Struktur und Reaktivität heterosubstituierter Nitrile. XVII [1]. Kinetik und Mechanismus der Phenol-Addition an Arylcyanate in Gegenwart tertiärer Amine

Structure and Reactivity of Heterosubstituted Nitriles. XVII. Kinetics and Mechanism of the Addition of Phenols to Aryl Cyanates in Presence of Tertiary Amines The rate of carbonic acid diaryl ester imides formation by the addition of phenols to aryl cyanates in the presence of tertiary amines was determined by IR-spektroscopy. The rate constants are first order in aryl cyanates and correlate linear with [ArOH] [ArO⁻ ∥ R₃NH⁺]. The third order rate constants depend linear on the (σ + σ⁻)-values of the phenol substituents, the σ⁰-values of the aryl cyanate substituents, and the pK_a of the tertiary ammonium salts. These results support a transition state formed by the nucleophilic attack of a phenoxide trialkyl ammonium ion pair to an aryl cyanate phenol associate.     

Struktur und Reaktivität heterosubstituierter Nitrile. XIX [1]. Kinetik und Mechanismus der Addition sekundärer aliphatischer Amine an Arylcyanate

Structure and Reactivity of Heterosubstituted Nitriles. XIX. Kinetics and Mechanism of the Addition of Secondary Aliphatic Amines to Aryl Cyanates The N,N-dialkyl-O-aryl isourea formation by the addition of secondary aliphatic amines to aryl cyanates was studied by kinetic methods in dioxane and dioxane water mixtures. Linear relationships between the rate constants and the water concentrations, the basicity of the amines and the electrophilicity of the aryl cyanates have been found. These data and the activation parameters support two concurrent reactions, a direct nucleophilic attack of the amine to aryl cyanate and one involving a six membered transition state between a molecule of cyanate, amine and water.     

Simple model of the optical characteristics of bubbles and sediments in seawater of the surf zone

The development of a simple model of the seawater inherent optical properties (IOPs) associated with bubbles and sediments would represent a great advance in surf zone optics. We present one solution for this problem using a combination of geometrical optics and Fraunhofer diffraction. An analytic model of the IOPs of bubbles and sediments (the extinction and absorption coefficients, and phase function) is developed in terms of the moments of the particle size distribution and the complex refractive index of particles.     

An Overview of Oxidative Stress,Neuroinflammation, and Neurodegenerative Diseases

Oxidative stress has been linked with a variety of diseases, being involved in the debut and/or progress of several neurodegenerative disorders. This review intends to summarize some of the findings that correlate the overproduction of reactive oxygen species with the pathophysiology of Alzheimer’s disease, Parkinson’s disease, Huntington’s disease, and amyotrophic lateral sclerosis. Oxidative stress was also noted to modify the inflammatory response. Even though oxidative stress and neuroinflammation are two totally different pathological events, they are linked and affect one another. Nonetheless, there are still several mechanisms that need to be understood regarding the onset and the progress of neurodegenerative diseases in order to develop efficient therapies. As antioxidants are a means to alter oxidative stress and slow down the symptoms of these neurodegenerative diseases, the most common antioxidants, enzymatic as well as non-enzymatic, have been mentioned in this paper as therapeutic options for the discussed disorders.     

Rational design of potentiometric trace level ion sensors. A Ag+-selective electrode with a 100 ppt detection limit

Submicromolar to picomolar lower detection limits have recently been obtained with various polymer membrane ion-selective electrodes by minimizing biases due to ion fluxes through the membrane. For the best performance, the compositions of the membrane and inner solution should be optimized for each application. Given the number of parameters to be adjusted, it has been difficult to find the best parameters for a target sample. In this paper, a much simplified and more practical steady-state model of zero-current ion fluxes is derived, which is based on measurable parameters. The model allows one to predict achievable lower detection limits for a membrane with given selectivities. It can also be used to predict the optimal composition of the inner filling solution for the measurement of samples with a known, typical ionic background. Selectivity coefficients of monovalent and divalent analyte ions required for desired detection limits in drinking water are calculated. As an application of the proposed general recipe, a silver-selective electrode is developed on the basis of the ionophore O,O'-bis[2-(methylthio)ethyl]-tert-butylcalix[4]arene. With the predicted optimal composition of the inner electrolyte, its lower detection limit is found to be 10(-9) M or 100 ppt Ag+ with an ionic background of 10(-5) M LiNO3, which is very close to the expected value.     

