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Biologically relevant monolayer and bilayer films often consist of micron-scale high viscosity domains in a continuous low viscosity matrix. Here we show that this morphology can cause the overall monolayer fluidity to vary by orders of magnitude over a limited range of monolayer compositions. Modeling the system as a two-dimensional suspension in analogy with classic three-dimensional suspensions of hard spheres in a liquid solvent explains the rheological data with no adjustable parameters. In monolayers with ordered, highly viscous domains dispersed in a continuous low viscosity matrix, the surface viscosity increases as a power law with the area fraction of viscous domains. Changing the phase of the continuous matrix from a disordered fluid phase to a more ordered, condensed phase dramatically changes the overall monolayer viscosity. Small changes in the domain density and/or continuous matrix composition can alter the monolayer viscosity by orders of magnitude.

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Evidence for the validity of the pairing glue interpretation of high temperature superconductivity is presented using a modified Eliashberg analysis of experimental superconductor-insulator-superconductor (SIS) tunneling data in B2Sr2CaCu2O8 (Bi2212) over a wide range of doping. This is accomplished by extracting detailed information on the diagonal and anomalous contributions to the quasiparticle self-energy. In particular, a comparison of the imaginary part of the anomalous self-energy ImΦ(ω) and the pairing glue spectral function α2F(ω) used in the model is consistent with Hubbard model simulations in the literature. In addition, the real part of the diagonal self-energy for optimal doped Bi2212 bears a strong resemblance to that obtained from photoemission experiments.

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Two-dimensional films of surface-active agents-from phospholipids and proteins to nanoparticles and colloids-stabilize fluid interfaces, which are essential to the science, technology and engineering of everyday life. The 2D nature of interfaces present unique challenges and opportunities: coupling between the 2D films and the bulk fluids complicates the measurement of surface dynamic properties, but allows the interfacial microstructure to be directly visualized during deformation. Here we present a novel technique that combines active microrheology with fluorescence microscopy to visualize fluid interfaces as they deform under applied stress, allowing structure and rheology to be correlated on the micron-scale in monolayer films. We show that even simple, single-component lipid monolayers can exhibit viscoelasticity, history dependence, a yield stress and hours-long time scales for elastic recoil and aging. Simultaneous visualization of the monolayer under stress shows that the rich dynamical response results from the cooperative dynamics and deformation of liquid-crystalline domains and their boundaries.

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Monolayers based on the composition of the cytoplasmic (CYT) or extracellular (EXT) sides of the myelin bilayer form coexisting immiscible liquid phases similar to the liquid-ordered/liquid-disordered phases in phospholipid/cholesterol monolayers. Increasing the temperature or surface pressure causes the two liquid phases to mix, although in significantly different fashion for the CYT and EXT monolayers. The cerebroside-rich EXT monolayer is near a critical composition and the domains undergo coalescence and a circle-to-stripe transition along with significant roughening of the domain boundaries before mixing. The phase transition in the cerebroside-free cytoplasmic side occurs abruptly without domain coalescence; hence, the cytoplasmic monolayer is not near a critical composition, although the domains exhibit shape instabilities within 1-2 mN/m of the transition. The change in mixing pressure decreases significantly with temperature for the EXT monolayer, with dΠ(crit)/dT ∼ 1.5 mN/m/°C, but the mixing pressure of the CYT monolayer varies little with temperature. This is due to the differences in the nonideality of cholesterol interactions with cerebrosides (EXT) relative to phospholipids (CYT). EXT monolayers based on the composition of white matter from marmosets with experimental allergic encephalomyelitis (EAE), an animal model of multiple sclerosis, remain phase-separated at higher surface pressures than control, while EAE CYT monolayers are similar to control. Myelin basic protein, when added to the CYT monolayer, increases lipid miscibility in CYT monolayers; likely done by altering the dipole density difference between the two phases.

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The magnetically driven rotation of 300 nm diameter rods shows the surface viscosity of albumin at an air-water interface increases from 10(-9) to 10(-5) N s/m over 2 h while the surface pressure saturates in minutes. The increase in surface viscosity is not accompanied by a corresponding increase in elasticity, suggesting that the protein film anneals with time, resulting in a more densely packed film leading to increased resistance to shear. The nanometer dimensions of the rods provide the same sensitivity as passive microrheology with an improved ability to measure more viscous films.

