Interaction of giant extracellular Glossoscolex paulistus hemoglobin (HbGp) with zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS): Effects of oligomeric dissociation

The present work focuses on the interaction between the zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp). Electronic optical absorption, fluorescence emission and circular dichroism spectroscopy techniques, together with Gel-filtration chromatography, were used in order to evaluate the oligomeric dissociation as well as the autoxidation of HbGp as a function of the interaction with HPS. A peculiar behavior was observed for the HPS-HbGp interaction: a complex ferric species formation equilibrium was promoted, as a consequence of the autoxidation and oligomeric dissociation processes. At pH 7.0, HPS is more effective up to 1 mM while at pH 9.0 the surfactant effect is more intense above 1 mM. Furthermore, the interaction of HPS with HbGp was clearly less intense than the interaction of this hemoglobin with cationic (CTAC) and anionic (SDS) surfactants. Probably, this lower interaction with HPS is due to two factors: (i) the lower electrostatic attraction between the HPS surfactant and the protein surface ionic sites when compared to the electrostatic interaction between HbGp and cationic and anionic surfactants, and (ii) the low cmc of HPS, which probably reduces the interaction of the surfactant in the monomeric form with the protein. The present work emphasizes the importance of the electrostatic contribution in the interaction between ionic surfactants and HbGp. Furthermore, in the whole HPS concentration range used in this study, no folding and autoxidation decrease induced by this surfactant were observed. This is quite different from the literature data on the interaction between surfactants and tetrameric hemoglobins, that supports the occurrence of this behavior for the intracellular hemoglobins at low surfactant concentration range. Spectroscopic data are discussed and compared with the literature in order to improve the understanding of hemoglobin-surfactant interaction as well as the acid isoelectric point (pI) influence of the giant extracellular hemoglobins on their structure-activity relationship. (c) 2007 Elsevier B.V. All rights reserved.

Electronic synergism in [RuCl(2)(PPh(3))(2)(amine)] complexes differing the reactivity for ROMP of norbornene and norbornadiene

The reactivity of the new complex [RuCl(2)(PPh(3))(2)(3,5-Me(2)piperidine)], complex 1, was investigated for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD) in the presence of ethyl diazoacetate (EDA) in CHCl(3). The aim is to observe the combination of PPh(3) and an amine as ancillary ligands concerning the steric hindrance and the electronic perturbation in the properties of the N-bound site when replacing the amines. Thus, the results with 1 were compared to the results obtained when the amine is piperidine (complex 2). Reaction with 1 provides 70% yield of isolated polyNBE (M(n) =8.3 x 10(4) g/mol; PDI = 2.03), whereas 2 provides quantitative reaction (M(n) = 1.2 x 10(5) g/mol; PDI = 1.90) with [NBE]/[Ru] = 5000, [EDA]/[Ru] = 48 and 1.1 mu mol of Ru for 5 min at 25 degrees C. The resulting polymers showed c.a. 62% of trans-polyNBE, determined by (1)H NMR, and T(g) = 32 degrees C, determined by DSC and DMTA. For ROMP of NBD, 1 showed quantitative yield with PDI =2.62 when [NBD]/[Ru] = 5000 for 20 min at 25 degrees C, whereas the reaction with 2 reached 55% with PDI = 2.16 in the same conditions. It is concluded that the presence of the two methyl groups in the piperidine ring provides an increase in the induction period to produce the Ru-carbene species justifying better polyNBE results with 2, and a greater amine(sigma)-> Ru(pi)-> monomer synergism which contributed to the best activation of less tensioned olefin as NBD. (C) 2010 Elsevier B.V. All rights reserved.

Dessimetrização e enriquecimento enantiomérico de derivados do triciclo[5.2.1.0 2,6] decano através de enzimas e de indutores quirais. Preparação dos respectivos pseudopeptídeos restritos

Uma série de derivados quirais (e.e. > 99%) foram sintetizados a partir do meso- exo-(3R,5S)-3,5-dihidróximetilenotriciclo[5,2.1.02,6]decano com altos rendimentos, usando catálise enzimática (lipases) em reações de transesterificação. A resolução do respectivo diéster racêmico através da hidrólise catalisada com esterase (PLE) não forneceu o monoéster opticamente enriquecido; enquanto que a dessimetrização do anidrido usando indutores quirais (quinina e quinidina) resultou no monoéster opticamente enriquecido (e.e.≅ 60%). O respectivo amino-álcool protegido foi preparado. Alguns análogos inéditos de peptídeos restritos incorporados do triciclodecano foram sintetizados.

Antimycobacterial and antitumor activities of Palladium(II) complexes containing isonicotinamide (isn): X-ray structure of trans-[Pd(N-3)(2)(isn)(2)]

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ghost free dual vector theories in 2+1 dimensions

We explore here the issue of duality versus spectrum equivalence in dual theories generated through the master action approach. Specifically we examine a generalized self-dual (GSD) model where a Maxwell term is added to the self-dual model. A gauge embedding procedure applied to the GSD model leads to a Maxwell-Chern-Simons (MCS) theory with higher derivatives. We show here that the latter contains a ghost mode contrary to the original GSD model. By figuring out the origin of the ghost we are able to suggest a new master action which interpolates between the local GSD model and a nonlocal MCS model. Those models share the same spectrum and are ghost free. Furthermore, there is a dual map between both theories at classical level which survives quantum correlation functions up to contact terms. The remarks made here may be relevant for other applications of the master action approach.

