Pentapnictogen heterocyclic monoanions: Structure,stability, and aromaticity

Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X _nY_5-n⁻ (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η⁵-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials.     

Synthesis and Self-Assembly of Mixed-Graft Block Copolymers

Mixed-graft block copolymers (mGBCPs) consist of two or more types of polymeric side chains grafted on a linear backbone in a random, alternating, or pseudo-alternating sequence. They can phase-separate with the backbone serving as the interface of the blocks, and the side chains dominate their self-assembly behavior. mGBCPs are an accessible polymer architecture for exploring the idea of encoding polymer properties through the macromolecular architecture, as there are two distinct structural components that can be tuned: the backbone and the side chains. In this Concept article, the current literature on the synthesis of mGBCPs is reviewed, and the advantages and disadvantages of each synthetic method are noted. The self-assembly of mGBCPs is also discussed where possible. Finally, directions for future research on mGBCP synthesis and self-assembly are suggested.     

Theory of relaxed density matrices: Application to second-order response properties

The evaluation of second derivatives of the electronic energy for nonvariational wave functions using an energy functional is discussed. It is shown that, in certain cases, the formation of the first-order relaxed density matrix leads to an efficient algorithm for the calculation of second-order response properties. Detailed formulas are given for second-order Møller–Plesset perturbation theory. © 1994 John Wiley & Sons, Inc.     

Sequencing of antisense DNA analogues by capillary gel electrophoresis with laser-induced fluorescence detection

A method using capillary gel electrophoresis with laser-induced fluorescence detection is described which permits complete sequence determination of antisense DNA analogues of unknown sequence. This method, originally created as a tool to confirm the sequence of antisense oligonucleotides being developed as therapeutic drugs, utilizes data collected under a range of experimental conditions described by the Ogston model as applied to gel electrophoresis. A linear relationship independent of experimental conditions between the relative electrophoretic migration time and the oligonucleotide base number was observed and is shown to be consistent with a simplified version of this model and can be used to facilitate the sequence determination.     

AGE method simulations of a turbulent far‐wake compared to spectral DNS

Turbulent flow simulation methods based on finite differences are attractive for their simplicity, flexibility and efficiency, but not always for accuracy or stability. This paper demonstrates that a good compromise is possible with the advected grid explicit (AGE) method. Starting from the same initial field as a previous spectral DNS, AGE method simulations of a planar turbulent wake were carried out as DNS, and then at three levels of reduced resolution. The latter cases were in a sense large‐eddy simulations (LES), although no specific sub‐grid‐scale model was used. Results for the two DNS methods, including variances and power spectra, were very similar, but the AGE simulation required much less computational effort. Small‐scale information was lost in the reduced resolution runs, but large‐scale mean and instantaneous properties were reproduced quite well, with further large reductions in computational effort. Quality of results becomes more sensitive to the value chosen for one of the AGE method parameters as resolution is reduced, from which it is inferred that the numerical stability procedure controlled by the parameter is acting in part as a sub‐grid‐scale model. Copyright © 2002 John Wiley & Sons, Ltd.     

Inclusion of carbon nanotubes in a TiO2 sol-gel matrix

We report here the successful inclusion of carbon nanotubes (CNs) into a TiO₂ matrix prepared by a sol-gel method. The presence of CNs in the sol-gel matrix and the structure of the film were analyzed principally by transmission electron microscopy. Complementary information about the behavior of embedded carbon nanotubes versus heat treatment and ion irradiation were obtained by X-ray photoelectron spectroscopy. The elaboration of an inorganic matrix containing embedded carbon nanotubes leads to a new nanocomposite. The possible applications of this nanocomposite are discussed.     

(2 + 1) Resonance enhanced multiphoton ionization of hydrogen chloride in a pulsed supersonic jet: Vacuum wavenumbers of rotational lines with detailed band analysis for excited electronic states of HCl

A comprehensive study of the excited electronic states of HCl is reported. Using resonance enhanced multiphoton ionization ((2 + 1) REMPI) and time-of-flight mass spectrometry (TOFMS) over 120 band systems are analyzed. Supersonic jet techniques are used to prepare rotationally cold species for laser spectroscopy in the 77 000 to 96 000 cm⁻¹ region. At least 50 new electronic states are characterized as well as several features only tentatively assigned previously. A long vibrational progression consisting of 29 vibrational levels of the deeply bound V¹Σ⁺(0⁺) valence/ion-pair state is studied. We also extend the identification and analysis to high vibrational levels of low-lying Rydberg states. The assignments of [²Π_i] Rydberg state complexes are evaluated in terms of spin-orbit coupling and united-atom calculations. In several band systems, the spectra exhibit anomalous rotational line intensities and broadened linewidths which are consistent with predissociation. Multiphoton ionization with mass spectrometry permits the investigation of isotope effects as well as the appearance of fragment species associated with repulsive potential curves.