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In the formation of chiral crystals, the tendency for twist in the orientation of neighboring molecules is incompatible with ordering into a lattice: Twist is expelled from planar layers at the expense of local strain. We report the ordered state of a neat material in which a local chiral structure is expressed as twisted layers, a state made possible by spatial limitation of layering to a periodic array of nanoscale filaments. Although made of achiral molecules, the layers in these filaments are twisted and rigorously homochiral--a broken symmetry. The precise structural definition achieved in filament self-assembly enables collective organization into arrays in which an additional broken symmetry--the appearance of macroscopic coherence of the filament twist--produces a liquid crystal phase of helically precessing layers.

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A d-wave, Eliashberg analysis of break-junction and STM tunneling spectra on Bi2Sr2CaCu2O(8+delta) (Bi2212) reveals that the spectral dip feature is directly linked to strong electronic coupling to a narrow boson spectrum, evidenced by a large peak in alpha2F(omega). The tunneling dip feature remains robust in the overdoped regime of Bi2212 with bulk T(c) values of 56 K-62 K. This is contrary to recent optical conductivity measurements of the self-energy that suggest the narrow boson spectrum disappears in overdoped Bi2212 and therefore cannot be essential for the pairing mechanism. The discrepancy is resolved by considering the way each technique probes the electron self-energy, in particular, the unique sensitivity of tunneling to the off-diagonal or pairing part of the self-energy.

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Surfactant protein B (SP-B) is essential for normal lung surfactant function. Theoretical models predict that the disulfide cross-linked, N- and C-terminal domains of SP-B fold as charged amphipathic helices, and suggest that these adjacent helices participate in critical surfactant activities. This hypothesis is tested using a disulfide-linked construct (Mini-B) based on the primary sequences of the N- and C-terminal domains. Consistent with theoretical predictions of the full-length protein, both isotope-enhanced Fourier transform infrared (FTIR) spectroscopy and molecular modeling confirm the presence of charged amphipathic alpha-helices in Mini-B. Similar to that observed with native SP-B, Mini-B in model surfactant lipid mixtures exhibits marked in vitro activity, with spread films showing near-zero minimum surface tensions during cycling using captive bubble surfactometry. In vivo, Mini-B shows oxygenation and dynamic compliance that compare favorably with that of full-length SP-B. Mini-B variants (i.e. reduced disulfides or cationic residues replaced by uncharged residues) or Mini-B fragments (i.e. unlinked N- and C-terminal domains) produced greatly attenuated in vivo and in vitro surfactant properties. Hence, the combination of structure and charge for the amphipathic alpha-helical N- and C-terminal domains are key to SP-B function.

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Study of a diverse set of chiral smectic materials, each of which has twist grain boundary (TGB) phases over a broad temperature range and exhibits grid patterns in the Grandjean textures of the TGB helix, shows that these features arise from a common structure: "giant" smectic blocks of planar layers of thickness l(b) > 200 nm terminated by GBs that are sharp, mediating large angular jumps in layer orientation between blocks (60 degrees < Delta < 90 degrees ), and lubricating the thermal contraction of the smectic layers within the blocks. This phenomenology is well described by basic theoretical models applicable in the limit that the ratio of molecular tilt penetration length-to-layer coherence length is large, and featuring GBs in which smectic ordering is weak, approaching thin, melted (nematic-like) walls. In this limit the energy cost of change of the block size is small, leading to a wide variation of block dimension, depending on preparation conditions. The models also account for the temperature dependence of the TGB helix pitch.

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Near-infrared (NIR) femtosecond laser irradiation of metallodielectric core-shell silica-gold (SiO(2)-Au) nanoparticles can induce extreme local heating prior to the rapid dissipation of energy caused by the large surface area/volume ratio of nanometer-scale objects. At low pulse intensities, the dielectric silica core is removed, leaving an incomplete gold shell behind. The gold shells with water inside and out still efficiently absorb NIR light from subsequent pulses, showing that a complete shell is not necessary for absorption. At higher pulse intensities, the gold shell itself is melted and disrupted, leading to smaller, approximately 20-nm gold nanoparticles. Spectroscopic measurements show that this disruption is accompanied by optical hole burning of the peak at 730 nm and formation of a new peak at 530 nm. The silica removal and gold shell disruption confirms significant temperature rise of the core-shall nanoparticle. However, the entire process leads to minimal heating of the bulk solution due to the low net energy input.

