Simple models of complex aggregation: Vesicle formation by soft repulsive spheres with dipolelike interactions

Structural and thermodynamic properties of spherical particles carrying classical spins are investigated by Monte Carlo simulations. The potential energy is the sum of short range, purely repulsive pair contributions, and spin-spin interactions. These last are of the dipole-dipole form, with however, a crucial change of sign. At low density and high temperature the system is a homogeneous fluid of weakly interacting particles and short range spin correlations. With decreasing temperature particles condense into an equilibrium population of free floating vesicles. The comparison with the electrostatic case, giving rise to predominantly one-dimensional aggregates under similar conditions, is discussed. In both cases condensation is a continuous transformation, provided the isotropic part of the interatomic potential is purely repulsive. At low temperature the model allows us to investigate thermal and mechanical properties of membranes. At intermediate temperatures it provides a simple model to investigate equilibrium polymerization in a system giving rise to predominantly two-dimensional aggregates.

The emerging role of serine proteases in apoptosis

Unregulated apoptosis can be due to a disruption in the balance and control of both intra- and inter-cellular proteolytic activities leading to various disease states. Many proteases involved in apoptotic processes are yet to be identified; however, several are already well characterized. Caspases traditionally held the predominant role as prime mediators of execution. However, latterly, evidence has accumulated that non-caspases, including calpains, cathepsins, granzymes and the proteasome have roles in mediating and promoting cell death. Increasingly, research is implicating serine proteases within apoptotic processing, particularly in the generation of nuclear events such as condensation, fragmentation and DNA degradation observed in late-stage apoptosis. Serine proteases therefore are emerging as providing additional or alternative therapeutic targets.

Inscribir el declive en el tiempo. Detroit: Auge y crisis de la ciudad industrial

A comienzos del siglo XX, Detroit era una ciudad dinámica en pleno desarrollo. Pronto se convirtió en la cuarta ciudad de Estados Unidos, la capital de la naciente industria automovilística. El crecimiento se prolongó hasta finales de los años 50, cuando, a pesar del auge económico de Estados Unidos y de su área metropolitana, Detroit comenzó a mostrar los primeros signos de estancamiento. La crisis se ha prolongado hasta hoy, cuando Detroit constituye el paradigma de la ciudad industrial en declive. Estas dos imágenes contrapuestas, el auge y la crisis, no parecen explicar por sí mismas las causas de la intensidad y persistencia del declive de Detroit. Analizar las interacciones entre crecimiento económico, políticas públicas locales y desarrollo urbano a lo largo del tiempo permitirá subrayar las continuidades y comprender en qué medida el declive de Detroit ancla sus raíces en el modelo planteado durante la etapa de auge.

Supported and liquid phase task specific ionic liquids for base catalysed Knoevenagel reactions

A series of Hunig's base tethered ammonium ionic liquids have been used to catalyse the Knoevenagel condensation of aldehydes/ketones with malononitrile and ethyl cyanoacetate. The reactions were performed under homogeneous and under biphasic, liquid-liquid and liquid-silica supported ionic liquid, conditions with the biphasic systems employing cyclohexene as the second phase. By increasing the distance between the ammonium head group and Hunig's base the activity of the catalyst was found to increase. Higher activity, in general, was found under homogeneous reaction conditions; however, the recyclability of the catalyst was improved by supporting the BIL under biphasic conditions. (c) 2007 Elsevier B.V. All rights reserved.

One-pot multistep synthetic strategies for the production of fenpropimorph using an ionic liquid solvent

The one-pot synthesis of the fungicide fenpropimorph has been achieved using two different synthetic strategies in an ionic liquid. The first pathway consists of a Heck coupling followed by reductive amination; the second pathway consists of an aldol condensation followed by hydrogenation/reductive amination. Homogeneous and heterogeneous palladium catalysts have been utilised in the ionic liquid to provide a catalyst/solvent system that is suitable for recycling and process optimisation.

Gas-phase photocatalytic oxidation of dichlorobutenes

Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO2 and 3%WO3/TiO2 supported on SiO2. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO2 formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O-2 concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.

