Electronic structures and nonlinear optical properties of supramolecular associations of benzo-2,1,3-chalcogendiazoles by the elongation method

The investigations of one-dimensional periodic associations of benzo-2,1,3-chalcogendiazoles have been carried out by the elongation method. S, Se and Te chalcogens have been in use. For the polymers, band structures and local densities of states were extracted from ab initio calculations of electronic structure of the 15 units’ oligomers. Static electric (hyper)polarizabilities were studied by the elongation finite-field method.     

Influence of viscoelasticity on drop deformation and orientation in shear flow: Part 1. Stationary states

The influence of matrix and droplet viscoelasticity on the steady deformation and orientation of a single droplet subjected to simple shear is investigated microscopically. Experimental data are obtained in the velocity–vorticity and velocity–velocity gradient plane. A constant viscosity Boger fluid is used, as well as a shear-thinning viscoelastic fluid. These materials are described by means of an Oldroyd-B, Giesekus, Ellis, or multi-mode Giesekus constitutive equation. The drop-to-matrix viscosity ratio is 1.5. The numerical simulations in 3D are performed with a volume-of-fluid algorithm and focus on capillary numbers 0.15 and 0.35. In the case of a viscoelastic matrix, viscoelastic stress fields, computed at varying Deborah numbers, show maxima slightly above the drop tip at the back and below the tip at the front. At both capillary numbers, the simulations with the Oldroyd-B constitutive equation predict the experimentally observed phenomena that matrix viscoelasticity significantly suppresses droplet deformation and promotes droplet orientation. These two effects saturate experimentally at high Deborah numbers. Experimentally, the high Deborah numbers are achieved by decreasing the droplet radius with other parameters unchanged. At the higher capillary and Deborah numbers, the use of the Giesekus model with a small amount of shear-thinning dampens the stationary state deformation slightly and increases the angle of orientation. Droplet viscoelasticity on the other hand hardly affects the steady droplet deformation and orientation, both experimentally and numerically, even at moderate to high capillary and Deborah numbers.     

A Festschrift in honor of Sándor Suhai’s 65th birthday

This is a multidisciplinary multifocus issue of TCA titled the Suhai Festschrift Honorary Issue commemorating the 65th birthday of Professor Sándor Suhai and his many contributions to the fields of molecular biophysics, bioinformatics, theoretical chemistry, chemical physics and molecular biology.     

Mechanistic study of 7-endo selective radical cyclization of the aryl radical

Mechanistic studies on the novel 7-endo selective radical cyclization were carried out. The reaction afforded three products, 7-endo product, 6-exo product, and reduced product. The distribution of these products was estimated by GC analyses. The 7-endo/6-exo selectivity was almost constant against variation in the concentration of Bu₃SnH, while the reduction/cyclization ratio was sensitive to the concentration of Bu₃SnH. The reduction/cyclization ratio was mainly affected by the rotational isomeric ratio of the cyclization precursor. Kinetic analyses indicated that the cyclization process should be irreversible, and the rate constant of 7-endo/6-exo radical cyclization was estimated to be about 3.3 × 10⁸ s⁻¹ at 80 °C.     

Langmur monolayers of cerebroside with different head groups originated from sea cucumber: Binary systems with dipalmitoylphosphatidylcholine (DPPC)

Surface properties (Langmuir monolayer) of two different cerebrosides which are extracted from the sea cucumber (Bohadschia argus) were investigated. A main difference in chemical structure of cerebroside between BAC-2a and BAC-4 is their head groups (glucose and galactose, respectively). Furthermore, miscibility and interaction between dipalmitoylphosphatidylcholine (DPPC) and cerebrosides (BAC-2a and BAC-4) in the monolayer have been systematically examined. The surface pressure (π)−area (A), the surface potential (ΔV)−A, and the dipole moment (μ)−A isotherms for monolayers of DPPC, cerebrosides, and their binary combinations have been measured using the Wilhelmy method and the ionizing electrode method. BAC-4 forms a stable liquid-expanded (LE) monolayer, whereas BAC-2a has a first-order phase transition from the LE phase to the liquid-condensed (LC) state on 0.15 M NaCl at 298.2 K. The fundamental properties for each cerebroside monolayer were elucidated in terms of the surface dipole moment based on the three-layer model [R.J. Demchak, T. Fort Jr., J. Colloid Interface Sci. 46 (1974) 191–202] for both cerebrosides and the apparent molar quantity change (Δs^γ, Δh^γ, and Δu^γ) for BAC-2a. In addition, their miscibility with DPPC was examined by the variation of the molecular areas and the surface potentials as a function of cerebroside mole fractions, the additivity rule. The miscibility was also confirmed by constructing the two-dimensional phase diagrams. The phase diagrams for the both binary systems were of negative azeotropic type. That is, the two-component DPPC/BAC-2a and DPPC/BAC-4 monolayers are miscible. Furthermore, the Joos equation for the analysis of the collapse pressure of binary monolayers allowed calculation of the interaction parameter and the interaction energy between the DPPC and cerebroside monolayers. The miscibility in the monolayer state was also confirmed by the morphological observation with Brewster angle microscopy (BAM), fluorescence microscopy (FM), and atomic force microscopy (AFM).     

