Effect of the chemistry and structure of the native oxide surface film on the corrosion properties of commercial AZ31 and AZ61 alloys

The purpose of this study has been to advance in knowledge of the chemical composition, structure and thickness of the thin native oxide film formed spontaneously in contact with the laboratory atmosphere on the surface of freshly polished commercial AZ31 and AZ61 alloys with a view to furthering the understanding of protection mechanisms. For comparative purposes, and to more fully describe the behaviour of the native oxide film, the external oxide films formed as a result of the manufacturing process (as-received condition) have been characterised. The technique applied in this research to study the thin oxide films (thickness of just a few nanometres) present on the surface of the alloys has basically been XPS (X-ray photoelectron spectroscopy) in combination with ion sputtering. Corrosion properties of the alloys were studied in 0.6 M NaCl by measuring charge transfer resistance values, which are deduced from EIS (electrochemical impedance spectroscopy) measurements after 1 h of exposure. Alloy AZ61 generally showed better corrosion resistance than AZ31, and the freshly polished alloys showed better corrosion resistance than the alloys in as-received condition. This is attributed to a combination of (1) higher thickness of the native oxide film on the AZ61 alloy and (2) greater uniformity of the oxide film in the polished condition. The formation of an additional oxide layer composed by a mixture of spinel (MgAl₂O₄) and MgO seems to diminish the protective properties of the passive layer on the surface of the alloys in as-received condition.     

Water-soluble carbosilane dendrimers: synthesis biocompatibility and complexation with oligonucleotides; evaluation for medical applications

Novel amine- or ammonium-terminated carbosilane dendrimers of type nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe2)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe2}]x and nG-[Si{(CH2)3NH2}]x or nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe3 +I-)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe3 +I-}]x, and nG-[Si{(CH2)3NH3 +Cl-}]x have been synthesized and characterized up to the third generation by two strategies: 1) alcoholysis of Si--Cl bonds with amino alcohols and subsequent quaternization with MeI, and 2) hydrosilylation of allylamine with Si--H bonds of the dendritic systems and subsequent quaternization with HCl. Quaternized carbosilane dendrimers are soluble in water, although degradation is apparent due to hydrolysis of Si--O bonds. However, dendrimers containing Si--C bonds are water-stable. The biocompatibility of the second-generation dendrimers in primary cell cultures of peripheral blood mononuclear cells (PBMCs) and erythrocytes have been analyzed, and they show good toxicity profiles over extended periods. In addition, we describe a study on the interactions between the different carbosilane dendrimers and DNA oligodeoxynucleotides (ODNs) and plasmids along with a comparative analysis of their toxicity. They can form complexes with DNA ODNs and plasmids at biocompatible doses via electrostatic interaction. Also a preliminary transfection assay has been accomplished. These results demonstrate that the new ammonium-terminated carbosilane dendrimers are good base molecules to be considered for biomedical applications.     

A Versatile Near‐Infrared Asymmetric Tricarbocyanine for Zinc Ion Sensing in Water

We have synthesized a near‐infrared emissive asymmetric tricarbocyanine conveniently functionalized to improve bioconjugation. The leading structure contains a versatile derivatization point at the meso position for facile radical‐nucleophilic aromatic substitution. We have evaluated a DPEN (N,N‐di(2‐picolyl)ethylendiamine) derivative of this dye as a highly selective sensor for zinc (II) in aqueous medium, which performs in an appropriate sensitivity range for biological studies. The probe was successfully conjugated to a protein‐ligand model with high affinity and specificity (biotin–streptavidin technology) rendering an excellent performance of sensing. In a general strategy to obtain sensitive probes combining fluorescent nanoparticles and molecular fluorophores, a preliminary design of a supramolecular assembly derived from the conjugation of the molecular sensor to quantum dots (QDs) was also investigated. The advantages and problems of FRET‐based sensors are also discussed.     

