A CASSCF study of the singlet-singlet and triplet-triplet spectroscopy of naphthalene

Ab initio complete active space (CAS) SCF calculations have been carried out for the singlet and triplet excited states of naphthalene molecule. The CASSCF active space comprised 10-type molecular orbitals. The basis set was of ANO type and included both diffuse functions and polarization functions. The calculated excitation energies and transition moment provide a sound theoretical basis for the assignment of the experimental singlet-singlet and triplet-triplet spectra of the naphthalene molecule.     

Evaluation of density functional theory methods for the electronic interactions between indole and substituted benzene: Applications to horseradish peroxidase

In an effort to evaluate and design fast, accurate density functional theory (DFT) methods for calculating electrostatic and dispersion interactions between proteins and ligands, we have set up a model system examining interactions between mono‐substituted benzene and indole in seven different stable conformations. We first optimized the geometries of the monomers at the B3LYP/6‐31G level, and then scanned the potential curves with MP2, HF, B3LYP, SVWN, and HCTH407 [all at the 6‐311++G(d,p) level] to find the optimum separation. We used the approximate counterpoise method to calculate the basis set superposition error‐corrected interaction energies at the optimum geometries. We then applied these methods to the interactions between aromatic active site residues of horseradish peroxidase C with indole‐3‐propionic acid at two different binding sites. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Novel 17 substituted pregnadiene derivatives as 5 alpha-reductase inhibitors and their binding affinity for the androgen receptor

The in vitro antiandrogenic activity of four new progesterone derivatives: 4, 5, 6 and 7 (8 is a known compound) was determined. These compounds were evaluated as 5alpha-reductase inhibitors as well as by their capacity to bind to the androgen receptor in gonadectomized hamster prostate. The IC(50) value was determined using increasing concentrations of 4, 5, 6, 7 and 8 in the presence of [(3)H]T and the microsomal fraction of the hamster prostate containing the 5alpha-reductase enzyme. In this paper we also demonstrated the effect of increasing concentrations of the novel steroids upon [(3)H]DHT binding to the androgen receptors from hamster prostate which produces competition for the androgen receptor sites. The in vitro studies showed that steroids 4, 5, 6, 7 and 8 had an inhibitory activity for the 5alpha-reductase with IC(50) of: 4 (0.17 microM), 5 (0.19 microM), 6 (1 microM), 7 (4.2 microM), and 8 (2.7 microM). On the other hand, the IC(50) value for compounds 4, 5, 6, 7, 8 and DHT showed the following order of affinity for the androgen receptor: 6>7>5>DHT. Surprisingly compounds 4 and 8 did not bind to the androgen receptor. The overall data indicate that all synthesized compounds are inhibitors for the enzyme 5alpha-reductase present in the hamster prostate. In contrast, compounds 5, 6 and 7, which have a cyclohexyl group in the side chain showed a high affinity for the androgen receptor.     

Influence of ligand rigidity and ring substitution on the structural and electronic behavior of trivalent iron and gallium complexes with asymmetric tridentate ligands

Species 1-6 are [M(III)(L)2]ClO4 complexes formed with the PhO--CH=N-CH2-Py imines, (L(I))- and (L(tBuI))-, and PhO--CH2-NH-CH2-Py amines, (L(A))- and (L(tBuA))-, in which PhO- is a phenolate ring and Py is a pyridine ring and the prefix tBu indicates the presence of tertiary butyl groups occupying the positions 4 and 6 of the phenol ring. Monometallic species with d5 high-spin iron (1, 2, 3, 4) and d10 gallium (5, 6) were synthesized and characterized to assess the influence of the ligand rigidity and the presence of tertiary butyl-substituted phenol rings on their steric, electronic, and redox behavior. Characterization by elemental analysis, mass spectrometry, IR, UV-visible, and EPR spectroscopies, and electrochemistry has been performed, and complexes [FeIII(L(tBuI))2]ClO4 (2), [FeIII(L(tBuA))2]ClO4 (4), and [Ga(III)(L(tBuI))2]ClO4 (5) have been characterized by X-ray crystallography. The crystal structures show the imine ligands meridionally coordinated to the metal centers, whereas the amine ligands are coordinate in a facial mode. Cyclic voltammetry shows that the complexes with the ligands (L(tBuI))- and (L(tBuA))- were able to generate ligand-based phenoxyl radicals, whereas unsubstituted ligands displayed ill-defined redox processes. EPR spectroscopy supports high-spin configurations for the iron complexes. UV-visible spectra are dominated by charge-transfer phenomena, and imine compounds exhibit dramatic hyperchromism when compared to equivalent amines. The tertiary butyl groups on the phenolate ring enhance this trend. Detailed B3LYP/6-31G(d)-level calculations have been used to account for the results observed.     

Search for an enhanced production of low energy pions in C(p, π+)X,Cu(p, π+)X,and Cu(p, π∘)X reactions for 300 MeV≦Tp≦400 MeV

The observation of an enhancement in the production of low energy pions in the Cu(p, ⁺)X reaction is confirmed. The width of the bump is about 5 MeV around 350 MeV. A similar enhancement appears at 330 MeV for C(p, ⁺)X but the width has not been measured. An attempt to observe this behaviour in Cu(p, )X is described. From the data one cannot conclude about the existence of a structure around 350 MeV proton energy. The lack of resolution in the spectrometer may have washed out the small effect expected from ⁺ measurements.     

A continuous approach to inductive inference

In this paper we describe an interior point mathematical programming approach to inductive inference. We list several versions of this problem and study in detail the formulation based on hidden Boolean logic. We consider the problem of identifying a hidden Boolean function:{0, 1} ⁿ {0, 1} using outputs obtained by applying a limited number of random inputs to the hidden function. Given this input—output sample, we give a method to synthesize a Boolean function that describes the sample. We pose the Boolean Function Synthesis Problem as a particular type of Satisfiability Problem. The Satisfiability Problem is translated into an integer programming feasibility problem, that is solved with an interior point algorithm for integer programming. A similar integer programming implementation has been used in a previous study to solve randomly generated instances of the Satisfiability Problem. In this paper we introduce a new variant of this algorithm, where the Riemannian metric used for defining the search region is dynamically modified. Computational results on 8-, 16- and 32-input, 1-output functions are presented. Our implementation successfully identified the majority of hidden functions in the experiment.     

Comultiplications on free groups and wedges of circles

By means of the fundamental group functor, a co-H-space structure or a co-H-group structure on a wedge of circles is seen to be equivalent to a comultiplication or a cogroup structure on a free group . We consider individual comultiplications on and their properties such as associativity, coloop structure, existence of inverses, etc. as well as the set of all comultiplications of . For a comultiplication of we define a subset of quasi-diagonal elements which is basic to our investigation of associativity. The subset can be determined algorithmically and contains the set of diagonal elements . We show that is a basis for the largest subgroup of on which is associative and that is a free factor of . We also give necessary and sufficient conditions for a comultiplication on to be a coloop in terms of the Fox derivatives of with respect to a basis of . In addition, we consider inverses of a comultiplication, the collection of cohomomorphisms between two free groups with comultiplication and the action of the group on the set of comultiplications of . We give many examples to illustrate these notions. We conclude by translating these results from comultiplications on free groups to co-H-space structures on wedges of circles.