Picosecond Dynamics of the Prototropic Reactions of 7-Hydroxyflavylium Photoacids Anchored at an Anionic Micellar Surface

Three water-insoluble, micelle-anchored flavylium salts, 7-hydroxy-3-octyl-flavylium chloride, 4`-hexyl-7-hydroxyflavylium chloride, and 6-hexyl-7-hydroxy-4-methyl-flavylium chloride, have been employed to probe excited-state prototropic reactions in micellar sodium dodecyl sulfate (SDS). In SDS micelles, the fluorescence decays of these three flavylium salts are tetraexponential functions in the pH range from 1.0 to 4.6 at temperatures from 293 to 318 K. The four components of the decays are assigned to Four kinetically coupled excited species in the micelle: specifically, promptly deprotonable (AH(+)*) and nonpromptly deprotonable (AH(h)(+)*) orientations of the acid in the micelle. the base-proton geminate pair (A*center dot center dot center dot H(+)), and the free conjugate base (A*). The initial prompt deprotonation to form the germinate pair occurs at essentially the same rate (k(d) similar to 6-7 x 10(10) s(-1)) for all three photoacids. Recombination of the germinate pair is similar to 3-fold faster than the rate of proton escape from the pair (k(rec) similar to 3 x 10(10) s(-1) and k(diss) similar to 1 x 10(10) s(-1)), corresponding to an intrinsic recombination efficiency of the pair of similar to 75%. Finally, the reprotonation of the short-lived free A* (200-350 ps, depending oil the photoacid) has two components, only one of which depends oil the proton concentration in the intermicellar aqueous phase. Ultrafast transfer of the proton to water and substantial compartmentalization of the photogenerated proton at the micelle surface Oil the picosecond time scale strongly suggest preferential transfer of the proton to preformed hydrogen-bonded water bridges between the photoacid and the anionic headgroups. This localizes the proton in the vicinity of the excited base much more efficiently than ill bulk water, resulting ill the predominance of geminate re reprotonation at the micelle surface.

Unraveling the Role of Sulfur Compounds in Acid Rain Formation: Experiments on a Wetted Glass pH Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Isoelectric Point Determination for Glossoscolex paulistus Extracellular Hemoglobin: Oligomeric Stability in Acidic pH and Relevance to Protein-Surfactant Interactions

The extracellular hemoglobin from Glossoscolex paulistus (HbGp) has a molecular mass of 3.6 M Da, It has a high oligomeric stability at pH 7.0 and low autoxidation rates, as compared to vertebrate hemoglobins. In this work, fluorescence and light scattering experiments were performed with the three oxidation forms of HbGp exposed to acidic pH. Our focus is on the HbGp stability at acidic pH and also on the determination of the isoelectric point (pI) of the protein. Our results show that the protein in the cyanomet form is more stable than in the other two forms, in the whole range. Our zeta-potential data are consistent with light scattering results. Average values apt obtained by different techniques were 5.6 +/- 0.5, 5.4 +/- 0.2 and 5.2 +/- 0.5 for the oxy, met, and cyanomet forms. Dynamic light scattering (DLS) experiments have shown that, at pH 6.0, the aggregation (oligomeric) state of oxy-, met- and cyanomet-HbGp remains the same as that at 7.0. The interaction between the oxy-HbGp and ionic surfactants at pH 5.0 and 6.0 was also monitored in the present study. At pH 5,0, below the protein pI, the effects of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium chloride (CTAC) are inverted when compared to pH 7.0. For CTAC, in acid pH 5.0, no precipitation is observed, while for SDS an intense light scattering appears due to a precipitation process. HbGp interacts strongly with the cationic surfactant at pH 7.0 and with the anionic one at pH 5.0. This effect is due to the predominance, in the protein surface, of residues presenting opposite charges to the surfactant headgroups. This information can be relevant for the development of extracellular hemoglobin-based artificial blood substitutes.

Effect of pH of colloidal suspension on crystallization and activation energy of deep levels in SnO2 thin films obtained via sol-gel

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Search for production of single top quarks via tcg and tug flavor-changing-neutral-current couplings

We search for the production of single top quarks via flavor-changing-neutral-current couplings of a gluon to the top quark and a charm (c) or up (u) quark. We analyze 230 pb(-1) of lepton+jets data from p (p) over tilde collisions at a center of mass energy of 1.96 TeV collected by the D0 detector at the Fermilab Tevatron Collider. We observe no significant deviation from standard model predictions, and hence set upper limits on the anomalous coupling parameters kappa(c)(g)/Lambda and kappa(u)(g)/Lambda, where kappa(g) define the strength of tcg and tug couplings, and Lambda defines the scale of new physics. The limits at 95% C.L. are kappa(c)(g)/Lambda < 0.15 TeV-1 and kappa(u)(g)/Lambda < 0.037 TeV-1.

