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PubMed2006

Plasmid DNA encapsulation within cationic diblock copolymer vesicles for gene delivery.

We report the design and structural characterization of cationic diblock copolymer vesicles loaded with plasmid DNA based on a single emulsion technique. For this purpose, a DNA solution was emulsified in an organic solvent and stabilized by an amphiphilic diblock copolymer. The neutral block forms an interfacial brush, whereas the cationic attachment complexes with DNA. A subsequent change of the quality of the organic solvent results in the collapse of the brush and the formation of a capsule. The capsules are subsequently dispersed in aqueous medium to form vesicles and stabilized with an osmotic agent in the external phase. Inside the vesicles, the plasmid is compacted in a liquid-crystalline fashion as shown by the appearance of birefringent textures under crossed polarizers and the increase in fluorescence intensity of labeled DNA. The compaction efficiency and the size distribution of the vesicles were determined by light and electron microscopy, and the integrity of the DNA after encapsulation and subsequent release was confirmed by gel electrophoresis. We demonstrate reverse transfection of in vitro cultured HeLa cancer cells growing on plasmid-copolymer vesicles deposited on a glass substrate.

Cations↗
PubMed2006

Liquid crystal model of membrane flexoelectricity.

An interfacial liquid crystal model is formulated and used to derive a membrane shape equation that takes into account pressure, tension, bending, torsion, and flexoelectric forces. Flexoelectricity introduces electric field-induced curvature and is of relevance to the study and characterization of biological membranes. It is shown that flexoelectricity renormalizes the membrane mechanical tension, shear, and bending effects, and hence it offers diverse pathways to manipulate the membrane's shape. The derived electroelastic shape equation provides systematic guidance on how to use electric fields in membrane studies.

Journal Article↗
PubMed2006

Mechanical behavior of quartz fiber reinforced epoxy resins for teeth restoration.

In this work composite materials, based on quartz fibers and epoxy resins, were employed with the aim to restore damaged teeth. The composite materials were chosen because they show biomechanical features very similar to that of the dentine, the main constituent of the tooth. Extracted teeth were rebuilt with two different restorative procedures: in the first, the composite material was pre-formed in a conical trunk shape abutment (PA) and then bonded to a fiber quartz post with a dental bonder. In the second rebuilt system the abutment was prepared by cross linking the resin on the fiber quartz post with a halogen lamp (CRA). The restored teeth were then mechanically tested and observed with a Scanning Electron Microscope (SEM) with the aim to study the interaction between the reconstructive materials. Wetting and roughness measurements were also carried out in order to study the interface adhesion between the post and the abutments. Characterization analysis evidenced that the CRA restorative procedure improves the adhesion between the substitutive materials and shows higher fracture strength than the PA ones. Anyway both the rebuilt systems are able to support the masticator load. An explanation of the interfacial post-abutment interaction phenomenon is discussed.

Adhesiveness↗
PubMed2004

Experimental isotherms of HCl on H2O ice under stratospheric conditions: connections between bulk and interfacial thermodynamics.

The adsorption of HCl on the surface of H(2)O ice has been measured at temperatures and pressures relevant to the upper troposphere and lower stratosphere. The measured HCl surface coverage is found to be at least 100 times lower than currently assumed in models of chlorine catalyzed ozone destruction in cold regions of the upper atmosphere. Measurements were conducted in a closed system by simultaneous application of surface spectroscopy and gas phase mass spectrometry to fully characterize vapor/solid equilibrium. Surface adsorption is clearly distinguished from bulk liquid or solid phases. From 180 to 200 K, submonolayer adsorption of HCl is well described by a Bragg-Williams modified Langmuir model which includes the dissociation of HCl into H(+) and Cl(-) ions. Furthermore, adsorption is consistent with two distinct states on the ice substrate, one in which the ions only weakly adsorb on separate sites, and another where the ions adsorb as an H(+)-Cl(-) pair on a single site with adsorption energy comparable to the bulk trihydrate. The number of substrate H(2)O molecules per adsorption site is also consistent with the stoichiometry of bulk hydrates under these conditions. The ionic states exist in equilibrium, and the total adsorption energy is a function of the relative population of both states. These observations and model provide a quantitative connection between the thermodynamics of the bulk and interfacial phases of HCl/H(2)O, and represent a consistent physicochemical model of the equilibrium system.

Journal Article↗
PubMed2006

Coarse-grained molecular dynamics simulations of membrane proteins and peptides.

