NMR spectroscopic characterization of new 2,3‐dihydro‐1,3,4‐thiadiazole derivatives

The ¹H and ¹³C NMR resonances of twenty‐seven 2,2‐dimethyl‐5‐(2‐nitrophenyl‐5‐substituted)‐2,3‐dihydro‐1,3,4‐thiadiazoles, and twenty‐seven 3‐acyl‐5‐(2‐amino‐5‐substituted)‐2,2‐dimethyl‐2,3‐dihydro‐1,3,4‐thiadiazoles were assigned completely using the concerted application of one‐dimensional and two‐dimensional experiments (DEPT, HMQC and HMBC). NOESY experiments, X‐ray crystallography and conformational analysis confirm the preferred conformation of these compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of vagal nerve stimulation on laryngeal function

Functional electrical stimulation is a developing methodology that shows significant potential in the management of peripheral neuromuscular deficits. Potential applications in the head and neck area, including control of bilateral vocal fold paralysis and spasmodic dysphonia, have recently been explored. Despite promising early results, very little is known about the mechanisms of action or the long-term effects of electrical stimulation on human laryngeal function. Recent development of implantable vagal nerve stimulators as a method to control intractable seizures in individuals who have not responded to medication provides a unique opportunity to study its effect on the normal human larynx. Laryngeal and vocal function testing was studied on five individuals who had undergone vagal nerve stimulator implants for intractable seizures. Consistent abduction/adduction of the left vocal fold was achieved at 20 and 40 Hz, respectively. Higher levels of electrical stimulation produced hemispasm of the larynx. Results were consistent with studies in the literature of recurrent laryngeal nerve stimulation in animal and human models. The vagus nerve provides relatively easy access for implantation of electrodes to provide electrical stimulation to the muscles of the larynx. Vagal nerve stimulation may prove efficacious in the treatment of movement disorders of the larynx; further study is needed.     

Effects of the structure on the properties of new poly(arylene ether sulfone)s containing naphthalene units

A series of new poly(arylene ether sulfone)s has been obtained by solution condensation polymerisation starting from 1,5- and 2,6-bis-(4-fluorosulfonyl)naphthalene with various aromatic dihydroxy compounds. The polymers, obtained in quantitative yields, possessed inherent viscosities in the range 0.28-0.68 dl g⁻¹, had good thermal stability (10% weight loss temperatures were above 405 and 420 °C respectively in nitrogen and air) and high glass transition temperatures (in the range 217-258 °C). They have been characterised by elemental and infrared analyses, GPC and wide-angle X-ray diffraction. The properties of these poly(arylene ether sulfone)s have been compared with those of the corresponding poly(arylene ether ketone)s.     

Proton and α sequential emission in the 16O + 58Ni deep inelastic reaction: A semi-classical approach

The 132 MeV ¹⁶O + ⁵⁸Ni reaction has been experimentally investigated by using coincident charged particle techniques. A closed-form theoretical approach, describing in a simple picture the non-equilibrium component and the evaporative one of the angular correlation between light particles and reaction residues emitted in a peripheral heavy-ion collision, is applied — in the hypotesis of a sequential process — to the (C,N,O)-α and (C,N,O)-p differential multiplicities for the ¹⁶O + ⁵⁸Ni at 8.25 MeV/A deep inelastic collision. From this analysis some reaction mechanism information is deduced.     

New trends in the analysis of masonry structures

The modern theory of masonry structures has been set up on the hypothesis of no-tension behaviour, with the aim of offering a reference model, independent of materials and building techniques employed. This hypothesis gives rise to inequalities which have to be satisfied by the stress tensor components and, as a dual aspect, to the kinematic behaviour characteristics of media which can be classified as lying between solids and fluids: the structure of the masonry material consists of particles reacting elastically only when in contact. An examination of the plane-stress problem leads us to define, within the prescribed domain under admissible loads, three different subdomains with null, regular, or non-regular principal stress tensors, respectively. As the boundaries of such subdomains are not known a priori, the problem can be classified as a free boundary value problem. The analysis concerns mainly the subdomains where the stress tensor is non-regular; and a non-regularity condition det =0 is added to the equilibrium equations. This condition makes the stress problem isostatic and leads to a violation of Saint-Venant's compliance conditions on strains. Hence there is a need to introduce a strain tensor, not related to the stress tensor, which can be decomposed into an extensional component and a shearing component; we prove that such strains, of the class ^c, are similar to those of the theory of plastic flow. From the point of view of computational analysis the anelastic strains are considered as given distortions; they are computed by means of the Haar-Kármán principle, modified for computational purposes by an idea of Prager and Hodge.

