Microwave-assisted solid-phase peptide synthesis at 60 degrees C: alternative conditions with low enantiomerization

Several conditions have been used in the coupling reaction of stepwise SPPS at elevated temperature (SPPS-ET), but we have elected the following as our first choice: 2.5-fold molar excess of 0.04-0.08 M Boc or Fmoc-amino acid derivative, equimolar amount of DIC/HOBt (1:1)or TBTU/DIPEA(1:3), 25% DMSO/toluene, 60 degrees C, conventional heating. In this study, aimed to further examine enantiomerization under such condition and study the applicability of our protocols to microwave-SPPS, peptides containing L-Ser, L-His, L-Cys and/or L-Met were manually synthesized traditionally, at 60 degrees C using conventional heating and at 60 degrees C using microwave heating. Detailed assessment of all crude peptides (in their intact and/or fully hydrolyzed forms) revealed that, except for the microwave-assisted coupling of L-Cys, all other reactions occurred with low levels of amino acid enantiomerization (<2%). Therefore, herein we (i) provide new evidences that our protocols for SPPS at 60 degrees C using conventional heating are suitable for routine use, (ii) demonstrate their appropriateness for microwave-assisted SPPS by Boc and Fmoc chemistries, (iii) disclose advantages and limitations of the three synthetic approaches employed. Thus, this study complements our past research on SPPS-ET and suggests alternative conditions for microwave-assisted SPPS. Copyright (C) 2009 European Peptide Society and John Wiley & Sons, Ltd.

Chemoselective cross-coupling Suzuki-Miyaura reaction of (Z)-(2-chlorovinyl)tellurides and potassium aryltrifluoroborate salts

An ultrasound-assisted synthesis of functionalized vinylic chlorides is described by palladium-catalyzed cross-coupling reaction of potassium aryltrifluoroborate salts and (Z)-2-chloro vinylic tellurides. This procedure offers easy access to vinylic chlorides architecture that contains sterically demanding groups in good yields. (C) 2008 Elsevier Ltd. All rights reserved.

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Selective Coupling between Theta Phase and Neocortical Fast Gamma Oscillations during REM-Sleep in Mice

TORT, A. B. L. ; SCHEFFER-TEIXEIRA, R ; Souza, B.C. ; DRAGUHN, A. ; BRANKACK, J. . Theta-associated high-frequency oscillations (110-160 Hz) in the hippocampus and neocortex. Progress in Neurobiology , v. 100, p. 1-14, 2013.

Changing inter-molecular spin-orbital coupling for generating magnetic field effects in phosphorescent organic semiconductors

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Tensor coupling and pseudospin symmetry in nuclei

In this work we study the contribution of the isoscalar tensor coupling to the realization of pseudospin symmetry in nuclei. Using realistic values for the tensor coupling strength, we show that this coupling reduces noticeably the pseudospin splittings, especially for single-particle levels near the Fermi surface. By using an energy. decomposition of the pseudospin energy splittings, we show that the changes in these splittings come mainly through the changes induced in the lower radial wave function for the low-lying pseudospin partners and through changes in the expectation value of the pseudospin-orbit coupling term for surface partners. This allows us to confirm the conclusion already reached in previous studies, namely that the pseudospin symmetry in nuclei is of a dynamical nature.

Real spectra for the non-Hermitian Dirac equation in 1+1 dimensions with the most general coupling

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Body sway and sensory motor coupling adaptation in children: Effects of distance manipulation

The purpose of this investigation was to examine coupling between visual information and body sway in children and young adults at various distances from a moving room front wall. Sixty children (from 4 to 14 years old) and 10 young adults stood upright inside a moving room that was oscillated at .2 and .5 Hz, at distances of .25, .5, 1, and 1.5 m from a front wall. Visual information induced body sway in all participants in all conditions. Young children swayed more than older participants, whether the moving room was oscillated or not. Coupling between visual information and body sway became stronger and the room movement influence became weaker with age. Up to the age of 10, coupling strength between visual information and body sway and the room movement influence were distance dependent. Postural control development appears to be dependent on how children reweight the contribution of varying sensory cues available in environment in order to control body sway. (C) 2007 Wiley Periodicals, Inc.

Strength of the trilinear Higgs boson coupling in technicolor models

We discuss the strength of the trilinear Higgs boson coupling in technicolor (or composite) models in a model independent way. The coupling is determined as a function of a very general ansatz for the technicolor self-energy, and turns out to be equal or smaller than the one of the Standard Model Higgs boson depending on the dynamics of the theory. (c) 2006 Published by Elsevier B.V.

