Medium effect on the rotational barrier of carbamates and its sulfur congeners

The solvent effect on rotation about the conjugated C-N bond has been studied for methyl N,N-dimethylcarbamate (1), S-methyl N,N-dimethylthiocarbamate (2), O-methyl N,N-dimethylthiocarbamate (3), and methyl N,N-dimethyldithiocarbamate (4). The present investigation included experimental determination of activation parameters (DeltaH, DeltaS, and DeltaG) combined with theoretical calculations via both quantum and classical approaches. Rotational barriers were measured through dynamic NMR experiments in solvents of varied polarity and proton donor ability. In the less polar solvents, the values were 15.3+/-0.5 (CS2), 14.0+/-1.1 (CS2), 17.5+/-0.4 (CCl4), and 14.6+/-0.5 kcal/mol (CCl4) for 1, 2, 3, and 4, respectively. Upon changing to an aqueous solution, the greatest variations occurred for 2 and 4, whereas for 1 and 3, there was no observable effect. Quantum chemical calculations at the HF/6-311+G(2d,p) and B3LYP/6-311+G(2d,p) levels, with the inclusion of solvation effects via the isodensity polarizable continuum model (IPCM), correctly reproduced the experimentally observed trends but failed to account for some of the measured rotational barrier's magnitudes. Hydrogen-bonding effects were included by performing molecular dynamic simulations. For these latter calculations, it was necessary to parametrize the force field against energies of water-solute complexes calculated at B3LYP/6-31+G(d,p). Through the results of radial distribution functions, solution rotational barriers could be calculated, presenting good agreement with experimental determinations and revealing the role of hydrogen bonding. Interestingly, only for 2, the rotational barrier is predicted to increase as a result of complexation with water. For the remaining compounds, hydrogen bonding causes the barrier to decrease, contrasting with most of the molecular systems studied up to now.     

Surface hydrophobicity modulates the operation of actomyosin-based dynamic nanodevices

We studied the impact of surface hydrophobicity on the motility of actin filaments moving on heavy-meromyosin (HMM)-coated surfaces. Apart from nitrocellulose (NC), which is the current standard for motility assays, all materials tested are good candidates for microfabrication: hydrophilic and hydrophobic glass, poly(methyl methacrylate) (PMMA), poly(tert-butyl methacrylate) (PtBuMA), and a copolymer of O-acryloyl acetophenone oxime with a 4-acryloyloxybenzophenone (AAPO). The most hydrophilic (hydrophilic glass, contact angle 35 degrees) and the most hydrophobic (PtBuMA, contact angle 78 degrees) surfaces do not maintain the motility of actin filaments, presumably because of the low density of adsorbed HMM protein or its high levels of denaturation, respectively. The velocity of actin filaments presents higher values in the middle of this "surface hydrophobicity motility window" (NC, PMMA), and a bimodal distribution, which is more apparent at the edges of this motility window (hydrophobic glass and AAPO). A molecular surface analysis of HMM and its S1 units suggests that the two very different, temporally separated conformations of the HMM heads could exacerbate the surface-modulated protein behavior, which is common to all microdevices using surface-immobilized proteins. An explanation for the above behavior proposes that the motility of actin filaments on HMM-functionalized surfaces is the result of the action of three populations of motors, each in a different surface-protein conformation, that is, HMM with both heads working (high velocities), working with one head (low velocities), and fully denatured HMM (no motility). It is also proposed that the molecularly dynamic nature of polymer surfaces amplifies the impact of surface hydrophobicity on protein behavior. The study demonstrates that PMMA is a good candidate for the fabrication of future actomyosin-driven dynamic nanodevices because it induces the smoothest motility of individual nano-objects with velocities comparable with those obtained on NC.     

Studies of the quantum Hall to quantum Hall insulator transition in InSb-based 2DESs

The temperature dependence of ρ_xx is studied in the vicinity of the quantum Hall to quantum Hall insulator transition (ν=1→0) in InSb/InAlSb based 2DESs. ρ_xx displays a symmetric temperature dependence about the transition with on the QH side and on the insulating side. A plot of 1/T₀ for successive ν displays power-law divergence with 1/T₀∝|ν−ν_c|^−γ,² with γ=2.2±0.3. This critical behavior in addition to the behavior expected of the quantum transport regime confirms that the QH/QHI transition is indeed a good quantum phase transition.     

Pharmacological and Therapeutic Potential of Myristicin: A Literature Review

Natural products have been used by humanity for many centuries to treat various illnesses and with the advancement of technology, it became possible to isolate the substances responsible for the beneficial effects of these products, as well as to understand their mechanisms. In this context, myristicin, a substance of natural origin, has shown several promising activities in a large number of in vitro and in vivo studies carried out. This molecule is found in plants such as nutmeg, parsley, carrots, peppers, and several species endemic to the Asian continent. The purpose of this review article is to discuss data published in the last 10 years at Pubmed, Lilacs and Scielo databases, reporting beneficial effects, toxicity and promising data of myristicin for its future use in medicine. From 94 articles found in the literature, 68 were included. Exclusion criteria took into account articles whose tested extracts did not have myristicin as one of the major compounds.     