Generalized duality between local vector theories in D=2+1

The existence of an interpolating master action does not guarantee the same spectrum for the interpolated dual theories. In the specific case of a generalized self-dual (GSD) model defined as the addition of the Maxwell term to the self-dual model in D = 2 + 1, previous master actions have furnished a dual gauge theory which is either nonlocal or contains a ghost mode. Here we show that by reducing the Maxwell term to first order by means of an auxiliary field we are able to define a master action which interpolates between the GSD model and a couple of non-interacting Maxwell-Chern-Simons theories of opposite helicities. The presence of an auxiliary field explains the doubling of fields in the dual gauge theory. A generalized duality transformation is defined and both models can be interpreted as self-dual models. Furthermore, it is shown how to obtain the gauge invariant correlators of the non-interacting MCS theories from the correlators of the self-dual field in the GSD model and vice-versa. The derivation of the non-interacting MCS theories from the GSD model, as presented here, works in the opposite direction of the soldering approach.

Dual descriptions of spin-two massive particles in D=2+1 via master actions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Noether and topological currents equivalence and soliton/particle correspondence in affine sl(2)((1)) Toda theory coupled to matter

A submodel of the so-called conformal affine Toda model coupled to the matter field (CATM) is defined such that its real Lagrangian has a positive-definite kinetic term for the Toda field and a usual kinetic term for the (Dirac) spinor field. After spontaneously broken the conformal symmetry by means of BRST analysis, we end up with an effective theory, the off-critical affine Toda model coupled to the matter (ATM). It is shown that the ATM model inherits the remarkable properties of the general CATM model such as the soliton solutions, the particle/soliton correspondence and the equivalence between the Noether and topological currents. The classical solitonic spectrum of the ATM model is also discussed. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Higher-derivative theory of (2+1)-dimensional gravity

Higher-derivative gravity in 2 + 1 dimensions is considered. The general solution of the linearized field equations in a three-dimensional version of the Teyssandier gauge is obtained, and from that the solution for a static pointlike source is found. The deflection of light rays is also analysed. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Relativistic particle dynamics in D=2+1

We propose a SUSY variant of the action for a massless spinning particles via the inclusion of twistor variables. The action is constructed to be invariant under SUSY transformations and tau-reparametrizations even when an interaction field is including. The constraint analysis is achieved and the equations of motion are derived. The commutation relations obtained for the commuting spinor variables lambda(alpha) show that the particle states have fractional statistics and spin. At once we introduce a possible massive term for the non-interacting model.

Gravity, antigravity and gravitational shielding in (2+1) dimensions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Search for squarks and gluinos in events with jets and missing transverse energy using 2.1 fb(-1) of p(p)over-bar collision data at root s=1.96 TeV - D phi Collaboration

A data sample corresponding to an integrated luminosity of 2.1 fb(-1) collected by the D phi detector at the Fermilab Tevatron Collider was analyzed to search for squarks and gluinos produced in p (p) over bar collisions at a center-of-mass energy of 1.96 TeV. No evidence for the production of such particles was observed in topologies involving jets and missing transverse energy, and 95% C.L. lower limits of 379 GeV and 308 GeV were set on the squark and gluino masses, respectively, within the framework of minimal supergravity with tan beta = 3, A(0) = 0, and mu < 0. The corresponding previous limits are improved by 54 GeV and 67 GeV. (c) 2008 Elsevier B.V. All rights reserved.

Dynamics of Enceladus and Dione inside the 2:1 mean-motion resonance under tidal dissipation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Molecular structures and vibrational frequencies for cis-[PdCl2(tmen)] and cis-[Pd(N-3)(2)(tmen)]: A DFT study

Theoretical molecular structures of the complexes cis-[PdCl2(tmen)] and cis-[Pd(N-3)(2)(tmen)] (tmen = N,N,N',N'-tetramethylethylenediamine) were investigated using B3LYP/DFT method. The calculated molecular parameters, bond distances and angles, revealed a square-planar geometry around the metallic center for both compounds with the azide being linear. The theoretical infrared spectra of C, symmetry (electronic state (1)A) of the compounds are in agreement with the experimental data. (C) 2007 Elsevier B.V. All rights reserved.

Quantization of (2+1)-spinning particles and bifermionic constraint problem

This work is a natural continuation of our recent study in quantizing relativistic particles. There it was demonstrated that, by applying a consistent quantization scheme to the classical model of a spinless relativistic particle as well as to the Berezin-Marinov model of a 3 + 1 Dirac particle, it is possible to obtain a consistent relativistic quantum mechanics of such particles. In the present paper, we apply a similar approach to the problem of quantizing the massive 2 + 1 Dirac particle. However, we stress that such a problem differs in a nontrivial way from the one in 3 + 1 dimensions. The point is that in 2 + 1 dimensions each spin polarization describes different fermion species. Technically this fact manifests itself through the presence of a bifermionic constant and of a bifermionic first-class constraint. In particular, this constraint does not admit a conjugate gauge condition at the classical level. The quantization problem in 2 + 1 dimensions is also interesting from the physical viewpoint (e.g., anyons). In order to quantize the model, we first derive a classical formulation in an effective phase space, restricted by constraints and gauges. Then the condition of preservation of the classical symmetries allows us to realize the operator algebra in an unambiguous way and construct an appropriate Hilbert space. The physical sector of the constructed quantum mechanics contains spin-1/2 particles and antiparticles without an infinite number of negative-energy levels, and exactly reproduces the one-particle sector of the 2 + 1 quantum theory of a spinor field.