A Note on Distance Matrices Yielding Elementary Landscapes for the TSP

Symmetric and antisymmetric distance matrices in the single agent traveling salesman problem (TSP) are not the only distance matrices to generate elementary landscapes for swap and 2-opt neighborhoods.     

Constructions of Large Graphs on Surfaces

We consider the degree/diameter problem for graphs embedded in a surface, namely, given a surface Σ and integers Δ and k, determine the maximum order N(Δ,k,Σ) of a graph embeddable in Σ with maximum degree Δ and diameter k. We introduce a number of constructions which produce many new largest known planar and toroidal graphs. We record all these graphs in the available tables of largest known graphs. Given a surface Σ of Euler genus g and an odd diameter k, the current best asymptotic lower bound for N(Δ,k,Σ) is given by $$\sqrt{\frac{3}{8}}g \Delta^{\lfloor k/2 \rfloor}.$$ Our constructions produce new graphs of order $$\left\{\begin{array}{ll}6 \Delta^{\lfloor k/2 \rfloor} \qquad \qquad \qquad \qquad {\rm if \Sigma\;is\;the\;Klein\;bottle} \\ \left(\frac{7}{2} + \sqrt{6g + \frac{1}{4}}\right) \Delta^{\lfloor k/2 \rfloor} \quad {\rm otherwise},\end{array}\right.$$ thus improving the former value.     

Laplace-transformed diagonal Dyson correction to quasiparticle energies in periodic systems

We present a method to self-consistently evaluate quasiparticle energies of periodic systems within the diagonal approximation for solving Dyson's equation. Our method is based on the Laplace transform of the second-order M?ller-Plesset perturbation (MP2) theory kernel in the atomic basis formulation. The overhead computational cost of evaluating the fully self-consistent diagonal correction over the MP2 band energy calculation is negligible. We present numerical benchmark results for the band structure of trans-polyacetylene and compare it with MP2 and other approaches.     

Isothermal Vapor–Liquid Equilibria for the Ternary System 2-Propanol + Tetrahydrofuran + 1-Chlorobutane at 25°C

Isothermal vapor–liquid equilibria (VLE) for mixtures containing 2-propanol + tetrahydrofuran + 1-chlorobutane have been measured using a modified version of a Boublik–Benson still at 25°C. A test of thermodynamic consistency, like the McDermott–Ellis method was applied to the activity coefficients. Excess molar Gibbs free energies were calculated over the entire range composition. Different expressions existing in the literature were used to predict activity coefficients.     

Study of bulk chain coupling reactions. II. Reaction between bisoxazolones and amine-terminated polyether: Synthesis of polyether-block-polyamides

The bulk reactions between 2,2′-bis(4,4-dimethyl-5(4H)-oxazolone) ( B3 ) or 2,2′-(1,2-ethylene)-bis(4,4-dimethyl-5(4H)-oxazolone) ( B4 ) and amine-terminated polyether (Jeffamine ED-900) have been studied by SEC, and ¹H-and ¹³C-NMR and the resulting polymers were characterized by DSC and TGA. These chain coupling reactions have been applied to the synthesis of polyether-block-polyamides, starting from mixtures of amineterminated polyether and polyamide-12. High molar mass block copolymers were synthesized in the bulk within 1 h at 200°C and under atmospheric pressure, instead of several hours at 240°C under vacuum for the usual reaction between dicarboxy polyamides and dihydroxy polyethers. No other side reactions than the formation of a very small amount of 2-imidazolin-5-ones has been found. The DSC studies of block copolymers show the existence of a phase separation between the soft (polyether) and hard (polyamide) blocks. © 1993 John Wiley & Sons, Inc.     