Ferroelectric and dielectric multilayer heterostructures based on KTa0.65Nb0.35O3 and Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y grown by pulsed laser deposition and chemical solution deposition for high frequency tunable devices

Epitaxial growth of Bi_1.5-xZn_0.92-yNb_1.5O_6.92-1.5x-y (BZN) thin films was achieved on (100)_pc LaAlO₃ substrate by pulsed laser deposition (PLD) and by chemical solution deposition based on Pechini process. Effect of bismuth and zinc deficiency on the BZN thin films obtained by PLD was discussed, in relation with the starting target composition. Dielectric permittivity and bandgap values were determined from electrical and spectroscopic ellipsometry measurements performed on randomly oriented films grown on Pt/Si substrate. BZN thin films obtained by PLD exhibit, at 100 kHz, a dielectric constant of ε_r = 203 and quite low dielectric losses of tanδ = 5 × 10^− 2. Epitaxial ferroelectric − dielectric KTa_0.65Nb_0.35O₃ (KTN) − Bi_1.5-xZn_0.92-yNb_1.5O_6.92-1.5x-y (KTN on BZN and BZN on KTN) bilayers were obtained by PLD on (100)_pc LaAlO₃ with the insertion of a suitable buffer layer of KNbO₃ in the case of KTN on BZN. Such multilayer heterostructures with an epitaxial growth control of each layer are promising candidates for potential integration in microwave devices.     

Designing and building SDN testbeds for energy-aware traffic engineering services

As experimenting with energy-aware techniques on large-scale production infrastructure is prohibitive, a large number of proposed traffic engineering strategies have been evaluated only using discrete-event simulations. The present work discusses (i) challenges towards building testbeds that allow researchers and practitioners to validate and evaluate the performance and quality of energy-aware traffic engineering strategies, (ii) requirements to fulfil when porting simulations to testbeds, and (iii) two proof-of-concept testbeds. One testbed uses and provides software-defined network (SDN) services created on the open-network operating system while the other is a composition of virtual Open vSwitches controlled by the Ryu SDN framework. The aim of the testbeds is to validate previously proposed energy-aware traffic engineering strategies in different environments. We detail the platforms and illustrate how they have been used for performance evaluation. Additionally, the paper compares results obtained in the testbeds with evaluations performed using discrete-event simulations and presents challenges faced while implementing energy-aware traffic engineering mechanisms as SDN services in testbed environments.     

Perovskite type lanthanum manganite: Morpho-structural analysis and electrical investigations

Perovskite-type oxides of LaMnO_3 were synthesized by means of the sol-gel method, in the presence of citric acid as gelling agent. The precursors used were Mn(NO_3)_2·H_2O, La_2O_3, and NaOH,mixed in the stoichiometric ratio to obtain perovskite materials. The obtained gel was heat-treated at 400, 600 and 800 ℃ respectively, for 6 h. X-ray diffraction and FT-IR spectroscopy were used to analyze the phase transformation as a function of temperature, and the Rietveld refinement was used in order to characterize the materials obtained structurally. The average crystallite size of the products was calculated from XRD data and the average particle size was measured from the TEM micrographs. At 600 ℃, the synthesized compound is well-crystallized, showcases a perovskite structure(Pm-3m space group), and exhibits uniform and homogeneous hexagonally-shaped particles, with sizes in the 20-50 nm range.Complex impedance measurements in the 20-2 × 10~6 Hz frequency range were carried out at different temperatures(26-115 ℃), and the electrical conduction mechanism is discussed.     

Thermally acceptable temperature drifts can reduce the energy consumption for cooling in office buildings

The energy consumption and cost in large office buildings can be reduced by allowing the indoor environment to deviate from the optimum comfort conditions to situations which are still acceptable by most occupants. One such strategy is to allow the indoor temperature to increase in the afternoon in summer. A computer program was developed to predict the thermal sensation and discomfort under transient conditions, and the detailed computer program BLAST was used to evaluate the indoor temperature, space cooling load, chilled water consumption and seasonal energy use. This paper presents a comparison performed for a reference office building in Montréal between a conventional design, with constant set-point temperature during the operating hours, and a new design, where the indoor temperature is allowed to increase after 3:00 p.m. The results show a reduction of seasonal consumption for chilled water between 34 and 40%, and a reduction of energy budget for HVAC systems of 11%.