One-pot synthesis and physicochemical properties of an organo-modified saponite clay

An organo-saponite clay containing intercalated cetyltrimethylammonium (CTA(+)) cations was synthesized by an efficient one-step hydrothermal method and was compared with a CTA-exchanged saponite prepared by a classical postsynthesis intercalation route. In both hybrid samples, surfactant loading up to 10% was achieved. A comparative investigation of the physicochemical properties of both solids was carried out by a multidisciplinary approach, by using a combination of spectroscopic, structural, and thermal characterization tools. Powder X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) data indicated that the one-pot-prepared solid showed that the presence of CTA(+) molecules in the synthesis gel did not affect the clay structure. In addition, thermal analysis suggested that the inorganic layers play an active role in stabilizing and protecting the surfactant molecules by increasing their thermal stability. A different arrangement of intercalated CTA(+) ions in the two hybrid clays was observed by solid state NMR in combination with Fourier transform infrared (FTIR) spectroscopy and assigned to a different all-trans/gauche conformation ratio of the surfactant depending on the synthetic method used to prepare the two final materials. The surfactant organization is also influenced by the lamellae charge density, which is different in the two organo-modified materials as found by (27)Al and (29)Si MAS NMR experiments.     

Proteins conjugation with ZnO sol–gel nanopowders

The conjugation between probe biomolecules and inorganic nanoparticles has been studied. Three different and biologically relevant proteins, bovine serum albumin (BSA), lysozyme (LSZ) and Ribonuclease A (RNAseA), have been selected as model systems because of their difference in size and isoelectric point. Zinc oxide nanoparticles, synthesized via sol–gel, have been thoroughly characterized by X-ray Photoelectron Spectroscopy, Scanning Electron Microscopy and X-ray Diffraction, and subsequently used as platforms for immobilization of the biomolecules. The interaction of the three proteins with the ZnO surface was performed in phosphate buffer solutions at pH 7.2 in order to mimic physiological fluids and was investigated through fluorescence experiments. The obtained results indicate that conjugation of BSA, LZS and RNAseA on the oxide nanoparticles was mostly dictated by the overall charge of the different proteins. Electrostatic bonds dominate the formation of the protein/ZnO conjugates, whereas the size of the proteins seems to play a negligible role under the adopted experimental conditions.     

Biosorbents from Plant Fibers of Hemp and Flax for Metal Removal: Comparison of Their Biosorption Properties

Lignocellulosic fibers extracted from plants are considered an interesting raw material for environmentally friendly products with multiple applications. This work investigated the feasibility of using hemp- and flax-based materials in the form of felts as biosorbents for the removal of metals present in aqueous solutions. Biosorption of Al, Cd, Co, Cu, Mn, Ni and Zn from a single solution by the two lignocellulosic-based felts was examined using a batch mode. The parameters studied were initial metal concentration, adsorbent dosage, contact time, and pH. In controlled conditions, the results showed that: (i) the flax-based felt had higher biosorption capacities with respect to the metals studied than the hemp-based felt; (ii) the highest removal efficiency was always obtained for Cu ions, and the following order of Cu > Cd > Zn > Ni > Co > Al > Mn was found for both examined biosorbents; (iii) the process was rapid and 10 min were sufficient to attain the equilibrium; (iv) the efficiency improved with the increase of the adsorbent dosage; and (v) the biosorption capacities were independent of pH between 4 and 6. Based on the obtained results, it can be considered that plant-based felts are new, efficient materials for metal removal.     

A Bernoulli problem with non-constant gradient boundary constraint

In this article, we present a result about the existence and convexity of solutions to a free boundary problem of Bernoulli type, with non-constant gradient boundary constraint depending on the outer unit normal. In particular, we prove that, in the convex case, the existence of a subsolution guarantees the existence of a classical solution, which is proved to be convex.     

Effect of low-temperature high-pressure sintering on BiFeO3 density,electrical magnetic and structural properties

Single-phase multiferroic BiFeO₃ (BFO) powders were prepared by hydrothermal microwave synthesis and dense BiFeO₃ ceramics were fabricated for the first time by the low-temperature high-pressure (LTHP) sintering technique. Effect of sintering temperature ranging from 400 to 800 °C (3 min and 10 min) and pressure of 3–8 GPa on structural, microstructural, electric and magnetic properties were investigated through X-ray diffraction, scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), density and magnetic measurements. The results highlighted that LTHP sintering method, thanks to the high pressure involved, requires lower temperature and shorter time than other techniques, avoiding BiFeO₃ phase degradation. SEM images show that for short experimental time (t = 3 min) the average grain size of the sintered samples was approximately the same size of raw powder. Extending the sintering time up to 10 min the grain growth phenomena occurred. Moreover the results indicate that the best obtained density value was around 98% of theoretical density. The dielectric behavior of BiFeO₃ ceramics was not significantly influenced by the LTHP sintering conditions. Magnetic measurements showed that ceramic BiFeO₃ is weakly ferromagnetic at room temperature.     

Fast approximation to pixelwise relaxivity maps: Validation in iron overloaded subjects

Purpose

Liver iron quantification by MRI has become routine. Pixelwise (PW) fitting to the iron-mediated signal decay has some advantages but is slower and more vulnerable to noise than region-based techniques. We present a fast, pseudo-pixelwise mapping (PPWM) algorithm.

Materials and Methods

The PPWM algorithm divides the entire liver into non-contiguous groups of pixels sorted by rapid relative relaxivity estimates. Pixels within each group of like-relaxivity were binned and fit using a Levenberg–Marquadt algorithm.