Reduced-complexity iterative equalization for severe time-dispersive MIMO channels

In this paper, a reduced-complexity soft-interference-cancellation minimum mean-square-error.(SIC-MMSE) iterative equalization method for severe time-dispersive multiple-input-multiple-output (MIMO) channels is proposed. To mitigate the severe time dispersiveness of the channel, a single carrier with cyclic prefix is employed, and the equalization is per-formed in the frequency domain. This simplifies the challenging problem of equalization in MIMO channels due to both the intersymbol interference (ISI) and the coantenna interference (CAI). The proposed iterative algorithm works in two stages. The first stage estimates the transmitted frequency-domain symbols using a low-complexity SIC-MMSE equalizer. The second stage converts the estimated frequency-domain symbols in the time domain and finds their means and variances to incorporate in the SIC-MMSE equalizer in the next iteration. Simulation results show the bit-/symbol-error-rate performance of the SIC-MMSE equalizer, with and without coding, for various modulation schemes.

Persistence of antimicrobial activity through sustained release of triclosan from pegylated silicone elastomers

Microbial adhesion to silicone elastomer biomaterials is a major problem often resulting in infection and medical device failure. Several strategies have been employed to modulate eukaryotic cell adhesion and to hamper bacterial adherence to polymeric biomaterials. Chemical modification of the surface by grafting of polyethylene glycol (PEG) chains or the incorporation of non-antibiotic antimicrobial agents such as triclosan into the biomaterial matrix may reduce bacterial adhesion. Here, such strategies are simultaneously applied to the preparation of both condensation-cure and addition-cure silicone elastomer systems, seeking a sustained release antimicrobial device biomaterial. The influence of triclosan incorporation and degree of pegylation on antimicrobial release, surface microbial adherence and persistence (Escherichia coli and Staphylococcus epidermidis) were evaluated in vitro. Non-pegylated silicone elastomers provided an increased percentage release of triclosan extending over a relatively short duration (99% release by day 64) compared with their pegylated (4% w/w) counterparts (65% and 72% release by day 64, for condensation and addition-cure systems respectively). Viable E. coli adherence to a non-pegylated silicone elastomer containing 1% w/w triclosan was reduced by over 99% after 24 h compared to the non-pegylated silicone elastomer containing no triclosan. No viable S. epidermidis adhered to any of the triclosan-loaded (>0.1% w/w) formulations other than the control. Persistence of the antimicrobial activity of the triclosan-loaded pegylated silicone elastomers continued for at least 70 days compared to the triclosan-loaded non-pegylated elastomers (at least 49 days). Understanding how PEG affects the release of triclosan from silicone elastomers may prove useful in the development of a biomaterial providing prolonged, effective antimicrobial activity.

Kinetics of Aqueous Phase Dehydration of Xylose into Furfural Catalyzed by ZSM-5 Zeolite

ZSM-5 zeolite in H+ form with an average pore size of 1.2 nm was used for aqueous phase dehydration of xylose to furfural at low temperatures;, that is, from 413 to 493 K. The selectivity in furfural increased with the temperature to a value of 473 K. Beyond this temperature, condensation reactions were significant and facilitated by the intrinsic structure of ZSM-5. A reaction mechanism that included isomerization of xylose to lyxose, dehydration of lyxose and xylose to furfural, fragmentation of furfural to organic acids, oligomerization of furfural to bi- and tridimensional furilic species, and complete dehydration of organic acids to carbonaceous deposits was developed, and the associated kinetic parameters were estimated. The rate of furfural production was found to be more sensitive to temperature than the rates of side reactions, with an estimated activation energy of 32.1 kcal/mol. This value correlated well with data in the literature obtained by homogeneous catalytic dehydration.

Structural motifs of cholesterol nanoparticles

The growth sequence of gas-phase cholesterol clusters (Ch(N)) with up to N=36 molecules has been investigated by atomistic simulation based on an empirical force field model. The results of long annealings from high temperature show that the geometric motifs characterizing the structure of pure cholesterol crystals already appear in nanometric aggregates. In all clusters molecules tend to align along a common direction. For cluster sizes above the smallest ones, dispersion interactions among the hydrocarbon body and tails of cholesterol cooperate with hydrogen bonding to give rise to a bilayer structure. Analysis of snapshots from the annealing shows that the condensation of hydrogen bonds into a connected network of rings and chains is an important step in the self-organization of cholesterol clusters. The effect of solvation on the equilibrium properties of medium-size aggregates is investigated by short molecular dynamics simulations for the N=30 and N=40 clusters in water at near ambient conditions and in supercritical carbon dioxide at T=400 K.

