Electrochemical chlorination of azulene derivatives: Insight into the mechanism of anodic oxidative chlorination

The cyclic voltammetry behavior of a series of five 1-substituted azulenes has been investigated as well as the electrochemical chlorination of these compounds. In the case of azulene compounds containing electron withdrawing groups which have higher oxidation potentials than that of the chloride ion, the electrochemical chlorination led usually to 3-chloro derivatives. The electrochemical chlorination fails for azulenes with lower oxidation potentials. Additionally some polyhalogenated compounds were obtained by controlled potential electrolyses. The paper also discusses the reaction mechanism of the electrochemical halogenation of 1-substituted azulenes.     

Electrochemical study of azo-azulene compounds

An electrochemical study of several azo-azulene compounds (Az-NN-Y, where Y = substituted phenyl, pyridine, thiazole) was performed with cyclic and differential pulse voltammetry, as well as rotating-disk electrode methods. The objective of this work was to characterize their electrochemical properties and establish the influence of donor and acceptor substituents on azulene and azo group behaviour. Calculations were performed, using quantum mechanics-based methods, to correlate electrochemical reactivity with structure. Satisfactory correlations were found between experimental oxidation and reduction potentials as well as calculated ionization potentials and LUMOs.     

Antibacterial polymeric coating based on polypyrrole and polyethylene glycol on a new alloy TiAlZr

In order to enhance properties of the polymer composite films, composite coatings based on polypyrrole (PPy) and polyethylene glycol (PEG), using various percentages of PEG (0.5%, 2%, 4%), were electrodeposited on a new titanium alloy electrode as insulating material. The structure of the coatings was investigated via infrared (FTIR) analysis, and the surface features were studied using contact angle determination, atomic force microscopy (AFM) and scanning electronic microscopy (SEM). When testing the antibacterial properties of the coatings, the best effect was found for the coating with 2% PEG concentration, which has hydrophilic character and small roughness. Such results are in concordance with mechanism of biomaterial–bacteria interaction which involves as factors affecting bacterial adhesion and growth an initial physicochemical interaction stage, where roughness and wettabilitty are factors promoting bacterial adhesion and biofilm deposition.     

Light interactions with gold nanorods and cells: implications for photothermal nanotherapeutics

Gold nanorods (AuNR) can be tailored to possess an intense and narrow longitudinal plasmon (LP) absorption peak in the far-red to near-infrared wavelength region, where tissue is relatively transparent to light. This makes AuNRs excellent candidates as contrast agents for photoacoustic imaging, and as photothermal therapeutic agents. The favorable optical properties of AuNR which depend on the physical parameters of shape, size and plasmonic coupling effects, are required to be stable during use. We investigate the changes that are likely to occur in these physical parameters in the setting of photothermal therapeutics, and the influence that these changes have on the optical properties and the capacity to achieve target cell death. To this end we study 3 sets of interactions: pulsed light with AuNR, AuNR with cells, and pulsed light with cells incubated with AuNR. In the first situation we ascertain the threshold value of fluence required for photothermal melting or reshaping of AuNR to shorter AuNR or nanospheres, which results in drastic changes in optical properties. In the second situation when cells are exposed to antibody-conjugated AuNR, we observe using transmission electron microscopy (TEM) that the particles are closely packed and clustered inside vesicles in the cells. Using dark-field microscopy we show that plasmonic interactions between AuNRs in this situation causes blue-shifting of the LP absorption peak. As a consequence, no direct lethal damage to cells can be inflicted by laser irradiation at the LP peak. On the other hand, using irradiation at the transverse peak (TP) wavelength in the green, at comparative fluences, extensive cell death can be achieved. We attribute this behavior on the one hand to the photoreshaping of AuNR into spheres and on the other hand to clustering of AuNR inside cells. Both effects create sufficiently high optical absorption at 532 nm, which otherwise would have been present at the LP peak. We discuss implications of these finding on the application of these particles in biomedicine.     

