RNA catalysis in model protocell vesicles.

We are engaged in a long-term effort to synthesize chemical systems capable of Darwinian evolution, based on the encapsulation of self-replicating nucleic acids in self-replicating membrane vesicles. Here, we address the issue of the compatibility of these two replicating systems. Fatty acids form vesicles that are able to grow and divide, but vesicles composed solely of fatty acids are incompatible with the folding and activity of most ribozymes, because low concentrations of divalent cations (e.g., Mg(2+)) cause fatty acids to precipitate. Furthermore, vesicles that grow and divide must be permeable to the cations and substrates required for internal metabolism. We used a mixture of myristoleic acid and its glycerol monoester to construct vesicles that were Mg(2+)-tolerant and found that Mg(2+) cations can permeate the membrane and equilibrate within a few minutes. In vesicles encapsulating a hammerhead ribozyme, the addition of external Mg(2+) led to the activation and self-cleavage of the ribozyme molecules. Vesicles composed of these amphiphiles grew spontaneously through osmotically driven competition between vesicles, and further modification of the membrane composition allowed growth following mixed micelle addition. Our results show that membranes made from simple amphiphiles can form vesicles that are stable enough to retain encapsulated RNAs in the presence of divalent cations, yet dynamic enough to grow spontaneously and allow the passage of Mg(2+) and mononucleotides without specific macromolecular transporters. This combination of stability and dynamics is critical for building model protocells in the laboratory and may have been important for early cellular evolution

Zinc-rich paint coatings containing either ionic surfactant-modified or functionalized multi-walled carbon nanotube-supported polypyrrole utilized to protect cold-rolled steel against corrosion

The intense anodic action of sacrificial zinc pigments ensured viable galvanic function of the highly porous liquid zinc-rich paints (ZRPs) result in deteriorated long-term corrosion resistance often accompanied by cathodic delamination phenomena. In our approach, such a efficacy problem related to the corrosion preventive function of ZRPs is addressed by the application of intimately structured anodic inhibitor particles composed of nano-size alumina and either polyelectrolyte-modified or chemically functionalized multi-walled carbon nanotubes (MWCNT) supported polypyrrole (PPy) in one specific zinc-rich hybrid paint formulation providing balanced active–passive protective functionality. High dispersity of the nanotube-free PPy-deposited inhibitor particles (PDIPs) with uneven polymer distribution on the alumina carrier was confirmed by transmission electron microscopy (TEM) observations. Furthermore, the MWCNT-embedded PDIPs indicated almost complete surface coverage of the alumina-nanotube carriers by PPy with decreased microstructure dispersity which is attributed to the effect of double-flocculants type co-deposition of the oppositely charged polymers causing coalescence of the modified particles. Depending on the amount of the nanotubes and their proportion to the quantities of the deposited PPy and polyelectrolyte as well as the concentration of the surfactant, varied micron-scale association of the PDIPs in the suspensions of dissolved alkyd matrix was disclosed by rheology characterization carried out at particular solid contents similar to hybrid paint formulation. The evenly distributed but less densely packed nano-structure of PPy was evidenced on the polyelectrolyte-modified nanotubes by Fourier-transform infrared (FTIR) spectroscopy whereas more compact polymer film formation was confirmed on the surface of functionalized nanotubes. According to the greater electrical conductivity, enhanced electroactivity and reversibility of the nanotube-embedded PDIPs were indicated over the nanotube-free particles by cyclic voltammetry, depending on the type and the amount of the nanotubes and their modification. Protection function of the hybrid paint coatings (formulated with spherical zinc pigment at 70 wt.%) was investigated by immersion and salt-spray chamber tests over 254 and 142 day periods, respectively. Firm barrier nature of the nanotube-embedded PDIP contained hybrids was proved by electrochemical impedance spectroscopy (EIS) and radio-frequency glow-discharge optical-emission-spectroscopy (RF-GD-OES). Furthermore, due to the increased conductivity of the nanotube-embedded PDIPs cemented in epoxy primers optimally at 0.4 and 0.6 wt.%, altered corrosion preventive behaviour of the hybrid coatings was indicated by the positively polarized open-circuit potentials (OCPs) and the X-ray photoelectron spectroscopy (XPS) detected lower relative quantities of the interfacially accumulated zinc corrosion products, moderate oxidative degradation of the epoxy vehicle. Decreasing oxidative conversion of iron at the surface was indicated by XPS found to correlate with the increasing intensity of zinc corrosion and decreasing oxidative degradation of the epoxy binder, according to the higher nanotube contents of hybrid coatings. In addition, inhibited zinc corrosion caused low rate of oxidative degradation of epoxy, allowing increased durability of coating adhesion and cohesion thereby ensuring reliable protection by zinc-rich compositions. As a conclusion, modified or functionalized MWCNTs acting as unexchangeable doping agents promote enhanced reversibility and increased conductivity of PPy, forming nano-size inhibitor particles with advanced features. Thus, such inhibitor nano-particles in zinc-rich hybrid compositions afford improved barrier and high efficiency galvanic–cathodic corrosion preventive function, exceeding long-term protection capability of the conventional ZRPs

Model Based Development of Quality-Aware Software Services

Modelling languages and development frameworks give support for functional and structural description of software architectures. But quality-aware applications require languages which allow expressing QoS as a first-class concept during architecture design and service composition, and to extend existing tools and infrastructures adding support for modelling, evaluating, managing and monitoring QoS aspects. In addition to its functional behaviour and internal structure, the developer of each service must consider the fulfilment of its quality requirements. If the service is flexible, the output quality depends both on input quality and available resources (e.g., amounts of CPU execution time and memory). From the software engineering point of view, modelling of quality-aware requirements and architectures require modelling support for the description of quality concepts, support for the analysis of quality properties (e.g. model checking and consistencies of quality constraints, assembly of quality), tool support for the transition from quality requirements to quality-aware architectures, and from quality-aware architecture to service run-time infrastructures. Quality management in run-time service infrastructures must give support for handling quality concepts dynamically. QoS-aware modeling frameworks and QoS-aware runtime management infrastructures require a common evolution to get their integration

States of matter in massive planets

This brief article addresses the question: among the very large number of interesting condensed matter physics issues, which are particularly interesting from a planetary perspective? Following some definitions and background, it is argued that we need to understand relevant first-order phase transitions (especially the nature of the hydrogen phase diagram), the behaviour of the entropy (i.e., the Gruneisen parameter), the solubility and partitioning of minor elements (e.g. noble gases mixed with hydrogen), and microscopic transport properties, especially electrical and thermal conductivity. Examples are presented of how these issues influence current interpretations of the observations of Jupiter in particular. In the future, it may be possible to observe spectroscopically the compositions of extra-solar-system planets and brown dwarfs, and thereby learn more about the physics of these bodies