Hybrid MCM-41 grafted by a general microwave-assisted procedure: a characterization study

Hybrid materials obtained through a Microwave-assisted grafting of organic functional groups on mesoporous silica (MCM-41 type) have been characterized by X-ray powder diffraction, TG-DSC, N₂ adsorption, solid state ¹³C- and ²⁹Si-NMR, TEM and SEM. The studied grafting procedure is effective in the preparation of hybrid organosilicas under solvent-free conditions. Microwaves allows an ultra-fast and clean functionalization of the mesoporous materials and the method has been applied to produce a wide series of functional materials. The hybrid materials maintain the original mesoporous structure when the loading of linked organic groups does not exceed 10 %. In this cases, the slight pore volume reduction is linearly correlated to the organic amount in the product. If functional groups able to interact among them through hydrogen bond are used, hybrid materials exhibit high Organic/SiO₂ ratios and low pore volumes due to the formation of a network occluding the pores, where functional groups of free organosilane molecules interacts with the functional groups of molecules linked to the matrix. NMR data confirm that the network is composed by organosilane molecules linked or not to the framework. Acid washing is able to labilize hydrogen bond and open the network. In the case of bulky but chemically inert functionalising agents the network is not produced.     

Cyclic Stretch Induces Inducible Nitric Oxide Synthase and Soluble Guanylate Cyclase in Pulmonary Artery Smooth Muscle Cells

In the pulmonary vasculature, mechanical forces such as cyclic stretch induce changes in vascular signaling, tone and remodeling. Nitric oxide is a potent regulator of soluble guanylate cyclase (sGC), which drives cGMP production, causing vasorelaxation. Pulmonary artery smooth muscle cells (PASMCs) express inducible nitric oxide synthase (iNOS), and while iNOS expression increases during late gestation, little is known about how cyclic stretch impacts this pathway. In this study, PASMC were subjected to cyclic stretch of 20% amplitude and frequency of 1 Hz for 24 h and compared to control cells maintained under static conditions. Cyclic stretch significantly increased cytosolic oxidative stress as compared to static cells (62.9 ± 5.9% vs. 33.3 ± 5.7% maximal oxidation), as measured by the intracellular redox sensor roGFP. Cyclic stretch also increased sGCβ protein expression (2.5 ± 0.9-fold), sGC activity (1.5 ± 0.2-fold) and cGMP levels (1.8 ± 0.2-fold), as well as iNOS mRNA and protein expression (3.0 ± 0.9 and 2.6 ± 0.7-fold, respectively) relative to control cells. An antioxidant, recombinant human superoxide dismutase (rhSOD), significantly decreased stretch-induced cytosolic oxidative stress, but did not block stretch-induced sGC activity. Inhibition of iNOS with 1400 W or an iNOS-specific siRNA inhibited stretch-induced sGC activity by 30% and 68% respectively vs. static controls. In conclusion, cyclic stretch increases sGC expression and activity in an iNOS-dependent manner in PASMC from fetal lambs. The mechanism that produces iNOS and sGC upregulation is not yet known, but we speculate these effects represent an early compensatory mechanism to counteract the effects of stretch-induced oxidative stress. A better understanding of the interplay between these two distinct pathways could provide key insights into future avenues to treat infants with pulmonary hypertension.     

Microwave assisted combustion synthesis in the system Ti–Si–C for the joining of SiC: Experimental and numerical simulation results

Microwaves at 2.45 GHz have been applied to ignite the combustion synthesis of compacted Ti–Si–C powders mixtures, having 1:1:1 atomic ratio, in order to join SiC-based components. A mixture of different refractory phases such as TiC and TiSi₂ were obtained. Depending on the synthesis conditions, no residual silicon in the joint was detected, suggesting the suitability of the here proposed experimental joining approach for nuclear plants and high temperature applications. A simplified model was developed with the aim of obtaining a deeper understanding of the here proposed rapid, almost pressure-less and localized heating joining method. Experimental and numerical simulation results demonstrate that joining of SiC can be rapidly obtained with minimization of heat affected zones in the SiC substrates. Maximum apparent shear strength values of the joints ranged from 9.9 to 45.1 MPa, depending on the process conditions.     

