Structure and magnetism of Eu2IrD5

A powder neutron diffraction study of Eu¹⁵³₂IrD₅ has shown it to be isostructural with Sr₂IrD₅ at room temperature. Unlike the latter compound, it does not undergo a deuterium-ordering transition at low temperatures. Magnetic scattering at helium temperatures confirms the suggestion that it becomes ferromagnetic below 20 K with a moment corresponding to that of divalent europium.     

An order-disorder transition in Sr2IrD5: Evidence for square pyramidal IrD5 units from powder neutron diffraction data

Neutron diffraction data have been collected on a powdered sample of Sr₂IrD₅ over a range of temperatures. The compound, which is cubic at room temperature, has been found to exhibit a gradual transformation to a tetragonal phase in the temperature range 200-140 K. As a result of the transition, deuterium atoms which randomly occupy sixfold positions in the cubic phase, become tetragonally ordered. A small fraction of the cubic phase remained untransformed at 4.2 K. Both the cubic and tetragonal structures are consistent with square pyramidal IrD₅ units with average Ir---D distances of 1.714 and 1.718 Å, respectively. Agreement factors, R₁, for the two structural analyses are 3.44 and 4.94%.     

Prediction of Complexation Properties of Crown Ethers Using Computational Neural Networks

A computational neural network method was used for the prediction of stability constants of simple crown ether complexes. The essence of the method lies in the ability of a computer neural network to recognize the structure-property relationships in these host-guest systems. Testing of the computational method has demonstrated that stability constants of alkali metal cation (Na+, K+, Cs+)-crown ether complexes in methanol at 25 °C can be predicted with an average error of ±0.3 log K units based on the chemical structure of the crown ethers alone. The computer model was then used for the preliminary analysis of trends in the stabilities of the above complexes.     

Solvent extraction of Li+, H3O+ and NH4 + into nitrobenzene by using sodium dicarbollylcobaltate and calix[4]arene-bis(t-octylbenzo-18-crown-6)

From extraction experiments and $ \gamma $ -activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺ (aq) + NaL⁺ (nb) ? ML⁺ (nb) + Na⁺ (aq) taking place in the two–phase water–nitrobenzene system (M⁺= Li⁺, H₃O⁺, NH₄ ⁺; L = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML⁺ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: H₃O⁺ < Li⁺ < NH₄ ⁺.     

Calix[4]arene-bis(t-octylbenzo-18-crown-6) as an extraordinarily effective macrocyclic receptor for the univalent thallium cation

From extraction experiments and $ \gamma $ -activity measurements, the exchange extraction constant corresponding to the equilibrium Tl⁺ (aq) + 1·Cs⁺ (org) ? 1·Tl⁺ (org) + Cs⁺ (aq) taking place in the two-phase water–phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log K _ex (Tl⁺, 1·Cs⁺) = 1.7 ± 0.1. Further, the extraordinarily high stability constant of the 1·Tl⁺ complex in FS 13 saturated with water was calculated for a temperature of 25 °C: log β _org(1·Tl⁺) = 13.1 ± 0.2. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1·Tl⁺ was derived. In the resulting 1·Tl⁺ complex, the “central” cation Tl⁺ is bound by eight bond interactions to six oxygen atoms from the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent receptor 1 via cation–π interaction.     

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Ohne Zusammenfassung     

Air-stable iron catalyst for the Oppenauer-type oxidation of alcohols

An alcohol oxidation process using an air-stable iron tricarbonyl compound structurally similar to Shvo’s diruthenium bridging hydride was developed. Secondary benzylic and allylic alcohols are oxidized in high yields, and evidence for an Oppenauer-type mechanism is presented.     

Arytenoid Cartilage Dislocation: A 20-year Experience

SUMMARY: Arytenoid cartilage dislocation is an infrequently diagnosed cause of vocal fold immobility. Seventy-four cases have been reported in the literature to date. Intubation is the most common origin, followed by external laryngeal trauma. Decreased volume and breathiness are the most common presenting symptoms. We report on 63 patients with arytenoid cartilage dislocation treated by the senior author (RTS) since 1983. Significantly more posterior than anterior dislocations were represented. Although reestablishing joint mobility is difficult, endoscopic reduction should be considered to align the heights of the vocal processes. This process may result in significant voice improvement even long after the dislocation. Strobovideolaryngoscopy, laryngeal electromyography, and laryngeal computed tomography (CT) imaging are helpful in the evaluation of patients with vocal fold immobility to help distinguish arytenoid cartilage dislocation from vocal fold paralysis. Familiarity with signs and symptoms of arytenoid cartilage dislocation and current treatment techniques improves the chances for optimal therapeutic results.     

Optimal control problems that test for envelope contacts

Systems are studied whose state vector x is governed by the usual set of first-order differential equations. When the extremals x(t) that originate at a fixed point inn-dimensional state-variable space are stopped at a fixed final time, the locus of their endpoints defines a hypersurface called the wavefront. The well-known adjoint vector is normal to the wavefront. The principal point of this paper is that a second wavefront normal can be constructed from the x(t) vectors that are available if the test for Jacobi conjugate points is performed. Verifying that the two normals are almost collinear shows that the errors due to computer truncation and numerical integration are negligible. This check is particularly useful when using the finite-difference approximation x(t) x ⁱ (t) – x ^j (t), where x ⁱ (t) and x ^j (t) are close but nonneighboring extremals. This approximation can simplify considerably the analysis and computation required for a conjugate-point test, particularly if the extremals have corners.