A New Asymmetric Synthesis of β-Aminophosphonic Acids

Addition of α-phosphonate carbanions to (S)-sulfinimines 2 gives N-sulfinyl-β-aminophosphonates 3 with a high diastereoselectivity (up to 10:1). The major diastereomer of 3 (R=Ph) was converted into (+)-(R)-β-amino-β-phenylethanephosphonic acid 5.     

Studies on hydrogen diffusivity in iron aluminides using the Devanathan–Stachurski method

An electrolytic method for cathodic hydrogen saturation developed by Devanathan and Stachurski was successfully used to study hydrogen diffusivity in iron aluminides. Both an appropriate electrolyte and a saturating current density are required for this method. A proper form of the saturation curve was only obtained with 35% NaCl electrolyte, which removed the oxide film blocking hydrogen penetration without further corrosive destruction of the iron aluminide. The optimum saturation current density for determining the most reliable diffusivity was 1.91 A/cm², yielding D_eff,H = 4.81 × 10⁻⁶ cm²/s for Fe–40 at.% Al.     

Compactness and sequential completeness in some spaces of operators

Let \(X\) be a completely regular Hausdorff space and \(C_b(X)\) be the Banach lattice of all real-valued bounded continuous functions on \(X\) , endowed with the strict topologies \(\beta _\sigma ,\) \(\beta _\tau \) and \(\beta _t\) . Let \(\mathcal{L}_{\beta _z,\xi }(C_b(X),E)\) \((z=\sigma ,\tau ,t)\) stand for the space of all \((\beta _z,\xi )\) -continuous linear operators from \(C_b(X)\) to a locally convex Hausdorff space \((E,\xi ),\) provided with the topology \(\mathcal{T}_s\) of simple convergence. We characterize relative \(\mathcal{T}_s\) -compactness in \(\mathcal{L}_{\beta _z,\xi }(C_b(X),E)\) in terms of the representing Baire vector measures. It is shown that if \((E,\xi )\) is sequentially complete, then the spaces \((\mathcal{L}_{\beta _z,\xi }(C_b(X),E),\mathcal{T}_s)\) are sequentially complete whenever \(z=\sigma \) ; \(z=\tau \) and \(X\) is paracompact; \(z=t\) and \(X\) is paracompact and ?ech complete. Moreover, a Dieudonné–Grothendieck type theorem for operators on \(C_b(X)\) is given.     

Surface electronic structure calculations using the MBJLDA potential: Application to Si(111)2 × 1

The Si(111)2 × 1 surface has been widely studied via a range of different experimental and theoretical techniques, and found to adopt a π‐bonded chain configuration. To determine an accurate electronic structure for this system, however, it has been found necessary to use sophisticated and very computationally expensive methods such as GW or hybrid functionals. In this article, we show that the MBJLDA approach, originally proposed by Tran and Blaha for bulk materials (Tran and Blaha, Phys. Rev. Lett. 2009, 102, 226401), yields results which are comparable to GW, and generally superior to those obtained from hybrid functional density functional theory calculations. The MBJLDA method is also substantially more computationally efficient. A procedure and justification for the application of the MBJLDA approach to surfaces in general is also provided. © 2014 Wiley Periodicals, Inc.     

Synthesis of 4-hydroxymethyl-2,4-methanoproline

The synthesis of 4-hydroxymethyl-2,4-methanoproline, a novel conformationally restricted amino acid, was performed in four steps. This close analogue of naturally occurring amino acids (i.e., proline, hydroxyproline, serine and threonine) was prepared in good overall yield through two intramolecular recyclization reactions of cyclobutane derivatives.     