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Sommario La moderna teoria delle strutture murarie, fondata sulla rigorosa non reagenza a trazione del materiale, ha lo scopo di fornire un modello di riferimento indipendente sia dalle caratteristiche del materiale sia dalle techniche costruttive impiegate. L'ipotesi di non reagenza a trazione si traduce in disuguaglianze che le componenti del tensore di stress devono verificare; dualmente il comportamento caratteristico cinematico può esser classificato di confine, come del resto la stessa statica, tra solidi e fluidi: la struttura ipotizzata del materiale muratura consiste di particelle che reagiscono solo se sono in contatto. L'esame del problema piano porta a definire all'interno del dominio di definizione tre differenti tipi di sub-regioni in cui lo stress è nullo, canonico, o singolare. Poiché le frontiere di queste sub-regioni non sono note a priori il problema può anche essere classificato di frontiera libera. L'analisi concerne fondamentalmente la sub-regione in cui il tensore è non regolare, perché deve verificare anche la condizione det =0. Ciò rende isostatico il problema e conduce anche alla violazione della condizione di integrabilità delle deformazioni. Questo passaggio può essere superato introducendo un tensore di deformazioni a tensioni nulle che si può decomporre in una componente estensionale ed in una componente di scorrimento; si dimostra che queste deformazioni sono equivalenti a quelle che intervengono nella Teoria del flusso plastico. Dal punto di vista computazionale le deformazioni anelastiche sono considerate come distorsioni impresse determinate attraverso il principio di Haar-Kármán modificato, per le techniche computazionali, su idee di Prager e Hodge.

     

Surface and Structural Investigation of a MnOx Birnessite‐Type Water Oxidation Catalyst Formed under Photocatalytic Conditions

Catalytically active MnO_x species have been reported to form in situ from various Mn‐complexes during electrocatalytic and solution‐based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnO_x catalysts form without supports in situ under photocatalytic conditions. Our most active ⁴MnO_x catalyst (～0.84 mmol O₂ mol Mn^?1 s^?1) forms from a Mn₄O₄ bearing a metal–organic framework. ⁴MnO_x is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR‐TEM as a disordered, layered Mn‐oxide with high surface area (216 m²g^?1) and small regions of crystallinity and layer flexibility. In contrast, the ^SMnO_x formed from Mn²⁺ salt gives an amorphous species of lower surface area (80 m²g^?1) and lower activity (～0.15 mmol O₂ mol Mn^?1 s^?1). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p_3/2 core levels detects enriched Mn³⁺ and Mn²⁺ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.     

Synthesis of cobalt doped silica thin film for low temperature optical gas sensor

A modified sol–gel method was used to prepare cobalt doped silica thin film with a cobalt content of 10, 20 and 30 mol% (10Co, 20Co and 30Co). The prepared films were annealed at different temperatures in the range 400–1,000 °C, and their structural evolution examined. The mixed valence cobalt oxide, Co₃O₄, crystallizes only in the sample with the higher cobalt content, while cobalt silicate is the only crystalline phase detected in the sample 10Co and 20Co. Both the cobalt content and the temperature of heat treatment resulted to affect the nature of cobalt species dispersed in the silica matrix. The 30Co was selected for further investigations by FTIR spectroscopy to follow the structural evolution of 30Co film as function of the temperature and UV–Vis to get information on the cobalt valence state. The optical gas-sensing properties of 30Co films, containing Co₃O₄ as the major cobalt phase, were studied through the measuring of the film transmittance in dry air and in presence of dry air containing variable concentrations of polluting gases, CO and NO₂. The 30Co samples resulted to be highly sensitive to CO at room temperature. An explanation for the CO sensing characteristics, at low temperature, was proposed by referring to the physisorption-related mechanics of CO.