Synthesis, structural and emission studies of a bis (carbamoyl methyl) sulfone complex of uranyl nitrate

A new tri-functional ligand (Bu2NCOCH2SO2CH2CONBu2)-Bu-i-Bu-i (L) was prepared and characterized. The coordination chemistry of this ligand with uranyl nitrate was studied with IR, (HNMR)-H-1, ES-MS, TG and elemental analysis methods. The structure of the compound [UO2(NO3)(2)L] was determined by single crystal X-ray diffraction techniques. In the structure the uranium(VI) ion is surrounded by eight oxygen atoms in a hexagonal bi-pyramidal geometry. Four oxygen atoms from two nitrate groups and two oxygen atoms from the ligand form a planar hexagon. The ligand acts as a bidentate chelate and bonds through both the carbamoyl groups to the uranyl nitrate. An ES-MS spectrum shows that the complex retains the bonding in solution. The compound displayed vibronically coupled fluorescence emission.

Femtosecond pulse shaping using differential evolutionary algorithm and wavelet operators

Evolutionary meta-algorithms for pulse shaping of broadband femtosecond duration laser pulses are proposed. The genetic algorithm searching the evolutionary landscape for desired pulse shapes consists of a population of waveforms (genes), each made from two concatenated vectors, specifying phases and magnitudes, respectively, over a range of frequencies. Frequency domain operators such as mutation, two-point crossover average crossover, polynomial phase mutation, creep and three-point smoothing as well as a time-domain crossover are combined to produce fitter offsprings at each iteration step. The algorithm applies roulette wheel selection; elitists and linear fitness scaling to the gene population. A differential evolution (DE) operator that provides a source of directed mutation and new wavelet operators are proposed. Using properly tuned parameters for DE, the meta-algorithm is used to solve a waveform matching problem. Tuning allows either a greedy directed search near the best known solution or a robust search across the entire parameter space.

Chapter 16: Electrospinning of polymer solutions

Electrospinning is a technique that involves the production of nanoscale to microscale sized polymer fibres through the application of an electric field to a droplet of polymer solution passed through a spinneret tip. This chapter considers the optimisisation of the electrospinning process and in particular the variation with solution concentration. We show the strong connection between overlapping chains and the successful spinning of fibres. We use small-angle neutron scattering to evaluate the molecular conformations in the solutions and in the fibres.

Electrochemical sensing of 2D condensation in amyloid peptides

The interfacial behavior of the model amyloid peptide octamer YYKLVFFC (peptide 1) and two other amyloid peptides YEVHHQKLVFF (peptide 2) and KKLVFFA (peptide 3) at the metal|aqueous solution interface was studied by voltammetric and constant current chronopotentiometric stripping (CPS). All three peptides are adsorbed in a wide potential range and exhibit different interfacial organizations depending on the electrode potential. At the least negative potentials, chemisorption of peptide 1 occurs through the formation of a metal sulfur bond. This bond is broken close to −0.6 V. The peptide undergoes self-association at more negative potentials, leading to the formation of a “pit” characteristic of a 2D condensed film. Under the same conditions the other peptides do not produce such a pit. Formation of the 2D condensed layer in peptide 1 is supported by the time, potential and temperature dependences of the interfacial capacity and it is shown that presence of the 2D layer is reflected by the peptide CPS signals due to the catalytic hydrogen evolution. The ability of peptide 1 to form the potential-dependent 2D condensed layer has been reported neither for any other peptide nor for any protein molecule. This ability might be related to the well-known oligomerization and aggregation of Alzheimer amyloid peptides.

Use of simulated intestinal fluids with Caco-2 cells and rat ileum

In most in vitro studies of oral drug permeability, little attempt is made to reproduce the gastrointestinal lumenal environment. The aim of this study was to evaluate the compatibility of simulated intestinal fluid (SIF) solutions with Caco-2 cell monolayers and Ussing chamber-mounted rat ileum under standard permeability experiment protocols. In preliminary experiments, fasted-state simulated intestinal fluid (FaSSIF) and fed-state simulated intestinal fluid (FeSSIF) solutions based on the dissolution medium formulae of Dressman and co-workers (1998) were modified for compatibility with Caco-2 cells to produce FaS-SIF and FeSSIF "transport" solutions for use with in vitro permeability models. For Caco-2 cells exposed to FaSSIF and FESSIF transport solutions, the transepithelial electrical resistance was maintained for over 4 h and mannitol permeability was equivalent to that in control (Hank's Balanced Salt Solution-treated) cell layers. Scanning electron microscopy revealed that microvilli generally maintained a normal distribution, although some shortening of microvilli and occasional small areas of denudation were observed. For rat ileum in the Ussing chambers, the potential difference (PD) collapsed to zero over 120 min when exposed to the FaSSIF transport solution and an even faster collapse of the PD was observed when the FeSSIF transport solution was used. Electron micrographs revealed erosion of the villi tips and substantial denudation of the microvilli after exposure of ileal tissue to FaSSIF and FeSSIF solutions, and permeability to mannitol was increased by almost two-fold. This study indicated that FaSSIF and FeSSIF transport solutions can be used with Caco-2 monolayers to evaluate drug permeability, but rat ileum in Ussing chambers is adversely affected by these solutions. Metoprolol permeability in Caco-2 experiments was reduced by 33% using the FaSSIF and 75% using the FeSSIF compared to permeability measured using HBSS. This illustrates that using physiological solutions can influence permeability measurements.

Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

Evaluating perceptual separation in a pilot system for affective composition

Research evaluating perceptual responses to music has identified many structural features as correlates that might be incorporated in computer music systems for affectively charged algorithmic composition and/or expressive music performance. In order to investigate the possible integration of isolated musical features to such a system, a discrete feature known to correlate some with emotional responses – rhythmic density – was selected from a literature review and incorporated into a prototype system. This system produces variation in rhythm density via a transformative process. A stimulus set created using this system was then subjected to a perceptual evaluation. Pairwise comparisons were used to scale differences between 48 stimuli. Listener responses were analysed with Multidimensional scaling (MDS). The 2-Dimensional solution was then rotated to place the stimuli with the largest range of variation across the horizontal plane. Stimuli with variation in rhythmic density were placed further from the source material than stimuli that were generated by random permutation. This, combined with the striking similarity between the MDS scaling and that of the 2-dimensional emotional model used by some affective algorithmic composition systems, suggests that isolated musical feature manipulation can now be used to parametrically control affectively charged automated composition in a larger system.

Energy savings in buildings or UHI mitigation? Comparison between green roofs and cool roofs

The intensification of the Urban Heat Island effect (UHI) is a problem that involves several fields, and new adequate solutions are required to mitigate its amplitude. The construction sector is strictly related with this phenomenon; in particular, roofs are the envelope components subject to the highest solar irradiance, hence any mitigation strategy should start from them and involve their appropriate design process. For this purpose, cool materials, i.e. materials which are able to reflect a large amount of solar radiation and avoid overheating of building surfaces have been deeply analyzed in the last years both at building and urban scales, showing their benefits especially in hot climates. However, green roofs also represent a possible way to cope with UHI, even if their design is not straightforward and requires taking into account many variables, strictly related with the local climatic conditions. In this context, the present paper proposes a comparison between cool roofs and green roofs for several Italian cities that are representative of different climatic conditions. In search of the most effective solution, the answers may be different depending on the perspective that leads the comparison, i.e. the need to reduce the energy consumption in buildings or the desire to minimize the contribution of the UHI effect.

Reliability of a method for evaluating porosity in denture base resins

Background: The method of porosity analysis by water absorption has been carried out by the storage of the specimens in pure water, but it does not exclude the potential plasticising effect of the water generating unreal values of porosity. Objective: The present study evaluated the reliability of this method of porosity analysis in polymethylmethacrylate denture base resins by the determination of the most satisfactory solution for storage (S), where the plasticising effect was excluded. Materials and methods: Two specimen shapes (rectangular and maxillary denture base) and two denture base resins, water bath-polymerised (Classico) and microwave-polymerised (Acron MC) were used. Saturated anhydrous calcium chloride solutions (25%, 50%, 75%) and distilled water were used for specimen storage. Sorption isotherms were used to determine S. Porosity factor (PF) and diffusion coefficient (D) were calculated within S and for the groups stored in distilled water. anova and Tukey tests were performed to identify significant differences in PF results and Kruskal-Wallis test and Dunn multiple comparison post hoc test, for D results (alpha = 0.05). Results: For Acron MC denture base shape, FP results were 0.24% (S 50%) and 1.37% (distilled water); for rectangular shape FP was 0.35% (S 75%) and 0.19% (distilled water). For Classico denture base shape, FP results were 0.54% (S 75%) and 1.21% (distilled water); for rectangular shape FP was 0.7% (S 50%) and 1.32% (distilled water). FP results were similar in S and distilled water only for Acron MC rectangular shape (p > 0.05). D results in distilled water were statistically higher than S for all groups. Conclusions: The results of the study suggest that an adequate solution for storing specimens must be used to measure porosity by water absorption, based on excluding the plasticising effect.

