Review of quantitative structure‐activity/property relationship studies of dyes: recent advances and perspectives

Dyes have been applied and are playing an increasingly important role in many industries, including the textile, printing, medical and energy industries. Their wide applications imply that specific dyes possessing given properties need to be effectively designed. The present review aims to survey information related to activity/property research of dyes that has been published in the past two decades. Emphasis is laid particularly on studies based on quantitative structure–activity/property relationships that have contributed to the theoretical design and application of dyes. Finally, the perspectives of quantitative structure‐activity/property relationship studies are set out in order to show how this method may be used to design new dyes and to evaluate their different properties. The challenges facing these studies are also outlined.     

Organic–Inorganic Hybrid Films Based on Hydroxylated Soybean Oils

Hybrid organic–inorganic films were prepared using four different hydroxylated soybean oils (HSO) or epoxidized soybean oil as organic precursor and tetraethyl orthosilicate (TEOS) as inorganic precursor in a mass ratio of HSO:TEOS of 90:10. The films were macroscopically homogeneous and were characterized by swelling and extraction in solvent, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) including energy dispersive spectroscopy (EDX), adhesion and hardness. Their properties varied as a function of the number of OH groups present in the HSO. The best hybrid system was HSOF198/TEOS, with an OH value of 198 mg of KOH/g, which presents lower swelling coefficient, very good adhesion on aluminium surface and good hardness.     

High level communication functionalities for wireless sensor networks

In this paper we show how to establish a reliable and efficient high level communication system in a randomly deployed network of sensors equipped with directional antennas. This high level communication system enables the programming of the sensor network using high level communication functionalities without the burden of taking care of their physical capacities (low range, unidirectional links, single frequency, presence of collisions, etc.). The high level communication functionalities we offer include point-to-point communication, point-to-area communication, and one-to-all communication. The basic idea to implement this system is to simulate a virtual network that emerges from the ad-hoc network using self-organization, self-discovery and collaborative methods. We also analyse the efficiency, scalability and robustness of the proposed protocols.     

Study of Europa’s crust via a Stefan model with convection

We present results of a numerical simulation of the thermal convection in the subsurface mushy ice layer of Europa, one of the Jupiter’s moons. Beside fluid dynamics and heat transfer within such a layer, heat conduction in the solid crustal surface and heat exchange between the two phases – mushy ice and solid crust – are included in our model in order to follow also the evolution of the phase front.     

A SAXS study of the structure of gels formed by mixtures of polyoxyalkylene triblock copolymers

Small‐angle X‐ray scattering was used to characterise aqueous micellar gels of triblock copolymers E₁₃₇S₁₈E₁₃₇, E₈₂S₉E₈₂, E₇₆S₅E₇₆, E₆₂P₃₉E₆₂, and of two mixtures: E₁₃₇S₁₈E₁₃₇ and E₆₂P₃₉E₆₂ (Mix 1) and E₈₂S₉E₈₂ and E₆₂P₃₉E₆₂ (Mix 2), each 50/50 wt%. E = oxyethylene, CH₂CH₂O; S = oxyphenylethylene, OCH₂CH(C₆H₅); and P = oxypropylene, OCH₂CH(CH₃). Within the concentration and temperature ranges investigated (30–40 wt% copolymer, 20–80 °C), spherical micelles of copolymers E₁₃₇S₁₈E₁₃₇, E₈₂S₉E₈₂ and E₆₂P₃₉E₆₂ packed into body‐centred cubic (BCC) structures. Gels of E₇₆S₅E₇₆ were stable only at high concentrations and low temperatures, and a 70 wt% copolymer solution at T = 30 °C formed a hexagonal gel consistent with cylindrical micelles. It is likely that the mixed copolymers would form two distributions of micelles, and more complex structures were expected. However, gels of Mix 2 had well‐ordered BCC structures, while the less ordered gels of Mix 1 were also best characterised as BCC. Copyright © 2006 Society of Chemical Industry     

Pd[tBuNH(S)NHP(O)(OiPr)2-S]2Cl2 Complex as Air- and Moisture-Stable Catalyst for Palladium Catalyzed Suzuki Cross-Coupling Reaction

A highly efficient Suzuki cross-coupling reaction between phenyl bromide and phenylboronic acid catalyzed by the palladium complex Pd[tBuNH(S)NHP(O)(OiPr)₂-S]₂Cl₂ in acetonitrile, toluene, THF or DMF has been investigated. The bases we have employed for this reaction were Na₂CO₃, K₂CO₃ or Cs₂CO₃. It was established that using DMF and K₂CO₃ at 100 °C shows excellent yields of the product at the catalyst amount of 0.1 mmol. The cross-coupling reactions of iodo- and chloro-benzene with phenylboronic acid were also investigated. The influence of the halide nature was as expected.     

