Synthesis, characterisation and anti-protozoal activity of carbamate-derived polyazamacrocycles

A short, highly efficient approach for the synthesis of a novel class of polyazamacrocycles containing N-functionalised carbamate side-chains has been developed. The key steps involved a phase-transfer mediated macrocyclisation to form the ring system as well as a tin-catalysed reaction with isocyanates to introduce the carbamate side-chains. X-Ray crystallography confirmed successful formation of the 1,4,7,10-tetraazacyclododecane ring and N-functionalisation of all the amine centres. Preliminary testing of the biological activity of the compounds revealed significant anti-parasitic activity against bloodstream form African trypanosomes.     

Non-edible babassu oil as a new source for energy production–a feasibility transesterification survey assisted by ultrasound

Ethyl esters of babassu oil were synthesized by alkaline catalysis to make the green production of biodiesel feasible with simple methods and available technology. Babassu oil is a transparent, light yellow oil extracted from the seeds of the babassu palm (Orbinya sp), and due to its high saturated fatty acid composition (83%), it is considered a non-inedible oil. Transesterification using ethanol represents a valid alternative to using methanol because of ethanol’s lower toxicity and the higher yield on weight compared to methanol. Statistical methodology was applied to optimize the transesterification reaction, which was promoted by ultrasonic waves and mechanical agitation. Nuclear magnetic resonance spectroscopy was used to quantify the conversion attained. Alkaline transesterification assisted by ultrasound produced the best results with respect to reaction time and the phase separation step. The model obtained showed that conversions higher than 97% may be achieved in 10 min with correct tuning of the process variables.     

A new approach for scheduling independent tasks with multiple modes

Heuristic algorithms for scheduling tasks with multiple modes and minimizing the schedule length involve in general two distinct phases, task mode assignment and then task scheduling. We propose a novel approach where these two features are managed in an integrated mechanism with mode assignment embedded in scheduling. The problem is first reformulated as a special single-mode task scheduling problem, and then is modeled as a graph interval T-coloring. Finally, a tabu-like metaheuristic is proposed for this latter graph coloring problem, and the performance of our approach is compared to known multi-mode scheduling heuristics.     

Structural modifications of ionic liquid surfactants for improving the water dispersibility of carbon nanotubes: an experimental and theoretical study

The 1-hexadecyl-3-vinylimidazolium bromide (hvimBr), a water-soluble long-chain imidazolium ionic liquid (IL) with surfactant properties, showed the ability to produce stable homogeneous aqueous dispersions of pristine Single-Walled Carbon Nanotubes (SWNTs). The purpose of this study is the improvement of SWNT dispersing ability by assessing the effect of different groups in position 3 of the imidazole ring. In this regard structural analogues were synthesized and, after characterization, their capability to dissolve SWNTs in water was investigated. Molecular Dynamics (MD) simulations have been performed to provide a semi-quantitative indication of the affinity of each dispersing agent toward SWNT and to attempt an explanation of the experimental results.     

Ultrasound-mediated structural changes in cells revealed by FTIR spectroscopy: a contribution to the optimization of gene and drug delivery

Ultrasound effects on biological samples are gaining a growing interest concerning in particular, the intracellular delivery of drugs and genes in a safe and in a efficient way. Future progress in this field will require a better understanding of how ultrasound and acoustic cavitation affect the biological system properties. The morphological changes of cells due to ultrasound (US) exposure have been extensively studied, while little attention has been given to the cells structural changes. We have exposed two different cell lines to 1 MHz frequency ultrasound currently used in therapy, Jurkat T-lymphocytes and NIH-3T3 fibroblasts, both employed as models respectively in the apoptosis and in the gene therapy studies. The Fourier Transform Infrared (FTIR) Spectroscopy was used as probe to reveal the structural changes in particular molecular groups belonging to the main biological systems. The genotoxic damage of cells exposed to ultrasound was ascertained by the Cytokinesis-Block Micronucleus (CBMN) assay. The FTIR spectroscopy results, combined with multivariate statistical analysis, regarding all cellular components (lipids, proteins, nucleic acids) of the two cell lines, show that Jurkat cells are more sensitive to therapeutic ultrasound in the lipid and protein regions, whereas the NIH-3T3 cells are more sensitive in the nucleic acids region; a meaningful genotoxic effect is present in both cell lines only for long sonication times while in the Jurkat cells also a significant cytotoxic effect is revealed for long times of exposure to ultrasound.     

