A Verified Optimization Technique to Locate Chaotic Regions of Hénon Systems

We present a new verified optimization method to find regions for Hénon systems where the conditions of chaotic behaviour hold. The present paper provides a methodology to verify chaos for certain mappings and regions. We discuss first how to check the set theoretical conditions of a respective theorem in a reliable way by computer programs. Then we introduce optimization problems that provide a model to locate chaotic regions. We prove the correctness of the underlying checking algorithms and the optimization model. We have verified an earlier published chaotic region, and we also give new chaotic places located by the new technique.     

Letter: Models of Relativistic Particle with Curvature and Torsion Revisited

Models, describing relativistic particles, where Lagrangian densities depend linearly on both the curvature and the torsion of the trajectories, are revisited in D=3 space forms. The moduli spaces of trajectories are completely and explicitly determined using the Lancret program. The moduli subspaces of closed solitons in the three sphere are also determined.     

An isochore versal deformation theorem

We introduce a cohomological approach to isochore deformation problems. We use this formulation in order to prove an isochore versal deformation theorem for holomorphic function germs.     

Structure,Chirality, and Formation of Giant Icosahedral Fullerenes and Spherical Graphitic Onions

We describe the topology, structure, and stability of giant fullerenes exhibiting various symmetries (I, I _h , D _2h , T). Our results demonstrate that it is possible to create two new families of nested chiral icosahedral (I) fullerenes namely C₂₆₀@C₅₆₀@C₉₈₀@C₁₅₂₀@, ...,and C₁₄₀@C₃₈₀@C₇₄₀@C₁₂₂₀@ ..., which exhibit interlayer separations of ca. 3.4 Å. These chiral fullerenes are thought to possess metalliclike conduction properties. We discuss in detail the transformation of polyhedral graphitic particles into quasispherical nested giant fullerenes by reorganization of carbon atoms, which result in the formation of additional pentagonal and heptagonal carbon rings. These spherical structures are metastable and we believe they could be formed under extreme conditions, such as those produced by high-energy electron irradiation. There is circumstantial experimental evidence for the presence of heptagonal rings within these spherical fullerenes.     

Effect of the reaction state on the polymerization of p-xylenesulfonium salts

1,4-Phenylenebis(methylene) sulfonium salts were polymerized under different conditions to yield p-xylylene sulfonium salt polyelectrolytes in a broad range of molecular weights. The aqueous reaction mixture formed a reversible gel at initial monomer concentrations higher than 1.0M, but at lower concentrations it remained as an emulsion until reaction completion. The effect of reaction time on intrinsic viscosities and polymer yields for both the emulsion and the gel state is discussed. The higher yields obtained when the reaction was carried out in the presence of a water-immiscible organic solvent were apparently due to the effect of this solvent on increasing the concentration of the reactive intermediate that led to the polyelectrolyte. Both the addition of an organic solvent and the variation of the initial monomer concentrations allowed some control over the molecular weight of the polyelectrolyte formed.     

Self-interaction-corrected electronegativities and hardness for atoms

Electronegativity χ and hardness η for 54 atoms and their positive and negative ions are calculated by means of self-interaction-corrected DFT including correlation terms. The exchange potential energy is treated by local spin density approximation corrected to account for self-interaction effects as suggested by Rae. The highest occupied orbital eigenvalues for ions are identified to the chemical potential μ^± for positive and negative charged atoms depending upon the developing charge process. Values of χ^±δ and η^± for the different ionic species are given for several values of δ. Average values for 〈χ〉 and 〈η〉 in the sense of Mulliken finite formula for neutral atoms are also tabulated and compared with Mulliken values from experimental data. The agreement among them is almost quantitative.     