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Assembling structures to divide space controllably and spontaneously into subunits at the nanometer scale is a significant challenge, although one that biology has solved in two distinct ways: prokaryotes and eukaryotes. Prokaryotes have a single compartment delimited by one or more lipid-protein membranes. Eukaryotes have nested-membrane structures that provide internal compartments--such as the cell nucleus and cell organelles in which specialized functions are carried out. We have developed a simple method of creating nested bilayer compartments in vitro via the "interdigitated" bilayer phase formed by adding ethanol to a variety of saturated phospholipids. At temperatures below the gel-liquid crystalline transition, T(m), the interdigitated lipid-ethanol sheets are rigid and flat; when the temperature is raised above T(m), the sheets become flexible and close on themselves and the surrounding solution to form closed compartments. During this closure, the sheets can entrap other vesicles, biological macromolecules, or colloidal particles. The result is efficient and spontaneous encapsulation without disruption of even fragile materials to form biomimetic nano-environments for possible use in drug delivery, colloidal stabilization, or as microreactors. The vesosome structure can take full advantage of the 40 years of progress in liposome development including steric stabilization, pH loading of drugs, and intrinsic biocompatibility. However, the multiple compartments of the vesosome give better protection to the interior contents in serum, leading to extended release of model compounds in comparison to unilamellar liposomes.

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Any polar-ordered material with a spatially uniform polarization field is internally frustrated: The symmetry-required local preference for polarization is to be nonuniform, i.e., to be locally bouquet-like or "splayed." However, it is impossible to achieve splay of a preferred sign everywhere in space unless appropriate defects are introduced into the field. Typically, in materials like ferroelectric crystals or liquid crystals, such defects are not thermally stable, so that the local preference is globally frustrated and the polarization field remains uniform. Here, we report a class of fluid polar smectic liquid crystals in which local splay prevails in the form of periodic supermolecular-scale polarization modulation stripes coupled to layer undulation waves. The polar domains are locally chiral, and organized into patterns of alternating handedness and polarity. The fluid-layer undulations enable an extraordinary menagerie of filament and planar structures that identify such phases.

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In mixtures of cetyltrimethylammonium bromide (CTAB) and sodium perfluorooctanoate (FC(7)) in aqueous solution, novel bilayer cylinders with hemispherical end caps and open, flat discs coexist with spherical unilamellar vesicles, apparently at equilibrium. Such equilibrium among bilayer cylinders, spheres, and discs is only possible for systems with a spontaneous curvature, R(o), and a positive Gaussian curvature modulus, kappa. We have measured the size distributions of the spherical vesicles, cylinders, and discs by using cryo-electron microscopy; a simple analysis of this length distribution allows us to independently determine that the mean curvature modulus, kappa approximately 5 +/- 1 k(B)T and kappa approximately 2 +/- 1 k(B)T. This is one of the few situations in which R(o), kappa, and kappa can be determined from the same experiment. From a similar analysis of the disk size distribution, we find that the edges of the discs are likely stabilized by excess CTAB. The fraction of discs, spherical vesicles, and cylinders depends on the CTABFC(7) mole ratio: increasing CTAB favors discs, while decreasing CTAB favors cylinders. This control over aggregate shape with surfactant concentration may be useful for the design of templates for polymerization, mesoporous silicates, etc.

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Superconductor-insulator-superconductor tunnel junctions have been fabricated on MgB2 that display Josephson and quasiparticle currents. These junctions exhibit a gap magnitude, Delta approximately 2.5 meV, that is considerably smaller than the BCS value, but which clearly and reproducibly closes near the bulk T(c). In conjunction with fits of the conductance spectra, these results are interpreted as direct evidence of two-band superconductivity.

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Endogenous lung surfactant, and lung surfactant replacements used to treat respiratory distress syndrome, can be inactivated during lung edema, most likely by serum proteins. Serum albumin shows a concentration-dependent surface pressure that can exceed the respreading pressure of collapsed monolayers in vitro. Under these conditions, the collapsed surfactant monolayer can not respread to cover the interface, leading to higher minimum surface tensions and alterations in isotherms and morphology. This is an unusual example of a blocked phase transition (collapsed to monolayer form) inhibiting bioactivity. The concentration-dependent surface activity of other common surfactant inhibitors including fibrinogen and lysolipids correlates well with their effectiveness as inhibitors. These results show that respreading pressure may be as important as the minimum surface tension in the design of replacement surfactants for respiratory distress syndrome.