Molecular dynamics (MD) simulations provide a valuable approach to the dynamics, structure, and stability of membrane-protein systems. Coarse-grained (CG) models, in which small groups of atoms are treated as single particles, enable extended (>100 ns) timescales to be addressed. In this study, we explore how CG-MD methods that have been developed for detergents and lipids may be extended to membrane proteins. In particular, CG-MD simulations of a number of membrane peptides and proteins are used to characterize their interactions with lipid bilayers. CG-MD is used to simulate the insertion of synthetic model membrane peptides (WALPs and LS3) into a lipid (PC) bilayer. WALP peptides insert in a transmembrane orientation, whilst the LS3 peptide adopts an interfacial location, both in agreement with experimental biophysical data. This approach is extended to a transmembrane fragment of the Vpu protein from HIV-1, and to the coat protein from fd phage. Again, simulated protein/membrane interactions are in good agreement with solid state NMR data for these proteins. CG-MD has also been applied to an M3-M4 fragment from the CFTR protein. Simulations of CFTR M3-M4 in a detergent micelle reveal formation of an alpha-helical hairpin, consistent with a variety of biophysical data. In an I231D mutant, the M3-M4 hairpin is additionally stabilized via an inter-helix Q207/D231 interaction. Finally, CG-MD simulations are extended to a more complex membrane protein, the bacterial sugar transporter LacY. Comparison of a 200 ns CG-MD simulation of LacY in a DPPC bilayer with a 50 ns atomistic simulation of the same protein in a DMPC bilayer shows that the two methods yield comparable predictions of lipid-protein interactions. Taken together, these results demonstrate the utility of CG-MD simulations for studies of membrane/protein interactions.

Amino Acid Sequence↗
PubMed1998

Molecular dynamics simulation of melittin in a dimyristoylphosphatidylcholine bilayer membrane.

Molecular dynamics trajectories of melittin in an explicit dimyristoyl phosphatidylcholine (DMPC) bilayer are generated to study the details of lipid-protein interactions at the microscopic level. Melittin, a small amphipathic peptide found in bee venom, is known to have a pronounced effect on the lysis of membranes. The peptide is initially set parallel to the membrane-solution interfacial region in an alpha-helical conformation with unprotonated N-terminus. Solid-state nuclear magnetic resonance (NMR) and polarized attenuated total internal reflectance Fourier transform infrared (PATIR-FTIR) properties of melittin are calculated from the trajectory to characterize the orientation of the peptide relative to the bilayer. The residue Lys7 located in the hydrophobic moiety of the helix and residues Lys23, Arg24, Gln25, and Gln26 at the C-terminus hydrophilic form hydrogen bonds with water molecules and with the ester carbonyl groups of the lipids, suggesting their important contribution to the stability of the helix in the bilayer. Lipid acyl chains are closely packed around melittin, contributing to the stable association with the membrane. Calculated density profiles and order parameters of the lipid acyl chains averaged over the molecular dynamics trajectory indicate that melittin has effects on both layers of the membrane. The presence of melittin in the upper layer causes a local thinning of the bilayer that favors the penetration of water through the lower layer. The energetic factors involved in the association of melittin at the membrane surface are characterized using an implicit mean-field model in which the membrane and the surrounding solvent are represented as structureless continuum dielectric material. The results obtained by solving the Poisson-Bolztmann equation numerically are in qualitative agreement with the detailed dynamics. The influence of the protonation state of the N-terminus of melittin is examined. After 600 ps, the N-terminus of melittin is protonated and the trajectory is continued for 400 ps, which leads to an important penetration of water molecules into the bilayer. These observations provide insights into how melittin interacts with membranes and the mechanism by which it enhances their lysis.

Amino Acid Sequence↗
PubMed2006

Molecular structure of a supported VO4 cluster and its interfacial geometry as a function of the SiO2, Nb2O5, and ZrO2 support.

The influence of the support oxide on the molecular structure of a VO(4) cluster and its interfacial geometry has been determined for SiO(2), Nb(2)O(5), and ZrO(2) as supports. Raman, IR, UV-vis-NIR diffuse reflectance, electron spin resonance, and extended X-ray absorption fine structure (EXAFS) spectroscopies were used to characterize the supported vanadium oxide clusters after dehydration. It has been found that for all supports under investigation the vanadium ion is tetrahedral coordinated and consists of one V=O and three V-O bonds. For a VO(4)/SiO(2) catalyst it has been established that only one O neighbor is shared with the SiO(2) support via a V-O(b)-Si(support) bond with an angle of approximately 101 degrees (+/-0.5 degrees ) and a V...Si distance of 2.61 A. The absence of a second vanadium atom in the vicinity of the vanadium oxide cluster further subverts the classical assignment of the 920 cm(-1) Raman band to a V-O-V related vibration. The EXAFS results combined with structural modeling using Cerius(2) software lead to structural constraints, which imply a similar V-O(b)-M(support) interaction for Nb(2)O(5) and ZrO(2) as well. The V-O(b) and the V...M(support) distances depend on the geometry of each support surface. The results show that the classical model with three V-O(b)-M(support) bonds could not be experimentally observed with EXAFS under the applied measuring conditions. Additional experiments with IR and Raman spectroscopy under experimental conditions mimicking those of the EXAFS measurements reveal the presence of V-OH groups, giving further support for the presence of a O=V(OH)(2)-O(b)-M moiety at the support surface.