Bismuth Film Voltammetric Sensor on Pyrolyzed Photoresist/Alumina Support for Determination of Heavy Metals

Voltammetric sensors based on bismuth film electrodes are an attractive alternative to other sensors for application in electroanalysis of heavy metals. Bismuth film electrodes can be formed by a similar method on the same substrates as mercury. These systems were used most frequently for simultaneous determination of heavy metals such as Pb, Cd and Zn by anodic stripping voltammetry. Our voltammetric sensor was fabricated on an alumina substrate. A photoresist film prepared by pyrolysis of positive photoresist S‐1813 SP15 on the alumina substrate was used as an electrode support for bismuth film deposition. The influence of the Nafion membrane on the measurement sensitivity of the sensor and mechanical stability of the bismuth film were investigated. The sensor was successfully applied for determination of Pb, Cd and Zn in an aqueous solution in the concentration range of 0.2 to 10 µg L^?1 by square wave anodic stripping voltammetry on an in‐situ formed bismuth film electrode with Nafion‐coating. Parameters of the sensor such as sensitivity, linearity, detection limit, repeatability and life‐time were evaluated. In the best case, the detection limits were estimated as 0.07, 0.11 and 0.63 µg L^?1 for Pb, Cd and Zn, respectively. Finally, the applicability of the sensor was tested in analysis of Pb, Cd and Zn in real samples of tap and river water using the method of standard additions.     

Electron spin-spin coupling from multireference configuration interaction wave functions

We present the implementation of two-electron spin-spin coupling as a quasidegenerate perturbative treatment of the Breit-Pauli spin-spin Hamiltonian. The evaluation is based on a multireference CI treatment and constitutes one of the first efforts in the calculation of this effect within a highly sophisticated consideration of both nondynamical and dynamical correlation. The extension of existing schemes for efficient calculation, in particular, of the spin-coupling elements necessitated some involved derivations, the outline of which is presented herein. Application of the program to calculations of diagonal as well as off-diagonal spin-coupling elements is illustrated with the test cases O(2) and NH.     

Diastereomers of N-alpha-phenylethyl-t-butylsulfinamide: absolute configurations and predominant conformations

N-alpha-Phenylethyl-t-butylsulfinamide is a complicated system for determining molecular stereochemistry because of numerous possibilities for assigning the absolute configuration and a predominant conformation. Two diastereomers of N-alpha-phenylethyl-t-butylsulfinamide derived from (-)-(S)-alpha-phenylethyl amine, a (+)-diastereomer and a (-)-diastereomer, have been synthesized and their experimental chiroptical spectroscopic properties have been measured. These properties include vibrational circular dichroism, electronic circular dichroism and optical rotatory dispersion. Using these experimental data, in conjunction with corresponding density functional theoretical predictions, the absolute configuration and predominant conformations of these two diastereomers have been determined. Also, the absolute configuration of (-)-diastereomer has been independently confirmed by determining its structure from X-ray diffraction data.     

Luminescent Copper(I)-Complexes with an Anionic NHC obtained via a Coordination Polymer as Versatile Precursor**

The anionic diamido N-heterocyclic carbene 1 is used to prepare a series of linear as well as trigonal, heteroleptic Cu^I complexes with small molecular ligands such as pyridine derivatives or triphenylphosphine. A key role lies in the versatile precursor for these complexes, a moisture- and air-stable 1D coordination polymer [1 ⋅ Cu] _n composed of only the NHC ligand and Cu^I, such that the copper is linearly coordinated by the carbene carbon atom and one oxygen atom of the backbone of the carbene. This polymer can easily be cleaved into monomeric complexes by addition of the desired ligand to dispersions of the polymer in dichloromethane. In solution, the complexes are in equilibrium with this highly insoluble polymer and free ligand. Thus, analytical and spectroscopical experiments with the compounds are limited to their crystalline state, characterized by single crystal X-ray diffraction experiments. Some of the complexes exhibit visible luminescence in the solid state upon irradiation with ultraviolet light. The spectral features (emission wavelength, Stokes shift, width of the emission band, vibrational fine structure) significantly differ among the complexes. Quantum mechanical computations reveal a subtle interplay of several factors such as coordination number and charge transfer character of the emissive state.