Compressive properties of pristine and SiC-Te-added MgB2 powders,green compacts and spark-plasma-sintered bulks

Pristine and (SiC+Te)-added MgB₂ powders, green and spark plasma sintered (SPS) compacts were investigated from the viewpoint of quasi-static and dynamic (Split-Hopkinson Pressure Bar, SHPB) compressive mechanical properties The amount of the additive (SiC+Te) was selected to be the optimum one for maximization of the superconducting functional parameters. Pristine and added MgB₂ show very similar compressive parameters (tan δ, fracture strength, Vickers hardness, others) and fragment size in the SHPB test. However, for the bulk SPSed samples the ratio of intergranular to transgranular fracturing changes, the first one being stronger in the added sample. This is reflected in the quasi-static K_IC that is higher for the added sample. Despite this result, sintered samples are brittle and have roughly similar fragmentation behavior as for brittle engineering ceramics. In the fragmentation process, the composite nature of our samples should be considered with a special focus on MgB₂ blocks (colonies) that show the major contribution to fracturing. The Glenn-Chudnovsky model of fracturing under dynamic load provides the closest values to our experimental fragment size data.     

Thin‐film nanostructure and polymer architecture in semicrystalline syndiotactic poly(p‐methylstyrene)–(cis‐1,4‐polybutadiene) multiblock copolymers

The thin‐film morphology of stereoregular syndiotactic poly(p‐methylstyrene)–(cis‐1,4‐polybutadiene) (sP(pMS–B)) multiblock copolymers has been investigated using tapping mode atomic force microscopy with variation of the polymer composition and monomer block lengths. The morphology of the thin films ranges from isolated circular domains of sP(pMS) embedded into a matrix of polybutadiene (PB) to isolated domains of PB embedded into a matrix of sP(pMS), passing through bicontinuous (jagged) lamellae when the pMS concentration is in the range 20–67 mol%. Multiple folding of the polymer segments, i.e. where reciprocal inclusions of polymer segments to each other phase are able to generate greater domain, has been postulated and validated by considerations on the polymer architecture and the thermal and crystalline behaviour. © 2019 Society of Chemical Industry     

Colour research with architectural relevance: How can different approaches gain from each other?

Colour research from different scientific traditions start from different basic questions and use different methods and concepts. This makes it difficult to communicate and to judge result relevance in a wider perspective. Here we start from architects' need of colour knowledge and discuss recent studies of colour appearance and colour emotion, with and without explicit connection to architecture. We stress the need for further development and clarification of concepts and conclude that the multitude of studies with different approaches can be seen as cases, jointly adding to a widened and deepened understanding of colour. © 2010 Wiley Periodicals, Inc. Col Res Appl, 2010     

Structural and magnetic properties of Li2O–Fe2O3 ceramic nanostructures

xLi₂O–(1−x)α-Fe₂O₃ (x=0.1, 0.3, 0.5, and 0.7) nanoparticle systems were successfully synthesized by mechanochemical activation of Li₂O and α-Fe₂O₃ mixtures for 0–12 h of ball milling time. The study aims at exploring the formation of magnetic oxide semiconductors at the nanoscale, which is of crucial importance for catalysis, sensing and electrochemical applications. X-ray powder diffraction (XRD), Mössbauer spectroscopy and magnetic measurements were used to study the phase evolution of xLi₂O–(1−x)α-Fe₂O₃ nanoparticle systems under the mechanochemical activation process. Rietveld refinement of the XRD patterns yielded the values of the particle size as function of composition and milling times and indicated the presence of Li-substituted hematite and tetra lithium iron oxide LiFeO₂, along with the formation of multiple phases for large x values and long milling times. The Mössbauer studies showed that the spectrum of the mechanochemically activated composites evolved from a sextet for hematite to sextets and a doublet upon duration of the milling process with lithium oxide. Magnetic measurements recorded at 5 K to room temperature (RT) in an applied magnetic field of 50,000 Oe showed that the magnetization of the milled samples is larger at low temperatures than at RT and increases with decreasing particle size. Zero field cooling measurements made possible the determination of the blocking temperatures of the specimens as function of ball milling time and evidenced the occurrence of superparamagnetism in the studied samples. This result correlates well with the observed presence of a quadrupole-split doublet in the Mössbauer spectra.