Search for stopped gluinos from p(p)over-bar collisions at root s=1.96 TeV

Long-lived, heavy particles are predicted in a number of models beyond the standard model of particle physics. We present the first direct search for such particles' decays, occurring up to 100 h after their production and not synchronized with an accelerator bunch crossing. We apply the analysis to the gluino (g), predicted in split supersymmetry, which after hadronization can become charged and lose enough momentum through ionization to come to rest in dense particle detectors. Approximately 410 pb(-1) of p (p) over bar collisions at root s = 1.96 TeV collected with the D0 detector during Run II of the Fermilab Tevatron collider are analyzed in search of such stopped gluinos decaying into a gluon and a neutralino ((chi) over tilde (0)(1)). Limits are placed on the (gluino cross section) x (probability to stop) x [BR((g) over tilde -> g (chi) over tilde (0)(1))] as a function of the gluino and (chi) over tilde (0)(1) masses, for gluino lifetimes from 30 mu s-100 h.

Measurement of the top quark mass in the lepton plus jets channel using the ideogram method

A measurement of the top quark mass using events with one charged lepton, missing transverse energy, and jets in the final state, collected by the D0 detector from p (p) over bar collisions at root s=1.96 TeV at the Fermilab Tevatron collider, is presented. A constrained fit is used to fully reconstruct the kinematics of the events. For every event a top quark mass likelihood is calculated taking into account all possible jet assignments and the probability that an event is signal or background. Lifetime-based identification of b jets is employed to enhance the separation between t (t) over bar signal and background from other physics processes and to improve the assignment of the observed jets to the quarks in the t (1) over bar hypothesis. We extract a multiplicative jet energy scale (JES) factor in situ, greatly reducing the systematic effect related to the jet energy measurement. In a data sample with an integrated luminosity of 425 pb(-1), we observe 230 candidate events, with an estimated background of 123 events, and measure m(t)=173.7 +/- 4.4(stat+JES)(-2.0)(+2.1)(syst) GeV. This result represents the first application of the ideogram technique to the measurement of the top quark mass in lepton+jets events.

Measurement of the CP-violation parameter of B-0 mixing and decay with p(p)over-bar ->mu mu X data

We measure the dimuon charge asymmetry A in p (p) over bar collisions at a center of mass energy root s=1960 GeV. The data was recorded with the D0 detector and corresponds to an integrated luminosity of approximately 1.0 fb(-1). Assuming that the asymmetry A is due to asymmetric B-0 <->(B) over bar (0) mixing and decay, we extract the CP-violation parameter of B-0 mixing and decay: ((epsilon B0))/(1+vertical bar epsilon B0 vertical bar 2)=(AB0)/(4)= -0.0023 +/- 0.0011(stat)+/- 0.0008(syst).A(B)(0) is the dimuon charge asymmetry from decays of B-0(B) over bar (0) pairs. The general case, with CP violation in both B-0 and B-s(0) systems, is also considered. Finally we obtain the forward-backward asymmetry that quantifies the tendency of mu(+) to go in the proton direction and mu(-) to go in the antiproton direction. The results are consistent with the standard model and constrain new physics.

Search for CP violation in B-s(0) -> mu(+) D-s(-) X decays in p(p)over-bar collisions at root s=1.96 TeV

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

Search for scalar neutrino superpartners in e+mu final states in p(p)over-bar collisions at root s=1.96 TeV

We report a search for R-parity-violating production and decay of sneutrino particles in the e mu final state with 1.04 +/- 0.06 fb(-1) of data collected with the D(0) detector at the Fermilab Tevatron Collider in 2002-2006. Good agreement between the data and the standard model prediction is observed. With no evidence for new physics, we set limits on the R-parity-violating couplings lambda'(311) and lambda(312) as a function of the sneutrino mass.

Measurement of Dijet Angular Distributions at s=1.96 TeV and Searches for Quark Compositeness and Extra Spatial Dimensions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Search for New Physics with a Monojet and Missing Transverse Energy in pp Collisions at root s=7 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Search for Charged Massive Long-Lived Particles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Model indedpendent search for new phenomena in p(p)over-bar collisions at root s=1.96 TeV

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