Theoretical study on nonlinear optical properties of the Li+[calix[4]pyrrole]Li−dimer,trimer and its polymer with diffuse excess electrons

The static (hyper)polarizabilities of the dimer and trimer with diffuse excess electrons, [Li⁺[calix[4]pyrrole]Li^?]_n, are firstly investigated by the DFT(B3LYP) method in detail. For the dimer and trimer, a Li atom inside each calix[4]pyrrole unit is ionized to form a diffuse excess electron. The results show that the dimer and trimer containing two and three excess electrons, respectively, have very large first hyperpolarizablities as 2.3 × 10⁴ and 4.0 × 10⁴ au, which are 30 and 40 times larger than that of the corresponding [calix[4]pyrrole]_n (n = 2, 3) without Li atom. Also, β values of dimer and trimer are twice and four times as large as that of monomer containing one excess electron. Obviously, not only excess electron but also the number of excess electron plays an important role in increasing the first hyperpolarizability. Moreover, the (hyper)polarizabilities of the [Li⁺[calix[4]pyrrole]Li^?]_n polymer are investigated at ab initio level by using the elongation finite‐field (elongation FF) method. All the oligomers of the [Li⁺[calix[4]pyrrole]Li^?]_n with many excess electrons exhibit very large first hyperpolarizability and large second hyperpolarizability. The present investigation shows that by introducing several and more excess electrons into the nonlinear optical (NLO) materials will be an important strategy for improving their NLO properties, which will be helpful for design of NLO materials. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

General Heart Construction on a Triangulated Category (II): Associated Homological Functor

In the preceding part (I) of this paper, we showed that for any torsion pair (i.e., t-structure without the shift-closedness) in a triangulated category, there is an associated abelian category, which we call the heart. Two extremal cases of torsion pairs are t-structures and cluster tilting subcategories. If the torsion pair comes from a t-structure, then its heart is nothing other than the heart of this t-structure. In this case, as is well known, by composing certain adjoint functors, we obtain a homological functor from the triangulated category to the heart. If the torsion pair comes from a cluster tilting subcategory, then its heart coincides with the quotient category of the triangulated category by this subcategory. In this case, the quotient functor becomes homological. In this paper, we unify these two constructions, to obtain a homological functor from the triangulated category, to the heart of any torsion pair.     

Degraded and oxetane-bearing limonoids from the roots of Melia azedarach

Brine shrimp lethality test (BST)-guided fractionation of a methanol extract of the roots of Melia azedarach resulted in the isolation of two new limonoids, 9alpha-hydroxy-12alpha-acetoxyfraxinellone (1) and 7,14-epoxy-azedarachin B (2), together with the known compounds, 12alpha-hydroxyfraxinellone (4), 9alpha-hydroxyfraxinellone (5), azedarachin B (6), and neoazedarachin B (7). The structures of 1 and 2 were elucidated by analysis of spectroscopic data and comparison of their NMR data with those of the known compounds. Compounds 1, 2 and 4-7 exhibited significant activity in the BST, in particular, azedarachin B (6) showed remarkable BST activity with an LC(50) value of 0.0098 microM.     

Efficiency and accuracy of the elongation method as applied to the electronic structures of large systems

Current state of development of the elongation method originally proposed by Imamura is presented. Recent progress in methodology, including geometry optimization and employment of the fast multiple method, is highlighted. The accuracy and efficiency of the elongation method as compared to exact canonical Hartree-Fock and Kohn-Sham approaches are discussed. Potential applications are illustrated by wide range of calculations for model systems. The elongation calculations are demonstrated to be much more efficient compared to the conventional ones with high accuracy maintained. The elongation CPU time is shown by the model calculations as linear or sub-linear scaling for quasi-one-dimensional systems. Future work of development into post-Hartree-Fock methodologies are pointed out.