Hydrogen Bond Compression during Triple Proton Transfer in Crystalline Pyrazoles. A Dynamic 15N NMR Study

Using dynamic solid state ¹⁵N CPMAS NMR spectroscopy (CP ≡ cross polarization, MAS ≡ magic-angle spinning), the kinetics of degenerate intermolecular triple proton and deuteron transfers in the cyclic trimers of ¹⁵N-labeled polycrystalline 4-nitropyrazole (4NO₂P) and 4-bromopyrazole (4BrP) have been studied as a function of temperature and are compared to the kinetics of triple proton transfer in bulk solid 3,5-dimethylpyrazole (DMP) studied previously. The results show that the transfer kinetics in the new trimers are much faster than in DMP. However, the kinetic HHH/HHD/HDD/DDD isotope effects of 4NO₂P are similar to those of DMP. These effects indicate a single barrier for the triple proton transfers where all three protons lose zero-point energy in the transition state, as expected for a structure with three compressed hydrogen bonds. At low temperatures, strong deviations from an Arrhenius-behavior are observed which are described in terms of a modified Bell tunneling model and a concerted proton motion. The barrier for the triple proton transfer in 4NO₂P and 4BrP is substantially smaller than in DMP. As there is no correlation with the electronic properties of the substituents, we assign this finding to steric effects where the bulky methyl groups of DMP in the 3- and 5-positions hinder the hydrogen bond compression, in contrast to 4NO₂P and 4BrP exhibiting substitutents in the 4-position. These results lead to a minimum energy pathway of the proton transfer following in the absence of steric hindering the hydrogen bond correlation line q₁ = f(q₂), established previously, where q₁ represents the deviation of the proton from the hydrogen bond center and q₂ the N…N distance. Tunneling occurs at constant N…N distances.     

On the correctness of upper layers of automotive systems

Formal verification of software systems is a challenge that is particularly important in the area of safety-critical automotive systems. Here, approaches like direct code verification are far too complicated, unless the verification is restricted to small textbook examples. Furthermore, the verification of application logic is of limited use in industrial context, unless the underlying operating system and the hardware are verified, too. This paper introduces a generic model stack, allowing the verification of all system layers as well as the concrete application models being used in the upper layers. The presented models and proofs close the gap between the correctness proof for the lower layers of car electronics developed at the Saarland University and the verification procedure for distributed applications developed at the Technische Universität München.     

Corrosion protection of AA2024-T3 using rare earth diphenyl phosphates

Existing corrosion protection technologies for aluminium alloys utilising chromates are environmentally damaging and extremely toxic. This paper presents a preliminary investigation into rare earth diphenyl phosphates as new environmentally benign corrosion inhibitors. Full immersion weight loss experiments, cyclic potentiodynamic polarisation measurements and Raman spectroscopy were used in this study. Results show cerium diphenyl phosphate (Ce(dpp)₃) acts as a cathodic inhibitor, decreasing cathodic current density and E_corr by passivating cathodic intermetallic particles on the alloy surface. Mischmetal diphenyl phosphate (Mm(dpp)₃) acts a mixed inhibitor, shifting E_corr to more noble values, decreasing cathodic current density, increasing the breakdown potential and suppressing pitting.     

Spoilage potential of ice-stored whole musky octopus (Eledone moschata)

The spoilage potential of fresh musky octopus ( Eledone moschata ) was determined by evaluating the changes in biochemical and physical properties, microbial growth and sensory quality of the mantle and tentacles, over a period of 18 days. Whole musky octopus, stored in melting ice from the time of harvest, had a storage life of 10 days. Early deterioration in the sensory quality resulted primarily from autolytic reactions. Pseudomonas spp. dominated the spoilage flora, reaching an average count of 10⁸ CFU g⁻¹ at the end of the trial. The bacterial metabolic end products (trimethylamine, total volatile bases) were not useful as objective indicators of freshness, and measurements of pH would only provide an indicator of decomposition. Changes in the dielectric properties of the mantle were reflective of quality deterioration, but could not yield precise information on the storage history of the cephalopod. The common sulphide producer, Shewanella putrefaciens , was not a major spoiler of ice-stored musky octopus.