A squalene epoxidase is involved in biosynthesis of both the antitumor compound clavaric acid and sterols in the basidiomycete H. sublateritium

The basidiomycete Hypholoma sublateritium produces the triterpenoid antitumor clavaric acid, an inhibitor of the human Ras-farnesyl transferase. The H. sublateritium squalene epoxidase gene (erg1) has been cloned and shown to encode a flavoprotein monooxygenase that requires FAD, NADPH, and P450 cofactors. Silencing of the erg1 gene in H. sublateritium using constructions expressed from the gdh promoter of Agaricus bisporus showed that the squalene epoxidase is involved in clavaric acid formation and in ergosterol biosynthesis; silenced expression of erg1 resulted in an ergosterol-dependent phenotype for full growth. Overexpression of erg1 gene resulted in up to 32% to 97% increment of clavaric acid production confirming its involvement in the biosynthesis of this antitumor product. Oxidosqualene (or dioxidosqualene) appears to be the branching point for primary metabolism (sterols) and secondary metabolites in basidiomycetes.     

A DFT/TDDFT study of porphyrazines and phthalocyanine oxo‐titanium derivatives as potential dyes in solar cells

Density functional theory and time dependent density functional theory calculations at the level of LDA/BP86/TZ2P were performed systematically on several Ti(IV) complexes of porphyrazines and one phthalocyanine. We performed an analysis of the frontier molecular orbitals of the ground state electronic structures and also discuss in particular the good concordance of our results with the experimental data, which affords to predict the geometrical and optical properties of new complexes ( 3 , 4 , and 7 ). We also emphasize the characterization of the UV–vis absorption spectra and propose transitions that contribute to the Q and B bands. Some useful calculated properties in complexes 2 , 3 , and 7 , like: high light absorption in the visible region of the spectra, transitions involved in these bands with a determined direction, charge separation, bigger highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO‐LUMO) gaps than complexes 4 and 5 , and the energy of their LUMO orbitals (that are higher than the lowest energy level of the conduction band of the TiO₂) indicate that system complexes 2 , 3 , and 7 could act as light‐harvesting sensitizers for dye‐sensitized solar cells (DSCs). These proposals were made using a model of the previously experimentally known phthalocyanine, which was used as sensitizer in DSCs devices, comparing its electronic properties with the herein proposed sensitizers. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements

The relativistic electronic structure calculations of N,N′-chelated pnictogenium cations containing aminotroponiminate units, (E = P(1), As(2), Sb(3), Bi(4)), have been investigated employing density functional (DF) methods, including spin-orbit relativistic corrections, via the two-component zeroth order regular approximation (ZORA) Hamiltonian. The role of replacement of the pnictogen atom when going down into the 15 group was discussed on the basis of geometrical parameters, Hirshfield charge analyses, DF reactivity indexes. The degree of electronic delocalization into the five- and seven membered rings was estimated via the electron localization function (ELF) and the nuclear independent chemical shifts (NICS) indexes.Our results show an existence of a lack of systems 2-4 to act as donor ligands for the metal complexation, compared with 1, due to the positive charge over the pnictogen atoms besides the lone-pair orbital of the pnictogen atom which lies at low energies from their corresponding reacting HOMO’s. It is also interesting to note some effects over the aromaticity when going down into the 15 group, i.e., the C₅ ring is affected by the change of the pnictogen atom, while the aromaticity on the C₇ ring is not affected, as suggested by the analysis of the ELF, NICS and geometrical parameters.     

NMR assignment in regioisomeric hydroquinones

A set of regioisomeric pairs of tricyclic hydroquinones, analogues of antitumor 9,10-dihydroxy-4,4-dimethyl-5,8-dihydroanthracen-1(4H)-one (1) and other derivatives, were synthesized and their regiochemistry and NMR spectra assigned by using (1)H-detected one-bond (C-H) HMQC and long-range C-H HMBC, in good agreement with theoretical O3LYP/Alhrichs-pVTZ calculations. The 5-hydroxymethyl derivatives (11, 15, 19) showed a (3)J(H, H) coupling constant of methylene protons evidencing the presence of a seven-membered intramolecular hydrogen bonded ring, not observed for the 8-hydroxymethyl isomers.