Structural and thermal characterization of dioctadecyldimethylammonium bromide dispersions by spin labels

Dioctadecyldimethylammonium bromide (DODAB) dispersions obtained by simply mixing the amphiphile in water, and by bath-sonication, were investigated by electron spin resonance (ESR) of stearic acids and their methyl ester derivatives, labeled at the 5th and 16th carbons of the acyl chain. The ESR spectra indicate that the non-sonicated dispersions are formed mainly by one population of DODAB vesicles, either in the gel (T < T-m) or in the liquid-crystalline (T > T-m) state. Around T-m there is a co-existence of the two phases, with a thermal hysteresis of about 3.2 degreesC. In sonicated DODAB dispersions, spin labels indicate two different environments even for temperatures far below T-m: one similar to that obtained with non-sonicated samples, a gel phase, and another one in the liquid-crystalline state. The fluid phase domain present below T-m could correspond to either the periphery of bilayer fragments, reported to be present in sonicated DODAB dispersions, or to high curvature vesicles. (C) 2001 Elsevier B.V. Ireland Ltd. All rights reserved.

Preferential location of lidocaine and etidocaine in lecithin bilayers as determined by EPR, fluorescence and H-2 NMR

We have examined the effect of the uncharged species of lidocaine (LDC) and etidocaine (EDC) on the acyl chain moiety of egg phosphatidylcholine liposomes. Changes in membrane organization caused by both anesthetics were detected through the use of EPR spin labels (5, 7 and 12 doxyl stearic acid methyl ester) or fluorescence probes (4, 6, 10, 16 pyrene-fatty acids). The disturbance caused by the LA was greater when the probes were inserted in more external positions of the acyl chain and decreased towards the hydrophobic core of the membrane. The results indicate a preferential insertion of LDC at the polar interface of the bilayer and in the first half of the acyl chain, for EDC. Additionally, 2 H NMR spectra of multilamellar liposomes composed by acyl chain-perdeutero DMPC and EPC (1:4 mol%) allowed the determination of the segmental order (S-mol) and dynamics (T-1) of the acyl chain region. In accordance to the fluorescence and EPR results, changes in molecular orientation and dynamics are more prominent if the LA preferential location is more superficial, as for LDC while EDC seems to organize the acyl chain region between carbons 2-8, which is indicative of its positioning. We propose that the preferential location of LDC and EDC inside the bilayers creates a "transient site", which is related to the anesthetic potency since it could modulate the access of these molecules to their binding site(s) in the voltage-gated sodium channel. (C) 2007 Elsevier B.V. All rights reserved.

Conformational basis for the biological activity of TOAC-labeled angiotensin II and bradykinin: Electron paramagnetic resonance, circular dichroism, and fluorescence studies

N-Terminally and internally labeled analogues of the hormones angiotensin (AII, DRVYIHPF) and bradykinin (BK, RPPGFSPFR) were synthesized containing the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4- carboxylic acid (TOAC). TOAC replaced Asp 1 (TOAC 1-AII) and Val 3 (TOAC 3-AII) in AII and was inserted prior to Arg 1 (TOAC 0-BK) and replacing Pro 3 (TOAC 3-BK) in BK. The peptide conformational properties were examined as a function of trifluoroethanol (TFE) content and pH. Electron paramagnetic resonance spectra were sensitive to both variables and showed that internally labeled analogues yielded rotational correlation times (TC) considerably larger than N-terminally labeled ones, evincing the greater freedom of motion of the N-terminus. In TFE, τ C increased due to viscosity effects. Calculation of τ Cpeptide/τ CTOAC ratios indicated that the peptides acquired more folded conformations. Circular dichroism spectra showed that, except for TOAC 1-AII in TFE, the N-terminally labeled analogues displayed a conformational behavior similar to that of the parent peptides. In contrast, under all conditions, the TOAC 3 derivatives acquired more restricted conformations. Fluorescence spectra of All and its derivatives were especially sensitive to the ionization of Tyr 4. Fluorescence quenching by the nitroxide moiety was much more pronounced for TOAC 3-AII The conformational behavior of the TOAC derivatives bears excellent correlation with their biological activity, since, while the N-terminally labeled peptides were partially active, their internally labeled counterparts were inactive [Nakaie, C. R., et al., Peptides 2002, 23, 65-70]. The data demonstrate that insertion of TOAC in the middle of the peptide chain induces conformational restrictions that lead to loss of backbone flexibility, not allowing the peptides to acquire their receptor-bound conformation. © 2004 Wiley Periodicals, Inc.

Estudo comparativo entre as alterações produzidas pelas biomoléculas floretina e barbaloína na estrutura e na hidratação de membranas modelo negativamente carregadas de DMPG

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interaction of biologically-relevant peptides with membrane model systems

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

Towards coherent optical control of a single hole spin: Rabi rotation of a trion conditional on the spin state of the hole

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electron spin resonance of Gd3+ in the antiferromagnetic heavy fermion CeIn3 and its reference compound LaIn3

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

Magnetic interactions and spin-reversal mechanism in ErMn1-xCoxO3-delta samples

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

Fast optical preparation, control, and readout of a single quantum dot spin

We propose and demonstrate the sequential initialization, optical control, and readout of a single spin trapped in a semiconductor quantum dot. Hole spin preparation is achieved through ionization of a resonantly excited electron-hole pair. Optical control is observed as a coherent Rabi rotation between the hole and charged-exciton states, which is conditional on the initial hole spin state. The spin-selective creation of the charged exciton provides a photocurrent readout of the hole spin state.

Incommensurate spin-density-wave and metal-insulator transition in the one-dimensional periodic Anderson model

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

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

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Relating pseudospin and spin symmetries through charge conjugation and chiral transformations: the case of the relativistic harmonic oscillator

We solve the generalized relativistic harmonic oscillator in 1+1 dimensions, i.e., including a linear pseudoscalar potential and quadratic scalar and vector potentials which have equal or opposite signs. We consider positive and negative quadratic potentials and discuss in detail their bound-state solutions for fermions and antifermions. The main features of these bound states are the same as the ones of the generalized three-dimensional relativistic harmonic oscillator bound states. The solutions found for zero pseudoscalar potential are related to the spin and pseudospin symmetry of the Dirac equation in 3+1 dimensions. We show how the charge conjugation and gamma(5) chiral transformations relate the several spectra obtained and find that for massless particles the spin and pseudospin symmetry-related problems have the same spectrum but different spinor solutions. Finally, we establish a relation of the solutions found with single-particle states of nuclei described by relativistic mean-field theories with scalar, vector, and isoscalar tensor interactions and discuss the conditions in which one may have both nucleon and antinucleon bound states.

Confinement of spin-0 and spin-1/2 particles in a mixed vector-scalar coupling with unequal shapes for the potentials

The Klein - Gordon and the Dirac equations with vector and scalar potentials are investigated under a more general condition, V-v = V-s + constant. These isospectral problems are solved in the case of squared trigonometric potential functions and bound states for either particles or antiparticles are found. The eigenvalues and eigenfunctions are discussed in some detail. It is revealed that a spin-0 particle is better localized than a spin-1/2 particle when they have the same mass and are subjected to the same potentials.

Estados estacionários de partículas sem spin em potenciais quadrados

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