Results

The developed algorithm worked about 30 times faster than the traditional PW approach and generated R2* maps qualitatively and quantitatively similar. No systematic difference was observed in median R2* values with a coefficient of variability (CoV) of 2.4%. Intra-observer and inter-observer errors were also under 2.5%. Small systematic differences were observed in the right tail of the R2* distribution resulting in slightly lower mean R2* values (CoV of 4.2%) and moderately lower SD of R2* values for the PPWM algorithm. Moreover, the PPWM provided the best accuracy, giving a lower error of R2* estimates.

Conclusion

The PPWM yielded comparable reproducibility and higher accuracy than the TPWM. The method is suitable for relaxivity maps in other organs and applications.     

Polygons in Minkowski three space and parabolic Higgs bundles of rank 2 on \mathbb{C}{{\mathbb{P}}^1}

Consider the moduli space of parabolic Higgs bundles (E, Φ) of rank two on ??¹ such that the underlying holomorphic vector bundle for the parabolic vector bundle E is trivial. It is equipped with the natural involution defined by $ \left( {E,\varPhi } \right)\mapsto \left( {E,-\varPhi } \right) $ . We study the fixed point locus of this involution. In [GM], this moduli space with involution was identified with the moduli space of hyperpolygons equipped with a certain natural involution. Here we identify the fixed point locus with the moduli spaces of polygons in Minkowski 3-space. This identification yields information on the connected components of the fixed point locus.     

GAP-43 mRNA detection by in situ hybridization, direct and indirect in situ RT-PCR in hippocampal and cerebellar tissue sections of adult rat brain

The growth-associated protein GAP-43 is a presynaptic membrane phosphoprotein that is expressed at high levels during development and axonal growth. To evaluate the cellular distribution of GAP-43 mRNA in the hippocampus and cerebellum of adult rats we applied in situ hybridization (ISH) as well as direct and indirect in situ RT-PCR using biotin as a reporter molecule. ISH resulted in a positive signal in most cerebellar granular cells and in 30% of hippocampal CA3 neurons. Direct in situ RT-PCR yielded cells with strong signals in every region investigated, with elevated background levels most likely related to incorporation of labeled nucleotides into non-specific amplicons through internal priming and DNA repair activity. Indirect in situ RT-PCR turned out to be the best approach for detecting GAP-43 mRNA positive cells. Cerebellar cells exhibiting a positive signal for GAP-43 mRNA were of the granular cell type (98%). Hippocampal neurons with a positive reaction for GAP-43 mRNA included all the neuron groups analyzed, namely CA1 (99%) and CA3 pyramidal cells (94%) and dentate gyrus granule cells (92%). Dentate gyrus granule cells have not tested positive for GAP-43 mRNA detection by molecular morphology analysis. These data show that in normal rats GAP-43 mRNA is present in different cell populations of hippocampal formation, supporting the role of this protein in the ongoing processes of synaptic plasticity.     

An integrated Raman and petrographic characterization of Italian mediaeval artifacts in pietra ollare (soapstone)

Ten fragments of pots made by pietra ollare (basic and ultrabasic metamorphic rocks belonging to greenschist facies) found in the archaeological site of Crocetta di Sant'Agata Bolognese (Bologna, Italy) have been studied to characterize them and to define their provenance. The fragments, dated between the 9^th and 10^th century AD, show traces of blackening from fire, indicating the use of these findings as pots by fire. The extensive use of a non‐destructive technique, Raman spectroscopy, in both laboratory and portable forms, for the provenance analysis of pietra ollare artifacts has been evaluated. Micro‐Raman spectroscopy was used for a detailed study of the main components, to identify the secondary minerals and to study the distribution of the mineral phases in the samples. The samples show schistose texture, are fine grained and consist mainly of talc and chlorite, and subordinate carbonates, oxides and serpentine. Olivine is rare. Based on the mineralogical composition, the material can be defined as chlorite and carbonate talc‐schist. Our samples of pietra ollare may be assigned to chlorite and magnesite‐bearing talc‐schists. The alpine areas of origin of this lithotype are Valtellina, Valchiavenna and Val Bregaglia. In particular, we can hypothesize that the origin of these findings is Valchiavenna, which had great commercial importance in the Middle Ages. Further measurements, obtained with a portable Raman spectrometer, directly on a quarry near Chiavenna, support our hypothesis. Copyright © 2013 John Wiley & Sons, Ltd.     

Photon statistics and speckle visibility spectroscopy with partially coherent X‐rays

A new approach is proposed for measuring structural dynamics in materials from multi‐speckle scattering patterns obtained with partially coherent X‐rays. Coherent X‐ray scattering is already widely used at high‐brightness synchrotron lightsources to measure dynamics using X‐ray photon correlation spectroscopy, but in many situations this experimental approach based on recording long series of images (i.e. movies) is either not adequate or not practical. Following the development of visible‐light speckle visibility spectroscopy, the dynamic information is obtained instead by analyzing the photon statistics and calculating the speckle contrast in single scattering patterns. This quantity, also referred to as the speckle visibility, is determined by the properties of the partially coherent beam and other experimental parameters, as well as the internal motions in the sample (dynamics). As a case study, Brownian dynamics in a low‐density colloidal suspension is measured and an excellent agreement is found between correlation functions measured by X‐ray photon correlation spectroscopy and the decay in speckle visibility with integration time obtained from the analysis presented here.