Freezing of the QCD coupling constant and the pion form factor

The possibility that the QCD coupling constant (alpha(s)) has an infrared finite behavior (freezing) has been extensively studied in recent years. We compare phenomenological values of the frozen QCD running coupling between different classes of solutions obtained through non-perturbative Schwinger-Dyson Equations. With these solutions were computed QCD predictions for the asymptotic pion form factor which, in turn, were compared with experiment.

Strong coupling QCD and effective hadronic interactions

The aim of this work is to implement the mechanism of link rearrangement predicted in the strong coupling limit of Hamiltonian lattice QCD - in a constituent quark model in which constituent quarks, links and junctions are the dominant degrees of freedom. The implications of link rearrangement for the meson-meson interaction are investigated.

Analysis of the Hb(b)over-bar coupling constant and CP-violation effects at the future e(+)e(-) collider

The e(+)e(-)-->b (B) over bar nu(ν) over bar process, where nu is an electron, muon, or tau-lepton neutrino, is analyzed in detail for the general form of the coupling constant of a Higgs boson with b quarks, with the (m(b)/v)(a + igamma(5)b) parameterization of the Hb (b) over bar interaction. This process is shown to be highly sensitive to this coupling constant. Experiments at the future with roots = 500-GeV linear collider will provide limits of 2 and 20% for deviations of the parameters a and b, respectively, from their Standard Model values. Results concerning the e(+)e(-)-->b (b) over bar nu(ν) over bar process in combination with the independent measurements of the partial width Gamma(H --> b (b) over bar) can testify to the CP origin of the Higgs sector of the theory. (C) 2003 MAIK Nauka/Interperiodica.

Investigation of the H tau tau and Hbb coupling constants for a scalar (Pseudoscalar) higgs Boson at a future linear electron-positron collider

The possibility of setting constraints on the Couplings of a scalar (pseudoscalar) Higgs boson to the tau lepton and the b quark in the reactions e(+)e(-)-->v (v) over bar tau(+)tau(-) and e(+)e(-)-->v (v) over barb (b) over bar at a future linear electron-positron collider of total energy roots = 500 GeV is studied. The admixture of a new hypothetical pseudoscalar state of the Higgs boson in the Hf (f) over bar vertex is parametrized in the form (mf/v)(a+igamma(5)b). on the basis of an analysis of differential distributions for the processes under study, it is shown that data from the future linear collider TESLA will make it possible to constrain the parameters a and b as -0.32 less than or equal to Deltaa less than or equal to 0.24 and -0.73 less than or equal to b less than or equal to 0.73 in the case of the reaction e(+)e(-)-->v (v) over bar tau(+)tau(-) and as -0.026 less than or equal to Deltaa less than or equal to 0.027 and -0.23 less than or equal to b less than or equal to 0.23 in the case of the reaction e(+)e(-) --> v (v) over barb (b) over bar. It is emphasized that the contribution of the fusion Subprocess WW --> H in the channel involving an electron neutrino is of particular importance, since this contribution enhances the sensitivity of data to the parameters being analyzed. (C) 2004 MAIK Nauka/Inierperiodica.

Bright solitons in coupled defocusing NLS equation supported by coupling: Application to Bose-Einstein condensation

We demonstrate the formation of bright solitons in coupled self-defocusing nonlinear Schrodinger (NLS) equation supported by attractive coupling. As an application we use a time-dependent dynamical mean-field model to study the formation of stable bright solitons in two-component repulsive Bose-Einstein condensates (BECs) supported by interspecies attraction in a quasi one-dimensional geometry. When all interactions are repulsive, there cannot be bright solitons. However, bright solitons can be formed in two-component repulsive BECs for a sufficiently attractive interspecies interaction, which induces an attractive effective interaction among bosons of same type. (c) 2005 Elsevier B.V. All rights reserved.

Freezing of the QCD coupling constant and solutions of Schwinger-Dyson equations

We compare phenomenological values of the frozen QCD running coupling constant (alpha(s)) with two classes of infrared finite solutions obtained through nonperturbative Schwinger-Dyson equations. We use these same solutions with frozen coupling constants as well as their respective nonperturbative gluon propagators to compute the QCD prediction for the asymptotic pion form factor. Agreement between theory and experiment on alpha(s)(0) and F (pi)(Q(2)) is found only for one of the Schwinger-Dyson equation solutions.