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Defects in the layering of Langmuir-Blodgett (LB) films can be eliminated by depositing from the appropriate monolayer phase at the air-water interface. LB films deposited from the hexagonal phase of cadmium arachidate (CdA2) at pH 7 spontaneously transform into the bulk soap structure, a centrosymmetric bilayer with an orthorhombic herringbone packing. A large wavelength folding mechanism accelerates the conversion between the two structures, leading to a disruption of the desired layering. At pH > 8.5, though it is more difficult to draw LB films, almost perfect layering is obtained due to the inability to convert from the as-deposited structure to the equilibrium one.

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New break-junction tunneling data are reported in Bi(2)Sr(2)CaCu(2)O(8+delta) over a wide range of hole concentration from underdoped (T(c) = 74 K) to optimal doped (T(c) = 95 K) to overdoped (T(c) = 48 K). The conductances exhibit sharp dips at a voltage, Omega/e, measured with respect to the superconducting gap. Clear trends are found such that the dip strength is maximum at optimal doping and that Omega scales as 4.9kT(c) over the entire doping range. These features link the dip to the resonance spin excitation and suggest quasiparticle interactions with this mode are important for superconductivity.

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Langmuir isotherms, fluorescence microscopy, and atomic force microscopy were used to study lung surfactant specific proteins SP-B and SP-C in monolayers of dipalmitoylphosphatidylglycerol (DPPG) and palmitoyloleoylphosphatidylglycerol (POPG), which are representative of the anionic lipids in native and replacement lung surfactants. Both SP-B and SP-C eliminate squeeze-out of POPG from mixed DPPG/POPG monolayers by inducing a two- to three-dimensional transformation of the fluid-phase fraction of the monolayer. SP-B induces a reversible folding transition at monolayer collapse, allowing all components of surfactant to remain at the interface during respreading. The folds remain attached to the monolayer, are identical in composition and morphology to the unfolded monolayer, and are reincorporated reversibly into the monolayer upon expansion. In the absence of SP-B or SP-C, the unsaturated lipids are irreversibly lost at high surface pressures. These morphological transitions are identical to those in other lipid mixtures and hence appear to be independent of the detailed lipid composition of the monolayer. Instead they depend on the more general phenomena of coexistence between a liquid-expanded and liquid-condensed phase. These three-dimensional monolayer transitions reconcile how lung surfactant can achieve both low surface tensions upon compression and rapid respreading upon expansion and may have important implications toward the optimal design of replacement surfactants. The overlap of function between SP-B and SP-C helps explain why replacement surfactants lacking in one or the other proteins often have beneficial effects.

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This work reports the first x-ray scattering measurements to determine the effects of SP-B(1-25), the N-terminus peptide of lung surfactant-specific protein SP-B, on the structure of palmitic acid (PA) monolayers. In-plane diffraction shows that the peptide fluidizes a portion of the monolayer but does not affect the packing of the residual ordered phase. This implies that the peptide resides in the disordered phase, and that the ordered phase is essentially pure lipid, in agreement with fluorescence microscopy studies. X-ray reflectivity shows that the peptide is oriented in the lipid monolayer at an angle of approximately 56 degrees relative to the interface normal, with one end protruding past the hydrophilic region into the fluid subphase and the other end embedded in the hydrophobic region of the monolayer. The quantitative insights afforded by this study lead to a better understanding of the lipid/protein interactions found in lung surfactant systems.

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Langmuir isotherms and fluorescence and atomic force microscopy images of synthetic model lung surfactants were used to determine the influence of palmitic acid and synthetic peptides based on the surfactant-specific proteins SP-B and SP-C on the morphology and function of surfactant monolayers. Lung surfactant-specific protein SP-C and peptides based on SP-C eliminate the loss to the subphase of unsaturated lipids necessary for good adsorption and respreading by inducing a transition between monolayers and multilayers within the fluid phase domains of the monolayer. The morphology and thickness of the multilayer phase depends on the lipid composition of the monolayer and the concentration of SP-C or SP-C peptide. Lung surfactant protein SP-B and peptides based on SP-B induce a reversible folding transition at monolayer collapse that allows all components of surfactant to be retained at the interface during respreading. Supplementing Survanta, a clinically used replacement lung surfactant, with a peptide based on the first 25 amino acids of SP-B also induces a similar folding transition at monolayer collapse. Palmitic acid makes the monolayer rigid at low surface tension and fluid at high surface tension and modifies SP-C function. Identifying the function of lung surfactant proteins and lipids is essential to the rational design of replacement surfactants for treatment of respiratory distress syndrome.

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