Synthesis of chitosan/hydroxyapatite membranes coated with hydroxycarbonate apatite for guided tissue regeneration purposes

Chitosan, which is a non-toxic, biodegradable and biocompatible biopolymer, has been widely researched for several applications in the field of biomaterials. Calcium phosphate ceramics stand out among the so-called bioceramics for their absence of local or systemic toxicity, their non-response to foreign bodies or inflammations, and their apparent ability to bond to the host tissue. Hydroxyapatite (HA) is one of the most important bioceramics because it is the main component of the mineral phase of bone. The aim of this work was to produce chitosan membranes coated with hydroxyapatite using the modified biomimetic method. Membranes were synthesized from a solution containing 2% of chitosan in acetic acid (weight/volume) via the solvent evaporation method. Specimens were immersed in a sodium silicate solution and then in a 1.5 SBF (simulated body fluid) solution. The crystallinity of the HA formed over the membranes was correlated to the use of the nucleation agent (the sodium silicate solution itself). Coated membranes were characterized by means of scanning electron microscopy - SEM, X-ray diffraction - XRD, and Fourier transform infrared spectroscopy - FTIR. The results indicate a homogeneous coating covering the entire surface of the membrane and the production of a semi-crystalline hydroxyapatite layer similar to the mineral phase of human bone. (C) 2010 Elsevier B.V. All rights reserved.

Non-LTE Monte Carlo radiative transfer. II. Nonisothermal solutions for viscous Keplerian disks

We discuss the basic hydrodynamics that determines the density structure of the disks around hot stars. Observational evidence supports the idea that these disks are Keplerian (rotationally supported) gaseous disks. A popular scenario in the literature, which naturally leads to the formation of Keplerian disks, is the viscous decretion model. According to this scenario, the disks are hydrostatically supported in the vertical direction, while the radial structure is governed by the viscous transport. This suggests that the temperature is one primary factor that governs the disk density structure. In a previous study we demonstrated, using three-dimensional non-LTE Monte Carlo simulations, that viscous Keplerian disks can be highly nonisothermal. In this paper we build on our previous work and solve the full problem of the steady state nonisothermal viscous diffusion and vertical hydrostatic equilibrium. We find that the self-consistent solution departs significantly from the analytic isothermal density, with potentially large effects on the emergent spectrum. This implies that nonisothermal disk models must be used for a detailed modeling of Be star disks.

A NEW METHOD TO OBTAIN GOOD ANATOMICAL SLIDES OF HETEROGENEOUS PLANT PARTS

A new method is presented to prepare anatomical slides of plant materials including a combination of soft and hard tissues, such as stems with cambial variants, arboreal monocotyledons, and tree bark The method integrates previous techniques aimed at softening the samples and making them thereby more homogeneous, with the use of anti-tearing polystyrene foam solution In addition, we suggest two other alternatives to protect the sections from tearing adhesive tape and/or Mayer`s albumin adhesive, both combined with the polystyrene foam solution This solution is cheap and easy to make by dissolving any packaging polystyrene m butyl acetate It is applied before each section is cut on a sliding microtome and ensures that all the tissues in the section will hold together This novel microtechnical procedure will facilitate the study of heterogeneous plant portions, as shown in some illustrated examples

Evolutionary model trees for handling continuous classes in machine learning

Model trees are a particular case of decision trees employed to solve regression problems. They have the advantage of presenting an interpretable output, helping the end-user to get more confidence in the prediction and providing the basis for the end-user to have new insight about the data, confirming or rejecting hypotheses previously formed. Moreover, model trees present an acceptable level of predictive performance in comparison to most techniques used for solving regression problems. Since generating the optimal model tree is an NP-Complete problem, traditional model tree induction algorithms make use of a greedy top-down divide-and-conquer strategy, which may not converge to the global optimal solution. In this paper, we propose a novel algorithm based on the use of the evolutionary algorithms paradigm as an alternate heuristic to generate model trees in order to improve the convergence to globally near-optimal solutions. We call our new approach evolutionary model tree induction (E-Motion). We test its predictive performance using public UCI data sets, and we compare the results to traditional greedy regression/model trees induction algorithms, as well as to other evolutionary approaches. Results show that our method presents a good trade-off between predictive performance and model comprehensibility, which may be crucial in many machine learning applications. (C) 2010 Elsevier Inc. All rights reserved.

Robust tori in a double-waved Hamiltonian model

A Hamiltonian system perturbed by two waves with particular wave numbers can present robust tori, which are barriers created by the vanishing of the perturbed Hamiltonian at some defined positions. When robust tori exist, any trajectory in phase space passing close to them is blocked by emergent invariant curves that prevent the chaotic transport. Our results indicate that the considered particular solution for the two waves Hamiltonian model shows plenty of robust tori blocking radial transport. (C) 2010 Elsevier B.V. All rights reserved.

Antiferromagnetic spherical spin-glass model

We study the thermodynamic properties and the phase diagrams of a multi-spin antiferromagnetic spherical spin-glass model using the replica method. It is a two-sublattice version of the ferromagnetic spherical p-spin glass model. We consider both the replica-symmetric and the one-step replica-symmetry-breaking solutions, the latter being the most general solution for this model. We find paramagnetic, spin-glass, antiferromagnetic and mixed or glassy antiferromagnetic phases. The phase transitions are always of second order in the thermodynamic sense, but the spin-glass order parameter may undergo a discontinuous change.