Dramatic changes in geometry after ionization: experimental and theoretical studies on the electronic properties of fluorocarbonyl (mono-, di-, and tri-) sulfur compounds

In this work, we present a complete study on He I photoelectron spectroscopy (PES) for the fluorocarbonyl mono-, di-, and trisulfur compounds FC(O)SCl, FC(O)SSCH(3), and FC(O)SSSC(O)F. After optimizations of the structure for stable conformers at different levels of theory, a complete theoretical study involving the calculation of the ionization energies using orbital valence Green's functional (OVGF) was performed. Calculations of radical-cationic forms were carried out in order to compare their properties with those of the neutral molecules. The first IP values are 10.7, 9.0, and 10.5 eV for FC(O)SCl, FC(O)SSCH(3), and FC(O)SSSC(O)F, respectively. The groups bonded to the S atom mainly influence the ionizations originating from the sulfur lone pairs. A wide electronic delocalization in the FC(O)S moiety can be deduced from experimental and theoretical results, which leads to a strong energetic stabilization of the n' '(S) (sulfur lone pair pi orbital). Other conclusions relate to effects on the substituents attached to the S atom and the importance of the molecular planarity in the orbital stabilization of the FC(O)S moiety for the neutral molecules. It is worthwhile mentioning that FC(O)SCl retains its planar structure after ionization, but drastic changes occur in the geometry of both FC(O)SSCH(3) and FC(O)SSSC(O)F. The FC(O)SSCH(3) molecule adopts a heavy atom planar structure after ionization. The FC(O)SSS moiety becomes a planar form after the ionization of the FC(O)SSSC(O)F molecule, whereas the second C(O)F group maintains its original conformation with respect to the SSS group.     

Mass spectrometric characterization of two novel inflammatory peptides from the venom of the social wasp Polybia paulista

The social wasp P. paulista is relatively common in southeast Brazil causing many medically important stinging incidents. The seriousness of these incidents is dependent on the amount of venom inoculated by the wasps into the victims, and the characteristic envenomation symptoms are strongly dependent on the types of peptides present in the venom. In order to identify some of these naturally occurring peptides available in very low amounts, an analytical protocol was developed that uses a combination of reversed-phase and normal-phase high-performance liquid chromatography (HPLC) of wasp venom for peptide purification, with matrix-assisted laser desorption/ionization time-of-flight post-source decay mass spectrometry (MALDI-Tof-PSD-MS) and low-energy collision-induced dissociation (CID) in a quadrupole time-of-flight tandem mass spectrometry (QTof-MS/MS) instrument for peptide sequencing at the sub-picomole level. The distinction between Leu and Ile was achieved both by observing d-type fragment ions obtained under CID conditions and by comparison of retention times of the natural peptides and their synthetic counterparts (with different combinations of I and/or L at N- and C-terminal positions). To distinguish the isobaric residues K and Q, acetylation of peptides was followed by Q-Tof-MS analysis. The primary sequences obtained were INWLKLGKMVIDAL-NH(2) (MW 1611.98 Da) and IDWLKLGKMVMDVL-NH(2) (MW 1658.98 Da). Micro-scale bioassay protocols characterized both peptides as presenting potent hemolytic action, mast cell degranulation, and chemotaxis of polymorphonucleated leukocyte (PMNL) cells. The primary sequences and the bioassay results suggest that these toxins constitute members of a new sub-class of mastoparan toxins, directly involved in the occurrence of inflammatory processes after wasp stinging.     

Hydrolytic protein cleavage mediated by unusual mononuclear copper(II) complexes: X-ray structures and solution studies

The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes.     

Quantum chemical study of several monocyclic complex β‐lactam C‐3, C‐4, and N‐derivatives,and β‐ring model molecules

A quantum chemical study of several complex monocyclic 4‐benzoyl‐4‐phenyl‐β‐lactam derivatives was carried out using cyclobutane, azetidine, 2‐azetidinone, 1‐methyl‐2‐azetidinone, and 3‐methyl‐2‐azetidinone as model compounds. The optimum geometry was obtained for the different conformations. The planarity of the ring was discussed in terms of the influence of the substituents on the amide resonance. To better analyze the amide resonance and the activity of the β‐lactam ring, a vibrational study was also carried out. To examine the influence of solvent polarity on the carbonyl bands, the Fourier transform–infrared (FT‐IR) spectra of the β‐lactam monocyclic derivatives were recorded in CCl₄, C₆H₆, and CHCl₃ solutions. The normal vibrations of the β‐lactam ring in the model compounds were characterized and used in the analysis of the β‐ring of more complex derivatives. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002