high-grade gliomas (PDHGG) are aggressive tumors affecting children and young adults, with no effective treatment. These highly heterogeneous malignancies arise in different sites of the Central Nervous System (CNS), carrying distinctive molecular alterations and clinical outcomes (inter-tumor heterogeneity). Moreover, deep cellular and molecular profiling studies highlighted the coexistence of genetically and phenotypically different subpopulations within the same tumor mass (intra-tumor heterogeneity). Despite the recent advances made in the field, the marked heterogeneity of PDHGGs still impedes the development of effective targeted therapies and the identification of suitable biomarkers. In order to fill the existing gap, we used mass cytometry to dissect PDHGG inter- and intra-heterogeneity. This is one of the most advanced technologies of the “-omics” era that, using antibodies conjugated to heavy metals, allows the simultaneous measurement of more than 40 markers at single-cell level. To this end, we analyzed eight PDHGG patient-derived cell lines from different locational and molecular subgroups. By using a panel of 15 antibodies, directly conjugated to metals or specifically customized to detect important histone variants, significant differences were highlighted in the expression of the considered antigens. The single-cell multiparametric approach realized has deepened our understanding of PDHGG, confirming a high degree of intra- and inter-tumoral heterogeneity and identifying some antigens that could represent useful biomarkers for the specific PDHGG locational or molecular subgroups

Mixed matrix membranes based on MIL-101 metal–organic frameworks in polymer of intrinsic microporosity PIM-1

This work presents a study on mixed matrix membranes (MMMs) of the polymer of intrinsic microporosity PIM-1, embedding the crystalline Cr-terephthalate metal-organic framework (MOF), known as MIL-101. Different kinds of MIL-101 were used: MIL-101 with an average particle size of ca. 0.2 µm, NanoMIL-101 (ca. 50 nm), ED-MIL-101 (MIL-101 functionalized with ethylene diamine) and NH2-MIL-101 (MIL-101 synthesized using 2-aminoterephthalic acid instead of terephthalic acid). Permeability, diffusion and solubility coefficients and their corresponding ideal selectivities were determined for the gases He, H2, O2, N2, CH4 and CO2 on the “as-cast” samples and after alcohol treatment. The performance of the MMMs was evaluated in relation to the Maxwell model. The addition of NH2-MIL-101 and ED-MIL-101 does not increase the membrane performance for the CO2/N2 and CO2/CH4 separation because of an initial decrease in selectivity at low MOF content, whereas the O2 and N2 permeability both increase for NH2-MIL-101. In contrast, MIL-101 and NanoMIL-101 cause a strong shift to higher permeability in the Robeson diagrams for all gas pairs, especially for CO2, without significant change in selectivity. Unprecedented CO2 permeabilities up to 35,600 Barrer were achieved, which are among the highest values reached with PIM-1 based mixed matrix membranes. For various gas pairs, the permeability and selectivity were far above the Robeson upper bound after alcohol treatment. Short to medium time aging shows that alcohol treated samples with MIL-101 maintain a systematically higher permeability in time. Mixed gas permeation experiments on an aged as-cast sample with 47 vol% MIL-101 reveal that the MMM sample maintains an excellent combination of permeability and selectivity, far above the Robeson upper bound (CO2 = 3500–3800 Barrer, CO2/N2 = 25–27; CO2/CH4 = 21–24). This suggests good perspectives for these materials in thin film composite membranes for real applications.</p

