A non-empirical LCAO-SCF-MO investigation of cross sections through the potential energy surface for the [C2H2Cl]+ systems; comparison with the [C2H5+] and [C2H4F]+ systems

Non-empirical LCAO MO SCF calculations are reported on cross sections through the C₂H₄Cl⁺ system and comparisons are drawn with the C₂H₅⁺ and C₂H₄F⁺ systems. Barriers to rotation in the classical 1- and 2-substituted ethyl cations have been computed and an investigation made of the bridged chloronium and fluoronium ions. The results suggest that the relative stabilities of bridged ions with respect to the corresponding classical 2-substituted ethyl cations increase in the order H < F < Cl. The results are discussed in terms of available experimental data and consideration given to correlation and solvation energy effects.     

The activity of calcium chloride in aqueous solutions of some amino acids at 25°C

The activity coefficients of calcium chloride in aqueous solutions of the amino acids glycine, β-alanine, γ-amino butyric acid, ε-aminocaproic acid, and glycylglycine have been determined with cells utilizing a calcium ion-exchange electrode. Application of the cross-differential relationship allows a measure of the variation of the salting-in parameter across the series of amino acids. The variation of this parameter is discussed using a semiempirical approach developed earlier.     

Ionic conductivity in crystalline PEO6:Li(AsF6)1-x(SbF6)x

The ionic conductivity of PEO6:LiXF6 (X = As, Sb) complexes may be raised by over an order of magnitude by forming solid solutions of PEO6:Li(AsF6)1-x(SbF6)x.     

Bulk-wave and guided-wave photoacoustic evaluation of the mechanical properties of aluminum/silicon nitride double-layer thin films

The development of devices made of micro- and nano-structured thin film materials has resulted in the need for advanced measurement techniques to characterize their mechanical properties. Photoacoustic techniques, which use pulsed laser irradiation to nondestructively induce very high frequency ultrasound in a test object via rapid thermal expansion, are suitable for nondestructive and non-contact evaluation of thin films. In this paper, we compare two photoacoustic techniques to characterize the mechanical parameters of edge-supported aluminum and silicon nitride double-layer thin films. The elastic properties and residual stresses in such films affect their mechanical performance. In a first set of experiments, a femtosecond transient pump–probe technique is used to investigate the Young’s moduli of the aluminum and silicon nitride layers by launching ultra-high frequency bulk acoustic waves in the films. The measured transient signals are compared with simulated transient thermoelastic signals in multi-layer structures, and the elastic moduli are determined. Independent pump–probe tests on silicon substrate-supported region and unsupported region are in good agreement. In a second set of experiments, dispersion curves of the A₀ mode of the Lamb waves that propagate along the unsupported films are measured using a broadband photoacoustic guided-wave method. The residual stresses and flexural rigidities for the same set of double-layer membranes are determined from these dispersion curves. Comparisons of the results obtained by the two photoacoustic techniques are made and discussed.     

Accurate molecular weight measurements of nucleoside phosphoramidites: a suitable matrix of mass spectrometry

Nucleoside phosphoramidites (PAs) are the most widely used building blocks in contemporary solid-phase synthesis of oligonucleotides. The accurate molecular weight (MW) measurements of such molecules, which contain acid-labile moieties, may be easily determined by mass spectrometry using a matrix system, triethanolamine (TEOA)-NaCl, on liquid secondary ion mass spectrometry (LSIMS) equipped with a double-focusing mass spectrometer. The present method measures rapidly and easily the accurate MWs of various PAs as adduct ions [M+Na]⁺ with average mass error smaller than 0.4 ppm, allowing the formulas of various PAs in place of elemental analysis. Further, it was found that intensities of molecular-related ions could be enhanced to the highest degree by adjustment of the mole ratio of PA and NaCl fixing the amount of TEOA on LSIMS, making the present method powerful tool for the MS identification of PAs.     

Advancing understanding of actinide(iii) (Ac,Am, Cm) aqueous complexation chemistry

The positive impact of having access to well-defined starting materials for applied actinide technologies – and for technologies based on other elements – cannot be overstated. Of numerous relevant 5f-element starting materials, those in complexing aqueous media find widespread use. Consider acetic acid/acetate buffered solutions as an example. These solutions provide entry into diverse technologies, from small-scale production of actinide metal to preparing radiolabeled chelates for medical applications. However, like so many aqueous solutions that contain actinides and complexing agents, 5f-element speciation in acetic acid/acetate cocktails is poorly defined. Herein, we address this problem and characterize Ac³⁺ and Cm³⁺ speciation as a function of increasing acetic acid/acetate concentrations (0.1 to 15 M, pH = 5.5). Results obtained via X-ray absorption and optical spectroscopy show the aquo ion dominated in dilute acetic acid/acetate solutions (0.1 M). Increasing acetic acid/acetate concentrations to 15 M increased complexation and revealed divergent reactivity between early and late actinides. A neutral Ac(H₂O)₆₍₁₎(O₂CMe)₃₍₁₎ compound was the major species in solution for the large Ac³⁺. In contrast, smaller Cm³⁺ preferred forming an anion. There were approximately four bound O₂CMe¹⁻ ligands and one to two inner sphere H₂O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH₄)₂M(O₂CMe)₅ (M = Eu³⁺, Am³⁺ and Cm³⁺) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).

Actinide complexation from aqueous acetic acid/acetate buffered solutions is described. The number of water ligands was directly correlated with the acetate concentration and characterized by X-ray absorption and optical spectroscopy.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

The chirality of a four-way helical junction in RNA

We have used a novel electrophoretic approach to determine the chirality of a four-way helical junction in RNA. From our experiments we conclude that the handedness of the helical junction in the complete ribozyme is opposite to that found in the free junction and is therefore constrained by the interaction between the unpaired loops of the ribozyme.     

Conductivity relaxations in single crystals of sodium chloride containing suzuki phase precipitates

Single crystals of NaCl containing volume fractions of up to 28% of the Suzuki phase Cd□Na₆Cl₈ have been subjected to a.c. electrical measurements over a range of frequencies (10-10⁷ Hz). Complex modulus plots and modulus spectra reveal two distinct electrical relaxations arising in the matrix, and the precipitates. The Maxwell layer model and the Maxwell-Wagner model for dispersions of two phases are used to separate the two ionic conductivities. The activation energy for ionic conduction in the Suzuki phase is found to be 0.93 ± 0.05 eV, which is in agreement with a previously reported value obtained on polycrystalline Cd□Na₆Cl₈.     

Novel ligands for a purine riboswitch discovered by RNA-ligand docking

The increasing number of RNA crystal structures enables a structure-based approach to the discovery of new RNA-binding ligands. To develop the poorly explored area of RNA-ligand docking, we have conducted a virtual screening exercise for a purine riboswitch to probe the strengths and weaknesses of RNA-ligand docking. Using a standard protein-ligand docking program with only minor modifications, four new ligands with binding affinities in the micromolar range were identified, including two compounds based on molecular scaffolds not resembling known ligands. RNA-ligand docking performed comparably to protein-ligand docking indicating that this approach is a promising option to explore the wealth of RNA structures for structure-based ligand design.