Compactness properties of operator multipliers

We continue the study of multidimensional operator multipliers initiated in~cite{jtt}. We introduce the notion of the symbol of an operator multiplier. We characterise completely compact operator multipliers in terms of their symbol as well as in terms of approximation by finite rank multipliers. We give sufficient conditions for the sets of compact and completely compact multipliers to coincide and characterise the cases where an operator multiplier in the minimal tensor product of two C*-algebras is automatically compact. We give a description of multilinear modular completely compact completely bounded maps defined on the direct product of finitely many copies of the C*-algebra of compact operators in terms of tensor products, generalising results of Saar

The soundscape as time capsule: A creative project based on the sounds of the first train station of Cuenca

This article reflects on the changing environment through the passage of time and how certain technologies for a creative proposal allow the preservation and transmission of a significant part of that ephemeral heritage for future generations. The general purpose of this particular project is aimed to achieve the sound synthesis of a specific and representative cityscape as the old train station in Cuenca –located in the heart of the city– that could be preserved and reproduced as an unique document of a present time, ascertainable in the future: a memory that interpret sound as a time capsule. This soundscape was made to mark the arrival of the high speed train in 2010 to a brand new station in the outskirts of the city. Therefore, the goal of this research was focused on achieving a synthetic document that provided a sound memory capable of reflecting the significant social, cultural and logistical features, of what was until then the only railway communication symbol in the city of Cuenca from 1883 to the first decade of the 21st century.

The Rhetorical Construction of Corporate Logos

This research is set in the context of today’s societies, in which the corporate visual symbology of a business, corporation or institution constitutes an essential way to transmit its corporate image. Traditional discursive procedures can be discovered in the development of these signs. The rhetorical strategies developed by the great classical authors appear in the logo-symbols expressing the corporate values of today’s companies. Thus, rhetoric is emerging once again in the sense it had many centuries ago: A repertory of rules that, paradoxically, standardizes the deviations of language and whose control is synonymous with power. The main objective of this study is to substantiate the rhetorical construction of logos using as a model of analysis the classical process of creating discourse. This involves understanding logos as persuasive discourses addressed to a modern audience. Our findings show that the rhetorical paradigm can be considered as a creative model for the con­struction of an original logo consistent with a company’s image.

About infamy: the filthiness of Art and its diogenic disease

In this paper, we postulate the direct relationship that exists between waste production and artistic objects; its manufacturing system, consumption, and subsequent waste. What arises in this relationship then, is another character of interest –and that will serve as a reference to compare its modus operandi with the place of artists and the arts–, in this sick world, the Diogenes. The obsessed that lives among the garbage. The absurdity of the conquest of the infinite of the illogical within the logical. The amount clouded and blinded, nothing is enjoyed, nothing is appreciated; the countless abandons its place in the memory –memorable– and there only exists a pathological accumulation, mountains of garbage, desires to hold on to vital faith of the belief of doing Something for themselves. Working just to work and building something that will not last, like a sand castle, accumulation of detritus and dust. A new logic is born, the enjoyment of diseases and emptiness, the destruction of a world without a history. «Artists of the world, abandon! You have nothing to lose but your own professions!» (Kaprow, 2007, p. 37).

Rheological Evaluation of the Isothermal Cure Characteristics of Medical Grade Silicone Elastomers

Silicone elastomer systems have been shown to offer potential for the fabrication of medical devices and sustained release drug delivery devices comprising low molecular weight drugs and protein therapeutics. For drug delivery systems in particular, there is often no clear rationale for selection of the silicone elastomer grade, particularly in respect of optimizing the manufacturing conditions to ensure thermal stability of the active agent and short cycle times. In this study, the cure characteristics of a range of addition-cure and condensation-cure, low-consistency, implant-grade silicone elastomers, either as supplied or loaded with the model protein bovine serum albumin (BSA) and the model hydrophilic excipient glycine, were investigated using oscillatory rheology with a view to better understanding the isothermal cure characteristics. The results demonstrate the influence of elastomer type, cure temperature, protein loading, and glycine loading on isothermal cure properties. By measuring the cure time required to achieve tan delta values representative of early and late-stage cure conditions, a ratio t(1)/t(2) was defined that allowed the cure characteristics of the various systems to be compared. Sustained in vitro release of BSA from glycine-loaded silicone elastomer covered rod devices was also demonstrated over 14 days. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 2320-2327, 2010