Stochastic uniform observability of general linear differential equations

The aim of this article is to discuss the uniform observability property of general linear differential equations with multiplicative white noise in Hilbert spaces. Based on perturbation theory for evolution operators on Hilbert Schmidt spaces and on the space of nuclear operators, new representations of the covariance operators associated to the mild solutions of the investigated stochastic differential equations are given. Using these results we obtain deterministic characterizations of the stochastic uniform observability property. We also identify an entire class of stochastic differential equations which are never stochastic uniformly observable. Some examples will illustrate the theory.     

Online Tracking of Component Interactions for Failure Detection and Localization in Distributed Systems

This paper proposes a novel failure-detection approach that can handle high-dimensional observation and frequent system changes. We extract two statistics from the subspace decomposition of observations, and use the mixture of Gaussians to model their probability density. Instead of monitoring the original data, the density model of extracted statistics is adaptively updated and examined regularly to detect failures. We also present a localization method to identify the faulty components once the failure happens. Applying our technique to monitor the component interactions in an e-commerce application shows satisfactory results in detecting a variety of injected failures.     

Behaviour of multi-span cold-formed Z-purlins with bolted lapped connections

In traditional design, multi-span Z-purlins of bolted lapped connections over the internal supports are considered as fully continuous, while the strength and rigidity properties of the lapped zone are obtained as the sum of the two corresponding sections. Starting from experimental evidence, the authors of the present paper assume that purlins are semi-continuous at the junction between the single and lapped sections, and propose to take into account the web crippling action at the edge of the lapped zone in interaction with the bending moment. In author's opinion this type of interaction is a new approach, compared with the traditional interaction bending moment and shear force. Based on this assumption, relevant design formulae are proposed for both strength and stability checking, accounting for different types of overall and local stress interactions. In order to support this proposal, numerical and experimental tests results are used for the comparison with results obtained based on other models.     

Recent research advances on ECBL approach.: Part I: Plastic–elastic interactive buckling of cold-formed steel sections

The objective of this two parts paper is to present some recent developments and applications of erosion of critical bifurcation load (ECBL) approach for the interactive buckling. Two different types of problems are analysed: (1) plastic–elastic interactive buckling which implements into the Ayrton–Perry interaction formula the plastic strength of the stub columns evaluated by means of local plastic mechanism analysis, and (2) elastic–elastic interactive buckling for members with perforations.The first part of the paper analyses the occurrence of local plastic mechanisms in cold-formed steel sections in compression, and how they can be implemented in the ultimate limit state analysis of the members. Actually, the failure of thin-walled cold-formed members in compression always occurs with a local plastic mechanism. Starting from this observation, the authors suggest to use in the interactive local-overall buckling analysis the sectional plastic mechanism strength instead of traditional ‘effective section’. The ECBL approach is used to implement the proposed interactive buckling model. Results are compared with those of other two recent methods, namely the direct strength method and plastic effective width approach. Relevant tests are used to evaluate the three methods. Comparisons with European and American design codes are also presented in the paper.     

Structural and optical properties of the SiO2-P2O5 films obtained by sol-gel method

A comparative study of the sol-gel films prepared in the SiO₂-P₂O₅ system starting with triethylphosphate, triethylphosphite and phosphoric acid as P precursors was performed. The work addresses basic aspects of physics, chemistry, and engineering of oxide films for applications in microelectronics, sensing, nano-photonics, and optoelectronics by establishing the influence of different precursors on the composition, structure and optical properties of the obtained films. The influence of the type of substrate (glass and indium tin oxide coated glass) and of the thermal treatment (200 and 500 °C) on their structure and properties was studied. By spectroscopic ellipsometry, X-Ray photoemission spectroscopy and atomic force microscopy measurements the high vaporization of the phosphorous during the densification of the films by thermal treatment was noticed when P-alkoxides were used. The phosphoric acid that forms chemical bond with silica network during the sol-gel process leads to better incorporation of P in the silica network as compared to the P-alkoxides.