Journal Article↗
PubMed2006

Vstx1, a modifier of Kv channel gating, localizes to the interfacial region of lipid bilayers.

VSTx1 is a tarantula venom toxin which binds to the archaebacterial voltage-gated potassium channel KvAP. VSTx1 is thought to access the voltage sensor domain of the channel via the lipid bilayer phase. In order to understand its mode of action and implications for the mechanism of channel activation, it is important to characterize the interactions of VSTx1 with lipid bilayers. Molecular dynamics (MD) simulations (for a total simulation time in excess of 0.2 micros) have been used to explore VSTx1 localization and interactions with zwitterionic (POPC) and with anionic (POPE/POPG) lipid bilayers. In particular, three series of MD simulations have been used to explore the net drift of VSTx1 relative to the center of a bilayer, starting from different locations of the toxin. The preferred location of the toxin is at the membrane/water interface. Although there are differences between POPC and POPE/POPG bilayers, in both cases the toxin forms favorable interactions at the interface, maximizing H-bonding to lipid headgroups and to water molecules while retaining interactions with the hydrophobic core of the bilayer. A 30 ns unrestrained simulation reveals dynamic partitioning of VSTx1 into the interface of a POPC bilayer. The preferential location of VSTx1 at the interface is discussed in the context of Kv channel gating models and provides support for a mode of action in which the toxin interacts with the Kv voltage sensor "paddle" formed by the S3 and S4 helices.

Archaeal Proteins↗
PubMed2006

Probing the interfacial structure of aqueous electrolytes with femtosecond second harmonic generation spectroscopy.

The existence of polarizable anions at the outermost layer of electrolyte solutions has received much recent attention from both theory and experiment, but remains controversial. Anions can be probed directly in the UV via their strong charge-transfer-to-solvent (CTTS) transitions. We have recently described experimental characterizations of enhanced concentrations of several anions at the air-water interface, using the surface-specific technique of second harmonic generation. Here we present a detailed description of the experimental design and methodology used in these experiments, as well as a proof of principle experiment with the known surfactant tetrabutylammonium iodide (TBAI), yielding surface enhancements in excellent agreement with surface tension measurements. Furthermore, we analyze the observed increase in the nonresonant contribution to the SHG response from the water background of alkali halide solutions. The observed change in the water structure of alkali halide (except iodide) solutions is linear in concentration and correlates with the fractional saturation concentration of the salt and with the ionic volume fraction. Finally, the surface adsorption of iodide at high bulk concentrations is analyzed, but it is not possible to differentiate between a Gibbs free energy of adsorption of zero (surface concentration proportional to the bulk) or -0.8 kcal/mol, as predicted by recent molecular dynamics simulations.

Journal Article↗
PubMed2006

A simple two-phase route to silver nanoparticles/polyaniline structures.

Novel silver nanoparticles/polyaniline composites were obtained through a two-phase water/toluene interfacial reaction. We show that by rigorously controlling the reaction time, different structures of the nanocomposites can be obtained, such as a thin sheet of polyaniline around the silver nanoparticles or a polymer mass with nanoparticles homogeneously embedded within it. Samples were characterized by FT-IR, UV-vis-NIR and Raman spectroscopy, X-ray diffraction, cyclic voltammetry, TEM, and HRTEM. Conductivity and current-voltage characteristics of the nanocomposites were measured, and the results indicate that different properties result from the different structures in which the nanocomposites were formed.

Journal Article↗
PubMed2006

Supramolecular chirality from an achiral azobenzene derivative through the interfacial assembly: effect of the configuration of azobenzene unit.

The Langmuir-Schaefer (LS) films of an achiral azobenzene derivative, 4-octyl-4'-(5-carboxypentamethyleneoxy) azobenzene (C8AzoC5), were fabricated and their optical activities were investigated. It was found that the LS film of the trans-C8AzoC5 showed strong Cotton effect, while that of cis-C8AzoC5 did not. The characterization of the LS films by UV-vis, Fourier transform infrared (FT-IR) spectra, and X-ray diffraction (XRD) revealed that this interesting phenomenon was due to the different packing of the azobenzene unit in the LS film. The planar conjugated trans-azobenzene favored ordered cooperative packing in a helical sense and produced the supramolecular chirality, while the cis-isomer did not due to the bulky twisted configuration.