A GNR e as Operações de Apoio à Paz: Legitimidade e limites de actuação

O presente trabalho de investigação aplicada está subordinado ao tema: ―A GNR e as Operações de Apoio à Paz: Legitimidade e Limites de Actuação‖. As operações de apoio à paz são uma realidade do mundo actual e a participação da GNR nestas operações tem sido uma constante. Neste sentido, a legitimidade desta participação tem sido ao longo dos anos questionada, tese esta que é debatida neste trabalho. Para além da legitimidade, são também aqui debatidos quais são os limites de actuação desta força militar em operações deste tipo. Neste contexto, desenvolve-se um estudo através da pergunta de partida: "De que forma a participação nas OAP é importante para a GNR? E para o País?." Os principais objectivos do trabalho são responder às perguntas supra mencionadas, verificar a legitimidade da participação da GNR neste tipo de operações, compreender o conceito das regras de empenhamento e a sua criação e, finalmente , identificar a importância destas regras para a decisão de um comandante. O trabalho iniciou-se com uma fase exploratória, procedendo-se em seguida à pesquisa com particular incidência em livros, legislação e textos relacionados com o tema, tendo sido tam bém utilizada a internet como fontes de informação sobre as operações de apoio à paz. A investigação de campo baseou-se na análise de conteúdo das entrevistas efectuadas, o que permitiu responder às perguntas de investigação através da verificação das hipó teses formuladas. Após a análise dos dados, conclui-se que a GNR tem legitimidade para participar nestas operações, o que está contemplado na sua lei orgânica, e que, em simultâneo, estas participações revelam elevada importância não só para a GNR como para o País. No entanto, para que exista uma melhor preparação das forças que executam estas missões será necessário que o novo Centro de Treino e Aprontamento para Forças de Missões Internacionais entre em funcionamento com uma estrutura diferente da planeada. O presente trabalho foi realizado entre Janeiro e Março de 2009.Abstract This investigation project was developed under the theme: ―The GNR (Portuguese Republican National Guard) and the Peace Operations: Legitimacy and Action Limits. The peace-support operations are a reality in our contemporary world and the GNR's participation in these operations has been a constant. Considering this, the legitimacy of such participations has been questioned over the years, fact that led to the thesis discussed along this work. In addition to legitimacy, the limits of military force in such operations are also debated. In this context, this project was based on two former question s: "What is the meaning of the GNR participation in the peace operations? And for the country?". The main goals of the project are answering the questions above, confirming the legitimacy of GNR's participation in such operations, understanding the rules of engagement and its creation and, at last, identifying the rules importance for a commander’s decision. The project began with an exploratory phase, followed by a research work supported by books, legislation and texts on the subject as well as the Internet as sources of information on peace-support operations. The field research was developed by analysing the conducted interviews, which allowed the research to answer the questions while checking the assumptions previously made. After analyzing the data, it is concluded that the GNR is entitled to participate in these operations, which is included in its organic law, and, simultaneously, these actions reveal high importance not only for the GNR but for the country also. Nevertheless, in order to get a better preparation of the forces that will carry out these missions, changes in structure and functioning of the new Training Centre are needed. This work was developed from January to March 2009

Ejection of damaged mitochondria and their removal by macrophages ensure efficient thermogenesis in brown adipose tissue

Recent findings have demonstrated that mitochondria can be transferred between cells to control metabolic homeostasis. Although the mitochondria of brown adipocytes comprise a large component of the cell volume and undergo reorganization to sustain thermogenesis, it remains unclear whether an intercellular mitochondrial transfer occurs in brown adipose tissue (BAT) and regulates adaptive thermogenesis. Herein, we demonstrated that thermogenically stressed brown adipocytes release extracellular vesicles (EVs) that contain oxidatively damaged mitochondrial parts to avoid failure of the thermogenic program. When re-uptaken by parental brown adipocytes, mitochondria-derived EVs reduced peroxisome proliferator-activated receptor-γ signaling and the levels of mitochondrial proteins, including UCP1. Their removal via the phagocytic activity of BAT-resident macrophages is instrumental in preserving BAT physiology. Depletion of macrophages in vivo causes the abnormal accumulation of extracellular mitochondrial vesicles in BAT, impairing the thermogenic response to cold exposure. These findings reveal a homeostatic role of tissue-resident macrophages in the mitochondrial quality control of BAT