2-Dimensional Network Formation from a Graft Copolymer at the Air-Water Interface

Summary: The UV induced cross-linking of a well defined graft copolymer polynorbornene-g-poly(ethylene oxide) at the air-water interface has been investigated. Network formation has been monitored qualitatively by observing changes in surface pressure with UV exposure time working under constant area conditions. Surface film concentration has been used as the design parameter to manipulate initial film organization, and consequently position of the functional groups. Exposure of the copolymer film to UV light at different surface concentrations in the liquid condensed region shows the closer the molecules pack together the faster the cross-linking reaction, while no cross-linking occurs when the molecules are far apart in the liquid expanded state.     

New Considerations on Analytical Solutions Employed in Tracer Flow Modeling

A methodology commonly used to obtain analytical and semi-analytical solutions to describe spike and finite-step tracer injection tests is discussed. In these cases, solutions to the diffusion–convection equation are derived from the solution of a different problem, namely the continuous injection of a tracer. Within this procedure, spike injection results from the time derivative of this solution, and finite-step injection from the superposition of two solutions shifted in time. In this paper we show that although this methodology is mathematically correct, attention should be paid to the properties of the solutions. Their boundary conditions may not represent physically acceptable situations, since these conditions are inherited from a different problem. The application of the methodology to a simple one-dimensional case of a tracer pulse diffusing in a homogeneous, semi-infinite reservoir shows serious problems regarding boundary conditions and mass conservation. These problems has not probably been found before since tracer breakthrough curves are not very sensitive to them. However, the problems clearly show up when the tracer distribution in space is analyzed. We conclude that the traditional methodology should not be employed. Equations should be solved imposing the specific boundary and initial conditions corresponding to the original system under consideration.     

Kramecyne--a new anti-inflammatory compound isolated from Krameria cytisoides

In the present work we describe the structure and anti-inflammatory activity of a new compound, kramecyne, isolated from a methanol extract of Krameria cytisoides (Krameriaceae). The structure of kramecyne was determined by IR, NMR, MS, and elemental analysis, which indicated that the structure corresponded to a hexamer of cyclic peroxide monomers. This compound exhibited good anti-inflammatory activity in the 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced mouse ear edema (51.8 ± 6.9% inhibition) and carrageenan-induced rat paw edema models at doses of 50 mg/kg. The compound significantly reduced edema to 63.1% after 1.0 h, and the effect was unchanged for 5 h. Kramecyne did not present acute toxicity, even at doses of 5,000 mg/kg.     

Mimicking the LCDM model with stealths

We present a new cosmological model that mimics the Lambda Cold Dark Matter by using a stealth field. This kind of field is characterized as not coupling directly to gravity; however, it is connected to the underlying matter content of the universe model. As is well known, stealth fields do not back-react on the space-time; however, their mimicry skills show how this field and its self-interaction potential determines the cosmic evolution. We show the study of the simplest model that can be developed with the stealth field.     

Hardware implementation of pseudo-random number generators based on chaotic maps

We show the usefulness of bifurcation diagrams to implement a pseudo-random number generator (PRNG) based on chaotic maps. We provide details on the selection of the best parameter values to obtain high entropy and positive Lyapunov exponent from the bifurcation diagram of four chaotic maps, namely: Bernoulli shift map, tent, zigzag, and Borujeni maps. The binary sequences obtained from these maps are analyzed to implement a PRNG both in software and in hardware. The software implementation is realized using 32 and 64 bits microprocessor architectures, and with floating point and fixed point computer arithmetic. The hardware implementation is done by using a field-programmable gate array (FPGA) architecture. We developed a serial communication interface between the PRNG on the FPGA and a personal computer to obtain the generated sequences. We validate the randomness of the generated binary sequences with the NIST test suite 800-22-a both in floating point and fixed point arithmetic. At the end, we show that those chaotic maps are suitable to implement a PRNG but according to the hardware resources, the one based on the Bernoulli shift map is better. In addition, another advantage is that the required initial value for the sequences can be within the whole interval \([-1,1]\), including its bounds.