Copula-Type Estimators for Flexible Multivariate Density Modeling Using Mixtures

Copulas are popular as models for multivariate dependence because they allow the marginal densities and the joint dependence to be modeled separately. However, they usually require that the transformation from uniform marginals to the marginals of the joint dependence structure is known. This can only be done for a restricted set of copulas, for example, a normal copula. Our article introduces copula-type estimators for flexible multivariate density estimation which also allow the marginal densities to be modeled separately from the joint dependence, as in copula modeling, but overcomes the lack of flexibility of most popular copula estimators. An iterative scheme is proposed for estimating copula-type estimators and its usefulness is demonstrated through simulation and real examples. The joint dependence is modeled by mixture of normals and mixture of normal factor analyzer models, and mixture of t and mixture of t-factor analyzer models. We develop efficient variational Bayes algorithms for fitting these in which model selection is performed automatically. Based on these mixture models, we construct four classes of copula-type densities which are far more flexible than current popular copula densities, and outperform them in a simulated dataset and several real datasets. Supplementary material for this article is available online.     

Spondias tuberosa (Anacardiaceae) leaves: profiling phenolic compounds by HPLC‐DAD and LC–MS/MS and in vivo anti‐inflammatory activity

Spondias tuberosa is a medicinal plant used by several local communities in northeast Brazil to treat infections, digestive disorders and inflammatory conditions. The study aimed to identify and quantify the major phenolic in hydroethanolic extract of leaves from S. tuberosa and to evaluate its anti‐inflammatory potential. The chemical profile of extract was analyzed by HPLC‐DAD and HPLC–MS. The in vivo anti‐inflammatory activity was investigated in carrageenan‐induced hind paw edema and peritonitis models in mice. Identified and quantified through HPLC‐DAD or HPLC‐MS analyses of S. tuberosa extract were the following compounds: chlorogenic acid, caffeic acid, rutin and isoquercitrin. The inflammatory response to carrageenan was significantly reduced in both models by S. tuberosa extract. In hind paw edema, the edematogenic response was reduced by up to 63.6% and the myeloperoxidase activity was completely inhibited. In the peritonitis model, the total cell migration into the peritoneal cavity was reduced by up to 65%. The results obtained give evidence of the anti‐inflammatory action of S. tuberosa and suggest the potential therapeutic benefit of this plant on inflammatory conditions. The chlorogenic acid, caffeic acid, rutin and isoquercitrin identified and quantified in S. tuberosa leaves enable us to suggest that these compounds could be used as chemical markers for quality control of derivative products from this species. Copyright © 2016 John Wiley & Sons, Ltd.     

Direct submolecular scale imaging of mesoscale molecular order in supported dipalmitoylphosphatidylcholine bilayers

Supported dipalmitoylphosphatidylcholine (DPPC) bilayers are widely used membrane systems in biophysical and biochemical studies. Previously, short-range positional and orientational order of lipid headgroups of supported DPPC bilayers was observed at room temperature using low deflection noise frequency modulation atomic force microscopy (FM-AFM). While this ordering was supported by X-ray diffraction studies, it conflicted with diffusion coefficient measurements of gel-phase bilayers determined from fluorescence photobleaching experiments. In this work, we have directly imaged mica-supported DPPC bilayers with submolecular resolution over scan ranges up to 146 nm using low deflection noise FM-AFM. Both orientational and positional molecular ordering were observed in the mesoscale, indicative of crystalline order. We discuss these results in relation to previous biophysical studies and propose that the mica support induces mesoscopic crystalline order of the DPPC bilayer at room temperature. This study also demonstrates the recent advance in the scan range of submolecular scale AFM imaging.     

Kinetic and thermodynamic parameters of volatilization of biodiesel from babassu, palm oil and mineral diesel by thermogravimetric analysis (TG)

The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol^?1), followed by babassu biodiesel (E = 76.37 kJ mol^?1), and palm biodiesel (E = 87.00 kJ mol^?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol^?1 K^?1, ΔH = +80.38 kJ mol^?1 and ΔG = +142.74 kJ mol^?1. For palm biodiesel ΔS = ?119.26 J mol^?1 K^?1, ΔH = + 90.53 kJ mol^?1 and ΔG = +141.21 kJ mol^?1, and for diesel ΔS = ?131.3 J mol^?1 K^?1, ΔH = +53.29 kJ mol^?1 and ΔG = +115.13 kJ mol^?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.     

Generalized Weighted Morrey Estimates for Marcinkiewicz Integrals with Rough Kernel Associated with Schrödinger Operator and Their Commutators

Let L =-?+V(x) be a Schr?dinger operator, where ? is the Laplacian on ■~n,while nonnegative potential V(x) belonging to the reverse H?lder class. The aim of this paper is to give generalized weighted Morrey estimates for the boundedness of Marcinkiewicz integrals with rough kernel associated with Schr?dinger operator and their commutators.Moreover, the boundedness of the commutator operators formed by BMO functions and Marcinkiewicz integrals with rough kernel associated with Schr?dinger operators is discussed on the generalized weighted Morrey spaces. As its special cases, the corresponding results of Marcinkiewicz integrals with rough kernel associated with Schr?dinger operator and their commutators have been deduced, respectively. Also, Marcinkiewicz integral operators, rough Hardy-Littlewood(H-L for short) maximal operators, Bochner-Riesz means and parametric Marcinkiewicz integral operators which satisfy the conditions of our main results can be considered as some examples.