Pharmaceuticals and Their Main Metabolites in Treated Sewage Sludge and Sludge-Amended Soil: Availability and Sorption Behaviour

This work evaluated the availability and sorption behaviour of four pharmaceuticals and eight of their metabolites in sewage sludge and sludge-amended soil. Digested sludge and compost were evaluated. The highest levels found in digested sludge corresponded to caffeine (up to 115 ng g⁻¹ dm), ibuprofen (45 ng g⁻¹ dm) and carbamazepine (9.3 ng g⁻¹ dm). The concentrations measured in compost were even lower than in digested sludge. No compound was detected in sludge-amended soils. This fact could be due to the dilution effect after sludge application to soil. Different adsorption capacities in sludge–soil mixtures were measured for the studied compounds at the same spike concentration. In general, except for paraxanthine and 3-hydroxycarbamazepine, the metabolite concentrations measured in the mixtures were almost two-fold lower than those of their parent compounds, which can be explained by their mobility and lixiviation tendency. The log K_d ranged from −1.55 to 1.71 in sludge samples and from −0.29 to 1.18 in soil–sludge mixtures. The log K_d values calculated for compost were higher than those calculated for digested sludge. The obtained results implied that the higher organic carbon content of compost could influence soil contamination when it is applied to soil.     

A Categorical View to Structural Complexity

In the present work we are interested in to provide a universal language for supporting formalisms to specify the approximation hierarchy system for an abstract NP‐hard optimization problem. This work grew from the idea of providing a categorical view of structural complexity to optimization problems. The direction is aimed towards actually exploring the connections among the structural complexity aspects and categorical concepts, which may be viewed in a high‐level, in a structuralistic sense. After introducing the optimization problems categories OPTS and OPT, as well as related questions, a formal system modelling the approximation hierarchy of a given optimization problem is provided, based on categorical shape theory. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Orientational diffusivities measured by Rayleigh scattering in a lyotropic calamitic nematic () liquid crystal phase: the backflow problem revisited

Using a light-beating technique we have measured the damping time of thermal fluctuations of the nematic director for the so called cylindrical or calamitic nematic (N_C) phase of the lyotropic system K-laurate/decanol/. By varying the scattering angle in suitable geometries, we have been able to estimate the orientational diffusivities associated to the three pure deformations of splay, twist and bend. A former measurement made in the disk-like N_D phase of the same system yielded a large deviation between the splay and twist diffusivities. The effect was then attributed to induced flows, or backflow, which could be responsible for the reduction of the splay viscosity. In fact, this is the analogous effect, for disks, to the one recognized since long time ago arriving for rod-like molecules in a classical nematic, though in this case it is associated with bend deformations. The analogy comes about thanks to the interchange of the role played by disks and cylinders for, respectively, splay and bend fluctuations.The measurements reported here provide a new test on the applicability of the backflow model to a nematic system composed of micelles, that is, aggregates made of amphiphilic (surfactant) molecules, in its cylindrical-like variant, i.e. the N_C phase. In addition, the comparative study made here with the previous results existing in the literature for the N_D phase, allows us to conjecture on structural issues concerning lyotropic nematics. Received: 29 April 1998 / Revised: 19 August 1998 / Accepted: 31 August 1998     

Magnetic interactions in the monoclinic ludwigite Cu FeO BO

The system Cu₂FeO₂BO₃ is an oxyborate belonging to the family of the ludwigites. In this paper we present AC susceptibility, magnetization measurements and M?ssbauer spectroscopy on this material which allows for a complete characterization of its complex magnetic behavior. We find an hierarchy of interactions which clearly defines three regimes with decreasing temperature. These are associated with, the freezing of the Fe moments, the antiferromagnetic ordering of the Cu sub-lattice and finally the coupling between both systems. Received 25 September 1998     

Probabilistic temporal networks: A unified framework for reasoning with time and uncertainty

Complex real-world systems consist of collections of interacting processes/events. These processes change over time in response to both internal and external stimuli as well as to the passage of time itself. Many domains such as real-time systems diagnosis, story understanding, and financial forecasting require the capability to model complex systems under a unified framework to deal with both time and uncertainty. Current models for uncertainty and current models for time already provide rich languages to capture uncertainty and temporal information, respectively. Unfortunately, these semantics have made it extremely difficult to unify time and uncertainty in a way which cleanly and adequately models the problem domains at hand. Existing approaches suffer from significant trade offs between strong semantics for uncertainty and strong semantics for time. In this paper, we explore a new model, the Probabilistic Temporal Network (PTN), for representing temporal and atemporal information while fully embracing probabilistic semantics. The model allows representation of time constrained causality, of when and if events occur, and of the periodic and recurrent nature of processes.     

On the compactness of constant mean curvature hypersurfaces with finite total curvature

In this work we consider a complete submanifold M with parallel mean curvature vector h immersed in a space form of constant sectional curvature c ￡ 0c\leq 0. If M has finite total curvature and |H|² > -c|H|^2>-c, we prove that M must be compact.