Journal Article↗
PubMed2006

Local waiting time fluctuations along a randomly pinned crack front.

The propagation of an interfacial crack along a heterogeneous weak plane of a transparent Plexiglas block is followed using a high resolution fast camera. We show that the fracture front dynamics is governed by local and irregular avalanches with very large size and velocity fluctuations. We characterize the intermittent dynamics observed, i.e., the local pinnings and depinnings of the crack front by measuring the local waiting time fluctuations along the crack front during its propagation. The deduced local front line velocity distribution exhibits a power law behavior, P(v) alpha v-eta with eta=2.55+/-0.15, for velocities v larger than the average front speed . The burst size distribution is also a power law, P(S) alpha S-gamma with gamma=1.7+/-0.1. Above a characteristic length scale of disorder Ld approximately 15 microm, the avalanche clusters become anisotropic providing an estimate of the roughness exponent of the crack front line, H=0.66.

Journal Article↗
PubMed1992

Rat platelet phospholipase A2. Kinetic characterization using the monomolecular film technique.

We have determined some kinetic parameters of rat platelet phospholipase A2, such as surface pressure dependency and substrate specificity, using the monomolecular film technique. We found that rat platelet phospholipase A2 is very specific for phospholipids having a negatively charged headgroup, no activity was detected when using zwitterionic phospholipids such as phosphatidylcholine. Furthermore, the interfacial pressure window which permits enzyme activity is very narrow as compared to pancreatic phospholipase A2. Maximal enzyme activity is found at 22 mN/m when using 1,2-dilauroylphosphatidylglycerol as substrate. Studies of the competitive inhibition of mixed films containing 2-acylaminophosphatidylglycol show that platelet phospholipase A2 is less sensitive than pancreatic and intestinal phospholipase A2. These results imply that, despite the high degree of sequence similarity, one must be very cautious in extrapolating inhibition data from one phospholipase A2 to similar enzymes from other origins.

Animals↗
PubMed2005

Photocatalytic storing of O2 as H2O2 mediated by high surface area CuO. Evidence for a reductive-oxidative interfacial mechanism.

CuO powders with a high specific surface area are shown to be able to produce H(2)O(2) in aqueous solution under simulated light irradiation. The highest rate of peroxide production was observed under mild experimental conditions using O(2) and a large surface area photocatalyst CuO irradiated with a solar simulator having light intensities between 60 and 90 mW/cm(2). The CuO employed had a specific surface area (SSA) of 64.8-70.1 m(2)/g and was prepared in a tubular furnace by controlled thermal decomposition of precipitated copper oxalate. The CuO particles produced were 1 mum cubes with primary particles around 15 nm. No peroxide was produced under the same conditions with commercial CuO, with SSA 200 times lower. The CuO synthesized during this work was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), specific surface area [Brunauer-Emmett-Teller (BET)], porosity, and X-ray photoelectron spectroscopy (XPS). From XPS, it was observed that only Cu(II) was present in the unused and used CuO. This indicates that the redox transient species involving other Cu oxidation states disappear very fast during the reaction, regenerating Cu(II) during H(2)O(2) production. Diverse experiments provided some evidence for the possible interfacial reaction mechanism leading to H(2)O(2), following the initial step of O(2)(-)(.) formation on the CuO surface under irradiation with photons, with energies exceeding the band gap of CuO. A photocatalyzed degradation of a concentrated 4-chlorophenol (4-CP) solution was observed under solar-simulated light in the presence of CuO.

Adsorption↗
PubMed2005

Surface modification of magnetic nanoparticles capped by oleic acids: characterization and colloidal stability in polar solvents.

The lyophobic surface of monodisperse magnetic nanoparticles capped by oleic acid was made to be more lyophilic by ozonolysis to increase the stability of the suspension in polar solvents like ethanol. The ozone oxidatively cleaved the double bond of oleic acid to form carbonyl and carboxyl groups on the surface of the nanoparticles. Additionally, interfacial ligand exchange of the capping molecules was applied to make the hydrophobic particle surface more hydrophilic. The magnetic particles showed enhanced miscibility and short-term stability in water after interfacial ligand exchange. The structure changes of the capping molecules on the nanoparticle surfaces were investigated using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). From these spectroscopy studies, the cleavage of the oleic acid and the formations of the carboxyl and carbonyl groups on the particle surface were confirmed. The shape and the magnetic properties of the nanoparticles were maintained after the surface modification. Ozonolysis is an effective method in modifying the lyophobic surface of the magnetic nanoparticles.

Journal Article↗
PubMed1994

Poly(alkylcyanoacrylate) nanocapsules: physicochemical characterization and mechanism of formation.

Nanocapsules of poly(isobutylcyanoacrylate) and poly(isohexylcyanoacrylate) were prepared by addition of the monomer to an organic phase and subsequent mixing of the organic phase to an aqueous phase containing poloxamer 188, 238 or 407. Gel permeation chromatography indicated that in contrast to literature reports, polymerization occurred in the organic phase and nanocapsules were obtained by interfacial precipitation of the polymer without any significant change of the molecular weight. Addition of SO2 to the organic phase before the introduction of the monomer allowed preparation of nanocapsules with a lower molecular weight. Nanospheres were prepared in a similar way albeit using an organic phase that was completely miscible within the aqueous phase so that solid spheres were obtained. Density gradient centrifugation revealed that nanocapsules had a density intermediate between nanospheres and an emulsion prepared in the same way without addition of monomer to the organic phase. Further, the process used to prepare nanocapsules had a high yield since no oil droplets or nanospheres were obtained by this process. Zeta potential of the nanocapsules and spheres was found to be related to the molecular weight of the polymer: values as high as approximately -42 mV were obtained for low molecular weight nanocapsules (MW approximately 1000) compared to approximately -10mV for the emulsion and the high molecular weight nanocapsules (MW approximately 100,000). Surface charge of the nanocapsules and molecular weight of their polymeric wall conditioned the adsorption capacity of poloxamers. Moreover, the highest adsorption was measured with the most hydrophobic poloxamer. These observations agree with previous work conducted on hydrophobic surfaces.

Adsorption↗
PubMed1997

Osteoblastic phenotype expression on the surface of hydroxyapatite ceramics.

To analyze the bone-bonding property of hydroxyapatite ceramics (HA), composites of rat marrow cells and porous HA were implanted subcutaneously and harvested at 3 to 4 weeks postimplantation. De novo bone formation was observed primarily on the HA surface without fibrous tissue interposition. The HA/tissue interface was analyzed by the observations of thin undecalcified histological sections and fractured surfaces of the implants. The observations were done with a light microscope and a scanning electron microscope (SEM) connected to an energy dispersive spectrometer. The interfacial analyses showed the appearance of osteoblastic cells on the HA surface and that the cells had initiated partially mineralized bone (osteoid) formation directly onto the surface. The osteoid matured into fully mineralized bone, resulting in firm bone bonding to the HA surface. Characterization of osteoblastic cells on the surface was done by determining levels of protein and gene expression of bone Gla protein (BGP, a.k.a. Osteocalcin), i.e., immunohistochemistry and in situ hybridization, respectively. The existence of BGP and mRNA in the cytoplasmic area of the cells confirmed that active osteoblast apposition fabricated primary bone on the HA surface. All of these results indicate the importance of the HA surface in supporting osteoblastic differentiation of marrow stromal stem cells, which leads to firm bone bonding.

Animals↗
PubMed2005

Solvation of coumarin 314 at water/air interfaces containing anionic surfactants. I. Low coverage.

Through the use of molecular dynamics techniques, we analyze equilibrium and dynamical aspects of the solvation of Coumarin 314 adsorbed at water/air interfaces in the presence of sodium dodecyl sulfate surfactant molecules. Three different coverages in the submonolayer regime were considered, 500, 250, and 100 A(2)/SDS molecule. The surfactant promotes two well-differentiated solvation environments, which can be clearly distinguished in terms of their structures for the largest surfactant coverage considered. The first one is characterized by the probe lying adjacent or exterior to two-dimensional spatial domains formed by clustered surfactant molecules. A second type of solvation environment is found in which the coumarin appears embedded within compact surfactant domains. Equilibrium and dynamical aspects of the interfacial orientation of the probe are investigated. Our results show a gradual transition from parallel to perpendicular dipolar alignment of the probe with respect to the interface as the concentration of surfactant rho(s) increases. The presence of the surfactant leads to an increase in the roughness and in the characteristic width of the water/air interface. These modifications are also manifested by the decorrelation times for the probe reorientational dynamics, which become progressively slower with rho(s) in both solvation states, although much more pronounced for the embedded ones. The dynamical characteristics of the solvation responses of the charged interfaces are also analyzed, and the implications of our findings to the interpretation of available experimental measurements are discussed.

Air↗